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WO2016050798A1 - (co)polymères, dont des diamides cycliques - Google Patents

(co)polymères, dont des diamides cycliques Download PDF

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Publication number
WO2016050798A1
WO2016050798A1 PCT/EP2015/072475 EP2015072475W WO2016050798A1 WO 2016050798 A1 WO2016050798 A1 WO 2016050798A1 EP 2015072475 W EP2015072475 W EP 2015072475W WO 2016050798 A1 WO2016050798 A1 WO 2016050798A1
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Prior art keywords
formula
polymer
alkyl
group
alkali
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Stéphane JEOL
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Solvay Specialty Polymers USA LLC
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Solvay Specialty Polymers USA LLC
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C08G65/4031—(I) or (II) containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
    • C08G65/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols
    • C08G65/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives derived from phenols from phenols (I) and other compounds (II), e.g. OH-Ar-OH + X-Ar-X, where X is halogen atom, i.e. leaving group
    • C08G65/4012—Other compound (II) containing a ketone group, e.g. X-Ar-C(=O)-Ar-X for polyetherketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
    • C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
    • C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK

Definitions

  • the invention relates to (co)polymers including cyclic diamides, for example, poly(aryl ether) (co)polymers including cyclic diamides, methods for making the (co)polymers, articles made from the (co)polymers, and
  • compositions including the (co)polymers including the (co)polymers.
  • the (co)polymers exhibit improved physical and chemical properties.
  • poly(aryl ether) polymers which exhibit advantages offered by commercially available polymers, while featuring other beneficial properties such as resistance to chlorinated solvents like dichloromethane, tetrachloromethane, and monochlorobenzene.
  • new (co)polymers derivable from bio-based resources.
  • DKP Diketopiperazine
  • the diketopiperazine (DKP) moiety includes two asymmetric carbon atoms.
  • the diketopiperazine (DKP) moiety may be present in the (co)polymers described herein in a pure cis configuration, a pure trans configuration, or a mixture of cis and trans configurations.
  • a ratio cis DKP moiety / trans DKP moiety in some embodiments of the (co)polymer may range from 0.1 % / 99.9 % to 99.9 % / 0.01 %.
  • the diketopiperazine (DKP) is sourced from a renewable bio- based resource, and may be derived from the combination of different amino acids such as tyrosine, serine, threonine, lysine, and cysteine.
  • DKP diketopiperazine
  • tyrosine DKP a diketopiperazine monomer precursor derivable from tyrosine
  • Exemplary embodiments include a (co)polymer including a recurring unit of Formula (I) :
  • B and B' are independently selected from -0-, -NH-, and -S-.
  • a and A' are independently selected from a bond, -CH 2 -, an alkyl, an aryl group, and an arylalkyl group.
  • the (co)polymer may further include at least one recurring unit of
  • B* and B'* are independently selected from -0-, -NH-, and -S-.
  • Z is selected from :
  • Each R s is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
  • k is 0, 1, 2, 3, or 4, and k' is independently 0, 1, 2, or 3.
  • A* and A'* are independently selected from a bond, -CH 2 -, an alkyl, an aryl group, and an arylalkyl group.
  • At least one of Y and Y* may include a moiety of Formula (IV) :
  • Each of R is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium.
  • i and i' are independently 0, 1, 2, 3, or 4.
  • At least one of Y and Y* is independently selected from at least one gr
  • Each of R' is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, or an amine and quaternary ammonium.
  • Each of j' is independently selected from zero and an integer ranging from 1 to 4.
  • At least one of Y and Y* is preferably independently selected from at least
  • At least one of Y and Y* is preferably independently selected from at least one moiety of Formula (V) :
  • n and m are independently 0, 1, 2, 3 or 4.
  • Ar 1 , Ar 2 are equal or different from each other and are selected from an aromatic moiety of formula :
  • Ar 3 is selected from :
  • Each R' ' is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium
  • Each v is independently selected from zero and an integer ranging from 1 to 4.
  • n and m are zero.
  • B and B' are -0-, and A and A' are an aryl group or an arylalkyl group.
  • a and A' are selected from a phenylene group and a group of formula :
  • Z is selected from at least one of the following moieties :
  • the (co)polymer has a number average molecular weight (Mn) ranging from about 1,000 to about 30,000 g/mol, preferably from about 5,000 to about 25,000 g/mol.
  • the (co)polymer may have a glass transition temperature (Tg) ranging from about 100°C to about 300°C, preferably from about 150°C to about 280°C.
  • Tg glass transition temperature
  • a weight fraction, [Moieties of Formula (I)] / [Moieties of Formula (I) + Moieties of Formula (II)], may range from about 0.5 wt.- % to about 99.5 wt.- %.
