Functionalized poly(aryl ether sulfones) copolymers and polymer adducts obtained therefrom

Abstract

To provide copolymers comprising moieties able to undergo a crosslinking reaction under certain stimuli, thereby forming polymer adducts having improved or additional properties, such as resistance to solvents, increased thermal performance and increased adhesion to surfaces.SOLUTION: There is provided an adduct obtained from the crosslinking of a copolymer based on amorphous sulfone recurring units such as formula (M) and formula (N), such adduct being, notably, well-suited to prepare membranes with the required set of mechanical properties (e.g. elongation and flexural strengths).SELECTED DRAWING: None

Description

[Technical Field]

[0001] Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 897,450, filed September 9, 2019, and European Patent Application Publication No. 19208913.4, filed November 13, 2019, the entire contents of which are incorporated herein by reference for all purposes.

[0002] The present invention relates to copolymers that contain sites that can undergo crosslinking reactions under certain stimuli, thereby forming polymer adducts with improved or additional properties such as resistance to solvents, improved thermal performance, and improved adhesion to surfaces. [Background technology]

[0003] Certain polymers can change their properties under certain conditions, such as humidity, pH, UV light, or heat. As an example, changes in molecular structure under conditions of water permeability or acidic / basic pH can be used to design certain polymers or to allow bonding or reactions to occur in situ. One example of such a change in molecular structure is present in polymers that contain crosslinkable sites that can undergo crosslinking under certain conditions or treatments.

[0004] Polyolefins functionalized with silanol side chains are one example of such polymers containing crosslinkable sites. The thermal dimensional stability of polyolefins can be significantly improved by side-chain crosslinking. Such crosslinkable polyolefins can be prepared by melt extrusion of polyolefins using a free-radical initiator and a silanol crosslinker, or by exposure to an electron beam. The polyolefin backbone undergoes proton abstraction and reacts with the silanol crosslinker to form a silanol-functionalized polyolefin, which can then be crosslinked in the presence of heat and moisture. However, the melt-extrusion preparation process is not applicable to all types of polymers, such as aromatic poly(aryl ether sulfone) polymers (PAES). In fact, when polymers are melt-extruded in the presence of an initiator and a silanol crosslinker, such side-chain functionalization does not actually occur because the backbones of most polysulfones, such as polyphenylsulfone (PPSU) and polyethersulfone (PES), lack protons that can be abstracted and lead to subsequent functionalization.

[0005] The present invention provides an alternative approach to preparing crosslinkable sulfone polymers.

[0006] A paper by NI JING et al. (J. Mater. Chem. 2010, 20, 6352-6358) concerns a crosslinked hybrid membrane 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).

[0007] 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.

[0008] DING FC et al. (Journal of Power Sources 170, 2007, 20-27) relates to the preparation of crosslinked sulfonated fluorene-containing PEEK for proton exchange membranes using diallylbiphenol (daBP).

[0009] These papers describe the preparation of functionalized PEEK polymers for preparing membranes, however, PEEK polymers are semi-crystalline polymers that lack the elongation and flexibility necessary to prepare membranes with a good set of mechanical properties.

[0010] WO 2005095491 (Gharda) and U.S. Patent Application Publication No. 20050228149 (Solvay) relate to processes for preparing block copolymers in the polysulfone family, i.e., polymers containing sulfone bonds, particularly polysulfone (PSU), polyethersulfone (PES), and polyphenylenesulfone (PPSU), and the block copolymers prepared therefrom. These documents do not describe sulfone copolymers having repeating units with functionalized silanol thioether side chains.

