CA1201242A - Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphite - Google Patents
Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphiteInfo
- Publication number
- CA1201242A CA1201242A CA000413158A CA413158A CA1201242A CA 1201242 A CA1201242 A CA 1201242A CA 000413158 A CA000413158 A CA 000413158A CA 413158 A CA413158 A CA 413158A CA 1201242 A CA1201242 A CA 1201242A
- Authority
- CA
- Canada
- Prior art keywords
- resin
- polyphenylene ether
- composition according
- trineopentylene
- diphosphite
- 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
- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
Abstract
POLYPHENYLENE ETHER RESINS AND
COMPOSITIONS HEAT STABILIZED WITH
TRINEOPENTYLENE DIPHOSPHITE
ABSTRACT OF THE DISCLOSURE
Polyphenylene ether resins and resin compositions in admixture with trineopentylene diphosphite as a thermal oxidative stabilizer are described. These can be used with or without an impact modifier for the polyphenylene ether resin. An additional benefit is that the resins and compositions exhibit a higher heat distortion temperature.
COMPOSITIONS HEAT STABILIZED WITH
TRINEOPENTYLENE DIPHOSPHITE
ABSTRACT OF THE DISCLOSURE
Polyphenylene ether resins and resin compositions in admixture with trineopentylene diphosphite as a thermal oxidative stabilizer are described. These can be used with or without an impact modifier for the polyphenylene ether resin. An additional benefit is that the resins and compositions exhibit a higher heat distortion temperature.
Description
UNITED STATES PATENT APPLICATION
OF: ROBERT JAY AXELROD
FOR: POLYPHENYLENE ETHER ROSINS AND
COMPOSITIONS ~3AT STABILXZED WITH
TRINEOPENTYLENE DIPHOSPHITE
BACKGROUND OF THE INVENTION
The term "polyphenylene ether resin" is well known as defining class of thermoplastic materials which possess outstanding physical properties, including hvdrolytic stability, dimensional stability and excellent dielectric characteristics. Methods of preparation are known in the art and described in the patent literature, e.g., Hay, U.S. Pat.Nos. 3,306,874, and 3,306~875 and Stamatoff, U.S. Pat. Nos. 3,257,357 and 3,257,358. Other patents which show the preparation of polyphenylene ether resins include Bennett and Cooper, U.S. Pat. Nos. 3,369,656 and 3,838,102, as well as Cooper and Bennett, U.S. Pat.
Nos. 3,642,699, 3,661,849 and 3,733,299.
A shortcoming of such thermoplastic materials is that they are thermally unstable at elevated temperatures considerably above room temperature, and even at lower temperatures upon prolonged exposure. As a result, the polymer can undergo oxidation and degradation when extruded or molded, as indicated by a tell-tale yellowish tinge. This imparts an unsightly appearance to the extruded or molded article and can adversely affect mechanical properties as well.
It is known that the thermal oxidative stability o polyphenylene ether resins can be improved by including I.
certain stabilizers with the resin. One such stabilizer is diphenyl decyl phosphite. See also U.S. Patent Number
OF: ROBERT JAY AXELROD
FOR: POLYPHENYLENE ETHER ROSINS AND
COMPOSITIONS ~3AT STABILXZED WITH
TRINEOPENTYLENE DIPHOSPHITE
BACKGROUND OF THE INVENTION
The term "polyphenylene ether resin" is well known as defining class of thermoplastic materials which possess outstanding physical properties, including hvdrolytic stability, dimensional stability and excellent dielectric characteristics. Methods of preparation are known in the art and described in the patent literature, e.g., Hay, U.S. Pat.Nos. 3,306,874, and 3,306~875 and Stamatoff, U.S. Pat. Nos. 3,257,357 and 3,257,358. Other patents which show the preparation of polyphenylene ether resins include Bennett and Cooper, U.S. Pat. Nos. 3,369,656 and 3,838,102, as well as Cooper and Bennett, U.S. Pat.
