CA2015526A1 - Polyphenylene ether composition characterized by improved melt flow - Google Patents
Polyphenylene ether composition characterized by improved melt flowInfo
- Publication number
- CA2015526A1 CA2015526A1 CA002015526A CA2015526A CA2015526A1 CA 2015526 A1 CA2015526 A1 CA 2015526A1 CA 002015526 A CA002015526 A CA 002015526A CA 2015526 A CA2015526 A CA 2015526A CA 2015526 A1 CA2015526 A1 CA 2015526A1
- Authority
- CA
- Canada
- Prior art keywords
- composition
- polyphenylene ether
- intrinsic viscosity
- weight
- component
- 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.)
- Abandoned
Links
Classifications
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S525/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S525/905—Polyphenylene oxide
Abstract
A POLYPHENYLENE ETHER COMPOSITION CHARACTERIZED BY
IMPROVED MELT FLOW
ABSTRACT
An improved polyphenylene ether composition is described herein, comprising at least two polyphenylene ether resins, one having an intrinsic viscosity of at least about 0.38 dl/g, and another having an intrinsic viscosity of no greater than about 0.33 dl/g.
IMPROVED MELT FLOW
ABSTRACT
An improved polyphenylene ether composition is described herein, comprising at least two polyphenylene ether resins, one having an intrinsic viscosity of at least about 0.38 dl/g, and another having an intrinsic viscosity of no greater than about 0.33 dl/g.
Description
~cN-s3s3 201~326 A POLYPHENYLENE ETHER COMPOSITION CHARACTERIZED BY
IMPROVED MELT FLOW
This invention relates generally to thermoplastic compositions, and more specifically to polyphenylene 5 ether-based compositions suitable for a wide range of processing techniques.
Polyphenylene ether resin (sometimes referred to by the terms "polyphenylene oxide", "PPE", or PPO~ resin~ has enjoyed wide acceptance in the plastics industry because of L0 its desirable physical and chemical properties, such as high heat resistance and dimensional stability.
One area in which PPE compositions have required improvement is melt flow capability, ie., the ability to flow freely at elevated temperatures during various processing stages, such as extrusion and molding. Poor melt flow capability or "processability" can result in the commercial exclusion of materials which otherwise possess an enviable set of properties.
As pointed out in the teachings of G. Lee, Jr.'s U.S.
Patent 4,154,712, processability can be improved by desreasing the molecular weight of the PPE. However, lower molecular weights sometimes adversely affect other properties, such as impact strength. Impact s~rength in the Lee, Jr. patent is maintained by the presence of an 25 elastomeric block copolymer of a vinyl aromatic compound and a conjugated diene, along wi~h a plasticizer such as triphenyl phosphate.
Even in the relatively short period since the issuance of the Lee, ~r. patent, extrusion and molding methods for 30 thermoplastics have undergone improvements so that processing times could be reduced, and larger parts could be fabricated more efficiently. However, these improvements have required concurrent improvements in the resins themselves, ie, ever-higher levels of melt flow, without substantial sacrifice of any of the other key physical . . . ~ .- . .:
8CN -8393 2 ~ 2 ~
properties of the material. Thus, one can readily discern the need for new thermoplastic compositions which satisfy all of these requirements.
SUMMARY ~F THE INVENTION
In response to the industry requirements set forth above, the applicants for the present invention have discovered polymer compositions which compris~:
la) at least one polyphenylene ether resin having an intrinsic viscosity of at least about 0.38 dl/g; and (b) at least one polyphenylene ether resin having an intrinsic viscosity no greater than about 0.33 dl/g, each of said viscosities being measured in a chloroform solution at 25~C.
The use of a blend of two PPE resins as specified 15 above unexpectedly resulted in a level of increased melt flow which was much greater than one would predict from the calculated melt flow for a PPE resin having an intrinsic viscosity (IV) which was the average of that of two such PPE resins. Furthermore, the desirable physical properties, 20 such as heat distortion temperature~ tensile s+rength, and flexural modulus, are substantially maintained.
Included within the scope of this invention are compositions which contain relatively high amounts of the blend of PPE resins, as further described below.
Furthermore, various embodiments of this invention include the presence of other suitable components, such as plasticizers, flame retardants, fillers, and various block copolymer materials, as also described below.
This invention also includes a method for preparing 3G PPE resins having improved melt flow capabilities.
:, . .
3 2~1~i5 DETAILED DESCRIPTION OF THE INVENTION
The PPE resins of this invention are generally well-known and readily available Many are described in two applications for Sterling B. Brown et al., Serial Number 210,547 and Serial Number 210,266, both filed on June 23, 1988 and incorporated herein by reference. Both homopslymer and copolymer polyphenylene ethers are within the scope of this invention.
The preferred PPE resins are homo- and copolymers of the formula ~ Jo wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; n is an integer of at least 50; and each Q is a monovalent substituent such as hydrogen, halogen, hydrocarbon groups, halohydrocarbon groups having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy groups, and halohydrocarbonoxy groups having 20 at least two carbon atoms between the halogen atom and the phenyl nucleus. In preferred embodiments, each Q is an alkyl group having from 1-4 carbon atoms r such as methyl, ethyl, propyl, and the like. In the most preferred embodiments, at least one of the polyphenylene ether resins 25 iS deri~ed from a monomer selected from the group consisting of 2,6-dimethyl phenol; 2,3,6-trimethyl phenol;
and mixtures of these monomers.
The preparation of PPE resins is well-known in the art and is described, for example, in U.S. Patents 3,306,874;
~: : . : ' : , :
8CN-83g3 2 ~1~ rj 2 ~
3,306,875; and 3,432,469 of Allan Hay; and U.S. patents 3,257,357 and 3,257,358 of Gelu Stamatoff, all incorporated herein by reference.
As noted above, one of the PPE resins must have an 5 "intrinsic viscosity" (a measurement well-known in the art, which generally correlates with molecular weight) of at least about 0.38 dl/g, while the other must have an intrinsic viscosity of no grel~ter than about 0.33 dl/g.
Methods of preparing PPE resins and controlling the lO molecular weight thereof are known in the art, as shown, for example, in U.S. Patents 4,252,913 and 4,154,712, issued to Katchman et al and Lee, Jr., respectively, and incorporated herein by reference.
In preferred embodiments, component (a), ie., the 15 higher molecular weight PPE, has an intrinsic viscosity of at least about 0.40 dl/g, and most preferably, at least about 0.45 dl/g.
Furthermore, preferred embodiments call for the lower molecular weight PPE, component (b), to have an intrinsic 20 viscosity of no greater than about 0.30 dl/g; more preferably~- no greater than about 0.25 dl/g; and most preferably, no greater than about 0.20 dl/g.