[0011] A paper by Yan Li et al. (J. Mater. Chem. A, 2017, 5, 17549-17562) describes the synthesis of networks based on epoxy / polysiloxane monomers (SH-EP) in a one-pot synthesis. Korean Patent Application Publication No. 20170075105A (Samyang Corp.) relates to bisphenol-based epoxy compounds having alkoxysilylalkyl-S-alkyl groups, their preparation method, and cured products. None of these documents describes sulfone copolymers, let alone the side-chain functionalized copolymers of the present invention. These systems are based on small molecules to form crosslinkable structures. These small molecules have two different functional groups, one epoxy and one silanol, and the epoxy group requires a compatible crosslinker, such as a diamine or dialcohol. Crosslinking of such structures results in brittle structures because they are based on small molecule precursors. Furthermore, the thermal resistance of such systems is expected to be low.

[0012] One object of the present invention is an adduct obtained from the crosslinking of copolymers based on amorphous sulfone repeating units, such adducts being particularly well suited for preparing membranes with the required set of mechanical properties (e.g. elongation and flexural strength). Summary of the Invention

[0013] One aspect of the present disclosure is - Formula (M): [ka] Repeating units (R P1 ), - Formula (N): [ka] Repeating units (R* P1 ) (In the formula, -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; R2 is —(CH2)r—Si(OCH3)3, where r is selected from 1 to 5; R3 is an alkyl group, an aryl group or a halogen group; each k is independently selected from 1 to 4; each j is independently selected from 3 to 7; - T and Q are each 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, independently of one another, 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), a linear or branched aliphatic divalent group of up to 6 carbon atoms, and combinations thereof) The present invention relates to a polymer adduct obtained by crosslinking a copolymer (P1) comprising:

[0014] The present invention also relates to the use of the copolymers (P1) described herein in the preparation of adducts to be used as coatings, as additives in composite materials to improve the bond between fillers (such as glass or carbon fibers) and the polymer matrix, and as self-crosslinking resins for preparing composite products. DETAILED DESCRIPTION OF THE INVENTION

[0015] The copolymers (P1) described herein can be effectively crosslinked via reaction between functionalized polymer side chains to form polymer adducts.

[0016] The formation of these adducts represents a convenient method for obtaining high molecular weight polymer structures, i.e., adducts, from lower molecular weight polymers in the melt or liquid phase. It also represents an advantageous method for obtaining high molecular weight polymer structures without rearrangement and randomization of the repeating units of the polymer, since the adduct formation occurs under mild conditions. It also represents a useful method for strengthening the surface of articles by in situ crosslinking of compositions containing copolymer (P1).

[0017] Furthermore, this chemistry can be used to increase the bond between the polymer and the inorganic filler (e.g., glass fiber), for example, by reacting the copolymer (P1) with a sizing agent located on the surface of the sized fiber. Increasing the interaction between the resin and the filler improves the mechanical performance of the resulting product combination.

[0018] The present invention is based on the crosslinking of copolymers (P1), which are copolymers containing crosslinkable sites, e.g., functionalized with silanol thioether side chains. During crosslinking, the silanol functional groups can specifically self-condense to form -Si-O-Si- bonds, with the elimination of alcohol molecules. As a result, the polymer chains are crosslinked together by strong covalent bonds that have interesting properties, such as solvent resistance and thermal performance.

[0019] Silanol thioether side chains offer several technical advantages. The silanol groups can self-crosslink using mild conditions in the presence of moisture and acid catalysts to form, for example, crosslinked coatings, composites, and stacks within other structures. No additional crosslinking agents are required to form network structures. Because the adducts are based on copolymers, i.e., entities with specific molecular weights compared to monomers or small molecules, the adducts obtained from crosslinking such copolymers retain the thermomechanical properties, such as impact strength, that are inherent to the polymer matrix. The silanol groups also offer the advantage of bonding with inorganic fillers, such as carbon and glass fibers, improving the mechanical properties of composite structures due to increased bonding between the interface of the filler and the polymer structure.

[0020] The copolymers of the present invention can also be used as compatibilizers for polymer blends, particularly for incompatible polymer blends. Due to the molecular weight of the polymers and the resulting high thermal stability, the copolymers described herein can be used to compatibilize heat-resistant polymer blends by creating chemical interactions between the silanol groups of the copolymers of the present invention at the chain ends of other blended polymer structures.

[0021] By "crosslinkable" it is meant that the polymer has not yet been cured or crosslinked and that the polymer contains sites that cause or promote substantial crosslinking when subjected to or exposed to such treatments (e.g., exposure to heat, humidity, and / or water).

[0022] By "crosslinked" it is meant that the copolymer has been subjected to or exposed to a treatment which induces crosslinking of its crosslinkable sites.

[0023] 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.

[0024] The present invention relates to polymer adducts obtained by crosslinking a side-chain functionalized copolymer (P1), which comprises at least two types of repeating units, namely repeating units (R 1 ) of formula (M) as described below: P1 ) and a repeating unit of formula (N) (R* P1 ) containing repeating units (R* P1 ) is functionalized with a thioether functional group, which is —(CH2)jS—R2, where j varies from 1 to 4, and R2 is —(CH2)r—Si(OCH3)3, where r is selected from 1 to 5, preferably r is 1, 2 or 3.

[0025] The functionality of the copolymer (P1) is internally functionalized 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.

[0026] The copolymer of the present invention (P1) - Formula (M): [ka] Repeating units (RP1 ), - Formula (N): [ka] Repeating units (R* P1 ) (In the formula, -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; R2 is —(CH2)r—Si(OCH3)3, where r is selected from 1 to 5; R3 is an alkyl group, an aryl group or a halogen group; each k is independently selected from 1 to 4; each j is independently selected from 3 to 7; - T and Q are each 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, independently of one another, 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) Includes:

[0027] 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 differ 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.

[0028] In some embodiments, copolymer (P1) contains no epoxy groups or contains less than 2 mol %, preferably less than 1 mol %, more preferably less than 0.5 mol % epoxy groups based on the total number of moles of copolymer (P1).

[0029] In some embodiments, the copolymer (P1) is such that it comprises at least 50 mol %, for example at least 55 mol % or at least 60 mol % of repeating units (RP1) of formula (M), based on the total number of moles of the copolymer (P1).

[0030] In some embodiments, the copolymer (P1) contains a total of at least 50 mole % of repeat units (R P1 ) and (R* P1 The copolymer (P1) may, for example, comprise at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units (R P1 ) and (R* P1 The copolymer (P1) may preferably comprise the repeating unit (R P1 ) and (R* P1 ) can consist essentially of

[0031] In some embodiments, the copolymer (P1) is such that it is - Repeating unit (R* P1 ) (wherein the group G N is the formula (GN1 ) according to the repeating unit (R* P1 ) are preferably at least 25 mol %, more preferably at least 30 mol %, even more preferably at least 35 mol % of the N is 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 ) It is something that includes.

[0032] 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.

[0033] Repeating unit (R P1 ) T is preferably —C(CH 3 ) 2 —.

[0034] 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.

[0035] In some preferred embodiments, G N is selected from the group consisting of at least one of the following formulas: [ka]

[0036] In some embodiments, the copolymer (P1) is such that each R1 is independently selected from the group consisting of C1-C12 moieties optionally containing one or more heteroatoms, sulfonic acids and sulfonic acid groups, phosphonic acids and phosphonic acid groups, amines and quaternary ammonium groups.

[0037] 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.

[0038] In some embodiments, the copolymer (P1) comprises a repeating unit (R* P1 ), where k is zero and j is three.

[0039] In some embodiments, the copolymer (P1) comprises a repeating unit (R P1 ) / (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.

[0040] In some embodiments, the copolymer (P1) comprises a repeating unit (R P1 ) is expressed as formula (M1): [ka] It is like following the

[0041] In some embodiments, the copolymer (P1) comprises a repeating unit (R* P1 ) where R2 is -(CH2)3-Si(OCH3)3.

[0042] According to one embodiment, the copolymer (P1) of the 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.

[0043] Optional Ingredients The copolymer (P1) may be mixed with optional ingredients, such as one or more solvents, before being crosslinked.

[0044] The solvent may in particular be a polar solvent selected from N-methyl-pyrrolidone (NMP), dichloromethane, dimethylformamide (DMF), 1,3-dimethyl-2-imidazolidinone (DMI), dimethylacetamide (DMAc), diphenylsulfone, sulfolane, dimethylsulfoxide (DMSO) and chlorobenzene.

[0045] The copolymer (P1) may also be mixed with one or more additives.

[0046] The additives may in particular be selected from the group consisting of fillers (eg glass fibers, carbon fibers), lubricants, plasticizers, flame retardants, rheology modifiers, stabilizers and pigments.

[0047] The copolymer (P1) may also be mixed with one or more thermal adduct formers.

[0048] The thermal adduct former is, in particular, fullerene (C 60 , C 70 , fullerite), bismaleimide (4,4'-bismaleimide-diphenylmethane), phenylene dimaleimide (e.g., N,N'-(1,2-phenylene)dimaleimide, N,N'-(1,3-phenylene)dimaleimide, N,N'-(1,4-phenylene)dimaleimide).

[0049] Additions The present invention relates to polymer adducts obtained by crosslinking the copolymer (P1) described above. Crosslinking is a reaction in which two or more molecules join together to create a polymeric composite network.

[0050] The crosslinking of the copolymer (P1) can be obtained by at least one of the following steps: - heating at a temperature ranging from 60°C to 250°C, preferably from 65°C to 200°C, - exposure to acidic / basic conditions, respectively pH<5 or pH>9, and / or - exposing to humidity, for example to a humidity percentage of at least 30% in the presence of moisture, water or water-generating compounds.

[0051] In particular, exposure to humidity can be at a humidity percentage of at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, or at least 90%.

[0052] Preparation process of 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.

[0053] The process for preparing the copolymer (P1) comprises reacting the allyl-functionalized copolymer (P0) with the compound R2-SH, where R2 is -(CH2)r-Si(OCH3)3, where r is selected from 1 to 5, preferably r is 1, 2 or 3.

[0054] The copolymer (P0) used in the process of the present invention is in particular a repeating unit (R*) having two pendant allyl / vinylene side chains that react 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 ) (In the formula, -G P 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 0 to 4; - T and Q are each a bond, -CH2-, -O-, -SO2-, -S-, -C(O)-, -C(CH3)2-, -C(CF3)2-, -C(=CCl2)-, -C(CH3)(CH2CH2COOH)-, -N=N-, -R aC=CR b -(where each R a and R b are, independently of one another, 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) Includes:

[0055] In some embodiments, the copolymer (P0) is a copolymer in which k is a repeating unit (R* P0 ) is zero.

[0056] In some embodiments, G P is the following formula: [ka] and selected from the group consisting of at least one of Each k is independently selected from 0 to 4.

[0057] 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), 1,3-dimethyl-2-imidazolidinone (DMI), 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] Repeating unit (R P0 ) T is preferably —C(CH 3 ) 2 —.

[0062] In some embodiments, the copolymer (P0) is such that each R1 is independently selected from the group consisting of C1-C12 moieties optionally containing one or more heteroatoms, sulfonic acid and sulfonate groups, phosphonic acid and phosphonate groups, amines, and quaternary ammonium groups.

[0063] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) and repeating units (R* P0 ) such that for each R1, i is zero.

[0064] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) where j is 2.

[0065] 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.

[0066] In some embodiments, the copolymer (P0) comprises a repeating unit (R P0 ) is expressed as formula (M1): [ka] It is like following the

[0067] 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, for example, comprise at least 60 mol%, at least 70 mol%, at least 80 mol%, at least 90 mol%, at least 95 mol%, or at least 99 mol% of repeating units (R P0 ) and (R* P0 The copolymer (P0) may preferably contain the repeating unit (R P0 ) and (R* P0 ) can consist essentially of

[0068] 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.

