US20060149030A1 - Lactide and glycolide(co)polymerization catalytic system - Google Patents

Lactide and glycolide(co)polymerization catalytic system Download PDF

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Publication number
US20060149030A1
US20060149030A1 US10/541,735 US54173505A US2006149030A1 US 20060149030 A1 US20060149030 A1 US 20060149030A1 US 54173505 A US54173505 A US 54173505A US 2006149030 A1 US2006149030 A1 US 2006149030A1
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Prior art keywords
hydrogen
catalytic system
group
polymerization
alkyl
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US10/541,735
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English (en)
Inventor
Blanca Martin-Vaca
Anca Dumitrescu
Lidija Vranicar
Jean-Bernard Cazaux
Didier Bourissou
Roland Cherif-Cheikh
Frederic Lacombe
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Ipsen Pharma SAS
Centre National de la Recherche Scientifique CNRS
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Individual
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Assigned to CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (C.N.R.S.) reassignment CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (C.N.R.S.) ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CHERIF-CHEIKH, ROLAND, LACOMBE, FREDERIC, VRANICAR, LIDIJA, DUMITRESCU, ANCA, CAZAUX, JEAN-BERNARD, BOURISSOU, DIDIER, MARTIN-VACA, BLANCA
Publication of US20060149030A1 publication Critical patent/US20060149030A1/en
Priority to US12/316,328 priority Critical patent/US7999061B2/en
Assigned to CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (C.N.R.S.), SOCIETE DE CONSEULS DE RECHERCHES ET D'APPLICATIONS SCIENTIFIQUES (S.C.R.A.S.) reassignment CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE (C.N.R.S.) CORRECTIVE ASSIGNMENT TO CORRECT THE CORRECTIVE ASSIGNMENT TO ADD SECOND ASSIGNEE PREVIOUSLY RECORDED ON REEL 017511 FRAME 0958 PREVIOUSLY RECORDED ON REEL 017511 FRAME 0955. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNED TO BOTH (C.N.R.S.) AND (S.C.R.A.S.). Assignors: CHERIF-CHEIKH, ROLAND, LACOMBE, FREDERIC, VRANICAR, LIDIJA, DUMITRESCU, ANCA, CAZAUX, JEAN-BERNARD, BOURISSOU, DIDIER, MARTIN-VACA, BLANCA
Abandoned legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/81—Preparation processes using solvents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/87—Non-metals or inter-compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]

Definitions

  • the present invention relates to a catalytic lactide and glycolide (co)polymerization system, said system comprising a trifluoromethanesulfonate as a catalyst and a (co)polymerization additive.
  • the present invention also relates to a lactide and glycolide (co)polymerization process including the use of such a catalytic system.
  • the polymers concerned must meet a certain number of criteria and, in particular, they must be biocompatible.
  • the biodegradable character is an additional advantage if the polymer is to be eliminated after an appropriate implantation period in an organism.
  • the copolymers based on lactic and glycolic acid (PLGA) have a great advantage because they are sensitive to hydrolysis and are degraded in vivo with the release of non-toxic by-products.
  • the range of uses of PLGAs is vast ( Adv. Mater. 1996, 8, 305 and Chemosphere 2001, 43, 49). In the surgical field, they are used for the synthesis of multifilament threads, sutures, implants, prostheses etc. In pharmacology, they allow the encapsulation, transfer and controlled release of active ingredients.
  • the applicant therefore proposes a simple catalytic system, comprising a catalyst and a (co)polymerization additive, and which allows control of the chain length but also of the nature of the chain ends of the prepared (co)polymers.
  • the subject of the present invention is therefore a catalytic system comprising (a) a trifluoromethanesulfonate of general formula (1) in which
  • E′ 14 is an element of group 14;
  • T 14 , T′ 14 and T′′ 14 represent, independently, the hydrogen atom; the deuterium atom; one of the following substituted or non-substituted radicals: alkyl, cycloalkyl or aryl, and in which said substituent or substituents are chosen from: halo, hydroxy, alkyl, alkoxy, cycloalkyl, cycloalkoxy, aryl, aryloxy, carboxy, alkoxycarbonyl, cycloalkoxycarbonyl and aryloxycarbonyl.
  • halo signifies fluoro, chloro, bromo or iodo, and preferably chloro.
  • alkyl preferably represents a linear or branched alkyl radical having 1 to 6 carbon atoms and in particular an alkyl radical having 1 to 4 carbon atoms such as the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and ter-butyl radicals.
  • alkoxy designates the radicals in which the alkyl radical is as defined above such as for example the methoxy, ethoxy, propyloxy or isopropyloxy radicals but also linear, secondary or tertiary butoxy, pentyloxy.
  • alkoxycarbonyl preferably designates the radicals in which the alkoxy radical is as defined above such as for example methoxycarbonyl, ethoxycarbonyl.
  • the cycloalkyl radicals are chosen from the saturated or unsaturated monocyclic cycloalkyls.
  • the saturated monocyclic cycloalkyl radicals can be chosen from the radicals having 3 to 7 carbon atoms such as the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl radicals.
  • the unsaturated cycloalkyl radicals can be chosen from the cyclobutene, cyclopentene, cyclohexene, cyclopentadiene, cyclohexadiene radicals.
  • cycloalkoxy designates the radicals in which the cycloalkyl radical is as defined above such as for example the cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclobutenyloxy, cyclopentenyloxy, cyclohexenyloxy, cyclopentadienyloxy, cyclohexadienyloxy radicals.
  • cycloalkoxycarbonyl designates the radicals in which the cycloalkoxy radical is as defined above such as for example the cyclopropyloxycarbonyl, cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cycloheptyloxycarbonyl, cyclobutenyloxycarbonyl, cyclopentenyloxycarbonyl, cyclohexenyloxycarbonyl radicals.
  • the aryl radicals can be of mono- or polycyclic type.
  • the monocyclic aryl radicals can be chosen from the phenyl radicals optionally substituted by one or more alkyl radicals such as tolyl, xylyl, mesityl, cumenyl.
  • the polycyclic aryl radicals can be chosen from the naphthyl, anthryl, phenanthryl radicals.
  • aryloxy designates the radicals in which the aryl radical is as defined above such as for example the phenyloxy, tolyloxy, naphthyloxy, anthryloxy and phenanthryloxy radicals.
  • aryloxycarbonyl preferably designates the radicals in which the aryloxy radical is as defined above, such as for example phenyloxycarbonyl, tolyloxycarbonyl.
  • lactide and glycolide (co)polymerization signifies polymerization or copolymerization.
  • lactide and glycolide (co)polymerization covers lactide polymerization, glycolide polymerization but also lactide and glycolide copolymerization.
  • the quantity of the (co)polymerization additive with respect to the catalyst is comprised between 0.05 and 5 molar equivalents and, very preferably, between 0.5 and 2 molar equivalents.
  • a subject of the invention is more particularly a catalytic system as defined above, with a compound of formula (I) in which R 1 represents either a hydrogen atom or a group of formula -E 14 (R 14 )(R′ 14 )(R′′ 14 ).
  • R 1 represents the hydrogen atom and compound (1) thus represents trifluoromethanesulphonic acid.
  • R 1 represents a group of formula -E 14 (R 14 )(R′ 14 )(R′′ 14 ) in which E 14 is a carbon or silicon atom, very preferably E 14 is a carbon atom and R 14 , R′ 14 and R′′ 14 represent, independently, a hydrogen atom or an alkyl radical.
  • the (co)polymerization additive of formula (2) thus used acts as a (co)polymerization initiator (or co-initiator). Its presence is indispensable because in the absence of such a compound of formula (2), the (co)polymerization reactions are much slower, lead to much lower yields, are not reproducible, and therefore cannot be exploited industrially.
  • a more particular subject of the invention is a catalytic system as defined above, with a compound of general formula (2) in which
  • a more particular subject of the invention is a catalytic system as defined above and characterized in that the (co)polymerization additive of general formula (2) is water or an aliphatic alcohol.
  • the aliphatic alcohols there can be mentioned for example methanol, ethanol, n-propanol, isopropanol, n-butanol or pentan-1-ol.
  • the aliphatic alcohol is chosen from isopropanol and pentan-1-ol.
  • a subject of the invention is also a lactide and glycolide (co)polymerization process which consists of bringing together the monomer or monomers considered, a catalytic system as defined above comprising a compound of general formula (1) and a (co)polymerization additive of general formula (2), and optionally a polymerization solvent.
  • the lactide and glycolide (co)polymerization according to the invention is carried out by ring-opening (co)polymerization. Such a process can be carried out either in solution or in surfusion.
  • the reaction solvent can be the (or one of the) substrate(s) used in the catalytic reaction. Solvents which do not interfere with the catalytic reaction itself are also suitable.
  • the aromatic hydrocarbons such as toluene, a xylene or mesitylene
  • the aromatic hydrocarbons can be mentioned, optionally substituted by one or more nitro groups (such as nitrobenzene), ethers (such as methyltertbutylether, tetrahydrofuran or dioxane), aliphatic or aromatic halides (such as dichloromethane, chloroform, dichloroethane or a dichlorobenzene).
  • the reactions are carried out at temperatures comprised between ⁇ 20° C. and approximately 150° C.
  • the temperature is preferably comprised between 0° C. and 30° C.
  • the reaction times are comprised between a few minutes and 48 hours, and preferably between 30 minutes and 20 hours.
  • the quantity of the (co)polymerization additive with respect to the catalyst is preferably comprised between 0.05 and 5 molar equivalents and, very preferably, between 0.5 and 2 molar equivalents.
  • the yield of a (co)polymerization process according to the present invention is generally higher than 80% and can even reach 100% under relatively mild conditions (ambient temperature, a few hours) as illustrated in the examples.
  • a more particular subject of the invention is also a process as defined above, with a catalytic system as defined above which contains the compound of formula (1) in which R 1 represents either a hydrogen atom or a group of formula -E 14 (R 14 )(R′ 14 )(R′′ 14 ).
  • a subject of the invention is a process as defined above characterized in that R 1 represents the hydrogen atom, in this case, compound (1) represents trifluoromethanesulphonic acid.
  • R 1 represents a group of formula -E 14 (R 14 )(R′ 14 )(R′′ 14 ) in which E 14 is a carbon or silicon atom, and very preferably E 14 is a carbon atom and R 14 , R′ 14 , R′′ 14 represent a hydrogen atom or an alkyl radical.
  • a more particular subject of the invention is also a (co)polymerization process as defined above, with a catalytic system as defined above which contains the compound of general formula (2) in which
  • a more particular subject of the invention is a lactide and glycolide (co)polymerization process as defined above, with a catalytic system the (co)polymerization additive of which is either water or an aliphatic alcohol, and preferably the aliphatic alcohol is chosen from methanol, ethanol, propanol and butanol.
  • the lactide and glycolide (co)polymerization process according to the present invention therefore allows control of the nature of the (co)polymer chain ends and is particularly suitable for obtaining (co)polymers with acid-alcohol or ester-alcohol ends as illustrated in the experimental part.
  • the lactide and glycolide (co)polymerization process according to the present invention is also particularly well suited for obtaining (co)polymers of mass comprised between 500 and 50,000 Dalton, more particularly between 1,000 and 20,000 Dalton.
  • lactide and glycolide (co)polymerization process according to the present invention has numerous advantages, in particular,
  • the invention finally relates to lactide and glycolide polymers or copolymers which are obtained or are able to be obtained by implementing a process as described above.
  • Such (co)polymers can have controlled acid-alcohol or ester-alcohol ends.
  • Such (co)polymers can also be of low mass, with a mass comprised between 500 and 50,000 Dalton, and preferably between 1,000 and 20,000 Dalton.
  • GPC Gel Permeation Chromatography
  • the nature of the ester-alcohol chain ends is determined by mass spectrometry (electrospray ionization, detection in positive ion mode, sample dissolved in acetonitrile with a trace of ammonium hydroxide).
  • the polymer is characterized by proton NMR; the conversion of each of the monomers is greater than 95%.
  • the ratio of the signal integrals corresponding to the polylactide part (5.2 ppm) and polyglycolide part (4.85 ppm) allows the composition of the copolymer to be evaluated as 79% lactide and 21% glycolide.
  • GPC Gel Permeation Chromatography
  • PS polystyrene standards
  • the nature of the chain ends is determined by mass spectrometry (electrospray ionization, detection in positive ion mode, sample dissolved in acetonitrile with a trace of ammonium hydroxide).
  • GPC Gel Permeation Chromatography
  • the nature of the ester-alcohol chain ends is determined by mass spectrometry (electrospray ionization, detection in positive ion mode, sample dissolved in acetonitrile with a trace of ammonium hydroxide).
  • the ratio of the signal integrals corresponding to the polylactide part (5.2 ppm) and polyglycolide part (4.85 ppm) allows the composition of the copolymer to be evaluated as 80% lactide and 20% glycolide.
  • a GPC Gel Permeation Chromatography
  • PS polystyrene standards
  • the nature of the chain ends is determined by mass spectrometry (electrospray ionization, detection in positive ion mode, sample dissolved in acetonitrile with a trace of ammonium hydroxide).
  • the ratio of the signal integrals corresponding to the polylactide part (5.2 ppm) and polyglycolide part (4.85 ppm) allows the composition of the copolymer to be evaluated as 60% lactide and 40% glycolide.
  • a GPC Gel Permeation Chromatography
  • PS polystyrene standards
  • the nature of the chain ends is determined by mass spectrometry (electrospray ionization, detection in positive ion mode, sample dissolved in acetonitrile with a trace of ammonium hydroxide).

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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)
  • Polyesters Or Polycarbonates (AREA)
  • Biological Depolymerization Polymers (AREA)
US10/541,735 2003-01-21 2004-01-19 Lactide and glycolide(co)polymerization catalytic system Abandoned US20060149030A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/316,328 US7999061B2 (en) 2003-01-21 2008-12-11 Catalytic lactide and glycolide (co)polymerization system

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP03290134A EP1440992A1 (fr) 2003-01-21 2003-01-21 Système catalytique de (co)polymérisation du lactide et du glycolide
JP03290134.0 2003-01-21
PCT/FR2004/000100 WO2004067602A1 (fr) 2003-01-21 2004-01-19 Systeme catalytique de (co)polymerisation du lactide et du glycolide

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US12/316,328 Expired - Fee Related US7999061B2 (en) 2003-01-21 2008-12-11 Catalytic lactide and glycolide (co)polymerization system

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US (2) US20060149030A1 (fr)
EP (2) EP1440992A1 (fr)
JP (1) JP5268254B2 (fr)
KR (1) KR101074609B1 (fr)
CN (1) CN1329424C (fr)
AU (1) AU2004207648B2 (fr)
BR (1) BRPI0406517B1 (fr)
CA (1) CA2513594C (fr)
DK (1) DK1587851T3 (fr)
ES (1) ES2423411T3 (fr)
IS (1) IS2954B (fr)
MX (1) MXPA05007682A (fr)
NO (1) NO337440B1 (fr)
NZ (1) NZ540860A (fr)
PL (1) PL217078B1 (fr)
PT (1) PT1587851E (fr)
RU (1) RU2318836C2 (fr)
WO (1) WO2004067602A1 (fr)

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US20100121024A1 (en) * 2007-02-16 2010-05-13 Arkema France Method for producing a copolymer of at least one cyclic monomer
US20100121021A1 (en) * 2007-02-16 2010-05-13 Arkema France Process for the preparation of polylactones and polylactams
FR2967415A1 (fr) * 2010-11-15 2012-05-18 Ipsen Pharma Sas Procede de preparation de polymeres etoiles
EP2044251A4 (fr) * 2006-07-14 2013-05-29 Kimberly Clark Co Polyester aliphatique biodégradable destiné à être utilisé dans des tissus non tissés
WO2013087812A1 (fr) * 2011-12-15 2013-06-20 Total Research & Technology Feluy Procédé de préparation d'oligomères d'acide lactique fonctionnels définis
US20130317121A1 (en) * 2010-11-15 2013-11-28 Ipsen Pharma S.A.S. Method for the preparation of plymers with varied archtecture and amide initiation
CZ305046B6 (cs) * 2013-12-05 2015-04-08 Vysoké Učení Technické V Brně Způsob přípravy blokového kopolymeru
EP3482964A1 (fr) * 2017-11-13 2019-05-15 Mitsubishi HiTec Paper Europe GmbH Matériau d'enregistrement thermosensible à base de pla

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CN101445595B (zh) * 2008-12-26 2011-01-19 上海新上化高分子材料有限公司 聚乙丙交酯及其制备方法和应用
JP5858387B2 (ja) * 2011-02-02 2016-02-10 国立大学法人 名古屋工業大学 有機触媒によるポリエステル合成方法
CN107722250B (zh) * 2017-11-07 2019-07-12 青岛科技大学 一种二元催化体系的制备方法与应用
EP3603650A1 (fr) 2018-08-01 2020-02-05 Edix O Sarl Compositions injectables et a duree d'action prolongee pour leur utilisation dans le traitement de maladies de l'ongle et/ou pour accelerer la croissance de l'ongle
CN112888443A (zh) 2018-08-01 2021-06-01 爱迪克斯-欧有限公司 用于其在治疗指或趾甲疾病中的使用和/或用于加速指或趾甲生长的具有延长的作用持续时间的可注射组合物
RU2715383C1 (ru) * 2019-06-20 2020-02-27 Общество с ограниченной ответственностью "ТВС" Способ получения (со)полимера гликолида и/или лактида для изготовления рассасывающихся хирургических изделий
WO2023287478A1 (fr) * 2021-07-13 2023-01-19 Purdue Research Foudation Copolyester aliphatique de séquence sensiblement uniforme et son procédé de fabrication

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US9260802B2 (en) 2006-07-14 2016-02-16 Kimberly-Clark Worldwide, Inc. Biodegradable aliphatic polyester for use in nonwoven webs
EP2044251A4 (fr) * 2006-07-14 2013-05-29 Kimberly Clark Co Polyester aliphatique biodégradable destiné à être utilisé dans des tissus non tissés
US8609808B2 (en) 2006-07-14 2013-12-17 Kimberly-Clark Worldwide, Inc. Biodegradable aliphatic polyester for use in nonwoven webs
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ES2423411T3 (es) 2013-09-20
CA2513594A1 (fr) 2004-08-12
HK1088913A1 (en) 2006-11-17
CA2513594C (fr) 2012-09-11
RU2005126414A (ru) 2006-03-20
NO20052806L (no) 2005-07-06
PL217078B1 (pl) 2014-06-30
AU2004207648B2 (en) 2009-11-12
BRPI0406517B1 (pt) 2016-09-27
RU2318836C2 (ru) 2008-03-10
WO2004067602A1 (fr) 2004-08-12
PT1587851E (pt) 2013-07-18
MXPA05007682A (es) 2005-09-30
EP1440992A1 (fr) 2004-07-28
PL376506A1 (en) 2005-12-27
JP2006515899A (ja) 2006-06-08
NO337440B1 (no) 2016-04-11
CN1738846A (zh) 2006-02-22
US20090171066A1 (en) 2009-07-02
IS7968A (is) 2005-08-02
BRPI0406517A (pt) 2005-12-20
EP1587851B1 (fr) 2013-05-22
NZ540860A (en) 2008-11-28
EP1587851A1 (fr) 2005-10-26
AU2004207648A1 (en) 2004-08-12
IS2954B (is) 2016-11-15
DK1587851T3 (da) 2013-08-26
KR20050113174A (ko) 2005-12-01
KR101074609B1 (ko) 2011-10-17
CN1329424C (zh) 2007-08-01
US7999061B2 (en) 2011-08-16
JP5268254B2 (ja) 2013-08-21

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