WO2017187279A1 - Résines thermoplastiques auto-réparantes - Google Patents

Résines thermoplastiques auto-réparantes Download PDF

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Publication number
WO2017187279A1
WO2017187279A1 PCT/IB2017/050760 IB2017050760W WO2017187279A1 WO 2017187279 A1 WO2017187279 A1 WO 2017187279A1 IB 2017050760 W IB2017050760 W IB 2017050760W WO 2017187279 A1 WO2017187279 A1 WO 2017187279A1
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Prior art keywords
thermoplastic resin
monomers
disulfide
healing
dithiobis
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PCT/IB2017/050760
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English (en)
Inventor
Mukesh Agrawal
Gaurav Mediratta
Gurunath POZHAL VENGU
Arun SIKDER
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Sabic Global Technologies B.V.
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Publication of WO2017187279A1 publication Critical patent/WO2017187279A1/fr

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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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/1064—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing sulfur
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound

Definitions

  • the disclosure concerns healable thermoplastic resins comprising at least about 1 mol % of disulfide units.
  • Healing materials represent a class of the smart materials which have the ability to repair damages.
  • polymer substrates may be coated with a healing layer.
  • healing layers offer healing properties only to the surface and cannot repair the damages developed in the bulk of the material.
  • healing layers often contain solvents and surfactants, which result in a high initial haze of the healed polymer, making it ill-suited for many applications.
  • Polymer resins may also be mixed with healing agents such as those encapsulated in capsules and catalysts.
  • the presence of such foreign materials in the polymer matrix affects other key properties such as transparency.
  • healing systems are driven by irreversible reactions and, therefore, are not effective for repairing multiple events of the damages.
  • Thermoplastic resins are amorphous high performance polymers, characterized by excellent thermal properties, good chemical resistance, inherent flame retardance and exceptional dimensional stability. High performance and design flexibility allow these resins to be used for a wide range of applications such as automotive, aviation, medical and electrical and lighting, telecom and fluid handling devices. In many areas, especially in wire insulation and other outdoor applications, such resins have been found to undergo slow degradation over time due to polymer chain break down initiated by presence of water vapor, high temperature, sunlight or other adverse weathering conditions. As a result, they become brittle and susceptible to damage from mechanical and electrical stresses leading to the poor surface aesthetics and in some cases, failure of the structural integrity and functional properties. Such problems in electrical wiring systems are an important threat to the safety of aircrafts and space crafts as well as other electrical devices.
  • US Patent Publication No. 2011/0212334 discloses low melt polyetherimides and poly(amic acids) based materials, which readily imidize with a polyetherimide wire insulation layer or other surfaces made of high performance polyetherimide resins under mild heating conditions. Although such low- melt materials are useful for repair purposes, reworking the fractured wire insulation system is very difficult and not cost effective compared to the replacement with the new wiring system.
  • US Patent Publication No. 2012/0321828 discusses microcapsule technology to deliver self-healing properties to electrical wire insulation or in other high performance, thin wall technologies such as inflatable structures. Such microcapsules are encapsulated with a solvent, which is released in a damage event, softens the
  • thermoplastic resins which are capable of healing without any catalysts and can accomplish multiple healings of damages over time.
  • the disclosure concerns healable thermoplastic resins comprising at least about 1 mol% of disulfide units.
  • the thermoplastic resins comprise about 5 to about 30 mol% of aromatic disulfide units.
  • the disclosure also concerns articles comprising the healable thermoplastic resins described herein as well as methods of activating healable thermoplastic resins described herein by exposing the healable thermoplastic resins to heat and/or radiation.
  • FIG.1 is the proposed mechanism for the healing process of disulfide-containing thermoplastic resins.
  • healing thermoplastic resins have healing properties.
  • the term "heal” as used herein refers to the ability of a polymer to repair damage to the polymer article.
  • the healing properties of the thermoplastic resins are attributed to the ability of a first sulfur-sulfur bond to undergo metathesis with a second sulfur-sulfur bond (see, e.g., FIG. 1).
  • the first and second sulfur-sulfur bonds are within the same thermoplastic resin molecule.
  • the first and second sulfur-sulfur bonds are in different thermoplastic resin molecules.
  • the location of the sulfur-sulfur bond e.g., within the thermoplastic resin molecule, on one or both ends of the thermoplastic resin molecule, and/or linking two or more thermoplastic resin molecules, does not affect the metathesis involved with healing damage in the thermoplastic resins.
  • the damage to the polymer may be microscopic or macroscopic, i.e., viewable to the eye and is the result of the breaking of chemical bonds within the polymer.
  • the damage is due to cleavage of sigma bonds, hemolytic bonds, or heterolytic bonds.
  • the damage is due to microcracks which are formed from damaging neighboring polymer chains.
  • the damage is due to losing interactions such as hydrogen bonding, metal coordination, and van der Waals forces in the polymer.
  • the damage to the thermoplastic resins may be on the surface and/or within the bulk portion of the resin, e.g., within and beneath the surface of the resin. Further, the damage may occur at substantially the same location as other points of damage on or within the resin or may occur at another location on or within the resin. In addition to the healing properties, the thermoplastic resins have good impact properties, heat properties, and/or flow characteristics.
  • thermoplastic resins described herein are typically healed upon activation.
  • activation refers to initiating the disulfide metathesis as described above and in FIG. 1 at one or more locations in the resin.
  • healing of the thermoplastic resins is activated using heat and/or radiation.
  • the temperature, i.e., "healing temperature" required to heal the thermoplastic resin is a temperature which is greater than the glass transition temperature (T g ) of the thermoplastic resin and will depend on the particular thermoplastic resin prepared.
  • T g glass transition temperature
  • the temperature required to heal the thermoplastic resin is about 30 to about 80 °C (Celsius) above the T g .
  • the temperature required to heal the thermoplastic resin is about 35 to about 40 °C.
  • the healing temperature is typically less than the processing temperature at which the thermoplastic resin flows smoothly.
  • the radiation has a wavelength between about 350 to about 550 nm (nanometer).
  • the thermoplastic resins are capable of healing in the absence of healing agents/repairing materials, healing layers, catalysts, microcapsules, pressure, electricity, pH and/or fillers such as carbon nanotubes to accelerate the healing mechanism.
  • Healing agents include agents which polymerize, i.e., monomers, in response to the generation of a crack in a polymer resin.
  • Healing agents are customarily incorporated into the bulk form of the polymer or may be present in a polymer layer applied to a substrate, i.e., a healing layer.
  • “Carbon nanotubes” refer to allotropes of carbon with a cylindrical nanostructure which may be incorporated into polymer matrices in an effort to increase the strength of the polymer matrix and mitigate the formation of micro-cracks in the polymer matrix.
  • “Microcapsules” refer to a "container” which encapsulates a polymer matrix, monomer, catalyst, crosslinker, or other reagents.
  • the microcapsule is a capsule having an outer wall and an inner compartment and which contains a polymer matrix that melts at a temperature below 300° C and a volatile solvent that when released from the microcapsules melts or softens the polymer matrix, allowing it to flow in the defect caused by the damage. The solvent then evaporates, leaving more solidified polymer in the defect that heals the defect.
  • thermoplastic resins of the present disclosure are capable of being healed in connection with multiple events of damage.
  • multiple refers to the ability of the thermoplastic resin to heal damage (e.g. cracks) over multiple cycles, including damage occurring at substantially the same location of a previously healed area of the resin.
  • the thermoplastic resins are capable of healing following a single event of damage, and can also heal following multiple events of damage at approximately the same site, including, for example, at least about 5, 10, 15, 20, or 25 events.
  • thermoplastic resin includes mixtures of two or more thermoplastic resins.
  • alkyl refers to a saturated hydrocarbon group which is straight-chained or branched, saturated or unsaturated.
  • alkyl groups include, without limitation, methyl, ethyl, propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, i-butyl, s-butyl, t-butyl), pentyl (e.g., n-pentyl, i- pentyl, n-pentyl).
  • An alkyl group can contain from 1 to about 30, from 2 to about 20, from 1 to about 10, from 1 to about 8, from 1 to about 6, from 1 to about 4, or from 1 to about 3 carbon atoms.
  • “Ci -6 alkyl” refers to an alkyl group having from 1 to 6 carbon atoms.
  • cycloalkyl refer to a saturated, cyclic hydrocarbon group.
  • examples of cycloalkyl groups include, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, among others.
  • a cycloalkyl group can contain from 3 to about 20, from 3 to about 10, from 3 to about 8, or from 4 to about 6.
  • aryl refers to refers to aromatic carbocyclyl groups including monocyclic or polycyclic aromatic hydrocarbons such as, for example, phenyl, naphthyl, anthracenyl, phenanthrenyl, indanyl, indenyl, and the like. In some embodiments, aryl groups have from 4 to about 18 carbon atoms, from 5 to 10, or 5 to 7 carbon atoms.
  • alkaryl refers to an alkyl moiety as described above substituted by an aryl group, both described above.
  • Example aralkyl groups include benzyl and naphthylmethyl groups.
  • alkoxy refers to an -O-alkyl group, where alkyl is defined above. Examples of alkoxy groups include methoxy, ethoxy, propoxy (e.g., n-propoxy and i-propoxy), t-butoxy, and the like.
  • Aryloxy refers to an -O-aryl group, wherein aryl is defined above. Examples of aryloxy groups include, without limitation, -O-phenyl, -O-naphthyl, -O-anthracenyl, -O-phenanthrenyl, -O-indanyl, -O-indenyl, and the like.
  • halogen As used herein, "halogen”, “halo”, or “halide” are used interchangeably and refer to F, CI, Br, and I.
  • carbonate refers to -OC(0)0- and “sulfone” refers to -S0 2 -.
  • sulfide refers to -S-
  • ether refers to -0-
  • amide refers to -C(0)-N-
  • imide refers to -C(0)-N-C(0)-
  • ester refers -C(0)0-
  • diol refers to a chemical compound having two hydroxy groups.
  • polyester refers to a polymer containing an ester functional group in the backbone of the polymer.
  • Polystyrenes contain optionally substituted styrene groups, i.e., -C(Ph)-C-, in the backbone of the polymer.
  • polyacrylonitrile refers to polymers prepared from optionally substituted acrylonitrile and containing optionally substituted acrylonitrile monomers, i.e., -CH 2 CH(CN)-.
  • polyetherimide refers to polymers containing ether and optionally substituted imide functional groups in the backbone of the polymer.
  • polyphenylene oxide refers to polymers containing optionally substituted phenyl rings linked with O.
  • Polyphenylene sulfide refers to polymers containing optionally substituted phenyl rings linked with S.
  • polyamide refers to polymers containing repeating units linked by amide bonds.
  • polyetherketone refers to polymers containing ether and carbonyl groups in each monomer. In some embodiments, the polyetherketone contains two ethers and one carbonyl group in each monomer. “Polyethersulfone” refers to polymers containing ether and sulfone groups in each monomer. In some embodiments, the polyetherketone contains two ethers and one sulfone group in each monomer.
  • polybenzimidazole refers to polymers containing optionally substituted benzimidazole groups.
  • divalent group refers to a group capable of forming 2 chemical bonds between two chemical elements to form an organic or inorganic group.
  • a “tetravalent” linker is a group capable of forming 4 chemical bonds.
  • the term "monocyclic” refers to cyclic moieties having about 3 to about 50 carbon atoms, are substituted or unsubstituted, are saturated, unsaturated or aromatic. In some embodiments, a monocyclic group contains about 5 to about 30 carbon atoms.
  • polycyclic refers to optionally substituted cyclic moieties having about 5 to about 50 carbon atoms and at least two rings fused together. In some embodiments, polycyclic groups have two, three, four, five, six, seven or more rings fused to form a single polycyclic ring. In further embodiments, a polycyclic ring contains two or more monocyclic groups fused together. In other embodiments, a polycyclic group contains about 5 to about 30 carbon atoms.
  • aliphatic diamine refers to an alkyl as described above containing two amine substituents.
  • an aliphatic diamine is a C 5 to C 40 diamine.
  • substituted refers to where at least one hydrogen atom of a chemical group is replaced by a non-hydrogen moiety.
  • substituents include OH, oxo, Ci -6 alkyl, Ci -6 alkoxy, aryl, Ci -6 alkaryl, halogen, Ci -6 haloalkyl, or aryl.
  • an amount, size, formulation, parameter or other quantity or characteristic is “about” or “approximate” whether or not expressly stated to be such. It is understood that where "about” is used before a quantitative value, the parameter also includes the specific quantitative value itself, unless specifically stated otherwise.
  • the molecular weight for a given polymer refers to the weight average molecular weight (M w ).
  • M is the molecular weight of a chain
  • N is the number of chains of that molecular weight.
  • unit refers to a portion of the thermoplastic resin chain.
  • thermoplastic resin chain contains multiple units. Accordingly, the thermoplastic resin described herein is comprised of multiple thermoplastic resin units which may be separate from each other (not bound together chemically) or are attached (bound together chemically). Each unit is typically repeated in the polymer chain, i.e., "repeat unit".