[0069] In some embodiments, the compound R2-SH used to react the copolymer (P0) is a repeating unit (R* P1 ) where R2 is -(CH2)3-Si(OCH3)3.

[0070] 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.

[0071] 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

[0072] 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.

[0073] 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.

[0074] Preparation process of copolymer (P0) In some embodiments, the allyl / vinylene functionalized copolymer (P0) used in the process of the present invention has been prepared by condensation of at least one aromatic dihydroxy monomer (a1) with at least one aromatic sulfone monomer containing at least two halogen substituents (a2) and at least one allyl-substituted aromatic dihydroxy monomer (a3).

[0075] 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), 1,3-dimethyl-2-imidazolidinone (DMI), 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.

[0076] 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.

[0077] 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.

[0078] 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.

[0079] 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).

[0080] In some embodiments, monomer (a3) ​​comprises at least 50% by weight of 2,2'-diallylbisphenol A (daBPA), based on the total weight of monomer (a1).

[0081] According to the principles of condensation polymerization for preparing the copolymer (P0), the monomers of the reaction mixture generally react 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.

[0082] 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.

[0083] 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.

[0084] 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).

[0085] 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.

[0086] 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.

[0087] Purpose The adducts of the present invention can 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.

[0088] 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.

[0089] The present invention provides a method for coating a surface, comprising the steps of: a) applying a copolymer (P1) according to any one of claims 1 to 10 to a surface, optionally in combination with one or more solvents and / or additives, b) heating the surface at a temperature in the range of 60°C to 250°C, preferably 65°C to 200°C, and / or exposing the surface to a humidity of at least 30% humidity. The present invention also relates to a method comprising:

[0090] The present invention also relates to the use of the copolymer (P1) described herein in the preparation of an adduct to be used as a coating.

[0091] The present invention also relates to the use of the copolymer (P1) described herein in a sizing formulation containing a resin to improve compatibility between the resin and the sized fibers by heating the sized fibers and / or exposing the sized fibers to a humidity percentage of at least 30%.

[0092] To the extent that the disclosure of any patents, patent applications, and publications incorporated herein by reference contradicts the statements of this application to the extent that the term may become unclear, the statements of this application shall control.

[0093] 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]

[0094] raw materials DCDPS (4,4'-dichlorodiphenyl sulfone) available from Solvay Specialty Polymers BPA (Bisphenol A) available from Covestro, USA BP (Biphenol), polymer grade, available from Honshu Chemicals, Japan DHDPS (4,4'-dihydroxydiphenyl sulfone) 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 MCB (methylchlorobenzene) available from Sigma-Aldrich, USA DMSO (dimethyl sulfoxide) available from Sigma-Aldrich, USA DCM (dichloromethane) available from Sigma-Aldrich, USA Sulfolane available from Chevron Phillips Chemicals AIBN (azobisisobutyronitrile) available from Sigma-Aldrich, USA Thiopropyltrimethoxysilane (HS-(CH2)3Si(OCH3)3) available from Sigma-Aldrich, USA

[0095] 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.

[0096] 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.

[0097] 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.

[0098] 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 noted.

[0099] I. Preparation of allyl / vinylene-modified PSU copolymer (P0-A) The functionalized PPSU polymer (P0-A) was prepared according to Scheme 1.

[0100] The copolymerization was carried out in a glass reactor (1 L) equipped with an overhead stirrer, nitrogen inlet, and overhead distillation setup. DCDPS monomer (143.58 g), BPA (102.73 g), and daBPA (15.42 g) were first added to the vessel, followed by KCO (78.29 g), NMP (690 g), and MCB (170 g) as azeotropic distillation solvents.

[0101] The reaction mixture is heated from room temperature to 190°C using a heating ramp of 1°C / min. The temperature of the reaction mixture is maintained for 6-8 hours depending on the viscosity of the solution. The reaction is terminated by stopping heating. The reaction mixture is filtered, coagulated in methanol, and dried at 110°C.

