WO1993006171A1 - Polymer blends of norbornene dicarboximides - Google Patents
Polymer blends of norbornene dicarboximides Download PDFInfo
- Publication number
- WO1993006171A1 WO1993006171A1 PCT/US1992/007953 US9207953W WO9306171A1 WO 1993006171 A1 WO1993006171 A1 WO 1993006171A1 US 9207953 W US9207953 W US 9207953W WO 9306171 A1 WO9306171 A1 WO 9306171A1
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- WIPO (PCT)
- Prior art keywords
- norbornene
- polymer
- monomer units
- polymer blend
- acid
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Ethene-propene or ethene-propene-diene copolymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- thermoplastics 15 typically characterized as semicrystalline thermoplastics and are widely used in a wide range of applications. Due to high strength polyamides are commonly and advantageously used as tire cord, carpet fiber, tough fabrics, etc. However, due to other
- polyamides have limited use in other engineering thermoplastic applications. For instance, due to low impact strength, polyamides often require toughening, e.g. with rubber impact modifier, to provide sufficient impact strength required of many
- Polyamides also typically have unsatisfactory load bearing properties at moderate to high temperatures due to the low glass transition temperature of the polyamide. Heat distortion temperature determined under the force of a load
- HDTUL High-modified polyamides, having high impact strengths that commend their use for many engineering thermoplastic
- Metathesis ring-opening polymers of norbornene * dicarboximides especially the N-methyl, N-ethyl, N-propyl and N-phenyl i ides, exhibit high glass transition temperatures, e.g. about 200 °C, and high HDTUL, e.g. about 150 to 180 °C.
- high glass transition temperatures e.g. about 200 °C
- high HDTUL e.g. about 150 to 180 °C.
- metathesis ring-opening polymers of norbornene dicarboximides can be effectively blended with polyamides to provide blends having the attendant advantageous properties of polyamides but with an exceptionally high heat distortion temperature. Even more advantageous blends - are achieved when the metathesis ring-opened unsaturated polymer of norbornene dicarboximide includes a small amount of an acid containing species.
- this invention provides . polymer blends comprising a metathesis ring-opening polymerized unsaturated polymer of norbornene dicarboximide and a polyamide or other polymer having acid-reactive functionality.
- this invention provides polymer blends comprising a metathesis ring-opening polymerized unsaturated copolymer of monomer units of norbornene dicarboximide and a norbornene carboxylic acid.
- Such copolymer can be used alone in blends with acid-reactive polymers or, alternatively, as a compatibilizer in blends of norbornene dicarboximide polymer and acid-reactive polymers.
- the polymer blends of this invention comprise polymers having acid-reactive functionality such as polyamides and metathesis ring-opening polymerized unsaturated polymers of a norbornene dicarboximide, e.g. about 10 to 90 parts by weight of polymer having acid-reactive functionality and, conversely, about 90 to 10 parts by weight of metathesis ring-opening polymerized unsaturated polymer. More preferred blends, depending on the desired properties, can comprise at least about 30 parts by weight of each polymer.
- Preferred polymers having acid-reactive functionality include polyamides having amine end groups such as nylon-6 or nylon-6,6 and, optionally, toughened polyamides, e.g. having 5 rubber toughening agents.
- Other useful acid-reactive functional polymers include polyesters having hydroxyl end groups.
- the norbornene dicarboximide of the metathesis ring-opening polymerized polymers can be
- alkyl, cycloalkyl or aromatic i ides 10. alkyl, cycloalkyl or aromatic i ides.
- Polymers having advantageously high glass transition temperatures, e.g. above 150 °C, and preferably above 200 ⁇ C, include polymers and copolymers comprising monomer units of N-methyl, N-ethyl, N-propyl, N-isopropyl,
- Such polymers can be prepared by known methods for metathesis ring-opening polymerization of norbornene derivative monomers which provide unsaturated polymer. Especially preferred methods are disclosed by Hardiman 0 in WIPO International Publication Number WO 91/18938.
- the metathesis ring- opening polymerized polymer comprises a copolymer of a norbornene derivative monomer having acid functionality that allows reactive interaction with . 5 polymers having acid-reactive functionality.
- Preferred metathesis ring-opening polymerized unsaturated copolymers comprise monomer units of norbornene dicarboximide and a norbornene carboxylic acid or ester.
- the 0 norbornene carboxylic acid will comprise a dicarboxylic acid or the acid anhydride, mono ester or diester thereof.
- copolymer will generally 5 comprise less than about 10 mole percent of the acid monomer units, e.g. about 0.5 to 3 mole percent of acid monomer units.
- compatibilizer copolymers can readily be prepared from mixtures of monomer using metathesis ring-opening polymerization methods generally useful for norbornene derivative monomers.
- the acid-functional copolymers of this invention can be used by themselves in blends with polymers having acid-reactive functionality, e.g. to provide blends of copolymer and polyamide.
- the acid-functional copolymers of this - invention can be used as additives to compatibilize blends of norbornene dicarboximide polymer and polymers having acid-reactive functionality, e.g. blends of poly(N-methyl norbornene dicarboximide) and nylon-6.
- the compatibilization of such blends is facilitated in that the.low level of acid functiorrality provides reactive compatibilization with the polyamide and the structural similarity provides miscibility compatibilization with the norbornene dicarboximide polymer.
- a polymer of N-methyl norbornene dicarboximide monomer units was prepared by dissolving 4.5 kilograms of N-methyl norbornene dicarboximide in 9.9 kilograms of toluene at 65 °C. After adding 38.5 ml of hexene-1, a molecular weight controlling agent, to the agitated solution, polymerization was effected by adding 114.5 ml of a catalyst solution (0.5 M tungsten hexachloride and 1.5 M diethylacetal of formaldehyde in toluene) and 214 ml of diethyl aluminum chloride. The exothermic metathesis ring- opening polymerization raised the solution temperature to 105 °C in about 20 minutes.
- a catalyst solution 0.5 M tungsten hexachloride and 1.5 M diethylacetal of formaldehyde in toluene
- the homopolymer was intimately blended with an equal parts by weight of an EPDM rubber-modified nylon-6,6 (Zytel ST-801 from DuPont) in a Braybender twin screw extruder having barrel and nozzle tempera ⁇ tures of about 300 °C and screw speed of 80-90 rpm. Samples for analysis were extruded through an Arburg molder at about 300 ⁇ C and 6900 kPa into molds at about 130 "C. Analytical results of the properties of each of the blend are reported in Table 1.
- the polymers and blends were injection molded into specimen bars (127 X 12.7 X 3.2 mm) which were conditioned for at least 24 hours at 23 "C and 50% relative humidity.
- HDTUL was measured according to ASTM D-648; tensile strength, tensile modulus and elongation were measured according to ASTM D-638; flexural strength and flexural modulus were measured according to ASTM D- 790; and notched Izod impact strength was measured according to ASTM D-256.
- EXAMPLE 3 The polymerization of N-methyl norbornene dicarboximide was repeated essentially in the manner of Example 1 except that monomer solution contained about 2 percent norbornene dicarboxylic acid anhydride, providing an acid functionalized copoly(N- methyl norbornene dicarboximide/norbornene dicarboxylic anhydride) comprising about 1 percent monomer with acid functionality and having an inherent viscosity of 0.47, an HDTUL of 160 °C, Flexural strength of 140 MPa and flexural modulus of 3 GPa.
- Equal parts of acid anhydride-modified copolymer were blended with equal parts of each of the following polymers: (a) nylon-6,6 (Vydyne 21 from
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Abstract
Polymer blends comprising (a) a metathesis ring-opening polymerized unsaturated polymer of norbornene dicarboximide monomer units and/or a metathesis ring-opened unsaturated copolymer of norbornene dicarboximide and a norbornene carboxylic acid monomer units and (b) a polymer having acid-reactive functionality, e.g. a polyamide such as nylon-6 or nylon-6,6. The norbornene dicarboximide monomers can be alkyl, cycloalkyl or aromatic imide, preferably methyl, ethyl, propyl, isopropyl, cyclohexyl or phenyl imides. Preferred norbornene carboxylic acid monomer units are norbornene dicarboxylic acids, acid anhydrides, monoesters or diesters.
Description
POLYMER BLENDS OF NORBORNENE DICARBOXIMIDES - Disclosed herein are metathesis ring-opened
' unsaturated polymers of norbornene dicarboximides and
5 copolymers of norbornene dicarboximide and norbornene dicarboxylic acid, anhydride, mono ester or diester. Also disclosed are blends of such polymers and copolymers with polymers having acid-reactive functionality, e.g. a polyamide such as nylon-6 or
10 • nylon-6,6 and, optionally, a rubber toughening agent. Also disclosed are methods of using such blends for high performance thermoplastic applications. BACKGROUND OF THE INVENTION Polyamides, e.g. nylon-6 and nylon-6,6, are
15 typically characterized as semicrystalline thermoplastics and are widely used in a wide range of applications. Due to high strength polyamides are commonly and advantageously used as tire cord, carpet fiber, tough fabrics, etc. However, due to other
20 properties polyamides have limited use in other engineering thermoplastic applications. For instance, due to low impact strength, polyamides often require toughening, e.g. with rubber impact modifier, to provide sufficient impact strength required of many
25 molded parts. Polyamides also typically have unsatisfactory load bearing properties at moderate to high temperatures due to the low glass transition temperature of the polyamide. Heat distortion temperature determined under the force of a load
30 (typically 1820 Kpa) is widely known by the acronym "HDTUL". For instance, nylon-6 and nylon-6,6 have HDTUL in the range of 60 to 80 °C. Rubber-modified polyamides, having high impact strengths that commend their use for many engineering thermoplastic
35 applications, generally have even lower HDTUL. Metathesis ring-opening polymers of norbornene * dicarboximides, especially the N-methyl,
N-ethyl, N-propyl and N-phenyl i ides, exhibit high glass transition temperatures, e.g. about 200 °C, and high HDTUL, e.g. about 150 to 180 °C. What I have discovered is that such metathesis ring-opening polymers of norbornene dicarboximides can be effectively blended with polyamides to provide blends having the attendant advantageous properties of polyamides but with an exceptionally high heat distortion temperature. Even more advantageous blends - are achieved when the metathesis ring-opened unsaturated polymer of norbornene dicarboximide includes a small amount of an acid containing species.
SUMMARY OF THE INVENTION In one aspect this invention provides . polymer blends comprising a metathesis ring-opening polymerized unsaturated polymer of norbornene dicarboximide and a polyamide or other polymer having acid-reactive functionality. In another aspect this invention provides polymer blends comprising a metathesis ring-opening polymerized unsaturated copolymer of monomer units of norbornene dicarboximide and a norbornene carboxylic acid. Such copolymer can be used alone in blends with acid-reactive polymers or, alternatively, as a compatibilizer in blends of norbornene dicarboximide polymer and acid-reactive polymers.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS The polymer blends of this invention comprise polymers having acid-reactive functionality such as polyamides and metathesis ring-opening polymerized unsaturated polymers of a norbornene dicarboximide, e.g. about 10 to 90 parts by weight of polymer having acid-reactive functionality and, conversely, about 90 to 10 parts by weight of metathesis ring-opening polymerized unsaturated polymer. More preferred blends, depending on the desired properties, can comprise at least about 30
parts by weight of each polymer. Preferred polymers having acid-reactive functionality include polyamides having amine end groups such as nylon-6 or nylon-6,6 and, optionally, toughened polyamides, e.g. having 5 rubber toughening agents. Other useful acid-reactive functional polymers include polyesters having hydroxyl end groups.
The norbornene dicarboximide of the metathesis ring-opening polymerized polymers can be
10. alkyl, cycloalkyl or aromatic i ides. Polymers having advantageously high glass transition temperatures, e.g. above 150 °C, and preferably above 200 βC, include polymers and copolymers comprising monomer units of N-methyl, N-ethyl, N-propyl, N-isopropyl,
15 N-cyclohexyl or N-phenyl norbornene dicarboximide. Such polymers can be prepared by known methods for metathesis ring-opening polymerization of norbornene derivative monomers which provide unsaturated polymer. Especially preferred methods are disclosed by Hardiman 0 in WIPO International Publication Number WO 91/18938.
In preferred blends the metathesis ring- opening polymerized polymer comprises a copolymer of a norbornene derivative monomer having acid functionality that allows reactive interaction with . 5 polymers having acid-reactive functionality. Preferred metathesis ring-opening polymerized unsaturated copolymers comprise monomer units of norbornene dicarboximide and a norbornene carboxylic acid or ester. In more preferred copolymers the 0 norbornene carboxylic acid will comprise a dicarboxylic acid or the acid anhydride, mono ester or diester thereof. Although the amount of norbornene carboxylic acid functional monomer units in the copolymer can vary, preferred copolymer will generally 5 comprise less than about 10 mole percent of the acid monomer units, e.g. about 0.5 to 3 mole percent of
acid monomer units. Such compatibilizer copolymers can readily be prepared from mixtures of monomer using metathesis ring-opening polymerization methods generally useful for norbornene derivative monomers. The acid-functional copolymers of this invention can be used by themselves in blends with polymers having acid-reactive functionality, e.g. to provide blends of copolymer and polyamide. Alterna¬ tively, the acid-functional copolymers of this - invention can be used as additives to compatibilize blends of norbornene dicarboximide polymer and polymers having acid-reactive functionality, e.g. blends of poly(N-methyl norbornene dicarboximide) and nylon-6. The compatibilization of such blends is facilitated in that the.low level of acid functiorrality provides reactive compatibilization with the polyamide and the structural similarity provides miscibility compatibilization with the norbornene dicarboximide polymer. EXAMPLE 1
A polymer of N-methyl norbornene dicarboximide monomer units was prepared by dissolving 4.5 kilograms of N-methyl norbornene dicarboximide in 9.9 kilograms of toluene at 65 °C. After adding 38.5 ml of hexene-1, a molecular weight controlling agent, to the agitated solution, polymerization was effected by adding 114.5 ml of a catalyst solution (0.5 M tungsten hexachloride and 1.5 M diethylacetal of formaldehyde in toluene) and 214 ml of diethyl aluminum chloride. The exothermic metathesis ring- opening polymerization raised the solution temperature to 105 °C in about 20 minutes. After the temperature was reduced to 65 °C stabilizers, e.g. 200 ml of methanol solution of 46 g of an ortho di-t-butyl phenol (Irganox 3125 antioxidant from Ciba-Geigy) and 24 g of tris nonyl phenyl phosphate (Polyguard U.V. stabilizer from Uniroyal) were mixed into the
polymer. The reaction product was chopped, dried, ground and washed with methanol providing 4.4 kg of a poly(N-methyl norbornene dicarboximide) homopolymer. The homopolymer was intimately blended with an equal parts by weight of an EPDM rubber-modified nylon-6,6 (Zytel ST-801 from DuPont) in a Braybender twin screw extruder having barrel and nozzle tempera¬ tures of about 300 °C and screw speed of 80-90 rpm. Samples for analysis were extruded through an Arburg molder at about 300 βC and 6900 kPa into molds at about 130 "C. Analytical results of the properties of each of the blend are reported in Table 1.
For characterization, the polymers and blends were injection molded into specimen bars (127 X 12.7 X 3.2 mm) which were conditioned for at least 24 hours at 23 "C and 50% relative humidity. HDTUL was measured according to ASTM D-648; tensile strength, tensile modulus and elongation were measured according to ASTM D-638; flexural strength and flexural modulus were measured according to ASTM D- 790; and notched Izod impact strength was measured according to ASTM D-256.
TABLE 1
*poly(N-methyl norbornene dicarboximide)
EXAMPLE 2 A rubber modified polymer of N-methyl norbornene dicarboximide was prepared in the manner of Example 1, except that a solution of 15 g of Hycar™ nitrile rubber (Goodrich) and 135 g of 1,2-dichloro- ethane was polymerized using 3.4 ml of the 0.5 tungsten hexachloride catalyst solution and 5.6 ml of a 2 M solution of diethyl aluminum chloride in heptane. After the polymerization, 1.5 g of Irganox ■ 1076 hindered phenol antioxidant (Ciba-Geigy) and 0.75 g of Polygard U.V. stabilizer (Uniroyal) were added to the polymer. The polymer was characterized and blended with an equal part of nylon-6. Properties of the polymers and blends are reported in Table 2. TABLE 2
*nitrile rubber-modified poly(N-methyl norbornene dicarboximide)
EXAMPLE 3 The polymerization of N-methyl norbornene dicarboximide was repeated essentially in the manner of Example 1 except that monomer solution contained about 2 percent norbornene dicarboxylic acid anhydride, providing an acid functionalized copoly(N- methyl norbornene dicarboximide/norbornene dicarboxylic anhydride) comprising about 1 percent monomer with acid functionality and having an inherent
viscosity of 0.47, an HDTUL of 160 °C, Flexural strength of 140 MPa and flexural modulus of 3 GPa.
Equal parts of acid anhydride-modified copolymer were blended with equal parts of each of the following polymers: (a) nylon-6,6 (Vydyne 21 from
Monsanto), (b) EPDM rubber-modified nylon-6,6 (Zytel ST-801 from DuPont) and (c) a rubber-modified nylon-6 (65% nylon-6, 292 Kraton G 1652 styrene-butadiene block copolymer and 6% Kraton 1901X maleated styrene- butadiene block copolymer) . The polymers were blended in the manner of Example 1 in a Braybender twin screw extruder; properties of molded samples of the 50/50 blends are reported in Table 3.
TABLE 3 50/50 Blends of Acid Anhydride-modified Copolymer with:
While specific embodiments have been described herein, it should be apparent to those skilled in the art that various modifications thereof can be made without departing from the true spirit and scope of the invention. Accordingly, it is intended that the following claims cover all such modifications within the full inventive concept.
Claims
1. A polymer blend comprising a metathesis ring-opening polymerized unsaturated polymer of norbornene dicarboximide monomer units and a polyamide.
2. A polymer blend according to claim 1 wherein said norbornene dicarboximide monomer units are alkyl, cycloalkyl or aromatic i ides.
3. A polymer blend according to claim 2 - wherein said norbornene dicarboximide monomer units are methyl, ethyl, propyl, isopropyl, cyclohexyl or phenyl imides.
4. A polymer blend according to claim 3 wherein said polyamide is nylon-6 or nylon-6,6.
5. A polymer blend according to claim 4 wherein said polyamide further comprises a rubber toughening agent.
6. A polymer blend according to claim 1 further comprising a metathesis ring-opening polymerized unsaturated copolymer of norbornene dicarboximide and norbornene carboxylic acid, acid anhydride, monoester or diester monomer units.
7. A polymer blend comprising (a) a metathesis ring-opening polymerized unsaturated copolymer of norbornene dicarboximide and norbornene carboxylic acid, acid anhydride, monoester or diester monomer units and (b) a polymer having acid-reactive functionality.
8. A polymer blend according to claim 7 wherein said norbornene dicarboximide monomer units are alkyl, cycloalkyl or aromatic imides.
9. A polymer blend according to claim 8 wherein said norbornene dicarboximide monomer units are an methyl, ethyl, propyl, isopropyl, cyclohexyl or phenyl imides.
10. A polymer blend according to claim 9 wherein said polymer having acid-reactive functionality is a polyamide.
11. A polymer blend according to claim 10 wherein said polyamide is nylon-6 or nylon-6,6.
12. A polymer blend according to claim 11 further comprising a rubber toughening agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US76529291A | 1991-09-25 | 1991-09-25 | |
| US765,292 | 1991-09-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1993006171A1 true WO1993006171A1 (en) | 1993-04-01 |
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ID=25073151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/US1992/007953 WO1993006171A1 (en) | 1991-09-25 | 1992-09-22 | Polymer blends of norbornene dicarboximides |
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| Country | Link |
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| WO (1) | WO1993006171A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6395851B1 (en) | 2000-06-09 | 2002-05-28 | Eastman Chemical Company | Copolymerization of norbornene and functional norbornene monomers |
| EP1553131A1 (en) * | 2004-01-09 | 2005-07-13 | E.I. du Pont de Nemours and Company | Compositions with polymers for advanced materials |
| JP2009209324A (en) * | 2008-03-06 | 2009-09-17 | Kuraray Co Ltd | Oxygen absorptive resin composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2249913A1 (en) * | 1973-11-05 | 1975-05-30 | Showa Denko Kk | |
| JPS5213548A (en) * | 1975-07-22 | 1977-02-01 | Showa Denko Kk | Heat-resistant resin composition |
| EP0409291A2 (en) * | 1987-11-17 | 1991-01-23 | Japan Synthetic Rubber Co., Ltd. | Thermoplastic resin composition |
-
1992
- 1992-09-22 WO PCT/US1992/007953 patent/WO1993006171A1/en active Application Filing
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2249913A1 (en) * | 1973-11-05 | 1975-05-30 | Showa Denko Kk | |
| JPS5213548A (en) * | 1975-07-22 | 1977-02-01 | Showa Denko Kk | Heat-resistant resin composition |
| EP0409291A2 (en) * | 1987-11-17 | 1991-01-23 | Japan Synthetic Rubber Co., Ltd. | Thermoplastic resin composition |
Non-Patent Citations (1)
| Title |
|---|
| PATENT ABSTRACTS OF JAPAN vol. 1, no. 54 (C-014)25 May 1977 & JP,A,52 013 548 ( SHOWA DENKO ) 2 January 1977 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6395851B1 (en) | 2000-06-09 | 2002-05-28 | Eastman Chemical Company | Copolymerization of norbornene and functional norbornene monomers |
| US6512065B2 (en) | 2000-06-09 | 2003-01-28 | Eastman Chemical Company | Copolymers of norbornene and functional norbornene monomers |
| EP1553131A1 (en) * | 2004-01-09 | 2005-07-13 | E.I. du Pont de Nemours and Company | Compositions with polymers for advanced materials |
| JP2009209324A (en) * | 2008-03-06 | 2009-09-17 | Kuraray Co Ltd | Oxygen absorptive resin composition |
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