Polyarylene ether

Abstract

A polyarylene ether comprising in polymerized form A) at least one trifunctional or higher functional compound and B) isosorbide, isomannide, isoidide or a mixture thereof, wherein the polyarylene ether is polyarylene ether sulfone or polyarylene ether ketone; a process for its preparation and its use in the preparation of coatings, films, fibers, foams, membranes or molded articles.

Description

[0001] The present invention relates to polyarylene ether sulfones or polyarylene ether ketones based on diols derived from anhydrosugars.

[0002] Polyarylene ether sulfone and polyarylene ether ketone are classified as high-performance thermoplastics. In some scientific publications, the preparation and properties of polyarylene ether sulfone and polyarylene ether ketone derived from bio-based diols are disclosed (Kricheldorf et al., J Polm. Sci. Part A: Polymer Chemistry, Vol. 33, 2667-2671 (1995); Chatti et al., High Performance Polymers, 21: 105-118, 2009; Abderrazak et al., Macromol. Chem. Phys. 2013, 214, 1423-1433; Belgacem et al., Designed Monomers and Polymers, 2016, Vol. 19, No. 3, 248-255). Polyarylene ether sulfones derived from 1,4:3,6-dianhydrohexitol are also disclosed in WO 2014 / 072473 and US 2017 / 0240708 A1. Compositions having improved melt stability and comprising up to 20% by weight (wt%) of polyarylene ether sulfones containing up to 10% by weight of units derived from 1,1,1-tris(4-hydroxyphenyl)ethane are known from US 7,163,987 B2.

[0003] The problem solved by the present disclosure is to provide a new polyarylene ether, which contains at least one -SO2- or -CO- group and is derived from isosorbide, isomannide, isoidide or a mixture thereof. In addition, the polyarylene ether should support the preparation of coatings, fibers, films, foams and molded articles that are resistant to high temperatures and have good chemical resistance. One motivation is to provide a new polyarylene ether suitable for preparing membranes. The membrane with high flux recovery and high permeability is intended to be particularly used in contact with water, body fluids or liquids in food production. In addition, a method for preparing the new polyarylene ether with good yield within an industrially acceptable reaction time should be provided.

[0004] Hereinafter, a poly(arylene ether) is disclosed, which comprises a polymerized form of

[0005] A) at least one trifunctional or higher functional compound, and

[0006] B) isosorbide, isomannide, isoidide or a mixture thereof,

[0007] The polyarylene ether is polyarylene ether sulfone or polyarylene ether ketone.

[0008] In addition, a method for preparing a polyarylene ether is disclosed, which comprises reacting a) at least one trifunctional or higher functional compound, and b) isosorbide, isomannide, isoidol or a mixture thereof, with c) at least one difunctional compound comprising dichlorodiaryl sulfone, dichlorodiaryl ketone or a mixture thereof. Also disclosed is the use of at least one polyarylene ether described or obtained in the preparation or for the preparation of a coating, fiber, film, foam, membrane or molded article, and a fiber or membrane comprising at least one polyarylene ether described or obtained in the preparation. Also disclosed is at least one article comprising at least one said membrane. In addition, disclosed is the use of the membrane in contact with water, body fluids or liquids in food production.

[0009] In the following, "at least one" generally means one or two or more, such as three or four or five or more, wherein more may mean multiple or uncountable species. For example, "at least one" may mean a mixture of one or two or more. If used in conjunction with a compound, "at least one" in this sense means describing one or two or more compounds that differ in their chemical composition, i.e., chemical properties.

[0010] Hereinafter, "polymer" may mean a homopolymer or a copolymer or a mixture thereof. It will be appreciated by those skilled in the art that any polymer, which may be a homopolymer or a copolymer, is essentially a mixture of individual polymers whose structures, such as chain length, degree of branching or end group properties, are usually different. This fact is also commonly referred to as distribution. Therefore, hereinafter, "at least one" as a prefix of a polymer means that different types of polymers may be covered, so that each type may have the above-mentioned specific distribution.

[0011] It will also be understood by those skilled in the art that any polymer is derived from monomers or oligomers or mixtures thereof which are then included in the polymer in reacted polymerized form.

[0012] In the following

[0013] Compound A is at least one trifunctional or higher functional compound;

[0014] Compound B is isosorbide, isomannide, isoidide or a mixture thereof;

[0015] The diol C1 is at least one compound having two hydroxyl groups and is not compound B;

[0016] Compound C2 is at least one compound comprising at least one dichlorodiaryl sulfone or dichlorodiaryl ketone or a mixture thereof;

[0017] The starting compounds are the compounds A, B, C2 and, if present, the diol C1 before polymerization.

[0018] Compound D is at least one compound having one functional group reactive toward a reactive group in a polymer chain;

[0019] Solvent L is at least one solvent

[0020] In principle, the present disclosure encompasses polyarylene ether of any structure, provided that the polyarylene ether comprises compound A and compound B, and provided further that it is polyarylene ether sulfone or polyarylene ether ketone.

[0021] At least one trifunctional or higher functional compound (compound A) contained in the polyarylene ether is known per se, or, if not known per se, can be prepared by methods known to those skilled in the art. Compound A can produce branched polyarylene ethers. Therefore, it can be a branching agent. Although the disclosed polyarylene ether can be branched, it is generally not crosslinked. If it is crosslinked, most of it is crosslinked to a lesser extent or a very lesser extent. Compound A can be a monomer or an oligomer. Compound A has three or more functional groups. The number of functional groups as well as their properties and the amount of compound A can affect the branching of the polyarylene ether. It is generally preferred that at least one compound A has 3 to 6 such functional groups. If it is intended to obtain a less branched polyarylene ether, it is more preferred that compound A can have 3 or 4 functional groups. If less branching is required, it is particularly advantageous that at least one compound A can be a trifunctional compound. With the help of functional groups, at least one trifunctional or higher functional compound can react with the compound that builds the polyarylene ether. Compound C2 or a mixture of compound C2 and diol C1 can be such a compound for building up the polyarylene ether. Compound A can also react with compound B.

[0022] Typical suitable functional groups, such as hydroxyl, nitro or halogen, can be substituted under the preparation conditions of the polyarylene ether. Compound A can have functional groups of different natures. This can be advantageous if it is desired to control branching by different reactivities of the functional groups. All functional groups of compound A can also be identical. They can show the same reactivity; however, depending on the chemical composition of compound A, the reactivity of the functional groups during the polymerization reaction can still be different. Hydroxyl and / or halogen can be preferred. Among the halogen groups, chlorine is particularly preferred. Compound A with 3 to 6, in particular 3 or 4 hydroxyl groups and / or halogens (in particular chlorine) can be most preferred. It can be very preferred that compound A has three hydroxyl groups, so that it is a triol.

[0023] Compound A may be an aromatic compound. Aromatic compounds may be preferred if the polyarylene ether is intended for the preparation of heat-resistant and / or sterilizable coatings, films, fibers, foams, membranes or moldings.

[0024] As compounds A of the aromatic compound type containing three or more hydroxyl groups, mention may be made of: phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxy-5-phenyl)-heptene-2 ​​(triisopropenylphenol), 4,6-dimethyl-2,4,6-(4-hydroxyphenyl)-heptane (triisopropenylphenol hydrogenated), 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, 1,1,1-tri-(4-hydroxyphenyl)-propane, tetrakis-(4-hydroxyphenyl)-methane, 1,4-bis-(4′,4″-dihydroxytriphenyl)-methyl]- Benzene and 2,2-bis-[4,4′-bis-(4-hydroxyphenyl)-cyclohexyl]-propane. Also suitable are trivalent or greater than trivalent phenols that can be obtained by the reaction of a monophenol having an unsubstituted ortho-paraalkyl substitution with formaldehyde or a compound that generates formaldehyde, such as the triphenol from p-cresol and formaldehyde, 2,6-bis-(2′-hydroxy-5′-methylbenzyl)-4-methylphenol. Other examples of suitable aromatic compounds include 2,6-bis-(2′-hydroxy-5′-isopropyl-1-benzyl)-4-isopropenyl 1-phenol and bis-hydroxy-3-(2′-hydroxy-5′-methylbenzyl-5-methylphenyl]-methane.

