Classifications

• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J15/00—Arrangements of devices for treating smoke or fumes
  • F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
  • F23J15/022—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow
  • F23J15/025—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material for removing solid particulate material from the gasflow using filters
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
  • D01D5/00—Formation of filaments, threads, or the like
  • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
  • D01D5/30—Conjugate filaments; Spinnerette packs therefor
  • D01D5/36—Matrix structure; Spinnerette packs therefor
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/66—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers
  • D01F6/665—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyethers from polyetherketones, e.g. PEEK
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/96—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from other synthetic polymers
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/16—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one other macromolecular compound obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds as constituent
• • D—TEXTILES; PAPER
  • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
  • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
  • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
  • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
  • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
  • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
  • B01D2239/0216—Bicomponent or multicomponent fibres
  • B01D2239/0233—Island-in-sea
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
  • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
  • B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
  • B01D2253/20—Organic adsorbents
  • B01D2253/202—Polymeric adsorbents
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
  • F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES 
  • F23J2217/00—Intercepting solids
  • F23J2217/10—Intercepting solids by filters
  • F23J2217/101—Baghouse type

Definitions

• the present invention relates to fibers made of certain polymers, filter assemblies incorporating such fibers, and systems incorporating such filter assemblies.
• DESCRIPTION OF THE RELATED ART Polymers can be manufactured into different forms, such as, for example, pellets, powders, strips, tubes, films, and fluids.
• fibers provide the preferred form.
• poly(phenylene sulphide) fibers are commonly used as part of filter systems in the coal- fired power generation industry.
• Polyethylene (PE) fibers, polyimide (PI) fibers, polytetrafluoroethylene (PTFE) fibers, aromatic polyamides fibers, and glass fibers are also used in various applications, including air pollution control systems. Different fibers are used for different applications, depending on the environment, including the temperature and acidity levels of the application.
• Flue gas contains carbon dioxide, nitrogen, oxygen, fly ash, and water vapor, as well as other substances such as nitrogen oxides, sulfur oxides, hydrofluoric acid (HF), hydrochloric acid (HCl), sulfurous acid, nitric acid, sulfuric acid, mercury, sulfur nitrate (SNO 3 ), low levels of uranium, thorium, and other naturally-occurring radioactive isotopes and many other toxic substances are also produced during the combustion of coal.
• Flue gas contains typically well above 5 vol. % of CO 2 , very often above 10 vol. % of CO 2 , and often 12.5 vol. % CO 2 or more.
• Flue gas contains typically well above 150 ppm of NO, very often above 300 ppm of NO and often at least 400 ppm of NO. Flue gas contains typically well above 150 ppm of NO x , very often above 300 ppm of NO x and often at least 400 ppm of NO x (x being an integer >1).
• Cement plants cause similar environmental impacts to the ones associated with coal-burning power generation plants since they also generally use coal as primary fuel.
• a first aspect of the present invention relates to a new fiber (F) made with a polymer material (P) that has not previously been fiber- formed.
• the present invention also relates to a new fabric incorporating fibers (F) not previously incorporated into fabrics.
• the present invention also relates to a new filter assembly incorporating such fabrics.
• the present invention further relates to a system, such as a filtration system in a coal-fired power generation plant, incorporating such filter assemblies.
• the fiber (F) can include an amorphous sulfone polymer and/or a semi-crystalline polymer.
• the fiber (F) can comprise at least one polymer material (P) selected from the group consisting of : poly(aryl ether ketone)s, including polyetheretherketones ; blends composed of at least one poly(aryletherketone) and at least one poly(aryl ether sulfone), in particular blends composed of at least one poly(etheretherketone) and at least one poly(biphenyl ether sulfone) such as polyphenylsulfone ; poly(biphenyl ether sulfone)s, including polyphenylsulfones ; poly(aryl ether sulfone)s other than poly(biphenyl ether sulfone)s, including polyethersulfones and polyetherethersulfones ; polyamide-imides ; polyarylenes, including
• the fiber (F) comprises the polymer material (P) in a weight amount of generally above 10 %, preferably above 50 %, more preferably above 80 %, still more preferably above 95 %, based on the total weight of the fiber (F).
• the fiber (F) consists essentially of, or even consists of, the polymer material (P).
• the fiber (F) can also further comprise notably any engineering polymer (P*) other than the polymer(s) of the polymer material (P) and/or any conventional ingredient of engineering polymer compositions, including but not limited to ingredients selected from the group consisting of : heat stabilizers, anti-static agents, extenders, organic and/or inorganic pigments like TiO 2 , carbon black, acid scavengers, such as MgO, stabilizers, metal oxides and sulphides such as zinc oxide and zinc sulphide, metal carboxylates such as alkaline-earth and transition metal stearates, antioxidants, flame retardants, smoke- suppressing agents, particulate fillers and nucleating agents such as talc, mica, titanium dioxide, kaolin, and blends thereof.
• the weight of the said conventional ingredients, based on the total weight of the fiber (F), ranges advantageously from
• the fiber (F) according to the present invention can be incorporated into a fabric. Accordingly, another aspect of the present invention is directed to a fabric comprising a plurality of fibers identical to the fiber (F) as above described.
• the fabric may comprise the plurality of fibers identical to the fiber (F) in a weight amount of above 1 %, 2 %, 5 %, 10 %, 20 %, 30 %, 50 %, 75 %, 90 % or 95 %, based on the total weight of the fabric ; the fabric may consist essentially of, or even consists of, the plurality of fibers identical to the fiber (F) ; the fabric may comprise the plurality of fibers identical to the fiber (F) in a weight amount of less than 99 %, 98 %, 95 %, 90 %, 80 %, 70 %, 50 %, 25 %, 10 % or 5 %, based on the total weight of the fabric.
• the fabric When the fabric is incorporated into a filter assembly, it comprises the plurality of fibers identical to the fiber (F) in a weight amount of generally above 10 %, preferably above 50 %, more preferably above 80 %, still more preferably above 95 %, based on the total weight of the fabric.
• the fabric may further comprise other conventional ingredients of fabrics, such as fibers other than the fiber (F).
• Non limitative examples of such fibers include : glass fibers ; asbestos fibers ; organic fibers formed from high temperature engineered resins like poly(benzothiazole) fibers, poly(benzimidazole) fibers, poly(benzoxazole) fibers, polyarylether fibers and aramide fibers ; carbon fibers ; PTFE fibers ; boron fibers (e.g. obtained by deposition of boron microgranules on a tungsten or carbonate yarn) ; metal fibers ; ceramic fibers like silicon nitride Si3N4 ; talc-glass fibers ; calcium silicate fibers like wollastonite micro-fibers ; silicon carbide fibers ; metal borides fibers (e.g.
• the carbon fibers can be obtained notably by heat treatment and pyrolysis of different polymeric precursors such as, for example, rayon, polyacrylonitrile (PAN), aromatic polyamide or phenolic resin ; other carbon fibers useful for the present invention can be obtained from pitchy materials.
• the term "graphite fiber” intends to denote carbon fibers obtained by high temperature pyrolysis (over 2000 0 C) of carbon fibers, wherein the carbon atoms place in a way similar to the graphite structure.
• Certain carbon fibers useful for the present invention are chosen from the group composed of PAN based carbon fibers, pitch based carbon fibers, graphite fibers, and mixtures thereof.
• the fabric may be used notably in textile industry and aerospace, automotive, medical, military, safety, chemical, pharmaceutical and metallurgical industries.
• the fabric can be incorporated into different devices and systems.
• the fabric can be incorporated into a filter assembly.
• still another aspect of the present invention is directed to a filter assembly comprising a frame ; and a fabric mounted on said frame, wherein said fabric comprises a plurality of fibers identical to the fiber (F) as above described.
• the filter assembly can be used for numerous applications, including but not limited to filter assemblies for industrial plants, such as electric power plants and cement plants. Accordingly, still another aspect of the present invention is directed to a filtration system comprising a plurality of filter assemblies, at least one of them being the filter assembly as above described ; possibly, each filter assembly is as above described.
• Figure 1 is a diagram illustrating a non-limiting embodiment of a filter assembly including fibers (F) according to the present invention
• Figure 2 is a diagram illustrating a non-limiting embodiment of a filtration system (baghouse) including filter assemblies including fibers (F) according to the present invention.
• the fibers (F) according to the present invention include fibers comprising at least one polymer material (P) that has not previously been fiber-formed. Some of these polymer materials (P) are known in other forms.
• poly(aryl ether ketone)s include polyetheretherketones ; blends composed of at least one poly(aryl ether ketone) and at least one poly(aryl ether sulfone), in particular blends composed of at least one poly(etheretherketone) and at least one poly(biphenyl ether sulfone) such as polyphenylsulfone ; poly(biphenyl ether sulfone)s, including polyphenylsulfones ; poly(aryl ether sulfone)s other than poly(biphenyl ether sulfone)s, including polyethersulfones and polyetherethersulfones ; polyamide-imides ; polyarylenes, including kinked rigid-rod polyphenylenes ; poly(imide sulfone)s ; blends composed of at least one poly(arylene sulphide)
• the term “blend” refers to a physical combination of two or more different polymers, in contrast with “copolymers”, where two or more different polymers are chemically linked to each other so as to form blocky structures and/or where polymerized recurring units of two or more different types are randomly distributed in a polymer chain.
• the different polymer components of the blend are diffused to some extent among each other inside the fiber (F), and, often, they are diffused intimately inside the fiber so that their individuality in the fiber is obscured.
• polymer material denotes indifferently a single polymer, or a blend composed of two or more polymers, as above defined.
• the fibers (F) according to the present invention can also further comprise one or more polymers (P*) other than those above listed.
• the weight ratio of polymer (P*) and of polymer material (P) [(P*):(P)] ranges usually from 0 to 5, preferably from 0 to less than 1.00, more preferably from 0 to 0.30 and still more preferably from 0 to 0.10.
• the fiber (F) is essentially free, or even is free, of polymer (P*).
• poly(aryl ether ketone) is intended to denote any polymer of which more than 50 wt. % of the recurring units are recurring units (Rl) of one ore more of the following formulae :
• - Ar is independently a divalent aromatic radical selected from phenylene, biphenylene or naphthylene,
• - n is an integer of from 0 to 3
• - b, c, d and e are 0 or 1
• d is 0 when b is 1.
• recurring units (Rl) are of the formula :
• a polyetheretherketone is intended to denote any polymer of which more than 50 wt. % of the recurring units are recurring units (Rl) of formula (VI).
• the poly(aryl ether ketone) is a polyetheretherketone homopolymer, i.e. a polymer of which essentially all, if not all, the recurring units are of formula (VI).
• VICTREX ® 150 P, VICTREX ® 380 P, VICTREX ® 450 P and VICTREX ® 90 P from Victrex Manufacturing Ltd., VESTAKEEP ® PEEK from Degussa, and KETASPIRETM and GATONE ® PEEK from Solvay Advanced Polymers, L.L.C. are examples of polyetheretherketone homopolymers.
• poly(biphenyl ether sulfone) is intended to denote any polymer, generally a polycondensate, of which more than 50 wt. % of the recurring units are recurring units (R2) of one or more formulae containing at least one p-biphenylene group : least one ether group (-O-) and at least one sulfone group (-SO 2 -).
• recurring units (R2) are recurring units of one or more formulae of the general type :
• Ri through R 4 are -O-, -SO 2 -, -S-, -CO-, with the proviso that at least one of Ri through R 4 is -SO 2 - and at least one of Ri through R 4 is -O- ;
• Ar 1 , Ar 2 and Ar 3 are arylene groups containing 6 to 24 carbon atoms, and are preferably phenylene or p-biphenylene ; and a and b are either 0 or 1.
• recurring units (R2) are more preferably of one or more of the following formulae :
• a polyphenylsulfone is intended to denote any polycondensation polymer of which more than 50 wt. % of the recurring units are recurring units (R2) of formula (IX).
• the poly(biphenyl ether sulfone) may be notably a homopolymer, a random, alternating or block copolymer.
• its recurring units (R2) may be a mix composed of recurring units of two or more distinct formulae, such as a mix composed of recurring units of formula (VIII) and recurring units of formula (X)
• the weight amount of the recurring units (VIII) contained in said mix is between 10 % and 99 %, preferably between 50 % and 95 % and more preferably between 75 % and 95 %.
• poly(biphenyl ether sulfone) when the poly(biphenyl ether sulfone) is a copolymer, its recurring units may also be notably composed of (i) recurring units (R2) of formula (IX) and recurring units (R2*), different from recurring units (R2), such as :
• the recurring units of the poly(biphenyl ether sulfone) are recurring units (R2).
• the poly(biphenyl ether sulfone) is a polyphenylsulfone homopolymer, i.e. a polymer of which essentially all, if not all, the recurring units are of formula (IX).
• RADEL ® R polyphenylsulfone from Solvay Advanced Polymers, L.L.C. is an example of a polyphenylsulfone homopolymer.
• the poly(biphenyl ether sulfone) is a homopolymer, i.e. a polymer of which essentially all, if not all, the recurring units are of formula (VIII).
• the poly(biphenyl ether sulfone) is a copolymer essentially all, if not all, the recurring units are a mix composed of recurring units of formula (VIII) and recurring units of formula (X), wherein the weight amount of the recurring units (VIII), based on the total amount of the recurring units (VIII) and (X) of which the mix consists, is between 50 % and 95 %, and preferably between 75 % and 95 %.
• EPISPIRE ® poly(biphenyl ether sulfone)s commercially available from Solvay Advanced Polymers, L.L.C, are examples of such copolymers. The polvCaryl ether sulfone).
• the poly(aryl ether sulfone) comprises above 50 wt. %, more preferably above 90 wt. % of recurring units (R3). Still more preferably, the poly(aryl ether sulfone) contains recurring units (R3) as sole recurring units. Unless otherwise specified, the poly(aryl ether sulfone) may be the poly(biphenyl ether sulfone) as previously described, such as the polyphenylsulfone as previously described.
• the poly(aryl ether sulfone)s may be chosen from polyethersulfones, poly etherethersulf ones and bisphenol A polysulfones.
• Blends composed of at least one poly(biphenyl ether sulfone) and at least one poly(aryl ether sulfone) s other than a poly(biphenyl ether sulfone) can also be used.
• the poly(aryl ether sulfone) is a polyethersulfone.
• a polyethersulfone is intended to denote any polymer of which more than 50 wt. % of the recurring units are recurring units (R4) of formula (XI) :
• the polyethersulfone may be notably a homopolymer, or a copolymer such as a random or a block copolymer.
• a copolymer such as a random or a block copolymer.
• its recurring units are advantageously a mix of recurring units (R6) and of recurring units (R6*), different from recurring units (R6), such as :
• the polyethersulfone is a homopolymer, i.e. essentially all, if not all, the recurring units of polyethersulfone are recurring units of formula (XI), or it is a copolymer essentially all, if not all, the recurring units of which are a mix composed of recurring units of formula (XI) and recurring units of formula (XII), wherein the weight amount of the recurring units (XI), based on the total amount of the recurring units (XI) and (XII) of which the mix consists, is above 50 %. More preferably, the polyethersulfone is a homopolymer essentially all, if not all, the recurring units of polyethersulfone are recurring units of formula (XI).
• Certain polyethersulfones are commercially available from SOLVAY ADVANCED POLYMERS, L.L.C. as RADEL ® A.
• the poly(aryl ether sulfone) is a polyetherethersulfone.
• a polyetherethersulfone is intended to denote any polymer of which more than 50 wt. % of the recurring units are recurring units (R5) of formula (XII)
• the polyetherethersulfone may be notably a homopolymer, or a copolymer such as a random or a block copolymer.
• the poly(aryl ether sulfone) is a bisphenol A polysulfone.
• a bisphenol A polysulfone is intended to denote any polymer of which more than 50 wt. % of the recurring units are recurring units (R6) of formula (XIII) :
• the bisphenol A polysulfone may comprise more than 75 wt. % or 90 wt. % of recurring units of formula (XIII).
• the bisphenol A polysulfone may be a homopolymer, i.e. a polymer essentially all, if not all, the recurring units of which are of formula (XIII), or it may be a copolymer such as a random or a block copolymer.
• its recurring units are advantageously a mix of recurring units (R4) and of recurring units (R4*), different from recurring units (R4), such as :
• the bisphenol A polysulfone is a homopolymer.
• Bisphenol A polysulfones are commercially available notably from SOLVAY ADVANCED POLYMERS, L.L.C. as UDEL ® .
• Blends composed of at least one poly(aryl ether ketone) and at least one poly(aryl ether sulfone)
• blends (B) With respect to blends composed of at least one poly(aryl ether ketone) and at least one poly(aryl ether sulfone), hereinafter referred to as blends (B) : the poly(aryl ether ketone) contained in the blend (B) meets advantageously all the characteristics of the poly(aryl ether ketone) s as above described, at any level of preference ; in particular, it is preferably, a polyetheretherketone ; the poly(aryl ether sulfone) contained in the blend (B) meets advantageously all the characteristics of the poly(aryl ether sulfone) as above described, at any level of preference ; it may be chosen from poly(aryl ether sulfone)s other than poly(biphenyl ether sulfone)s, although it is preferably a poly(biphenyl ether sulfone) ; the case being, the said poly(biphenyl ether sulfone)
• the weight of the poly(aryl ether ketone) plus the weight of the poly(aryl ether sulfone)] is advantageoulsy of at least 15 %, preferably at least 25 %, more preferably at least 35 %, still more preferably at least 40 %, and most preferably at least 45 % ; besides, the weight of the poly(aryl ether ketone), based on the total weight of the blend (B) is advantageously of at most 90 %, preferably at most 80 %, and still more preferably at most 70 % ; in certain embodiments, it is of at most 55 % ; in certain other embodiments, it is above 55 %, and possibly of at least 60 %.
• an "aromatic polyamide-imide” is intended to denote any polymer comprising of which more than 50 wt. % of the recurring units are recurring units (R7) comprising at least one aromatic ring, at least one imide group, as such and/or in its amic acid form, and at least one amide group which is not included in the amic acid form of an imide group.
• the aromatic polyamide-imide comprises more than 90 wt. % of recurring units (R7). More preferably, it contains no recurring unit other than recurring units (R7).
• the recurring units (R7) are advantageously of formula (XIV) :
• n 0,1,2,3,4 or 5.
• Recurring units (R7) are preferably chosen from :
• Recurring units (R7) are very preferably a mixture of recurring units (XVI) and (XVII). Excellent results are obtained with aromatic polyamide-imides consisting essentially all, if not all, the recurring units of which are a mix of recurring units (XVI) and (XVII).
• Polymers commercialized by Solvay Advanced Polymers as TORLON ® polyamide-imides comply with this criterion.
• an arylene group is a hydrocarbon divalent group consisting of one core composed of one benzenic ring or of a plurality of benzenic rings fused together by sharing two or more neighboring ring carbon atoms, and of two ends.
• Non limitative examples of arylene groups are phenylenes, naphthylenes, and anthrylenes.
• the arylene groups (especially the numbering of the ring carbon atoms) were named in accordance with the recommendations of the CRC Handbook of Chemistry and Physics, 64 th edition, pages C1-C44, especially p. Cl 1-C12.
• Arylene groups present usually a certain level of aromaticity ; for this reason, they are often reported as "aromatic" groups.
• the level of aromaticity of the arylene groups depends on the nature of the arylene group ; as thoroughly explained in Chem. Rev. 2003, 103, 3449-3605, "Aromaticity of Polycyclic Conjugated Hydrocarbons", the level of aromaticity of a polycyclic aromatic hydrocarbon can be notably quantified by the "index of benzene character" B, as defined on p. 3531 of the same paper ; values of B for a large set of polycyclic aromatic hydrocarbon are reported on table 40, same page.
• An end of an arylene group is a free electron of a carbon atom contained in a (or the) benzenic ring of the arylene group, wherein an hydrogen atom linked to said carbon atom has been removed.
• Each end of an arylene group is capable of forming a linkage with another chemical group.
• An end of an arylene group, or more precisely the linkage capable of being formed by said end can be characterized by a direction and by a sense ; to the purpose of the present invention, the sense of the end of an arylene group is defined as going from the inside of the core of the arylene group to the outside of said core.
• the ends of which have the same direction such ends can be either of the same or opposite sense ; also, their ends can be in the straight foregoing of each other, or not (otherwise said, they can be disjoint).
• a polyarylene is intended to denote any polymer of which more than 25 wt. % of the recurring units are recurring units (R8) of one or more formulae consisting of an optionally substituted arylene group, provided said optionally substituted arylene group is linked by each of its two ends to two other optionally substituted arylene groups via a direct C-C linkage.
• arylene groups of which the recurring units (R8) consist can be unsubstituted. Alternatively, they can be substituted by at least one monovalent substituting group.
• the monovalent substituting group is usually not polymeric in nature ; its molecular weight is preferably below 300.
• the monovalent substituting group is advantageously a solubilizing group.
• a solubilizing group is one increasing the solubility of the polyarylene in at least one organic solvent, in particular in at least one of dimethylformamide, N-methylpyrrolidinone, hexamethylphosphoric triamide, benzene, tetrahydrofuran and dimethoxyethane, which can be used as solvents during the synthesis of the polyarylene by a solution polymerization process.
• the monovalent substituting group is also advantageously a group which increases the fusibility of the polyarylene, i.e. it lowers its glass transition temperature and its melt viscosity, so as to desirably make the polyarylene suitable for thermoprocessing.
• the core of the optionally substituted arylene group of the recurring units (R8) is composed of preferably at most 3, and more preferably of one benzenic ring. Then, when the core of the optionally substituted arylene group of the recurring units (R8) is composed of one benzenic ring, the recurring units (R8) are of one or more formulae consisting of an optionally substituted phenylene group, provided said optionally substituted phenylene group is linked by each of its two ends to two other optionally substituted arylene groups via a direct C-C linkage.
• the optionally substituted arylene group of the recurring units (R8) is linked by each of its two ends to two other optionally substituted arylene groups via a direct C-C linkage.
• it is linked by each of its two ends to two other optionally substituted phenylene groups via a direct C-C linkage.
• both ends of the optionally substituted arylene group of the recurring units (R8) can be characterized notably by a direction and by a sense.
• a first set of recurring units suitable as recurring units (R8) is composed of optionally substituted arylene groups, the ends of which - have the same direction,
• Non limitative examples of such optionally substituted arylene groups include : 1,4-phenylene (also named p-phenylene)
• 1,4-phenanthrylene and 2,7-phenanthrylene and any of these groups substituted by at least one monovalent substituting group, as above defined, in particular by a phenylketone group.
• a second set of recurring units suitable as recurring (R8) is composed of optionally substituted arylene groups, the ends of which - either have a different direction, forming thus together an angle between 0 and 180°, said angle being possibly acute or obtuse,
• a first subset of recurring units (R8-b) suitable as recurring units (R8) is composed of optionally substituted arylene groups, the ends of which have a different direction, forming together an acute angle [recurring units (R8-bl)].
• optionally substituted arylene groups the ends of which have a direction different from each other, include :
• a second subset of recurring units (R8-b) suitable as recurring units (R8) is composed of optionally substituted arylene groups, the ends of which have a different direction, forming together an obtuse angle [recurring units (R8-b2)].
• optionally substituted arylene groups the ends of which have a direction different from each other, include :
• a third subset of recurring units (R8-b) is composed of optionally substituted arylene groups, the ends of which have the same direction and the same sense [recurring units (R8-b3)].
• optionally substituted arylene groups the ends of which the same direction and the same sense include :
• a fourth subset of recurring units (R8-b) is composed of optionally substituted arylene groups, the ends of which have the same direction, are of opposite sense and are disjoint [recurring units (R8-b4)].
• optionally substituted arylene groups include :
• recurring units (R8-b) are chosen from recurring units (R8-bl), recurring units (R8-b2) and recurring units (R8-b4). More preferably, recurring units (R8-b) are chosen from recurring units (R8-bl) and recurring units (R8-b2). Still more preferably, recurring units (R8-b) are chosen from recurring units (R8-bl). Good results were obtained when recurring units (R8-b) are optionally substituted m-phenylenes.
• Recurring units (R8-b) when contained in the polyarylene, result in more or less kinked polymer chains, exhibiting a higher solubility and fusibility than straight polymer chains. For this reason, such polyarylenes are commonly referred to as "kinked polymers".
• Recurring units (R8) are preferably chosen from :
• Choice (B) is generally more preferred than choice A.
• Recurring units of choice (A) are recurring units (R8-a) which are substituted by at least one monovalent substituting group. Said recurring units are preferably p-phenylenes substituted by at least one monovalent substituting group.
• Recurring units of choice (B) are a mix of recurring units (R8-a), which can be substituted or not by at least one monovalent substituting group, with recurring units (R8-b), which can be substituted or not by at least one monovalent substituting group.
• R8-a recurring units
• R8-b recurring units
• the recurring units of choice (B) are preferably a mix (MB) of recurring units (R8-a) chosen from optionally substituted p-phenylenes, with recurring units (R8-b) chosen from (i) optionally substituted m-phenylenes and (ii) mixes of optionally substituted m-phenylenes with optionally substituted o-phenylenes.
• the mole ratio of the recurring units (R8-b), based on the total number of moles of the recurring units (R8-a) and (R8-b), is usually of at least 1 %, preferably at least 20 %, more preferably at least 40 %.
• the mole ratio of the recurring units (R8-b), based on the total number of moles of the recurring units (R8-a) and (R8-b), is usually of at most 99 %, preferably at most 80 %, and more preferably at most 60 %. Good results were obtained when the recurring units of choice (B) were a mix of p-phenylene substituted by a phenylketone group with unsubstituted m-phenylene, in a mole ratio of about 50:50.
• the polyarylene may be notably a homopolymer, a random, alternating or block copolymer.
• the polyarylene may further comprise recurring units (R8*), different from recurring units (R8).
• Certain recurring units (R8*) contain at least one strong divalent electron withdrawing group linked on each of its ends to an arylene group, in particular a p-phenylene group.
• Preferably more than 90 wt. % of the recurring units of the polyarylene are recurring units (R8). More preferably, essentially all, if not all, the recurring units of the polyarylene are recurring units (R8).
• Excellent results are obtained when the polyarylene is a polypheny lene copolymer, essentially all, if not all, the recurring units of which consist of a mix of p-phenylene substituted by a phenylketone group with unsubstituted m-phenylene in a mole ratio p-phenylene:m-phenylene of from 5:95 to 95:5, preferably of from 70:30 to 30:70, more preferably of from 60:40 to 40:60, and still more preferably of about 50:50.
• Polyphenylene copolymers essentially all, if not all, the recurring units of which consist of a mix of p-phenylene substituted by a phenylketone group with unsubstituted m-phenylene in a mole ratio p-phenylene:m-phenylene of from 5:95 to 95:5 are commercially available from SOLVAY ADVANCED POLYMERS, L.L.C. as PRIMOSPIRE ® PR- 120 polyphenylene, and as PRIMOSPIRE ® PR-250 polyphenylene. Outstanding results are obtained with PRIMOSPIRE ® PR-250.
• a poly(imide sulfone) is intended to denote imide-containing, sulfone-containing polymer comprising structural units (R9) having the general formula (XVIII) :
• V is a tetravalent linker without limitation, as long as the linker does not impede synthesis or use of the poly(imide sulfone) ; and R in formula (XVIII) is a substituted or unsubstituted divalent organic radical wothout limitation, as long as the divalent organic radical does not impede synthesis or use of the poly(imide sulfone).
• the poly(imide sulfone) comprises generally above 5 wt. %, preferably above 50 wt. %, and more preferably above 90 wt. % of structural units (R9), based on the total weight of the poly(imide sulfone). Most of poly(imide sulfone)s represent a particular class of poly(aryl ether sulfone)s as above defined.
• the a poly(imide sulfone) is a poly(imide sulfone) homopolymer, i.e. essentially all, if not all, the structural units of the poly(imide sulfone) are structural units (R9).
• the number of structural units (R9) (hereinafter, "a") per polymer chain is, by essence, above 1 ; it is typically from about 10 to about 1000 or more, and preferably from about 10 to about 500.
• Suitable linkers include but are not limited to : (a) substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic or polycyclic groups having about 5 to about 50 carbon atoms, (b) substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl groups having 1 to about 30 carbon atoms ; or mixtures thereof.
• Preferred linkers include but are not limited to tetravalent aromatic radicals, such as
• R in formula (XVIII) includes but is not limited to substituted or unsubstituted divalent organic radicals such as : (a) aromatic hydrocarbon radicals having about 6 to about 20 carbon atoms and halogenated derivatives thereof ; (b) straight or branched chain alkylene radicals having about 2 to about 20 carbon atoms ; (c) cycloalkylene radicals having about 3 to about 20 carbon atoms, or (d) divalent radicals of the general formula (XIX) :
• Q includes but is not limited to a divalent moiety selected from the group consisting of-O-,-S-,-C (O)-, -SO 2 -, -C y H 2y - (y being an integer from 1 to 5) such as -C(CH 3 ) 2 , and halogenated derivatives thereof, including perfluoroalkylene groups.
• R is essentially free of benzylic hydrogens.
• the poly(imide sulfone) is a polyetherimide sulfone and R also contains aryl sulfone and/or aryl ether linkages such that at least 50 mole % of the repeat units of any polyetherimide sulfone contain at least one aryl ether linkage, at least one aryl sulfone linkage and at least two aryl imide linkages.
• R 3 is selected from the group consisting of halogen, fluoro, chloro, bromo, C 1-32 alkyl, cycloalkyl, or alkenyl ; C 1-32 alkoxy or alkenyloxy ; or cyano, and "q” has a value of 0-3. In some particular embodiments the value of "q” is zero ; and wherein “D” is a divalent aromatic group derived from a dihydroxy substituted aromatic hydrocarbon, and has the general formula (XX) :
• a 1 represents an aromatic group including, but not limited to, phenylene, biphenylene, naphthylene, etc.
• "E” may be an alkylene or alkylidene group including, but not limited to, methylene, ethylene, ethylidene, propylene, propylidene, isopropylidene, butylene, butylidene, isobutylidene, amylene, amylidene, isoamylidene, etc.
• E when “E” is an alkylene or alkylidene group, it may also consist of two or more alkylene or alkylidene groups connected by a moiety different from alkylene or alkylidene, including, but not limited to, an aromatic linkage ; a tertiary nitrogen linkage ; an ether linkage ; a carbonyl linkage ; a silicon-containing linkage, silane, siloxy ; or a sulfur-containing linkage including, but not limited to, sulphide, sulfoxide, sulfone, etc. ; or a phosphorus-containing linkage including, but not limited to, phosphinyl, phosphonyl, etc.
• E may be a cycloaliphatic group non- limiting examples of which include cyclopentylidene, cyclohexylidene, 3, 3,5- trimethylcyclohexylidene, methylcyclohexylidene, bicyclo [2.2. 1] hept-2-ylidene, 1,7, 7-trimethylbicyclo [2.2.
• hept-2-ylidene isopropylidene, neopentylidene, cyclopentadecylidene, cyclododecylidene, and adamantylidene ; a sulfur-containing linkage, including, but not limited to, sulphide, sulfoxide or sulfone ; a phosphorus- containing linkage, including, but not limited to, phosphinyl or phosphonyl ; an ether linkage ; a carbonyl group ; a tertiary nitrogen group ; or a silicon-containing linkage including, but not limited to, silane or siloxy.
• a sulfur-containing linkage including, but not limited to, sulphide, sulfoxide or sulfone
• a phosphorus- containing linkage including, but not limited to, phosphinyl or phosphonyl
• an ether linkage ; a carbonyl group
• R 4 independently at each occurrence comprises a monovalent hydrocarbon group including, but not limited to, alkenyl, allyl, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl.
• the dihaloalkylidene group is a dichloroalkylidene, particularly gem-dichloroalkylidene group.
• Y 1 independently at each occurrence may be an inorganic atom including, but not limited to, halogen (fluorine, bromine, chlorine) ; an inorganic group containing more than one inorganic atom including, but not limited to, nitro ; an organic group including, but not limited to, a monovalent hydrocarbon group including, but not limited to, alkenyl, allyl, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl, or an oxy group including, but not limited to, OR 5 wherein R 5 is a monovalent hydrocarbon group including, but not limited to, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl ; it being only necessary that Y 1 be inert to and unaffected by the reactants and reaction conditions used to prepare the polymer
• Y 1 comprises a halo group or C 1 -C 6 alkyl group.
• the letter “m” represents any integer from and including zero through the number of replaceable hydrogens on A available for substitution ;
• "p” represents an integer from and including zero through the number of replaceable hydrogens on E available for substitution ;
• "t” represents an integer equal to at least one ;
• "s” represents an integer equal to either zero or one ;
• "u” represents any integer including zero.
• "u” is an integer with a value of from 0 to about 5.
• D when more than one Y 1 substituent is present, they may be the same or different. The same holds true for the R'substituent.
• both A 1 radicals are unsubstituted phenylene radicals ; and E is an alkylidene group such as isopropylidene.
• both Al radicals are p-phenylene, although both may be o-or m-phenylene or one o-or m-phenylene and the other p- phenylene.
• E may be an unsaturated alkylidene group.
• Suitable dihydroxy- substituted aromatic hydrocarbons of this type include those of the formula (XXI) :
• each Z is hydrogen, chlorine or bromine, subject to the provision that at least one Z is chlorine or bromine.
• Suitable dihydroxy- substituted aromatic hydrocarbons also include those of the formula (XXII) :
• dihydroxy- substituted aromatic hydrocarbons that may be used include, but are not limited to, bis (4-hydroxyphenyl) sulphide, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, 1,4-dihydroxybenzene, 4,4'-oxydiphenol, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 4, 4'- (3, 3,5- trimethylcyclohexylidene) diphenol ; 4,4'-bis (3,5-dimethyl) diphenol, 1,1-bis (4- hydroxy-3-methylphenyl) cyclohexane ; 4,4-bis (4-hydroxyphenyl) heptane ; 2, 4'--
• the dihydroxy- substituted aromatic hydrocarbon comprises bisphenol A.
• the moiety "E" when the moiety "E" is an alkylene or alkylidene group, it may be part of one or more fused rings attached to one or more aromatic groups bearing one hydroxy substituent.
• Suitable dihydroxy- substituted aromatic hydrocarbons of this type include those containing indane structural units such as 3- (4-hydroxyphenyl)-l, 1, 3- trimethylindan-5-ol and 1- (4-hydroxyphenyl)-l, 3, 3-trimethylindan-5-ol.
• suitable dihydroxy- substituted aromatic hydrocarbons of the type comprising one or more alkylene or alkylidene groups as part of fused rings are the 2,2, 2', 2'-tetrahydro-l, l'-spirobi [lH-indene] diols, illustrative examples of which include 2,2, 2', 2'-tetrahydro-3,3, 3', 3'-tetramethyl-l, l'-spirobi [lH-indene]-6, 6'-diol (sometimes known as "SBI" ).
• Mixtures comprising any of the foregoing dihydroxy- substituted aromatic hydrocarbons may also be employed.
• Preferred poly(imide sulfone) resins are polyetherimide sulfone resins comprising more than 1, typically about 10 to about 1000 or more, and more preferably about 10 to about 500 structural units, of the formula (XXIII)
• a polyetherimide sulfone may be a copolymer, which, in addition to the etherimide units described above, further contains polyimide structural units of the formula (XXIV)
• R is as previously defined for formula (XVIII) and M includes, but is not limited to, radicals of one or more formulae : ⁇ Jir s ⁇ md
• Thermoplastic poly(imide sulfone)s of the invention can be derived from reactants comprising one or more aromatic diamines or their chemically equivalent derivatives and one or more aromatic tetracarboxylic acid cyclic dianhydrides (sometimes referred to hereinafter as aromatic dianhydrides), aromatic tetracarboxylic acids, or their derivatives capable of forming cyclic anhydrides.
• aromatic dianhydrides sometimes referred to hereinafter as aromatic dianhydrides
• aromatic tetracarboxylic acids or their derivatives capable of forming cyclic anhydrides.
• at least a portion of one or the other of or at least a portion of each of the reactants comprising aromatic diamines and aromatic dianhydrides comprises a sulfone linkage.
• all of one or the other of or each of the reactants comprising aromatic diamines and aromatic dianhydrides comprises a sulfone linkage.
• the reactants react to form polymers comprising cyclic imide linkages and sulfone linkages.
• aromatic dianhydrides comprise : 4,4'-bis (3,4- dicarboxyphenoxy) diphenyl sulfone dianhydride ; 4,4'-bis (2,3- dicarboxyphenoxy) diphenyl sulfone dianhydride ; 4- (2,3-dicarboxyphenoxy)-4'- (3, 4- dicarboxyphenoxy) diphenyl sulfone dianhydride and mixtures thereof.
• aromatic dianhydrides comprise : 2,2-bis (4- (3, 4- dicarboxyphenoxy) phenyl) propane dianhydride ; 4,4'-bis (3,4- dicarboxyphenoxy) diphenyl ether dianhydride ; 4,4'-bis (3,4- dicarboxyphenoxy) diphenyl sulphide dianhydride ; 4,4'-bis (3,4- dicarboxyphenoxy) benzophenone dianhydride ; 2,2-bis ( [4- (2, 3- dicarboxyphenoxy) phenyl] propane dianhydride ; 4,4'-bis (2,3- dicarboxyphenoxy) diphenyl ether dianhydride ; 4,4'-bis (2,3- dicarboxyphenoxy) diphenyl sulphide dianhydride dianhydride ; 4,4'-bis (2,3- dicarboxyphenoxy) benzophenone dianhydride ; 2- [4- (3, 4-dicarboxyphenoxy) phenyl
• the aromatic dianhydride employed in the synthesis of the poly(imide sulfone) composition comprises an aromatic bis (ether anhydride) composition comprising at least about 90 mole % 2,2-bis [4- (3, 4-dicarboxyphenoxy) phenyl] propane dianhydride, or at least about 95 mole % 2,2-bis [4- (3, 4-dicarboxyphenoxy) phenyl] propane dianhydride based on total moles dianhydride present.
• this particular aromatic bis (ether anhydride) composition is referred to as bisphenol A dianhydride or "BPADA".
• preferred aromatic dianhydrides are bisphenol A dianhydride, pyromellitic dianhydride, biphenyltetracarboxylic acid dianhydride, oxydiphthalic anhydride and mixtures thereof.
• suitable aromatic diamines comprise a divalent organic radical selected from aromatic hydrocarbon radicals having 6 to about 24 carbon atoms and substituted derivatives thereof.
• said aromatic hydrocarbon radicals may be monocyclic, polycyclic or fused.
• suitable aromatic diamines comprise divalent aromatic hydrocarbon radicals of the general formula (XXV)
• y is an integer from 1 to 5 inclusive.
• y has the value of one or two.
• Illustrative linking groups include, but are not limited to, methylene, ethylene, ethylidene, vinylidene, halogen- substituted vinylidene, and isopropylidene.
• the unassigned positional isomer about the aromatic ring in formula (XXV) is para to Q.
• the two amino groups in aromatic diamines are separated by at least two and sometimes by at least three ring carbon atoms.
• aromatic diamines comprise aromatic hydrocarbon radicals including, but not limited to, phenyl, biphenyl, naphthyl, bis (phenyl) -2, 2-propane, and their substituted derivatives.
• substituents include one or more halogen groups, such as fluoro, chloro, or bromo, or mixtures thereof ; or one or more straight-chain-, branched-, or cycloalkyl groups having from 1 to 22 carbon atoms, such as methyl, tert-butyl, or mixtures thereof.
• substituents for aromatic hydrocarbon radicals when present, are selected from the group consisting of halogens, chloro, ethers, sulfones, perfluoroalkyl, methyl, t-butyl and mixtures thereof. In other particular embodiments said aromatic hydrocarbon radicals are unsubstituted.
• suitable aromatic diamines comprise meta- phenylenediamine ; para-phenylenediamine ; mixtures of meta-and para- phenylenediamine ; isomeric 2-methyl-and 5-methyl-4, 6-diethyl-l, 3-phenylene- diamines or their mixtures ; bis (4-aminophenyl)-2, 2-propane ; bis (2-chloro-4-amino-3,5-diethylphenyl) methane, 4,4'-diaminodiphenyl, 3,4'- diaminodiphenyl, 4, 4'-diaminodiphenyl ether (sometimes referred to as 4, 4'- oxydianiline) ; 3, 4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4, 4'- diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone
• diamines may also be employed.
• the most preferred diamines are meta- and para-phenylene diamines, 4,4'- diaminodiphenyl sulfone and oxydianiline.
• the preferred aromatic diamines are free of benzylic hydrogens and also contain aryl sulfone linkages.
• Diaminodiphenyl sulfone (DDS), bis (aminophenoxy phenyl) sulfones (BAPS) and mixtures thereof are particularly preferred aromatic diamines.
• the sulfone groups contained in the poly(imide sulfone) are generally contained in tetravalent linker V and/or in the divalent radical R.
• a first suitable tetravalent linker V including a sulfone group is
• W is an -O-D-0-group, wherein D is
• Still another suitable tetravalent linker V including a sulfone group is wherein R 3 is selected from the group consisting of halogen, fluoro, chloro, bromo, C-32 alkyl, cycloalkyl, or alkenyl ; Cl-32 alkoxy or alkenyloxy ; or cyano, and "q" has a value of 0-3 ; wherein "D” is a divalent aromatic group derived from a dihydroxy substituted aromatic hydrocarbon, and has the general formula :
• E consists of two or more alkylene or alkylidene groups connected by sulfone moiety, or E is a sulfone linkage ;
• a 1 represents an aromatic group including, but not limited to, phenylene, biphenylene, naphthylene, etc.
• R 4 independently at each occurrence comprises a monovalent hydrocarbon group including, but not limited to, alkenyl, allyl, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl ;
• Y 1 independently at each occurrence may be an inorganic atom including, but not limited to, halogen (fluorine, bromine, chlorine) ; an inorganic group containing more than one inorganic atom including, but not limited to, nitro ; an organic group including, but not limited to, a monovalent hydrocarbon group including, but not limited to, alkenyl, allyl, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl, or an oxy group including, but not limited to, OR 5 wherein R 5 is a monovalent hydrocarbon group including, but not limited to, alkyl, aryl, aralkyl, alkaryl, or cycloalkyl ; it being only necessary that Y 1 be inert to and unaffected by the reactants and reaction conditions used to prepare the polymer ; - the letter "m” represents any integer from and including zero through the number of replaceable hydrogens on A available for substitution ; "p" represents an integer from and including
• a suitable divalent radical R including a sulfone group is
• the divalent radical R contains a sulfone group, and more preferably the divalent radical R is
• the tetravalent linker V is preferably free of sulfone group.
• Blends composed of at least one poly(arylene sulphide) and at least one poly(aryl ether sulfone)
• blends composed of at least one poly(arylene sulphide) and at least one poly(aryl ether sulfone), hereinafter referred to as blends (B2) :
• the poly(aryl ether sulfone) contained in the blend (B2) meets advantageously all the characteristics of the poly(aryl ether sulfone) as above described, at any level of preference ; it may be chosen from poly(aryl ether sulfone)s other than poly(biphenyl ether sulfone)s, although it is preferably a poly(biphenyl ether sulfone) ; the case being, the said poly(biphenyl ether sulfone) meets advantageously all the characteristics of the poly(biphenyl ether sulfone)s as above described, at any level of preference ; - the weight of the poly(arylene sulphide), based on the total weight of the blend (B2) [i.e.
• the weight of the poly(arylene sulphide) plus the weight of the poly(aryl ether sulfone) may be of at least 10 %, 20 %, 30 %, 40 %, 50 %, 60 %, 70 %, 80 % or 90 % ; besides, the weight of the poly(arylene sulphide), based on the total weight of the blend (B2), may be of at most 90 %, 80 %, 70 %, 60 %, 50 %, 40 %, 30 %, 20 % or 10 %.
• a poly(arylene sulphide) is intended to a polymer other than a poly(aryl ether sulfone) as above defined, of which more than 5 wt. % of the recurring units are recurring units (RlO) of one or more formula of the general type :
• Ar* group denotes an optionally substituted arylene group, such a phenylene or a naphthylene group, which is linked by each of its two ends to two sulphur atoms forming sulphide groups via a direct C-S linkage.
• Preferred recurring units Ar* are optionally substituted p-phenylene (resulting in recurring
• the optionally substituted arylene group Ar* may be unsubstituted, which is often preferred.
• the optionally substituted arylene group Ar* may be substituted by one or more substituting groups, including but not limited to halogen atoms, Ci-Ci 2 alkyls, C 7 -C 24 alkylaryls, C 7 -C 24 aralkyls, C ⁇ -Cig aryls, Ci-Ci 2 alkoxy groups, and C ⁇ -Cig aryloxy groups, and substituted or unsubstituted arylene sulphide groups themselves, the arylene groups of which are also linked by each of their two ends to two sulphur atoms forming sulphide groups via a direct C-S linkage, like in :
• the poly(arylene sulphide) contains preferably more than 25 wt. % ; more preferably more than 50 wt. %, and still more preferably more than 90 wt. % of recurring units (RlO). Most preferably, it contains no recurring unit other than (RlO).
• a preferred poly(arylene sulphide) is poly(phenylene sulphide), i.e., a polymer other than a poly(aryl ether sulfone) as above defined, of which more than 5 wt.
• % of the recurring units are recurring units (Rl 1) of one or more formula of the general type : - pPh* - S - (XXVII) wherein the pPh* group denotes an optionally substituted p-phenylene group which is linked by each of its two ends to two sulphur atoms forming sulphide groups via a direct C-S linkage.
• pPh* may be unsubstituted, which is often preferred.
• pPh* may be substituted by one or more substituting groups, including but not limited to halogen atoms, Ci-Ci 2 alkyls (resulting in substituted units (RIl) like
• C7-C24 alkylaryls C 7 -C 24 aralkyls, C ⁇ -Ci8 aryls, C1-C12 alkoxy groups, C ⁇ -Ci8 aryloxy groups, and substituted or unsubstituted arylene sulphide groups themselves (possibly, substituted or unsubstituted p-phenylene sulphide groups themselves), the arylene groups of which are also linked by each of their two ends to two sulphur atoms forming sulphide groups via a direct C-S linkage, such as :
• the polyphenylene sulphide contains preferably more than 25 wt. % ; more preferably more than 50 wt. %, and still more preferably more than 90 wt. % of recurring units (RIl).
• the poly(arylene sulphide), in particular the poly(phenylene sulphide), may further comprise recurring units (RlO*) other than recurring units (RlO) ; non limitative examples of recurring units (RlO*) are those recurring units capable of being formed by the reaction between Na 2 S and a dihalocompound of general formula Cl-Ar°-D-Ar°-Cl through the elimination of the chlorine atoms from the dihalocompound : Na 2 S + Cl - Ar 0 - D - Ar 0 - Cl -> - Ar 0 - D - Ar 0 - S - recurring unit of formula (XXVIII) wherein Ar 0 is an optionally substituted arylene group and D may be any diradical other than sulphide (- S - ) or than a sulphide-diterminated diradical (- S - D'- S -, where D' may be any diradical).
• RlO* recurring
• Both fragments - Ar 0 - S - of the recurring units (RlO*) of formula (XXVIII) differ from a recurrring unit (RlO) in that none of the optionally substituted groups Ar 0 is linked by each of its two ends to two sulphur atoms forming sulphide groups via a direct C-S linkage, at least one end of each arylene group Ar 0 being linked to D as above defined.
• Non limitative examples of recurring units (RlO*) include :
• diradical D is respectively an oxy, sulfonyl or carbonyl diradical.
• the poly(arylene sulphide) contains no recurring unit other than recurring units (RlO). Very good results are obtained when the poly(arylene sulphide) is a poly(phenylene sulphide) which contains no recurring unit other than recurring units (Rl 1). Excellent results can be obtained when the poly(arylene sulphide) is a poly(phenylene sulphide) which contains no recurring unit other than unsubstituted p-phenylene recurring units.
• the molecular weight of the poly(arylene sulphide) may vary within wide measures.
• melt index of the poly(arylene sulphide) is between 5 g/10 min and 10,000 g/10 min, preferably between 10 g/10 min and 500 g/10 min (determined according to ASTM D 1238-74 T at a temperature of 315 0 C under a 5-kg load).
• Poly(arylene sulphide)s are commercially available from sources such as Chevron Phillips Chemical Company, Fortron Industries, and GE Plastics. Commercial grades of poly(arylene sulphide)s include PRIMEF ® , RYTON ® , FORTRON ® , and SUPEC ® poly(phenylene sulphide)s. As above explained, poly(arylene sulphide)s may be in the form of a linear polymer, a branched polymer and/or a cross-linked polymer.
• Poly(arylene sulphide)s may be prepared according to those procedures generally known in the art. Processes for their manufacture which can be employed according to the invention are well known. For example, a process that includes heating an alkali metal sulphide, in most cases a sodium sulphide hydrate, in a polar solvent in order to remove the water of hydration, followed by the addition of a dihalogenated aromatic compound, in particular p-dichlorobenzene, and polymerization at higher temperature (see, for example, U.S. patent no. 3,354,129 incorporated herein by reference in its entirety). Blends composed of at least one polvfbiphenyl ether sulfone) and at least one polv(aryl ether sulfone) other than a polv(biphenyl ether sulfone)
• blends composed of at least one poly(biphenyl ether sulfone) and at least one poly(aryl ether sulfone) other than a poly(biphenyl ether sulfone), hereinafter referred to as blends (B 3) : - the poly(biphenyl ether sulfone) contained in the blend (B3) meets advantageously all the characteristics of the poly(biphenyl ether sulfone)s as above described, at any level of preference ;
• the poly(aryl ether sulfone) other than a poly(biphenyl ether sulfone) contained in the blend (B3) meets advantageously all the characteristics of the poly(aryl ether sulfone)s as above described, at any level of preference, with the proviso that it differs from a poly(aryl ether sulfone) ; it may be notably a polysulfone, a polyethersulfone or a polyetherethersulfone ;
• the weight of the poly(biphenyl ether sulfone), based on the total weight of the blend (B3) [i.e. based on the weight of the poly(biphenyl ether sulfone) plus the weight of the poly(aryl ether sulfone) other than a poly(biphenyl ether sulfone)], may be of at least 10 %, 20 %, 30 %, 40 %, 50 %, 60 %, 70 %, 80 % or 90 % ; besides, it may be of at most 90 %, 80 %, 70 %, 60 %, 50 %, 40 %, 30 %, 20 % or 10 % - preferred blends are those composed of poly(biphenyl ether sulfone) and polysulfone, poly(biphenyl ether sulfone) and polyethersulfones, poly(biphenyl ether sulfone) and poly
• the fibers according to the present invention can be made with a melt- spinning method.
• pellets (or a powder) of polymer materials (P) can be pre-dried.
• the pellets are then fed into an extruder.
• the extruded polymer material (P) is melted and the melted polymer material (P) is passed through die holes.
• the strands of fibers can be pulled from the die holes using for example a series of rollers.
• the pulled strands can then be rolled on a reel.
• the viscosity, strength and extensibility of the strands can be controlled by varying different parameters, such as the level of additives in the polymer material (P), the polymer molecular weight, molecular weight distribution and molecular architecture.
• melt-spin process works particularly well for resins that can be readily melt processed in general, and will lend themselves to melt spinning.
• polymer materials (P) that are melt-spun are relatively clean (free of contaminants such as gels, black specs, char, etc).
• polyethersulfones such as RADEL ® A
• polyphenylsulfones such as RADEL ® R
• polymer materials such as AVASPIRE ®
• polyamide-imides such as TORLON ®
• polyphenylenes such as PRIMOSPIRE ®
• polyetheretherketones such as KETASPIRE ®
• a system for manufacturing the fibers according to the present invention can include an extruder, for example a 1.5" diameter extruder.
• the extruder can feed two melt pumps, each feeding a die with clusters of die holes.
• each melt pump can feed two clusters of 20 die holes, each 0.8 mm in diameter.
• the strands of fibers can be pulled by a set of rollers.
• the pulling linear velocity of the initial set of rollers can be for example about 600 m/min.
• Successive sets of rollers can further pull the strand, for example by increasing the pulling linear velocity for each successive set of rollers.
• the forth set of rollers can have a pulling linear velocity of about 900 m/min.
• the pulled strands can then be rolled on a high speed reel.
• the fibers according to the present invention are not limited to the above method and system.
• This solvent-based method provides the advantage of not requiring elevated temperature to melt the polymer material (P).
• This method may be well suited for polymer materials (P) that are relatively difficult to handle and/or that react to heat.
• the solvent process can work particularly well for polyamide-imides such as TORLON ® grades and polyarylenes such as PRIMOSPIRE ® polyphenylenes .
• This method can also work well for resins that have been chemically activated for which the active groups might be lost in a thermal environment. Therefore, solution spinning can accommodate materials that cannot withstand the temperatures needed to melt.
• a surface active fiber i.e., providing active chemistry on its surface
• fiber including a hydroxyl, amine, siloxane etc type of active group can be manufactured with a solution spinning method.
• solution spinning can be used to manufacture a fiber including both materials.
• the melt-spinning method provides a fluid polymer material (P) without the use of a solvent, which can be beneficial because solvents can require additional steps in order to comply with environmental concerns.
• the fibers according to the present invention can also be made using a spun-bond process.
• Spun-bonded fabrics are nonwoven fabrics formed by filaments which have been extruded drawn, then laid down on a continuous belt. Bonding can be accomplished by several methods such as hot-calendering or by passing the web through a saturated steam chamber at elevated temperature.
• a spun fabric is a fabric made from staple fibers which may contain one or a mixture of two or more fiber types.
• a spun-laced fabric is a nonwoven fabric produced by entangling fibers in a repeating pattern to form a strong fabric free of binders.
• a staple can be made up of natural fibers or cut lengths of fiber from filaments. The staple length can vary from less than one inch to several feet.
• Man-made staple fibers can be cut to a definite length so that they can be processed in spinning systems.
• the term staple is used in the textile industry to distinguish cut fiber from filaments.
• Melt blown can be thought of as molten resin forced thru small orifices and 'blown' down onto a substrate or conveyor belt. This can be done in a random way making a nonwoven or felt-like swatch of material.
• the fibers according to the present invention can have any number of profiles, including but not limited to, lobes, stripes, segments, etc.
• the fibers can also be made with one resin, two resins, or multiple resins.
• one resin can form the core of the fiber and another resin can form the shell of the fiber.
• the fibers according to the present invention can produce fibers within a very broad range in diameter, with a number average diameter generally from as low as 1 nm to as high as 100 ⁇ m.
• the fibers according to the present invention may be notably nanofibers, i.e.
• the fibers according to the present invention may also be microfibers, i.e. fibers the number average diameter of which is of at least 1 ⁇ m (1000 nm) ; microfibers may have a number average diameter of at least 2, 4, 8 or 12 ⁇ m ; microfibers may have a number average diameter of at most 50, 30 or 20 ⁇ m.
• preferred fibers have a number average diameter ranging froml2 to 20 ⁇ m.
• the number average length of the fibers according to the present invention is advantageously of at least 10 cm, preferably of at least 25 mm and more preferably of at least 50 mm. Fibers with a number average length of at least 50 mm have a good filtration efficiency.
• the number average length of the fibers according to the present invention is not particularly restricted. It can be of at most 100, 200 or 500 mm, but it can also be much higher as it is the case with continuous fibers. Still other diameters and lengths are possible.
• strands (e.g., 600) of one polymer material (P) can be formed in a matrix of a polymer material (P2) different from polymer material (P), all totaling a few microns in number average diameter (often, at least 2.0 ⁇ m), e.g., 10 ⁇ m.
• P2 polymer material
• Such a technique is sometimes referred to as the "islands in the sea” technique. If the matrix polymer material (P2) is washed away (e.g. it is disssolved by a solvent), one can obtain as many nanofibers as the number of strands formed in the matrix (here, 600 nanofibers).
• the fibers according to the present invention can have diameters from nanometers to millimeters and can be very short to reels in length.
• a fiber is a unit of material which forms the basic element of fabrics or textile structures.
• the fibers according to the present invention can have a number average length at least 10, 100, 1,000 or, in certain instances, even 10,000 times its number average diameter.
• the fibers according to the present invention can have different cross-sectional profiles, such as circular, oval, star-like, core/shell, etc.
• the Applicant is of the opinion that, in certain embodiments of the present invention, non-circular fiber profiles of the fibers, in particular the star-like profile, are preferred, because they provide enhanced filtration capabilities.
• the fibers according to the present invention can have a waviness (or crimps per unit length) taking different values, for example, 11-12 crimps/inch. Other crimp values are possible. Description of the filter assemblies incorporating the fibers
• FIG. 1 is a diagram illustrating a non-limiting embodiment of a filter assemby 100 including fibers 110 according to the present invention.
• the filter assembly 100 includes a filtering fabric
• the filtering fabric can be felt, or non- woven, fabric, as well as woven fabric, made from the fibers 110.
• the filter assembly 100 can filter particulates from a particulate laden gas as the gas passes through each filter assembly 100.
• Each filter assembly 100 can be supported at its upper end by a flange 140 coupled to a tube sheet 250 of the filtration system 200 (Fig. 2) and can hang downwardly in a substantially vertical direction.
• the flange 140 can bear the weight of the filter assembly 100 when attached to the tube sheet 250.
• the flange is made from a suitable material, such as stamped, drawn or otherwise formed metal.
• the length of the filter assembly 100 can vary, for example from a few centimeters to a few meters.
• the filter assemblies 100 can be connected in series.
• the filter assemblies 100 can be modules of a filtration system made of several filter assemblies.
• the filter assembly 100 is preferably open on both ends.
• the filter assembly 100 can be closed at one or both ends.
• the filter assembly 100 can have any suitable configuration cross- section, such as for example circular, oval or square.
• the filtering fabric 120 can be mounted on a frame 130 configured to support the filtering fabric 120 in a radial direction.
• the frame 130 can include support rings sewn into the filtering fabric 120.
• the frame 130 can include a support cage or a perforated tube on which the filtering fabric 120 is mounted.
• the support rings 130 and/or the support cage and/or the tube can be made of metal, perforated sheet metal, expanded metal or mesh screen, or other suitable materials.
• the support rings, tube and/or cage can be coupled to the flange 140.
• the filtering fabric 120 can be formed in a substantially tubular shape.
• the filtering fabric 120 includes a pleaded element with accordion folds at its inner and outer peripheries.
• the filtering fabric 120 can be attached to the flange and/or support rings/cage/tube, for example via a potting material.
• the filter assembly 100 can be incorporated, for example, in a filtration system, or baghouse, of any manufacturing or production plant that needs to control and/or clean its emission, such as a coal-fired power generation plant or a cement plant.
• the filter assembly 100 could replace the presently used filter assemblies comprising poly(phenylene sulphide) fibers.
• the fibers 110 according to the present invention can thus provide an alternative source of material to address the limited supply of conventional materials used in industrial filter assemblies, which need to be periodically replaced.
• the fibers 110 can also provide a filter assembly 100 that can sustain high operating temperatures and acidic environments.
• the fibers 110 can be made from poly(biphenyl ether sulfone)s ; in particular, the fibers 110 can be made from polyphenylsulfones (such as RADEL ® R) and from poly(biphenyl ether sulfone) homo- and copolymers including recurring units of formula (VIII) (such as EPISPIRE ® ). Fibers made from poly(biphenyl ether sulfone) s proved unexpectedly to be particularly beneficial notably because they can provide a much stronger resistance to oxydation compared to poly(phenylene sulphide) fibers.
• poly(biphenyl ether sulfone)s proved unexpectedly to be particularly beneficial notably because they can provide a much stronger resistance to oxydation compared to poly(phenylene sulphide) fibers.
• Fibers made from poly(biphenyl ether sulfone)s also presented a higher resistance to hydrolysis.
• the filter assembly 100 including filters made from poly(biphenyl ether sulfone) s can offer a number of benefits for industrial filter assemblies.
• poly(biphenyl ether sulfone)s fibers 110 since they do not breakdown oxidatively, improve the longevity of the filter assembly 100, which does not clog up as quickly and need not be replaced as frequently.
• the filter assembly 100 can operate at higher temperatures, thus providing improved operational efficiencies of the overall unit.
• the filter assembly 100 can be operated through more shaker cycles thereby extending the filter assembly life.
• the physical attributes of the fibers 110 provide new and improved design options allowing for even further filtration improvements.
• Fibers made out of poly(imide sulfone)s, of bisphenol A polysulfones such as UDEL ® , of polyethersulfones such as RADEL ® A and of blends of a poly(biphenyl ether sulfone) and a poly(aryl ether ketone) [in particular blends of a polyphenylsulfone and a polyetheretherketone] are also advantageous because they are of such chemical compositions that they have also great oxidative stability and resistance to hydrolysis compared to PPS fibers.
• fibers made out of a poly(biphenyl ether sulfone) and a poly(aryl ether ketone), in particular fibers comprising a polyphenylsulfone and a polyetheretherketone, are also advantageous because they are less costly and can provide similar characteristics to fibers made of polyetheretherketones only.
• fibers made from certain particular poly(aryl ether sulfone) s namely those including recurring units that can be obtained by the polycondensation reaction between (i) 4,4'-dihydroxy-diphenylsulfone and/or 4-4'-diamino-diphenylsulfone on one hand, and (ii) at least one dihalocompound and/or an aromatic tetracarboxylic acid cyclic dianhydride on the other hand.
• polyethersulfones poly(biphenyl ether sulfone) s which are comprised of recurring units of formula (VIII), and poly(imide sulfone) s which are comprised of structural units (R9) of formula
• V is a tetravalent linker
• Fibers made out of polyarylenes provide surprisingly an outstanding resistance to oxydation, and also excellent mechanical and thermal properties ; among them, fibers made of kinked rigid-rod polyarylenes with a high amount of kink forming recurring units (such as PRIMOSPIRE PR-250 polyphenylene) prove unexpectedly to be more easily spun compared to fibers made of other polyarylenes. Description of the systems incorporating the filter assemblies
• FIG. 2 is a diagram illustrating a non-limiting embodiment of a filtration system (or scrubber system, or baghouse) 200 including filter assemblies 100 with fibers 110 according to the present invention.
• This filtration system 200 can be incorporated in a coal-fired power generation plant or in a processing plant, such as a rock and/or cement plants ad steel and/or coke mills.
• the filtration system 200 includes a gas inlet 210, in which flu gas to be filtered is inserted. The gas is then passed through multiple filter assemblies (or filter bags) 220.
• Each of the filter assemblies 220 can be similar to the filter assemblies 100 with filtering fabric 120 shown in Fig. 1, but other configurations are possible.
• the filter assemblies 220 include a fabric made of fibers, such as fibers 110 made according to the present invention.
• the filter assemblies 220 can be attached to the tube sheet 250 via their flanges.
• the filter assemblies 220 can hang vertically inside the unit and can be held in place by clamps, snapbands or hold- downs.
• the filter assemblies 220 can trap various components from the gas, including sulfur dioxide, SO 3 , CO2, mercury, nitrogen dioxide, and other pollution molecules and combustion residues.
• the filter assemblies 220 can trap these components mechanically and/or chemically, for example via a surface active fiber.
• the filtered gas then exits the filtration system 200 via gas outlet 290.
• the filter assemblies 220 can function in a high temperature environment, for example around 375 0 F, and in an acidic environment (e.g., in the presence of sulfuric acid) for an extended amount of time (e.g., three or more years). During this time, the filter assemblies 220 can be regularly cleaned, or discharged of debris, via some type of agitation system, such as a pulse jet, a shaker system, reverse air or some mixture thereof.
• the filtration system 200 can include a pulse jet system 260 configured to generate a blast of compressed air, which is injected into the top of the opening of the filter assemblies 220. The air can be supplied from a blowpipe which feeds into venturies located above the filter assembly.
• a filtration system 200 can include thousands of such filter assemblies 220.
• a filtration system 200 can include 10,000 filter assemblies 220, representing thousands of pounds of fibers.
• the fibers 110 can be non-woven, or woven. This fabric can be incorporated in articles used in the textile industry and aerospace, automotive, medical, military and safety industries.
• the fibers 110 can be incorporated in flame resistant materials.
• the fibers 110 can be incorporated in fire blocking felts, gaskets, hoses, belts, ropes.
• the fibers 110 can be incorporated in rechargeable battery separators.
• the fibers 110 can be incorporated in sterilizable fabrics, including in-situ webbing.
• the fibers 110 can be incorporated in military apparel, geotextiles, protective fabrics, threads, and composite filler materials.
• the fibers 110 can be incorporated in filters for utilities, cement plants, and chemical processes plants.
• the fibers 110 can be incorporated in chemical scrubber units.
• the fibers 110 can be incorporated in flame resistant textiles, protective apparel for environmentally aggressive environments, chemical handling, hazardous waste, radiation, tear resistance, impact resistance, protective fabrics, carpets, bedding, upholstery, woven and nonwoven clothing, garments, and belts.

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• Engineering & Computer Science (AREA)
• Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Nanotechnology (AREA)
• Mechanical Engineering (AREA)
• Composite Materials (AREA)
• Materials Engineering (AREA)
• Crystallography & Structural Chemistry (AREA)
• General Physics & Mathematics (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Physics & Mathematics (AREA)
• General Engineering & Computer Science (AREA)
• Filtering Materials (AREA)
• Artificial Filaments (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Nonwoven Fabrics (AREA)
• Woven Fabrics (AREA)
• Filtering Of Dispersed Particles In Gases (AREA)

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• 2008
  • 2008-03-20 AT AT08734715T patent/ATE510945T1/de not_active IP Right Cessation
  • 2008-03-20 ES ES08718136T patent/ES2359769T3/es active Active
  • 2008-03-20 CN CN2013101295049A patent/CN103361758A/zh active Pending
  • 2008-03-20 WO PCT/EP2008/053401 patent/WO2008116837A2/en not_active Ceased
  • 2008-03-20 CN CN200880016573.6A patent/CN101680126B/zh not_active Expired - Fee Related
  • 2008-03-20 JP JP2009553978A patent/JP5309040B2/ja not_active Expired - Fee Related
  • 2008-03-20 WO PCT/EP2008/002287 patent/WO2008116606A2/en not_active Ceased
  • 2008-03-20 EP EP08734715A patent/EP2129820B1/en not_active Not-in-force
  • 2008-03-20 DE DE202008003982U patent/DE202008003982U1/de not_active Expired - Lifetime
  • 2008-03-20 US US12/531,620 patent/US20100095876A1/en not_active Abandoned
  • 2008-03-20 CN CNA200880000017XA patent/CN101605932A/zh active Pending
• 2009
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