  • the thermoplastic resin units are derived from the one or more monomers discussed herein. Accordingly, the thermoplastic resin may contain units from one, two, three, four or more monomers in varying amounts and having varying M w as defined above.
  • Ranges can be expressed herein as from one particular value to another particular value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent "about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint. It is also understood that there are a number of values disclosed herein, and that each value is also herein disclosed as "about” that particular value in addition to the value itself. For example, if the value "10” is disclosed, then “about 10" is also disclosed. It is also understood that each unit between two particular units are also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.
  • compositions of the disclosure Disclosed are the components to be used to prepare the compositions of the disclosure as well as the compositions themselves to be used within the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds cannot be explicitly disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed and a number of modifications that can be made to a number of molecules including the compounds are discussed, specifically contemplated is each and every combination and permutation of the compound and the modifications that are possible unless specifically indicated to the contrary.
  • the described compounds are defined herein using structural formulas that do not specifically recite the mass numbers or the isotope ratios of the constituent atoms. It is intended that the present application includes compounds in which the constituent atoms are present in any ratio of isotope forms. For example, carbon atoms may be present in any ratio of 12 C, 13 C, and 14 C; hydrogen atoms may be present in any ratio of H, H, and H; among others. In one embodiment, the constituent atoms in the compounds of the present application are present in their naturally occurring ratios of isotope forms.
  • thermoplastic resin includes polymers that that become pliable or moldable above a specific temperature.
  • the thermoplastic resin may include at least one (homopolymer), two (copolymer), three (terpolymer), four (tetrapolymer), five (pentapolymer) or more repeating units. At least one repeating unit must be capable of conveying thermoplastic properties when incorporated into a polymer. At least one repeating unit must also be a disulfide unit.
  • the healable thermoplastic resin contains at least about 1 mol% to about 50 mole% of disulfide units, e.g., as the monomer, co-monomer, end -cap, crosslinker, or combinations thereof. In some embodiments, the healable thermoplastic resin contains about 5 mol% to about 50 mol% of disulfide units. In other embodiments, the healable thermoplastic resin contains about 5 to about 30 mol% of disulfide units. In further embodiments, the healable thermoplastic resin contains about 5 to about 25 mol% of disulfide units. In other embodiments, the healable thermoplastic resin contains about 15 mol% to about 40 mol% of disulfide units.
  • the healable thermoplastic resin contains about 15 mol% to about 25 mol% of disulfide units. In still other embodiments, the healable thermoplastic resin contains about 20 mol% to about 30 mol% of disulfide units. In further embodiments, the healable thermoplastic resin contains about 5 mol% to about 10 mol% of disulfide units.
  • the disulfide units may be present within the thermoplastic resin polymer chain, i.e., co-monomer / repeat unit, on one or both ends of the thermoplastic polymer chain, i.e., end-caps, or may bridge two or more thermoplastic polymer chain, i.e. , cross-linkers.
  • the disulfide units comprise disulfide co-monomer fragments.
  • the disulfide units comprise disulfide fragments of the following structures:
  • the disulfide units comprise disulfide end caps.
  • the disulfide unit comprises a disulfide cross-linker. In some embodiments, the disulfide unit contains at least 3 hydroxy moieties. In further embodiments, the disulfide unit is the following:
  • the disulfide units may be any disulfide linkage which undergoes metathesis with another disulfide linkage.
  • the disulfide unit comprises aromatic or aliphatic disulfide units.
  • aromatic refers to a chemical group which contains localized sigma bonds and delocalized pi bonds.
  • the aromatic disulfide unit is a cyclic, aromatic group.
  • the aromatic disulfide unit is an optionally substituted phenyl disulfide.
  • aliphatic refers to a chemical group which contains localized sigma bonds.
  • the aliphatic disulfide unit is an acyclic or cyclic disulfide. In other embodiments, the aliphatic disulfide unit is an optionally substituted alkyl or cycloalkyl disulfide.
  • the thermoplastic resin described herein may be a homopolymer, i.e. , contains the same monomer repeating unit.
  • the monomer repeating unit contains a disulfide bond, i.e., is a disulfide unit as defined above.
  • the monomer may be selected by those skilled in the art.
  • the monomer utilized to form the homopolymer is:
  • the homopolymer is a polyphenylene oxide, polyphenylene sulfide, polystyrene, or polyacrylate comprising disulfide units.
  • the homopolymer has the following structures, wherein a is about 3 to about 500, b is about 3 to about 500, c is about 3 to about 500, and d is about 3 to about 500.
  • a is about 30 to about 300, b is about 30 to about 300, c is about 30 to about 300, and d is about 30 to about 300.
  • the thermoplastic resin also may be a copolymer, i.e., contains two monomer repeating units, terpolymer, i.e., contains three monomer repeating units, or tetrapolymer, i.e., contains four monomer repeating units, or more.
  • One monomer repeating unit is a disulfide unit as described above and the other monomer repeating unit is a comonomer.
  • the comonomer may be selected by those skilled in the art depending on the thermoplastic properties desired in the healable thermoplastic resin.
  • the co-monomer although it may be selected by one skilled in the art, must be capable being co-polymerized with the disulfide unit, e.g., disulfide co-monomer, disulfide end-cap, disulfide crosslinking agent, or combination thereof.
  • the comonomer is an aliphatic diol such as adipic acid, ene,
  • the thermoplastic resin is a disulfide-containing polyetherimide, polyester, polyphenylene oxide, polyphenylene sulfide, polystyrene, acrylate, polyamide, polyacrylonitrile, polyetherketone, polyethersulfone, or polybenzimidazole.
  • the thermoplastic resin is a disulfide-containing polyetherimide.
  • the thermoplastic resins described herein lack low molecular-weight polyetherimides/polyamic acids as repairing materials.
  • the polyetherimides can include both homo- and copolyetherimides which contain a disulfide as a co-monomer, endcapper, or crosslinker.
  • the co-polyetherimides may contain about 1.0 mole % to about 50 mole % of disulfide units. In some embodiments, the co-polyetherimides contain about 2.5 mole % to about 25 mole % of disulfide units. In other embodiments, the polyetherimides contain about 1.0 mole % to about 25 mole % of disulfide end cappers. In further embodiments, the polyetherimides contain about 1 mole % to about 10 mole % of disulfide endcappers.
  • the polyetherimide compositions may comprise repeating units derived in part from one or more aromatic dihydroxy monomers.
  • aromatic dihydroxy monomers suitable for use in the polyetherimides of the invention include phenolic monomers. These phenolic monomers can comprise dihydric phenols (also known as bisphenols), mono phenols, or a combination thereof.