  • the (co)polymer is preferably insoluble in dichloromethane.
  • Exemplary embodiments are directed to a method of making a (co)polymer including reacting in a solvent and in the presence of a base :
  • DKP diketopiperazine
  • B and B' are independently selected from -0-, NH / , and -S-.
  • a and A' are independently selected from a bond, -CH 2 -, an alkyl, an aryl group, and an arylalkyl group.
  • X is a halogen
  • Y preferably comprises a moiety of Formula (IV) :
  • Each of R is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium.
  • i and i' are independently 0, 1, 2, 3, or 4.
  • Exemplary embodiments are directed to a method including reacting in the solvent and in the presence of the base : - the at least one diketopiperazine (DKP) monomer precursor,
  • B* and B'* are independently selected from -0-, NH / , and -S-.
  • Z is selected from :
  • Each R s is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
  • k is 0, 1, 2, 3, or 4, and k' is independently 0, 1, 2, or 3.
  • A* and A'* are independently selected from a bond, -CH 2 -, an alkyl, an aryl group, and an arylalkyl group.
  • the solvent may include a polar aprotic solvent.
  • the base may include at least one alkali metal carbonate or at least one alkali metal hydroxide.
  • Y in formula X-Y-X above is preferably selected from at least one group of formu
  • Each of R' is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, or an amine and quaternary ammonium.
  • Each of j ' is independently selected from zero and an integer ranging from 1 to 4.
  • Y in formula X-Y-X above is more preferably selected from at least one
  • Y in formula X-Y-X above is preferably selected from at least one moiety of Formula (V) :
  • n and m are independently 0, 1, 2, 3 or 4.
  • Ar 1 , Ar 2 are equal or different from each other and are selected from an aromatic moiety of formula
  • Ar 3 is selected from :
  • Each R' ' is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
  • Each v is independently selected from zero and an integer ranging from 1 to 4.
  • the dihalo compound is preferably selected from 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone.
  • B and B' are -OH
  • a and A' are an aryl group or an arylalkyl group in the methods described herein.
  • Exemplary embodiments are directed to a composition including the (co)polymer.
  • the composition includes at least one other ingredient chosen from a polymer, a solvent, a filler, a lubricant, a mould release agent, an antistatic agent, a flame retardant, an anti- fogging agent, a matting agent, a pigment, a dye, and an optical brightener.
  • (co)polymer is used herein to designate a polymer that may be either homopolymer or a copolymer.
  • Exemplary embodiments include a (co)polymer comprising a recurring unit of Formula (I) :
  • B and B' are independently selected from -0-, -NH-, and -S-.
  • B and B' are the same. More preferably, B and B' are both -0-.
  • a and A' are independently selected from a bond, -CH 2 -, an alkyl, an aryl group, and an arylalkyl group.
  • a and A' are an aryl group or an arylalkyl group.
  • a and A' may both be an aryl group, preferably the same aryl group.
  • a and A' may each be a phenylene group.
  • a and A' are an arylalkyl group, preferably the same arylalkyl group.
  • the arylalkyl group may be :
  • B and B' are -0-, and A and A' are a substituted or unsubstituted aryl or arylalkyl group.
  • Y is a moiety of Formula (IV) :
  • Each of R which may be equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium.
  • i and i' is independently 0, 1, 2, 3, or 4.
  • Y may independently be selected from at least one group of
  • Each of R' which may be equal to or different from each other, is selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine and a quaternary ammonium.
  • Each of j' equal to or different from each other, is zero or an integer ranging from 1 to 4.
  • the respective phenylene moieties may independently have 1,2-, 1,4- or 1,3 -linkages to the other moieties different from R' in the respective moiety.
  • the phenylene moieties have 1,3- or 1,4- linkages, and more preferably they have 1,4-linkages.
  • Y is selected from at least one moiety of formula (J'- A) to (J * -0) :
  • Y is selected from at least one moiety of Formula (V) :
  • n and m are independently 0, 1, 2, 3 or 4.
  • n and m are both zero.
  • Ar 1 , Ar 2 are equal or different from each other and are preferably selected from an aromatic moiety of formula :
  • Ar 3 is selected from :
  • Each R' ' is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
  • Each v is independently selected from zero and an integer ranging from 1 to 4.
  • the (co)polymer includes at least one moiety selected from :
  • the (co)polymer includes at least one recurring unit selected from :
  • the (co)polymer may be a homopolymer or a copolymer.
  • the copolymer may be a random or a block copolymer.
  • the preferred architecture of the (co)polymer is linear but the architecture of the (co)polymer can be tailored to modify the viscosity of the polymer, for instance by introducing polyfunctional molecules having more than two reactive groups able to react with a dihalo or a diphenol, for
  • end-groups of the (co)polymer are independently selected from a phenol, a phenoxide, a halo, an alkoxy (preferably an methoxy), and a phenoxy.
  • the (co)polymer including recurring units of Formula (I) may further comprise at least one recurring unit of
  • Y* is independently selected from any moiety disclosed for Y in
  • Y and Y* may be the same or different. Preferably, Y and Y* are the same.
  • B* and B'* are independently selected from any moiety disclosed for B and B', respectively, in Formula (I).
  • B* and B'* may be the same or different and may each be the same or different from B and B'.
  • B* and B'* are the same. More preferably, B, B', B*, and B'* are all the same.
  • B* and B'* may both be -0-, and in some embodiments B, B', B*, and B'* may all be -0-.
  • Z may be selected from a group of formula :
  • Each R s is independently selected from a halogen, an alkyl, an alkenyl, an alkynyl, an aryl, an ether, a thioether, a carboxylic acid, an ester, an amide, an imide, an alkali or alkaline earth metal sulfonate, an alkyl sulfonate, an alkali or alkaline earth metal phosphonate, an alkyl phosphonate, an amine, and a quaternary ammonium.
  • Each k is 0, 1, 2, 3, or 4, and each k' is independently 0, 1, 2, or 3.
  • Z may also be selected from a group of Formula (III) :
  • A* and A'* are independently selected from any moiety disclosed for A and A', respectively, in Formula (I).
  • A* and A'* are an aryl group.
  • T is a bond, -S0 2 - or -C(CH 3 ) 2 -
  • Z is selected from at least one of the following moieti
  • Z is the following moiety
  • the (co)polymer preferably has a number average molecular weight (Mn) ranging from about 1,000 to about 30,000 g/mol, more preferably from about 5,000 to about 25,000 g/mol, still more preferably from about 10,000 to about 20,000 g/mol.
  • the (co)polymer is a thermoplastic (co)polymer.
  • the (co)polymer may be cross-linked.
  • the (co)polymer includes hydrogen bond cross-links.
  • the (co)polymer may be reversibly cross-linkable as a function of temperature.
  • the (co)polymers according to the present invention may feature some or all of the benefits of the currently sold polysulfones, polyketones, etc., while also surprisingly and unexpectedly exhibiting a high glass transition temperature (Tg), for example a Tg greater than about 200°C, and at least some insolubility in solvents such as dichloromethane.
  • Tg glass transition temperature
  • All glass transition temperatures (Tg) described herein are midpoint glass transition temperatures (Tg) determined by differential scanning calorimetry (DSC) according to ASTM D3418.
  • the (co)polymer preferably has a glass transition temperature (Tg) ranging from about 100°C to about 300°C, preferably from about 150°C to about 280°C, more preferably from about 170°C to about 250°C, still more preferably from about 200°C to about 250°C, even more preferably from about 230°C to about 250°C.
  • the Tg greater than about 100°C, preferably greater than about 150°C, preferably greater than about 170°C, preferably greater than about 200°C, preferably greater than about 205°C, preferably greater than about 210°C, preferably greater than about 215°C, preferably greater than about 220°C, preferably greater than about 225°C, preferably greater than about 230°C, preferably greater than about 235°C, preferably greater than about 240°C, preferably greater than about 245°C, preferably greater than about 250°C, preferably greater than about 255°C, preferably greater than about 260°C, preferably greater than about 265°C, preferably greater than about 270°C, preferably greater than about 275°C, preferably greater than about 280°C.
  • insoluble means that when 0.1 g of (co)polymer powder is placed in 10 mL (concentration of 10 g/L) of solvent at room
  • the (co)polymer is insoluble in one or more solvents selected from dichloromethane, tetrachloroethane, chloroform, chlorobenzene, and dimethylformamide.
  • the (co)polymer is insoluble in one or more solvents selected from dichloromethane, tetrachloroethane, chloroform, chlorobenzene, and dimethylformamide.
  • the (co)polymer is insoluble in
  • the (co)polymer is homopolymer comprising recurring units of Formula (I).
  • the (co)polymer is a homopolymer consisting essentially of recurring units of Formula (I).
  • the (co)polymer is a copolymer comprising recurring units of Formula (I) and recurring units of Formula (II).
  • the (co)polymer is a copolymer consisting essentially of recurring units of Formula (I) and recurring units of Formula (II). End chains, defects, or minor constituents may be present in the microstructure of the (co)polymer without substantially modifying its properties or affecting its basic and novel characteristics.