Nos. 3,642,699, 3,661,849 and 3,733,299.
A shortcoming of such thermoplastic materials is that they are thermally unstable at elevated temperatures considerably above room temperature, and even at lower temperatures upon prolonged exposure. As a result, the polymer can undergo oxidation and degradation when extruded or molded, as indicated by a tell-tale yellowish tinge. This imparts an unsightly appearance to the extruded or molded article and can adversely affect mechanical properties as well.
It is known that the thermal oxidative stability o polyphenylene ether resins can be improved by including I.
certain stabilizers with the resin. One such stabilizer is diphenyl decyl phosphite. See also U.S. Patent Number
2,952,701 to McConnell et al dated September 13, 1960.
A continulng need exis-ts for ways of improving the thermal oxidative stability of polyphenylene ether resins and compositions containing such resins.
I T~ODUCTION TO _HE INVENTION
The discovery has now been made that trineopentylene diphosphite (hereinafter also referred to as "TNP"), is a more effective thermal oxidative stabilizer for poly-phenylene ether resins and compositions,on a weight for weight basis, than diphenyl decyl phosphite (hereinafter also ''DPDP'I).
Trineopentylene diphosphite is also sometimes referred to as 2,2-dimethyl-1,3-propanediol bis (2,2-dimethyl-1,
A continulng need exis-ts for ways of improving the thermal oxidative stability of polyphenylene ether resins and compositions containing such resins.
I T~ODUCTION TO _HE INVENTION
The discovery has now been made that trineopentylene diphosphite (hereinafter also referred to as "TNP"), is a more effective thermal oxidative stabilizer for poly-phenylene ether resins and compositions,on a weight for weight basis, than diphenyl decyl phosphite (hereinafter also ''DPDP'I).
Trineopentylene diphosphite is also sometimes referred to as 2,2-dimethyl-1,3-propanediol bis (2,2-dimethyl-1,
3-propanediol cyclic phosphite).
DESCRIPTION OF THE INVEMTION
In greater de-tail, the polyphenylene ethers which are preferred for use in this invention are homopolymers and copolymers having the formula:
Q"' Q' j O -L _ .
n wherein Q, Q', Q" and Q"', are independently selected from the group consisting of hydrogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus, hydro-carbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and the phenol nucleus, and Q', and Q" and Q"' in addition may be halogen with the proviso that Q and Q' are preferably free of a tertiary carbon atom; and n represents the total number of monomer residues and is an integer of at least 50.
Especially preferred is poly (2,6-dimethyl-1,4-phenylene) ether.
The compositions of the invention can also comprise polyphenylene ether resins in admixture with alkenyl aromatic resins as defined by Cizek, U.S. 3,383,435 dated May 14, 1968,and other thermoplastic elastomers convention-ally used as auxiliary or modifying resins. These are employed to lmprove the impact resistance of articles molded from the mixtures.
As is described in the Cizek U.S. Patent, modifiers such as butadiene may be incorporated into the alkenyl aromatic resins to improve the properties of resultant compositions. Other such modifiers are also known.
These include block and hydrogenated block copolymers such as are described in U.S. Patent No. 3,660,531 of Lauchlan et al dated May 2, 1972 or U.S. Patent No.4,167,507 to Haaf dated September 11, 1979. Similarly, graftmodified polymers are described in U.S. Patent Nos. 3,943,191 dated March 9, 1976, 3,959,211 dated May 25, 1976, 3,974,235 dated August 10, 1976, 4,101,503, 4,101,504, 4,101,505 dated July 18, 1978 and 4,102,850 dated July 25, 1978 all to Glen D. Cooper et al. All of these modified polyalkenyl aromatic resins are also within the scope of the present invention.
Specific examples of alkenyl aromatic monomers include styrene, chlorostyrene, alpha-methylstyrene, vinyl xylene, divinylbenzene and vinyl naphthalene. Styrene is particularly preferred.