[0102] The copolymer (P0-A) is in the form of a racemic product. Due to the presence of base and high temperature during polymerization, the daBPA monomer racemizes during polymerization, causing the position of the double bond along the side chain to change. This results in the formation of 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 immediately preceding the end of the side chain, as shown above.

[0103] Characterization of allyl / vinylene-modified PSU copolymer (P0-A) GPC: Mn = 10,948 g / mol, Mw = 37,123 g / mol, PDI = 3.39 TGA: 474℃ DSC: 175℃ 1 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm, indicating the incorporation of 2,2′-diallyl BPA monomer in the polymer.

[0104] II. Preparation of allyl / vinylene-modified PPSU copolymer (P0-B) The functionalized PPSU polymer (P0-B) was prepared according to Scheme 2.

[0105] The copolymerization was carried out in a 1 L kettle reactor equipped with an overhead stirrer, nitrogen inlet, thermocouple, and Dean-Stark trap. DCDPS monomer (143.58 g), BPA (88.45 g), and daBPA (7.71 g) were first added to the vessel and purged with nitrogen for 30 minutes. Sulfolane (470 g) and potassium carbonate (78 g) were then added to the vessel.

[0106] The reaction mixture is then heated to 210°C. When the reaction mixture reaches this temperature, the reaction is maintained for 6-8 hours. After this time, the heating is stopped and the reaction mixture is allowed to cool to room temperature. The reaction mixture is filtered, coagulated in methanol, and washed with hot deionized water.

[0107] The copolymer (P0-B) is in the form of a racemic product.

[0108] Characterization of allyl / vinylene-modified PPSU copolymer (P0-B) GPC: Mn = 26430 g / mol, Mw = 126547 g / mol, PDI = 4.78 TGA: 493℃ DSC: 199℃ 1 1 H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.2-6.4 ppm, indicating the incorporation of 2,2′-diallyl BPA monomer in the polymer.

[0109] III. Preparation of allyl / vinylene-modified PES copolymer (P0-C) The functionalized PES polymer (P0-C) was prepared according to Scheme 3.

[0110] The copolymerization was carried out in a 1 L kettle reactor equipped with an overhead stirrer, nitrogen inlet, thermocouple, and Dean-Stark trap. The monomers DCDPS (146.45 g), DHDPS (112.37 g), and 2,2'-daBPA (15.72 g) were first added to the vessel and purged with nitrogen for 30 minutes. NMP (283 g) and K2CO3 (69.8 g) were then added to the vessel.

[0111] The reaction mixture is then heated to 190°C. When the reaction mixture reaches this temperature, the reaction is maintained for 6-8 hours. After this time, the heating is stopped and the reaction mixture is allowed to cool to room temperature. The reaction mixture is filtered, coagulated in methanol, and washed with hot deionized water.

[0112] The copolymer (P0-C) is in the form of a racemic product.

[0113] Characterization of allyl / vinylene-modified PES copolymer (P0-C) GPC: Mw = 29,997 g / mol, Mn = 12,042 g / mol, PDI = 2.49 TGA: 415℃ DSC: Tg = 214°C 11 H NMR: The presence of unsaturated groups was confirmed by the appearance of a multiplet at 6.1-6.4 ppm, indicating the incorporation of 2,2′-diallyl BPA monomer in the polymer. [ka] [ka] [ka]

[0114] IV. Preparation of functionalized PSU copolymer (P1-A) via free radical reaction The functionalized PSU polymer (P1-A) was prepared according to the following procedure in accordance with Scheme 4. 12.44 g of the allyl / vinylene-modified copolymer (P0-A) prepared according to Scheme 1 above was dissolved in 49.76 g of NMP at a temperature of 60-70 °C. 19.8 g of 3-(trimethoxysilyl)propanethiol was then added to the reaction vessel and stirred. 1.64 g of AIBN (free radical initiator) was then added to the reaction vessel and stirred under N2 for 6-12 hours. The temperature was maintained at 70 °C for 6-12 hours. The reaction mixture was then coagulated in methanol and dried at 110 °C. 12.44 g of silanol-functionalized polymer was obtained.