  • Phenolic monomers may include, without limitation, resorcinol, hydroquinone, methyl hydroquinone, t-butyl hydroquinone, di-t- butyl hydroquinones (DTBHQ), biphenols, tetramethyl bisphenol-A, spiro biindane bisphenols (SBIBP), bis- (hydroxy aryl)-N-aryl isoindolinones, or any combination thereof.
  • the polyetherimides are of formula (A) and contain "a" number of disulfide units.
  • the disulfide units may be bound to V or R, provided that the binding of which is chemically stable.
  • a is more than 1, for example 10 to 1,000 or more, or more specifically 10 to 500.
  • V is a tetravalent linker containing an ether.
  • linkers include but are not limited to: (a) C 5-5 o substituted or unsubstituted, saturated, unsaturated or aromatic monocyclic and polycyclic groups, optionally substituted with ether, aryl sulfone, or a combination of ether and aryl sulfone; or (b) Ci -30 substituted or unsubstituted, linear or branched, saturated or unsaturated alkyl and optionally substituted with ether or a combination of ether and aryl sulfone; or combinations thereof.
  • Suitable additional substitutions include, but are not limited to, ethers, amides, esters, and combinations thereof.
  • R is a substituted or unsubstituted divalent group such as an aromatic C 6-2 o hydrocarbon or halogenated derivative thereof, C 2- 2o straight or branched chain alkyl, C 3-2 o cycloalkyl, or divalent groups of
  • Q is a divalent group such as O, S, C(O), S0 2 , SO, C y H 2y (y is 1 to 5), or halogenated derivatives thereof, including perfluoroalkylene.
  • W is a divalent group such as O, S0 2 , or -0-Z-O- wherein the divalent bonds of O or -O-Z- O- are in the 3,3'-, 3,4'-, 4,3'-, or the 4,4'-positions, and wherein Z includes the divalent group of formulae
  • Q is a divalent group such as 0, S, C(O), S0 2 , SO, C y H 2y (y is 1 to 5), or halogenated derivatives thereof, including perfluoroalkylene.
  • the polyetherimide comprises more than 1, specifically 10 to 1,000, or more rmula (E):
  • T is O or -0-Z-O- wherein the divalent bonds are in the 3,3'-, 3,4'-, 4,3'-, or the 4,4- positions;
  • Z is of formula (C); and
  • R is of formula (B).
  • the polyetherimide comprises structural units of formula (E) wherein each R is independently p-phenylene or m-phenylene or a mixture comprising at least one of the foregoing; and T is -
  • the polyetherimides can have an M w of about 5,000 to about 100,000 g/mol as measured by gel permeation chromatography (GPC). In some embodiments, M w is about 10,000 to about 80,000.
  • the polyetherimide comprises bis(4-hydroxyphenyl)disulfide and 5,5'-
  • the polyetherimide has the following structure: wherein, x is about 70 to about 99 and y is about 1 to about 30.
  • the polyetherimides can be synthesized by any conventionally known process for the manufacture of a polyetherimide.
  • the polyetherimides can be prepared by a conventional displacement polymerization reaction whereby a halo or nitro substituted bisphthalamide, such as a bis 4-chloro phthalimide, bis 4-fluoro phthalimide or bis 4-nitro phthalimide is reacted with a dianion salt of a disclosed aromatic dihydroxy compound under conditions effective to result in the desired
  • phase transfer catalyst such as a terra butyl ammonium chloride, tetra phenyl phosphonium bromide, hexa ethyl guanidinium chloride or other conventionally known phase transfer catalysts.
  • polyetherimde polymerization may be conducted in an aprotic polar solvent.
  • the resulting resin can also be end capped to control molecular weight.
  • Exemplary and non-limiting endcapping agents that can be used include mono chloro phthalimides or
  • the polyetherimides can be prepared by various methods, including, but not limited to, the reaction
  • Bis-phthalimides (H) can be formed, for example, by the condensation of the corresponding anhydride of formula (K):
  • X is a N0 2 or halogen, with H 2 N-R-NH 2 (L), wherein R is as described above.
  • the amino compound is a fatty acid amine.
  • the amine compound includes ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine,
  • nonamethylenediamine decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3- methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5- methylnonam ethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2,2-dimethylpropylenediamine, N-methyl-bis(3-aminopropyl) amine, 3 -methoxyhexam ethylenediamine, 1,2- bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1 ,4-cyclohexanediamine, bis-(4-aminocyclohexyl) methane, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene,
  • xylylenediamine p-xylylenediamine, 2-methyl-4,6-diethyl- 1,3 -phenylene-diamine, 5-methyl-4,6-diethyl-l,3- phenylene-diamine, benzidine, 3, 3 '-dimethylbenzidine, 3, 3 '-dimethoxybenzidine, 1,5-diaminonaphthalene, bis(4-aminophenyl) methane, bis(2-chloro-4-amino-3,5-diethylphenyl) methane, bis(4-aminophenyl) propane, 2,4-bis(b-amino-t-butyl) toluene, bis(p-b-amino-t-butylphenyl)ether, bis(p-b-methyl-o-aminophenyl) benzene, bis(p-b-methyl-o-aminopentyl) benzene, l,3-d
  • the polyetherimides can be synthesized by the reaction of the bis(phthalimide) (H) with an alkali metal salt of a dihydroxy substituted aromatic hydrocarbon such as HO-V-OH wherein V is described above, in the presence or absence of phase transfer catalyst.
  • a dihydroxy substituted aromatic hydrocarbon such as HO-V-OH wherein V is described above
  • phase transfer catalysts are disclosed in U.S. Pat. No. 5,229,482.
  • the dihydroxy substituted aromatic hydrocarbon a bisphenol such as bisphenol A, or a combination of an alkali metal salt of a bisphenol and an alkali metal salt of another dihydroxy substituted aromatic hydrocarbon can be used.
  • the polyetherimides may also contain "aliphatic blocks".
  • aliphatic block refers to an additional unit of the polymer which enhances the healing and improves mobility of the polyetherimide molecules at lower temperatures, thereby promoting disulfide metathesis, or combinations thereof. These blocks may be incorporated into the thermoplastic resin as co- monomers, end cappers, pendant groups, crosslinkers or combinations thereof.
  • the block is a diamine.
  • the block is an aliphatic diamine.
  • the block is an aliphatic diamine block such as a long carbon chain aliphatic diamine block.
