Side-chain functionalized poly(aryl ether sulfone) copolymers containing reactive termini

Abstract

The present invention relates to a side-chain functionalized copolymer (P1) containing reactive end groups. The present invention also relates to a process for preparing the copolymer (P1) starting from the copolymer (P0) and to the use of the copolymer (P1) in the preparation of membranes, composites or coatings. The present invention also relates to a resin composition comprising at least the copolymer (P1) according to the present invention.

Description

[Technical Field]

[0001] Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 950,289, filed December 19, 2019, and European Patent Application Publication No. 20162149.7, filed March 10, 2020, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to a side-chain functionalized copolymer (P1) comprising reactive end groups and to a process for preparing this copolymer (P1) starting from the copolymer (P0) which is also the object of the present invention. The present invention also relates to the use of the copolymer (P1) in the preparation of membranes, composites or coatings, and to resin compositions comprising at least the copolymer (P1) according to the invention. [Background technology]

[0003] Poly(aryl ether sulfone) (PAES) polymers are very thermally stable polymers with excellent toughness and impact strength. These resins are typically produced by a polycondensation reaction using 4,4'-dichlorodiphenyl sulfone (DCDPS) with other aromatic diols such as bisphenol A (BPA), 4,4'-biphenol (BP), or 4,4'-dihydroxydiphenyl sulfone (DHDPS, also known as bisphenol S or BPS).

[0004] PAES is used as a toughening agent in epoxy resin composites. The toughness or impact properties of the composite can be improved by increasing the amount of PAES in the matrix. However, these polymers have poor solubility in the epoxy composite matrix, making it difficult to incorporate PAES polymers into the epoxy composite matrix.

[0005] To overcome the above problems, PAES, which has reactive end groups with lower solubility than PAES itself, has been used to improve the interfacial properties of epoxy resins. For example, U.S. Patent Application Publication No. 2014 / 329973 (Solvay) describes an epoxy resin composition comprising an epoxy resin, a curing agent, an accelerator, and at least two PAES polymers with different reactive end groups.

[0006] Although such PAES containing reactive end groups have been shown to have better solubility and reactivity with epoxy resins compared to other PAES, there is a limit to the amount they can be added to an epoxy composite matrix, thereby limiting their beneficial effect in composite applications.

[0007] One object of the present invention is to further improve the impact properties and toughness of composites by increasing the amount of PAES in the epoxy matrix, which is achieved by incorporating the side-chain functionalized PAES copolymer (P1) object of the present invention into the matrix of such composites.

[0008] Such approaches to polymer side chain functionalization have been reported in the literature, and the preparation and use of side chain functionalized poly(ether ether ketone) (PEEK) polymers have been described in several papers.

[0009] A paper by NI JING et al. (J. Mater. Chem., 2010, 20, 6352-6358) concerns crosslinked hybrid membranes based on sulfonated poly(ether ether ketone) (PEEK). This paper describes the preparation of a copolymer containing partially sulfonated PEEK repeating units starting from diallyl bisphenol A (daBPA), 4,4-difluorobenzophenone (DFB), and 5,5-carbonyl-bis(2-fluorobenzenesulfonate) (SDFR), and the preparation of a membrane starting from this copolymer, phosphotungstic acid (PWA), and 3-methacryloxypropyltrimethoxysilane (KH570).

[0010] Xuehong Huang et al. (Applied Surface Science 258, 2012, 2312-2318) describes the synthesis of side-chain ion exchange membranes. This paper describes the preparation of a copolymer starting from DFB, bisphenol A, and diallyl bisphenol A, and the grafting reaction of this copolymer is carried out in the presence of sodium styrene sulfonate and KH570.

[0011] The paper by DING FC et al. (Journal of Power Sources 170, 2007, 20-27) concerns the preparation of crosslinked sulfonated fluorene-containing PEEK for proton exchange membranes using diallylbiphenol (daBP).

[0012] U.S. Patent No. 5,212,264 (Ciba) describes a substantially linear PAES polymer with specific segments in the main chain. According to the examples, the PAES is prepared from a mixture of DHDPS and DCDPS (Example A) and reacted with bisphenol A diglycidyl ether (BGEBPA), thereby describing the synthesis of a semi-aromatic / semi-aliphatic block copolymer consisting of polyarylethersulfone blocks and glycidyl ether groups. The polymer has pendant aliphatic hydroxyl groups obtained by reacting the phenolic end groups with an epoxy agent. The concentration of these groups is less than 100 microequivalents / g. This document does not describe the synthesis of a linear polymer with a fully aromatic main chain functionalized with side chains in the sense of the present invention. The inventors show herein that the crosslinking reactivity of such copolymers is not comparable to that of the copolymers of the present invention.

[0013] However, these papers contain the structures detailed below and contain at least 50 μeq / g These articles do not describe the copolymers of the present invention containing hydroxyl, amine or acid reactive end groups. These articles also do not describe the use of such copolymers as toughening agents for epoxy resin compositions. Summary of the Invention

[0014] A first aspect of the present disclosure relates to a side-chain functionalized poly(aryl ether sulfone) (PAES) copolymer (P1), which comprises: - PAES repeating unit (R P1 )and, - pendant group (R* P1 ), more precisely PAES repeat units functionalized with side groups, - At least 50 μeq / g and hydroxyl, amine or acid end groups of Includes.

[0015] The present invention also relates to a process for preparing these copolymers (P1) from copolymers (P0) having reactive end groups and allyl / vinylene side chains (i.e., unsaturated carbon-carbon double bond functionality). Thus, the present invention provides a method for introducing both side chain functionality and end groups into PAES polymers. The resulting copolymers can then be used in various applications, for example, in composites to improve the mechanical properties (e.g., impact properties and toughness) of the composites.

[0016] The invention also relates to the copolymer (P0) itself, as an intermediate for the copolymer (P1), having reactive end groups and allyl / vinylene side chains.

[0017] The present invention also relates to the use of the copolymer (P0) in a composite material. DETAILED DESCRIPTION OF THE INVENTION

[0018] This chemistry can be used, inter alia, to increase the solubility of PAES in certain materials (e.g., epoxy resins, polyurethane resins, or unsaturated polyesters) and to increase the bonding between components in compositions of matter, for example, containing polymers and / or inorganic fillers (such as glass fibers). Increasing the interaction between the components of a composition improves the mechanical performance of the material, for example, the polymer components and inorganic fillers in a composite.

[0019] In this application: - any description, even if made in relation to a particular embodiment, is applicable to and interchangeable with other embodiments of the present disclosure; - when an element or component is said to be included in and / or selected from a list of enumerated elements or components, it is to be understood that in the relevant embodiments expressly contemplated herein, the element or component may be any one of the individually enumerated elements or components, or may be selected from a group consisting of any two or more of the explicitly enumerated elements or components, and that any element or component enumerated in a list of elements or components may be omitted from such list; - Any recitation herein of numerical ranges by endpoints includes all numbers subsumed within the recited range, as well as the endpoints of the range and equivalents thereof.

[0020] Copolymer (P1) The present invention relates to a side-chain functionalized copolymer (P1).

[0021] This copolymer (P1) contains at least two types of repeating units, namely repeating units (P P1 ) and a repeating unit of formula (N) (R* P1 ) and at least 50 μeq / g The hydroxyl, amine or acid end groups are included.