~2~ 2 The term "styrene resin" as used broadly throughout this disclosure includes, by way of example, homopolymers such as polystyrene and polychlorostyrene, as well as polystyrenes which have been modified by natural or synthetic rubber, e.g., polybutadiene, polyisoprene, butyl rubber, EPDM rubber, ethylene propylene copolymers, natural rubber, polysulfide rubbers, polyurethane rubbers, epichlorohydrin, and the like; styrene containing copolymers such as the styrene-acrylonitrile copolymers (SANS styrene-butadiene copolymers, styrene-maleic anhydride copolymers, styrene-acrylonitrile-bu-tadiene terpolymers (ABS), poly-alpha-methylstyrene, copolymers of ethylvinylbenzene and divinyl~
benzene, and the llke; block copolymers of the A-B-A and A-B type type wherein A is polystyrene and B is an elasto-meric diene, e.g., polybutadiene, radial -teleblock co-polymers of s-tyrene and a conjugated diene, acrylic resin modified sty:renebutadiene resins and the like, and blends of homopolystyrene and copolymers of the aforementioned types.
The polyphenylene ether and modifying resin, e.g., polyalkenyl aromatic resin, may be present in virtually any proportion in the present blends. For optimum physical properties in the blend, however, they are preferably in a weight ratio of from about 4:1 to 1:2, respectively.
The trineopentylene diphosphite stabilizer is normally present in an amount of at least about 0.5 part per 100 parts of resin to be effective in conferring the desired thermal oxidative stability. For optimum results, amounts in the range between 0.1 and 2.0 parts based on 100 parts of resin are employed.
The molding compositions can also contain one or more of the supplemen-tary non-resinous agents which have heretofore been customarily present in polyphenylene ether resin molding compositions to improve certain other physlcal and chemical properties of the moldings. These agents include L2~2 flame retardants, plasticizers, strengthening fibers (for example, glass fibers and graphite whiskers), mineral fillers, abrasion resistant components, dyes, and pigments.
Many of such agents are disclosed in said U.S. Patent No.
DESCRIPTION OF THE INVEMTION
In greater de-tail, the polyphenylene ethers which are preferred for use in this invention are homopolymers and copolymers having the formula:
Q"' Q' j O -L _ .
n wherein Q, Q', Q" and Q"', are independently selected from the group consisting of hydrogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atom and the phenol nucleus, hydro-carbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atoms and the phenol nucleus, and Q', and Q" and Q"' in addition may be halogen with the proviso that Q and Q' are preferably free of a tertiary carbon atom; and n represents the total number of monomer residues and is an integer of at least 50.
Especially preferred is poly (2,6-dimethyl-1,4-phenylene) ether.
The compositions of the invention can also comprise polyphenylene ether resins in admixture with alkenyl aromatic resins as defined by Cizek, U.S. 3,383,435 dated May 14, 1968,and other thermoplastic elastomers convention-ally used as auxiliary or modifying resins. These are employed to lmprove the impact resistance of articles molded from the mixtures.
As is described in the Cizek U.S. Patent, modifiers such as butadiene may be incorporated into the alkenyl aromatic resins to improve the properties of resultant compositions. Other such modifiers are also known.
These include block and hydrogenated block copolymers such as are described in U.S. Patent No. 3,660,531 of Lauchlan et al dated May 2, 1972 or U.S. Patent No.4,167,507 to Haaf dated September 11, 1979. Similarly, graftmodified polymers are described in U.S. Patent Nos. 3,943,191 dated March 9, 1976, 3,959,211 dated May 25, 1976, 3,974,235 dated August 10, 1976, 4,101,503, 4,101,504, 4,101,505 dated July 18, 1978 and 4,102,850 dated July 25, 1978 all to Glen D. Cooper et al. All of these modified polyalkenyl aromatic resins are also within the scope of the present invention.
Specific examples of alkenyl aromatic monomers include styrene, chlorostyrene, alpha-methylstyrene, vinyl xylene, divinylbenzene and vinyl naphthalene. Styrene is particularly preferred.
~2~ 2 The term "styrene resin" as used broadly throughout this disclosure includes, by way of example, homopolymers such as polystyrene and polychlorostyrene, as well as polystyrenes which have been modified by natural or synthetic rubber, e.g., polybutadiene, polyisoprene, butyl rubber, EPDM rubber, ethylene propylene copolymers, natural rubber, polysulfide rubbers, polyurethane rubbers, epichlorohydrin, and the like; styrene containing copolymers such as the styrene-acrylonitrile copolymers (SANS styrene-butadiene copolymers, styrene-maleic anhydride copolymers, styrene-acrylonitrile-bu-tadiene terpolymers (ABS), poly-alpha-methylstyrene, copolymers of ethylvinylbenzene and divinyl~
benzene, and the llke; block copolymers of the A-B-A and A-B type type wherein A is polystyrene and B is an elasto-meric diene, e.g., polybutadiene, radial -teleblock co-polymers of s-tyrene and a conjugated diene, acrylic resin modified sty:renebutadiene resins and the like, and blends of homopolystyrene and copolymers of the aforementioned types.
The polyphenylene ether and modifying resin, e.g., polyalkenyl aromatic resin, may be present in virtually any proportion in the present blends. For optimum physical properties in the blend, however, they are preferably in a weight ratio of from about 4:1 to 1:2, respectively.
The trineopentylene diphosphite stabilizer is normally present in an amount of at least about 0.5 part per 100 parts of resin to be effective in conferring the desired thermal oxidative stability. For optimum results, amounts in the range between 0.1 and 2.0 parts based on 100 parts of resin are employed.
The molding compositions can also contain one or more of the supplemen-tary non-resinous agents which have heretofore been customarily present in polyphenylene ether resin molding compositions to improve certain other physlcal and chemical properties of the moldings. These agents include L2~2 flame retardants, plasticizers, strengthening fibers (for example, glass fibers and graphite whiskers), mineral fillers, abrasion resistant components, dyes, and pigments.
Many of such agents are disclosed in said U.S. Patent No.
4,172,929 to Cooper et al dated October 30, 1979.
The supplementary non-resinous agents are present in total amount between about l and 50%, so as to provide their customary benefits.
The manner in which the present compositions are prepared is not critical. In one procedure, a blend premix is formed by tumbling the ingredients. The blend premix is passed through an axtruder at an elevated temperature, e.g., from about 450 to about 600F., dependent on the needs of the particular composition. The extruder is cooled and chopped into pellets and the pellets are molded into any desired shape.
The following examples are given by way of illustration only alld are not intended as a limitation on the scope of this invention. Unless otherwise specified herein, all proportions are provided on a weight basis.
A base thermoplastic molding composition was prepared by tumbling 55 parts of poly(2,6-dimethyl-1,4-phenylene etherl resin (PPO, General Electric Co.), 45 parts of a rubber modified high impact polystyrene (Foster Grant's FG 834, containing about 9~ polybutadiene), 3.5 parts of tri(isopropylphenyl) phosphate flame retardant/plasticizer (FMC's Kronit~x 50~, 3 parts of titanium dioxide filler, 1,5 part of polyethylene, 0.15 parts of zinc sulfide and 0.15 part of zinc oxide. Three samples were set aside.
To one sample was added 1.0 part (based on 100 parts of total resin) of diphenyl decyl phosphite (DPDP), in accordance with the prior art. To a second sample was added 0.5 parts of 2,2-dimethyl-1,3-propanediol bis(2,2-dimethyl-1,3-propanediol cyclic phosphite) (TNP), in accordance with the invention. To a third sample three 8CN-32~6 was added 1.0 part of RNP, also according to the invention.