  • the aliphatic diamine block is a fatty acid amine. In yet further embodiments, the aliphatic diamine block is a C 5 to C 40 aliphatic block. In still other embodiments, the aliphatic diamine block is prepared from dianhydride monomers and (i) aliphatic fatty diamines such as (Z)-8-nonylidene-9- octylheptadecane-l, 17-diamine or (ii) aliphatic fatty monoamines such as (Z)-9,10-dioctylnonadec-10-en-l- amine, both having the following structures.
  • the polyetherimides contain about 1.0 mole % to about 25 mole % of the fatty acid amine. In other embodiments, the fatty acid amine end
  • the polyetherimides may alternatively, or in addition, contain an aromatic diamine as a block.
  • the aromatic diamine block is 1,3-diaminobenzene.
  • the polyetherimides may be a ter-polyetherimide.
  • the polyetherimide is a ter-polyetherimide of an aromatic diamine and long carbon chain fatty diamines.
  • the ter-polymer contains about 1.0 mole % to about 25 mole % of the disulfide units and long carbon chain fatty diamine unit. In some embodiments, the ter-polymer contains about 2.5 mole % to about 20 mole % units.
  • the polyetherimides may also contain a siloxane moiety. It is hypothesized that the presence of siloxane moiety will decrease glass transition temperature and hence will improve the mobility of the of polyetherimide chains. In doing so, the sulfur metathesis reaction occurs among the disulfide contacting polysiloxane/polyetherimide copolymer chains at relatively lower temperature than polyetherimide molecules lacking these moieties.
  • the siloxane moiety is a siloxane diamine. In other embodiments, the siloxane diamine has the following structure:
  • R 1 to R 6 are, independently, optionally substituted aromatic C 5-3 o monocyclic group, optionally substituted aromatic C 5-3 o polycyclic group, optionally substituted Ci -30 alkyl, or optionally substituted C 2- 3o alkenyl.
  • the polyetherimide is a siloxane containing ter-polyetherimide.
  • the polyetherimide is a ter-polyetherimide of an aromatic diamine, siloxane diamine and disulfide aromatic diamine.
  • the ter-polymer contains about 1.0 mole % to about 25 mole % of the aromatic disulfide unit and siloxane diamines unit.
  • the polyetherimide contains contain about 2.5 mole % to about 20 mole % of the aromatic disulfide unit and siloxane diamines unit.
  • the polyetherimides of the present invention can be siloxane containing tetra-polyetherimides.
  • the polyetherimide is a tetra-polyetherimide of an aromatic diamine, siloxane diamine, disulfide aromatic diamine and long carbon chain fatty diamines.
  • the tetra-polymer contains about 1.0 mole % to about 25 mole % of each of the aromatic disulfide unit, siloxane diamine, and long carbon chain fatty diamine.
  • the tetra-polymer contains about 2.5 mole % to about 20 mole % units each of the aromatic disulfide unit, siloxane diamine, and long carbon chain fatty diamine.
  • the healing polyetherimide thermoplastic resins may be synthesized by a variety of routes.
  • polyetherimides are prepared by reacting one or more dianhydride with one or more diamine.
  • the healable thermoplastic resin may also be a polyester or blends thereof.
  • the polyester is discussed in US Pat. No. 4346195, which is incorporated herein by reference.
  • the polyester is a polyalkylene terephthalate.
  • the polyester is a polybutylene terephthalate or polyethylene terephthalate.
  • the polyester is a polybutylene terephthalate / polycarbonate copolymer, polybutyleneterephthalate / polyethylene terephthalate copolymer, polycarbonate / polyethylene terephthalate copolymer, or combinations thereof.
  • the polyester contains 1,4-dihydroxybutylene monomers or 1,2-dihydroxy ethylene monomers.
  • the thermoplastic resin is a disulfide-containing polybutyleneterephthalate and comprises 4,4'-dithiobis-benzoic acid and 1,4-dihydroxybutylene co-monomers.
  • the thermoplastic resin is a polyethyleneterephthalate and comprises 4,4'-dithiobis-benzoic acid and 1,2- dihydroxyethylene co-monomers.
  • the polyester is LNPTM FARADEX compound, LNPTM LUBRICOMP compound, LNPTM STAT-KON compound, LNPTM STAT-LOY compound, LNPTM THERMOCOMP compound, LNPTM THERMOTUF compound, or XENOYTM resin available from SABIC Innovative Plastics.
  • the healable thermoplastic resin may further be a polyphenylene oxide or blends thereof.
  • the polyphenylene oxide is set forth in US Pat. No. 8309655 and International Pat. Publication No. WO-2001/040353, which are incorporated herein by reference.
  • the polyphenylene oxide is set forth in US Pat. No. 8309655 and International Pat. Publication No. WO-2001/040353, which are incorporated herein by reference.
  • the healable thermoplastic resin may further be a polyphenylene oxide or blends thereof.
  • the polyphenylene oxide is set forth in US Pat. No. 8309655 and International Pat. Publication No. WO-2001/040353, which are incorporated herein by reference.
  • the healable thermoplastic resin may further be a polyphenylene oxide or blends thereof.
  • the polyphenylene oxide is set forth in US Pat. No. 8309655 and International Pat. Publication No. WO-2001/040353, which are incorporated herein by reference.
  • polyphenylene oxide comprises 4,4'-dithiobis[2,6-dimethyl-phenol] monomers.
  • the polyphenylene oxide is the LNPTM LUBRICOMP compound, LNPTM LUBRILOY compound, LNPTM STAT- KON compound, LNPTM THERMOCOMP compound, PPOTM resin, LNPTM LUBRICOMP compound, or combinations thereof, available from SABIC Innovative Plastics.
  • the healable thermoplastic resin may be a polyphenylene sulfide or blends thereof.
  • the polyphenylene oxide is discussed in US Pat. No. 4769424, which is incorporated herein by reference.
  • the polyphenylene oxide comprises 4,4'-dithiobis-benzenethiol monomers.
  • the polyphenylene oxide is the LNPTM KONDUIT compound, LNPTM LUBRICOMP compound, LNPTM THERMOCOMP compound, or combinations thereof, available from SABIC Innovative Plastics.
  • the healable thermoplastic resin may also be a polyamide or blends thereof.
  • the polyamide is discussed in US Pat. No. 2130523, which is incorporated herein by reference.
  • the polyamide comprises adipic acid and hexamethylene diamine monomers.
  • the polyamide comprises 4,4'-dithiobis-benzoic acid, adipic acid, and hexamethylene diamine monomers.
  • the polyamide is a polyphenylene ether / polyamide blend.
  • the polyamide is the LNPTM COLORCOMP compound, LNPTM KONDUIT compound, LNPTM LUBRICOMP compound, LNPTM STAT-KON compound, LNPTM STAT-LOY compound, LNPTM
  • THERMOCOMP compound LNPTM THERMOTUF compound, LNPTM VERTON compound, LNPTM LUBRILOY compound, NORYL GTXTM resin, or combinations thereof, available from SABIC Innovative Plastics.
  • the healable thermoplastic resin may further be a polyetherketone or blends thereof.
  • the polyetherketone is discussed in US Pat. No. 8575298, which is incorporated herein by reference.
  • the polyetherketone comprises bis(4-fluorophenyl)methanone monomers.
  • the polyetherketone comprises 4,4'-dithiobis-phenol and bis(4- fluorophenyl)methanone co-monomers.
  • the polyetherketone is the LNPTM
  • LUBRICOMP compound LNPTM STAT-KON compound, LNPTM THERMOCOMP compound, or combinations thereof, available from SABIC Innovative Plastics.
  • the healable thermoplastic resin may further be a polyethersulfone or blends thereof.
  • the polyethersulfone is discussed in International Pat. Publication No. WO-2006/012453, which is incorporated herein by reference.
  • the polyethersulfone comprises 4,4'- sulfonylbis(chlorobenzene) monomers.
  • the polyethersulfone comprises 4,4'- dithiobis-phenol and 4,4'-sulfonylbis(chlorobenzene) co-monomers.
  • the polyethersulfone comprises 4,4'- dithiobis-phenol and 4,4'-sulfonylbis(chlorobenzene) co-monomers.
  • polyetherketone is the LNPTM LUBRICOMP compound, LNPTM STAT-KON compound, LNPTM
  • THERMOCOMP compound LNPTM LUBROCOMP compound, or combinations thereof, available from SABIC Innovative Plastics.
  • the healable thermoplastic resin may also be a polystyrene or blends thereof. In some
  • the polystyrene contains bis(4-ethenylphenyl)disulfide monomers.
  • the healable thermoplastic may further be an acrylate.
  • the acrylate comprises 2-propenoic acid, 2-methyl-, dithiodi-4,l-phenylene ester monomers.
  • the healable thermoplastic may also be a polyacrylonitrile.
  • the healable thermoplastic may also be a polyacrylonitrile.
  • polyacrylonitrile is an acrylonitrile butadiene styrene polymer. In other embodiments, the polyacrylonitrile is an acrylonitrile styrene acrylate / polycarbonate blend. In further embodiments, the polyacrylonitriles is an acrylonitrile-EPDM-styrene, polycarbonate, and styrene acrylonitrile blend. In yet other embodiments, the polyacrylonitrile is a polycarbonate + acrylonitrile butadiene styrene blend. In still further embodiments, the acrylonitrile is a styrene acrylonitrile.
  • the acrylonitrile comprises bis(4- ethenylphenyl)disulfide, styrene, acrylonitrile and polybutadiene monomers.
  • the acrylonitrile is the CYCOLACTM resin, LNPTM COLORCOMP compound, LNPTM FARADEX compound, LNPTM LUBRICOMP compound, LNPTM STAT-KON compound, LNPTM STAT-LOY compound, LNPTM THERMOCOMP compound, LNPTM LUBRILOY compound, GELOYTM resin, CYCOLOYTM resin, LNPTM VERTON compound or combinations thereof, available from SABIC Innovative Plastics.
  • the thermoplastic resin may also be a polybenzimidazole or blends thereof.
  • the polybenzimidazole contains diphenyl isophthalate co-monomers.
  • the polybenzimidazole contains 4,4'-dithiobis-(l,2-benzenediamine) and diphenyl isophthalate co-monomers.
  • thermoplastic resins described herein may be prepared using techniques known to those skilled in the art such as melt or interfacial polymerization.
  • the thermoplastic resins are prepared using melt polymerization.
  • the disulfide reagent can be utilized in, without limitation, four approaches (a) monomer, (b) co-monomer (c) end capper, (d) cross-linker, or combinations thereof.
  • the reaction can occur in one or more reactors using varying temperatures, pressures, catalysts, agitation rates, vessels, among others, all of which may be dependent on the particular disulfide and monomer(s) selected.
  • catalysts when used in reference to the preparation of the thermoplastic resin, differs from the catalysts which are used in the art to effect healing of a thermoplastic resin. Accordingly, catalysts may be used during the reactions for preparing the thermoplastic resin and include, for example, tetra methyl ammonium hydroxide (TMA), tetrabutyl phosphonium acetate, or sodium hydroxide (NaOH), among others.
  • TMA tetra methyl ammonium hydroxide
  • NaOH sodium hydroxide
  • the disulfide reagent may be utilized as a (a) co-monomer, (b) end capper, (c) cross-linker, and/or (d) pendant group.
  • the disulfide reagent contains a disulfide unit as described above.
  • the disulfide reagent contains one, two, or more hydroxy groups.
  • the disulfide reagent is an optionally substituted bis phenol.
  • the disulfide reagent is bis(4-hydroxyphenyl)disulfide of the following structure:
  • the disulfide reagent also may be an endcapper.
  • the disulfide reagent contains one hydroxy group.
  • the disulfide reagent is an optionally substituted phenol.
  • the disulfide reagent is 4-(phenyldisulfanyl)phenol disulfide of the following structure:
  • the disulfide reagent may also be a crosslinker.
  • the disulfide reagent comprises at least 3 hydroxy groups.
  • the disulfide reagent is 4,4',4"-((ethane-l,l,l- triyl-tris(benzene-4,l-diyl))tris(disulfanediyl))triphenol] of the following structure:
  • thermoplastic resins described herein are prepared by polymerizing a disulfide reagent such as those described above.
  • the disulfide reagent is the bulk of the thermoplastic resin and produces a thermoplastic resin containing disulfide units throughout the polymer.
  • thermoplastic resins are prepared in a suitable solvent, which may be selected by one skilled in the art.
  • solvent can refer to a single solvent or a mixture of solvents.
  • the solvent is aqueous (i.e., contains water) or organic. The solvent does not react with or degrade any of the reactants.
  • the solvent comprises a halogenated aliphatic solvent, a halogenated aromatic solvent, a non-halogenated aromatic solvent, a non-halogenated aliphatic solvent, or a mixture thereof.
  • Halogenated aromatic solvents include, without limitation, ortho-dichlorobenzene, chlorobenzene and the like.
  • Non-halogenated aromatic solvents comprise, without limitation, toluene, xylene, anisole, phenol, 2,6-dimethylphenol, and the like.
  • Halogenated aliphatic solvents include, without limitation, methylene chloride, chloroform, 1 ,2-dichloroethane, and the like.
  • Non-halogenated aliphatic solvents include, without limitation, ethanol, acetone, ethyl acetate, cyclohexanone, and the like.
  • thermoplastic resins can be manipulated by controlling, among other factors, the type of vessel or extruder, the extruder screw design and configuration, the residence time in the vessel or extruder, the feed rate of the reactants, the reaction temperature, and the pressure in the vessel/reactor or on the extruder.
  • the molecular weight of the thermoplastic resin can also depend on the purity and chemical structures of employed reactants.
  • the reactants for the polymerization are added to a reactor or vessel.
  • the reactor may be equipped with one or more heating mantles for heating the reactants and/or pressure reducing devices (e.g., vents) for removing byproducts.
  • the reactor may be purged with an inert gas such as nitrogen or helium. Purging may be performed prior to or concurrently with the reaction.
  • the reactor may also be treated using techniques known in the art to remove contaminants which may affect formation of the thermoplastic resin.
  • the method may be performed at a temperature of between about 100°C and about 340°C. In some embodiments, the temperature is between about 100°C and about 280°C. In other embodiments, the temperature is between about 140°C and about 240°C.
  • the pressure over the reaction mixture may be reduced from ambient pressure to a final pressure in a range between about 0.001 mmHg and about 400 mmHg. In some embodiments, the pressure is about 0.01 mmHg to about 100 mmHg. In other embodiments, the pressure is about 0.1 mmHg t about 10 mmHg. Control of the pressure over the reaction mixture allows the orderly removal of any by-products. In some embodiments, the reaction may be conducted at sub-ambient pressure. In an alternate embodiment, the reaction may be conducted at slightly elevated pressure, for example a pressure in a range between about 1 and about 2 atmospheres.
  • thermoplastic resin has less than about 1000 parts per million (ppm) of by-product. In other embodiments, the thermoplastic resin has less than about 500 ppm of by-products. In further embodiments, the thermoplastic resin has less than about 100 ppm by-product.
  • the methods described herein can be conducted as a batch or a continuous process. Any desired apparatus can be used for the reaction.
  • the material and the structure of the reactor used herein is not particularly limited as long as the reactor has an ordinary capability of stirring and the presence of catalyst can be controlled.
  • the reactor may be capable of stirring in high viscosity conditions as the viscosity of the reaction system is increased in later stages of the reaction.
  • the reaction mixture may optionally be blended with any conventional additives used in thermoplastics applications, such as preparing molded articles.
  • additives include, without limitation, UV stabilizers, antioxidants, heat stabilizers, mold release agents, coloring agents, antistatic agents, slip agents, antiblocking agents, lubricants, anticlouding agents, coloring agents, natural oils, synthetic oils, waxes, organic fillers, inorganic fillers, branching agents and mixtures thereof.
  • thermoplastic resin may be any thickness and will depend on the particular substrate and industry, among others.
  • thermoplastic resins described herein include, without limitation, lithium ion batteries, pipes for water, oil and gas, fire resistance, anti-fouling, outdoor applications such consumer electronics, electrical and lighting (wire insulator, cable jacket), automotive (including automotive interiors and exteriors), aircraft industries (including spacecrafts), energy storage, medical, inflatable structures, flexible conduits, flexible overmolds, among others.
  • the articles include, without limitation, polymers such as a plastic, glass, or metal which are optionally molded.
  • the healable thermoplastic resin may also be applied as an adhesive.
  • molded articles comprising the thermoplastic resins as described herein may be obtained by conventional molding techniques.
  • the molding techniques may include, without limitation, injection molding, blow molding, and compression molding. Molded articles may also be prepared from a blend of the thermoplastic resin with one or more additional polymers. Such blends may be prepared using extrusion methods may be molded using conventional techniques.
  • the molded article is prepared using injection molding.
  • the inventive compositions can be used for additive manufacturing (e.g., 3D printing, fused deposition molding (FDM), selective additive manufacturing (SLS), big area additive manufacturing (BAAM), LFAM,) composites, films, sheets, lenses, bezels, and the like.
  • additive manufacturing e.g., 3D printing, fused deposition molding (FDM), selective additive manufacturing (SLS), big area additive manufacturing (BAAM), LFAM, composites, films, sheets, lenses, bezels, and the like.
  • the present disclosure comprises at least the following aspects.
  • a healing thermoplastic resin comprising at least about 1 mol% of disulfide units.
  • thermoplastic resin of aspect 2 wherein said thermoplastic resin is a polyetherimide, polyester such as a polybutyleneterephthalate or polyethyleneterephthalate, polyphenylene oxide, polyphenylene sulfide, polystyrene, acrylate, polyamide, polyacrylonitrile such as acrylonitrile butadiene styrene, polyetherketone, polyether sulfone, or polybenzimidazole.
  • Aspect 3 The healing thermoplastic resin of aspect 2, which is:
  • said polyetherimide and comprises bis(4-hydroxyphenyl)disulfide and 5,5'-((propane-2,2- diylbis(4,l-phenylene))bis(oxy))bis(isobenzofuran-l,3-dione)co-monomers;
  • said polybutyleneterephthalate and comprises 4,4'-dithiobis-benzoic acid and 1,4- dihydroxybutylene co-monomers;
  • said polyethyleneterephthalate and comprises 4,4'-dithiobis-benzoic acid and 1,2- dihydroxy ethylene co-monomers;
  • said polyphenylene oxide and comprises 4,4'-dithiobis[2,6-dimethyl-phenol] monomers
  • said polyphenylene sulfide and comprises 4,4'-dithiobis-benzenethiol monomers
  • said polystyrene and comprises bis(4-ethenylphenyl)disulfide monomers
  • said acrylate comprises 2-Propenoic acid, 2-methyl-, dithiodi-4, 1 -phenylene ester monomers
  • said polyamide comprises 4,4'-dithiobis-benzoic acid, adipic acid, and hexamethylene diamine monomers;
  • said acrylonitrile butadiene styrene and comprises bis(4-ethenylphenyl)disulfide, styrene, acrylonitrile and polybutadiene monomers;
  • said polyetherketone comprises 4,4'-dithiobis-phenol and bis(4-fluorophenyl)methanone co-monomers;
  • said polyethersulfone comprises 4,4'-dithiobis-phenol and 4,4'- sulfonylbis(chlorobenzene) co-monomers; or
  • Aspect 4 The healing thermoplastic resin of aspect 2, which wherein said polyetherimide comprises siloxane diamines such a siloxane diamine of the following structure:
  • R 1 to R 6 are, independently, optionally substituted aromatic C5-30 monocyclic group, optionally substituted aromatic C5-30 polycyclic group, optionally substituted Ci-30 alkyl, or optionally substituted C2-30 alkenyl.
  • Aspect 5 The healing thermoplastic resin of aspect 2, wherein said polyetherimide comprises long carbon chain aliphatic monomers or endcappers.
  • Aspect 6 The healing thermoplastic resin of aspect 5, wherein said long carbon chain aliphatic monomers or endcappers are prepared from dianhydride monomers and (i) aliphatic fatty diamines such as (Z)-8-nonylidene-9-octylheptadecane-l,17-diamine or (ii) aliphatic fatty monoamines such as (Z)-9,10- dioctylnonadec- 10-en- 1 -amine.
  • Aspect 7 The healing thermoplastic resin of aspect 2, which is a polyetherimide of the following structure: wherein, x is about 70 to about 99 and y is about 1 to about 30.
  • Aspect 8 The healing thermoplastic resin of aspect 1, which is a homo-polymer, co-polymer, ter- polymer, or tetra-polymer.
  • Aspect 9 The healing thermoplastic resin of aspect 1, wherein said disulfide units are present in said resin as monomers, end-cappers, crosslinkers, or pendant groups.
  • Aspect 10 The healing thermoplastic resin of aspect 8 or 9, comprising about 5 mol% to about 50 mol% such as about 5 mol% to about 25 mol% of said disulfide units.
  • Aspect 11 The healing thermoplastic resin of aspect 8 or 9, wherein said thermoplastic resin comprises disulfide end caps such as 4-(phenyldisulfanyl)phenol.
  • Aspect 12 The healing thermoplastic resin of aspect 8, 9, or 11, comprising about 5 mol% to about 25 mol% such as 5 mol% to about 10 mol% of disulfide end-caps or pendant groups.
  • Aspect 13 The healing thermoplastic resin of any of the preceding aspects, which heals in the absence of pressure, electricity, healing agent, catalyst, or combination thereof.
  • Aspect 14 The healing thermoplastic resin of any of the preceding aspects, which heals in the presence of heat or radiation.
  • Aspect 15 The healing thermoplastic resin of any of the preceding aspects, which performs multiple healings over time.
  • Aspect 16 The healing thermoplastic resin of any of the preceding aspects which lacks microcapsules, carbon nanotubes, self-healing layers, repairing materials such as low molecular weight polyetherimide/polyamic acid repairing materials, or a combination thereof.
  • Aspect 18 An article comprising the healing thermoplastic resin of any one of aspects 1 to 16.
  • Aspect 19 The article of aspect 18, wherein the article is an electronic component, lighting component, medical device component, electrical component, telecom component, automobile part, aviation part, biomedical device, energy storage device, spacecraft part, or fluid handling device.
  • Aspect 20 The article of aspect 18, wherein the article is a wire insulator, cable jacket, flexible conduit, or flexible overmold.
  • Aspect 21 The article of aspect 18, wherein the article is formed using additive manufacturing. VI. Examples
  • the invention is illustrated by the following non-limiting examples.
  • the reactants for the polymerization reaction were fed to the reactor in solid (e.g. powder) form.
  • the reactor was equipped with heating mantles and pressure reducing devices (e.g., vents) that served to heat the reactants and remove the activated phenol byproduct, respectively, and thus drive the polymerization reaction toward completion.
  • Healable polyetherimides can be synthesized by step growth polymerization methods known in the art.
  • a glass tube is charged with 4,4-disulfanediyldibenzoic acid, 1 ,4-dibutanol along with a catalyst.
  • the reactants are heated in a melt reactor at increasing temperatures and decreasing pressures for a given time period in inert media.
  • the healable polybutyleneterephthalate is removed.
  • a glass tube is charged with 4,4-disulfanediyldibenzoic acid, 1 ,4-diethanol, and along with a catalyst.
  • the reactants are heated in a melt reactor at increasing temperatures and decreasing pressures for a given time period in inert media.
  • the healable polyethyleneterephthalate is removed.
  • Healable polyphenylene sulfides are synthesized by reacting l,2-bis(4-chlorophenyl)disulfane with sodium sulfide, using procedures reported in the art.
  • Healable polystyrenes are prepared by incorporating disulfide moieties into polystyrene by means of free radical polymerization, such as free radical polymerizations described in the art.
  • Healable polymethylmethacrylates are prepared by incorporating disulfide moieties into polymethtymethacrylates by means of free radical polymerization, such as free radical polymerizations described in the art.
  • Healable polyamides are synthesized by step growth polymerization methods known in the art.
  • Healable ABS is synthesized by incorporating disulfide moieties into the polymer backbone through free radical polymerization, such as free radical polymerizations described in the art.
  • Healable polyetherketones are prepared by step growth polymerization methods known in the art.
  • Healable polyethersulfones are prepared by step growth polymerization methods known in the art.
  • Healable polybenzimidazoles are prepared by step growth polymerization methods known in the art.
  • thermoplastic resins are analyzed by gel permeation chromatography (GPC) and results.
  • GPC analysis is carried out on Shimadzu VP instrument, equipped with a cross-linked styrene-divinyl-benzene column and UV-detector. Molecular weight is determined using polystyrene as a standard. Samples are dissolved in a solvent and filtered through 0.4 micron PTFE filters before injecting into the column.
  • thermoplastic resins of Examples 1-12 are exposed to UV radiation in a UV flood curing system with power (120 milliwatt/cm 2 ).
  • thermoplastic resins of Examples 1-12 It is expected that scratches on the thermoplastic resins of Examples 1-12 will heal after UV exposure.

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Abstract

L'invention concerne des résines thermoplastiques auto-réparantes qui comprennent au moins environ 1 % en moles d'unités disulfure, des articles comprenant ladite résine thermoplastique auto-réparante, et des procédés d'activation de la résine thermoplastique auto-réparante par exposition de celle-ci à de chaleur ou à un rayonnement.
PCT/IB2017/050760 2016-04-29 2017-02-10 Résines thermoplastiques auto-réparantes WO2017187279A1 (fr)

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CN108586299A (zh) * 2018-06-06 2018-09-28 北京化工大学 一种可引发、聚合及降低体积收缩的芳香二硫化合物的制备方法及用途
CN110183657A (zh) * 2019-06-18 2019-08-30 京东方科技集团股份有限公司 一种含二硫键的聚酰亚胺的合成方法及oled显示装置
US20210102012A1 (en) * 2017-04-01 2021-04-08 Arizona Board Of Regents On Behalf Of The University Of Arizona Chalcogenide hybrid inorganic/organic polymers (chips) for infrared optical materials and devices

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