[0025] Examples of compounds A of the aromatic compound type having a chlorine group are: 1,3,5-tris-(4-chlorophenylsulfonyl)-benzene, 2,4,4'-trichlorodiphenylsulfone, 1-chloro-2,6-bis-(4-chlorophenylsulfonyl)-benzene.

[0026] 1,1,1-trihydroxyphenylethane (THPE) may be particularly interesting from the perspective of being an aromatic compound, its ease of reaction under the conditions for preparing polyarylene ether, and industrial availability. THPE may promote the progress of the polymerization reaction between compound B and compound C, and thus may be very advantageous. In addition, THPE may be advantageously used in polyarylene ethers used in contact with water or liquids in fields where health and safety are important, such as the food industry or the medical field.

[0027] In order to change the branching quality, a mixture of different trifunctional or higher functional compounds can be included in the polyarylene ether. Thus, for example, 2 to 5, such as 2 to 4, trifunctional or higher functional compounds can be included. It is preferred to include 2 or 3 trifunctional or higher functional compounds. From the aspect of the complexity of industrial production, it is more preferred to include two trifunctional or higher functional compounds, in particular only one trifunctional or higher functional compound.

[0028] The amount of compound A can vary. If its content is too little, the molecular weight of the polyarylene ether is generally kept in a range that is too low for most applications. In addition, molecular weight accumulation may not occur fast enough for effective industrial production. Too high an amount may lead to the formation of a gel-like polyarylene ether. This may also be undesirable from the perspective of the range of applications of the polyarylene ether. Therefore, the polyarylene ether generally advantageously contains 0.5 to 5 mol% of compound A, such as 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol% or 5 mol% of compound A, based on the total amount of compound A and B and diol C1 contained in the polyarylene ether. Therefore, it may be preferred that it contains 0.5 to 4 mol% of compound A, based on the total amount of compound A and B and diol C1 contained in the polyarylene ether. Most preferably, it may contain 0.1 to 3 mol % of the compound A, based on the total amount of the compounds A and B and the diol C1 contained in the polyarylene ether.

[0029] The compound B contained in the polyarylene ether is isosorbide, isomannide, isoidide or a mixture thereof. Compound B is known to those skilled in the art. Isosorbide, isomannide and isoidide belong to the 1,4:3,6-dianhydrohexitol family and have formula I:

[0030]

[0031] Depending on the desired properties such as glass transition temperature and its modulation, the polyarylene ether may contain as compound B one of the dianhydrohexitols or a mixture of two or all three of the dianhydrohexitols. Thus, for example, it may contain isosorbide and isomannide, isosorbide and isoidide or isomannide and isoidide. It may preferably contain only isosorbide, isomannide or isoidide. Isosorbide may be most preferred, for example, because it is commercially available and it may impart thermal stability to the polyarylene ether. Isoidide may have advantages in terms of ease of reaction.

[0032] The polyarylene ether may contain compound B as the only diol. In addition, the polyarylene ether may also be derived from at least one other difunctional compound having two hydroxyl groups, i.e. a diol (diol C1) which is not compound B, and which is contained in the polyarylene ether in polymerized form. The polyarylene ether may be derived from 5 to 100 mol % of compound B, based on the total weight of the starting materials compound B and diol C1. The polyarylene ether may more preferably be derived from 25 to 100 mol %, most preferably 50 to 100 mol % of compound B, based on the total weight of the starting materials compound B and diol C1. In particular, if the polyarylene ether is sought to be used for the preparation of products in contact with water, liquids in the field of food production or medicine, more specifically for the preparation of hollow fibers or membranes in the said fields, it may be advantageous that it contains compound B as the only diol.

[0033] The diol C1 may be an aliphatic or aromatic compound. Generally, the diol C1 may preferably be an aromatic compound. For example, it may be a dihydroxyarylene sulfone or a dihydroxyarylene ketone. The following compounds are examples of preferred diols C1:

[0034] - dihydroxybenzenes, especially hydroquinone and resorcinol;

[0035] - dihydroxynaphthalene, in particular 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene and 2,7-dihydroxynaphthalene;

[0036] - dihydroxybiphenyls, especially 4,4′-biphenol and 2,2′-biphenol;

[0037] - bisphenyl ethers, in particular bis(4-hydroxyphenyl) ether and bis(2-hydroxyphenyl) ether;

[0038] - bisphenylpropanes, in particular 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane;

[0039] - bisphenylmethane, especially bis(4-hydroxyphenyl)methane;

[0040] - bisphenyl sulfones, especially bis(4-hydroxyphenyl)sulfone;

[0041] - bisphenyl sulfide, in particular bis(4-hydroxyphenyl) sulfide;

[0042] - bis(phenyl)ketones, in particular bis(4-hydroxyphenyl)ketone;

[0043] - bisphenylhexafluoropropane, especially 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)hexafluoropropane; and

[0044] - bisphenylfluorene, especially 9,9-bis(4-hydroxyphenyl)fluorene.

[0045] The diol C1 may preferably be hydroquinone, resorcinol, dihydroxynaphthalene, especially 2,7-dihydroxynaphthalene, 4,4'-biphenol or a mixture thereof.

[0046] Although a mixture of two or more diols may be included as diol C1 in the polyarylene ether, it may be preferred to include only one diol, which may most preferably be hydroquinone or 4,4'-biphenol. In some aspects, it may also be advantageous that diol C1 is dihydroxydiphenyl sulfone.

[0047] Polyarylene ether is polyarylene ether ketone or polyarylene ether sulfone. Typically, polyarylene ether ketone contains -O- and -CO- groups connecting arylene groups. Polyarylene ether ketone may contain only -O- and -CO- groups. It may also contain other groups connecting arylene groups. Examples of such other groups connecting arylene groups are -S-, -NN- or alkylene groups. Therefore, polyarylene ether ketones containing a certain amount of -SO2- groups or a certain amount of -SO2- groups and at least one other group are included in the present disclosure. In this case, less than 50 mol% of the theoretically possible -CO- groups present in polyarylene ether ketone are replaced by -SO2- groups. Typically, no more than about 30 to 40 mol% of the theoretically possible -CO- groups present in polyarylene ether ketone are replaced by -SO2- groups. If present in polyarylene ether ketone, 1 mol% or more, preferably 5 mol% or more of the theoretically possible -CO- groups present in polyarylene ether ketone may be replaced by -SO2- groups. Thus, for example, from 1 to 20 mol % of the theoretically possible —CO— groups present in the polyarylene ether ketone can be replaced by —SO 2 — groups.

[0048] Likewise, polyarylene ether sulfone may contain only -O- and -SO2- groups connecting arylene groups. It may also contain other groups connecting arylene groups. As examples thereof, groups such as -S-, -NN- or alkylene groups may be mentioned. Therefore, polyarylene ether sulfones containing a certain amount of -CO- groups or a certain amount of -SO2- groups and at least one other group are included in the present disclosure. In this case, less than 50 mol% of the theoretically possible -SO2- groups present in polyarylene ether sulfone are replaced by -CO- groups. Typically, no more than about 30 to 40% of the theoretically possible -SO2- groups present in polyarylene ether sulfones are replaced by -CO- groups. If present in polyarylene ether sulfones, then typically 1 mol% or more, preferably 5 mol% or more of the theoretically possible -SO2- groups present in polyarylene ether sulfones may be replaced by -CO- groups. Therefore, for example, 1 to 20 mol% of the theoretically possible -SO2- groups present in polyarylene ether sulfones may be replaced by -CO- groups.

[0049] It is preferred that the polyarylene ether comprises at least one unit of the general formula II (unit U1)

[0050]

[0051] and at least one unit (unit U2) derived from unit U1 and compound A,

[0052] The symbols t, q, Q, T, Y, Ar and Ar 1 is defined as follows:

[0053] r: 0 or 1

[0054] t, q: are independently 0, 1, 2 or 3,

[0055] Q, T, Y: are each independently a chemical bond or are selected from -O-, -S-, -So2-, S=O, C=O, -N=N- and -CR a R b - a group, wherein R a and R b are in each case independently of one another a hydrogen atom or a C1 to C12-alkyl, C1 to C12-alkoxy, C3 to C12-cycloalkyl or C6 to C18-aryl group, and wherein at least one of Q, T and Y is -SO2- or -CO-,

[0056] Z: is a group derived from ISOSO, ISOMA or ISOID, and

[0057] Ar and Ar 1 : are independently an arylene group having 6 to 18 carbon atoms.

[0058] Under the above premise, if Q, T or Y is a chemical bond, this means that the adjacent group on the left side and the adjacent group on the right side exist directly connected to each other through a chemical bond.

[0059] However, it may be preferred that, in formula II, Q, T and Y are independently selected from -O- and -SO2-, provided that at least one of Q, T and Y is -SO2-.

[0060] If Q, T or Y is -CR a R b -, then R a and R b In each case, independently of one another, it is a hydrogen atom or a C1 to C12 alkyl group, a C1 to C12 alkoxy group or a C6 to C18 aryl group.

[0061] It is preferred that C1 to C12-alkyl includes straight-chain and branched saturated alkyl radicals having 1 to 12 carbon atoms. In particular, the following moieties may be mentioned: C1 to C6-alkyl moieties, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, 2-methylpentyl or 3-methylpentyl, and longer chain moieties, such as straight-chain heptyl, octyl, nonyl, decyl, undecyl, lauryl, and their mono-branched or multi-branched analogs.

[0062] Alkyl moieties which may be used in the abovementioned C1 to C12-alkoxy groups are, for example, alkyl moieties having 1 to 12 carbon atoms as defined above.

[0063] C3-C12-cycloalkyl may in particular comprise C3 to C8 cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylethyl, cyclopentylpropyl, cyclopentyl-butyl, cyclopentylpentyl, cyclopentylhexyl, cyclohexylmethyl, cyclohexyldimethyl, and cyclohexyltrimethyl.

[0064] Ar and Ar 1 are independently difunctional C6 to C18-arylene radicals. Starting from the starting materials described above or below, Ar can preferably be derived from an electron-rich aromatic substance which is very susceptible to electrophilic attack, so that it can be hydroquinone, resorcinol, dihydroxynaphthalene, in particular, it can be 2,7-dihydroxynaphthalene or 4,4′-biphenol. Ar 1 An unsubstituted bifunctional C6- or C12-arylene group may be preferred.

[0065] Particularly preferred are difunctional C6 to C18 arylene groups Ar and Ar 1is a phenylene group, and is, independently of one another, for example, 1,2-phenylene, 1,3-phenylene and 1,4-phenylene; and a naphthylene group, for example, 1,6-naphthylene, 1,7-naphthylene, 2,6-naphthylene or 2,7-naphthylene; or a difunctional arylene group derived from anthracene, phenanthrene or tetracene.

[0066] Preferably, Ar and Ar 1 Independently of one another are 1,4-phenylene, 1,3-phenylene, naphthylene, in particular 2,7-dihydroxynaphthylene or 4,4′-biphenylene.

[0067] It may be preferred that the polyarylene ether comprises at least one of the following repeating units IIa to IId:

[0068]

[0069] Where x is between 0.05 and 1, and n is 1.

[0070] The polyarylene ether sulfone may particularly preferably have the following repeating units: wherein Ar is 1,4-phenylene, t is 1, q is 0, T and Y are SO2. Such polyarylene ether sulfones may be referred to as polyarylene ethers of the polyethersulfone (PESU) type (formula IIa or IIb, respectively).

[0071] The polyarylene ether sulfone may particularly preferably have the following repeating units: wherein Ar is 1,4-phenylene, t is 1, q is 0, T is C(CH3)2, and Y is SO2. Such polyarylene ether sulfone may be referred to as polysulfone (PSU) type polyarylene ether (Formula IIc).

[0072] The polyarylene ether sulfone may particularly preferably have the following repeating units: wherein Ar is 1,4-phenylene, t is 1, q is 0, T is a chemical bond, and Y is SO 2. Such polyarylene ether sulfone may be referred to as polyphenylene sulfone (PPSU) type polyarylene ether (Formula IId).

[0073] For the purposes of this disclosure, abbreviations such as PPSU, PESU and PSU conform to DIN EN ISO 1043-1:2001.

[0074] It will be understood by those skilled in the art that at least one unit U2 is structurally combined with the unit U1 as described above and the compound A as described above in any possible combination thereof.

[0075] Thus, for example, for a PESU-type polyarylene ether comprising repeating units IIb, the molecular structure of the polyarylene ether can be exemplarily represented as comprising units of formula IIa1 and / or IIa2 and compound A, which is 1,1,1-trihydroxyphenylethane:

[0076]

[0077]

[0078] Those skilled in the art should understand that, in the polyarylene ether, the molar ratio of at least one unit U1 to at least one unit U2 depends on the amount of compound A.

[0079] Optionally, the polyarylene ether may further comprise at least one additional repeating unit U3. The at least one additional repeating unit U3 may preferably be of the following formulae IIIa to IIIo:

[0080]

[0081]

[0082] Particularly preferred units U3 of the formula III are the units IIIa, IIIg and / or IIIk.

[0083] The polyarylene ether may comprise the units U1, U2 and / or U3 in a statistical manner.

[0084] The nature of the end groups of the polyarylene ether is not particularly limited. Generally, it may depend on whether reactive or non-reactive end groups are required as end groups. If it is intended to polymerize the polyarylene ether with at least one other monomer or polymer to produce a copolymer, such as a block copolymer or a polymer network, a reactive end group may, for example, be preferred. Possible end groups are phenolic OH end groups or phenolic acid ester end groups, phenolic alkoxy end groups (wherein -OCH3 end groups may be preferred), amino end groups (wherein -NH2 may be preferred), chlorine end groups. Among the end groups, Cl may be most preferred. The end group may also be a phenolic anhydride end group. The end groups may be one type or may be different from each other. Generally, it may be preferred that the end groups are Cl-, OH- and / or -OCH3. Inert end groups may generally be obtained by capping reactive end groups. In the case where the polyarylene ether is intended to be used for applications obtainable by a solution preparation method such as solution spinning or solution casting, end capping may not be required. Uncapped polyarylene ether may be used in conjunction with membrane preparation in particular. In this case, polyarylene ethers having Cl and / or OH end groups can be advantageous.

[0085] The relative viscosity of the polyarylene ether may preferably be 0.20 to 1.30 dl / g, in particular 0.30 to 0.95. The relative viscosity may be measured at 20° C. or 25° C. in a 1 wt% N-methylpyrrolidone solution, a mixture of phenol and dichlorobenzene, or in 96% sulfuric acid, depending on the solubility of the polyarylene ether.

[0086] The polyarylene ether may preferably have an average molecular weight Mn (number average) of 2000 to 75 000 g / mol, in particular 5000 to 45 000 g / mol, determined by GPC.

[0087] The weight average molar mass Mw of the polyarylene ether may preferably be 10 000 to 200 000 g / mol, in particular it may be 15 000 to 150 000 g / mol, and it may particularly preferably be 18 000 to 100 000 g / mol, determined by gel permeation chromatography as follows: in dimethylacetamide as solvent, relative to a narrow distribution polymethyl methacrylate as standard (calibrated at 800 to 1 820 000 g / mol), using 4 chromatography columns (pre-column, 3 separation columns based on polyester copolymers), operating at 80° C. The flow rate was set to 1 ml / min, the injection volume was 100 μl. Detection was performed using an RI detector.

[0088] The disclosed poly(arylene ether) can be advantageously prepared by the following process comprising reacting:

[0089] a) at least one trifunctional or higher functional compound (compound A), and

[0090] b) isosorbide, isomannide, isoidide or a mixture thereof (compound B), and

[0091] c) at least one difunctional compound comprising at least one dichlorodiaryl sulfone or dichlorodiaryl ketone or a mixture thereof (compound C2).

[0092] Compound A and Compound B are as described above.

[0093] Compound C2 is known or, if it is not known per se, can be prepared by methods known to those skilled in the art. Compound C2 is a difunctional compound. "Difunctional" means that it has two functional groups that are reactive toward compounds A, B and, if present, diol C1, and are not fluorine or chlorine. In general, compound C2 is not subject to any essential restrictions, provided that it is sufficiently reactive in nucleophilic aromatic substitution.

[0094] Compound C2 comprises at least one dichlorodiaryl sulfone or dichlorodiaryl ketone or a mixture thereof. In addition, compound C2 may comprise, for example, at least one bifunctional compound capable of preparing a diisocyanate containing -S-, S=O, -N=N- and / or -CR a R b -group polyarylene ether sulfone or polyarylene ether ketone.

[0095] For the preparation of polyarylene ether ketone, compound C2 may be at least one, for example one or more dichlorodiaryl ketones, such as 1 to 3 dichlorodiaryl ketones, whereby 1 or 2, in particular 1 dichlorodiaryl ketones may be preferred. Compound C2 may also be a mixture of at least 50 mol% of at least one dichlorodiaryl ketone and less than 50 mol% of at least one dichlorodiaryl sulfone. For example, compound C2 may be a mixture of 50 mol%, such as 60 mol% to 80 mol% or more, such as 90 mol%, of at least one dichlorodiaryl ketone and the remainder being at least one, for example 1 to 3 dichlorodiaryl sulfones, whereby 1 or 2, in particular 1, may be a preferred dichlorodiaryl sulfone.

[0096] For the preparation of polyarylene ether sulfone, compound C2 can be at least one, for example one or more dichlorodiaryl sulfones, such as 1 to 3 dichlorodiaryl sulfones, whereby 1 or 2, in particular one, dichlorodiaryl sulfone can be preferred. Compound C2 can also be a mixture of at least 50 mol% of at least one dichlorodiaryl sulfone and less than 50 mol% of at least one dichlorodiaryl ketone. For example, compound C2 can be a mixture of 50 mol%, such as 60 mol% to 80 mol% or more, such as 90 mol%, of at least one dichlorodiaryl sulfone and the remainder being at least one, for example 1 to 3, dichlorodiaryl ketones, whereby 1 or 2, in particular one, can be a preferred dichlorodiaryl ketone.

[0097] For the preparation of polyarylene ether sulfone, suitable compound C2 may be especially at least one, so that preferably one dichlorodiphenyl sulfone, such as 4,4'-dichlorodiphenyl sulfone, bis(2-chlorophenyl)sulfone, 2,2'-dichlorodiphenyl sulfone, may be particularly preferably 4,4'-dichlorodiphenyl sulfone. If PESU is sought, 4,4'-dichlorodiphenyl sulfone (DCDPS) may be used. Compared with the corresponding linear polymers of comparable molecular weight, the polyarylene ether sulfones disclosed herein generally show lower solution viscosities. Therefore, compared with the corresponding linear polymers of comparable molecular weight, polyarylene ether sulfones can generally be better handled from solutions, in particular for the preparation of membranes.

[0098] Most preference is given to processes which start from monomeric compounds A, B, C2 and, if present, diol C1, which means that the reaction can preferably be carried out starting from monomers rather than from prepolymers.

[0099] The starting compound is subjected to a polycondensation reaction to obtain a polyarylene ether copolymer, which can generally be carried out in the presence of at least a catalytic amount of a base. It can be carried out in the absence of a solvent L, or it can be preferably carried out in the presence of a solvent L. A reaction mixture is formed. The components of the reaction mixture are generally reacted simultaneously. The individual components can be mixed in an upstream step and then reacted. The individual components can also be fed into a reactor, where they are mixed and then reacted. Preferably, the reaction can be carried out in one step. This means that the deprotonation of the compound B with an OH group and, if present, the diol C1 and A and their condensation reaction with the compound C2 are carried out in a single reaction stage without the need to separate the intermediate product.

[0100] The preparation of polyarylene ethers with simultaneous control of the end groups is generally known to those skilled in the art and is described in more detail below. For polyarylene ether copolymers, this can be achieved, for example, by controlling the amount of functional groups of compounds A, B, C and, if present, D and / or E (i.e. as starting compounds) before the polymerization. The ratio of the starting compounds used is derived in principle from the stoichiometry of the polycondensation reaction, which proceeds with the theoretical elimination of hydrogen halide, such as hydrogen chloride, and is determined in a known manner by those skilled in the art.

[0101] It is generally preferred to control or adjust the molar ratio of the functional groups of the starting compounds that are reactive with each other. Thus, the molar ratio of the chlorine groups and the functional groups reactive to chlorine, such as hydroxyl groups in many cases, can vary, depending on factors such as control of the end groups or control of the reaction rate and molecular weight. It can be equimolar. Alternatively, the molar ratio of the chlorine groups can be higher than the molar ratio of the functional groups reactive to chlorine, such as hydroxyl groups in many cases, or vice versa. Thus, for example, the molecular weight of the polyarylene ether, which is a polyarylene ether sulfone containing phenolic acid ester end groups, can be adjusted using a shift in the stoichiometric ratio of the defined starting compounds B and C2. Typically, the molar ratio is not greater than about 3:1 to about 1:3, such as about 2:1 to about 1:2. In order to obtain higher molecular weights, the molar ratio is mostly closer to an equal molecular ratio.

[0102] As mentioned above, compound A and diol C1 may have functional groups reactive to chlorine. Compound A may also have a chlorine functional group. Similarly, compound C2 may have two chlorine groups or may have one chlorine group and one group reactive to chlorine. Therefore, the ratio of the starting compounds and the ratio of those functional groups therein must be selected accordingly.

[0103] For example, in order to increase the number of phenolic OH end groups, an excess of OH end groups is preferred. It may be preferred to adjust the ratio of chlorine end groups to phenolic OH end groups by controllably establishing an excess of a starting compound having a hydroxyl function. In this case, the ratio of OH groups to chlorine groups may be 1.005 to 1.2, in particular 1.01 to 1.15, most preferably 1.02 to 1.1, based on moles.

[0104] In the case of seeking a more stable end group, it is preferred to increase the number of chlorine end groups, in particular the number of phenyl chlorine, so that an excess of chlorine end groups is preferred. In a preferred embodiment, the ratio of functional groups and end groups (such as hydroxyl groups, which are preferred in many cases) to chlorine end groups is adjusted by controllably setting up an excess of chlorine-containing compounds. Preferably, in this case, the ratio of chlorine to OH groups can be 1.005 to 1.2, especially 1.01 to 1.15, most preferably 1.02 to 1.1 in moles.

[0105] Preferably, the conversion in the polycondensation is at least 0.9, which ensures a sufficiently high molecular weight.

[0106] In principle, the process can be carried out in the absence of solvents. In particular, if the aim is to obtain very light-colored polyarylene ethers, the process can in most cases be carried out more advantageously in the presence of at least one solvent (solvent L).

[0107] In the context of the present invention, the solvent L may preferably be an organic, especially aprotic polar solvent. Suitable solvents L may also have a boiling point of 80 to 320° C., especially 100 to 280° C., preferably 150 to 250° C. Suitable aprotic polar solvents are, for example, high-boiling ethers, esters, ketones, asymmetric chlorinated hydrocarbons, anisole, dimethylformamide, dimethyl sulfoxide, sulfolane, dimethylacetamide (DMAC), N-methyl-2-pyrrolidone (NMP) or N-ethyl-2-pyrrolidone (NEP) or any combination thereof. In order to increase the solubility, the solvent L may, for example, be a mixture of 2 to 3 solvents. In most cases, it is sufficient to use two or more, preferably only one solvent.

[0108] The solvent L may especially be DMAC, NMP or NEP or any mixture thereof.

[0109] Preferably, the method comprises reacting compounds A, B, C2 and, if present, diol C1 in at least one of the aprotic polar solvents, for example in DMAC, NMP or NEP or any mixture thereof, wherein N-methyl-2-pyrrolidone is particularly preferred. Therefore, it is preferred to start with a mixture of starting compounds A, B, C2 and, if present, diol C1. In order to promote the formation of block copolymers, it is of course also possible to add specific compounds A, B, C2 and, if present, diol C1 at different times during the reaction. In particular, it is preferred to start with a mixture of one compound A, one compound B, one diol C1 and one compound C2, in at least one aprotic polar solvent, for example in DMAC, NMP or NEP or any mixture thereof, wherein NMP may be particularly preferred. An example of a preferred way of carrying out the method is to react one compound A, one compound B and one compound C2 in at least one aprotic polar solvent such as DMAC, NMP or NEP or any mixture thereof, which may be particularly NMP.

[0110] In order to separate the water released during the reaction, a co-solvent forming an azeotrope can be used, such as toluene or chlorobenzene. Generally, it may be preferred not to use such a co-solvent forming an azeotrope. Generally, it may be preferred to separate the water and the solvent L during the heating process. The loss of solvent L can be compensated by, for example, starting with a large amount of solvent L or adding solvent L during the reaction. Controlling the viscosity increase during the reaction can also be a means of controlling the molecular weight of the polyarylene ether.

[0111] The disclosed methods may generally comprise reacting compounds A, B, C2 and, if present, diol C1 in the presence of at least one base. It will be appreciated by those skilled in the art that functional groups such as OH groups, e.g., phenolic OH groups, are preferably reacted in the presence of at least one base in order to increase reactivity to the chloro substituent of compound C2.

[0112] The at least one base can generally be a hydroxide, a carbonate or a bicarbonate. Thus, it can be a mixture of at least one hydroxide and at least one carbonate, or a mixture of at least one carbonate and at least one bicarbonate. Thus, at least one anhydrous alkali metal carbonate can be preferred. For example, mixtures of different hydroxides or different carbonates or different bicarbonates can also be used. It can be preferred to use one base. It can be preferred that one base is an alkali metal carbonate. In particular, sodium carbonate, potassium carbonate, calcium carbonate or mixtures thereof can be preferred, and potassium carbonate can be very particularly preferably used as the base. From the aspect of reaction rate, and if in particular very light-colored polyarylene ether is intended, the volume-weighted average particle size of potassium carbonate is less than 100 microns, for example 5 to 80 μm, preferably 10 to 60 μm, for example 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or 55 μm or any non-uniform μm size between 5 and 100 μm, as measured using a Malvern Mastersizer 2000 instrument as a suspension of the solid in chlorobenzene / sulfolane 60 / 40.

[0113] A particularly preferred combination is DMAC, NMP or NEP or any mixture thereof as solvent and potassium carbonate as base, especially potassium carbonate having a size of less than 100 μm. A particularly preferred combination is NMP as solvent and potassium carbonate as base, especially potassium carbonate having a size of less than 100 μm, such as 5 to 80 μm, preferably 10 to 60 μm, such as 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm or 55 μm or any non-uniform μm size between 5 and 100 μm, determined as described above.

[0114] The reaction of compounds A, B, C2 and, if present, C1 can be carried out at a temperature at which the reaction proceeds at an acceptable rate and poly(arylene ether) is obtained with acceptable quality, such as having a desired molecular weight and molecular weight distribution. Typically, the process can be carried out at a temperature of 80 to 250° C., preferably 100 to 220° C. When the process is carried out in the presence of a solvent L and at ambient pressure, the upper temperature limit is generally determined by the boiling point of the solvent L. In particular, when the process is carried out in the absence of a solvent, the stability of the reactants can be a factor limiting the reaction temperature.

[0115] Although the skilled person can adapt the reaction temperature and time to the specific poly(arylene ether) to be prepared, a reaction temperature of 180 to 205° C. may be suitable, and a temperature of 185 to 195° C. may be preferred. At a temperature of 185 to 195° C., the reaction may be carried out for 2 to 20 hours, such as 3 to 18 hours, such as 5 to 15 hours. In particular, if the process is carried out in a solvent L such as NMP, the conditions may be preferred conditions.

[0116] In the method, at least one compound (compound D) having a functional group reactive to the reactive groups contained in the polymer chain can be used. It is preferred to use a compound D. Thus, the chain length of the polyarylene ether copolymer can be controlled. Usually, after the polycondensation reaction, for example after reaching a conversion of at least 0.9, a reaction with compound D can be preferred. It is preferred that compound D is at least one aliphatic organic chloride. As a result, the reactive groups further react, and the reactive groups can be terminal groups, in particular hydroxyl terminal groups. The polyarylene ether copolymer then contains compound D in a reacted form. During further processing, such polyarylene ether copolymers are generally stable, in particular to prevent further extension of the polymer chain.

[0117] The preferred at least one aliphatic organic halide is at least one alkyl halide having a linear or branched alkyl group of 1 to 10 carbon atoms, in particular an alkyl chloride, which may in particular be a primary alkyl chloride, particularly preferably a halomethyl group, in particular methyl chloride.

[0118] The reaction with compound D can be preferably carried out at a temperature of 90° C. to 160° C., especially 100° C. to 150° C. The time can vary widely, usually at least 5 minutes, especially at least 15 minutes. The reaction time can usually preferably be 15 minutes to 8 hours, especially 30 minutes to 4 hours.

[0119] Various methods can be used for the reaction of compound D, more specifically at least one aliphatic organic chloride. In addition, the amount of compound D, more specifically at least one aliphatic organic chloride, can be stoichiometric or expressed as an excess, wherein the excess can be, for example, up to a 5-fold excess. For example, it can be preferred that at least one aliphatic organic chloride is added continuously, in particular by continuous introduction in the form of a gas stream.

[0120] The reaction with compound D can be carried out in a separate process unit or, preferably, directly in the polycondensation reactor.