[0022] The functionality of the copolymer (P1) is internal functionalization within the copolymer backbone. The internal functionalization results from sequential polymerization in the presence of allyl-substituted monomers, which advantageously makes the system versatile, since the content of functional groups can be adjusted by varying the content of allyl-substituted monomers in the reaction mixture. The allyl-substituted monomers, according to the present invention, contain two pendant allyl side chains, each containing 3 to 7 carbon atoms.

[0023] The copolymer (P1) of the present invention comprises at least - Formula (M): [ka] Repeating units (R P1 ), - Formula (N): [ka] Repeating units (R* P1 ), wherein - G N is the following formula: [ka] and selected from the group consisting of at least one of each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently selected from 0 to 4; - each k is independently selected from 1 to 4; - each j is independently selected from 3 to 7; T and Q are a bond, -CH2-; -O-; -SO2-; -S-; -C(O)-; -C(CH3)2-; -C(CF3)2-; -C(=CCl2)-; -C(CH3)(CH2CH2COOH)-; -N=N-; -Ra C=CR b -(where each R a and R b are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy or C6-C18 aryl group); -(CH2) m -and-(CF2) m - (wherein m is an integer from 1 to 6); linear or branched aliphatic divalent groups of up to 6 carbon atoms; and combinations thereof; - each R3 is independently selected from an alkyl group, an aryl group, or a halogen group; - Each R2 -(CH2)u-COOH, where u is selected from 1 to 5; -(CH2)k-OH (wherein k is selected from 1 to 5), -(CH2)p-NR a R b where p is selected from 1 to 5, and R a and R b are independently C1-C6 alkyl or H, provided that R a and R b (provided that both cannot be CH3) -(CH2)q-SO3Na, where q is selected from 1 to 5; -(CH2)a-COCH3, where a is selected from 0 to 10; -(CH2)r-Si(OCH3)3, where r is selected from 1 to 5; -(CH2)s-(CF2)t-CF3, where s is selected from 1 to 5 and t is selected from 1 to 10; -CO-R c (where R c is C1-C6 alkyl or H, preferably H), -(CH2)v-CH3, where v is selected from 5 to 30, and -(CH)-Ar, where w is selected from 0 to 10, and Ar contains 1 to 10 one or two aromatic or heteroaromatic rings, e.g., one or two benzene rings, and Ar is optionally NR a R b , e.g., substituted with NH2) are independently selected from the group consisting of:

[0024] The copolymer (P1) of the present invention is in the form of a racemic product. Due to the presence of a base and high temperature during polymerization, allyl-substituted monomers usually racemize during polymerization, so that the position of the double bond can vary along the side chain. This results in the formation of molecules that are different from each other due to the fact that the double bond can be at the end of the side chain or at the carbon immediately preceding the end of the side chain. The amount of racemization depends on the reaction time and temperature.

[0025] The copolymer (P1) of the present invention preferably comprises at least 50 mol %, for example at least 55 mol % or at least 60 mol %, based on the total number of moles in the copolymer (P1), of repeating units of formula (M) (R P1 ) may be included.

[0026] The copolymer (P1) of the present invention preferably comprises a total of at least 50 mol % of repeating units (R P1 ) and (R* P1 The copolymer (P1) may comprise, for example, at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least about 99 mol% of repeating units (R P1 ) and (R* P1 The copolymer (P1) may further preferably contain repeating units (R P1 ) and (R* P1 ) may essentially exist.

[0027] In some embodiments, the copolymer (P1) comprises a repeating unit (R* P1 ) in R2, -CH2-COOH, -(CH2)2-OH, -(CH2)2-NH2, -(CH2)3-SO3Na, -(CH2)3-Si(OCH3)3, -(CH2)2-(CF2)7-CF3 (or any other fluoroalkyl group), -C=OH, -(CH2)9-CH3 (or any other alkyl group), -CH2-Ph (where Ph is benzene) (or any other aromatic group), -Ph-NH (where Ph is benzene) (or any other aromatic group) are independently selected from the group consisting of:

[0028] In some embodiments, the copolymer (P1) is such that it is - Repeating unit (R* P1 ) (wherein the group G N is the formula (G N1 ) according to the repeating unit (R* P1 Preferably at least 25 mol %, more preferably at least 30 mol %, even more preferably 35 mol % of the groups GN are of the formula (G N1 ) - Repeating unit (R* P1 ) (wherein the group G N is the formula (G N1 ) and (G N3 ) according to the repeating unit (R* P1 ) are preferably at least 35 mol %, more preferably at least 40 mol %, and even more preferably at least 45 mol % of the N is the formula (G N1 ) and (G N3 ) or - At least one repeating unit (R* P1 ) (wherein the group G N is the formula (G N1 ), (G N2 ) and (G N3 ) according to the repeating unit (R*P1 ) are preferably at least 50 mol %, more preferably at least 60 mol %, even more preferably 70 mol %, 80 mol % or 90 mol % of the N is the formula (G N1 ) and (G N3 ) is like following It is something that includes.

[0029] In some embodiments, the copolymer (P1) comprises a repeating unit (R P1 ) in which T is selected from the group consisting of a bond, —SO—, —C(CH)— and mixtures thereof. The copolymer (P1) of the present invention can be, for example, a repeating unit (R P1 ) and the repeating unit where T is -SO2- (R P1 ) may be included.

[0030] Repeating unit (R P1 ) T is preferably —C(CH 3 ) 2 —.

[0031] In some embodiments, the copolymer (P1) comprises a repeating unit (R* P1 )'s (G N1 ), (G N2 ) and / or (G N3 ) is such that Q is selected from the group consisting of a bond, —SO 2 —, —C(CH 3 ) 2 —, and mixtures thereof.

[0032] In some preferred embodiments, G N is the following formula: [ka] and at least one of:

[0033] In some embodiments, the copolymer (P1) is such that each R1 is independently selected from the group consisting of a C1-C12 moiety, optionally containing one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine, amide, and quaternary ammonium groups.

[0034] In some embodiments, the copolymer (P1) comprises a repeating unit (R P1 ) and repeating units (R* P1 ) such that for each R1, i is zero.

[0035] In some embodiments, the copolymer (P1) comprises a repeating unit (R* P1 ), where k is zero and j is three.

[0036] In some embodiments, the copolymer (P1) comprises a repeating unit (R P1 ) / Repeating unit (R* P1 ) varies from 0.01 / 100 to 100 / 0.01, preferably from 1 / 100 to 100 / 1, more preferably from 1 / 1 to 12 / 1, and even more preferably from 4 / 1 to 10 / 1.

[0037] In some embodiments, the copolymer (P1) comprises a repeating unit (R P1 ) is expressed as formula (M1): [ka] It is like following the

[0038] According to one embodiment, the copolymer (P1) of the invention has a Tg ranging from 120 to 250°C, preferably from 170 to 240°C, more preferably from 180 to 230°C, measured by differential scanning calorimetry (DSC) according to ASTM D3418.

[0039] terminal group The polymer (P1) of the present invention has a viscosity of at least 50 μeq / gof hydroxyl, amine or acid end groups, e.g., at least 80 μeq / g , at least 100 μeq / g , at least 150 μeq / g or even at least 200 μeq / g These are also characterized by the fact that they contain these end groups:

[0040] The polymer (P1) of the present invention has a viscosity of 800 μeq. / g less than hydroxyl, amine or acid end groups, e.g., 600 μeq / g The polymer may contain less than 100 of these end groups.

[0041] End groups are moieties at each end of the PAES polymer chain.