  • the (co)polymer may include more than 1 % wt, preferably more than
  • the (co)polymer may include more than 1 % wt, preferably more than 10 % wt, preferably more than 30 % wt, more preferably more than 50 % wt, still more preferably more than 70 % wt and most preferably more than 90 % wt of recurring units of Formula (II), as detailed above.
  • a sum the % wt. of recurring units of Formula (I) and recurring units Formula (II) in the (co)polymer may be more than 10 % wt., preferably more than 30 % wt., more preferably more than 50 % wt., still more preferably more than 70 % wt. and most preferably more than 90 % wt. of a total wt % of recurring units in the (co)polymer.
  • the percent by weight of the DKP moiety in the (co)polymer ranges from about 15 wt.- % to about 35 wt.- %, preferably from about 20 wt.- % to about 25 wt.- %.
  • the weight fraction, [Moieties of Formula (I)] / [Moieties of Formula (I) + Moieties of Formula (II)] ranges from about
  • wt.- % 0.5 wt.- % to about 99.5 wt.- %, preferably from about 2 wt.- % to about 98 wt.- %, more preferably from about 3 wt.- % to about 70 wt.- %.
  • the (co)polymer may include less than 50 % wt. aliphatic moieties, preferably less than 30 % wt. aliphatic moieties, preferably less than 10 % wt. aliphatic moieties, preferably less than 1 % wt. aliphatic moieties, preferably less than 0.1 % wt. aliphatic moieties.
  • Exemplary embodiments include a method of making a (co)polymer comprising reacting in a solvent and in the presence of a base :
  • DKP diketopiperazine
  • B and B' are independently selected from -0-,
  • the groups BH and B ⁇ are independently selected from -OH, -NH 2 , and -SH.
  • a and A' in Formula (IA) are each independently selected from the moieties described above for A and A' in Formula (I), respectively.
  • Y in Formula (IA) is selected from the same moieties as described above for Y in Formula (I).
  • X is a halogen.
  • X is selected from F, CI, Br, and I, more preferably from F and CI.
  • X is CI.
  • Exemplary embodiments also include a method of making a (co)polymer comprising reacting in the solvent and in the presence of the base :
  • Z in Formula (IIA) is selected from the same moieties as described above for Z in Formula (II).
  • the diketopiperazine (DKP) monomer precursor of Formula (IA) may be the same as or different from the compound of Formula (IIA).
  • the diketopiperazine (DKP) monomer precursor of Formula (IA) is different from the compound of Formula (IIA).
  • Preferred diketopiperazine (DKP) monomer precursors include :
  • the diketopiperazine (DKP) monomer precursor is sourced or derivable from a renewable resource, such as a bio-based resource.
  • Preferred dihalo compounds include dihalodiphenyl sulfones such as 4,4'-dichlorodiphenyl sulfone, 4,4'-difluorodiphenyl sulfone, 4-chloro-4'- fluorodiphenyl sulfone, 4,4'-dibromodiphenyl sulfone, and 4,4'-diiododiphenyl sulfone, with 4,4'-dichlorodiphenyl sulfone being particularly preferred.
  • Preferred dihalo compounds also include 4,4'-difluorobenzophenone,
  • Particularly preferred compounds of Formula (IIA) include diols of formulae :
  • bisphenol A is most preferred.
  • the diketopiperazine (DKP) monomer precursor of Formula (IA) may be used in an amount ranging from about 0.5 mol- % to about 99.5 mol- % with respect to the sum of the mol- % of the compound of Formula (IIA) and the mol- % of the diketopiperazine (DKP) monomer precursor of Formula (IA).
  • the dihalo compound may be used in an amount ranging from about 45 mol- % to about 50 mol- %, preferably from about 48 mol- % to about
  • the (co)polymer may be made by one or more polycondensation reactions.
  • the polycondensation reaction(s) can be carried out according to known methods, i.e., a weak base process using an alkali metal carbonate or bicarbonate such as sodium carbonate or potassium carbonate; a strong base process using an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide; or a phase transfer catalyzed method.
  • a weak base process using an alkali metal carbonate or bicarbonate such as sodium carbonate or potassium carbonate
  • a strong base process using an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
  • phase transfer catalyzed method i.e., a phase transfer catalyzed method.
  • one or more polycondensation reactions as described herein and as known in the art may be used to form one or more precursor units which may used in a reaction to form the (co)polymer.
  • the moieties of formulae (J- A) to (J-O), (J'-A) to (J'-O), and Formula (V) may themselves be prepared by poly condensation reactions as described herein and as known in the art.
  • the solvent may be any suitable solvent known to those of skill in the art.
  • the solvent is a polar aprotic solvent.
  • the diketopiperazine (DKP) monomer precursor, the dihalo compound, and the compound of Formula (IIA) may be dissolved or dispersed in a solvent mixture comprising a polar aprotic solvent.
  • an additional solvent can be used together with the polar aprotic solvent which forms an azeotrope with water, whereby water formed as a by-product during the polymerization may be removed by continuous azeotropic distillation throughout the polymerization.
  • the reaction medium is maintained in substantially anhydrous conditions during the polymerization by removing water continuously from the reaction mass. Water can be removed by distillation or with the azeotrope-forming solvent as an azeotrope, as described above.
  • the by-product water and possibly carbon dioxide formed during the polymerization can alternatively be removed using a controlled stream of an inter gas such as nitrogen or argon over the reaction mixture in addition to or in the absence of an azeotrope-forming solvent as described above.
  • an inter gas such as nitrogen or argon
  • additional solvent is understood to denote a solvent different from the polar aprotic solvent and the reactants and the products of said reaction.
  • sulfur- comprising solvents that may be suitable for the purposes of this invention are dimethylsulfoxide, dimethylsulfone, diphenylsulfone, diethylsulfoxide, diethylsulfone, diisopropylsulfone, tetrahydrothiophene-1, 1 -dioxide (commonly called tetramethylene sulfone or sulfolane) and tetrahydrothiophene-1 -monoxide and mixtures thereof.
  • Nitrogen-containing polar aprotic solvents including dimethylacetamide, dimethylformamide and N-methyl pyrrolidone (i.e., NMP) and the like may also be used.
  • the additional solvent that forms an azeotrope with water may be selected to be inert with respect to the monomer components and polar aprotic solvent.
  • Suitable azeotrope-forming solvents for use in such polymerization processes include aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, chlorobenzene and the like.
  • the azeotrope-forming solvent and polar aprotic solvent are typically employed in a weight ratio of from about 1 : 10 to about 1 : 1, preferably from about 1 :5 to about 1 :3.
  • the base may be a strong base or a weak base.
  • the weak base may comprise an alkali metal carbonate and the strong base may comprise an alkali metal hydroxide.
  • the alkali metal carbonate is preferably sodium carbonate, potassium carbonate, rubidium carbonate or cesium carbonate. Sodium carbonate and especially potassium carbonate are preferred. Mixtures of more than one carbonate can be used. For example, a mixture of sodium carbonate or bicarbonate and a second alkali metal carbonate or bicarbonate having a higher atomic number than that of sodium may be used.
  • the amount of said alkali metal carbonate used when expressed by the ratio of the equivalents of alkali metal (M) per equivalent of hydroxyl group (OH) [eq. (M)/eq. (OH)] ranges from about 1.0 to about 3.0, preferably from about 1.05 to about 2.5, and more preferably from about 1.1 to about 2.0.
  • an alkali metal carbonate having an average particle size of less than about 100 ⁇ , preferably of less than about 50 ⁇ is particularly advantageous.
  • the use of an alkali metal carbonate having such a particle size may permit the synthesis of the polymers to be carried out at a relatively lower reaction temperature with faster reaction.
  • the temperature of the reaction mixture will be maintained in a range of advantageously from 150-220°C for about 3 to 8 hours.
  • the boiling temperature of the solvent selected usually limits the temperature of the reaction.
  • the reaction may be conveniently carried out in an inert atmosphere, e.g., nitrogen, at atmospheric pressure, although higher or lower pressures may also be used.
  • the polymer is treated with an activated aromatic halide or an aliphatic halide such as methyl chloride or benzyl chloride, and the like. Such treatment of the polymer converts the terminal hydroxyl groups into ether groups which stabilize the polymer.
  • the polymer so treated has good melt and oxidative stability.
  • the (co)polymers of the present invention are prepared by a polycondensation reaction which is carried out according to the alkali metal hydroxide method. While the carbonate method for preparing the polymer of this invention is simple and convenient, in some cases products of higher molecular weight can be made by said alkali metal hydroxide method.
  • a double alkali metal salt of a dihydric phenol is contacted with a dihalobenzenoid compound in the presence of a polar aprotic solvent, e.g. a sulfur containing solvent such as dimethylsulfoxide,
  • dimethylsulfone diphenylsulfone, diethylsulfoxide, diethylsulfone,
  • the (co)polymers of the present invention are prepared by a polycondensation reaction which is carried out according to the phase transfer catalyzed method. While the carbonate method and the alkali metal hydroxide method are normally conducted in the presence of polar aprotic solvents, the phase transfer catalyzed method can be carried out in non-polar solvents due to the employment of a phase transfer catalyst, facilitating incorporation of the salt of an aromatic bishydroxy monomer, in the organic phase.