[0115] Characterization DSC: Tg = 152.2°C

[0116] V. Preparation of Polymer Adducts by Heating The adduct of functionalized PSU polymer (P1-A) was prepared according to Scheme 5. The copolymer (P1-A) was heated in boiling water for 3 hours, and then the crosslinked material was dried.

[0117] Characterization The resulting material was completely insoluble in hot NMP. Increase in Tg after crosslinking seen by DSC: from 152.2°C to 193.3°C. [ka]

change

Claims

1. - Formula (M): 【Chemistry 1】 Repeating units (R Ｐ１ ), - Formula (N): 【Chemistry 2】 Repeating units (R* Ｐ１ ) (In the formula, - G Ｎ is the following formula: 【Transformation 3】 and selected from the group consisting of at least one of - 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; -R ２ is -(CH ２ )r-Si(OCH ３ ) ３ where r is selected from 1 to 5; -R ３ is an alkyl group, an aryl group, or a halogen group, each k is independently selected from 1 to 4; each j is independently selected from 3 to 7, and 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, independently of one another, 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), independently selected from the group consisting of linear or branched aliphatic divalent groups of up to 6 carbon atoms, and combinations thereof. A polymer adduct obtained by crosslinking a copolymer (P1) comprising:

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

3. Repeating unit (R* Ｐ１ ) of the formula (G Ｎ１ ), (G Ｎ２ ) and / or (G Ｎ３ ) Q is a bond, —SO ２ - and -C(CH ３ ) ２ The adduct 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 The adduct according to any one of claims 1 to 3, wherein

5. Repeating unit (R* Ｐ１ 5. The adduct according to claim 1, wherein k is 0 and j is 3.

6. Repeating unit (R Ｐ１ ) / repeating unit (R* Ｐ１ 6. The adduct according to any one of claims 1 to 5, wherein the molar ratio of α- and β-tert-butyl ether varies from 0.01 / 100 to 100 / 0.01, preferably from 1 / 100 to 100 / 1, more preferably from 1 / 1 to 10 / 1.

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

8. The repeating unit (R*) of the copolymer (P1) Ｐ１ ) in R ２ is -(CH ２ ) ３ -Si(OCH ３ ) ３ The adduct according to any one of claims 1 to 7,

9. A total of at least 50 mol % of repeating units (R Ｐ１ ) and (R* Ｐ１ 9. The adduct of claim 1, comprising:

10. The crosslinking of the copolymer (P1) is carried out by: heating at a temperature ranging from 60°C to 250°C, preferably from 65°C to 200°C; exposure to acidic / basic conditions, respectively pH<5 or pH>9, and / or - Exposure to humidity of at least 30% The adduct according to any one of claims 1 to 9, obtained by at least one of

11. 1. A method for coating a surface, comprising: a) applying to said surface a copolymer (P1) according to any one of claims 1 to 10, optionally in combination with one or more solvents and / or additives, b) heating said surface at a temperature in the range of 60°C to 250°C, preferably 65°C to 200°C, and / or exposing said surface to a humidity percentage of at least 30%. A method comprising:

12. Use of a copolymer (P1) according to any one of claims 1 to 10 in the preparation of an adduct to be used as a coating, as an additive in composites to improve the bond between fillers and the polymer matrix or as a self-crosslinking resin for the preparation of composite products.

13. Use of the copolymer (P1) according to any one of claims 1 to 10 in a sizing formulation comprising a resin to improve compatibility between the resin and the sized fibers by heating the sized fibers and / or exposing the sized fibers to a humidity of at least 30% humidity.

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