[0042] Depending on the method used to prepare the polymer (P1) and the possibility of using additional agents during the condensation process (e.g., an end-capping agent (e.g., aminophenol)) or the possibility of adding a protonating agent (e.g., oxalic acid) after polymerization (to obtain phenolic -OH end groups), P1 may have end groups derived from, for example, the monomer and / or the end-capping agent. Because P1 is typically prepared by a polycondensation reaction between a dihydroxy component and a dihalo component, the end groups typically contain hydroxyl and halo groups (e.g., chlorinated or fluorinated end groups). However, if an end-capping agent such as aminophenol is used, the remaining halo groups may be at least partially converted to amine end groups. The concentrations of acid, amine, and hydroxyl end groups can be determined by titration. The concentration of halogen groups can be determined with a halogen analyzer. These methods are described in detail in the examples below. However, any suitable method can be used to determine the end group concentration. For example, titration, NMR, FTIR, or a halogen analyzer can be used.

[0043] According to one embodiment, the polymer (P1) has at least 50 μeq / g of hydroxyl end groups (OH, μeq / g), for example at least 80 μeq / g of hydroxyl end groups, at least 100 μeq / g , at least 150 μeq / g or even at least 200 μeq / g containing hydroxyl end groups.

[0044] According to one embodiment, the polymer (P1) comprises at least 1.16 OH per 100 repeat units of the polymer (P1), for example at least 1.86, at least 2.32 or at least 3.48 OH per 100 repeat units of the polymer (P1).

[0045] According to one embodiment, the polymer (P1) has at least 50 μeq / g of amine termination. base, For example, at least 80 μeq / g of amine End groups, at least 100 μeq / g , at least 150 μeq / g or even at least 200 μeq / g of amine Contains end groups.

[0046] According to one embodiment, the polymer (P1) has at least 50 μeq / g of acid ends basis, For example, at least 80 μeq / g of acid end groups, at least 100 μeq / g , at least 150 μeq / g or even at least 200 μeq / g Contains an acid end group.

[0047] Process for preparing copolymer (P1) The copolymer (P1) can be prepared by various chemical processes, in particular by free radical-thermal, free radical-UV, base-catalyzed or nucleophilically catalyzed reactions.

[0048] The process for preparing the copolymer (P1) comprises reacting the allyl / vinylene-functionalized copolymer (P0) with a compound R2-SH, wherein R2 is -(CH)-COOH (wherein u is selected from 1 to 5, preferably u is 1 or 2); -(CH)-OH, where k is selected from 1 to 5, preferably k is 1 or 2; -(CH2)p-NR a R b , where p is selected from 1 to 5, and R a and R b are independently C1-C6 alkyl or H, provided that R a and R b provided that both cannot be CH3; p is preferably 1 or 2, and R a and R b is preferably CH3 or H), -(CH)-SONa, where q is selected from 1 to 5, preferably q is 1, 2 or 3; -(CH2)a-COCH3, where a is selected from 0 to 10; -(CH2)r-Si(OCH3)3, where r is selected from 1 to 5, preferably r is 1, 2 or 3; -(CH2)s-(CF2)t-CF3 (wherein s is selected from 1 to 5, preferably 1 or 2, and t is selected from 1 to 10, preferably 5 to 9), -CO-R c (where R c is C1-C6 alkyl or H, preferably H), -(CH2)v-CH3 (wherein v is selected from 5 to 30, preferably v is selected from 8 to 20), and -(CH)-Ar, where w is selected from 0 to 10, and Ar contains one or two aromatic or heteroaromatic rings, e.g., one or two benzene rings, and Ar is optionally -NR a R b where R aand R b is preferably CH3 or H) are independently selected from the group consisting of:

[0049] The copolymer (P0) used in the process of the invention is also one of the objects of the present invention and is notably composed of a repeating unit (R*) with two pendant allyl / vinylene side chains, which are reactive with the compound R2-SH. P0 ). The copolymer (P0) is more precisely - Formula (M): [ka] Repeating units (R P0 ), - Formula (P): [ka] Repeating units (R* P0 ), - At least 50 μeq / g hydroxyl end groups, amine end groups or acid end groups wherein each R1 is independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine and quaternary ammonium; - each i is independently selected from 0 to 4; - T is a bond, -CH2-;-O-;-SO2-;-S-;-C(O)-;-C(CH3)2-;-C(CF3)2-;-C(=CCl2)-;-C(CH3)(CH2CH2COOH)-;-N=N-;-R a C=CR b -(where each R a and R b are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy or C6-C18 aryl group); -(CH2) m -and-(CF2)m - (wherein m is an integer from 1 to 6); linear or branched aliphatic divalent groups of up to 6 carbon atoms; and combinations thereof; - G P is the following formula: [ka] is selected from the group consisting of one of Each k is independently selected from 0 to 4.

[0050] In some embodiments, the copolymer (P0) is a copolymer in which k is a repeating unit (R* P0 ) is zero.

[0051] The reaction for preparing the copolymer (P1) is preferably carried out in a solvent. When the reaction for preparing the copolymer (P1) is carried out in a solvent, the solvent is, for example, a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole, and sulfolane. The solvent can also be chloroform or dichloromethane (DCM). The reaction for preparing the copolymer (P1) is preferably carried out in sulfolane or NMP.

[0052] The molar ratio of compound (I) / polymer (P0) varies from 0.01 / 100 to 100 / 0.01, preferably from 1 / 100 to 100 / 1, more preferably from 1 / 1 to 10 / 1.

[0053] The temperature of the reaction for preparing the copolymer (P1) varies from 10°C to 300°C, preferably from room temperature to 200°C or more preferably from 35°C to 100°C.

[0054] The process for preparing the copolymer (P1) can be carried out by exposing the reaction mixture to UV light with a wavelength ranging from 300 nm to 600 nm, preferably from 350 nm to 450 nm, more preferably 365 nm.

[0055] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) in which T is selected from the group consisting of a bond, —SO—, —C(CH)— and mixtures thereof. The copolymer (P0) can be, for example, a repeating unit (R P0 ) and the repeating unit where T is -SO2- (R P1 ) may be included.

[0056] Repeating unit (R P0 ) T is preferably —C(CH 3 ) 2 —.

[0057] In some embodiments, the copolymer (P0) is such that each R1 is independently selected from the group consisting of a C1-C12 moiety, optionally containing one or more heteroatoms; sulfonic acid and sulfonate groups; phosphonic acid and phosphonate groups; amine and quaternary ammonium groups.

[0058] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) and repeating units (R* P0 ) such that i is zero for each R1.

[0059] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) where j is 2.

[0060] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) / Repeating unit (R* P0 ) is such that the molar ratio varies from 0.01 / 100 to 100 / 0.01, more preferably from 1 / 100 to 100 / 1.

[0061] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) is expressed as formula (M1): [ka] It is like following the

[0062] In some embodiments, the copolymer (P0) comprises a total of at least 50 mole % of repeat units (R P0 ) and (R* P0 The copolymer (P0) may comprise, for example, at least about 60 mol%, at least about 70 mol%, at least about 80 mol%, at least about 90 mol%, at least about 95 mol%, or at least about 99 mol% of repeat units (R P0 ) and (R* P0 The copolymer (P0) preferably comprises the repeating unit (R P0 ) and (R* P0 ) may essentially exist.

[0063] According to one embodiment, the copolymer (P0) of the present invention has a Tg in the range of 120 to 250°C, preferably 170 to 240°C, more preferably 180 to 230°C, measured by differential scanning calorimetry (DSC) according to ASTM D3418.

[0064] In some embodiments, the compound R2-SH used to react the copolymer (P0) is a repeating unit (R* P1 ) in R2, -CH2-COOH, -(CH2)2-OH, -(CH2)2-NH2, -(CH2)3-SO3Na, -(CH2)3-Si(OCH3)3, -(CH2)2-(CF2)7-CF3, and -C=OH, -(CH2)9-CH3, and -CH2-Ph (where Ph is benzene) are independently selected from the group consisting of:

[0065] In some embodiments, the reaction for preparing copolymer (P1) can be carried out in the presence of a base selected from the group consisting of potassium carbonate (K2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), and sodium tert-butoxide. The base can also be selected from the group consisting of N-ethyl-N-(propan-2-yl)propan-2-amine (Hunig's base), triethylamine (TEA), and pyridine.

[0066] In some embodiments, the reaction for preparing the copolymer (P1) is at least one free radical initiator, preferably 2,2'-azobis(2-methylpropionitrile) (AIBN), and / or at least one catalyst preferably chosen from peroxides and hydroperoxides The reaction is carried out in the presence of

[0067] According to one embodiment, the amount of copolymer (P1) at the end of the reaction is at least 10% by weight, for example at least 15% by weight, at least 20% by weight or at least 30% by weight, based on the total weight of copolymer (P0) and solvent.

[0068] At the end of the reaction, the copolymer (P1) is separated from the other components (salt, base, etc.) to obtain a solution. For example, filtration can be used to separate the copolymer (P1) from the other components. The solution can then be used directly to react the copolymer (P1) with other compounds, or alternatively, the copolymer (P1) can be recovered from the solvent, for example, by coagulation or solvent devolatilization.

[0069] The polymer (P0) of the present invention is such that it has a viscosity of at least 50 μeq / g of hydroxyl, amine or acid end groups, e.g., at least 80 μeq / g of these end groups, at least 100 μeq / g , at least 150 μeq / g or even at least 200 μeq / g The presence of hydroxyl, amine or acid end groups can be determined by titration as described above or by any other method available to one skilled in the art.

[0070] Process for preparing copolymer (P0) In some embodiments, the allyl / vinylene functionalized copolymer (P0) used in the process of the present invention is prepared by condensing at least one aromatic dihydroxy monomer (a1) with at least one aromatic sulfone monomer (a2) containing at least two halogen substituents and at least one allyl-substituted aromatic dihydroxy monomer (a3), and an additional agent, such as an end-capping agent or a protonating agent.

[0071] The condensation to prepare the copolymer (P0) is preferably carried out in a solvent. When the condensation to prepare the copolymer (P0) is carried out in a solvent, the solvent is, for example, a polar aprotic solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, and sulfolane. The condensation to prepare the copolymer (P0) is preferably carried out in sulfolane or NMP.

[0072] The condensation to prepare the copolymer (P0) can be carried out in the presence of a base selected from the group consisting of potassium carbonate (K2CO3), potassium tert-butoxide, sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na2CO3), cesium carbonate (Cs2CO3), and sodium tert-butoxide. The base serves to deprotonate components (a1) and (a3) during the condensation reaction.

[0073] The molar ratio (a1)+(a3) / (a2) can be from 0.9 to 1.1, for example, from 0.92 to 1.08 or from 0.95 to 1.05.

[0074] In some embodiments, monomer (a2) is a 4,4-dihalosulfone comprising at least one of 4,4'-dichlorodiphenylsulfone (DCDPS) or 4,4'-difluorodiphenylsulfone (DFDPS), preferably DCDPS.

[0075] In some embodiments, monomer (a1) comprises at least 50% by weight of 4,4'-dihydroxybiphenyl (biphenol), at least 50% by weight of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), or at least 50% by weight of 4,4'-dihydroxydiphenyl sulfone (bisphenol S), based on the total weight of monomer (a1).

[0076] In some embodiments, monomer (a3) comprises at least 50% by weight of 2,2'-diallylbisphenol A (DABA), based on the total weight of monomer (a1).

[0077] According to the condensation to prepare the copolymer (P0), the monomers of the reaction mixture are generally reacted simultaneously. The reaction is preferably carried out in one step. This means that the deprotonation of the monomers (a1) and (a3) and the condensation reaction between the monomers (a1) / (a3) and (a2) are carried out in a single reaction step without isolation of intermediate products.

[0078] According to one embodiment, the condensation is carried out in a mixture of a polar aprotic solvent and a solvent that forms an azeotrope with water. Examples of solvents that form an azeotrope with water include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and chlorobenzene. Toluene or chlorobenzene is preferred. The azeotrope-forming solvent and the polar aprotic solvent are typically used in a weight ratio of about 1:10 to about 1:1, preferably about 1:5 to about 1:1. Water is continuously removed from the reaction mixture as an azeotrope with the azeotrope-forming solvent, thereby maintaining substantially anhydrous conditions during polymerization. The azeotrope-forming solvent, e.g., chlorobenzene, is typically removed from the reaction mixture by distillation after the water formed in the reaction has been removed, leaving the copolymer (P0) dissolved in the polar aprotic solvent.

[0079] The temperature of the reaction mixture for preparing the copolymer (P0) is maintained at about 150°C to about 350°C, preferably about 210°C to about 300°C, for about 1 to 15 hours.

[0080] Depending on the method used to prepare the copolymer (P1) and the possible use of additional agents during the condensation process, such as an endcapping agent (e.g., aminophenol) or a protonating agent (e.g., oxalic acid), the copolymer (P0) may have end groups derived from the monomers and / or from the endcapping agent or protonating agent. Because the copolymer (P0) is typically prepared by a polycondensation reaction between a dihydroxy component and a dihalo component, its end groups typically contain hydroxyl and halo groups (such as chlorinated or fluorinated end groups). However, if an endcapping agent (e.g., aminophenol or a similar amine-functionalized phenol) is used based on the stoichiometry of the starting monomers (i.e., excess dihydroxy monomer or excess dihalo monomer), the remaining halo groups may be at least partially converted to amine end groups. If a protonating agent (e.g., an organic acid such as oxalic acid or acetic acid) is used, the copolymer (P0) may have hydroxyl end groups, depending on the stoichiometry of the starting monomers used. The concentration of end groups (i.e., acid, amine, and hydroxyl end groups) can be determined by titration. The concentration of halogen groups can be determined with a halogen analyzer. These methods are described in detail in the examples below. However, any suitable method can be used to determine the concentration of end groups. For example, titration, NMR, FTIR, or a halogen analyzer can be used.

[0081] Inorganic constituents, such as sodium chloride or potassium chloride or excess base, can be removed by suitable methods such as dissolution and filtration, sieving or extraction before or after isolation of the copolymer (P0).

[0082] According to one embodiment, the amount of copolymer (P0) at the end of the condensation is at least 30% by weight, for example at least 35% by weight, or at least or at least 37% by weight, or at least 40% by weight, based on the total weight of copolymer (P0) and the polar aprotic solvent.

[0083] At the end of the reaction, the copolymer (P0) is separated from the other components (salt, base, etc.) to obtain a solution. For example, filtration can be used to separate the copolymer (P0) from the other components. The solution can then be used directly to react the copolymer (P0) with the compound R2-SH in the process of the present invention, or alternatively, the copolymer (P0) can be recovered from the solvent, for example, by coagulation or solvent devolatilization.

[0084] Purpose The copolymers (P1) of the invention can be used to prepare functional membranes, for example, these membranes can be hydrophobic, hydrophilic, biolabeled, for example fluorescently tagged membranes.

[0085] The copolymers (P1) of the invention can also be used to prepare composite materials, in which the functionality improves the adhesion of the resin to the reinforcing fibers, thereby improving performance.

[0086] The copolymers (P1) of the present invention can also be used to prepare functional coatings: the chemical moieties on the surface of the coating can be selected to make the coating hydrophobic, hydrophilic, biorecognitive, antibacterial, antifouling and / or UV-curable.

[0087] The present invention also relates to the use of the copolymer (P0) in the preparation of a membrane, a composite or a coating, and to a resin composition comprising at least the above-mentioned copolymer (P0).

[0088] resin composition The resin composition of the present invention may be an epoxy resin, a polyurethane resin, or an unsaturated polyester resin. The composition comprises at least one copolymer (P1) as described above and an additional component, which may be, for example, at least one epoxy compound and / or a curing agent (e.g., a polyalkylene polyamine such as ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and polyethylenepolyamine (PEPA)).

[0089] The term "epoxy component" refers to a compound containing two or more epoxy groups, preferably two epoxy groups, per molecule. These epoxy compounds may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic, or heterocyclic, and may also contain hydroxyl groups. They are preferably glycidyl ethers derived from polyhydric phenols, especially bisphenols or aminophenols, and novolaks.

[0090] If the disclosure of any patent, patent application, or publication incorporated herein by reference contradicts the statement of this application to the extent that it may render a term unclear, the statement shall control.

[0091] The present invention will now be described in more detail with reference to the following examples, the purpose of which is merely illustrative and not intended to limit the scope of the invention. [Example]

[0092] raw materials DCDPS (4,4'-dichlorodiphenyl sulfone) available from Solvay Specialty Polymers BPA (Bisphenol A) available from Covestro, USA BP (4,4'-biphenol), polymer grade, available from Honshu Chemicals, Japan daBPA (2,2'-diallylbisphenol) available from Sigma-Aldrich, USA K2CO3 (potassium carbonate) available from Armand products NaHCO3 (sodium bicarbonate) available from Solvay SA, France NMP (2-methylpyrrolidone) available from Sigma-Aldrich, USA AIBN (azobisisobutyronitrile) available from Sigma-Aldrich, USA Cysteamine hydrochloride, 3-aminophenol available from Sigma-Aldrich, USA ADVN (2,2'-azobis(2,4 dimethylvaleronitrile)) available from Miller-Stephenson Chemical Co., Inc.

[0093] Test Method GPC-Molecular weight (Mn, Mw) Molecular weights were determined by gel permeation chromatography (GPC) using methylene chloride as the mobile phase. Two 5μ mixed D columns with guard columns from Agilent Technologies were used for the separation. A 254 nm UV detector was used to obtain the chromatograms. A flow rate of 1.5 mL / min and an injection volume of 20 μL of a 0.2 w / v% solution in the mobile phase were selected. Calibration was performed using 12 narrow molecular weight polystyrene standards (peak molecular weight range: 371,000–580 g / mol). The number average molecular weight, Mn, weight average molecular weight, Mw, and higher average molecular weight, Mz, were reported.

[0094] Thermogravimetric analysis (TGA) TGA experiments were performed using a TA Instrument TGA Q500. TGA measurements were obtained by heating the samples under nitrogen from 20°C to 800°C at a heating rate of 10°C / min. TGA values report the onset temperature of thermal decomposition.

[0095] 1 H NMR 1 H NMR spectra were recorded on a 400 MHz Bruker spectrometer using TCE or DMSO as the deuterated solvent, and all spectra are referenced to residual protons in the solvent.

[0096] DSC DSC was used to measure glass transition temperatures (Tg) and melting points (Tm), if present. DSC experiments were performed using a TA Instrument Q100. DSC curves were recorded by heating, cooling, reheating, and then recooling the sample from 25°C to 320°C at heating and cooling rates of 20°C / min. All DSC measurements were taken under a nitrogen purge. Reported Tg and Tm values were determined using the second heating curve unless otherwise specified.

[0097] Hydroxyl titration Hydroxyl groups were analyzed by dissolving a sample of the polymer in 5 ml of sulfolane:monochlorobenzene (50:50). 55 ml of methylene chloride was added to the solution, and the sample was titrated potentiometrically with tetrabutylammonium hydroxide in toluene using a Metrohm 686 Titroprocessor equipped with a Metrohm Solvotrode electrode and a Metrohm 665 Dosimat. Three possible equivalence points existed. The first equivalence point represented a strong acid. The second equivalence point represented a sulfonic acid hydroxyl. The third equivalence point represented a phenolic hydroxyl. The total hydroxyl count was calculated as the sum of the phenolic and sulfonic acid hydroxyls.

[0098] Amine titration A 0.2-0.3 g sample of polymer was dissolved in 55 mL of methylene chloride with stirring. 15 mL of glacial acetic acid was added. The sample was then titrated potentiometrically with 0.1 N perchloric acid in acetic acid using a Metrohm Titrando 809 Titrator equipped with a Metrohm Solvotrode electrode. The perchloric acid titrant reacts with the basic groups in the sample, producing an endpoint on the potential curve when all bases are neutralized. Two blanks and one control sample were run before testing the sample. Each sample was tested twice. Results were reported only after the two analyses agreed within 5% for base concentrations above 100 μeq / g and within 10 μeq / g for base concentrations below 100 μeq / g.

[0099] Calculate the base concentration:

number

[0100] The blank value is determined from the volume of titrant required to bring the electrode potential to the same mV as the sample titration endpoint potential.

[0101] Chlorine Analysis Chlorine end groups were analyzed using a ThermoGLAS 1200 TOX halogen analyzer. Samples of 1 mg to 10 mg were weighed into quartz boats and inserted into a heated combustion tube, where they were combusted in flowing oxygen at 1,000 °C. The combustion products passed through a concentrated sulfuric acid scrubber and entered a titration cell, where hydrogen chloride from the combustion process was absorbed in 75% v / v acetic acid. The chlorides entering the cell were then titrated with silver ions generated by coulometry. The chlorine content in the samples was calculated from the integrated current and sample weight. The resulting percent chlorine values were converted to chlorine end group concentrations in microequivalents per gram (μeq / g).

[0102] I. Preparation of Amine-Terminated Allyl / Vinylene-Modified PSU Copolymer (P0-A) The functionalized PSU polymer (P0-A) was prepared according to Scheme 1.

[0103] The copolymerization was carried out in a 2 L glass reactor equipped with an overhead stirrer, a nitrogen inlet, and an overhead distillation apparatus. The monomers DCDPS (430.47 g), BPA (257.51 g), and daBPA (86.97 g) were first placed in the vessel, followed by KCO (212.41 g) and NMP (900 g).

[0104] The reaction mixture is heated from room temperature to 190°C using a temperature ramp of 1°C / min. The temperature of the reaction mixture is maintained for 4 hours. K2CO3 (36 g) and 3-aminophenol (18.33 g) are then added and the reaction is continued for 4 hours. The reaction is terminated by stopping heating. The reaction mixture is filtered, coagulated in methanol, and dried at 110°C.

[0105] The copolymer is in the form of a racemic product. Due to the presence of base and high temperature during polymerization, the daBPA monomers racemize during polymerization such that the position of the double bond along the side chain changes. This results in molecules that differ from each other by the fact that the double bond can be at the end of the side chain or at the carbon before the end of the side chain, as shown in Scheme 1.

[0106] Characterization GPC: Mn = 9,458 g / mol, Mw = 24,952 g / mol, PDI = 2.64 TGA: 397℃ DSC: 160.5℃ Amine groups: 212 μeq / g 1 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of multiplets at 6.1-6.4 ppm, suggesting the incorporation of daBPA monomers into the polymer.

[0107] II. Preparation of phenolic hydroxyl-terminated allyl / vinylene-modified PSU copolymer (P0-B) The functionalized PSU polymer (P0-B) was prepared according to Scheme 2.

[0108] The copolymerization was carried out in a 2 L glass reactor equipped with an overhead stirrer, a nitrogen inlet, and an overhead distillation apparatus. The monomers DCDPS (430.47 g), BPA (257.51 g), and daBPA (86.97 g) were first charged to the vessel, followed by the addition of KCO (212.41 g) and NMP (900 g).

[0109] The reaction mixture is heated from room temperature to 190°C using a 1°C / min temperature ramp. The temperature of the reaction mixture is maintained for 4 hours. K2CO3 (24.87 g) and BPA (41 g) are added, and the reaction is continued for 4 hours. The reaction is terminated by stopping the heating, and oxalic acid (50 g) is added and stirred. The reaction mixture is filtered, coagulated in methanol, and dried at 110°C.

[0110] Like the copolymer (P0-A), this copolymer (P0-B) is in the form of a racemic product.

[0111] Characterization GPC: Mn = 9,536 g / mol, Mw = 24,327 g / mol, PDI = 2.55 TGA: 411℃ DSC: 154℃ Hydroxyl: 210.7 μeq / g Chlorine: 3.2 μeq / g

[0112] III. Preparation of Amine-Terminated Allyl / Vinylene-Modified PPSU Copolymer (P0-A) The functionalized PPSU polymer (P0-C) was prepared according to Scheme 3.

[0113] The copolymerization was carried out in a 2 L glass reactor equipped with an overhead stirrer, a nitrogen inlet, and an overhead distillation apparatus. The monomers DCDPS (430.74 g), BPA (210.04 g), and daBPA (86.97 g) were first charged to the vessel, followed by the addition of KCO (204.61 g) and NMP (900 g).

[0114] The reaction mixture is heated from room temperature to 190°C using a temperature ramp of 1°C / min. The temperature of the reaction mixture is maintained for 4 hours. K2CO3 and 3-aminophenol (18.33 g) are then added and the reaction is continued for 4 hours. The reaction is terminated by stopping heating. The reaction mixture is filtered, coagulated in methanol, and dried at 110°C.

[0115] Like the copolymer (P0-A), this copolymer (P0-C) is in the form of a racemic product.

[0116] Characterization GPC: Mn = 11,425 g / mol, Mw = 39,759 g / mol, PDI = 3.48 TGA: 422℃ DSC: 179.21℃ Amine groups: 212 μeq / g 1 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of multiplets at 6.1-6.4 ppm, suggesting the incorporation of daBPA monomers into the polymer.

[0117] IV. Preparation of amine-terminated allyl / vinylene-modified PES copolymer (P0-D) Functionalized PES polymer (P0-D) was prepared according to Scheme 4. The copolymerization was carried out in a glass reactor (1 L) equipped with an overhead stirrer, a nitrogen inlet, and an overhead distillation apparatus. The monomers DCDPS (215.37 g), DHDPS (175.88 g), and daBPA (24.02 g) were first placed in the vessel, followed by the addition of KCO (101.72 g) and NMP (340 g).

[0118] The reaction mixture is heated from room temperature to 190°C using a 1°C / min temperature ramp. The temperature of the reaction mixture is maintained for 4 hours. 3-Aminophenol (18.33 g) is then added and the reaction is continued for 3 hours. The reaction is terminated by stopping heating. The reaction mixture is filtered, coagulated in methanol, and dried at 110°C.

[0119] Like the copolymer (P0-A), this copolymer (P0-D) is in the form of a racemic product.

[0120] Characterization GPC: Mn = 5,128 g / mol, Mw = 9,550 g / mol, PDI = 1.86 TGA: 426℃ DSC: 187℃ Amine groups: 227 μeq / g 1 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of multiplets at 6.1-6.4 ppm, suggesting the incorporation of daBPA monomers into the polymer.

[0121] V. Preparation of Functionalized PSU Copolymer (P1-A) The functionalized PSU polymer (P1-A) was prepared according to Scheme 5 by the following procedure.

[0122] Amine functionalization was performed in a 1 L glass reactor equipped with an overhead stirrer and nitrogen inlet. Copolymer P0-A (100 g) and cysteamine hydrochloride (62.5 g) were dissolved in NMP (900 g) at room temperature. The reaction mixture was purged with N2 for at least 45 minutes, then the reaction was heated to 50 °C and ADVN (4 g) was added. The reaction was allowed to proceed for 12 hours, after which heating was stopped. The reaction mixture was then coagulated in 3,000 mL of ethanol to which 50 g of K2CO3 had been added. The coagulated polymer was then washed with water (3,000 mL), then twice with methanol (3,000 mL), and then dried at 110 °C.

[0123] Characterization GPC: Mn = 4,060 g / mol, Mw = 8,258 g / mol, PDI = 2.03 TGA: 302℃ DSC: 150℃ Amine groups: 944 μeq / g

[0124] VI. Preparation of Functionalized PSU Copolymer (P1-B) The functionalized PSU polymer (P1-B) was prepared according to Scheme 6 by the following procedure.

[0125] Amine functionalization was performed in a glass reactor (1 L) equipped with an overhead stirrer and nitrogen inlet. Copolymer P0-B (50 g) and cysteamine hydrochloride (48.1 g) were dissolved in NMP (450 g) at room temperature. The reaction mixture was purged with N2 for at least 45 minutes, then the reaction was heated to 50 °C and ADVN (2.9 g) was added. The reaction was allowed to proceed for 12 hours, after which heating was stopped. The reaction mixture was then coagulated in 3,000 mL of ethanol to which 50 g of K2CO3 had been added. The coagulated polymer was then washed with water (3,000 mL), then twice with methanol (3,000 mL), and then dried at 110 °C.

[0126] Characterization GPC: Mn = 2,878 g / mol, Mw = 6,253 g / mol, PDI = 2.17 TGA: 386℃ DSC: 143.16℃ Amine groups: 699 μeq / g

[0127] VII. Preparation of Functionalized PPSU Copolymer (P1-C) The functionalized PPSU polymer (P1-C) was prepared according to Scheme 7 by the following procedure.

[0128] Amine functionalization was performed in a glass reactor (1 L) equipped with an overhead stirrer and nitrogen inlet. Copolymer P0-C (100 g) and cysteamine hydrochloride (62.5 g) were dissolved in NMP (900 g) at room temperature. The reaction mixture was purged with N2 for at least 45 minutes, then the reaction was heated to 50 °C and ADVN (4 g) was added. The reaction was allowed to proceed for 12 hours, after which heating was stopped. The reaction mixture was then coagulated in 3,000 mL of ethanol to which 50 g of K2CO3 had been added. The coagulated polymer was then washed with water (3,000 mL), then twice with methanol (3,000 mL), and then dried at 110 °C.

[0129] Characterization GPC: Mn = 3,321 g / mol, Mw = 6,130 g / mol, PDI = 1.85 TGA: 302℃ DSC: 170.3℃ Amine groups: 900 μeq / g

[0130] VIII. Preparation of functionalized PES copolymer (P1-D) The functionalized PES polymer (P1-D) was prepared according to Scheme 8 by the following procedure.

[0131] Amine functionalization was carried out in a glass reactor (1 L) equipped with an overhead stirrer and nitrogen inlet. Copolymer P0-D (130 g) and cysteamine hydrochloride (63.6 g) were dissolved in DMSO (640 g) at room temperature. The reaction mixture was purged with N2 for at least 45 minutes, then the reaction was heated to 70 °C and AIBN (8 g) was added. The reaction was allowed to proceed for 12 hours, after which heating was stopped. The reaction mixture was then coagulated in 3,000 mL of ethanol to which 50 g of K2CO3 had been added. The coagulated polymer was then washed with water (3,000 mL), then twice with methanol (3,000 mL), and then dried at 110 °C.

[0132] Characterization GPC: Mn = 4,603 g / mol, Mw = 8,038 g / mol, PDI = 1.75 TGA: 190℃ DSC: 470℃ Amine groups: 369 μeq / g

[0133] IX. Preparation of Functionalized PSU Copolymer (P1-E) The functionalized PSU polymer (P1-E) was prepared according to Scheme 9 by the following procedure.

[0134] Carboxylic acid functionalization is carried out in a glass reactor (1 L) equipped with an overhead stirrer and nitrogen inlet. Copolymer P0-A (120 g) and thioglycolic acid (13.81 g) are dissolved in NMP (285 g) at room temperature. The reaction mixture is purged with N2 for at least 45 minutes, then the reaction is heated to 70 °C and AIBN (8.2 g) is added. The reaction is allowed to proceed for 12 hours, after which heating is stopped. The reaction mixture is then coagulated in 3,000 mL of methanol. The coagulated polymer is then washed twice with methanol (3,000 mL) and then dried at 110 °C.

[0135] Characterization GPC: Mn = 8,065 g / mol, Mw = 18,380 g / mol, PDI = 2.28 TGA: 390℃ DSC: 162℃ Carboxylic acid group: 315 μeq / g

[0136] X. Preparation of Crosslinked Materials The copolymer of Example 13 of US Pat. No. 5,212,264 (Ciba) was reproduced and crosslinked with different amounts of epoxy compound.

[0137] 1. Synthesis of base polymer First, base polymer G was synthesized using the polymerization procedure described in the patent.

[0138] Polymer characterization: Mw=78284 g / mol, Mn=28497 g / mol, PDI=2.75 Chlorine end groups = 45.6ueq / g, Phenol end groups = 6ueq / g, Relative viscosity = 0.686375 Tg(DSC) = 232.6℃

[0139] 2. Chain extension using bisphenol and diglycidyl ether (BGEBPA) Procedure: 160.71 g of the DPS polymerization reaction mixture (containing 75 g of polymer) is placed in a 500 mL round-bottom flask equipped with an overhead stirrer and strong N2 inflow. The reaction mixture is heated to 150 °C, and then 1.65 g of BGEBPA is added dropwise. This mixture is kept stirring at 150 °C for 2 hours, after which it is poured into a metal tray and crushed after cooling. The residue in the beaker is dissolved with 50 mL of NMP. The residue and the washings are combined, and then washed three times (acetone / water = 80 / 20; one wash with water). Concentrated acetic acid is added during aqueous extraction to liberate OH end groups.

[0140] Polymer characterization: Mw=79,511 g / mol, Mn=32,458 g / mol, PDI=2.45 Chlorine end groups = 92.6 μeq / g, Phenol end groups = 12.4 μeq / g, Aliphatic side chain hydroxyl groups (theoretical value): 100.89 μeq / g Tg(DSC) = 226.73℃ Relative viscosity = 0.68481

[0141] 3. Crosslinking of the above polymer with Araldite® MY 0510 Procedure: Dissolve 46 mg of Araldite® MY 0510 in 2 g of methylene chloride, then add this to 5 g of chain-extended PPSU. Shake the mixture so that the polymer is evenly coated with the epoxy solution. Dry in a hood at room temperature for 48 hours. Crosslink at 150°C for 12 hours.

[0142] Results: When the above polymer was crosslinked with an equimolar amount of N,N-diglycidyl-4-glycidyloxyaniline, the resulting crosslinked material had a Tg of 229.16°C, an increase of 2.39°C compared to the uncrosslinked base polymer.

[0143] 4. Crosslinking of the Copolymer P1-C of the Invention Characterization of copolymer P1-C: GPC: Mn = 3,321 g / mol, Mw = 6,130 g / mol, PDI = 1.85 TGA: 302℃ DSC: 170.3℃ Amine groups (aliphatic amine side chains + aromatic amine end groups): 900 μeq / g

[0144] When the above polymer was crosslinked with an equimolar amount of N,N-diglycidyl-4-glycidyloxyaniline, the resulting crosslinked material had a Tg of 176.91°C, an increase of 6.61°C compared to the uncrosslinked base polymer.

[0145] Crosslinking experiments have shown that the copolymers of the present invention have a denser network structure after crosslinking compared to copolymer structures described in the prior art. This is due to the higher concentration of side-chain functional groups in the copolymers of the present invention compared to the copolymers described in U.S. Patent No. 5,212,264 (Ciba). These copolymers rely on end-group chemistry that results in copolymers with reactivity that cannot be compared to the side-chain functionalization strategy of the present invention. [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

Claims

1. Copolymer (P1), - Formula (M): 【Chemical 1】 Repeating units (R Ｐ１ ), - Formula (N): 【Chemistry 2】 Repeating units (R* Ｐ１ ), at least 50 μeq / g of hydroxyl, amine or acid end groups (In the formula, - Each R １ are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each i is independently selected from 0 to 4; - G Ｎ is the following formula: 【Chemistry 3】 and selected from the group consisting of at least one of each k is independently selected from 1 to 4; each j is independently selected from 3 to 7; T and Q are a bond, —CH ２ -;-O-;-SO ２ -;-S-;-C(O)-;-C(CH ３ ) ２ -;-C(CF ３ ) ２ -; -C(=CCl ２ ) -; -C(CH ３ ) (CH ２ CH ２ COOH)-;-N=N-;-R ａ C=CR ｂ - (where each R ａ and R ｂ are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy or C6-C18 aryl group; -(CH ２ ) ｍ - and - (CF ２ ) ｍ - (wherein m is an integer from 1 to 6); linear or branched aliphatic divalent radicals of up to 6 carbon atoms; and combinations thereof; - Each R ２ teeth, - (CH ２ )u-COOH, where u is selected from 1 to 5; - (CH ２ ) k-OH, where k is selected from 1 to 5; - (CH ２ ) p-NR ａ R ｂ where p is selected from 1 to 5 and R ａ and R ｂ are independently C1-C6 alkyl or H, provided that R ａ and R ｂ are both CH ３ (provided that this is not possible) - (CH ２ ) q-SO ３ Na, where q is selected from 1 to 5; - (CH ２ ) a-COCH ３ where a is selected from 0 to 10. - (CH ２ )r-Si(OCH ３ ) ３ where r is selected from 1 to 5. - (CH ２ )s-(CF ２ ) t-CF ３ wherein s is selected from 1 to 5 and t is selected from 1 to 10; -CO-R ｃ (where R ｃ is C1-C6 alkyl or H), - (CH ２ ) v-CH ３ where v is selected from 5 to 30, and - (CH ２ ) w-Ar, where w is selected from 0 to 10 and Ar contains 1 to 10 aromatic or heteroaromatic rings, and Ar is optionally NR ａ R ｂ (replaced by are independently selected from the group consisting of - Each R ３ are independently an alkyl group, an aryl group, or a halogen group. A copolymer (P1) comprising:

