WO2002090403A1 - Polypropylene a base de maleate presentant des proprietes ameliorees - Google Patents

Polypropylene a base de maleate presentant des proprietes ameliorees Download PDF

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Publication number
WO2002090403A1
WO2002090403A1 PCT/US2002/014320 US0214320W WO02090403A1 WO 2002090403 A1 WO2002090403 A1 WO 2002090403A1 US 0214320 W US0214320 W US 0214320W WO 02090403 A1 WO02090403 A1 WO 02090403A1
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WO
WIPO (PCT)
Prior art keywords
maleic anhydride
polypropylene
bound
reaction
grafting
Prior art date
Application number
PCT/US2002/014320
Other languages
English (en)
Other versions
WO2002090403A8 (fr
Inventor
Scott M. Hacker
Robert A. Doerries
Peter F. Romeo
Richard B. Heath
Original Assignee
Honeywell International, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Honeywell International, Inc. filed Critical Honeywell International, Inc.
Priority to CA002446406A priority Critical patent/CA2446406A1/fr
Priority to EP02736665A priority patent/EP1434809A4/fr
Priority to KR10-2003-7014465A priority patent/KR20030096358A/ko
Priority to JP2002587479A priority patent/JP2005509688A/ja
Priority to AU2002309651A priority patent/AU2002309651B2/en
Publication of WO2002090403A1 publication Critical patent/WO2002090403A1/fr
Publication of WO2002090403A8 publication Critical patent/WO2002090403A8/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/46—Reaction with unsaturated dicarboxylic acids or anhydrides thereof, e.g. maleinisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms

Definitions

  • the present invention relates to maleated polypropylenes and to methods for producing maleated polypropylenes. More specifically, the invention relates to methods for producing maleated polypropylenes having a relatively high percentage of bound maleic anhydride moieties, and the maleated polypropylenes obtained from such methods.
  • maleated polyolefins and in particular maleated polypropylenes, are known in the art and find use in a wide range of applications.
  • maleated polypropylenes are useful for compatibilizing polymers, particularly polyolefins with various polar substrates, including polar polymers, mineral fillers, and the like.
  • Such copolymers are also known for use in metal bonding adhesive compositions.
  • maleic anhydride is grafted onto a polypropylene backbone by introducing maleic anhydride, or a precursor thereof, into a melt of polypropylene polymer, typically in the presence of a catalyst.
  • maleated polypropylene is as a compatibilizing agent, particularly for polar substrates, fibers and filler.
  • the present invention is directed to methods for advantageously producing maleated polypropylenes having a relatively high percentage of bound maleic anhydride, based on the total amount of maleic anhydride moieties present in the grafting reaction product, and the maleated polypropylenes produced therefrom.
  • the methods of the present invention overcome the disadvantages of the prior art by facilitating the production of maleated polypropylenes wherein at least about 60%, and preferably at least about 75% of the maleic anhydride moieties in the grafting reaction product are bound to the polypropylene. Unless indicated otherwise herein, all percentages are intended to refer to weight percent.
  • the improved process is characterized judiciously selecting the type and nature of the reactants used and adding maleic anhydride to the selected polypropylene, and preferably polypropylene melt, under time, temperature and pressure conditions effective to graft at least about 55 %, and even more preferably at least about 60 %, of maleic anhydride to the polymer backbone, said percentage being based on the total maleic anhydride moieties, including precursors thereto, present in the grafting reaction product.
  • grafting reaction product refers to maleated polypropylene, together with any unreacted components, by products and impurities, after the grafting reaction is deemed to be substantially completed, but before any subsequent purification steps.
  • polypropylene refers to and includes homopolymers of polypropylene and all forms of polypropylene copolymers, and in particular polypropylene- polyethylene copolymers, provided that at least about the majority of the polymer is formed of polypropylene moities on a mole percent basis.
  • copolymer refers to and includes terpolymers and the like.
  • the polyolefin reactant of the present invention is polypropylene homopolymer, or a copolymer of propylene and ethylene wherein the concentration by weight of ethylene is less than about 10%, and more preferably less than about 5%.
  • the term "maleated polypropylene” refers generally to the reaction product formed by grafting maleic anhydride, preferably by covalent bonding, to the polymer backbone of polypropylene. As is known in the art, therefore, such grafting reaction products in commercial applications generally comprise not only maleated polypropylene but also as unbound maleic anhydride and oligomeric maleic anhydride.
  • bound maleic anhydride refers generally to the moieties derived from maleic anhydride which are grafted to the polypropylene backbone according to the present invention.
  • Unbound maleic anhydride refers generally to unreacted maleic anhydride or oligomeric anhydride present in the grafting reaction product.
  • the grafting reaction product is generally the melt at the conclusion of the grafting reaction step.
  • the maleic anhydride is introduced to the polypropylene, and preferably a polypropylene melt, at a rate that maintains the concentration of maleic anhydride in the reaction mixture (e.g., in the melt) at no greater than about 120 %, and even more preferably no greater than 100 %, of the solubility limit of the maleic anhydride in the polypropylene at the reaction conditions.
  • grafting maleic anhydride to polypropylene in a reaction mixture wherein the amount of unreacted maleic anhydride in the mixture is maintained at a relatively low level is capable of producing a reaction product copolymer that either contains a very high level of bound maleic anhydride and/or contains a relatively low level of oligomeric maleic anhydride .
  • the amount of maleic anhydride which is bound in the grafting reaction is generally related to the amount of polyethylene in the copolymer. More particularly, it is generally preferred that the copolymer comprise up to about 10 mole % polyethylene, more preferably up to about 5 mole % of polyethylene, and even more preferably from about 0.5 mole% to about 3 mole% polyethylene. Applicants have discovered that polyethylene levels as described herein help to produce the claimed high levels of bound maleic anhydride without negatively effecting the compatibalization properties of the reaction product.
  • the present invention therefore provides an improved graft maleic anhydride/polypropylene copolymer product comprising polypropylene backbone, bound maleic anhydride and from about 0% to about 40% of unbound maleic anhydride wherein at least about 60 wt% of said maleic anhydride moieties, more preferably at least about 65wt% of said maleic anhydride moieties, and even more preferably at least about 70 % of said moieties are bound maleic anhydride, based on the total maleic anhydride moieties in the reaction product. In especially preferred embodiments, at least about 75 % of said moieties are bound maleic anhydride, based on the total maleic anhydride moieties in the reaction product.
  • One aspect of the present invention is directed to methods for producing maleated polypropylenes comprising reacting maleic anhydride, or a precursor thereof, with polypropylene in a reaction mixture. It is contemplated that various particular process and unit parameters can be adapted for use with the present reaction step, and a wide range of known methods and steps for combining and reacting maleic anhydride and polypropylene in a reaction mixture can be used according to the present invention. For example, it is contemplated that processes of the present invention may comprise one or more of the classes of reaction procedures known in the art, including: melt grafting, solid state grafting, solution grafting, and the like. However, present invention is preferably conducted by melt grafting.
  • the steps of the present invention may be conducted on a continuous basis, on a batch basis, or on a combination of both. Those of skill in the art will, in view of the teachings contained herein, be able to adopt the present invention to any of these modes of operation without undue experimentation.
  • the amount of maleic anhydride which is bound in the reaction step of the present invention can be affected by numerous reaction parameters, including the nature of the polypropylene as described above, and applicants believe that it is highly advantageous to control one or more of the relevant parameters in accordance with teachings of the present invention in order to achieve a high level of bound maleic anhydride and/or low levels of unreacted and oligomeric maleic anhydride.
  • the grafting reaction step of the present invention can be conducted under any combination of particular grafting reaction conditions, provided that the reaction of polypropylene with maleic anhydride is favored relative the reaction of maleic anhydride with itself or with other components in the reaction mixture, such as maleic anhydride oligomers.
  • One preferred mechanism for obtaining a reaction mixture in which the polypropylene/maleic anhydride grafting reaction is highly favored is to maintain the concentration of unreacted maleic anhydride in the reaction mixture at relatively low levels compared to those levels used in prior art processes.
  • applicants do not wish to be bound by or to any theory of operation, it is believed that the unexpectedly higher percentages of bound maleic anhydride found in the preferred products of the present method are achieved, at least in part, because maleic anhydride has a limited solubility in polypropylene, an in particular in a polypropylene polymer melt.
  • use of a low concentration of maleic anhydride results in less phase separation in the reaction mixture between the maleic anhydride, or the precursors thereof and polypropylene.
  • maleic anhydride concentrations that are not substantially greater than the solubility limit of the polymer has two distinct beneficial results.
  • the present invention minimizes the amount of unreacted maleic anhydride exposed to conditions which favor anhydride/anhydride reaction, as would occur with the maleic anhydride that exists in a phase separate from the polymer phase. Lower phase separation therefore allows for binding of a higher percentage of the maleic anhydride introduced to the polymer melt.
  • the initially formed, lightly maleated product is believed to help solubilize any additional maleic anhydride reactant that is subsequently introduced to the polymer melt in preferred embodiments of the present invention.
  • the methods of the present invention comprise reacting maleic anhydride with polypropylene under conditions effective to maintain the concentration of unreacted maleic anhydride in the reaction mixture at less than about 2.5 %, more preferably less than about 2 %, and even more preferably less than about 1 %, during a substantial portion, and preferably during at least about 75%, of the grafting step.
  • this grafting reaction step comprises adding maleic anhydride to a reaction mixture comprising polypropylene, and preferably a polypropylene melt, under conditions effective to maintain the concentration of maleic anhydride in the reaction mixture at less than about 2.5, more preferably less than about 2 %, and even more preferably less than about 1 % weight percent during a substantial portion, and preferably during at least about 75% of the adding step.
  • the term "substantial portion" with respect to the reaction step and adding step refers to any portion or portions of the grafting reaction in which, in the aggregate, at least 50% of the maleic anhydride-polypropylene bonds are formed.
  • the maleic anhydride is added to the reaction mixture at rate of less than about 0.045 pounds of maleic anhydride or precursor thereof ("MA") per pound of polypropylene (“PP”) per hour of grafting reaction conditions (MA/PP/hr), and even more preferably less than about 0.040 MA/PP/ hr.
  • the molecular weight of the polypropylene used in the maleation process, as well as the maleic anhydride content of the maleated polypropylene, typically characterized by the saponification number of the final product affect the percent of bound maleic anhydride found in the final product.
  • saponification number refers to the measure of the amount of saponifiable matter present, including bound single unit maleic anhydride, bound oligomeric maleic anhydride, unreacted maleic anhydride, unbound oligomeric maleic anhydride, and other hydrolyzable moieties, in the maleated polypropylene.
  • the SAP is generally calculated as the number of milligrams of potassium hydroxide required to hydrolyze one gram of sample (mg KOH/g).
  • Fig. 1 is a graphic depiction of the percent bound maleic anhydride plotted against the SAP of a low molecular weight polypropylene and a high molecular weight polypropylene. As illustrated in Fig.l, generally, the percent bound maleic anhydride decreases as the SAP increases. In addition, as the molecular weight of the polypropylene increases, the percent bound decreases. It is believed such variables are controlled in accordance with the present invention to produce useful maleated polypropylenes having high a percent of bound maleic anhydride.
  • the molecular weight of the polypropylene reactant and the SAP of the reactant is preferred to select the molecular weight of the polypropylene reactant and the SAP of the reactant to achieve bound maleic anhydride in accordance with the present invention.
  • the high molecular weight polypropylene has a SAP of no greater than about 70, more preferably no greater than about 75 and even more preferably no greater than 80.
  • the polypropylene has a SAP of no greater than about 100, more preferably no greater than about 120 and even more preferably no greater than 150.
  • maleic anhydride Any commercial grade of maleic anhydride, or a precursor thereof such as maleic acid (which is converted to maleic anhydride under many commonly used grafting reaction conditions) is suitable for use in the present invention.
  • suitable maleic anhydrides include those that are is commercially available, for example, though Monsanto Company (St. Louis , NO) as Maleic Anhydride, and Huntsman Petrochemical Corporation (Chesterfield, MO) as Manbri Maleic Anhydride.
  • Polypropylenes suitable for use in the present invention include those polypropylenes commercially available, for example, through Honeywell (Morristown, NJ) under the trade name ACX1089.
  • the weight ratio of polypropylene to maleic anhydride used in the present method is from about 5:1 to about 40:1. More preferably the weight ratio is from about 5: 1 to about 25: 1, and even more preferably is from about 10:1 to about 20:1.
  • the reacting step further comprises reacting the maleic anhydride with the polypropylene in the presence of a catalyst.
  • a catalyst Any of a wide range of catalysts can be used in the present invention. Suitable catalysts include, for example, free radical forming agents known in the art and include, for example,
  • dialkyl peroxides dialkyl peroxides, tertiary butyl hydroperoxide, cumene hydroperoxide, p-menthane peroxide,
  • p-menthane hydroperoxide or axo compounds such as azobis (isobutyronitrile), or irradiation sources.
  • the preferred free radical sources are the peroxides with the butyl peroxides being
  • ditertiary butyl peroxide di-t-butyl peroxide
  • the amount of peroxide or free radical agent used is generally quite low, being of the
  • reaction at a rate of preferably about 0.01 to about 3 wt % of the starting material per hour
  • the catalysts are added to the reaction mixture of
  • the catalyst can be added simultaneously and/or separately in relation
  • the maleic anhydride and catalyst are identical to the maleic anhydride.
  • the maleic anhydride and catalyst are identical to the maleic anhydride.
  • the maleic anhydride and catalyst are identical to the maleic anhydride.
  • maleic anhydride and catalyst are added to the reaction mixture in overlapping
  • the process of the present invention may further comprise the use of other additives in
  • substantially hinder the formation of a product of the present invention may be used in suitable amounts.
  • suitable additives include: comonomers, such as, styrene, chain transfer
  • reaction of the present invention may be carried out under any suitable reaction
  • the polypropylene comprise a polypropylene melt.
  • the temperature of reaction be above the melt temperature of the polypropylene, but preferably no greater than about 200°C.
  • reaction temperature is generally preferably between
  • the reaction pressure depends, among other things, upon the reaction temperature and desired rate of reaction. Generally, the reaction is conducted under a pressures preferably from about 0 to about 50 psig, more preferably from about 5 to about 30 psig, and even more
  • the grafting reaction of the present invention is conducted such that at least about 60wt% of maleic anhydride, based on total weight of maleic anhydride in the grafting
  • reaction product is bound to the polymer backbone.
  • reaction is conducted
  • This example illustrates the production of a maleated propylene in accordance with the
  • thermal degradation unit for an average contact time of 30 minutes.
  • the thermal degrader is operated at a temperature of 370C with the agitator operated at a speed of such that all of the
  • thermal energy for degradation is supplied by the friction of mixing. The degraded
  • polypropylene wax has a melt viscosity of about 800 centipoise measured at 190C. This
  • Example 1 weight of ditertiary butyl peroxide to a thermal agitated reactor maintained at about 200C to produce a reaction product mixture, and even after standard techniques for separating unreacted maleic hydride from the reaction mixture, had a concentration of bound maleic anhydride of less than about 50%.
  • Example 1
  • the reaction mixture is stirred for an additional 10 minutes.
  • Standard techniques are used in an effort to remove unreacted maleic anhydride. More particularly, a vacuum of 25" Hg is applied to the grafting reaction product and periodic samples are removed and tested for unreacted maleic anhydride. The vacuum is removed and the reaction mixture is cooled to 170°C, and the grafting reaction product mixture after the standard vacuum purification comprises greater than 70%, and more preferably greater than about 80%, and even more preferably greater than 85% bound maleic anhydride.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne des procédés pour produire, de manière avantageuse, des polypropylènes à base de maléate, présentant un pourcentage relativement élevé d'anhydride maléique lié, en fonction de la quantité totale de fractions d'anhydride maléique présente dans le produit de réaction de greffage. L'invention traite aussi des polypropylènes à base de maléate selon lesquels au moins 60 % environ des fractions d'anhydride maléique dans le produit de réaction de greffage sont liées au polypropylène.
PCT/US2002/014320 2001-05-06 2002-05-06 Polypropylene a base de maleate presentant des proprietes ameliorees WO2002090403A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CA002446406A CA2446406A1 (fr) 2001-05-06 2002-05-06 Polypropylene a base de maleate presentant des proprietes ameliorees
EP02736665A EP1434809A4 (fr) 2001-05-06 2002-05-06 Polypropylene a base de maleate presentant des proprietes ameliorees
KR10-2003-7014465A KR20030096358A (ko) 2001-05-06 2002-05-06 말레이트된 폴리프로필렌 및 그 제조방법
JP2002587479A JP2005509688A (ja) 2001-05-06 2002-05-06 マレエート化ポリプロピレンおよびその調製方法
AU2002309651A AU2002309651B2 (en) 2001-05-06 2002-05-06 Maleated polypropylenes and processes for the preparation thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US28926901P 2001-05-06 2001-05-06
US60/289,269 2001-05-06

Publications (2)

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WO2002090403A1 true WO2002090403A1 (fr) 2002-11-14
WO2002090403A8 WO2002090403A8 (fr) 2003-09-04

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PCT/US2002/014320 WO2002090403A1 (fr) 2001-05-06 2002-05-06 Polypropylene a base de maleate presentant des proprietes ameliorees

Country Status (7)

Country Link
EP (1) EP1434809A4 (fr)
JP (3) JP2005509688A (fr)
KR (3) KR20090006238A (fr)
CN (1) CN100491427C (fr)
AU (1) AU2002309651B2 (fr)
CA (1) CA2446406A1 (fr)
WO (1) WO2002090403A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005102689A1 (fr) * 2004-04-12 2005-11-03 Boston Scientific Limited Technique d'adherence pour polymeres incompatibles mettant en oeuvre des couches de liaison de polymeres modifies
CN101724128B (zh) * 2008-10-31 2012-03-07 中国石油化工股份有限公司 一种马来酸酐接枝的聚丙烯树脂接枝物的制备方法
WO2021113951A1 (fr) * 2019-12-11 2021-06-17 Greenmantra Recycling Technologies Ltd. Composition de polymères dérivés de la modification avec de l'acide maléique de polypropylène dépolymérisé
US11072693B2 (en) 2015-12-30 2021-07-27 Greenmantra Recycling Technologies Ltd. Reactor for continuously treating polymeric material
US11072676B2 (en) 2016-09-29 2021-07-27 Greenmantra Recycling Technologies Ltd. Reactor for treating polystyrene material
US11279811B2 (en) 2016-02-13 2022-03-22 Greenmantra Recycling Technologies Ltd. Polymer-modified asphalt with wax additive
US11987672B2 (en) 2016-03-24 2024-05-21 Greenmantra Recycling Technologies Ltd. Wax as a melt flow modifier and processing aid for polymers

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Publication number Priority date Publication date Assignee Title
CN100532413C (zh) * 2005-04-18 2009-08-26 中国科学院化学研究所 一种聚丙烯接枝共聚物及其制备方法与应用
US7750078B2 (en) * 2005-12-07 2010-07-06 Exxonmobil Chemical Patents Inc. Systems and methods used for functionalization of polymeric material and polymeric materials prepared therefrom
CN101597358B (zh) * 2008-06-02 2011-01-12 张发饶 一种马来酸酐接枝聚丙烯蜡的生产制备方法及其装置
CN101717474B (zh) * 2009-11-20 2012-02-15 广州市合诚化学有限公司 一种用于制备聚丙烯类热熔胶的胶粘剂母料及其制备方法
WO2016026121A1 (fr) * 2014-08-21 2016-02-25 Dow Global Technologies Llc Compositions adhésives comprenant des polymères à base d'oléfine fonctionnalisée de faible poids moléculaire
CN114316147A (zh) * 2021-12-15 2022-04-12 江苏中利集团股份有限公司 一种硅烷交联聚乙烯的方法及产品
CN114213590B (zh) * 2021-12-15 2024-03-19 江苏中利集团股份有限公司 一种硅烷交联聚乙烯的质量评估方法和***

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US6046279A (en) 1994-08-25 2000-04-04 Eastman Chemical Company Maleated high acid number high molecular weight polypropylene of low color

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US3480580A (en) 1965-10-22 1969-11-25 Eastman Kodak Co Modified polymers
US6046279A (en) 1994-08-25 2000-04-04 Eastman Chemical Company Maleated high acid number high molecular weight polypropylene of low color
WO1997011110A1 (fr) 1995-09-21 1997-03-27 Eastman Chemical Company Procede pour diminuer la couleur d'une emulsion contenant une cire polyolefinique modifiee chimiquement

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005102689A1 (fr) * 2004-04-12 2005-11-03 Boston Scientific Limited Technique d'adherence pour polymeres incompatibles mettant en oeuvre des couches de liaison de polymeres modifies
US7659000B2 (en) 2004-04-12 2010-02-09 Boston Scientific Scimed, Inc. Adhesion technique for incompatible polymers using modified polymer tie layers
CN101724128B (zh) * 2008-10-31 2012-03-07 中国石油化工股份有限公司 一种马来酸酐接枝的聚丙烯树脂接枝物的制备方法
US11072693B2 (en) 2015-12-30 2021-07-27 Greenmantra Recycling Technologies Ltd. Reactor for continuously treating polymeric material
US11739191B2 (en) 2015-12-30 2023-08-29 Greenmantra Recycling Technologies Ltd. Reactor for continuously treating polymeric material
US11279811B2 (en) 2016-02-13 2022-03-22 Greenmantra Recycling Technologies Ltd. Polymer-modified asphalt with wax additive
US11987672B2 (en) 2016-03-24 2024-05-21 Greenmantra Recycling Technologies Ltd. Wax as a melt flow modifier and processing aid for polymers
US11072676B2 (en) 2016-09-29 2021-07-27 Greenmantra Recycling Technologies Ltd. Reactor for treating polystyrene material
US11859036B2 (en) 2016-09-29 2024-01-02 Greenmantra Recycling Technologies Ltd. Reactor for treating polystyrene material
WO2021113951A1 (fr) * 2019-12-11 2021-06-17 Greenmantra Recycling Technologies Ltd. Composition de polymères dérivés de la modification avec de l'acide maléique de polypropylène dépolymérisé

Also Published As

Publication number Publication date
KR20100070383A (ko) 2010-06-25
EP1434809A4 (fr) 2005-04-27
JP2005509688A (ja) 2005-04-14
EP1434809A1 (fr) 2004-07-07
KR101040689B1 (ko) 2011-06-10
JP2015028180A (ja) 2015-02-12
KR20090006238A (ko) 2009-01-14
CN1524096A (zh) 2004-08-25
JP5837166B2 (ja) 2015-12-24
KR20030096358A (ko) 2003-12-24
CN100491427C (zh) 2009-05-27
CA2446406A1 (fr) 2002-11-14
JP2009280821A (ja) 2009-12-03
JP5718555B2 (ja) 2015-05-13
AU2002309651B2 (en) 2006-04-06
WO2002090403A8 (fr) 2003-09-04

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