The resultant sample compositions were separately passed through an extruder at about 550F. he extrudates were chopped into pellets and molded at an injection temperature of about 525F. and a mold temperature of about 180F. to product sample articles.
The molded articles were tested for their comparative physical properties, the results of which are reported in Table I.
In the Table, the abbrevations designate the following:
WI Whiteness index YI = Yellowness index DTUI, = Distortion Temp Under Load (E'.) MV = Melt viscosity (1500 sec ,282 C.) UL 9~ = Avg. flame out time (sec) 62 mil Gard = Gardner impact (in.-lbs.) Izod = Notched Izod impact (ft.lbs./in.n.) C.F. = injection molded channel flow (in.) , ,, . us In .
O
O O
N
H I) ('I (I
o o Ir LO ED
r-l l O
or I oo o a or O O O
o o o or Lr) or H H ¦ 00 (I
.
ED O ED
. l H
. ) I` or ^l o In O
I_ O
a) N I) .
a .~ Pi ,1 Z Z
En En Us X
Z O
a) f o Us O
~2~2~
The procedure of the previous example was repeated to prepare three additional molded samples which differ from those of the previous example only in that they contain 12 parts (per lOO parts or resin) of titanium dioxide and the stabilizer concentrations noted below. The actual test resul-ts are set forth in Table II, with abbreviations as explained above.
o o N I
H
O Ll~
on --I
or or o 1~7 . O O O
O O O
.
~`J N I
HE Ir) 'r Ha En H 00 H r` O 1--. l O O O
I_ f So N
~, Pi a a a) I, Z Pi .~ En .
Us . o o Z; 'so aJ *
o Us - 10 - 8CN-32~6 The foregoing results show that compositions in accordance with the invention, containing TNP, exhibit greater thermal oxidative stability than the comparison compositions containing DPDP on an equivalen-t molar phosphorus basis, as indicated by the lower yellowness index and higher whiteness index after heat aging. This effect is more pronounced at lower levels of titanium dioxide. In addition, it is seen tha-t with use of TNP
there is an increase in the ability of the compositions to withstand higher temperatures without deforming, as indicated by the higher DTUL.
Obviously o-ther modifications and variations of the present invention are possible in light o-f the above teachings. For instance, ins-tead of poly(2,6-dimethyl-1,4-phenylene) ether, there can be used a copolymer such as poly(2,6-dimethyl-co-2,3,6-trimethyl-1,4-phenylene) ether. The compositions can also include other ingredients such as other impac-t modifiers, drip retardants, reinforcements and/or fillers, antioxidants, coloring agents, pigments. It is, therefore, to be understood that changes may be made in the particular embodiments of the inven-tion described which are within the full intended scope of the invention as defined by the appended claims.
The supplementary non-resinous agents are present in total amount between about l and 50%, so as to provide their customary benefits.
The manner in which the present compositions are prepared is not critical. In one procedure, a blend premix is formed by tumbling the ingredients. The blend premix is passed through an axtruder at an elevated temperature, e.g., from about 450 to about 600F., dependent on the needs of the particular composition. The extruder is cooled and chopped into pellets and the pellets are molded into any desired shape.
The following examples are given by way of illustration only alld are not intended as a limitation on the scope of this invention. Unless otherwise specified herein, all proportions are provided on a weight basis.
A base thermoplastic molding composition was prepared by tumbling 55 parts of poly(2,6-dimethyl-1,4-phenylene etherl resin (PPO, General Electric Co.), 45 parts of a rubber modified high impact polystyrene (Foster Grant's FG 834, containing about 9~ polybutadiene), 3.5 parts of tri(isopropylphenyl) phosphate flame retardant/plasticizer (FMC's Kronit~x 50~, 3 parts of titanium dioxide filler, 1,5 part of polyethylene, 0.15 parts of zinc sulfide and 0.15 part of zinc oxide. Three samples were set aside.
To one sample was added 1.0 part (based on 100 parts of total resin) of diphenyl decyl phosphite (DPDP), in accordance with the prior art. To a second sample was added 0.5 parts of 2,2-dimethyl-1,3-propanediol bis(2,2-dimethyl-1,3-propanediol cyclic phosphite) (TNP), in accordance with the invention. To a third sample three 8CN-32~6 was added 1.0 part of RNP, also according to the invention.
The resultant sample compositions were separately passed through an extruder at about 550F. he extrudates were chopped into pellets and molded at an injection temperature of about 525F. and a mold temperature of about 180F. to product sample articles.
The molded articles were tested for their comparative physical properties, the results of which are reported in Table I.
In the Table, the abbrevations designate the following:
WI Whiteness index YI = Yellowness index DTUI, = Distortion Temp Under Load (E'.) MV = Melt viscosity (1500 sec ,282 C.) UL 9~ = Avg. flame out time (sec) 62 mil Gard = Gardner impact (in.-lbs.) Izod = Notched Izod impact (ft.lbs./in.n.) C.F. = injection molded channel flow (in.) , ,, . us In .
O
O O
N
H I) ('I (I
o o Ir LO ED
r-l l O
or I oo o a or O O O
o o o or Lr) or H H ¦ 00 (I
.
ED O ED
. l H
. ) I` or ^l o In O
I_ O
a) N I) .
a .~ Pi ,1 Z Z
En En Us X
Z O
a) f o Us O
~2~2~
The procedure of the previous example was repeated to prepare three additional molded samples which differ from those of the previous example only in that they contain 12 parts (per lOO parts or resin) of titanium dioxide and the stabilizer concentrations noted below. The actual test resul-ts are set forth in Table II, with abbreviations as explained above.
o o N I
H
O Ll~
on --I
or or o 1~7 . O O O
O O O
.
~`J N I
HE Ir) 'r Ha En H 00 H r` O 1--. l O O O
I_ f So N
~, Pi a a a) I, Z Pi .~ En .
Us . o o Z; 'so aJ *
o Us - 10 - 8CN-32~6 The foregoing results show that compositions in accordance with the invention, containing TNP, exhibit greater thermal oxidative stability than the comparison compositions containing DPDP on an equivalen-t molar phosphorus basis, as indicated by the lower yellowness index and higher whiteness index after heat aging. This effect is more pronounced at lower levels of titanium dioxide. In addition, it is seen tha-t with use of TNP
there is an increase in the ability of the compositions to withstand higher temperatures without deforming, as indicated by the higher DTUL.
Obviously o-ther modifications and variations of the present invention are possible in light o-f the above teachings. For instance, ins-tead of poly(2,6-dimethyl-1,4-phenylene) ether, there can be used a copolymer such as poly(2,6-dimethyl-co-2,3,6-trimethyl-1,4-phenylene) ether. The compositions can also include other ingredients such as other impac-t modifiers, drip retardants, reinforcements and/or fillers, antioxidants, coloring agents, pigments. It is, therefore, to be understood that changes may be made in the particular embodiments of the inven-tion described which are within the full intended scope of the invention as defined by the appended claims.
Claims (8)
1. A thermoplastic composition which comprises an intimate admixture of a polyphenylene ether resin with trineopentylene diphosphite in an amount effective to provide thermal oxidative stability for the resin.
2. A composition according to claim 1, wherein the trineopentylene diphosphite is present in an amount of between about 0.1 and 2.0 percent by weight based on the total amount of resin.
3. A composition according to claim 1, which additionally contains an alkenyl aromatic resin.
4. A composition according to claim 3, in which the alkenyl aromatic resin is a styrene resin.
5. A composition according to claim 4, in which the ratio of polyphenylene ether and styrene resin is from 4:1 and 1:2 respectively, on a weight basis.
6. A composition according to claim 4, in which the polyphenylene ether is poly(2,6-dimethyl-1,4-phenylene ether).
7. A composition according to claim 4, in which the styrene resin is a rubber modified high impact poly-styrene.
8. A composition according to claim 1, which also contains one or more additives selected from among flame retardants, plasticizers, fillers, reinforcements and coloring agents.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31589281A | 1981-10-28 | 1981-10-28 | |
| US315,892 | 1994-09-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1201242A true CA1201242A (en) | 1986-02-25 |
Family
ID=23226517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000413158A Expired CA1201242A (en) | 1981-10-28 | 1982-10-08 | Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphite |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS58101151A (en) |
| CA (1) | CA1201242A (en) |
| DE (1) | DE3238790A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102004031471A1 (en) | 2004-06-30 | 2006-01-26 | Zf Friedrichshafen Ag | Oil supply |
| DE102004031470A1 (en) | 2004-06-30 | 2006-01-26 | Zf Friedrichshafen Ag | Oil supply |
-
1982
- 1982-10-08 CA CA000413158A patent/CA1201242A/en not_active Expired
- 1982-10-20 DE DE19823238790 patent/DE3238790A1/en not_active Withdrawn
- 1982-10-27 JP JP18764582A patent/JPS58101151A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58101151A (en) | 1983-06-16 |
| DE3238790A1 (en) | 1983-05-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4154712A (en) | Low molecular weight polyphenylene ether compositions | |
| US3639506A (en) | Flame retardant composition of polyphenylene ether styrene resin aromatic phosphate and aromatic halogen compound | |
| US3960808A (en) | Polyphenylene ether composition | |
| GB2043083A (en) | Flame retardant polyphenylene ether compositions | |
| US3663654A (en) | Flame retardant composition of polyphenylene ether,styrene resin and phosphorus | |
| US5081185A (en) | Polyphenylene ether composition characterized by improved melt flow | |
| US4405739A (en) | Polyphenylene ether resins and compositions heat stabilized with phosphite compounds | |
| EP0090523B1 (en) | Ppe compositions comprising an ethylene polymer containing carbonyl and hydroxyl groups | |
| US3887646A (en) | Resinous compositions containing polyphenylene ether, styrene rubber and rubber-modified chlorostyrene polymer | |
| US4835201A (en) | Compositions of polyphenylene ether resin and high impact polystyrene resin having improved ultraviolet light resistance | |
| US3956423A (en) | Polyphenylene ethers composition containing N,N'-di-β-naphthyl-P-phenylene diamine stabilizer | |
| JPH068371B2 (en) | Flame-retardant resin composition | |
| JPS619450A (en) | Flame-retardant resin composition | |
| US4442251A (en) | Impact resistant polyphenylene ether resin compositions | |
| US4483953A (en) | Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphite | |
| EP0146878A2 (en) | Compositions of polyphenylene ether resin and high impact polystyrene resin having improved ultraviolet light resistance | |
| CA1201242A (en) | Polyphenylene ether resins and compositions heat stabilized with trineopentylene diphosphite | |
| GB1575457A (en) | Polyphenylene ether compositions | |
| EP0149454B1 (en) | Compositions of polyphenylene ether resin and high impact polystyrene resin having improved ultraviolet light resistance | |
| EP0085834B1 (en) | Colour inhibiting flame-retardant consisting of a stable halogenated organic compound and a boron compound | |
| CA1269787A (en) | Polyphenylene ether resin blends having improved ultraviolet light stability | |
| US4584332A (en) | Flame retardant polyphenylene oxide thermoplastics | |
| US4154719A (en) | Stabilized polyphenylene ether resin compositions containing hindered tris-phenols | |
| US4423176A (en) | Molding compositions comprising polyphenylene ether, polysulfone and vinyl aromatic-diene block copolymer | |
| US4593058A (en) | Flame retardant polyphenylene oxide thermoplastics |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |