Europalsches
`
`Patentamt
`European
`P'
`Patent Office
`Office européen
`des brevets
`
`Bescheinigung
`
`Certificate
`
`Attestation
`
`Die angehefteten
`Unterlagen stimmen mit der
`als urspriinglich eingereicht
`geltenden Fassung der auf
`dem nachsten Blatt
`bezeichneten europaischen
`Patentanmeldung Uberein.
`
`The attached documents are
`exact copies of the text in
`which the European patent
`application described on the
`following page is deemed to
`have been filed.
`
`Les documents joints a la
`présente attestation sont
`conformes au texte,
`considéré comme
`initialement déposé, de la
`demande de brevet
`européen qui est spécifiée a
`la page suivante.
`
`Patentanmeldung Nr.
`
`Patent application No.
`
`Demande de brevet n°
`
`13166233.0 / EP13166233
`
`The organization code and number of your priority application, to be used for filing abroad under the Paris
`Convention, is EP13166233.
`
`EPA/EPO/OEB Form 1014
`
`05.12
`
`Der Prasident des Europaischen Patentamts;
`Im Auftrag
`For the President of the European Patent Office
`Le President de |'Office européen des brevets
`p.o.
`
`U. Ingmann
`
`BASF SE
`Petitioner Exhibit 1011
`Page 1 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 1 of 37
`
`

`

`
`
`Anmeldung Nr:
`Application no.:
`Demande no:
`
`13166233.0
`
`Anmelder/ Applicant(s) / Demandeur(s):
`
`BASF SE
`67056 Ludwigshafen/DE
`
`Anmeldetag:
`Dateoffiling:
`Date de dépodt:
`
`02.05.13
`
`Bezeichnung der Erfindung / Title of the invention / Titre de l'invention:
`(Falls die Bezeichnung der Erfindung nicht angegeben ist, oder falls die Anmeldungin einer Nicht-Amtssprache des EPA eingereicht
`wurde, siehe Beschreibung beztglich ursprtinglicher Bezeichnung.
`If no title is shown, orif the application has been filed in a non-EPO language, pleaserefer to the description for the originaltitle.
`Si aucun titre n'est indiqué, ou si la demande a été déposée dans une langue autre qu'une langueofficielle de |'OEB, se référer ala
`description pour le titre original.)
`
`BLOGK COPOLYMERS
`
`In Anspruch genommenePrioritat(en) / Priority(Priorities) claimed / Priorité(s) revendiquée(s)
`Staat/Tag/Aktenzeichen / State/Date/File no. / Pays/Date/Numéro de dépét:
`
`Am Anmeldetag benannte Vertragstaaten / Contracting States designated at date offiling / Etats contractants désignéeslors
`du dépédt:
`
`AL AT BE BG CH GY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LILT LU LV MG MK MT NL NO PL
`PT RO RS SE SI SK SM TR
`
`EPA/EPO/OEB Form 1014
`
`05.12
`
`2
`
`BASF SE
`Petitioner Exhibit 1011
`Page 2 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 2 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`Block Copolymers
`
`Description
`
`The present invention relates to novel block copolymers comprising polyarylene ether blocks
`and polyalkylene oxide blocks, wherein said block copolymer comprises at least two different
`polyalkylene oxide blocks that are endcapped withdifferent alkyl groups.
`The present invention further relates processes for the manufacture of such block copolymers
`and their use as membrane material.
`
`Polyether sulfones and polysulfones belong to the group of high-performance thermoplastics
`(E.M. Koch, H.-M. Walter, Kunststoffe 80 (1990) 1146; E. Doring, Kunststoffe 80 (1990), 1149).
`Owing to their good biocompatibility, polyether sulfones and polysulfones are also used as ma-
`terial for the production of dialysis membranes (S. Savariar, G.S. Underwood, E.M. Dickinson,
`P.J. Schielke, A.S. Hay, Desalination 144 (2002) 15).
`
`The preparation of the polyether sulfones and polysulfones is usually effected by polycondensa-
`tion of suitable monomer building blocksin dipolar aprotic solvents at elevated temperature
`(R.N. Johnson et al., J. Polym. Sci. A-1 5 (1967) 2375, J.E. McGrath et al., Polymer 25 (1984)
`1827).
`
`The preparation of polyarylene ether sulfones from suitable aromatic bishalosulfones and aro-
`matic bisphenols or salts thereof in the presence of at least one alkali metal or ammonium car-
`bonate or bicarbonate in an aprotic solvent is described, for example, in US 4,870,153, EP 113
`112, EP-A 297 363 and EP-A 135 130.
`
`One disadvantage of pure polyarylene ethersis their low hydrophilicity. To enhance the hydro-
`philicity of polyarylene ethers, polyethersulfone (PESU) — polyethyleneoxide (PEO) block copol-
`ymers have been prepared.
`
`The synthesis of polyarylene ether-polyalkylene oxide copolymers described in Macromolecules
`29 (23) p. 7619 (1996) requires long reaction times.
`
`EP 739 925, US 5,700,902 and US 5,700,903 also describe polyarylene ether and polyalkylene
`oxide copolymers.
`
`US 5,700,902 discloses block copolymers with hydrophobic blocks and hydrophilic blocks,
`wherein hydrophilic blocks can be PEO blocks that are endcapped on one side with an alkyl
`group.
`
`10
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`25
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`30
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`35
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`40
`
`BASF SE
`Petitioner Exhibit 1011
`Page 3 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 3 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`US 5,798,437, US 5,834,583, WO 97/22406 disclose processes for the manufacture of hydro-
`philic copolymers.
`
`2
`
`US 5,911,880 discloses membranes made of polyether sulfone comprising an amphiphilic addi-
`tive.
`
`It was an object of the present invention to provide block copolymers that have a high glass
`transition temperature and that do not show the problems of copolymers knownfrom the art.
`
`10
`
`This problem has been solved by block copolymers comprising polyarylene ether blocks and
`polyalkylene oxide blocks, wherein said block copolymer comprises at least two different poly-
`alkylene oxide blocks that are endcapped with different endcapping groups.
`
`15
`
`The term “block copolymer’ shall not mean an individual polymer molecule but the entirety ofall
`polymeric components in a polymer.
`
`20
`
`25
`
`30
`
`Suitable polyarylene ether blocks of copolymers according to the invention are Known as such
`to those skilled in the art and can be formed from polyarylene ether units of the general formula
`
`poatr€
`
`popavftato}CL
`
`(II)
`
`with the following definitions:
`
`each independently 0, 1, 2 or 3,
`t, q:
`each independently a chemical bond or group selected from -O-, -S-, -SO2-, S=O,
`Q,T,Y:
`C=O, -N=N-, -CR?R- where R? and R> are each independently a hydrogen atom or a C1-Ci2-
`alkyl, C1-C12-alkoxy or Ce-Cis-aryl group, where at least one of Q, T and Y is not -O-, and at
`least one of Q, T and Y is -SO2-, and
`
`Ar, Art:
`D:
`
`each independently an arylene group having from 6 to 18 carbon atoms,
`a chemical bond or -O-.
`
`35
`
`In particular, D is an oxygen atom -O- when bound to another arylenether unit. D is a chemical
`bond when boundto a polyalkyleneoxide block.
`
`The polyarylene ethers are typically prepared by polycondensation of suitable starting
`compounds in dipolar aprotic solvents at elevated temperature (see, for example, R.N. Johnson
`et al., J. Polym. Sci. A-1 5 (1967) 2375, J.E. McGrath et al., Polymer 25 (1984) 1827). Possible
`
`BASF SE
`Petitioner Exhibit 1011
`Page 4 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 4 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`syntheses of the OH-terminated polyarylene ethers are also described in WO 2010/057822 on
`p.2 In. 27 to p.14, In. 35 as well as p. 16, In 8 to 18, In 29.
`
`3
`
`Suitable polyarylene ether blacks can be provided by reacting at least one starting compound of
`the structure X-Ar-Y (M1) with at least one starting compoundof the structure HO-Ar'-OH (M2)
`in the presence of a solvent (L) and of a base (B), where
`-
`Y is a halogen atom,
`-
`X is selected from halogen atoms and OH, preferably from halogen atoms,
`especially F, Cl or Br, and
`-
`Ar and Ar’ are each independently an arylene group having 6 to 18 carbon
`atoms.
`
`In one embodiment, a polyarylene ether which is formed from units of the general formula II with
`the definitions as above is provided in the presence of a solvent(L):
`
`10
`
`15
`
`
`
`oatr€ po{pavftato}(>t
`
`(Il).
`
`If Q, T or Y, with the abovementioned prerequisites, is a chemical bond, this is understood to
`mean that the group adjacent to the left and the group adjacent to the right are bonded directly
`to one another via a chemical bond.
`
`Preferably, Q, T and Y in formula (I), however, are independently selected from —O- and -SO>-,
`with the proviso that at least one of the group consisting of Q, T and Y is -SO>2-.
`
`When Q, T or Y are -CR'R?-, R? and R? are each independently a hydrogen atom or a Ci-Ci2-
`alkyl, C1-C12-alkoxy or Ce-Cis-aryl group.
`
`Preferred C1-Ci2-alkyl groups comprise linear and branched, saturated alkyl groups having from
`1 to 12 carbon atoms. Particularly preferred C1-C12-alkyl groups are: C1-Ce-alkyl radicals such
`as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2- or 3-methylpentyl and longer-chain
`radicals such as unbranched heptyl, octyl, nonyl, decyl, undecyl, lauryl, and the singularly or
`multiply branched analogs thereof.
`
`Useful alkyl radicals in the aforementioned usable C1-C12-alkoxy groups include the alkyl groups
`having from 1 to 12 carbon atoms defined above. Cycloalkyl radicals usable with preference
`comprise especially C3-C12-cycloalkyl radicals, for example cyclopropyl, cyclobutyl, cyclopentyl,
`cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl,
`cyclobutylmethyl, cyclobutylethyl, cyclpentylethyl, -propyl, -butyl, -pentyl, -hexyl,
`cyclohexylmethyl, -dimethyl, -trimethyl.
`
`20
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`BASF SE
`Petitioner Exhibit 1011
`Page 5 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 5 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`4
`
`Ar and Ar' are each independently a Ce-C:s-arylene group. Proceeding from the starting
`materials described below,Ar is preferably derived from an electron-rich aromatic substance
`whichis preferably selected from the group consisting of hydroquinone, resorcinol,
`dihydroxynaphthalene, especially 2,7-dihydroxynaphthalene, and 4,4’-bisphenol. Ar’ is
`preferably an unsubstituted Ce- or C12-arylene group.
`
`Useful Ce-C1s-arylene groups Ar and Ar’ are especially phenylene groups, such as 1,2-, 1,3-
`and 1,4-phenylene, naphthylene groups, for example 1,6-, 1,7-, 2,6- and 2,7-naphthylene, and
`the arylene groups derived from anthracene, phenanthrene and naphthacene.
`
`Preferably, Ar and Ar' in the preferred embodiments of the formula (Il) are each independently
`selected from the group consisting of 1,4-phenylene, 1,3-phenylene, naphthylene, especially
`2,7-dihydroxynaphthalene, and 4,4’-bisphenylene.
`
`Units present with preference within the polyarylene ether are those which comprise atleast
`one ofthe following repeat structural units Ila to Ilo:
`
`BASF SE
`Petitioner Exhibit 1011
`Page 6 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 6 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`oc 7a7a8 ee
`
`5
`
`foposox+
`
`"
`
`4Kpfpodsek+ .
`
`$2Or
`
`BASF SE
`Petitioner Exhibit 1011
`Page 7 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 7 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`H5
`H
`
`
`$22 <DEO-OFOH
`ROORODE
`
`3
`
`m
`
`HOOF,
`
`CHz
`
`H3C
`
`$e Kt
`S CH,
`
`H32C
`
`CHz
`
`llo
`
`5
`
`10
`
`15
`
`20
`
`25
`
`In addition to the units Ila to Ilo present with preference, preference is also given to those units
`in which one or more 1,4-dihydroxyphenyl units are replaced by resorcinol or
`dihydroxynaphthalene units.
`
`Particularly preferred units of the general formula II are units Ila, Ilg and IIk. It is also particularly
`preferred when the polyarylene ether blocks are formed essentially from one kind of units of the
`general formula II, especially from one unit selected from lla, Ilg and IIk.
`
`In a particularly preferred embodiment, Ar = 1,4-phenylene, t = 1, q = 0, T = SOz2 and Y = SOz.
`Such polyarylene ethers are referred to as polyether sulfone (PESU).
`
`Suitable polyarylene ether blocks preferably have a mean molecular weight Mn (number
`average) in the range from 2000 to 70000 g/mol, especially preferably 5000 to 40000 g/mol and
`particularly preferably 7000 to 30000 g/mol. The average molecular weight of the polyarylene
`ether blocks can be controlled and calculated by the ratio of the monomers forming the
`polyarylene ether blocks, as described by H.G. Elias in “An Introduction to Polymer Science”
`VCH Weinheim, 1997, p. 125.
`
`Suitable starting compounds are knownto thoseskilled in the art and are not subject to any
`fundamental restriction, provided that the substituents mentioned are sufficiently reactive within
`a nucleophilic aromatic substitution.
`
`BASF SE
`Petitioner Exhibit 1011
`Page 8 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 8 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`Preferred starting compounds are difunctional. "Difunctional" means that the number of groups
`reactive in the nucleophilic aromatic substitution is two per starting compound.Afurthercriterion
`for a suitable difunctional starting compound is a sufficient solubility in the solvent, as explained
`in detail below.
`
`7
`
`Preference is given to monomeric starting compounds, which means that the reaction is
`preferably performed proceeding from monomers and not proceeding from prepolymers.
`
`10
`
`The starting compound (M1) used is preferably a dihalodiphenyl sulfone. The starting
`compound (M2) used is preferably dihydroxydiphenyl sulfone.
`
`Suitable starting compounds (M1) are especially dihalodiphenyl sulfones such as 4,4’-
`dichlorodiphenyl sulfone, 4,4’-difluorodiphenyl sulfone, 4,4’-dibromodiphenyl sulfone, bis(2-
`chlorophenyl) sulfones, 2,2’-dichlorodiphenyl sulfone and 2,2’-difluorodipheny! sulfone,
`particular preference being given to 4,4’-dichlorodiphenyl sulfone and 4,4’-difluorodiphenyl
`sulfone.
`
`Preferred compounds (M2) are accordingly those having two phenolic hydroxyl groups.
`
`Phenolic OH groups are preferably reacted in the presence of a basein order to increase the
`reactivity toward the halogen substituents of the starting compound (M1).
`
`Preferred starting compounds (M2) having two phenolic hydroxyl groups are selected from the
`following compounds:
`
`dihydroxybenzenes, especially hydroquinone and resorcinol;
`-
`dihydroxynaphthalenes, especially 1,5-dihydroxynaphthalene, 1,6- dihydroxynaphthalene,
`-
`1,7-dihydroxynaphthalene, and 2,7-dihydroxynaphthalene;
`-
`dihydroxybiphenyls, especially 4,4'-biphenol and 2,2'-biphenol;
`-
`bisphenyl ethers, especially bis(4-hydroxyphenyl) ether and bis(2-hydroxyphenyl) ether;
`-
`bisphenylpropanes, especially 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-
`hydroxyphenyl)propane and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl) propane;
`-
`bisphenylmethanes, especially bis(4-hydroxyphenyl)methane;
`-
`bisphenyl sulfones, especially bis(4-hydroxyphenyl) sulfone;
`-
`bisphenyl sulfides, especially bis(4-hydroxyphenyl) sulfide;
`-
`bisphenyl ketones, especially bis(4-hydroxyphenyl) ketone;
`-
`bisphenylhexafluoropropanes, especially 2,2-bis(3,5-dimethyl-4-
`hydroxyphenyl)hexafluoropropane; and
`-
`bisphenylfluorenes, especially 9,9-bis(4-hydroxyphenyl)fluorene;
`-
`1,1-Bis(4-hydroxyphenyl)-3,3,5-trimethyl-cyclohexane (bisphenol TMC).
`
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`BASF SE
`Petitioner Exhibit 1011
`Page 9 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 9 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`8
`
`Itis preferable, proceeding from the aforementioned aromatic dihydroxyl compounds (M2), by
`addition of a base (B), to prepare the dipotassium or disodium salts thereof and to react them
`with the starting compound (M1). The aforementioned compounds can additionally be used
`individually or as a combination of two or more of the aforementioned compounds.
`
`Hydroquinone, resorcinol, dihydroxynaphthalene, especially 2,7-dihydroxynaphthalene,
`bisphenol A, dihydroxydiphenyl sulfone and 4,4’-bisphenol are particularly preferred as starting
`compound (M2).
`
`However,it is also possible to use trifunctional compounds. In this case, branched structures
`are the result. If a trifunctional starting compound (M2) is used, preference is given to 1,1,1-
`tris(4-hydroxyphenyl)ethane.
`
`The ratios to be used derivein principle from the stoichiometry of the polycondensation reaction
`which proceeds with theoretical elimination of hydrogen chloride, and are established by the
`person skilled in the art in a Known manner.
`
`In a preferred embodiment, the ratio of halogen end groups to phenolic end groups is adjusted
`by controlled establishment of an excess of the dihalogen starting compound (M1) in relation to
`a difunctional compound (M2) as starting compound and polyalkyleneoxide.
`
`More preferably, the molar (M1)/(M2) ratio in this embodimentis from 1.003 to 1.25, especially
`from 1.05 to 1.15, most preferably from 1.01 to 1.1.
`Preferably, the molar (M1) / (M2 + polyalkyleneoxide) ratio is1.005 to 1.2.
`
`Alternatively, it is also possible to use a starting compound (M1) where X = halogen and Y =
`OH. In this case, the ratio of halogen to OH end groups usedis preferably from 1.01 to 1.2,
`especially from 1.03 to 1.15, most preferably 1.05 to 1.1.
`
`Preferably, the conversion in the polycondensationis at least 0.9, which ensures a sufficiently
`high molecular weight.
`
`Solvents (L) preferred in the context of the present invention are organic, especially aprotic
`polar solvents. Suitable solvents also have a boiling point in the range from 80 to 320°C,
`especially 100 to 280°C, preferably from 150 to 250°C. Suitable aprotic polar solvents are, for
`example, high-boiling ethers, esters, ketones, asymmetrically halogenated hydrocarbons,
`anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone and/or N-
`ethyl-2-pyrrolidone. It is also possible to use mixtures of these solvents.
`
`A preferred solventis especially N-methyl-2-pyrrolidone and/or N-ethyl-2-pyrrolidone.
`
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`BASF SE
`Petitioner Exhibit 1011
`Page 10 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 10 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`Preferably, the starting compounds (M1) and (M2) and polyalkyleneoxide are reacted in the
`aprotic polar solvents (L) mentioned, especially N-methyl-2-pyrrolidone.
`
`i]
`
`The starting compounds (M1) and (M2) and polyalkyleneoxide are reacted in the presence of a
`base (B). The bases are preferably anhydrous. Suitable bases are especially anhydrous alkali
`metal and/or alkaline earth metal carbonate, preferably sodium carbonate, potassium
`carbonate, calcium carbonate or mixtures thereof, very particular preference being given to
`potassium carbonate, especially potassium carbonate with a volume-weighted mean particle
`size of less than 200 micrometers, determined with a particle size measuring instrument in a
`suspension of N-methyl-2-pyrrolidone.
`
`A particularly preferred combination is N-methyl-2-pyrrolidone as solvent (L) and potassium
`carbonate as base (B).
`
`The reaction of the suitable starting compounds (M1) and (M2) and polyalkyleneoxide is
`performed at a temperature of 80 to 250°C, preferably 100 to 220°C, the upper temperaturelimit
`being determined by the boiling point of the solvent.
`
`The reaction is effected preferably within a time interval of 2 to 12 h, especially of 3 to 8 h.
`
`Especially suitable starting materials, bases, solvents, ratios of all components involved,
`reaction times and reaction parameters like temperatures and pressures as well as suitable
`workup procedures are for example disclosed in US 4,870,153, col. 4, In. 11 to col. 17, In. 64,
`EP 113 112, p. 6, In. 1 to p. 9, In. 14, EP-A 297 363, p. 10, In. 38 to p. 11, In. 24, EP-A 135 130,
`p. 1, In. 37 to p. 4, In. 20, which are incorporatedin this application by reference.
`
`Suitable polyalkylene oxides are particularly polyethers of diols. Suitable polyalkylene oxides
`are normally produced by polymerization of at least one alkylene oxide. Suitable monomeric
`alkylene oxides are for example ethylene oxide or substituted ethylene oxides bearing one or
`more alkyl and/or aryl groups. Suitable monomeric alkylene oxides are for example styrene ox-
`ide or C2-Cao-alkylene oxides, such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-
`butylene oxide, isobutylene oxide, pentene oxide, hexene oxide, cyclohexene oxide, dodecene
`epoxide, octadecene epoxide. Ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-
`butylene oxide, isobutylene oxide and pentene oxide are particularly suitable, propylene oxide
`and ethylene oxide being particularly preferred.
`
`Suitable polyalkylene oxides can be homopolymers or copolymers.
`
`two different al-
`In one embodiment, suitable polyalkylene oxides are copolymers of at least
`kylene oxides. In one embodiment, suitable polyalkylene oxides are statistical copolymers ofat
`least two different alkylene oxides. In another embodiment, suitable polyalkylene oxides are
`block copolymersof at least two different alkylene oxides.
`
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`BASF SE
`Petitioner Exhibit 1011
`Page 11 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 11 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`In one preferred embodiment, suitable polyalkylene oxides are homopolymers of ethyleneoxide
`or propylene oxide.
`
`10
`
`In one embodiment, suitable polyalkylene oxides are statistical copolymers of ethylene oxide
`and propylene oxide.
`In one embodiment, suitable polyalkylene oxides are block copolymers of ethylene oxide and
`propylene oxide.
`
`Suitable polyalkylene oxides can be linear or branched. Branching of a polyalkylene oxide can
`for example be achieved by including monomers bearing an epoxide group and an OH ora
`chloro moiety into the polyalkylene oxide. Preferably, suitable polyalkylene oxides are linear.
`
`Suitable polyalkylene oxide blocks normally comprise 1 to 500 alkyleneoxide units. Preferably,
`suitable polyalkylene oxides comprise 2 to 300, more preferably 3 to 150, even more preferably
`5 to 100 and especially preferably 10 to 80 alkylene oxide units.
`
`Suitable polyalkylene oxide blocks are endcapped with an endcapping group. The term
`“endcapped” means that the polyalkylene oxide block bearsat its terminal position an endcap-
`ping group that is bound via an ether group and that does not comprise further OH groups.
`This means that the polyalkyleneoxide blocks are formally etherified with a monoalcohol.
`Suitable endcapping groups can bealiphatic or aromatic, and can for example be alkyl groups,
`substituted alkyl groups, phenyl groups or substituted phenyl groups.
`Preferably, suitable polyalkylene oxide blocks are endcapped with an C:, C2, C3, Ca, Cs, Ce, Cz,
`Cs, Co, Cio, C11, C12, C13, Cia, Cis, Crs, C17, Cis, C19, C20, C21 or Ca2o-alkyl group.
`More preferably, Suitable polyalkylene oxide blocks are endcapped with a group selected from
`methyl, ethyl, propyl, butyl, hexyl, C1s-alkyl, Cis-alkyl.
`
`Suitable endcapping groups can belinear or branched. Preferably, suitable polyalkylene oxide
`blocks are endcapped with a linear alkyl group.
`
`Block copolymers according to the invention comprises polyalkylene oxide blocks and poly-
`arylene ethers blocks, wherein said polyalkylene oxide blocks are covalently bound to the rest
`of said block copolymer. Normally, said polyalkylene oxide blocks are covalently bound to a
`polyarylene ether block via an -O- group (an ether group).
`In one preferred embodiment, block copolymer according to the invention have the general
`structure AB or ABA,with A being a polyalkylene oxide block and B being an polyarylene ether
`block.
`
`Block copolymers according to the invention comprise at least two polyalkylene oxide blocks
`that are endcapped with different endcapping groups, preferably at least two different alkyl
`groups.
`
`10
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`15
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`20
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`25
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`30
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`35
`
`40
`
`BASF SE
`Petitioner Exhibit 1011
`Page 12 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 12 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`Preferably, block copolymers according to the invention comprise at least two polyalkylene ox-
`ide blocks that are endcapped with different endcapping groups, preferably alkyl groups that are
`otherwise identical.
`
`11
`
`In one embodimentof the invention, the massof the at least two different endcapping alkyl
`groupsdiffer by one methylene group. For example, block copolymers according to the inven-
`tion may comprise polyalkylene blocks endcapped with a methyl group and polyalkylene oxide
`blocks that are endcapped with an ethyl group.
`
`In one embodimentof the invention, the mass of the at least two different endcapping alkyl
`groups differ by two methylene groups. For example, block copolymers according to the inven-
`tion may comprise polyalkylene blocks endcapped with a Cie-alkyl group and polyalkylene oxide
`blocks that are endcapped with a Cis-alkyl group.
`
`In one embodimentof the invention, the mass of the at least two different endcapping alkyl
`groups differ by more than two methylene groups. For example, block copolymers according to
`the invention may comprise polyalkylene blocks endcapped with a butyl group and polyalkylene
`oxide blocks that are endcapped with a methyl group.
`
`In one preferred embodiment, polyarylene oxide blocks in block copolymers according the em-
`bodiments that are given below, are polysulfones, polyethersulfones or polyphenylenesulfones.
`
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yalkylene oxide blocks endcapped with a methyl group and polyalkylene oxide blocks that are
`endcapped with an ethyl group.
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yalkylene oxide blocks endcapped with a methyl group and polyalkylene oxide blocks that are
`endcapped with a propyl group.
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yalkylene oxide blocks endcapped with an ethyl group and polyalkylene oxide blocks that are
`endcapped with a propyl group.
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yalkylene oxide blocks endcapped with an ethyl group and polyalkylene oxide blocks that are
`endcapped with a butyl group.
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yalkylene oxide blocks endcapped with a C:¢-alkyl group and polyalkylene oxide blocks that are
`endcapped with a C.s-alkyl group.
`In one embodimentof the invention, block copolymers according ta the invention comprise pol-
`yalkylene oxide blocks endcappedwith a linear Cig-alkyl group and polyalkylene oxide blocks
`that are endcappedwith a linear Cig-alkyl group.
`
`10
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`15
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`20
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`25
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`30
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`35
`
`40
`
`BASF SE
`Petitioner Exhibit 1011
`Page 13 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 13 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`12
`
`In one embodiment of the invention, block copolymers according to the invention comprise pol-
`yethylene oxide blocks endcapped with a methyl group and polyethylene oxide blocks that are
`endcapped with an ethyl group.
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yethylene oxide blocks endcapped with a methyl group and polyethylene oxide blocksthat are
`endcapped with a propyl group.
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yethylene oxide blocks endcapped with an ethyl group and polyethylene oxide blocks that are
`endcapped with a propyl group.
`In one embodimentof the invention, block copolymers according ta the invention comprise pol-
`yethylene oxide blocks endcapped with an ethyl group and polyethylene oxide blocks that are
`endcapped with a butyl group.
`In one embodimentof the invention, block copolymers according to the invention comprise pol-
`yethylene oxide blocks endcappedwith a Cig-alkyl group and polyethylene oxide blocks that are
`endcapped with a Cig-alkyl group.
`In one embodimentof the invention, block copolymers according ta the invention comprise pol-
`yethylene oxide blocks endcappedwith a linear Cie-alkyl group and polyethylene oxide blocks
`that are endcappedwith a linear Cis-alkyl group.
`
`In one embodimentof the invention block copolymers comprise polyarylene ether blocks and
`polyalkylene oxide blocks, wherein said block copolymer comprises at least two different poly-
`alkylene oxide blocks of the general formula
`
`R*A(OCH2-CHR8),-O-
`
`(I),
`
`wherein
`
`x is an index number,
`
`R*4 denotes an aliphatic or aromatic rest,
`R® denotes hydrogen or an aliphatic or aromatic rest,
`k is a number from 1 to 500,
`
`wherein said at least two different polyalkylene oxide blocksdiffer at least with respect to
`RA ;
`and wherein said polyalkylene oxide block is covalently bound to the rest of said block co-
`polymer.
`
`x is an index numberto differentiate polyalkylene blocks by the endcapping group R*.
`Polyalkylene blocks with the same endcapping group bear the same index numberx
`
`10
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`15
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`20
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`25
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`30
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`35
`
`In a preferred embodiment R®in formula (I) is H, methyl, ethyl, phenyl, especially preferably R®
`is H.
`
`40
`
`k is a numberfrom 1 to 500, preferably 2 to 300, more preferably 3 to 150, even more
`preferably 5 to 100 and especially preferably 10 to 80.
`
`BASF SE
`Petitioner Exhibit 1011
`Page 14 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 14 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`Block copolymers according to the invention comprise polyalkylene oxide blocks with at least
`two different rests R'* and R™.
`
`13
`
`In one embodiment, R™ in formula (I) is Cig alkyl and Ris Cig alkyl.
`In another embodiment, R™ in formula (I) is Cig alkyl and R* is Ci4 alkyl.
`In another embodiment, R™ in formula (I) is Cis alkyl and R* is C20 alkyl.
`In another embodiment, R™ in formula (I) is methyl and R”is ethyl.
`In another embodiment, R™ in formula (I) is methyl and R24 is propyl.
`In another embodiment, R* in formula (I) is methyl and R*is butyl.
`In another embodiment, R" in formula (I) is 2-ethylhexyl and R*is hexyl.
`In another embodiment, R™ in formula (I) is ethyl and R24 is propyl.
`In another embodiment, R™ in formula (I) is ethyl and R4 is butyl.
`
`In one embodiment, R™ in formula (I) is Cig alkyl and R* is Cy, alkyl and R®is H.
`In another embodiment, R™ in formula (I) is Cig alkyl and R* is Ci4 alkyl and R® is H.
`In another embodiment, R" in formula (I) is Cig alkyl and R24 is C2o alkyl and R®is H.
`In another embodiment, R* in formula (I) is methyl and R24 is ethyl and R®is H.
`In another embodiment, R™ in formula (I) is methyl and R* is propyl and R®is H.
`In another embodiment, R™ in formula (I) is methyl and R” is butyl and R®is H.
`In another embodiment, R™ in formula (I) is 2-ethylhexyl and R24 is hexyl and R® is H.
`In another embodiment, R™ in formula (I) is ethyl and R* is propyl and R®is H.
`In another embodiment, R™ in formula (I) is ethyl and R24 is butyl and R®is H.
`
`In the context of this application, a set of polyalkyleneoxide blocks shall be understood to com-
`prise all polyalkyleneoxide blocks present in a block copolymerthat are endcapped with the
`same endcapping group.
`
`In a preferred embodiment, at least two sets of polyalkylene oxides differ with respect to the
`endcapping group, but are otherwise essentially identical with respect to the composition of the
`polyalkylene oxide. “Essentially identical with respect to the composition” in this context means
`that the at least two sets of polyalkylene oxides comprise essentially identical amounts of mon-
`omeric alkylene oxides and have an essentially identical molecular mass distribution. This
`means that the content (the weight) of each of the monomeric alkylene oxides comprised in the
`polyalkylene oxide is comprised therein in an amountthatis identical or differs by maximally five
`% by weight relative to the set with the higher respective content. “Essentially identical molecu-
`lar mass distribution” means that the number average molecular weight (determined bytitration
`of the OH end groups) of the at least two sets of polyalkylene oxides differs by not more than 10
`%, preferably 5 %relative to the heavier set of polyalkylene oxides.
`
`In one preferred embodiment of the invention, block copolymers according to the invention
`comprise at least two sets of polyalkylene oxide blocks that are each present in an amount of at
`
`10
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`15
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`20
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`25
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`30
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`35
`
`40
`
`BASF SE
`Petitioner Exhibit 1011
`Page 15 of 37
`
`BASF SE
`Petitioner Exhibit 1011
`Page 15 of 37
`
`

`

`BASF SE
`
`INV 74733
`
`PF 74733 EP
`
`least 5 mol%, preferably 10 mol%, more preferably 20 mol% and especially preferably 30 mol%,
`relative to the molar amountofall polyalkylene oxide blocks present in the block copolymer.
`
`14
`
`In one preferred embodimentof the invention, block copolymers according to the invention
`comprise exactly two sets of polyalkylene oxide blocks.
`
`In one preferred embodiment of the invention, block copolymers according to the invention
`comprise two sets of polyalkylene oxide blocks that are each present in an amountof at least 5
`mol%, preferably 10 mol%, more preferably 20 mol% and especially preferably 30 mol%, rela-
`tive to the molar amountofall polyalkylene oxide blocks present in the block copolymer.
`
`In one preferred embodiment of the invention, block copolymers according to the invention
`comprise at least two polyalkylene oxide blocks that are endcapped with different alkyl groups,
`wherein at least two different alkyl groups are present in a molar ratio from 1:1 to 1:20, prefera-
`bly from 1:1.05 to 1:10, more preferably from 1:1 to 1:5.
`
`In one embodimentof the