CA2051902A1 - Molding compositions based on polyethylene having an average molecular weight of at least 500.000 g/mol - Google Patents
Molding compositions based on polyethylene having an average molecular weight of at least 500.000 g/molInfo
- Publication number
- CA2051902A1 CA2051902A1 CA002051902A CA2051902A CA2051902A1 CA 2051902 A1 CA2051902 A1 CA 2051902A1 CA 002051902 A CA002051902 A CA 002051902A CA 2051902 A CA2051902 A CA 2051902A CA 2051902 A1 CA2051902 A1 CA 2051902A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- mol
- molecular weight
- polyethylene
- molding composition
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Frankfurt, 25.09.1990 PAT/rcht-sei Hoe90/Y015 Hoechst Aktiengesellschaft, 6230 Frankfurt am Main 80 Abstract Molding compositions which have been stabilized against the effects of weathering and comprise polyethylene having an average molecular weight of at least 500,000 g/mol, preferably at least 1 x 105 g/mol, containing 0.05 to 0.5 % by weight of a sterically hindered amine and 0.1 to 0.5 % by weight of copper phthalocyanine (in each case based on the molding composition), and if appropriate other customary additives.
Description
2 ~
Moldinq com~Qsitions based on polyethylene havinq an averaqe molecular wei~ht of at least 500 r 000 g~mol The present invention relates to molding composition~ of polyethylene having an average molecular weight of at least 500,000 g/mol, preferably at least 1 x 10~ g/mol, which are stabilized against the effects of weathering, in particular against degradation by the action of heak and lightO The novel molding compo~itions contain sterically hindered amines and copper phthalocyanine as stabilizers.
As the degree of polymerization increases, a number of industrially important properties of polyethylene are improved considerably. Thus, the notched impact strength increases, the heat distortion point and tear strength at elevated temperature increase and the resistance to stress corrosion is increased. The high resis~ance to wear, the low coefficient of friction compared with othPr materials, the excellent toughness properties and the remarkable resistance to numerous chemicals are further-more to be emphasized. The industrial properties men tioned are particularly pronounced in the case of ultra-high molecular weight polyethylene, PE-UHMW, which has an average molecular weight of at least 2.5 x 106 g~mol to about 1 x 107 gJmol.
Like all polymers, high molecular weight polyethylen2 is chemically changed by heat and light and oxidation effects associated therewith, with the consequence that its mechanical properties are noticeably impaired.
Polyethylene, including the high molecular weight types, must therefore be protected from the action of heat and o~ygen. If the polyolefins are to be used in the open, protection against sunlight is also necessary, the W
content of sunlight damaginy the plastic with the assis-tance of atmospheric oxygen~ The polyolefins are there-fore stabilized by addition of antioxidants and if appropriate other additives which suppress photo-oxidation.
~ ~ ' .
' :: ' ~ :
2 ~
A large number of addi~ives which protect the pol~mer against oxidation during storage, against oxidation and heat during processing and against the surface oxidation caused by light and elevated temperature during use over long periods of time have been developed over the years.
Representatives of the following groups of substances have proved particularly suitable for light stabilization of polyolefins for external use: sterically hindered mono-, di- or trihydric phenols, sterically hindered bisphenols and trisphenols; sterically hindered, pre-dominantly aromatic, secondary amines; mercaptans, thioethers and disulfides; derivatives of phosphorous acid and of dithiophosphoric acid; and carbon black; and the following are used specifically for protection against W radiation: o-hydroxybenzophenones;
2-(o-hydroxyphenyl)-benzotriazoles; phenyl salicylates;
and cinnamic acid derivatives.
Apart from individual substances, combinations of two or more compounds also have a distinctly light-stabilizing influence. An example which may be mentioned is the use of a mixture of 2,6-di-(tert -butyl)-4-methylphenol and glycerol monostearate as a light stabilizer.
The life of polyolefins is not increased to an unlimited length of time by addition of light stabilizers; in general, it is increased three-fold in comparison with non-stabilized material, a period of time which does not always meet economic and industrial requirements. Efforts are therefore being made to develop novel, more effective stabilizers or to increase the effectiveness of known stabilizers by combination with other substances, w~ich do not themsel~es have to be light or W ~tabilizers.
In connection with high molecular weight polyethylene in particular, attempts are moreover being made to use additives which are already effective in amounts which do not lead to an impairment of the material properties of the polymer.
