EP1511797A2 - Highly active beta-nucleating additive for polypropylene - Google Patents
Highly active beta-nucleating additive for polypropyleneInfo
- Publication number
- EP1511797A2 EP1511797A2 EP03732345A EP03732345A EP1511797A2 EP 1511797 A2 EP1511797 A2 EP 1511797A2 EP 03732345 A EP03732345 A EP 03732345A EP 03732345 A EP03732345 A EP 03732345A EP 1511797 A2 EP1511797 A2 EP 1511797A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- polypropylene
- iron oxide
- melt
- crystalline
- temperature
- 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.)
- Ceased
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/201—Pre-melted polymers
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2268—Ferrous oxide (FeO)
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2272—Ferric oxide (Fe2O3)
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Definitions
- the invention relates to a method for increasing the proportion of the ⁇ -crystal modification in polypropylene.
- the ⁇ , ⁇ , and ⁇ phases are known from polypropylene.
- the ⁇ -crystalline PP When polypropylene melts cool down, the ⁇ -crystalline PP usually forms predominantly. A certain amount of ⁇ -crystalline phase can be generated by a certain temperature control when cooling a polypropylene melt. The proportion of ⁇ -crystalline PP produced in this way is less than 10%.
- the hexagonal ⁇ -modification of the PP is distinguished from the monoclinic ⁇ -modification by better mechanical properties, in particular increased impact resistance and stress crack resistance.
- the ⁇ -modification of polypropylene at 148-150 ° C has a significantly lower melting point compared to the ⁇ -modification with a melting point of 160 ° C.
- ß-crystalline PP therefore has a favorable effect on certain usage properties of polypropylene in some applications.
- some additives have been developed in the past which lead to even higher proportions of polypropylene in the ⁇ modification and are therefore generally referred to as ⁇ nucleators or ⁇ nucleating agents.
- the ⁇ -quinacridone dye is described in German patent 1188278 as a ⁇ -nucleator with high activity.
- the dye dihydroquinacridine is patented in German patent 344359 due to its ⁇ -nucleating effect.
- the disadvantage of this nucleating agent is the intense red color and the lack of thermal stability, which often leads to decomposition of the nucleating agent and thus to a loss of its activity when compounding.
- US Patent 3540979 the calcium salt of phthalic acid is considered to be thermally stable Nucleating agents described.
- the disadvantage of this nucleating agent is the low activity.
- the percentage of ß-crystalline PP thus obtained is at most 70% (K-0.5-0.7).
- DE 3610644 describes a two-component nucleation system consisting of calcium carbonate and organic dicarboxylic acids. In practice, however, this nucleation system shows a fluctuating activity. Therefore, there is a lack of reproducibility.
- the direct use of the calcium salts of the dicarboxylic acids described in DE 3610644 is described in patent DE 4420989.
- EP-0557721 describes the ⁇ -nucleating effect of various dicarboxamides, in particular N, N-dicyclohexyl-2,6-naphthalene dicarboxamides. Disadvantages of this nucleator are the high cost of the starting material and complicated synthetic steps in the production.
- the object of the present invention was to provide a process for producing ⁇ -crystalline polypropylene. This process is said to be able to reproducibly and reliably achieve high proportions of ⁇ . The process should be simple and efficient to carry out. Modification with a ß-nucleating agent must not impair the usual important properties of use of polypropylene.
- This object is achieved by processes for producing a polypropylene mixture with an increased proportion of ⁇ -crystalline polypropylene, in which a polypropylene mixture of nanoscale iron oxide and polypropylene is melted at a temperature of at least 150 ° C. and then cooled in such a way that the cooled polypropylene melt has an increased proportion of ß-crystalline polypropylene.
- the present invention is based on the discovery that nanoscale iron oxides cool down a PP melt containing these iron oxides to form a lead to a high proportion of ß-crystalline polypropylene.
- the cooled melt with a high proportion of ß forms a transparent PP matrix, since the particle size of the nanoscale iron oxides is significantly smaller than the wavelength of visible light.
- Nanoscale iron oxides generally have an average particle size of 1 to 50 nm.
- iron (II) and iron (III) oxides are particularly suitable as ⁇ -nucleating iron oxides.
- those iron oxides with a cubically densest spherical packing are particularly suitable, in which the O 2 " ions form a cubic lattice in which the Fe 3+ ions are randomly distributed over the octahedral and tetrahedral gaps (Fe 2 0 3 ) or in the case of mixed oxides (Fe 3 0 4 ) which occupy Fe 2+ the octahedral gaps and Fe 3+ the tetrahedral gaps
- nanoscale magnetite and nanoscale maghemite have proven to be particularly effective ß-nucleating agents in polypropylene.
- the iron oxide powders can be added by adding surface-active substances, e.g. can be hydrophobized with higher-quality carboxylic acids, silanes, amines or sulfonates.
- surface-active substances e.g. can be hydrophobized with higher-quality carboxylic acids, silanes, amines or sulfonates.
- Such methods are known per se in the prior art, for example in Macromol. Mater. Closely. 275, 8-17 (2000) and in GAK 5/1988 volume 41, page 211 ff or Macromol. Rapid Commun, 2001, 22, 176-180.
- Particularly preferred coatings of the nanoscale iron oxides consist of long-chain fatty acids, such as oleic acid or stearic acid.
- nanocrystalline iron oxides can be carried out using conventional methods known per se, such as, for example, the sol-gel process, flame pyrolysis, EDOC or precipitation reactions. According to these processes, nanoscale iron oxides with a particle size in the range from 1 to 50 nm, preferably 5 to 30nm, in particular 10 to 20nm can be produced. Precipitation from brines containing Fe 2+ and / or Fe 3+ ions by addition of alkali is particularly suitable (Nouveau Journal De Chimie, Vol. 7, N ° 5-1983, p. 325).
- the nanocrystalline iron oxides can optionally be subjected to a hydrothermal after-treatment step in order to increase the crystallinity by keeping the freshly precipitated nanoscale iron oxides for a certain time at elevated pressure and elevated temperature.
- nanoscale iron oxides described above are incorporated into the polypropylene matrix using customary methods.
- mechanical premixes are produced from propylene granules and the nanoscale iron powder and then compounded in a twin-screw extruder.
- Such methods for compounding nanoscale additives are, for example, in Macromol. Rapid Commun, 2001, 22, 176-180. These methods are also suitable for the production of compounds for the present invention.
- the mixture of polypropylene and nanoscale iron oxide generally contains at least 85% by weight, preferably 90 to ⁇ 100% by weight, in particular 98 to ⁇ 100% by weight, of a polypropylene.
- the propylene polymer contains at least 90% by weight, preferably 94 to 100% by weight, in particular 98 to 100% by weight, of propylene.
- the corresponding comonomer content of at most 10% by weight or 0 to 6% by weight or 0 to 2% by weight, if present, generally consists of ethylene and / or butylene. The percentages by weight relate to the propylene polymer.
- Suitable copolymers which contain ethylene and / or butylene as comonomer are statistical copolymers or block copolymers.
- Isotactic propylene homopolymers having a melting point of 140 to 170 ° C., preferably 155 to 165 ° C., and a melt flow index (measurement DIN 53735 at 21.6 N load and 230 ° C.) of 1.0 to 50 g / 10 min are preferred , preferably from 1.5 to 20 g / 10 min.
- the n-heptane-soluble fraction of the polymer is generally 1 to 10% by weight, preferably 2-5% by weight, based on the starting polymer.
- the molecular weight distribution of the propylene polymer can vary.
- the ratio of the weight average M w to the number average M n is generally from 1 to 15, preferably from 2 to 10, very particularly preferably from 2 to 6.
- Such a narrow molecular weight distribution of the propylene homopolymer is achieved, for example, by its peroxidic degradation or by the preparation of the polypropylene using suitable metallocene catalysts.
- the polypropylene used in the base layer is highly isotactic.
- the chain isotaxy index of the n-heptane-insoluble portion of the polypropylene determined by means of 13 C-NMR spectroscopy, is at least 95%, preferably 96 to 99%.
- a mixture of polypropylene and nanoscale iron oxide is first melted at suitable temperatures. This temperature is generally in the range of 150 to 165 ° C.
- the melting is preferably carried out in a suitable extruder, for example in a twin-screw extruder, which at the same time ensures good mixing of the nanoscale iron oxide in the polypropylene.
- the melted mixture is extruded and cooled at suitable temperatures.
- the mixture is produced in other process variants or the compound as described above in a preceding step. These compounds are then used together with pure polypropylene in the process according to the invention.
- the compounds can be melted in any extrusion tool or in a kneader and mixed with polypropylene. It is essential to the invention that after the extrusion the iron oxide-containing melt is cooled in such a way that the ⁇ -nucleating effect of the nanoscale iron oxides comes into play. For this purpose, it is preferred to cool the melt slowly at a temperature in a range from 60 to 130 ° C., preferably at 80 to 125 ° C. The closer this temperature is to the crystallization temperature of the ß-crystalline polypropylene (approx. 139 ° C), the more favorable the conditions for the formation of the ß-crystalline modification.
- ⁇ -polypropylene can be generated by the selection of the temperature during cooling.
- the dwell time of the cooling melt at the respective temperature has an influence on the ß fraction achieved.
- the melt should be slowly cooled at higher temperatures (120-130 ° C), the necessary dwell time at the given temperature depending on the shape during extrusion.
- ß-nucleating iron oxides have a positive effect in these cases, since the cooling rate can be increased, i.e. faster take-off speeds can be used.
- DSC method DSC measurements (method described below) of isotactic polypropylene with 1% by weight of nanoscale iron oxide accounted for ß-crystalline polypropylene of 92%.
- the method according to the invention can advantageously be used in the production of films, moldings, in particular tubes and hoses, fibers and other extrusions.
- the increased ⁇ -content in polypropylene has a favorable effect in a wide variety of extrusion applications, for example because the extrusion temperatures can be reduced.
- an increased proportion of ß-crystalline polypropylene is advantageous since this improves the properties of the polypropylene, e.g. one achieves a higher notched impact strength and stress crack resistance of the polypropylene.
- the high proportion of ⁇ in polypropylene is used for the production of porous films by converting the ⁇ -modification into the alpha modification when stretching films or for producing rough surfaces of a stretched film.
- nanoscale iron oxide and polypropylene are mixed and melted in an extruder at a temperature of at least 150 ° C.
- the melt is extruded through a flat die and cooled and solidified into a pre-film in such a way that the desired proportion of ⁇ -crystalline polypropylene is formed in the pre-film.
- a proportion of at least 40%, preferably 60 to 80%, of ⁇ -polypropylene (measured according to DSC) in the prefilm is generally sought, whereas smaller proportions of, for example, 10 to 40% are sufficient to produce surface roughness could be.
- the pre-film is then heated in a manner known per se and stretched in the longitudinal direction, preferably at a temperature less than 140 ° C., preferably 90 to 125 ° C. and with a stretch factor of 3: 1 to 5: 1.
- the longitudinally stretched film is heated again and stretched in the transverse direction, preferably at a temperature greater than 140 ° C. from 145 to 160 ° C. and with a Stretch ratio from 3: 1 to 6: 1.
- the selected temperature during stretching converts the ß-crystalline polypropylene of the pre-film into the alpha modification of the polypropylene and, depending on the process conditions, creates a continuous porous network structure in the film or at least a surface roughness due to crater-like depressions that arise during the conversion processes.
- Two methods can be used to determine the ⁇ -crystalline content in polypropylene which can be achieved by means of the method according to the invention.
- the ß component can be determined by means of DSC and on the other hand by means of wide-angle X-ray scattering.
- Heating rate from 20 ° C / min to 220 ° C and melted (1st heating).
- Heating is determined from the ratio of the enthalpies of fusion of the ß-crystalline phase (H ß ) to the sum of the enthalpies of fusion of ß- and ⁇ -crystalline phases (H ß + H ⁇ ) the degree of crystallinity K ß , D sc.
- Kß, X- ay [kßi] / [k ß1 ] / [k ß ⁇ + (k ⁇ ⁇ + k ⁇ 2 + k chair3)]
- K ß , ⁇ - Ra y is the ß component, ß ⁇ the height of the peak of the ß phase and k administrat ⁇ , k ⁇ , k ⁇ the height of the three peaks of the ⁇ phase.
- X-ray wide-angle scattering always has a higher ⁇ component than found using the DSC method.
- a nanocrystalline iron oxide (Fe304) was compounded into an isotactic polypropylene in a ZSK 30 twin-screw extruder at a temperature of 200 ° C.
- the polypropylene was an isotactic homopolymer with a melting point of 162 ° C and an MFI of ... (Exxon Escorene PP 4352 F1).
- the nanocrystalline iron oxide had an average particle size of 13 nm. It was magnetite, which had a characteristic black color. An amount of 3% by weight of the iron oxide was incorporated into the polypropylene.
- Example 2 A nanocomposite was produced as described in Example 1. In contrast to Example 1, the nanoscale iron oxide was surface-modified before compounding with stearic acid and the concentration of magnetite was reduced from 3 to 1% by weight.
- a nanocomposite was produced as described in Example 2.
- the nanoscale iron oxide was subjected to a hydrothermal after-treatment before the surface modification with stearic acid and the concentration was increased from 1 to 2% by weight.
- the respective ⁇ -proportion of the nanocomposites according to Examples 1 to 3 was determined as described using DSC from the 2nd heating curve.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10221310 | 2002-05-14 | ||
DE10221310A DE10221310A1 (en) | 2002-05-14 | 2002-05-14 | Highly active beta nucleation additive for polypropylene |
PCT/EP2003/004931 WO2003094832A2 (en) | 2002-05-14 | 2003-05-12 | HIGHLY ACTIVE β-NUCLEATING ADDITIVE FOR POLYPROPYLENE |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1511797A2 true EP1511797A2 (en) | 2005-03-09 |
Family
ID=29413782
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP03732345A Ceased EP1511797A2 (en) | 2002-05-14 | 2003-05-12 | Highly active beta-nucleating additive for polypropylene |
Country Status (7)
Country | Link |
---|---|
US (1) | US6992128B2 (en) |
EP (1) | EP1511797A2 (en) |
JP (1) | JP4332110B2 (en) |
CN (1) | CN1274745C (en) |
AU (1) | AU2003240222A1 (en) |
DE (1) | DE10221310A1 (en) |
WO (1) | WO2003094832A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011076805A1 (en) | 2009-12-21 | 2011-06-30 | Bollore | Separator film, its fabrication process, super capacitor, battery and capacitor that are provided with said film. |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE60234320D1 (en) * | 2001-02-21 | 2009-12-24 | New Japan Chem Co Ltd | SUCCESSIONALLY BIAXIALLY ORIENTED, POROUS POLYPROPYLENE FOIL AND METHOD OF PREPARING THEREOF |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
CN101724110B (en) | 2002-10-15 | 2013-03-27 | 埃克森美孚化学专利公司 | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
DE102004035407A1 (en) * | 2004-05-18 | 2005-12-15 | Bänninger Kunststoff-Produkte GmbH | Molded plastic for the production of pipelines |
MX2007003819A (en) * | 2004-10-07 | 2007-06-05 | Treofan Germany Gmbh & Co Kg | Label film for deep drawing methods. |
DE602006005049D1 (en) * | 2006-08-01 | 2009-03-19 | Borealis Tech Oy | Process for producing impact-resistant pipes |
DE602007003584D1 (en) * | 2007-07-12 | 2010-01-14 | Borealis Tech Oy | β-nucleated polypropylene composition |
DE102007050047A1 (en) * | 2007-10-17 | 2009-04-23 | Helsa-Automotive Gmbh & Co. Kg | Automotive cabin air filter is a porous polymer fleece, fibre layup or woven fibre incorporating a Beta-crystalline structure |
DE102010018374A1 (en) * | 2010-04-26 | 2011-10-27 | Treofan Germany Gmbh & Co. Kg | Highly porous separator film |
CN101900472A (en) * | 2010-08-18 | 2010-12-01 | 洛阳市河之阳高分子材料有限公司 | Material for refrigerator top cover |
US8101680B1 (en) * | 2010-10-12 | 2012-01-24 | Sabic Innovative Plastics Ip B.V. | Methods of preparing polymer nanocomposites |
DE102011120474A1 (en) * | 2011-12-08 | 2013-06-13 | Treofan Germany Gmbh & Co. Kg | Highly porous separator film with coating |
EP2657286B1 (en) * | 2012-04-25 | 2014-05-14 | Borealis AG | Process for preparing polypropylene with high content of beta modification |
EP2657285B1 (en) * | 2012-04-25 | 2015-07-22 | Borealis AG | moulded polypropylene with high content of beta form |
WO2014113854A1 (en) * | 2013-01-23 | 2014-07-31 | Vale S.A. | Composite material comprising uhmwpe and iron ore tailing and use of iron ore tailing in preparation of composite material |
WO2016003647A1 (en) * | 2014-06-19 | 2016-01-07 | Corning Optical Communications LLC | Loose-tube fiber optic cables having buffer tubes with beta phase crystallization |
WO2019117055A1 (en) * | 2017-12-15 | 2019-06-20 | 住友電気工業株式会社 | Resin composition for insulating material, insulating material, insulated electric wire, and cable |
CN112768235B (en) * | 2020-12-23 | 2022-05-17 | 天津大学 | Method for optimizing crystallization morphology of polypropylene film for capacitor |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE344359C (en) | 1900-01-01 | |||
US3540979A (en) * | 1966-07-11 | 1970-11-17 | Phillips Petroleum Co | Laminates of similarly constituted films of different crystal structure |
BE755966A (en) | 1969-09-11 | 1971-03-10 | Montedison Spa | PROCESS FOR PREPARING PIGMENTED POLYOLEFINIC FIBERS |
US3997494A (en) | 1972-07-19 | 1976-12-14 | General Electric Company | Compounded thermoplastic polymeric materials and fillers |
CN1004076B (en) * | 1985-04-01 | 1989-05-03 | 中国科学院上海有机化学研究所 | Process for preparation of beta-crystalline polypropylene |
JPS62283822A (en) * | 1986-05-31 | 1987-12-09 | Toda Kogyo Corp | Production of fine beta-ferric oxide hydrate particles |
US6235823B1 (en) * | 1992-01-24 | 2001-05-22 | New Japan Chemical Co., Ltd. | Crystalline polypropylene resin composition and amide compounds |
DE4420989B4 (en) | 1994-06-16 | 2005-04-14 | Borealis Polymere Holding Ag | Process for increasing the proportion of β-modification in polypropylene |
EP0790262B1 (en) * | 1995-08-31 | 2000-05-10 | Chisso Corporation | Propylene-ethylene copolymer compositions and process for the production thereof |
-
2002
- 2002-05-14 DE DE10221310A patent/DE10221310A1/en not_active Ceased
-
2003
- 2003-05-12 US US10/511,913 patent/US6992128B2/en not_active Expired - Fee Related
- 2003-05-12 EP EP03732345A patent/EP1511797A2/en not_active Ceased
- 2003-05-12 CN CNB038107732A patent/CN1274745C/en not_active Expired - Fee Related
- 2003-05-12 WO PCT/EP2003/004931 patent/WO2003094832A2/en active Application Filing
- 2003-05-12 AU AU2003240222A patent/AU2003240222A1/en not_active Abandoned
- 2003-05-12 JP JP2004502921A patent/JP4332110B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
---|
See references of WO03094832A2 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011076805A1 (en) | 2009-12-21 | 2011-06-30 | Bollore | Separator film, its fabrication process, super capacitor, battery and capacitor that are provided with said film. |
Also Published As
Publication number | Publication date |
---|---|
CN1653122A (en) | 2005-08-10 |
WO2003094832A3 (en) | 2004-07-22 |
US20050182175A1 (en) | 2005-08-18 |
CN1274745C (en) | 2006-09-13 |
WO2003094832A2 (en) | 2003-11-20 |
US6992128B2 (en) | 2006-01-31 |
DE10221310A1 (en) | 2003-12-11 |
JP4332110B2 (en) | 2009-09-16 |
AU2003240222A8 (en) | 2003-11-11 |
AU2003240222A1 (en) | 2003-11-11 |
JP2005525444A (en) | 2005-08-25 |
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