Chromatography of polyolefin polymers
Abstract
A method for chromatography of a polyolefin polymer, comprising the step of: introducing a solution of the polyolefin polymer in a liquid that flows through a stationary phase of liquid chromatography, the stationary phase of graphite carbon liquid chromatography comprising, leaving the polyolefin polymer of the stationary phase of liquid chromatography with a retention factor greater than zero.
Term
3 yearsto projected expiry
Projected expiry 1 October 2029, counted from filing; an application has no term until it is granted.
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15 claims: 8 independent, 7 dependent
- 1ES 2 478 286 T3 REIVINDICACIONES 1. Un método para la cromatografía de un polímero poliolefínico, que comprende la etapa de:introducir una disolución del polímero poliolefínico en un líquido que fluye a través de una fase estacionaria de cromatografía de líquidos, comprendiendo la fase estacionaria de cromatografía de líquidos carbono grafítico, saliendo el polímero poliolefínico de la fase estacionaria de cromatografía de líquidos con un factor de retención mayor que cero.
- 2El método de la reivindicación 1, donde el polímero poliolefínico es un copolímero que consiste esencialmente en etileno y una alfa-olefina.
- 3El método de la reivindicación 2, donde la alfa-olefina consiste esencialmente en 1-octeno.
- 4El método de la reivindicación 1, donde el polímero poliolefínico es un copolímero que consiste esencialmente en propileno y una alfa-olefina.
- 5El método de la reivindicación 4, donde la alfa-olefina consiste esencialmente en etileno.
- 6El método de cualquiera de las reivindicaciones 1, 2, 3, 4 ó 5, donde la concentración del polímero poliolefínico en la disolución de polímero poliolefínico es mayor que 0,1 mg por ml de disolución.
- 7El método de cualquiera de las reivindicaciones 1, 2, 3, 4 ó 5, donde la fase estacionaria de cromatografía de líquidos consiste esencialmente en carbono grafítico.
- 8El método de una cualquiera de las reivindicaciones 1, 2, 3, 4, 5, 6 ó 7, en donde el carbono grafítico está empaquetado en una columna de cromatografía.
- 9Un método para determinar la relación de monómero a comonómero de un copolímero que consiste esencialmente en etileno y un comonómero de alfa-olefina, que comprende las etapas de:(a) hacer fluir una fase móvil líquida en contacto con una fase estacionaria de cromatografía de líquidos que comprende carbono grafítico, para producir una corriente de efluente de fase móvil líquida de la fase estacionaria;(b) introducir una disolución del copolímero en la fase móvil líquida de modo que el copolímero sale en la corriente de efluente con un factor de retención que varía como una función matemática de la relación de monómero a comonómero del copolímero.
- 10El método de la reivindicación 9, donde la alfa-olefina consiste esencialmente en 1-octeno.
- 11Un método para determinar la relación de monómero a comonómero de un copolímero que consiste esencialmente en propileno y un comonómero de alfa-olefina, que comprende las etapas de:(a) hacer fluir una fase móvil líquida en contacto con una fase estacionaria de cromatografía de líquidos que comprende carbono grafítico, para producir una corriente de efluente de fase móvil líquida de la fase estacionaria;(b) introducir una disolución del copolímero en la fase móvil líquida de modo que el copolímero sale en la corriente de efluente con un factor de retención que varía como una función matemática de la relación de monómero a comonómero del copolímero.
- 12El método de la reivindicación 11, donde la alfa-olefina consiste esencialmente en etileno.
- 13El método de cualquiera de las reivindicaciones 6, 7, 9, 10, 11 ó 12, donde la concentración del polímero poliolefínico en la disolución de polímero poliolefínico es mayor que 0,1 mg por ml de disolución.
- 14El método de cualquiera de las reivindicaciones 6, 7, 9, 10, 11 ó 12, donde la fase estacionaria de cromatografía de líquidos consiste esencialmente en carbono grafítico.
- 15El método de la reivindicación 8, donde se añade un fraccionamiento adicional por cromatografía de exclusión por tamaños o fraccionamiento en flujo con campo de flujo asimétrico después de la cromatografía del polímero poliolefínico por una columna grafítica.
Independent claims15
47 paragraphs in 9 sections, as filed
ES 2 478 286 T3
DESCRIPTION
Chromatography of polyolefin polymers
Background of the invention
The invention described is in the field of liquid chromatography. Liquid chromatography is used in the art to analyze polymers for molecular size by size exclusion chromatography (SEC) and for chemical composition by high performance liquid chromatography (HPLC). This description refers to HPLC analysis of polymers in relation to chemical composition.
Polyolefinic polymers (such as polymers and copolymers comprising polymerized ethylene monomer and / or propylene monomer) have long been analyzed for their chemical composition distribution by temperature increase elution fractionation (TREF) and fractionation analytical by crystallization (CRYSTAF). However, neither TREF nor CRYSTAF can be used to analyze amorphous polyolefin polymers. Furthermore, both TREF and CRYSTAF require a relatively long analysis time. Therefore, the art has turned to HPLC in an attempt to reduce analysis time and extend the scope of analysis to amorphous polymers. It appears that Macko et al. They were the first to do so in 2003 studying the retention of polyethylene standards in stationary phases of silica and zeolite (J. Chrom. A, 1002 (2003) 55). Wang, et al. studied the retention of polyethylene and polypropylene by zeolites in 2005 (Macromolecules, V. 38, No. 25 (2005) 10341). Heinz and Pasch used a stationary phase of silica to analyze mixtures of polyethylene and polypropylene by HPLC (Polymer 46 (2005) 12040). Albrecht, et al., Used a silica stationary phase to analyze ethylene-vinyl acetate copolymers by HPLC (Macromolecules 2007, 40, 5545). Albrecht, et al., Used a silica stationary phase to analyze ethylene-propylene copolymers by HPLC (Macromol. Symp. 2007, 257, 46). A remaining problem for HPLC analysis of polyolefin polymers is the limited separation efficiency obtained by prior art methods.
Summary of the Invention
A primary benefit of this disclosure is that an HPLC method is provided that has improved separation efficiency for the analysis of a polyolefin polymer. More specifically, in one embodiment, this disclosure is a method for the chromatography of a polyolefin polymer, comprising the step of: introducing a solution of the polyolefin polymer in a liquid mobile phase that flows through a liquid chromatography stationary phase, the liquid chromatography stationary phase comprising graphitic carbon, the polyolefin polymer exiting the liquid chromatography stationary phase with a factor retention greater than zero.
In another embodiment, this disclosure is a method for determining the monomer to comonomer ratio of a copolymer consisting essentially of ethylene and an alpha-olefin comonomer, comprising the steps of:
(a) flowing a liquid mobile phase in contact with a liquid chromatography stationary phase comprising graphitic carbon, to produce a liquid mobile phase effluent stream from the stationary phase;
(b) introducing a solution of the copolymer into the liquid mobile phase so that the copolymer exits into the effluent stream with a retention factor that varies as a mathematical function of the monomer to comonomer ratio of the copolymer.
In another embodiment, this disclosure is a method for determining the monomer to comonomer ratio of a copolymer consisting essentially of propylene and an alpha-olefin comonomer, comprising the steps of: (a) flowing a liquid mobile phase in contact with a liquid chromatography stationary phase comprising graphitic carbon, to produce a liquid mobile phase effluent stream from the stationary phase; (b) introducing a solution of the copolymer into the liquid mobile phase so that the copolymer exits into the effluent stream with a retention factor that varies as a mathematical function of the monomer to comonomer ratio of the copolymer.
Brief description of the drawings
Figure 1 is a theoretical HPLC chromatogram depicting the elution of a retained component;
Figure 2 shows a typical HPLC system;
Figure 3 is an overlay of chromatograms of polymers of 1-octene, ethylene and copolymers of different ratios of 1-octene and ethylene using a described graphitic carbon stationary phase;
Figure 4 is an overlay of chromatograms of polymers of propylene, ethylene and copolymers of different ratios of propylene and ethylene using a described graphitic carbon stationary phase;
Figure 5 is an overlay of chromatograms of polymers of 1-octene, ethylene and copolymers of different ratios of 1-octene and ethylene using a described graphitic carbon stationary phase;
Figure 6 is an overlay of 3 polypropylenes with different tacticities.
ES 2 478 286 T3
Figure 7 is an overlay of chromatograms of polymers of 1-octene, ethylene, and copolymers of different ratios of 1-octene and ethylene using a prior art silica stationary phase;
Figure 8 is an overlay of chromatograms of polymers of propylene, ethylene, and copolymers of different ratios of propylene and ethylene using a prior art silica stationary phase; Y
Figure 9 is a calibration curve related to the chromatograms shown in Figure 3.
Detailed description
The theoretical HPLC chromatogram shown in Figure 1 represents the elution of COMPONENT A with maximum elution volume in Vr. An unretained low molecular weight component eluting from the stationary phase would elute at V0. The retention factor (k) for COMPONENT A is (Vr-V0) -V0.
Figure 2 shows a typical prior art HPLC system 10 including an eluent reservoir 11 loaded with a liquid mobile phase 12, or when using a gradient system, multiple reservoirs would be required. The liquid mobile phase 12 is pumped by the pump 13 through the injection valve 14 to the chromatography column 19. The chromatography column 19 is loaded with the liquid chromatography stationary phase 20 comprised in a granular packing. Liquid mobile phase 12 flows through liquid chromatography stationary phase 20, through detector 21 and into used eluent reservoir 22 as used liquid mobile phase 23. Syringe 15 contains a solution of a sample to be analyzed, and is dispensed through sample volume loop 16 to valve 14 at its sample loading position in excess sample reservoir 17 as excess sample 18. When the injection valve 14 is set to its sample injection position, the liquid mobile phase 12 is flowed through the sample volume loop 16 to flow the injected sample into the chromatography column 19. If a component of the injected sample is retained by stationary phase 20 so that the component flows through chromatography column 19 at a slower rate than mobile phase 12, then the component will exit chromatography column 19 with a retention factor greater than zero to be detected by detector 21. A general purpose digital computer 24 is in electrical communication with detector 21 and is programmed to manipulate the signal from detector 21 to provide, for example, a chromatogram of the injected sample.
This description is a method for the chromatography of a polyolefin polymer, comprising the step of: introducing a solution of the polyolefin polymer in a liquid that flows through a stationary phase of liquid chromatography, the stationary phase of liquid chromatography comprising carbon graphitic, the polyolefin polymer exiting the stationary phase of liquid chromatography with a retention factor greater than zero. The improvement of this description focuses on the use of a liquid chromatography stationary phase comprising graphitic carbon.
This disclosure is also a method for determining the monomer to comonomer ratio of a copolymer consisting essentially of ethylene or propylene and an alpha-olefin comonomer, comprising the steps of:
(a) flowing a liquid mobile phase in contact with a liquid chromatography stationary phase comprising graphitic carbon, to produce a liquid mobile phase effluent stream from the stationary phase;
(b) introducing a solution of the copolymer into the liquid mobile phase so that the copolymer exits into the effluent stream with a retention factor that varies as a mathematical function of the monomer to comonomer ratio of the copolymer.
The term polyolefin polymer in this description is defined as all polymers and copolymers (including high pressure low density polyethylene (LDPE), heterogeneous polymers, random, block and graft polymers, interpolymers and copolymers) that comprise one or more monomers polymerizates selected from the group consisting of ethylene, an alpha-olefin having 3-20 carbon atoms (such as 1-propylene, 1-butene, 1-hexene, 1-heptene, and 1-octene), 4-methyl-1-pentene, and / or unsaturated acetylenic monomers having 2-20 carbons, and / or diolefins having 4-18 carbons and any other monomer used in the art to modify the density of a polymer. Heterogeneous polymers include Ziegler-Natta polymerized polymers such as LLDPE and hDpE and include products such as DOWLEX ™ made by The Dow Chemical Company. Random copolymers include those polymerized using metallocene or constrained geometry catalyst technology and include polymers such as AFFINITY ™ and ENGAGE ™, both available from The Dow Chemical Company, and EXACT ™, available from Exxon-Mobil. Methods for polymerizing these random copolymers are well known in the art and include those described in USP 5,272,236 and 5,278,272. Block copolymers include those polymerized using chain transfer technology and two catalyst species, as described in USP 7,355,089, and include polymers such as INFUSE ™ olefinic block copolymers manufactured by The Dow Chemical Company. Furthermore, the term polyolefin polymer in this description is defined as a polymer having an average molecular weight, determined by light scattering, greater than 1,000 grams per mole (preferably greater than 2,000 grams per mole and more preferably greater than 4,000 grams per mole. ). The polyolefin polymer can be a copolymer consisting essentially of polymerized ethylene monomer and a polymerized alpha-olefin monomer such as 1-octene. The polyolefin polymer can be a copolymer consisting essentially of polymerized propylene monomer and a polymerized alpha-olefin monomer such as ethylene. Such polymers based on propylene
ES 2 478 286 T3 include polypropylene homopolymer, propylene-based impact copolymers and propylene-based random copolymers. Other more specialized polymers also benefit from the method and apparatus described herein and include ethylene / acrylic acid copolymer, ethylene / vinyl acetate copolymers and ethylene / styrene interpolymers, halogenated polymers, and polymers containing maleic anhydride moieties.
In most applications, the temperature of the polyolefin polymer solution, the temperature of the liquid chromatography stationary phase, and the detector temperature will be controlled at an elevated temperature to increase the solubility of the polyolefin polymer, e.g. g., to make the polyolefin polymer soluble. The concentration of the polyolefin polymer in the polyolefin polymer solution is preferably greater than 0.1 mg per ml of solution, especially greater than 2 mg / ml. The solvent used for the dissolution of the polyolefin polymer is preferably decanol when the polyolefin polymer is polyethylene or polypropylene. Any suitable liquid mobile phase can be used in the method of this disclosure. A gradient composition mobile phase is preferred in the method of this disclosure. The temperature of the liquid chromatography stationary phase can be increased during the method of this disclosure. A mobile phase that does not contain aliphatic hydrogens (such as 1,2,4-trichlorobenzene) facilitates the use of an infrared detector for the method of this disclosure.
Any liquid chromatography stationary phase comprising graphitic carbon can be used in the method of this disclosure. The term graphitic carbon in this description is defined as all varieties of materials that comprise the element carbon in the allotropic form of graphite regardless of the presence of structural defects if the long-range hexagonal three-dimensional crystalline order of graphite can be detected in the material. by diffraction methods (such as X-ray diffraction spectroscopy) independent of the volume fraction and homogeneity of the distribution of said crystalline domains. Carbon nanotubes and carbon buckyballs are examples of forms of graphitic carbon useful in the method of this disclosure. Preferably, the liquid chromatography stationary phase consists essentially of graphitic carbon, especially porous graphitic carbon. Graphitic carbon is normally packed in columns and comprises flat sheets of carbon atoms in hexagonal arrangement at the molecular level. The graphitic carbon conveniently has a particle size of 1 to 10 pm (microns), preferably a mean particle size of 3 pm (microns), or 5 pm (microns) or 7 pm (microns), and preferably has a mean pore size of 20nm (200) to 30nm (300 Angstroms), more preferably a mean pore size of about 25nm (250 Angstroms). The inner surface of graphitic carbon has a specific surface area of 100 to 140 m<sup>2</sup>/ g, preferably about 120 µm<sup>2</sup>/ g. The length of the columns is typically 30mm to 100mm and can have a diameter of 2mm to 5mm. An example of a commercially available liquid chromatography stationary phase consisting essentially of graphitic carbon is believed to include the HYPERCARB brand HPLC column from Thermo Scientific, Waltham MA. An example of a commercially available liquid chromatography stationary phase comprising graphitic carbon is believed to include the DlScOVERY ZR-CARBON brand HPLC column from Sigma Aldrich, St. Louis, MO. Leboda, et al., Materials Chemistry and Physics 55 (1998) pages 1-29, is a literature review of HPLC carbon adsorbents.
The method of this description can be coupled, connected or standalone, with other analytical methods. For example, the effluent from a SEC column containing a polyolefinic copolymer of ethylene and 1-octene of a selected molecular size can be analyzed by the method of this disclosure to determine the ethylene to 1-octene ratio of the copolymer of the molecular size selected.
The method of this disclosure can be scaled up to include large-scale fractionations of many grams or many pounds of polymer, increasing the size of the apparatus and the graphitic column.
In addition, this description could include a temperature gradient in addition to or instead of a solvent gradient as a way to perform fractionation.
In addition, this description could include fractionation in a commercial process to refine the purity of the comonomer distribution of the commercial product.
A preferred set of operating conditions for this description is an EGMBE / TCB gradient with an autosampler and injector temperature of approximately 160 ° C and a column temperature of 140 ° C. Another preferred set of operating conditions for this description is a decanol / TCB gradient with an autosampler, injector and column temperature of 175 ° C.
EXAMPLE 1
An HPLC system is set up using a 4.6 x 100 mm liquid chromatography column, packing size 5 microns, pore size 25 nm (250 A), brand HYPERCARB, a mobile phase with a gradient composition with a flow rate of 1.0 ml / min having an initial composition of 100 vol% of ethylene glycol monobutyl ether for 3 min after injection and then a change of composition with a linear gradient of 15 min at 100 vol% 1,2,4-trichlorobenzene followed by holding for 3 min at 100 vol%
1,2,4-trichlorobenzene, an injection volume of 10 microliters, a sample concentration of 2 mg of
ES 2 478 286 T3 polymer per ml of decanol at 160 ° C, a column temperature of 140 ° C, an injection valve temperature of 160 ° C, an evaporative light scattering detector ELS-1000 Polymer Laboratories ( Amherst, MA) operated with a gas flow of 1.4 liters per min, a nebulization temperature of 200 ° C, and an evaporation temperature of 250 ° C. 10 copolymer samples of different molar ratios of the polymerized ethylene and 1-octene monomers are prepared, and chromatographed as shown in figure 3. The retention factors shown in figure 3 vary as a mathematical function of the monomer ratio a comonomer of the copolymer, with 0 mole% 1-octene (100 mole% ethylene) having the highest retention factor and 100 mole% 1-octene having the lowest retention factor. Said mathematical function can be expressed as the calibration curve shown in Figure 9. Said mathematical function can be incorporated into the program of a general-purpose digital computer to determine the ratio automatically.
EXAMPLE 2
An HPLC system is set up using a 4.6 x 100 mm liquid chromatography column, packing size 5 microns, pore size 25 nm (250 A), brand HYPERCARB, a mobile phase with a gradient composition with a flow rate of 1.0 ml / min having an initial composition of 100 vol% of ethylene glycol monobutyl ether for 3 min after injection and then a change of composition with a linear gradient of 15 min at 100 vol% 1,2,4-trichlorobenzene followed by holding for 3 min at 100 vol%
1,2,4-trichlorobenzene, an injection volume of 10 microliters, a sample concentration of 2 mg of polymer per ml of decanol at 160 ° C, a column temperature of 140 ° C, a valve temperature of 160 ° C injection, an ELS-1000 Polymer Laboratories (Amherst, MA) evaporative light scattering detector operated with a gas flow of 1.4 liters per min, a nebulization temperature of 200 ° C and an evaporation temperature 250 ° C. 10 copolymer samples of different molar ratios of the polymerized ethylene and propylene monomers are prepared and chromatographed as shown in Figure 4. The retention factors shown in Figure 4 vary as a mathematical function of the monomer to comonomer ratio of the copolymer, with 100 mole% propylene (0 mole% ethylene) having the lowest retention factor and 0 mole% propylene (100 mole% ethylene) the highest retention factor.
EXAMPLE 3
An HPLC system is set up using a 4.6 x 50 mm liquid chromatography column, packing size 5 microns, from DISCOVERY ZR-CARBON brand, a mobile phase with a gradient composition with a flow rate of 1.0 ml / min having an initial composition of 100% by vol of ethylene glycol monobutyl ether for 3 min after injection and then a change of composition with a linear gradient of 15 min at 100 vol% 1,2,4-trichlorobenzene followed by maintenance for 3 min at 100 vol% 1,2,4-trichlorobenzene, an injection volume of 10 microliters, a sample concentration of 2 mg of polymer per ml decanol at 160 ° C, a column temperature of 140 ° C, an injection valve temperature of 160 ° C, an evaporative light scattering detector ELS-1000 Polymer Laboratories (Amherst, MA) operated with a gas flow of 1.4 liters per min, a nebulization temperature of 200 ° C and an evaporation temperature of 250 ° C. 10 copolymer samples of different molar ratios of polymerized ethylene and 1octene monomers are prepared and chromatographed as shown in Figure 5. The retention factors shown in Figure 5 vary as a mathematical function of the monomer to comonomer ratio of the copolymer, but with functionality that is not as good as that shown in Figure 3, because it appears that some samples that have different ratios they will have the same retention factor.
EXAMPLE 4
An HPLC system is set up using a 4.6 x 100 mm liquid chromatography column, packing size 5 microns, pore size 25 nm (250 A), brand HYPERCARB, a mobile phase with a gradient composition with a flow rate of 1.0 ml / min having an initial composition of 100 vol% of ethylene glycol monobutyl ether for 3 min after injection and then a change of composition with a linear gradient of 15 min at 100 vol% 1,2,4-trichlorobenzene followed by holding for 3 min at 100 vol%
1,2,4-trichlorobenzene, an injection volume of 10 microliters, a sample concentration of 2 mg of polymer per ml of decanol at 160 ° C, a column temperature of 140 ° C, a valve temperature of 160 ° C injection, an ELS-1000 Polymer Laboratories (Amherst, MA) evaporative light scattering detector operated with a gas flow of 1.4 liters per min, a nebulization temperature of 200 ° C and an evaporation temperature 250 ° C. 3 polypropylene samples with varying tacticity are prepared and chromatographed as shown in Figure 6. The retention of polymers varies as a function of tacticity. The atactic and isotactic have similar retention times, while the syndiotactic is retained.
COMPARATIVE EXAMPLE 1
An HPLC system is set up using a 4.6 x 250 mm silica liquid chromatography column, 5 micron packing size, 30 nm pore size (300 A), Macherey Nagel (Macherey Nagel GmbH & Co. KG, Düren, Germany), a mobile phase with gradient composition with a flow rate of 1.0 ml / min having an initial composition of 100% by vol of ethylene glycol monobutyl ether for 3 min after injection and then a change of composition with a linear gradient from 15 min to 100% by vol of 1,2,4-trichlorobenzene followed
ES 2 478 286 T3 maintenance for 3 min at 100 vol% 1,2,4-trichlorobenzene, an injection volume of 10 microliters, a sample concentration of 2 mg of polymer per ml of decanol at 160 ° C, a column temperature of 140 ° C, an injection valve temperature of 160 ° C, an evaporative light scattering detector ELS-1000 Polymer Laboratories (Amherst, MA) operated with a gas flow of 1.4 liters per min, a nebulization temperature of 200 ° C and an evaporation temperature of 250 ° C. 10 copolymer samples of different molar ratios of polymerized ethylene and 1-octene monomers are prepared and chromatographed as shown in Figure 7. A comparison of the chromatograms shown in Figure 7 with the chromatograms shown in Figure 3 demonstrates the superior separation efficiency obtained using the graphitic carbon stationary phase of the disclosure compared to using a prior art stationary silica phase. . Furthermore, artifacts are seen early in the chromatograms of Figure 7 between 1.5 and 3.5 min, especially for the sample containing 100 mole% 1-octene.
COMPARATIVE EXAMPLE 2
An HPLC system is set up using a 4.6 x 250 mm silica liquid chromatography column, 5 micron packing size, 30 nm pore size (300 A), Macherey Nagel (Macherey Nagel GmbH & Co. KG, Düren, Germany), a mobile phase with gradient composition with a flow rate of 1.0 ml / min having an initial composition of 100% by vol of ethylene glycol monobutyl ether for 3 min after injection and then a change of composition with a linear gradient from 15 min to 100% by volume of 1,2,4-trichlorobenzene followed by maintenance for 3 min at 100% by volume of 1,2,4-trichlorobenzene, an injection volume of 10 microliters, a sample concentration of 2 mg of polymer per ml of decanol at 160 ° C, a column temperature of 140 ° C, an injection valve temperature of 160 ° C, an evaporative light scattering detector ELS-1000 Polymer Laboratories (Amherst, MA) operated with a gas flow of 1.4 liters per min, a nebulization temperature of 200 ° C, and an evaporation temperature of 250 ° C. 10 copolymer samples of different molar ratios of polymerized ethylene and propylene monomers are prepared and chromatographed as shown in figure 8. A comparison of the chromatograms shown in figure 8 with the chromatograms shown in figure 4 demonstrates the efficiency superior separation obtained using the graphitic carbon stationary phase of the description compared to using a prior art stationary silica phase.
Contents9
21 members in 7 offices
Priority claims5
| Document | Office | Kind | Date |
|---|---|---|---|
| 195326P | United States of America | – | |
| 19532608 | United States of America | P | |
| 181015P | United States of America | – | |
| 18101509 | United States of America | P | |
| 2009059261 | United States of America | W |
Members21
| Document | Office | Kind | |
|---|---|---|---|
| US2010093964A1 | United States of America | A1 | |
| WO2010042389A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2010042389A3 | World Intellectual Property Organization (WIPO) | A3 | |
| EP2334425A2 | European Patent Office (EPO) | A2 | |
| CN102215952A | China | A | |
| US8076147B2 | United States of America | B2 | |
| JP2012504768A | Japan | A | |
| US2012047990A1 | United States of America | A1 | |
| US8476076B2 | United States of America | B2 | |
| EP2334425B1 | European Patent Office (EPO) | B1 | |
| JP5518875B2 | Japan | B2 | |
| JP2014122909A | Japan | A | |
| EP2754474A2 | European Patent Office (EPO) | A2 | |
| ES2478286T3This record | Spain | T3 | |
| CN102215952B | China | B | |
| EP2754474A3 | European Patent Office (EPO) | A3 | |
| JP5778806B2 | Japan | B2 | |
| BRPI0914041A2 | Brazil | A2 | |
| EP2754474B1 | European Patent Office (EPO) | B1 | |
| ES2628340T3 | Spain | T3 | |
| BRPI0914041B1 | Brazil | B1 |
Numbers
- Publication
- 2478286
- Application
- 9737260
Titles2
- Spanish
- Cromatografía de polímeros poliolefínicos
- English
- Polyolefin Polymers Chromatography
Classification
- CPC, 7
- B01J20/282
- B01D15/08
- B01D15/34
- B01J20/20
- B01J20/205
- B01J2220/54
- G01N2030/885
- IPC, 4
- B01J20 282
- B01D15 08
- B01J20 20
- G01N30 02