2. Repeating unit (R Ｐ１ ) T is a bond, —SO ２ - and -C(CH ３ ) ２ The copolymer (P1) according to claim 1, selected from the group consisting of:

3. Repeating unit (R* Ｐ１ ) formula (G Ｎ１ ), (G Ｎ２ ) and / or (G Ｎ３ ) Q is a bond, —SO ２ - and -C(CH ３ ) ２ The copolymer (P1) according to claim 1 or 2, selected from the group consisting of:

4. i is the repeating unit (R Ｐ１ ) and repeating units (R* Ｐ１ ) each R １ Copolymer (P1) according to any one of claims 1 to 3, wherein

5. Repeating unit (R Ｐ１ ) / repeating unit (R* Ｐ１ 5. Copolymer (P1) according to any one of claims 1 to 4, wherein the molar ratio of

6. Repeating unit (R Ｐ１ ) is represented by the formula (M1): 【Chemistry 4】 The copolymer (P1) according to any one of claims 1 to 5,

7. Formula (G Ｎ１ ), (G Ｎ２ ) or (G Ｎ３ ) in R ２ teeth, -CH ２ -COOH、 -(CH ２ ) ２ -OH、 -(CH ２ ) ２ -NH ２ 、 DR ２ ) ３ 10. The ３ 90、 -(CH ２ ) ３ -Si(OCH ３ ) ３ 、 -(CH ２ ) ２ -(CF ２ ) ７ -CF ３ 、 -C=O-H, -(CH ２ ) ９ -CH ３ 、 -CH ２ -Ph (wherein Ph is benzene), -Ph-NH ２ (where Ph is benzene) The copolymer (P1) according to any one of claims 1 to 6, independently selected from the group consisting of:

8. The repeating units (R Ｐ１ ) and (R* Ｐ１ 8. The copolymer (P1) according to claim 1, comprising:

9. Copolymer (P1) according to any one of claims 1 to 8, having a number average molecular weight (Mn) determined by GPC of less than 20,000 g / mol.

10. A process for preparing a copolymer (P1), comprising: - Formula (M): 【Chemistry 5】 Repeating units (R Ｐ０ ), - Formula (P): 【Chemistry 6】 Repeating units (R* Ｐ０ ), at least 50 μeq / g of hydroxyl, amine or acid end groups (In the formula, - Each R １ are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each i is independently selected from 0 to 4; - G Ｐ is the following formula: 【Chemistry 7】 and selected from the group consisting of at least one of each k is independently selected from 0 to 4; T and Q are a bond, —CH ２ -;-O-;-SO ２ -;-S-;-C(O)-;-C(CH ３ ) ２ -;-C(CF ３ ) ２ -; -C(=CCl ２ ) -; -C(CH ３ ) (CH ２ CH ２ COOH)-;-N=N-;-R ａ C=CR ｂ - (where each R ａ and R ｂ are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy or C6-C18 aryl group; -(CH ２ ) ｍ - and - (CF ２ ) ｍ - (wherein m is an integer from 1 to 6); linear or branched aliphatic divalent groups of up to 6 carbon atoms; and combinations thereof. a copolymer (P0) comprising the formula (I): R ２ -SH (In the formula, R ２ teeth, - (CH ２ )u-COOH, where u is selected from 1 to 5; - (CH ２ ) k-OH, where k is selected from 1 to 5; - (CH ２ ) p-NR ａ R ｂ where p is selected from 1 to 5 and R ａ and R ｂ are independently C1-C6 alkyl or H, provided that R ａ and R ｂ are both CH ３ (provided that this is not possible) - (CH ２ ) q-SO ３ Na, where q is selected from 1 to 5; - (CH ２ ) a-COCH ３ where a is selected from 0 to 10. - (CH ２ )r-Si(OCH ３ ) ３ where r is selected from 1 to 5. - (CH ２ )s-(CF ２ ) t-CF ３ wherein s is selected from 1 to 5 and t is selected from 1 to 10; -CO-R ｃ (where R ｃ is C1-C6 alkyl or H), - (CH ２ ) v-CH ３ where v is selected from 5 to 30, and - (CH ２ ) w-Ar, where w is selected from 0 to 10 and Ar contains 1 to 10 aromatic or heteroaromatic rings, and Ar is optionally NR ａ R ｂ (replaced by in a solvent at a temperature ranging from 10°C to 300°C, wherein the molar ratio of compound (I) / polymer (P0) varies from 0.01 / 100 to 100 / 0.

01.

11. in a solvent selected from the group consisting of N-methylpyrrolidone (NMP), N-butylpyrrolidone (NBP), N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAC), 1,3-dimethyl-2-imidazolidinone, tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), chlorobenzene, anisole, chloroform, dichloromethane (DCM) and sulfolane, in the presence of at least one free radical initiator, in the presence of at least one catalyst, and / or The process according to claim 10, which is carried out in the presence of a base.

12. Copolymer (P0), - Formula (M): 【Chemistry 8】 Repeating units (R Ｐ０ ), - Formula (P): 【Chemistry 9】 Repeating units (R* Ｐ０ ), - at least 50 μeq / g of amine or acid end groups (In the ceremony - Each R １ are independently selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, aryl, ether, thioether, carboxylic acid, ester, amide, imide, alkali or alkaline earth metal sulfonate, alkyl sulfonate, alkali or alkaline earth metal phosphonate, alkyl phosphonate, amine, and quaternary ammonium; each i is independently selected from 0 to 4; - G Ｐ is the following formula: 【Chemistry 10】 and selected from the group consisting of at least one of each k is independently selected from 0 to 4; T and Q are a bond, —CH ２ -;-O-;-SO ２ -;-S-;-C(O)-;-C(CH ３ ) ２ -;-C(CF ３ ) ２ -; -C(=CCl ２ ) -; -C(CH ３ ) (CH ２ CH ２ COOH)-;-N=N-;-R ａ C=CR ｂ - (where each R ａ and R ｂ are each independently hydrogen or a C1-C12 alkyl, C1-C12 alkoxy or C6-C18 aryl group; -(CH ２ ) ｍ - and - (CF ２ ) ｍ - (wherein m is an integer from 1 to 6); linear or branched aliphatic divalent groups of up to 6 carbon atoms; and combinations thereof. A copolymer (P0) comprising:

13. Use of a copolymer (P1) according to any one of claims 1 to 9 or a copolymer (P0) according to claim 12 in the preparation of a membrane, a composite or a coating.

14. Epoxy resin composition comprising at least one epoxy compound and at least one copolymer (P1) according to any one of claims 1 to 9 or at least one copolymer (P0) according to claim 12.

15. Use of the copolymer (P1) according to any one of claims 1 to 9 or the copolymer (P0) according to claim 12 as a toughening agent in an epoxy, polyurethane or unsaturated polyester resin composition.

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