When viewed together, a preferred PPE resin includes component (a) with an IY value of at least a~out 0.40 dl/g, 25 with component (b~ having an IV value of no greater than about 0.25 dl/g. However, those skilled in the art will be able to select other appropriate PPE IV values for a particular processing operation without undue experimentation, based on factors such as molding 30 temperature, throughput volume, physical property requirements, and the presence or absence of other components in the composition.
In some preferred embodiments, the weight ratio of component (a) to compsnent (b) ranges from about 60:40 to 35 about 40:60. However, under some circumstances, it is , . ~ , . .
, .
IMPROVED MELT FLOW
This invention relates generally to thermoplastic compositions, and more specifically to polyphenylene 5 ether-based compositions suitable for a wide range of processing techniques.
Polyphenylene ether resin (sometimes referred to by the terms "polyphenylene oxide", "PPE", or PPO~ resin~ has enjoyed wide acceptance in the plastics industry because of L0 its desirable physical and chemical properties, such as high heat resistance and dimensional stability.
One area in which PPE compositions have required improvement is melt flow capability, ie., the ability to flow freely at elevated temperatures during various processing stages, such as extrusion and molding. Poor melt flow capability or "processability" can result in the commercial exclusion of materials which otherwise possess an enviable set of properties.
As pointed out in the teachings of G. Lee, Jr.'s U.S.
Patent 4,154,712, processability can be improved by desreasing the molecular weight of the PPE. However, lower molecular weights sometimes adversely affect other properties, such as impact strength. Impact s~rength in the Lee, Jr. patent is maintained by the presence of an 25 elastomeric block copolymer of a vinyl aromatic compound and a conjugated diene, along wi~h a plasticizer such as triphenyl phosphate.
Even in the relatively short period since the issuance of the Lee, ~r. patent, extrusion and molding methods for 30 thermoplastics have undergone improvements so that processing times could be reduced, and larger parts could be fabricated more efficiently. However, these improvements have required concurrent improvements in the resins themselves, ie, ever-higher levels of melt flow, without substantial sacrifice of any of the other key physical . . . ~ .- . .:
8CN -8393 2 ~ 2 ~
properties of the material. Thus, one can readily discern the need for new thermoplastic compositions which satisfy all of these requirements.
SUMMARY ~F THE INVENTION
In response to the industry requirements set forth above, the applicants for the present invention have discovered polymer compositions which compris~:
la) at least one polyphenylene ether resin having an intrinsic viscosity of at least about 0.38 dl/g; and (b) at least one polyphenylene ether resin having an intrinsic viscosity no greater than about 0.33 dl/g, each of said viscosities being measured in a chloroform solution at 25~C.
The use of a blend of two PPE resins as specified 15 above unexpectedly resulted in a level of increased melt flow which was much greater than one would predict from the calculated melt flow for a PPE resin having an intrinsic viscosity (IV) which was the average of that of two such PPE resins. Furthermore, the desirable physical properties, 20 such as heat distortion temperature~ tensile s+rength, and flexural modulus, are substantially maintained.
Included within the scope of this invention are compositions which contain relatively high amounts of the blend of PPE resins, as further described below.
Furthermore, various embodiments of this invention include the presence of other suitable components, such as plasticizers, flame retardants, fillers, and various block copolymer materials, as also described below.
This invention also includes a method for preparing 3G PPE resins having improved melt flow capabilities.
:, . .
3 2~1~i5 DETAILED DESCRIPTION OF THE INVENTION
The PPE resins of this invention are generally well-known and readily available Many are described in two applications for Sterling B. Brown et al., Serial Number 210,547 and Serial Number 210,266, both filed on June 23, 1988 and incorporated herein by reference. Both homopslymer and copolymer polyphenylene ethers are within the scope of this invention.
The preferred PPE resins are homo- and copolymers of the formula ~ Jo wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit; n is an integer of at least 50; and each Q is a monovalent substituent such as hydrogen, halogen, hydrocarbon groups, halohydrocarbon groups having at least two carbon atoms between the halogen atom and the phenyl nucleus, hydrocarbonoxy groups, and halohydrocarbonoxy groups having 20 at least two carbon atoms between the halogen atom and the phenyl nucleus. In preferred embodiments, each Q is an alkyl group having from 1-4 carbon atoms r such as methyl, ethyl, propyl, and the like. In the most preferred embodiments, at least one of the polyphenylene ether resins 25 iS deri~ed from a monomer selected from the group consisting of 2,6-dimethyl phenol; 2,3,6-trimethyl phenol;
and mixtures of these monomers.
The preparation of PPE resins is well-known in the art and is described, for example, in U.S. Patents 3,306,874;
~: : . : ' : , :
8CN-83g3 2 ~1~ rj 2 ~
3,306,875; and 3,432,469 of Allan Hay; and U.S. patents 3,257,357 and 3,257,358 of Gelu Stamatoff, all incorporated herein by reference.
As noted above, one of the PPE resins must have an 5 "intrinsic viscosity" (a measurement well-known in the art, which generally correlates with molecular weight) of at least about 0.38 dl/g, while the other must have an intrinsic viscosity of no grel~ter than about 0.33 dl/g.
Methods of preparing PPE resins and controlling the lO molecular weight thereof are known in the art, as shown, for example, in U.S. Patents 4,252,913 and 4,154,712, issued to Katchman et al and Lee, Jr., respectively, and incorporated herein by reference.
In preferred embodiments, component (a), ie., the 15 higher molecular weight PPE, has an intrinsic viscosity of at least about 0.40 dl/g, and most preferably, at least about 0.45 dl/g.
Furthermore, preferred embodiments call for the lower molecular weight PPE, component (b), to have an intrinsic 20 viscosity of no greater than about 0.30 dl/g; more preferably~- no greater than about 0.25 dl/g; and most preferably, no greater than about 0.20 dl/g.
When viewed together, a preferred PPE resin includes component (a) with an IY value of at least a~out 0.40 dl/g, 25 with component (b~ having an IV value of no greater than about 0.25 dl/g. However, those skilled in the art will be able to select other appropriate PPE IV values for a particular processing operation without undue experimentation, based on factors such as molding 30 temperature, throughput volume, physical property requirements, and the presence or absence of other components in the composition.
In some preferred embodiments, the weight ratio of component (a) to compsnent (b) ranges from about 60:40 to 35 about 40:60. However, under some circumstances, it is , . ~ , . .
, .
2 ~
desirable that component (a) constitute at least about 70%
by weight of the total polyphenylene ether resin in the composition.
MoreoYer, in some instances, it is desirable that the 5 composition contain Yery high levels of PPE resin. For example, when greater heat resistance is required, the composition may comprise at least about 80% by wei~ht PPE
resin, based on total composition weight. In still other circumstances, the composition may comprise at least about 10 85% (or even 90%1 by wei~ht PPE resin.
Materials which some~imes enhance the impact strength of the compositions are not critical to this invention, but are sometimes desirable. They are usually of high molecular weight, and include natural rubbers, synthetic rubbers, and 5 thermoplastic elastomers. They may by homopolymers as well as copolymers, including random, block and graft copolymers derived from various suitable monomers such as butadiene, possibly in combination with a vinyl aromatic compound like styrene.
Specific examples of such materials are elastomeric block copolymers and core/shell polymers. The block copolymers are well-known in the art and are described, for example, in Application S.N. 254,519 of G. Lee, Jr., filed October 6, 1988, Application S.N. 282,081 of W. Abolins et al, filed December 9, 1988: Application S.N. 244,489 of G.
Lee, Jr., filed September 14, 1988; and in Application S.N.
347,105 of J. Gianchandani e~ al, filed May 3, 1989, all of which are incorporated herein by reference. Some of the patents mentioned abov~ also contain descriptions of 30 suitable block copolymers.
Commercial examples of block copolymers are the Kraton3 D and Kraton~ G materials, available from Shell Chemical Company.
The preferred block copolymers of this invention are 35 characterized by an A-B-A1 structure, wherein terminal - : :
- - :
8CN-8393 201 ~i~i 2 blocks A and A1 are the same or different, and are polymerized vinyl aromatic hydrocarbons, and center block B
is a polymerized conjugated diene, the molecular weight of B being higher than the combined molecular weights of A and A1. The conjugated diene block can be non-hydrogenated, partially hydrogenated, or entirely hydrogenated.
In some especially preferred embodiments, each A and A1 bloek of this type of copolymer is styrene, and the B
block is ethylene-butylene, often derived from post-hydrogenated butadiene.
Some of the core-shell materials suitable for this invention are described in U.S. Patents 3,944,631 of Yu et al; 4,681,915 of Bates et al; and 4,684,696 of Bates et al, all incorporated herein by reference. Preferred core-shell 5 materials include a cross-linked acrylate rubber core, such as polybutyl acrylate. Surrounding this core is a shell-like structure of cross-linked vinyl aromatic resin, preferably polystyrene, which surrounds and interpenetrates the cross-linked core.
The impact modifier is generally present at about 1 percent to about 10 percent by weight, based on the weight of the entire composition; a specific amount will of course be determined by end use requirements for the composition.
Compositions of this invention sometimes include at 25 least one polyolefin resin, usually present at about 0.1%
to about 10% by weight, based on the ~otal weight of the composition. Polyolefin resins and methods for their preparation are known in the art and described, for example, in European Patent 0,095,098; in the 30 above-mentioned application S.N. 254,519, and in U.S.
patent 4,166,055, the last-mentioned patent also being incorporated herein by reference. Illustrative polyolefin resins are polyethylene, polypropylene, and polyisobutylene, with the preferred homopolymer being 35 polyethylene.
:. .
, 8CN-8393 2~5526 -Copolymers of polyolefins may also be used, such as copolymers of ethylene with alpha olefins like propylene and 4-methylpentene-1.
In preferred embodiments, the polyolefin resin has a melt index of less than about 3V grams/10 minutes, and for some applications, less than about 5 grams/10 minutes.
Specific examples of ~olyolefins in this category are the linear low density polyethylene (LLDPE) copolymers, such as those described in US Patents 4,584,334 and 4,076,698, both incorporated herein by reference, and in the above-mentioned Application S.N. 254,519.
Various vinyl aromatic polymers may sometimes also be included in the compositions of this invention, such as homopolystyrene, polychlorostyrene, polyvinyl toluene, and rubber-modified polystyrene (sometimes referred to as "HIPS"), as well as mixtures of these materials. Mention should also be made of styrene-containing copolymers such as styrene-acrylonitrile copolymers (SAN), styrene-maleic anhydride copolymers, polyalpha-methylstyrene, and copolymers of ethylvinylbenzene and divinylbenzene. The amount of vinyl aromatic polymer present depends upon the particular properties contemplated, and usually ranges from about 5% to about 90% by weight (based on total composition weight), and more preferably, about 20% to about 60% by ;~5 wei ght .
Various additives which impart a variety of attributes to these compositions are also within the scope of this invention. Most are well-known in the art, as are their effective levels and methods of incorporation. Examples of 30 such additives are flame retardants, plasticizers, stabilizers (eg., oxidative, thermal, and ultraviolet light), fillers, reinforcing agents, lubricants, colorants.
dyes, pigments, drip retardants, and other processing aids.
Some of these additives are mentioned in the following . . . . , . ~
2 ~
8CN-8~93 examples; others are disclosecl in many of the re~erences described above.
The compositions of this invention may be prepared by well-known procedures. Preferably, the ingredients are 5 combined as a premix blend, and then extruded on a single or twin screw extruder, coolecl, and chopped into pellets.
The pellets are then molded into articles of a desired shape and size.
Thus, another aspect of this invention is a method for 10 preparing a polyphenylene ether composition having high melt flow characteristics and aood physical properties, wherein said method comprises mixing a PPE resin having an intrinsic viscosity of at least about 0.38 dl/g with a PPE
resin having an intrinsic viscosity no greater than about 15 0.33 dl/g.
The ~ollowing examples are provided to illustrate various embodiments of this invention. It is to be understood, however, that the embodiments are given for the purpose of illustration only, and do not and should not be 20 regarded as limiting the invention to any of the specific materials or conditions described therein.
EXAMPLES
Unless otherwise indicated, the PPE resins were each poly(2,6-dimethyl-1,4-phenylene) ether. Intrinsic viscosity 25 (IV) was measured in chloroform at 25C.
The components in each example were dry-blended and compounded, using a 30 mm Werner & Pfleiderer twin-screw extruder. The components are expressed as parts by weight, unless otherwise indicated.
30 The extrudate was quenched and pelletized. The products were then molded on a Toshiba injection molding machine (8 oz. barrel capacity) into various test specimens.
- . . ~
:: :
.
.
.
sc~-s3s3 2 ~ 2 ~
The following compositions were prepared as described above:
Sample Number(a) ComPonent 1* 2* 3 PPE (0.46 IV) 44.9 0 0 PPE (0.40 IY) O 44.9 38.0 PPE (0.19 IV) O 0 6.9 HIps(b) 44.9 44.9 44.9 10 F.R./Plasticizer(C) 13.0 13.0 13.0 TDp(d~ 0,45 0.45 0.45 Polyethylene(e~ 1.4 1.4 1.4 zns(f) 0.13 0.13 0.13 ZnO(g) 0.13 0.13 0.13 (a) Amounts given in parts-by-weight (pbw) (b) Rubber-Modified Polystyrene (c) Flame Retardant/Plas~icizer: Santicizer~ from Monsanto.
(d) Tridecyl Phosphite (e) Linear Low density Polyethylene 20 (f~ ~inc Sulfide (g) Zinc Oxide (*) Control Samples Tests on molded pieces resulted in the following ~5 properties:
. . . . ..
.~ . -.
2 ~ 2 ~
8cN-83s3 TABLEI
ProDertY _ Sam~le Number 1~t 2* 3 Flame Retardance (1/8")(a) 2.. 4,V0 3.6,V0 3.7,V0 Flame Retardance (1/16")( ) 4.9,V0 4.7,V0 6.0,V1 Heat Distortion Temperature (264 psi)(C~ 178 182 183 Flow Channel (inches) (d) 24.5 26.4 30.0 Izod Impact (notched~ 4.5 2.9 1.8 Strength (ft.lb/in)(e) Dynatup Impact 230 120 67 Strength(f)(in-lbs) Melt Viscosity (540CF)(g) 1500 sec~ 1101 960 934 100 sec~1 5099 4405 3714 (a) UL94 (b) UL94 (c) ASTM D648 (d) Measured at 520F-527F, 10,000 psi 20 (e) ASTM D256 (f) ASTM D3763 (g) ASTM D8385 (Measured in poises) The flow channel length for sample 3, which con~ains the mixture of PPE resins, is much higher than the value 25 predic~ed for a sample having an IV equal to the average IV
of the components in sample 3.
11 acN-8393 201 ~.~26 -Furthermore. although there is some decrease in flame retardance and impact values as compared to control samples 1 and 2, the overall physical properties for sample 3 are ill acceptable for many end use applications.
'.
~
~ .
8cN-8393 2 ~ 2 6 The following compositions were prepared as described above. Each componen~ is identical to that used in Example 1, unless otherwise indicated.
Sam~le Number Comoonent 4* S* 6 PPE (0.46 IV) 67.3 0 60 PPE (0.40 IV) O 67.3 0 PPE (0.19 IV) O 0 7.3 HIPS 22.4 22.4 22.4 F.R.JPlasticizer 13.0 13.0 13.0 TDP 0.45 0.45 O, Polyethylene 1.4 1.4 1.4 ZnS 0.13 0.13 0.13 7nO 0.13 0.13 0.13 * Control Samples Tests on molded pieces resulted in the following properties, as measured according to the standards described in Table 1.
. . . ~, -- - .
: :-: . . ~ - . : .
- . ~ . .
- . ~ .
- ~ - .
8CN-8393 2 91~
PropertY Sample Number 4* 5* 6 Flame Retardance (1/8") 1.6,V0 1.6,V0 1.9,V0 s Flame Retardance (1/16") 2.8,V0 2.4,V0 3.3,V0 Heat Distortion Temperature (264 psi) 211 207 209 Flow Channel (inches) 13.2 15.7 16.1 Izod Impact (~otched) 3.2 2.5 2.5 Strength (ft.lb/in) Dynatup Impact 406 125 172 Strength (in-lbs) Melt Viscosity (540F) (Poises) 1500 sec~1 1~56 1520 1413 100 sec~1 6148 6221 5221 * Control Samples The flow channel length for sample 6, which contains a mixture ~f PPE resins according to this invention, is much higher than one would expect for a sample having an IV
e~ual to the average of that of the components in sample 6.
The other physical properties for sample 6 were generally comparable to those of control samples 4 and 5, although flame-out times were slightly higher, and impact strength values were somewhat variable. In general, the 2s impact strength of sample 6 can be enhanced by the presence of one of the impact modifiers discussed above.
.. . . . ,. . ~ . .
- . . .
.. . . .
14 âCN-8393 The following compositions were prepared as described above. Each component is identical to that used in Example 1, unless otherwise indicated.
Sample Number _ v_ Component 7* 8* 9 PPE (0.46 IV) 67.3 0 52 PPE (0.40 IV~ 0 67.3 0 PPE (0.19 IY) 0 0 15.3 10 HIPS 22.4 22.4 22.4 F.R./Plasticizer 13.0 13O0 13.0 TDP 0.45 0.45 Polyethylene 1.4 1.4 1.4 ZnS 0.13 0.13 0.13 ZnO 0.13 0.13 0.13 * Control ~amples Tests on molded pieces resulted in the following properties:
.: . . . .
, ~ .
. - ~ . . . ~ .
8CN-8393 2~ 552S
ProDert~ SamPl~Numb~r_ 7~ ~* 9 Flame Retardance (1/8"~ 1.9,V0 1.3,V0 1.0,V0 Flame Retardance (1/16") 2.7,V0 3.3,V0 1.9,V0 Heat Distortion Temperature (264 psi) 214 21~ 212 Flow Channel (inches) 16.2 21.4 25.5 Izod Impact (Notched) 2.9 2.1 1.4 Strength (ft.lb/in) Dynatup Impact 162 155 72 Strength (in-lbs) Melt Viscosity (540F) (Poises) 1500 sec 1 NA** NA** NA**
100 sec 1 NA** NA** NA**
* Control Samples ** Not Available The flow channel length for sample 9, which contains a mixture of PPE resins accordin~ to this invention, is again 2~ higher than one would expect by averaging the IY values for the individual PPE components in sample 9 and then extrapolatin~ a melt flow value.
The physical properties for sample 9 are generally comparable :
to those of control samples 7 and 8, although impact values are 25 somewhat decreased. These values can be increased as mentioned in ~ :
Example 2.
. .. . . .
, .:
.
-, 8CN-8393 2~ 2 ~
The following compositions were prepared as described above. Each component is identical to that used in Example 1, unless otherwise indicated.
Sample Number Com wnent 10* 11* 12 PPE (0.46 IV) 59.0 0.0 50.0 PPE ~0.40 IV) O 59.0 0 PPE (0.19 IV) O O 9.0 o ~IPS 41.0 41.0 41.0 F.R./Plastici~er 4.5 4.5 4.5 TDP 1.0 1.0 1.0 Polyethylene 1.5 1.5 1.5 ZnS - 0.15 0.15 0.15 ZnO 0.15 0.15 0.15 * Control Samples Tests on molded pieces resulted in the following properties:
17 scN-a3s3 201~26 ProDerty _ _ SamPle Number ~Q~11*_ 12 S Flame Retardance (1/8") 5.1,V1 4.6,V0 4.2,U0 Flame Retardance (1/16") 10.8,Y1 7.3,Y1 g.7,V1 Heat Di storti on Temperature (264 psi) 224 235 233 Flow Channel (inches) 22.3 23.7 25.0 Izod Impact (Notched) Strength (ft.lb/in) 4.3 2.9 2.6 Dynatup Impact Strength (in-lbs) 267 304 158 Melt Yiscosity (540F) (Poises) 1500 sec~1 1756 1688 1739 100 sec~1 7879 7351 7564 * Control Samples The flow channel length for sample 12, which contains a mixture of PP resins according to this invention, is again higher ~-:
20 than one would predict by averaging the IV values for the individual PPE components in sample 12.
The physical properties for sample 12 were somewhat similar to thcse of control samples 10 and 11, although Dynatup impact values were somewhat lo~er. These values could be increased 25 by the use of an impact modifier, as described above.
It should of course be understood that this invention may be modified in various aspects related to composition ~ :
ingredients and processing details, such modifications falling within the scope of the claims which fol10w.
.
, ' . . . ' , ~ ~
' ,,, ' ' '. ~ ; . : ` ~
''. ' ' ` ' ~ . ` ~ ' ' . ' :
desirable that component (a) constitute at least about 70%
by weight of the total polyphenylene ether resin in the composition.
MoreoYer, in some instances, it is desirable that the 5 composition contain Yery high levels of PPE resin. For example, when greater heat resistance is required, the composition may comprise at least about 80% by wei~ht PPE
resin, based on total composition weight. In still other circumstances, the composition may comprise at least about 10 85% (or even 90%1 by wei~ht PPE resin.
Materials which some~imes enhance the impact strength of the compositions are not critical to this invention, but are sometimes desirable. They are usually of high molecular weight, and include natural rubbers, synthetic rubbers, and 5 thermoplastic elastomers. They may by homopolymers as well as copolymers, including random, block and graft copolymers derived from various suitable monomers such as butadiene, possibly in combination with a vinyl aromatic compound like styrene.
Specific examples of such materials are elastomeric block copolymers and core/shell polymers. The block copolymers are well-known in the art and are described, for example, in Application S.N. 254,519 of G. Lee, Jr., filed October 6, 1988, Application S.N. 282,081 of W. Abolins et al, filed December 9, 1988: Application S.N. 244,489 of G.
Lee, Jr., filed September 14, 1988; and in Application S.N.
347,105 of J. Gianchandani e~ al, filed May 3, 1989, all of which are incorporated herein by reference. Some of the patents mentioned abov~ also contain descriptions of 30 suitable block copolymers.
Commercial examples of block copolymers are the Kraton3 D and Kraton~ G materials, available from Shell Chemical Company.
The preferred block copolymers of this invention are 35 characterized by an A-B-A1 structure, wherein terminal - : :
- - :
8CN-8393 201 ~i~i 2 blocks A and A1 are the same or different, and are polymerized vinyl aromatic hydrocarbons, and center block B
is a polymerized conjugated diene, the molecular weight of B being higher than the combined molecular weights of A and A1. The conjugated diene block can be non-hydrogenated, partially hydrogenated, or entirely hydrogenated.
In some especially preferred embodiments, each A and A1 bloek of this type of copolymer is styrene, and the B
block is ethylene-butylene, often derived from post-hydrogenated butadiene.
Some of the core-shell materials suitable for this invention are described in U.S. Patents 3,944,631 of Yu et al; 4,681,915 of Bates et al; and 4,684,696 of Bates et al, all incorporated herein by reference. Preferred core-shell 5 materials include a cross-linked acrylate rubber core, such as polybutyl acrylate. Surrounding this core is a shell-like structure of cross-linked vinyl aromatic resin, preferably polystyrene, which surrounds and interpenetrates the cross-linked core.
The impact modifier is generally present at about 1 percent to about 10 percent by weight, based on the weight of the entire composition; a specific amount will of course be determined by end use requirements for the composition.
Compositions of this invention sometimes include at 25 least one polyolefin resin, usually present at about 0.1%
to about 10% by weight, based on the ~otal weight of the composition. Polyolefin resins and methods for their preparation are known in the art and described, for example, in European Patent 0,095,098; in the 30 above-mentioned application S.N. 254,519, and in U.S.
patent 4,166,055, the last-mentioned patent also being incorporated herein by reference. Illustrative polyolefin resins are polyethylene, polypropylene, and polyisobutylene, with the preferred homopolymer being 35 polyethylene.
:. .
, 8CN-8393 2~5526 -Copolymers of polyolefins may also be used, such as copolymers of ethylene with alpha olefins like propylene and 4-methylpentene-1.
In preferred embodiments, the polyolefin resin has a melt index of less than about 3V grams/10 minutes, and for some applications, less than about 5 grams/10 minutes.
Specific examples of ~olyolefins in this category are the linear low density polyethylene (LLDPE) copolymers, such as those described in US Patents 4,584,334 and 4,076,698, both incorporated herein by reference, and in the above-mentioned Application S.N. 254,519.
Various vinyl aromatic polymers may sometimes also be included in the compositions of this invention, such as homopolystyrene, polychlorostyrene, polyvinyl toluene, and rubber-modified polystyrene (sometimes referred to as "HIPS"), as well as mixtures of these materials. Mention should also be made of styrene-containing copolymers such as styrene-acrylonitrile copolymers (SAN), styrene-maleic anhydride copolymers, polyalpha-methylstyrene, and copolymers of ethylvinylbenzene and divinylbenzene. The amount of vinyl aromatic polymer present depends upon the particular properties contemplated, and usually ranges from about 5% to about 90% by weight (based on total composition weight), and more preferably, about 20% to about 60% by ;~5 wei ght .
Various additives which impart a variety of attributes to these compositions are also within the scope of this invention. Most are well-known in the art, as are their effective levels and methods of incorporation. Examples of 30 such additives are flame retardants, plasticizers, stabilizers (eg., oxidative, thermal, and ultraviolet light), fillers, reinforcing agents, lubricants, colorants.
dyes, pigments, drip retardants, and other processing aids.
Some of these additives are mentioned in the following . . . . , . ~
2 ~
8CN-8~93 examples; others are disclosecl in many of the re~erences described above.
The compositions of this invention may be prepared by well-known procedures. Preferably, the ingredients are 5 combined as a premix blend, and then extruded on a single or twin screw extruder, coolecl, and chopped into pellets.
The pellets are then molded into articles of a desired shape and size.
Thus, another aspect of this invention is a method for 10 preparing a polyphenylene ether composition having high melt flow characteristics and aood physical properties, wherein said method comprises mixing a PPE resin having an intrinsic viscosity of at least about 0.38 dl/g with a PPE
resin having an intrinsic viscosity no greater than about 15 0.33 dl/g.
The ~ollowing examples are provided to illustrate various embodiments of this invention. It is to be understood, however, that the embodiments are given for the purpose of illustration only, and do not and should not be 20 regarded as limiting the invention to any of the specific materials or conditions described therein.
EXAMPLES
Unless otherwise indicated, the PPE resins were each poly(2,6-dimethyl-1,4-phenylene) ether. Intrinsic viscosity 25 (IV) was measured in chloroform at 25C.
The components in each example were dry-blended and compounded, using a 30 mm Werner & Pfleiderer twin-screw extruder. The components are expressed as parts by weight, unless otherwise indicated.
30 The extrudate was quenched and pelletized. The products were then molded on a Toshiba injection molding machine (8 oz. barrel capacity) into various test specimens.
- . . ~
:: :
.
.
.
sc~-s3s3 2 ~ 2 ~
The following compositions were prepared as described above:
Sample Number(a) ComPonent 1* 2* 3 PPE (0.46 IV) 44.9 0 0 PPE (0.40 IY) O 44.9 38.0 PPE (0.19 IV) O 0 6.9 HIps(b) 44.9 44.9 44.9 10 F.R./Plasticizer(C) 13.0 13.0 13.0 TDp(d~ 0,45 0.45 0.45 Polyethylene(e~ 1.4 1.4 1.4 zns(f) 0.13 0.13 0.13 ZnO(g) 0.13 0.13 0.13 (a) Amounts given in parts-by-weight (pbw) (b) Rubber-Modified Polystyrene (c) Flame Retardant/Plas~icizer: Santicizer~ from Monsanto.
(d) Tridecyl Phosphite (e) Linear Low density Polyethylene 20 (f~ ~inc Sulfide (g) Zinc Oxide (*) Control Samples Tests on molded pieces resulted in the following ~5 properties:
. . . . ..
.~ . -.
2 ~ 2 ~
8cN-83s3 TABLEI
ProDertY _ Sam~le Number 1~t 2* 3 Flame Retardance (1/8")(a) 2.. 4,V0 3.6,V0 3.7,V0 Flame Retardance (1/16")( ) 4.9,V0 4.7,V0 6.0,V1 Heat Distortion Temperature (264 psi)(C~ 178 182 183 Flow Channel (inches) (d) 24.5 26.4 30.0 Izod Impact (notched~ 4.5 2.9 1.8 Strength (ft.lb/in)(e) Dynatup Impact 230 120 67 Strength(f)(in-lbs) Melt Viscosity (540CF)(g) 1500 sec~ 1101 960 934 100 sec~1 5099 4405 3714 (a) UL94 (b) UL94 (c) ASTM D648 (d) Measured at 520F-527F, 10,000 psi 20 (e) ASTM D256 (f) ASTM D3763 (g) ASTM D8385 (Measured in poises) The flow channel length for sample 3, which con~ains the mixture of PPE resins, is much higher than the value 25 predic~ed for a sample having an IV equal to the average IV
of the components in sample 3.
11 acN-8393 201 ~.~26 -Furthermore. although there is some decrease in flame retardance and impact values as compared to control samples 1 and 2, the overall physical properties for sample 3 are ill acceptable for many end use applications.
'.
~
~ .
8cN-8393 2 ~ 2 6 The following compositions were prepared as described above. Each componen~ is identical to that used in Example 1, unless otherwise indicated.
Sam~le Number Comoonent 4* S* 6 PPE (0.46 IV) 67.3 0 60 PPE (0.40 IV) O 67.3 0 PPE (0.19 IV) O 0 7.3 HIPS 22.4 22.4 22.4 F.R.JPlasticizer 13.0 13.0 13.0 TDP 0.45 0.45 O, Polyethylene 1.4 1.4 1.4 ZnS 0.13 0.13 0.13 7nO 0.13 0.13 0.13 * Control Samples Tests on molded pieces resulted in the following properties, as measured according to the standards described in Table 1.
. . . ~, -- - .
: :-: . . ~ - . : .
- . ~ . .
- . ~ .
- ~ - .
8CN-8393 2 91~
PropertY Sample Number 4* 5* 6 Flame Retardance (1/8") 1.6,V0 1.6,V0 1.9,V0 s Flame Retardance (1/16") 2.8,V0 2.4,V0 3.3,V0 Heat Distortion Temperature (264 psi) 211 207 209 Flow Channel (inches) 13.2 15.7 16.1 Izod Impact (~otched) 3.2 2.5 2.5 Strength (ft.lb/in) Dynatup Impact 406 125 172 Strength (in-lbs) Melt Viscosity (540F) (Poises) 1500 sec~1 1~56 1520 1413 100 sec~1 6148 6221 5221 * Control Samples The flow channel length for sample 6, which contains a mixture ~f PPE resins according to this invention, is much higher than one would expect for a sample having an IV
e~ual to the average of that of the components in sample 6.
The other physical properties for sample 6 were generally comparable to those of control samples 4 and 5, although flame-out times were slightly higher, and impact strength values were somewhat variable. In general, the 2s impact strength of sample 6 can be enhanced by the presence of one of the impact modifiers discussed above.
.. . . . ,. . ~ . .
- . . .
.. . . .
14 âCN-8393 The following compositions were prepared as described above. Each component is identical to that used in Example 1, unless otherwise indicated.
Sample Number _ v_ Component 7* 8* 9 PPE (0.46 IV) 67.3 0 52 PPE (0.40 IV~ 0 67.3 0 PPE (0.19 IY) 0 0 15.3 10 HIPS 22.4 22.4 22.4 F.R./Plasticizer 13.0 13O0 13.0 TDP 0.45 0.45 Polyethylene 1.4 1.4 1.4 ZnS 0.13 0.13 0.13 ZnO 0.13 0.13 0.13 * Control ~amples Tests on molded pieces resulted in the following properties:
.: . . . .
, ~ .
. - ~ . . . ~ .
8CN-8393 2~ 552S
ProDert~ SamPl~Numb~r_ 7~ ~* 9 Flame Retardance (1/8"~ 1.9,V0 1.3,V0 1.0,V0 Flame Retardance (1/16") 2.7,V0 3.3,V0 1.9,V0 Heat Distortion Temperature (264 psi) 214 21~ 212 Flow Channel (inches) 16.2 21.4 25.5 Izod Impact (Notched) 2.9 2.1 1.4 Strength (ft.lb/in) Dynatup Impact 162 155 72 Strength (in-lbs) Melt Viscosity (540F) (Poises) 1500 sec 1 NA** NA** NA**
100 sec 1 NA** NA** NA**
* Control Samples ** Not Available The flow channel length for sample 9, which contains a mixture of PPE resins accordin~ to this invention, is again 2~ higher than one would expect by averaging the IY values for the individual PPE components in sample 9 and then extrapolatin~ a melt flow value.
The physical properties for sample 9 are generally comparable :
to those of control samples 7 and 8, although impact values are 25 somewhat decreased. These values can be increased as mentioned in ~ :
Example 2.