.
,, ' ' .~ ~
2~3~2 The objec~ was therefore to develop compositions of high molecular weight polyethylene which have the excellent physical and chemical properties of the base material and at the same tLme are largely insensitive, and insensitive over long periods of time, ~o weathering influences.
This object is achieved by molding compositions of polyethylene having an average molecular weight, measured by viscometry, of at least 500,000 g/mol, preferably at least 1 x lo6 y/mol, which contain, in each case based on the molding composition, 0.05 to 0.5 ~ by weight of a sterically hindered amine and 0.1 to 0.5 ~ by weight of copper phthalocyanine, and if appropriate other customary additives.
Surprisingly, the light-stabilizing action of sterically hindered amines is increased significantly by copper phthalocyanine. It is particularly remarkable that the copper compound by itself has no influence on ~he behavior of polyethylene in visible light or under W
radiation. It is furthermore to be emphasized that the physical properties of polyethylene are not Lmpaired by the additives.
The preparation of polyethylene having an average mole-cular weight, measured by viscometry, of at least 500,000 g/mol, preferably at least 1 x 106 g/mol to 1 x 107 g/mol, is known. It can be carried out by various processes. A proven process, which is carried out under low pressure using a mixed catalyst of titanium(III~
halides and organoaluminum compounds, is described in DE-B 23 61 508. Other processes, which are also carried out under low pressures, use, for example, chromium oxide catalysts.
~he molecular weights quantified above are understood as being the values measured by viscometry. A method for their measurement is described, for example, in CZ-Chemietechnik 4 (1974), page 129 et seq.
, . . .
.. . ~ . ' ,, .. , . , . ' 2 ~
The molding composi~ions according to the invention con~ain sterically hindered amine~ and copper phthalo-cyanine as additivesO
The term sterically hindered amines is understood as meaning compounds in which one or more space filling organic radicals are bonded to their trivalent nitrogen atom. ~hese are mainly aromatic and secondary amines.
Examples which may be men~ioned are N,N'-disubstituted p-phenylenediamines, such as N,N'-diisopropyl-p-phenyl-enediamine, N,N~-di-sec.-butyl-p phenylenediamine, diphenylamine derivatives, such as N-phenyl-l-naphthyl-amine, and aminophenol derivatives, such as 4-dodecanoyl-aminophenol. Bis~2,2,6,6-~etramethyl-4-piperidyl) seba cate has p~oved to be particularly suitable. The sterically hindered amines are used in a concentration of 0.05 to 0.5 % by weight, in particular 0.1 to 0.3 % by weight, based on the total weight oE khe molding composition.
Copper phthalocyanine, which is employed as an organic pigmenk, is obtained industrially from ph~halic acid dinitrile and copper(I) chloride. It is added in the commercially available form to the molding compositions according to the invention. Taking into consideration the material properties sought, the preparation and the ~5 processahility of the novel molding composition~, it is advisable for the concentration of the copper compound to be adjusted to values of 0.1 to 0.5 % by weight, prefer-ably 0.2 to 0.35 % by weight, in each case based on the total weight of the molding composition.
Apart from amines and copper phthalocyanine, the molding compositions according to the invention can also contain other customary additives, such as lubricants and proces-sing stabilizers.
The stabiliæed molding compositions are prepared by .
~ . ..
', ' ', homogeneous mixing of the starting materials in a mixer and, depending on the molecular weight, by melting at temperatures of 125 to 145C or b~ sintering at tempera-tures of 180 to 250~C, in particular 200 to 230C. The pressure during sintering is 3 to 5 MPa, in particular 3 to 4 MPa. Cooling after sintering is also carried out under pressure, with 5 to 10 MPa, preferably 8 to 10 MPa, having proved suitable. The sinteriny and coollng tLme largely depend on the ~hickness of the material.
The novel molding compositions can be worked mechanic-ally, for example drilledr milled and sawed, in the customary manner; they can be shaped by compression molding.
The invention is illustrated in more detail in the following example, but is not limited to this e~odLment.
Example The behavior of stabilized and non-stabilized poly-ethylene under the weathering conditions prevailing in Central Europe was investigated under natural conditions in the open on test specimens which were stored on a test stand at an angle of 45 in the south-westerly direction.
Samples were taken at fixed inter~als of time over a period of 5 years.
The test specimens used were square sheets of 150 mm side face and 1.5 mm thick (test sheets) obtained from pressed sheets by hot ski~ing. The pressed sheets were produced from pulverulent polyethylene having a molecular weight, measured by viscometry, of 500,000 g/mol, which was pressed by itself (sample 1) or after admixing of 0.15 ~
by weight (based on the mixture) of bis(2,2,6,6-tetra-methyl-4-piperidyl) sebacate (sample 2) or 0.15 % by weight of the sebacate and 0.3 % by weight of copper phthalocyanine (in each case based on the mixture -sample 3), to give sheets having the dimensions 800 mm x . , . . . - . , . . ' .
. . . . . .. .
. -:, ,. . : -, . .:,.: , ., : , . - .
.
P~ 2 400 mm x 30 mmr which were first sin~ered at 180C under a pressure of 3 MPa for 2 hours and then cooled under a pressure of 8 MPa for 1.5 hours.
The mechanical properties of density, tear strength and elongation at break from the stress-elongation diagram at 23 and 120C as well as wear and notched impact strength were de~ermined on the samples exposed in the open. The density and the strength properties were tested on test specimens stamped out of the 1.5 mm thick sheets, while the notched impact strength and wear samples were taken by machining from the 20 mm sheets, from the weathered side, in a sample thickness of 10 or 6.25 mm.
To evaluate the change in the pattern of properties under natural clLmatic conditions, the stress and elonga~ion properties of the test sheets at 23C were selected, and the time taken for the original values to fall to 50 %
was determined.
The elongation at break of sample 1 had already reached the value 0 after 3 months of external weathering and the material had become embrittled. By addition o a light stabilizer (sample 23, the strength properties had improved under the climatic conditions of Central Europe and the elongation at break fell to half the original value after 9 months. Light stabilizer in combination with copper phthalocyanine (sample 3) significantly increases the resistance of high molecular weight poly-ethylene to weathering influences. The elongation at break dropped to 50 % of its original value only af er 3.5 years.
- .
. .
Moldinq com~Qsitions based on polyethylene havinq an averaqe molecular wei~ht of at least 500 r 000 g~mol The present invention relates to molding composition~ of polyethylene having an average molecular weight of at least 500,000 g/mol, preferably at least 1 x 10~ g/mol, which are stabilized against the effects of weathering, in particular against degradation by the action of heak and lightO The novel molding compo~itions contain sterically hindered amines and copper phthalocyanine as stabilizers.
As the degree of polymerization increases, a number of industrially important properties of polyethylene are improved considerably. Thus, the notched impact strength increases, the heat distortion point and tear strength at elevated temperature increase and the resistance to stress corrosion is increased. The high resis~ance to wear, the low coefficient of friction compared with othPr materials, the excellent toughness properties and the remarkable resistance to numerous chemicals are further-more to be emphasized. The industrial properties men tioned are particularly pronounced in the case of ultra-high molecular weight polyethylene, PE-UHMW, which has an average molecular weight of at least 2.5 x 106 g~mol to about 1 x 107 gJmol.
Like all polymers, high molecular weight polyethylen2 is chemically changed by heat and light and oxidation effects associated therewith, with the consequence that its mechanical properties are noticeably impaired.
Polyethylene, including the high molecular weight types, must therefore be protected from the action of heat and o~ygen. If the polyolefins are to be used in the open, protection against sunlight is also necessary, the W
content of sunlight damaginy the plastic with the assis-tance of atmospheric oxygen~ The polyolefins are there-fore stabilized by addition of antioxidants and if appropriate other additives which suppress photo-oxidation.
~ ~ ' .
' :: ' ~ :
2 ~
A large number of addi~ives which protect the pol~mer against oxidation during storage, against oxidation and heat during processing and against the surface oxidation caused by light and elevated temperature during use over long periods of time have been developed over the years.
Representatives of the following groups of substances have proved particularly suitable for light stabilization of polyolefins for external use: sterically hindered mono-, di- or trihydric phenols, sterically hindered bisphenols and trisphenols; sterically hindered, pre-dominantly aromatic, secondary amines; mercaptans, thioethers and disulfides; derivatives of phosphorous acid and of dithiophosphoric acid; and carbon black; and the following are used specifically for protection against W radiation: o-hydroxybenzophenones;
2-(o-hydroxyphenyl)-benzotriazoles; phenyl salicylates;
and cinnamic acid derivatives.
Apart from individual substances, combinations of two or more compounds also have a distinctly light-stabilizing influence. An example which may be mentioned is the use of a mixture of 2,6-di-(tert -butyl)-4-methylphenol and glycerol monostearate as a light stabilizer.
The life of polyolefins is not increased to an unlimited length of time by addition of light stabilizers; in general, it is increased three-fold in comparison with non-stabilized material, a period of time which does not always meet economic and industrial requirements. Efforts are therefore being made to develop novel, more effective stabilizers or to increase the effectiveness of known stabilizers by combination with other substances, w~ich do not themsel~es have to be light or W ~tabilizers.
In connection with high molecular weight polyethylene in particular, attempts are moreover being made to use additives which are already effective in amounts which do not lead to an impairment of the material properties of the polymer.
.
,, ' ' .~ ~
2~3~2 The objec~ was therefore to develop compositions of high molecular weight polyethylene which have the excellent physical and chemical properties of the base material and at the same tLme are largely insensitive, and insensitive over long periods of time, ~o weathering influences.
This object is achieved by molding compositions of polyethylene having an average molecular weight, measured by viscometry, of at least 500,000 g/mol, preferably at least 1 x lo6 y/mol, which contain, in each case based on the molding composition, 0.05 to 0.5 ~ by weight of a sterically hindered amine and 0.1 to 0.5 ~ by weight of copper phthalocyanine, and if appropriate other customary additives.
Surprisingly, the light-stabilizing action of sterically hindered amines is increased significantly by copper phthalocyanine. It is particularly remarkable that the copper compound by itself has no influence on ~he behavior of polyethylene in visible light or under W
radiation. It is furthermore to be emphasized that the physical properties of polyethylene are not Lmpaired by the additives.
The preparation of polyethylene having an average mole-cular weight, measured by viscometry, of at least 500,000 g/mol, preferably at least 1 x 106 g/mol to 1 x 107 g/mol, is known. It can be carried out by various processes. A proven process, which is carried out under low pressure using a mixed catalyst of titanium(III~
halides and organoaluminum compounds, is described in DE-B 23 61 508. Other processes, which are also carried out under low pressures, use, for example, chromium oxide catalysts.
~he molecular weights quantified above are understood as being the values measured by viscometry. A method for their measurement is described, for example, in CZ-Chemietechnik 4 (1974), page 129 et seq.
, . . .
.. . ~ . ' ,, .. , . , . ' 2 ~
The molding composi~ions according to the invention con~ain sterically hindered amine~ and copper phthalo-cyanine as additivesO
The term sterically hindered amines is understood as meaning compounds in which one or more space filling organic radicals are bonded to their trivalent nitrogen atom. ~hese are mainly aromatic and secondary amines.
Examples which may be men~ioned are N,N'-disubstituted p-phenylenediamines, such as N,N'-diisopropyl-p-phenyl-enediamine, N,N~-di-sec.-butyl-p phenylenediamine, diphenylamine derivatives, such as N-phenyl-l-naphthyl-amine, and aminophenol derivatives, such as 4-dodecanoyl-aminophenol. Bis~2,2,6,6-~etramethyl-4-piperidyl) seba cate has p~oved to be particularly suitable. The sterically hindered amines are used in a concentration of 0.05 to 0.5 % by weight, in particular 0.1 to 0.3 % by weight, based on the total weight oE khe molding composition.
Copper phthalocyanine, which is employed as an organic pigmenk, is obtained industrially from ph~halic acid dinitrile and copper(I) chloride. It is added in the commercially available form to the molding compositions according to the invention. Taking into consideration the material properties sought, the preparation and the ~5 processahility of the novel molding composition~, it is advisable for the concentration of the copper compound to be adjusted to values of 0.1 to 0.5 % by weight, prefer-ably 0.2 to 0.35 % by weight, in each case based on the total weight of the molding composition.
Apart from amines and copper phthalocyanine, the molding compositions according to the invention can also contain other customary additives, such as lubricants and proces-sing stabilizers.
The stabiliæed molding compositions are prepared by .
~ . ..
', ' ', homogeneous mixing of the starting materials in a mixer and, depending on the molecular weight, by melting at temperatures of 125 to 145C or b~ sintering at tempera-tures of 180 to 250~C, in particular 200 to 230C. The pressure during sintering is 3 to 5 MPa, in particular 3 to 4 MPa. Cooling after sintering is also carried out under pressure, with 5 to 10 MPa, preferably 8 to 10 MPa, having proved suitable. The sinteriny and coollng tLme largely depend on the ~hickness of the material.
The novel molding compositions can be worked mechanic-ally, for example drilledr milled and sawed, in the customary manner; they can be shaped by compression molding.
The invention is illustrated in more detail in the following example, but is not limited to this e~odLment.
Example The behavior of stabilized and non-stabilized poly-ethylene under the weathering conditions prevailing in Central Europe was investigated under natural conditions in the open on test specimens which were stored on a test stand at an angle of 45 in the south-westerly direction.
Samples were taken at fixed inter~als of time over a period of 5 years.
The test specimens used were square sheets of 150 mm side face and 1.5 mm thick (test sheets) obtained from pressed sheets by hot ski~ing. The pressed sheets were produced from pulverulent polyethylene having a molecular weight, measured by viscometry, of 500,000 g/mol, which was pressed by itself (sample 1) or after admixing of 0.15 ~
by weight (based on the mixture) of bis(2,2,6,6-tetra-methyl-4-piperidyl) sebacate (sample 2) or 0.15 % by weight of the sebacate and 0.3 % by weight of copper phthalocyanine (in each case based on the mixture -sample 3), to give sheets having the dimensions 800 mm x . , . . . - . , . . ' .
. . . . . .. .
. -:, ,. . : -, . .:,.: , ., : , . - .
.
P~ 2 400 mm x 30 mmr which were first sin~ered at 180C under a pressure of 3 MPa for 2 hours and then cooled under a pressure of 8 MPa for 1.5 hours.
The mechanical properties of density, tear strength and elongation at break from the stress-elongation diagram at 23 and 120C as well as wear and notched impact strength were de~ermined on the samples exposed in the open. The density and the strength properties were tested on test specimens stamped out of the 1.5 mm thick sheets, while the notched impact strength and wear samples were taken by machining from the 20 mm sheets, from the weathered side, in a sample thickness of 10 or 6.25 mm.
To evaluate the change in the pattern of properties under natural clLmatic conditions, the stress and elonga~ion properties of the test sheets at 23C were selected, and the time taken for the original values to fall to 50 %
was determined.
The elongation at break of sample 1 had already reached the value 0 after 3 months of external weathering and the material had become embrittled. By addition o a light stabilizer (sample 23, the strength properties had improved under the climatic conditions of Central Europe and the elongation at break fell to half the original value after 9 months. Light stabilizer in combination with copper phthalocyanine (sample 3) significantly increases the resistance of high molecular weight poly-ethylene to weathering influences. The elongation at break dropped to 50 % of its original value only af er 3.5 years.
- .
. .
Claims (5)
1.) A molding composition of polyethylene having an average molecular weight, measured by viscometry of at least 500,000 g/mol, preferably at least 1 x 106 g/mol, which contains, in each case based on the molding compo-sition, 0.05 to 0.5 % by weight of a sterically hindered amine and 0.1 to 0.5 % by weight of copper phthalo-cyanine, and if appropriate other customary additives.
2.) A molding composition as claimed in claim 1, wherein the concentration of the sterically hindered amine is 0.1 to 0.3 % by weight, based on the molding composition.
3.) A molding composition as claimed in claim 1 or 2, which contains, as the sterically hindered amine, a compound from the group comprising N,N'-disubstituted p-phenylenediamines, diphenylamine derivatives, aminophenol derivatives and in particular bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate.
4.) A molding composition according to one or more of claims 1 to 3, which contains copper phthalocyanine in a concentration of 0.2 to 0.35 % by weight.
5.) A process for the preparation of a molding composition as claimed in one or more of claims 1 to 4, which comprises mixing pulverulent polyethylene and additives and, depending on the molecular weight, either melting the mixture at temperatures of 125 to 145°C or sintering the mixture at temperatures of 180 to 250°C, in particular 200 to 230°C, under a pressure of 3 to 5 MPa, preferably 3 to 4 MPa, and after sintering cooling the mixture under a pressure of 5 to 10 MPa, preferably 8 to 10 MPa.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4030563A DE4030563A1 (en) | 1990-09-27 | 1990-09-27 | MOLDS BASED ON POLYETHYLENE WITH A MEDIUM MOLE WEIGHT OF AT LEAST 500,000 G / MOL |
| DEP4030563.5 | 1990-09-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2051902A1 true CA2051902A1 (en) | 1992-03-28 |
Family
ID=6415093
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002051902A Abandoned CA2051902A1 (en) | 1990-09-27 | 1991-09-19 | Molding compositions based on polyethylene having an average molecular weight of at least 500.000 g/mol |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP0477748B1 (en) |
| JP (1) | JPH0762095B2 (en) |
| AT (1) | ATE137518T1 (en) |
| AU (1) | AU640269B2 (en) |
| CA (1) | CA2051902A1 (en) |
| DE (2) | DE4030563A1 (en) |
| ES (1) | ES2089076T3 (en) |
| TW (1) | TW206977B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003037480A1 (en) * | 2001-10-29 | 2003-05-08 | Nittetsu Mining Co., Ltd. | Heat-resistant filter element and method for production thereof |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4030724B4 (en) * | 1990-09-28 | 2005-05-04 | Robert Bosch Gmbh | Anti-lock control system |
| US7271209B2 (en) | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
| US7652092B2 (en) | 2002-08-12 | 2010-01-26 | Exxonmobil Chemical Patents Inc. | Articles from plasticized thermoplastic polyolefin compositions |
| EP2083043B1 (en) | 2002-08-12 | 2017-01-18 | ExxonMobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7622523B2 (en) * | 2002-08-12 | 2009-11-24 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7652094B2 (en) | 2002-08-12 | 2010-01-26 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
| US7531594B2 (en) | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
| US8003725B2 (en) | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
| US7998579B2 (en) | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
| US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
| US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
| CN101218296B (en) | 2005-07-15 | 2010-12-08 | 埃克森美孚化学专利公司 | Elastomeric compositions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3708457A (en) * | 1971-02-16 | 1973-01-02 | Phillips Petroleum Co | Pigmented polyolefin compositions containing phthalocyanine compounds |
| JPS58113236A (en) * | 1981-12-28 | 1983-07-06 | Tounen Sekiyu Kagaku Kk | Polyolefin composition |
| JPS59147036A (en) * | 1983-02-09 | 1984-08-23 | Dainichi Nippon Cables Ltd | Crosslinked polyolefin composition for insulation |
| US4826898A (en) * | 1987-04-03 | 1989-05-02 | Dainippon Ink And Chemicals, Inc. | Colored polypropylene resin |
| US5049600A (en) * | 1990-01-23 | 1991-09-17 | The B. F. Goodrich Company | Multi-component stabilizer system for polyolefins pigmented with phthalocyanine pigments |
-
1990
- 1990-09-27 DE DE4030563A patent/DE4030563A1/en not_active Withdrawn
-
1991
- 1991-09-18 DE DE59107755T patent/DE59107755D1/en not_active Expired - Fee Related
- 1991-09-18 ES ES91115813T patent/ES2089076T3/en not_active Expired - Lifetime
- 1991-09-18 AT AT91115813T patent/ATE137518T1/en not_active IP Right Cessation
- 1991-09-18 EP EP91115813A patent/EP0477748B1/en not_active Expired - Lifetime
- 1991-09-19 TW TW080107418A patent/TW206977B/zh active
- 1991-09-19 CA CA002051902A patent/CA2051902A1/en not_active Abandoned
- 1991-09-20 JP JP3241835A patent/JPH0762095B2/en not_active Expired - Lifetime
- 1991-09-26 AU AU84754/91A patent/AU640269B2/en not_active Ceased
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003037480A1 (en) * | 2001-10-29 | 2003-05-08 | Nittetsu Mining Co., Ltd. | Heat-resistant filter element and method for production thereof |
| US7399522B2 (en) | 2001-10-29 | 2008-07-15 | Nittetsu Mining Co., Ltd. | Heat-resistant filter element and method for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU640269B2 (en) | 1993-08-19 |
| AU8475491A (en) | 1992-04-02 |
| EP0477748A3 (en) | 1992-09-16 |
| ATE137518T1 (en) | 1996-05-15 |
| TW206977B (en) | 1993-06-01 |
| ES2089076T3 (en) | 1996-10-01 |
| JPH04246445A (en) | 1992-09-02 |
| EP0477748B1 (en) | 1996-05-01 |
| DE4030563A1 (en) | 1992-04-02 |
| DE59107755D1 (en) | 1996-06-05 |
| EP0477748A2 (en) | 1992-04-01 |
| JPH0762095B2 (en) | 1995-07-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |