EP1881997A2 - Procédé de polymerisation d'une dispersion de polymer et dispersion de polymère - Google Patents

Procédé de polymerisation d'une dispersion de polymer et dispersion de polymère

Info

Publication number
EP1881997A2
EP1881997A2 EP06733482A EP06733482A EP1881997A2 EP 1881997 A2 EP1881997 A2 EP 1881997A2 EP 06733482 A EP06733482 A EP 06733482A EP 06733482 A EP06733482 A EP 06733482A EP 1881997 A2 EP1881997 A2 EP 1881997A2
Authority
EP
European Patent Office
Prior art keywords
polymer dispersion
sulphonic acid
acid
stabiliser
polymeric
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.)
Withdrawn
Application number
EP06733482A
Other languages
German (de)
English (en)
Inventor
Christian Przybyla
Oliver Struck
André LASCHEWSKY
Bernd Paulke
Mathias Hahn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Akzo Nobel NV
Nouryon Pulp and Performance Chemicals AB
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Akzo Nobel NV
Eka Chemicals AB
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 Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV, Akzo Nobel NV, Eka Chemicals AB filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Priority to EP06733482A priority Critical patent/EP1881997A2/fr
Publication of EP1881997A2 publication Critical patent/EP1881997A2/fr
Withdrawn legal-status Critical Current

Links

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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/20—Aqueous medium with the aid of macromolecular dispersing agents
    • 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
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide

Definitions

  • the present invention relates to a process for preparing a polymer dispersion. It also relates to a polymer dispersion, the use of the polymer dispersion and a process for producing paper.
  • aqueous dispersions of anionic charged polymers is retention and dewatering aid in paper manufacturing industry.
  • Further uses of such polymer dispersions are as aids in various processes where they act as, for example, flocculants when treating wastewater or aids in other solid-liquid separation processes in, for example, the metal-, ceramic-, printing-, biotechnological-, and pharmaceutical industries. They can also be used as thickeners in, e.g., chemical- biotechnological-, pharmaceutical-, and cosmetic industries and soil improving agents.
  • these polymer dispersions comprise a dispersed polymer and a dispersant in which the dispersant usually is a polymeric dispersant.
  • Anionic polymer dispersions are generally prepared by polymerising a reaction mixture of water-soluble anionic and non-ionic monomers in the presence of a salt. Finished polymer will precipitate from the aqueous salt solution and, by using a suitable dispersant, form a stable polymer dispersion.
  • WO 01/18063, US 5,837,776 and US 5,605,970 disclose processes for preparing a dispersion of a water-soluble polymer comprising polymerising water-soluble monomers in an aqueous reaction mixture containing a salt. Factors to consider are, for example, the process viscosity, active content, stability, good retention properties, and easiness of preparing the polymer dispersion sometimes including preparing the stabiliser.
  • criteria such as environmental and safety aspects are of importance.
  • criteria such as environmental and safety aspects are of importance.
  • criteria are for example low-cost production, rapid performance, effective flocculation or dewatering, and long shelf life.
  • Prior art anionic polymer dispersions described contain significant amounts of salt which makes up a great part of the weight of the polymer dispersion. There is presently a desire to reduce, or completely avoid, the use of salt in polymer dispersions due to environmental and economical reasons.
  • the viscosity of the reaction mixture when producing the polymer dispersion, "the process viscosity” should be kept low and viscosity peaks should be avoided, or at least reduced as much as possible, during the production of the polymer dispersion.
  • the shelf life of the dispersion i.e., the stability of the polymer dispersion over time, is an important property.
  • An efficient dispersant is needed for keeping the polymer particles stable in dispersion without settling as sediment.
  • a further factor to consider is the active content, i.e., the amount of dispersed polymer in the polymer dispersion.
  • a high active content minimises transportation costs and gives easier handling at the end-application.
  • dispersions with a high active content can be obtained at the same time the viscosity can be kept low.
  • an increase of the active content above a certain level may not always give improved performance in retention and dewatering in a papermaking process.
  • the polymer dispersion should also give good retention and dewatering results when used in papermaking processes, act as a good flocculant in other processes such as waste water treatment, act as a good thickener in various applications such as cosmetic formulations and also be possible to use in soil improvement processes.
  • stabiliser is herein meant a polymer which function is to keep dispersed polymer particles/droplets in dispersion.
  • co-stabiliser is herein meant a polymer which function is to make a polymer formed from polymerisation of one or more monomers to precipitate out from solution into solid particles or liquid droplets.
  • a highly stable polymer dispersion having high active content of a dispersed polymer and low process viscosity can be achieved by a process for preparing a polymer dispersion comprising polymerising one or more anionic monomers ([Ti 1 ) and one or more non-ionic vinyl monomers (m 2 ) present in a reaction mixture further comprising a polymeric stabiliser (B) and a polymeric co-stabilisers (C).
  • the invention further comprises a polymer dispersion comprising a dispersed polymer (A) of one or more anionic monomers ([Ti 1 ) and one or more non-ionic vinyl monomers (m 2 ), a polymeric stabiliser (B), and a polymeric co-stabiliser (C).
  • A dispersed polymer
  • A anionic monomers
  • m 2 non-ionic vinyl monomers
  • B polymeric stabiliser
  • C polymeric co-stabiliser
  • the reaction medium is suitably an aqueous medium.
  • the polymer dispersion is suitably an aqueous polymer dispersion.
  • the polymer dispersion is suitably water- soluble.
  • the polymer particles/droplets suitably has an average size (thickness) of up to about 25 ⁇ m, also suitably from about 0.01 to about 25 ⁇ m, preferably from about 0.05 to about 15 ⁇ m, most preferably from about 0.2 to about 10 ⁇ m.
  • the polymeric stabiliser (B) is suitably an organic polymer.
  • the polymeric stabiliser (B) is a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, itaconic acid, 2-acrylamido-2-methyl-1 -propane sulphonic acid (AMPS), 2-acrylamido-2-methyl-1 -butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacr ⁇ loyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, methacryloyloxypropyl sulphonic acid, vinyl sulphonic acid, allyl sulphonic acid, methallyl sulphonic acid, styrene sulphonic acid, maleic acid, maleamidic acid, and/or vinyl phosphonic acid.
  • polymeric stabilizers are copolymers of maleic acid or maleamidic acid, respectively, with styrene or vinyl ethers, or alpha-olefins which may contain additional comonomers.
  • the polymeric stabiliser (B) is a copolymer of acrylic acid or methacrylic acid with a further of the listed monomers, preferably 2- acrylamido-2-methyl-1 -propane sulphonic acid (AMPS).
  • AMPS 2- acrylamido-2-methyl-1 -propane sulphonic acid
  • the weight average molecular weight of the polymeric stabiliser (B) is suitably from about 5.000 to about 5.000.000 g/mole, preferably from about 10.000 to about 1.000.000 g/mole, more preferably from about 20.000 to about 1000.000 g/mole, most preferably from about 35.000 to about 500.000 g/mole.
  • the polymer dispersion suitably comprises from about 0.2 to about 5 weight % of the polymeric stabiliser (B) based on the total weight of the dispersion or reaction mixture, preferably from about 0.5 to about 3 weight %, most preferably from about 0.8 to about 1.5 weight %.
  • the polymeric co-stabiliser (C) is suitably an organic polymer.
  • the polymeric co-stabiliser (C) is a polymer of one or more monomers belonging to the group of acrylic acid, methacrylic acid, vinyl sulphonate, styrene sulphonic acid, itaconic acid, vinylphosphonic acid, 2-acrylamido-2-methyl-1 -propane sulphonic acid (AMPS), 2- acrylamido-2-methyl-1 -butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, and methacryloyloxypropyl sulphonic acid.
  • two or more co-stabilisers (C) are present in the reaction mixture and polymer dispersion.
  • the weight average molecular weight of the polymeric co-stabiliser (C) is suitably from about 100 to about 50.000 g/mol, preferably from about 500 to about 30.000 g/mol, more preferably from about 1.000 to about 20.000 g/mol, even more preferably from about 1.000 to about 15.000 g/mol, most preferably from about 1.000 to about 10.000 g/mol.
  • the polymer dispersion suitably comprises from about 2 to about 50 weight % of one or more polymeric co-stabilisers (C) based on the total weight of the dispersion or reaction mixture, preferably from about 3 to about 25 weight %, most preferably from about 5 to about 15 weight %.
  • C polymeric co-stabilisers
  • the polymeric stabiliser (B) and the polymeric co-stabiliser (C) in the reaction mixture or polymer dispersion are preferably made up from different monomers or, if they are made up from the same monomers, contain different monomer ratios.
  • the polymeric stabiliser (B) or polymeric co-stabiliser (C) is suitably not a dextrin or dextrin derivative.
  • the one or more anionic monomers ([Ti 1 ) suitably belong to the group of acrylic acid, methacrylic acid, (styrene sulphonic acid), 2-acrylamido-2-methyl-1 -propane sulphonic acid (AMPS), 2-acrylamido-2-methyl-1 -butane sulphonic acid (AMBS), acryloyloxyethyl sulphonic acid, methacryloyloxyethyl sulphonic acid, acryloyloxypropyl sulphonic acid, methacryloyloxypropyl sulphonic acid, vinyl sulphonic acid, and their alkali, earth alkali or ammonium salts.
  • the one or more non-ionic monomers (m 2 ) suitably belong to the group of acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N- ethylacrylamide, N-ethyl methacrylamide, N-isopropylacrylamide, N- isopropylmethacrylamide, N,N-dimethylacrylamide, N-t-butylacrylamide, N-t- butylmethacrylamide, N-hydroxyethylacrylamide, N-(tris-(hydroxymethyl)-methyl)- acrylamide, N-vinyl formamide, N-vinyl acetamide, hydroxyalkylacrylate or hydroxyalkylmethacrylate with C2-C4 alkyl, alkylacrylate or alkylmethacrylate with C1-C4 alkyl, benzylacrylate or benzyl methacrylate, esters of acrylic or methacrylic acid with dihydroxy-(polyethylene oxide) having 1-20
  • the one or more non-ionic monomers (m 2 ) belong to the group of acrylamide, acrylate or methacrylate esters.
  • the molar ratio between the anionic monomer ([Ti 1 ) and the non-ionic monomer ([Ti 2 ) is suitably from about 1 :99 to about 25:75, preferably from about 3:97 to about 20:80, most preferably from about 5:95 to about 15:85.
  • the weight average molecular weight of the dispersed polymer (A) is suitably from about 1.000.000 to about 15.000.000 g/mole, preferably from about 1.500.000 to about 10.000.000 g/mole, most preferably from about 2.000.000 to about 8.000.000 g/mole.
  • the polymerisation is suitably a free-radical polymerisation.
  • the initiator is suitably a radical former, preferably a water-soluble azo-initiator, a water-soluble peroxide, or a water-soluble redox initiator.
  • Preferred initiators include 2,2'-azobis- (amidinpropane) hydrochloride, 2,2'-azobis-(2-methyl-N-(2-hydroxyethyl)-propionamide, 4,4'-azobis-(4-cyanovaleric acid) and its alkali and ammonium salts, t-butylhydroperoxide, perhydrol, peroxydisulphate, or the before mentioned peroxides in combination with a reducing agent such as sodium metabisulphite or ferrous salts.
  • a reducing agent such as sodium metabisulphite or ferrous salts.
  • the polymer dispersion suitably comprises from about 5 to about 40 weight % of the dispersed polymer (A) based on the total weight of the dispersion, preferably from about 10 to about 30 weight %, most preferably from about 12 to about 25 weight %.
  • the amount of one or more inorganic salts in the polymer dispersion is suitably from 0 to about 1.9 weight % based on the total weight of the dispersion or reaction mixture, preferably from 0 to about 1 weight %, more preferably from 0 to about 0.5 weight %, most preferably from 0 to about 0.1 weight %, or substantially salt-free.
  • inorganic salts is herein suitably meant any inorganic salt, preferably salts belonging to the group of inorganic alkali metal, alkali earth metal or ammonium halides, sulphates and phosphates.
  • the polymer dispersion may also comprise additional substances, such as cross-linkers and branching agents.
  • the polymerisation temperature when may vary depending on, e.g., which monomers and polymerisation initiator are being used.
  • the polymerisation temperature is from about 30 to about 90°C, preferably from about 35 to about 70°C.
  • the process is suitably a semi-batch process, i.e., the monomers In 1 and m 2 are both present at the beginning of the polymerisation process and further added at a later stage, either in one or more portions or continuously over a period of time during the reaction.
  • the reaction mixture is suitably stirred during the polymerisation process at a stirring rate suitable for the process.
  • the stirring rate is from about 100 to about 1000 rpm.
  • the invention further comprises use of a polymer dispersion as retention and dewatering aid for paper manufacturing, as thickening agent, as soil improvement agent and/or as an additive for increasing the dry strength of paper.
  • the polymer dispersion of the present invention can more specifically be used as aid in various processes as, for example, flocculants when treating wastewater or aids in other solid-liquid separation processes in, for example, the metal-, ceramic-, printing-, biotechnological-, and pharmaceutical industries.
  • the polymer dispersion can also be used as thickener in, e.g., chemical- biotechnological-, pharmaceutical-, and cosmetic industries.
  • the present invention comprises a process for the production of paper from an aqueous suspension containing cellulosic fibres, and optional fillers, which comprises adding to the suspension an aqueous polymer dispersion according to the invention, forming and draining the suspension on a wire.
  • the dispersion is added to the suspension of cellulosic fibres, and optional fillers, to be dewatered in amounts which can vary within wide limits depending on, inter alia, type and number of components, type of furnish, filler content, type of filler, point of addition, etc.
  • the dispersed polymer is usually added in an amount of at least 0.001%, often at least 0.005% by weight, based on dry substance in the stock to be dewatered, and the upper limit is usually 3% and suitably 1.5% by weight.
  • the polymer dispersion according to the invention is suitably diluted before adding it to the cellulosic suspension.
  • Further additives which are conventional in papermaking can of course be used in combination with the polymer dispersion according to the invention, such as, for example, silica-based sols, dry strength agents, wet strength agents, optical brightening agents, dyes, sizing agents like rosin-based sizing agents and cellulose-reactive sizing agents, e.g.
  • the cellulosic suspension, or stock can also contain mineral fillers of conventional types such as, for example, kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, ground marble and precipitated calcium carbonate.
  • mineral fillers of conventional types such as, for example, kaolin, china clay, titanium dioxide, gypsum, talc and natural and synthetic calcium carbonates such as chalk, ground marble and precipitated calcium carbonate.
  • paper include not only paper and the production thereof, but also other cellulosic fibre-containing sheet or web-like products, such as for example board and paperboard, and the production thereof.
  • the process can be used in the production of paper from different types of suspensions of cellulose-containing fibres and the suspensions should suitably contain at least 25 % by weight and preferably at least 50 % by weight of such fibres, based on dry substance.
  • the suspension can be based on fibres from chemical pulp such as sulphate, sulphite and organosolv pulps, mechanical pulp such as thermo mechanical pulp, chemo-thermomechanical pulp, refiner pulp and groundwood pulp, from both hardwood and softwood, and can also be based on recycled fibres, optionally from de-inked pulps, and mixtures thereof.
  • a stabiliser made of methacrylic acid (MAA) and 2-acrylamido-2-methyl-1- propane sulphonic acid (AMPS) in a mole ratio of 80:20 was prepared: A mixture of 85g ultra-pure water, 8.24g AMPS (solid), 16.62g MAA and 11.5g NaOH (50%) was adjusted to pH 7 by means of NaOH (50%). 0.02g EDTA (solid) was given into the mixture. Further ultra-pure water was added to reach a total mass of 127g. This was filled into a double- wall 150ml glass reactor with anchor stirrer, nitrogen inlet, reflux condenser and bottom valve. The mixture was stirred with 150/min and purged with nitrogen. The reactor content was heated up to 45°C.
  • MAA methacrylic acid
  • AMPS 2-acrylamido-2-methyl-1- propane sulphonic acid
  • V-50 2,2'-Azobis-(2-amidinopropane) dihydrochloride
  • temperature was increased up to 50 0 C.
  • the mixture was polymerised over 72 h at 50°C and 150/min.
  • the stabiliser was purified and isolated by ultrafiltration and freeze-drying. The weight average molecular weight was about 15.000 g/mole.
  • a polymer dispersion was prepared by polymerising a monomer mixture comprising acrylamide and acrylic acid in the presence of a polymeric stabiliser and a polymeric co-stabiliser.
  • the process viscosity was low (lower than -2000 mPas) for all dispersions.
  • Example 8 The polymer dispersions prepared in Examples 2-4 were tested for retention and dewatering performance in papermaking processes by means of a Dynamic Drainage Analyser (DDA) available from Akribi, Sweden.
  • the furnish used was based on 60 % by weight of bleached 80/20 birch-pine pulp and 40 % by weight of calcium carbonate.
  • the stock volume was 800 ml, the pulp concentration 5 g/L and the conductivity 1.5 mS/cm.
  • the stock was stirred at a speed of 1500 rpm while the following was added to the stock: an anionic trash catcher (0.5 kg/t), polymer dispersion (1.0 kg/t) and finally anionic inorganic particles (0.5 kg/t).
  • the temperature was 22.5°C.
  • a vacuum of 0.35 bar was used for the analysis.
  • the retention time (s) and turbidity (NTU) was measured.
  • the shelf life measured as sedimentation stability, was tested for the dispersions according to Examples 2-7.
  • a 10 g sample of each dispersion was centrifuged for 30 minutes at 3000 rpm.
  • the amount of polymer sediment was determined for each sample. No sample gave any polymer sediment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Paper (AREA)
  • Polymerisation Methods In General (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne un procédé d'élaboration de dispersion de polymères par polymérisation d'au moins un monomère anionique hydrosoluble (m1) et d'au moins un monomère de vinyle non ionique (m2) présents dans un mélange de réaction comprenant également un stabilisant polymère (B) et un co-stabilisant polymère (C). L'invention concerne également une dispersion de polymères, l'utilisation de cette dispersion, et un procédé de production de papier.
EP06733482A 2005-05-20 2006-05-09 Procédé de polymerisation d'une dispersion de polymer et dispersion de polymère Withdrawn EP1881997A2 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP06733482A EP1881997A2 (fr) 2005-05-20 2006-05-09 Procédé de polymerisation d'une dispersion de polymer et dispersion de polymère

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP05445036 2005-05-20
EP06733482A EP1881997A2 (fr) 2005-05-20 2006-05-09 Procédé de polymerisation d'une dispersion de polymer et dispersion de polymère
PCT/SE2006/050112 WO2006123993A2 (fr) 2005-05-20 2006-05-09 Dispersion de polymeres et son procede d'elaboration

Publications (1)

Publication Number Publication Date
EP1881997A2 true EP1881997A2 (fr) 2008-01-30

Family

ID=34981217

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06733482A Withdrawn EP1881997A2 (fr) 2005-05-20 2006-05-09 Procédé de polymerisation d'une dispersion de polymer et dispersion de polymère

Country Status (12)

Country Link
EP (1) EP1881997A2 (fr)
JP (1) JP4799611B2 (fr)
KR (1) KR100923849B1 (fr)
CN (1) CN100558751C (fr)
AU (1) AU2006248161C1 (fr)
BR (1) BRPI0610071A2 (fr)
CA (1) CA2608408C (fr)
MX (1) MX276303B (fr)
NO (1) NO20076511L (fr)
RU (1) RU2394841C2 (fr)
WO (1) WO2006123993A2 (fr)
ZA (1) ZA200709250B (fr)

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WO2014148685A1 (fr) * 2013-03-20 2014-09-25 주식회사 송지이에프씨 Procédé de préparation d'un agent de couchage de papier respectueux de l'environnement faisant appel à une résine à base d'un polymère d'éthylène-acide (méth)acrylique hydrodispersable, et son utilisation
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CN114195933B (zh) * 2021-12-23 2022-12-30 诚达药业股份有限公司 纸张增厚剂制备方法及增厚纸张浆料制备方法

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Also Published As

Publication number Publication date
CA2608408A1 (fr) 2006-11-23
KR100923849B1 (ko) 2009-11-04
NO20076511L (no) 2008-02-20
RU2394841C2 (ru) 2010-07-20
ZA200709250B (en) 2009-02-25
MX2007013907A (es) 2008-03-25
KR20080012301A (ko) 2008-02-11
WO2006123993A2 (fr) 2006-11-23
BRPI0610071A2 (pt) 2010-05-25
WO2006123993A3 (fr) 2007-08-16
JP4799611B2 (ja) 2011-10-26
MX276303B (es) 2010-06-02
CN100558751C (zh) 2009-11-11
AU2006248161C1 (en) 2010-07-29
AU2006248161A1 (en) 2006-11-23
JP2008540796A (ja) 2008-11-20
AU2006248161B2 (en) 2010-02-18
RU2007147474A (ru) 2009-06-27
CA2608408C (fr) 2011-07-19
CN101180321A (zh) 2008-05-14

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