. .. . . .
, .:
.
-, 8CN-8393 2~ 2 ~
The following compositions were prepared as described above. Each component is identical to that used in Example 1, unless otherwise indicated.
Sample Number Com wnent 10* 11* 12 PPE (0.46 IV) 59.0 0.0 50.0 PPE ~0.40 IV) O 59.0 0 PPE (0.19 IV) O O 9.0 o ~IPS 41.0 41.0 41.0 F.R./Plastici~er 4.5 4.5 4.5 TDP 1.0 1.0 1.0 Polyethylene 1.5 1.5 1.5 ZnS - 0.15 0.15 0.15 ZnO 0.15 0.15 0.15 * Control Samples Tests on molded pieces resulted in the following properties:
17 scN-a3s3 201~26 ProDerty _ _ SamPle Number ~Q~11*_ 12 S Flame Retardance (1/8") 5.1,V1 4.6,V0 4.2,U0 Flame Retardance (1/16") 10.8,Y1 7.3,Y1 g.7,V1 Heat Di storti on Temperature (264 psi) 224 235 233 Flow Channel (inches) 22.3 23.7 25.0 Izod Impact (Notched) Strength (ft.lb/in) 4.3 2.9 2.6 Dynatup Impact Strength (in-lbs) 267 304 158 Melt Yiscosity (540F) (Poises) 1500 sec~1 1756 1688 1739 100 sec~1 7879 7351 7564 * Control Samples The flow channel length for sample 12, which contains a mixture of PP resins according to this invention, is again higher ~-:
20 than one would predict by averaging the IV values for the individual PPE components in sample 12.
The physical properties for sample 12 were somewhat similar to thcse of control samples 10 and 11, although Dynatup impact values were somewhat lo~er. These values could be increased 25 by the use of an impact modifier, as described above.
It should of course be understood that this invention may be modified in various aspects related to composition ~ :
ingredients and processing details, such modifications falling within the scope of the claims which fol10w.
.
, ' . . . ' , ~ ~
' ,,, ' ' '. ~ ; . : ` ~
''. ' ' ` ' ~ . ` ~ ' ' . ' :
Claims (26)
1) A polymer composition comprising:
(a) a polyphenylene ether resin having an intrinsic viscosity of at least about 0.38 dl/g; and (b) a polyphenylene ether resin having an intrinsic viscosity no greater than about 0.33 dl/g, each of said viscosities being measured in a chloroform solution at 25°C.
(a) a polyphenylene ether resin having an intrinsic viscosity of at least about 0.38 dl/g; and (b) a polyphenylene ether resin having an intrinsic viscosity no greater than about 0.33 dl/g, each of said viscosities being measured in a chloroform solution at 25°C.
2) The composition of claim 1 wherein at least one of the polyphenylene ether resins is derived from a monomer selected from the group consisting of 2,6-dimethyl phenol, 2,3,6-trimethyl phenol, and mixtures thereof.
3) The composition of claim 1 wherein at least one of the resins is poly(2,6-dimethyl-1,4-phenylene)ether.
4) The composition of claim 1 wherein component (a) has an intrinsic viscosity of at least about 0.40 dl/g.
5) The composition of claim 4 wherein component (b) has an intrinsic viscosity no greater than about 0.30 dl/g.
6) The composition of claim 5 wherein component (b) has an intrinsic viscosity no greater than about 0.25 dl/g.
7) The composition of claim 1 wherein component (a) has an intrinsic viscosity of at least about 0.45 dl/g.
8) The composition of claim 7 wherein component (b) has an intrinsic viscosity no greater than about 0.25 dl/g.
9) The composition of claim 8 wherein component (b) has an intrinsic viscosity no greater than about 0.20 dl/g.
10) The composition of claim 1 wherein component (a) comprises at least about 70% by weight of the total polyphenylene ether resin in the composition.
11) The composition of claim 1 wherein the weight ratio of component (a) to component (b) ranges from about 60:40 to about 40:60.
12) The composition of claim 1, further comprising an impact modifier.
13) The composition of claim 12, wherein the impact modifier is selected from the group consisting of core/shell polymers and elastomeric block copolymers.
14) The composition of claim 13, wherein the block copolymer is characterized by an A-B-A1 structure, wherein terminal blocks A and A1 are the same or different, and are polymerized vinyl aromatic hydrocarbons, and center block B
is a polymerized conjugated diene which may be non-hydrogenated or partially or entirely hydrogenated, the molecular weight of B being higher than the combined molecular weights of A and A1.
is a polymerized conjugated diene which may be non-hydrogenated or partially or entirely hydrogenated, the molecular weight of B being higher than the combined molecular weights of A and A1.
15) The composition of claim 14, wherein each A and A1 block is derived from styrene, and the B block is ethylene-butylene.
16) The composition of claim 1, further comprising about 0.1% to about 10% by weight of at least one polyolefin resin, said weight percentages based on the total weight of the composition.
17) The composition of claim 16, wherein the olefin resin has a melt index of less than about 30 grams/10 minutes.
18) The composition of claim 16, further comprising a block copolymer.
19) The composition of claim 1, comprising at least about 80% by weight polyphenylene ether resin, based on total composition weight.
20) The composition of claim 19, comprising at least about 90% by weight polyphenylene ether resin, based on total composition weight.
21) The composition of claim 1, further comprising a vinyl aromatic polymer.
22) The composition of claim 21, wherein the vinyl aromatic polymer is selected from the group consisting of homopolystyrene, styrene copolymers, rubber-modified polystyrene, and mixtures of these materials.
23) The composition of claim 1, further comprising at least one material selected from the group consisting of flame retardants, plasticizers, stabilizers, fillers, and reinforcing agents, lubricants, colorants, dyes, pigments, and drip retardants.
24) The composition of claim 21, further comprising at least one material selected from the group consisting of flame retardants, plasticizers, stabilizers, fillers, reinforcing agents, lubricants, colorants, dyes, pigments, and drip retardants.
25) A method for preparing a polyphenylene ether composition having high melt flow characteristics and good physical properties, wherein said method comprises mixing a polyphenylene ether resin having an intrinsic viscosity of at least about 0.38 dl/g with a polyphenylene ether resin having an intrinsic viscosity no greater than about 0.33 dl/g.
26) The invention as defined in any of the preceding claims including any further features of novelty disclosed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US361,160 | 1989-06-05 | ||
| US07/361,160 US5081185A (en) | 1989-06-05 | 1989-06-05 | Polyphenylene ether composition characterized by improved melt flow |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2015526A1 true CA2015526A1 (en) | 1990-12-05 |
Family
ID=23420894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002015526A Abandoned CA2015526A1 (en) | 1989-06-05 | 1990-04-26 | Polyphenylene ether composition characterized by improved melt flow |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5081185A (en) |
| EP (1) | EP0401690B1 (en) |
| JP (1) | JP2648887B2 (en) |
| CA (1) | CA2015526A1 (en) |
| DE (1) | DE69033652T2 (en) |
| ES (1) | ES2151878T3 (en) |
| WO (1) | WO1990015106A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04103663A (en) * | 1990-08-23 | 1992-04-06 | Nippon G Ii Plast Kk | Polyphenylene sulfide-based resin composition |
| EP0491191A1 (en) * | 1990-12-19 | 1992-06-24 | General Electric Company | Blends of polyphenylene ether resin mixtures and a polyetherimide siloxane copolymer |
| US5258455A (en) * | 1991-05-13 | 1993-11-02 | General Electric Company | Polyphenylene ether-olefin polymer compositions with improved properties |
| DE69227649T2 (en) * | 1991-05-13 | 1999-06-17 | Gen Electric | Polyphenylene ether-EPDM compositions |
| JPH10114857A (en) * | 1996-08-09 | 1998-05-06 | General Electric Co <Ge> | Crystalline polymer blend containing lowmolecular-weight polyphenylene ether resin |
| US6417255B1 (en) | 1999-12-15 | 2002-07-09 | General Electric Company | High performance thermoplastic compositions with improved melt flow behavior |
| US6576700B2 (en) * | 2000-04-12 | 2003-06-10 | General Electric Company | High flow polyphenylene ether formulations |
| US6414084B1 (en) | 2000-04-13 | 2002-07-02 | General Electric Company | High flow polyphenylene ether formulations with dendritic polymers |
| US6673872B2 (en) | 2000-05-17 | 2004-01-06 | General Electric Company | High performance thermoplastic compositions with improved melt flow properties |
| US6794450B2 (en) | 2002-03-06 | 2004-09-21 | General Electric Company | High flow compositions of compatibilized poly(arylene ether) polyamide blends |
| US6689825B1 (en) | 2002-11-27 | 2004-02-10 | General Electric Company | Additive for thermoplastic resins and flame retardant resin compositions |
| US6875387B2 (en) * | 2002-12-10 | 2005-04-05 | General Electric | Polyphenylene ether compositions with improved die lip buildup performance |
| US7183350B2 (en) * | 2003-02-28 | 2007-02-27 | General Electric Company | Poly(arylene ether) blends having low melt viscosity in the absence of plasticizer |
| US7683138B1 (en) * | 2005-05-16 | 2010-03-23 | Henkel Corporation | Molding compositions |
| US20080248278A1 (en) * | 2007-04-02 | 2008-10-09 | General Electric Company | Fiber reinforced thermoplastic sheets with surface coverings and methods of making |
| JP5666160B2 (en) * | 2009-04-01 | 2015-02-12 | 旭化成ケミカルズ株式会社 | Resin composition and molded body thereof |
| EP2253669B1 (en) * | 2009-05-20 | 2016-02-24 | Teknologian tutkimuskeskus VTT Oy | PPO composition as bonding base for electronic components, and method |
| US20130245182A1 (en) | 2010-10-13 | 2013-09-19 | Asahi Kasei Chemicals Corporation | Polyphenylene ether powder and polyphenylene ether resin composition |
| WO2012049743A1 (en) * | 2010-10-13 | 2012-04-19 | 旭化成ケミカルズ株式会社 | Polyphenylene ether as well as resin composition and molding thereof |
| EP3004208A4 (en) | 2013-06-03 | 2017-01-04 | PolyOne Corporation | Low molecular weight polyphenylene ether prepared without solvents |
| JP7297605B2 (en) * | 2019-09-03 | 2023-06-26 | 旭化成株式会社 | Polyphenylene ether resin composition and vehicle lamp extension |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252913A (en) * | 1976-12-22 | 1981-02-24 | General Electric Company | Low molecular weight polyphenylene ether compositions |
| US4154712A (en) * | 1977-09-30 | 1979-05-15 | General Electric Company | Low molecular weight polyphenylene ether compositions |
| US4383082A (en) * | 1981-12-01 | 1983-05-10 | General Electric Company | Polyphenylene ether resin compositions containing polyolefin in high amount |
| US4588806A (en) * | 1984-11-08 | 1986-05-13 | General Electric Company | Polyphenylene ether resins having bimodal molecular weight distributions and method of their formation |
| US4684696A (en) * | 1986-03-14 | 1987-08-04 | General Electric Company | Impact modified polyphenylene compositions |
| CA1336526C (en) * | 1987-09-09 | 1995-08-01 | Hiroji Oda | Cured polyphenylene ether resin and a curable polyphenylene ether resin |
| NL8800035A (en) * | 1988-01-08 | 1989-08-01 | Gen Electric | POLYMER MIXTURE WITH POLYPHENYLENE ETHER, POLYOCTENYLENE AND POLYETHYLENE. |
| EP0347539A3 (en) * | 1988-06-23 | 1991-05-08 | General Electric Company | Epoxytriazine-capped polyphenylene ethers and method for their preparation |
| US5089566A (en) * | 1988-06-23 | 1992-02-18 | General Electric Company | Compositions comprising polyphenylene ether-polyester copolymers from epoxytriazine-capped polyphenylene ethers |
| NL8802258A (en) * | 1988-09-14 | 1990-04-02 | Gen Electric | POLYMER MIXTURE WITH POLYPHENYLENE ETHERS AND POLYOCTENYLENE AND ARTICLES THEREFOR. |
-
1989
- 1989-06-05 US US07/361,160 patent/US5081185A/en not_active Expired - Lifetime
-
1990
- 1990-04-26 CA CA002015526A patent/CA2015526A1/en not_active Abandoned
- 1990-05-31 DE DE69033652T patent/DE69033652T2/en not_active Expired - Fee Related
- 1990-05-31 ES ES90110383T patent/ES2151878T3/en not_active Expired - Lifetime
- 1990-05-31 EP EP90110383A patent/EP0401690B1/en not_active Expired - Lifetime
- 1990-06-04 WO PCT/US1990/003144 patent/WO1990015106A1/en unknown
- 1990-06-04 JP JP2509839A patent/JP2648887B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US5081185A (en) | 1992-01-14 |
| EP0401690A2 (en) | 1990-12-12 |
| ES2151878T3 (en) | 2001-01-16 |
| JP2648887B2 (en) | 1997-09-03 |
| DE69033652D1 (en) | 2000-11-23 |
| EP0401690B1 (en) | 2000-10-18 |
| JPH04500094A (en) | 1992-01-09 |
| EP0401690A3 (en) | 1991-12-27 |
| DE69033652T2 (en) | 2001-05-17 |
| WO1990015106A1 (en) | 1990-12-13 |
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