[0121] If the process is carried out in the presence of a solvent L, and after the reaction is complete, further solvent L is generally added to cool the reaction mixture, the solvent L being, for example, the solvent L in which the reaction is carried out, such as DMAC, NMP, NEP or any mixture thereof, wherein NMP may be preferred. For example, the reaction mixture may be cooled to a temperature range in which compound D can react with the polyarylene ether in a separate unit or polycondensation reactor as described above. Thereafter, if necessary, the reaction mixture may be further cooled, so that about 80°C may be preferred. If the polyarylene ether does not react with compound D, the reaction mixture may be preferably cooled to about 80°C. At this temperature, the reaction mixture, which is generally a dispersion, is taken out from each reaction unit, which generally includes a reaction vessel, and transferred to at least one separation unit. The separation unit may preferably include a filtration unit to separate salts formed during the reaction, such as potassium chloride, from the reaction mixture. Depending on the viscosity of the dispersion, the process may take several minutes or hours, such as 30 min to 24 h. During this time, the filtrate may also be cooled to ambient temperature (23°C). The product may then be isolated, for example, by precipitation due to the addition of a non-solvent. The non-solvent can be, for example, a mixture of water and at least one polar aprotic solvent. A mixture of water and solvent L can be preferably used, the solvent L being, for example, DMAC, NMP, NEP or any mixture thereof, wherein NMP can be preferred. Therefore, water can usually be used at a ratio greater than solvent L, the solvent L being, for example, DMAC, NMP, NEP or any mixture thereof, wherein NMP can be preferred. Precipitation can most preferably be carried out in a water / NMP mixture (weight ratio of 80 / 20). Precipitation can also be carried out in an acidic medium, for example, in a water / NMP mixture containing an acid. Suitable acids are, for example, organic or inorganic acids, such as carboxylic acids such as acetic acid, propionic acid, succinic acid or citric acid, and inorganic acids such as hydrochloric acid, sulfuric acid or phosphoric acid. The obtained powder is collected, usually filtered, then usually washed and finally dried, wherein a temperature of 80 to 150° C. under vacuum can be used.

[0122] In addition to the above disclosure, the skilled person can use methods that can be obtained by applying his common sense. Preparation methods for producing polyarylene ether sulfones are described, for example, in "Encyclopedia of Polymer Science and Technology" by Herman F. Mark, third edition, volume 4, 2003, "Polysulfones" chapter, pages 2 to 8, and in "Aromatic Polyethers" by Hans R. Kricheldorf, Handbook of Polymer Synthesis, second edition, 2005, pages 427 to 443. More details on the synthesis of OH-terminated polyarylene ether sulfones are given, for example, in R. Viswanathan, BC Johnson, JEM McGrath, Polymer 25 (1984) 1827. Information on controlling molecular weight is disclosed, for example, in A. Noshay, M. Matzner, CN Merriam, J. Polym. Sci. A-1 9 (1971) 3147.

[0123] The general advantage of the method disclosed herein is that the incorporation rate of compound B into polyarylene ether sulfone is high or very high. Moreover, high molecular weight polyarylene ether sulfone can be obtained without using fluorinated monomers. Therefore, high molecular weight polyarylene ether sulfone can be prepared more environmentally friendly and cheaper.

[0124] Some examples of poly(arylene ether sulfones) and poly(arylene ether ketones) in the present disclosure and which can be prepared according to the above-mentioned method and which may be preferred are given in Table 1 below.

[0125]

[0126] Also disclosed herein is the use of at least one polyarylene ether disclosed herein or obtainable by the process disclosed herein, for example of the PPSU, PESU or PSU type, wherein most preferably the polyarylene ether may comprise THPE, isosorbide and DCDPS in polymerized form, for the preparation of coatings, fibers, films, foams, moldings and / or membranes.

[0127] Coating is to be understood as meaning, for example, a layer fixed on the surface of a carrier material, in particular a layer adhering thereto. The coating can be applied by a preparation method according to DIN 8580. In the context of the present application, the coating can be a thin layer or a thick layer, or one or more intrinsic adhesive layers. The carrier material used can be almost all known materials, such as metals, insulators, semiconductors, crystalline or amorphous materials, fabrics (woven fabrics, nonwoven fabrics, knitted fabrics) or films.

[0128] The fiber is, for example, a more or less flexible structure that is thin relative to its length. The fiber may be dense or hollow. The fiber may be round or nearly round, or may have different cross-sectional shapes. For example, it may be flat. The fiber may also be tubular. The fiber may have a smooth surface, or it may have holes or cavities. The fiber may be obtained, for example, by an extrusion method. It may be more preferred that the fiber is obtained by spinning from at least one polyarylene ether, and thus generally preferably one polyarylene ether. If thermal stress on at least one polyarylene ether is involved, spinning from a solution may be advantageous. In many cases, a solvent for spinning may be advantageously used, the solvent comprising or consisting of a solvent L, the solvent L being, for example, DMAC, NMP, NEP or any mixture thereof. If the method is carried out in the presence of a solvent L, spinning may, for example, be carried out directly after separating the polyarylene ether from the salt. It is also possible to first separate the polyarylene ether and then dissolve it in the solvent to be used for spinning. In order to improve the mechanical properties of the fiber, it is advantageous to spin at least one polyarylene ether in the solution by an electrospinning method including electromagnetic electrospinning, wherein generally a polyarylene ether is preferred, which may be preferred. For example, in the case where the fiber is prepared as a nanofiber, the electrospinning method may be most preferred. The electromagnetic electrospinning method can be used to prepare a nonwoven fabric from at least one polyarylene ether, wherein generally a polyarylene ether is preferred. Since the electrospinning method requires that the melt or the solution is preferably conductive, it is not necessary to separate salts, all or substantially all of the salts, from the reaction mixture after the reaction. For preparing fibers by electrospinning, it is preferred that the polyarylene ether comprises compound B as the only diol.

[0129] Film is for example a single layer. Film can be understood to mean an impermeable, partially impermeable or selectively permeable film, or a permeable film or a permeable film in one direction. The type of film is usually not limited. In addition, film can for example be a reverse osmosis (RO) membrane, a forward osmosis (FO) membrane, a nanofiltration (NF) membrane, an ultrafiltration (UF) membrane or a microfiltration (MF) membrane. In many cases, it is preferred that film is a UF, NF or MF membrane.

[0130] The poly(arylene ether) disclosed herein can be used for different filter membrane geometries. For example, it can be used for flat membranes and / or capillary hollow fiber membranes. The flow toward these membranes can take the form of terminal flow (dead-end flow) or cross flow.

[0131] The membrane can be prepared using at least one polyarylene ether, wherein it can be preferably prepared from one polyarylene ether. Generally, the membrane can be prepared according to methods known to those skilled in the art. The membrane can be prepared, for example, by solution casting. Thus, a casting solution of at least one polyarylene ether in a solvent L (e.g., DMAC, NMP, NEP or any mixture thereof, wherein NMP can be preferred) can be prepared. Dimethyl lactamide (DML) is another preferred solvent L. The casting solution generally contains at least one, preferably one, compound that can be removed from the membrane by washing in many cases. The compound is also generally referred to as a pore former. In order to prepare a membrane from at least one polyarylene ether, polyvinyl pyrrolidone and / or polyethylene glycol (PEG) can generally be used as a pore former in the casting solution.

[0132] Membranes can be used in contact with water, body fluids or liquids in food production. In some aspects, membranes can also be used for gas separation.

[0133] Therefore, the membrane can be used in combination with water treatment such as solid separation or medical technology. In the medical or industrial fields, the membrane can be used, for example, to recover vaccines or antibiotics from fermentation broth, laboratory-grade water purification, water disinfection (including removal of viruses, removal of hormones (endocrin) or pesticides). The membrane can be used, for example, in combination with blood treatment such as dialysis. It can be used, for example, to prepare blood treatment equipment.

[0134] Liquids in food production can be, for example, beverages, such as alcoholic or non-alcoholic beverages, such as juice or beer, which can be purified by the membranes disclosed herein. Likewise, the membranes can be used in the processing of milk or products derived from milk.

[0135] An article comprising at least one membrane may, for example, be a filtration system, such as a dialysis filter device, a module row or a module rack.

[0136] The molded articles can be essentially solid geometric bodies which can be produced, for example, by molding, injection molding, extrusion, calendering, rotational casting, foaming, blow molding, shaping or joining processes. Example

[0137] The following examples provide further explanation of the present invention but do not limit the present invention.

[0138] Definitions and Abbreviations:

[0139] Reaction time: the time the reaction mixture is kept at 190°C

[0140] DCDPS: 4,4'-dichlorodiphenyl sulfone

[0141] DHDPS 4,4'-Dihydroxydiphenyl sulfone

[0142] BP: 4,4'-dihydroxybiphenyl

[0143] ISOSO: Isosorbide

[0144] THPE 1,1,1-Trihydroxyphenylethane

[0145] NMP: N-methyl-2-pyrrolidone

[0146] PVP: Polyvinylpyrrolidone

[0147] PEG: Polyethylene glycol

[0148] PWP Pure Water Penetration

[0149] MWCO Molecular weight cut-off

[0150] As described above, the particle size of potassium carbonate was determined using a Malvern Mastersizer 2000 instrument as a suspension of the solid in chlorobenzene / sulfolane 60 / 40.

[0151] Examples C1 to 16 - Preparation of polyarylene ethers

[0152] General method:

[0153] In a container equipped with a stirrer, a Dean-Stark trap, a nitrogen inlet and a temperature control device, the monomers and the THPE and potassium carbonate used in the experiment of the present invention are suspended in NMP under a nitrogen atmosphere. Under stirring, the mixture is heated to a maximum of 190°C in one hour. The water formed in the reaction is continuously removed by distillation. Monitor the potential solvent loss to be compensated. Nitrogen is purged through the mixture, and the mixture is kept at 190°C for the condensation time. After this time, NMP is added under nitrogen to cool the mixture to room temperature (within one hour). In order to remove the potassium chloride formed, the reaction mixture is filtered. The polymer solution obtained is then precipitated in water, the polymer beads obtained are separated, and then extracted with hot water (85°C) for 20h. The beads are then dried at 120°C for 24h under reduced pressure (<100 mbar).

[0154] Comparative Example C1

[0155] The preparation was carried out according to the general method, as described below:

[0156] 580.06 g (2.02 mol) of DCDPS, 292.28 g (2.00 mol) of ISOSO, and 304.05 g (2.20 mol) of potassium carbonate (volume average particle size: 32.4 μm) were suspended in 1050 ml of NMP.

[0157] Condensation time: 9 hours

[0158] 1950 ml of NMP were added to cool the mixture.

[0159] Comparative Example C2

[0160] The preparation was carried out according to the general method, as described below:

[0161] 435.047 g (1.515 mol) of DCDPS, 219.21 g (1.50 mol) of ISOSO and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 790 ml of NMP.

[0162] Condensation time: 14 hours

[0163] 1460 ml of NMP were added to cool the mixture.

[0164] Embodiment 3 of the present invention

[0165] The preparation was carried out according to the general method, as described below:

[0166] 435.047 g (1.515 mol) of DCDPS, 212.852 g (1.4565 mol) of ISOSO, 9.19 g (0.03 mol) of THPE, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 790 ml of NMP.

[0167] Condensation time: 13 hours

[0168] 1460 ml of NMP were added to cool the mixture.

[0169] Embodiment 4 of the present invention

[0170] The preparation was carried out according to the general method, as described below:

[0171] 435.047 g (1.515 mol) of DCDPS, 210.441 g (1.44 mol) of ISOSO, 12.254 g (0.04 mol) of THPE and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 790 ml of NMP.

[0172] Condensation time: 13 hours

[0173] 1460 ml of NMP were added to cool the mixture.

[0174] Comparative Example C5

[0175] The preparation was carried out according to the general method, as described below:

[0176] 432.91 g (1.5075 mol) of DCDPS, 219.21 g (1.50 mol) of ISOSO, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 790 ml of NMP.

[0177] Condensation time: 14 hours

[0178] 1460 ml of NMP were added to cool the mixture.

[0179] Comparative Example C6

[0180] The preparation was carried out according to the general method, as described below:

[0181] 432.91 g (1.5075 mol) of DCDPS, 219.21 g (1.50 mol) of ISOSO, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 650 ml of NMP.

[0182] Condensation time: 14 hours

[0183] 1600 ml of NMP were added to cool the mixture to room temperature.

[0184] Comparative Example C7

[0185] The preparation was carried out according to the general method, as described below:

[0186] 432.91 g (1.5075 mol) of DCDPS, 153.48 g (1.05 mol) of ISOSO, 112.63 g (0.45 mol) of DHDPS, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 650 ml of NMP.

[0187] Condensation time: 14 hours

[0188] 1600 ml of NMP were added to cool the mixture.

[0189] Comparative Example C8

[0190] The preparation was carried out according to the general method, as described below:

[0191] 432.91 g (1.5075 mol) of DCDPS, 175.37 g (1.20 mol) of ISOSO, 75.08 g (0.3 mol) of DHDPS, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 650 ml of NMP.

[0192] Condensation time: 14 hours

[0193] 1600 ml of NMP were added to cool the mixture.

[0194] Example 9

[0195] The preparation was carried out according to the general method, as described below:

[0196] 432.91 g (1.5075 mol) of DCDPS, 153.48 g (1.05 mol) of ISOSO, 101.36 g (0.405 mol) of DHDPS, 9.19 g (0.03 mol) of THPE, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 650 ml of NMP.

[0197] Condensation time: 11 hours

[0198] 1600 ml of NMP were added to cool the mixture.

[0199] Example 10

[0200] The preparation was carried out according to the general method, as described below:

[0201] 432.91 g (1.5075 mol) of DCDPS, 175.37 g (1.20 mol) of ISOSO, 63.82 g (0.255 mol) of DHDPS, 9.19 g (0.03 mol) of THPE, and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size 8.7 μm) were suspended in 650 ml of NMP.

[0202] Condensation time: 12 hours

[0203] 1600 ml of NMP were added to cool the mixture.

[0204] Comparative Example C11

[0205] The preparation was carried out according to the general method, as described below:

[0206] 432.91 g (1.5075 mol) of DCDPS, 218.18 g (1.493 mol) of ISOSO, 1.37 g (0.0045 mol) of THPE and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 650 ml of NMP.

[0207] Condensation time: 14 hours

[0208] 1600 ml of NMP were added to cool the mixture.

[0209] Comparative Example C12

[0210] The preparation was carried out according to the general method, as described below:

[0211] 432.91 g (1.5075 mol) of DCDPS, 201.67 g (1.38 mol) of ISOSO, 24.51 g (0.08 mol) of THPE and 269.51 g (1.95 mol) of potassium carbonate (volume average particle size: 8.7 μm) were suspended in 650 ml of NMP.

[0212] Condensation time: 14 hours

[0213] 1600 ml of NMP were added to cool the mixture.

[0214] The results of these experiments are shown in Table 1.

[0215] Comparative Example C13

[0216] The preparation was carried out according to the general method, as described below:

[0217] 577.16 g (2.0 mol) of DCDPS, 146.14 g (1.00 mol) of ISOSO, 186.21 g (1.00 mol) of BP and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size: 32.7 μm) were suspended in 1050 ml of NMP.

[0218] Condensation time: 11 hours

[0219] 1500 ml of NMP were added to cool the mixture.

[0220] Comparative Example C14

[0221] The preparation was carried out according to the general method, as described below:

[0222] 577.16 g (2.0 mol) of DCDPS, 204.59 g (1.4 mol) of ISOSO, 111.73 g (0.60 mol) of BP and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size: 32.7 μm) were suspended in 1050 ml of NMP.

[0223] Condensation time: 11 hours

[0224] 1500 ml of NMP were added to cool the mixture.

[0225] Embodiment 15 of the present invention

[0226] The preparation was carried out according to the general method, as described below:

[0227] 577.16 g (2.0 mol) of DCDPS, 146.14 g (1.00 mol) of isosorbide, 175.04 g (0.94 mol) of BP, 12.25 g (0.04 mol) of THPE and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size: 32.7 μm) were suspended in 1050 ml of NMP.

[0228] Condensation time: 6 hours

[0229] 1500 ml of NMP were added to cool the mixture.

[0230] Embodiment 16 of the present invention

[0231] The preparation was carried out according to the general method, as described below:

[0232] 577.16 g (2.0 mol) of DCDPS, 204.59 g (1.4 mol) of ISOSO, 100.55 g (0.54 mol) of BP, 12.25 g (0.04 mol) of THPE and 317.88 g (2.30 mol) of potassium carbonate (volume average particle size: 32.7 μm) were suspended in 1050 ml of NMP.

[0233] Condensation time: 7.5 hours

[0234] 1500 ml of NMP were added to cool the mixture.

[0235] The results of these experiments are shown in Table 2.

[0236] Isolation and Testing of Polyarylene Ether

[0237] The polymer obtained is isolated by separating the filtered reaction mixture into droplets and transferring the droplets into a precipitation bath. The precipitation solvent is desalted water at room temperature. The precipitation height is 0.5 m. The flux is about 2.5 l / h. The beads thus obtained are then extracted with water at 85° C. for 20 h (water flux 160 l / h). The beads are subsequently dried under reduced pressure at a temperature below the glass transition temperature (Tg) to a residual moisture of less than 0.5% by weight.

[0238] The solution viscosity (VN) was determined using a 0.01 g / ml solution of the polymer in NMP at 25° C. (DIN EN ISO 1628-1 (October 2012)).

[0239] The content of isosorbide and trihydroxyphenylethane in polyarylene ether is determined by 1 H-NMR analysis was carried out in CDCl3 solution.

[0240] The Tg of the polymer was determined by DSC measurement using a heating rate of 10 K / min during the second heating.

[0241] The viscosity of the membrane coating solution was measured using a Brookfield rheometer at 60° C. and 20 rpm using a solution having the following composition: 19 wt % of the respective polymer, 6 wt % of polyvinylpyrrolidone (Luvitec K90, BASF SE) and 75 wt % of NMP.

[0242]

[0243] Table 2

[0244]

[0245] *Comparative Example

[0246] **Branched polyarylene ether containing ISOSO groups

[0247] a) Condensation time

[0248] Compared with linear polymers, the polyarylene ether of the present invention shows higher viscosity values. In addition, the yield is improved. Moreover, the incorporation rate of ISOSO is high. In particular, the incorporation rate is higher in a shorter condensation time. In addition, a higher yield is obtained in a shorter condensation time.

[0249] Examples MC1 to M5: Preparation of membranes

[0250] Preparation of casting solution and membrane:

[0251] In a three-necked flask equipped with a magnetic stirrer, 78 ml of NMP, 5 g of PVP ( K40) and 17 g of polyarylene ether. The mixture was heated at 60°C with gentle stirring until a uniform clear viscous solution was obtained. The solution was degassed overnight at room temperature. Afterwards, the film solution was heated at 60°C for another 2 hours and cast on a glass plate using an Erichsen Coating apparatus running at a speed of 5 mm / min at 60°C with a casting knife (300 microns). The film was allowed to stand for 30 seconds and then immersed in a water bath at 25°C for 10 minutes.

[0252] After the membrane was peeled off the glass plate, it was carefully transferred to a water bath for 12 h. Then, the membrane was transferred to a bath containing 2500 ppm NaOCl at 50 °C for 4.5 h to remove PVP. After this step, the membrane was washed with water at 60 °C and once with a 0.5 wt% sodium bisulfite solution to remove active chlorine. After several washing steps with water, the membrane was kept wet until the start of characterization.

[0253] In most cases, flat continuous films with dimensions of at least 10x15 cm were obtained, having the microstructural features of UF membranes. The membranes had a top thin skin layer (1-3 microns) and a porous layer underneath (thickness: 100-150 microns).

[0254] Membrane characterization

[0255] The PWP of the membrane was tested using ultrapure water (no saline, filtered through a Millipore UF system) using a pressure chamber with a diameter of 60 mm. In subsequent tests, different PEG standard solutions with molecular weights (Mw) ranging from 1000 to 1,000,000 g / mol and a concentration of PEG / PEO in water of 0.1 wt % were filtered at a pressure of 0.15 bar. The molecular weight cut-off was determined by GPC measurement of the feed and permeate. For the GPC-measurement, the obtained / prepared solution was used. The GPC measurement was carried out at 35 ° C, using two chromatographic columns with hydroxylated PMMA as the stationary phase and an RI detection system with a flow rate of 0.8 ml / min.

[0256] Table 3

[0257]

[0258] *Comparative Example

[0259] Membranes prepared from branched poly(arylene ether) containing ISOSO show high permeability.

[0260] To determine the MWCO, after filtering the PEO solution, the membrane was rinsed twice with 500 ml portions of ultrapure water. Thereafter, the PWP was measured again (PWP 2). The membranes prepared from the poly(arylene ether) disclosed herein showed higher flux recovery.

Claims

1. A polyarylene ether comprising A) 1,1,1-trihydroxyphenylethane, and B) isosorbide, isomannide, isoidide or a mixture thereof, wherein the poly(arylene ether) is poly(arylene ether sulfone), wherein the polyarylene ether comprises compound B as the only diol, and The polyarylene ether comprises 1 to 4 mol % of A) 1,1,1-trihydroxyphenylethane, based on the total amount of compounds A and B contained in the polyarylene ether.

2. The polyarylene ether according to claim 1, comprising B) Isosorbide.

3. The polyarylene ether according to claim 1, comprising at least one unit of formula II, The symbols t, q, Q, T, Y, Ar and Ar 1 is defined as follows: t, q: independently 0, 1, 2 or 3, Q, T, Y: are each independently a chemical bond or are selected from -O-, -S-, -SO2-, S=O, C=O, -N=N- and -CR a R b - a group, wherein R a and R b is in each case independently of one another a hydrogen atom or a C1-C 12 -alkyl, C1-C 12 -alkoxy or C6-C 18 -aryl, and wherein at least one of Q, T and Y is -SO2- or -CO-, Z: is a group derived from isosorbide, isomannide, or isoidide, and Ar and Ar 1 : are independently an arylene group having 6 to 18 carbon atoms.

4. A method for preparing polyarylene ether, comprising reacting the following substances: A) 1,1,1-trihydroxyphenylethane, and B) isosorbide, isomannide, isoidide or a mixture thereof, and C2) a difunctional compound comprising at least one dichlorodiaryl sulfone, wherein the polyarylene ether comprises compound B as the only diol, and The polyarylene ether comprises 1 to 4 mol % of A) 1,1,1-trihydroxyphenylethane, based on the total amount of compounds A and B contained in the polyarylene ether.

5. A process according to claim 4, comprising reacting the monomers in the presence of a polar aprotic solvent in the absence of azeotrope-forming compounds.

6. Use of the polyarylene ether according to any one of claims 1 to 3 or obtained by the process according to claim 4 or 5 for producing coatings, fibers, foams, films or moldings.

7. The use according to claim 6 for preparing a film.

8. Use of the polyarylene ether according to any one of claims 1 to 3 or obtained by the process according to claim 4 or 5 for the preparation of films.

9. Fiber comprising a polyarylene ether according to any one of claims 1 to 3 or obtained by the process of claim 4 or 5.

10. A film comprising a polyarylene ether according to any one of claims 1 to 3 or obtained by the process of claim 4 or 5.

11. An article comprising the film according to claim 10.

12. Use of the film according to claim 10 or the article according to claim 11 in contact with water or body fluids in food production.

13. Use of the film according to claim 10 or the article according to claim 11 in contact with liquids in food production.

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