  • the phase transfer catalyzed method can be conducted by contacting a substantially equimolar reaction of a double alkali metal salt of a dihydric phenol with a dihalobenzenoid compound, except that the presence of liquid organic sulfone or sulfoxide solvents and cosolvents under substantially anhydrous conditions are not required, and phase transfer catalysts are used for this reaction.
  • the (co)polymer can be recovered by well-known methods such as, for example, coagulation, solvent evaporation, or the like.
  • the resulting (co)polymer may be isolated by devolatilization of the reaction mixture after separation of salts with or without first adding additional solvent(s) such as sulfolane or a mixture of sulfolane with another solvent, optionally the azeotrope solvent, to fully dissolve any polymer and cause the precipitation of the metal halide.
  • additional solvent(s) such as sulfolane or a mixture of sulfolane with another solvent, optionally the azeotrope solvent, to fully dissolve any polymer and cause the precipitation of the metal halide.
  • the (co)polymer may be isolated by precipitation and/or coagulation by contacting the reaction mixture with a non-solvent for the (co)polymer such as an alcohol or water, or a mixture thereof.
  • a non-solvent for the (co)polymer such as an alcohol or water, or a mixture thereof.
  • precipitate/coagulate may be rinsed and/or washed with demineralized water prior to drying under reduced pressure and elevated temperature.
  • the resulting precipitate may be further processed by extruding and pelletizing.
  • the pelletized product or a powder obtained directly from the precipitation may subsequently be subjected to further melt processing such as injection moulding and/or extrusion.
  • the conditions for moulding, extruding, and thermoforming the resulting (co)polymer are well known in the art.
  • Exemplary embodiments also include polymer compositions that comprise at least one of the (co)polymers described herein, and at least one other ingredient.
  • Said other ingredient can be another (co)polymer. It can also be a polymer other than the (co)polymers described herein, such as
  • ingredients may also include a non-polymeric ingredient such as a solvent, a filler, a lubricant, a mould release agent, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye, an optical brightener, a stabilizer (UV, thermal, and/or oxygen stabilizer) or a combination thereof.
  • a non-polymeric ingredient such as a solvent, a filler, a lubricant, a mould release agent, an antistatic agent, a flame retardant, an anti-fogging agent, a matting agent, a pigment, a dye, an optical brightener, a stabilizer (UV, thermal, and/or oxygen stabilizer) or a combination thereof.
  • the polymer composition according to exemplary embodiments may be a filled or unfilled composition.
  • the composition may include reinforcing fillers selected from continuous or discontinuous fibrous fillers and particulate fillers.
  • Reinforcing fillers may include, for example, one or more mineral fillers, such as notably talc, mica, kaolin, calcium carbonate, calcium silicate, or magnesium carbonate; glass fiber; carbon fibers such as notably graphitic carbon fibers, amorphous carbon fibers, pitch-based carbon fibers, PAN-based carbon fibers; synthetic polymeric fiber; aramid fiber; aluminum fiber; aluminum silicate fibers; oxide of metals of such aluminum fibers; titanium fiber; magnesium fiber; boron carbide fibers; rock wool fiber; steel fiber; asbestos; wollastonite; silicon carbide fibers; boron fibers, boron nitride, graphene, carbon nanotubes (CNT), or a combination thereof.
  • mineral fillers such as notably talc, mica, kaolin, calcium
  • Exemplary embodiments include an article comprising the (co)polymer as described above.
  • the total weight of the (co)polymer is advantageously more than 50 %, preferably more than 80 %, more preferably more than 90 %, more preferably more than 95 %, and more preferably more than 99 %.
  • the article may consist of, or consist essentially of, the (co)polymer or a composition comprising the (co)polymer.
  • the article may be an injection moulded article, an extrusion moulded article, a shaped article, a coated article, or a casted article.
  • Non limiting examples of articles include bearing articles such as radial and axial bearings for auto transmission, bearings used in dampers, shock absorbers, bearings in any kind of pumps, e.g., acid pumps; hydraulically actuated seal rings for clutch components; gears or the like.
  • the article is a bearing article.
  • the bearing article may include several parts, wherein at least one of said parts, and optionally all of them, include the (co)polymer.
  • the (co)polymer can also notably be used for the manufacture of membranes, films and sheets, and three-dimensional moulded parts.
  • the (co)polymer can be advantageously processed to yield all of the above-mentioned articles by melt processing (including injection moulding, extrusion moulding, and compression moulding).
  • Non-limiting examples of shaped articles that can be manufactured from the (co)polymer using different processing technologies are generally selected from the group consisting of melt processed films, solution processed films (porous and non porous films, including solution casted membranes, and membranes from solution spinning), melt process monofilaments and fibers, solution processed monofilaments, hollow fibers and solid fibers, and injection and compression molded objects.
  • the (co)polymer of the invention is particularly suitable for manufacturing membranes intended for contact with aqueous media, including body fluids; thus, shaped articles which can be manufactured from the (co)polymer as above detailed are advantageously membranes for bioprocessing and medical filtrations, including hemodialysis membranes, membranes for food and beverage processing, membranes for waste water treatment and membranes for industrial process separations involving aqueous media.
  • membranes manufactured from the (co)polymer as above detailed may be provided under the form of flat structures (e.g. films or sheets), corrugated structures (such as corrugated sheets), tubular structures, or hollow fibers; as per the pore size is concerned, full range of membranes (non-porous and porous, including for micro filtration, ultrafiltration, nano filtration, and reverse osmosis) can be advantageously manufactured from the (co)polymers of the invention; pore distribution can be isotropic or anisotropic.
  • (co)polymer can be, as above mentioned, in the form of films and sheets. These shaped articles are particularly useful as specialized optical films or sheets, and/or suitable for packaging.
  • shaped articles manufactured from the (co)polymer of the invention can be three-dimensional moulded parts, in particular transparent or coloured parts.
  • Fields of use for such injection moulded parts include healthcare, in particular medical and dental applications, where shaped articles made from the (co)polymer may advantageously be used for replacing metal, glass, and other traditional materials in single-use and reusable instruments and devices.
  • the above described article may also be a food contact article such as a plumbing article such as a fitting, a valve, a manifold or a faucet, a food tray, a water bottle or a baby bottle, a cookware.
  • a food contact article such as a plumbing article such as a fitting, a valve, a manifold or a faucet, a food tray, a water bottle or a baby bottle, a cookware.
  • the above described article may also be a housing or cover for a mobile electronic device.
  • the above described article may also be a medical tray or an animal cage.
  • the (co)polymer of the present invention may be amorphous and may be transparent.
  • the Tg at the mid-point of the polymers was determined by differential scanning calorimetry (DSC) using a TA Instrument DSC Q20 under nitrogen at a heating speed of 20°C/min, according to the ASTM D3418.
  • the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by Gel Permeation Chromatography (GPC) in dimethylformamide (DMF) as a mobile phase. Two 5-micron mixed D Size Exclusion Chromatography columns with guard from Agilent Technologies were used for separation. An ultraviolet detector of 270 nm was used to obtain the chromatogram. A flow rate of 1.1 mL/min and injection volume of 10 of a 0.2 % w/v solution in the mobile phase was selected. The calibration was performed with a broad standard of RADEL® PPSU R5000 with
  • Empower Pro ® GPC software manufactured by Waters.
  • the peak integration start and end points were manually determined from significant difference on global baseline.
  • Solubility was tested in a variety of solvents by placing 0.1 g of polymer powder in 10 mL (concentration of 10 g/L) of solvent at room temperature for 2 hours and determining whether any of the polymer powder remained. If no polymer powder remained, the polymer was considered “soluble” in the solvent, and if any polymer powder remained, the polymer was considered “insoluble” in the solvent.
  • UDEL ® PSU polysulfone is made by condensing bisphenol A (BPA) and
  • DCDPS 4,4'-dichlorodiphenyl sulfone
  • RADEL ® PPSU polyphenylsulfone is made by reacting units of
  • Radel ® PPSU has a glass transition temperature (Tg) of about 220°C.
  • VERADEL ® PES has a glass transition temperature (Tg) of about 220°C.
  • Example 1 Homopolymer from Tyrosine DKP and 4,4'-Dichlorodiphenyl
  • the polymer solution was diluted with NMP to 10 wt- % (polymer basis in NMP after removal of salts) and filtrated to remove the potassium chloride formed during the reaction and the excess of potassium carbonate salts. The polymer solution was then coagulated in water to yield an orange precipitate that was washed 3 times with water and dried under vacuum overnight at 80°C.
  • Example 2 Copolymer from Tyrosine DKP (50 mol. % of the diphenol), Bisphenol A (50 mol.- % of the diphenol) and 4,4'-Dichlorodiphenyl Sulfone
  • Tyrosine DKP 50 mol. % of the diphenol
  • Bisphenol A 50 mol.- % of the diphenol
  • 4,4'-Dichlorodiphenyl Sulfone In a 200 mL 4-neck glass reactor equipped with a condenser and a trap were introduced 3.35 g (0.0102 mol) of tyrosine DKP at 99 %,
  • This polymer was soluble in amide solvent (dimethylformamide).
  • amide solvent dimethylformamide.
  • the copolymer was insoluble in dichloromethane and chlorobenzene according to the solubility test.
  • Example 3 Homopolymer from Hydroxyphenylglycine DKP and 4,4'- Dichlorodiphenyl Sulfone Synthesized in NMP
  • the polymer solution was filtrated to remove the potassium chloride formed during the reaction and excess of potassium carbonate salts. Then glacial acetic acid was added drop wise until the reaction mixture became clear (about 2 mL) and the polymer solution was then coagulated in water followed by 2 washes with water and one wash with methanol. The resulting polymer was dried under vacuum overnight at 80°C.
  • the glass transition temperature (Tg) was found to be 233.1°C, which is higher than the Tg of both Udel ® PSU (185°C) and Radel ® PPSU (220°C) (Comparative Examples 1 and 2).
  • Example 4 Copolymer from Hydroxyphenylglycine DKP (50mol. % of the diphenol), Bisphenol A (50moL- % of the diphenol) and
  • Tg glass transition temperature
  • This copolymer was insoluble in dichloromethane and in chlorobenzene.
  • the polymer was soluble in an amide solvent (dimethylformamide (DMF).
  • amide solvent dimethylformamide (DMF).
  • Example 5 Copolymer from Hydroxyphenylglycine DKP (50mol. % of the diphenol), 4,4'-biphenol (50moL- % of the diphenol) and
  • Tg temperature
  • amide solvent dimethylformamide (DMF)
  • Example 6 Homopolymer from Hydroxyphenylglycine DKP and
  • the polymer solution was filtrated to remove the potassium chloride formed during the reaction and excess of potassium carbonate salts. Then glacial acetic acid was added drop-wise until the reaction mixture became clear (about 2 mL) and the polymer solution was then coagulated in water followed by 2 washes with water and one wash with methanol. The resulting polymer was then dried under vacuum overnight at 80°C.
  • the glass transition temperature (Tg) was found to be 247.9°C, which is higher than the Tg of Radel ® PPSU (220°C).
  • This polymer is insoluble in dichloromethane and chlorobenzene.
  • the polymer was soluble in amide solvent (dimethylformamide (DMF)).
  • amide solvent dimethylformamide (DMF)
  • Example 7 Copolymer from Hydroxyphenylglycine DKP (lOmol. % of the diphenol), 4,4'-biphenol (90moL- % of the diphenol) and 4,4'- Dichlorodiphenyl Sulfone
  • DCDPS 4,4'-dichlorodiphenylsulfone
  • the reaction mixture was stirred and heated to 210°C and maintained at this temperature for 3 hours. A low viscosity was observed at the polymerization temperature and also after cooling.
  • the viscous polymer solution was diluted with 35.7 g of NMP and was filtrated to remove the potassium chloride formed during the reaction and excess of potassium carbonate salts.
  • the polymer solution was then coagulated in water followed by 2 washes with water and one wash with methanol.
  • the resulting polymer was then dried under vacuum overnight at 80°C.
  • the glass transition temperature (Tg) was found to be 219.4°C, which is close to the Tg of PPSU.
  • This copolymer was insoluble in tetrachloroethane, in dichloromethane, and in chlorobenzene.
  • the polymer was soluble in amide solvent

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyethers (AREA)

Abstract

Cette invention concerne un (co)polymère comprenant un motif récurrent de Formule (I) : Y comprend au moins un groupe aryle et au moins un groupe choisi parmi C = O, O = S = O, -NH -, et -CF2- ; B et B' sont indépendamment choisis parmi -O -, -NH -, et -S - ; et A et A' sont indépendamment choisis parmi une liaison, -CH2-, un groupe alkyle, un groupe aryle, et un groupe arylalkyle.
PCT/EP2015/072475 2014-10-02 2015-09-29 (co)polymères, dont des diamides cycliques Ceased WO2016050798A1 (fr)

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WO2013142969A1 (fr) * 2012-03-28 2013-10-03 Jian Ping Gao Uréthanes et urées, et procédés associés
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US20120108677A1 (en) * 2010-11-01 2012-05-03 Rutgers, The State University Of New Jersey Iminic monomers and polymers thereof
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CN113754598A (zh) * 2021-09-29 2021-12-07 四川大学 含环肽结构的二胺、聚酰亚胺及其制备方法
CN113754598B (zh) * 2021-09-29 2023-06-06 四川大学 含环肽结构的二胺、聚酰亚胺及其制备方法

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