WO2023099178A1 - Oligomères aromatiques et polymères fabriqués à partir de ceux-ci - Google Patents

Oligomères aromatiques et polymères fabriqués à partir de ceux-ci Download PDF

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WO2023099178A1
WO2023099178A1 PCT/EP2022/081782 EP2022081782W WO2023099178A1 WO 2023099178 A1 WO2023099178 A1 WO 2023099178A1 EP 2022081782 W EP2022081782 W EP 2022081782W WO 2023099178 A1 WO2023099178 A1 WO 2023099178A1
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component
alkyl
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Ryan MONDSCHEIN
Joel POLLINO
Kermit S. Kwan
David KERCHER
Valeriy KAPELYUSHKO
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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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/061—Polyesters; Polycarbonates
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
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    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/185—Acids containing aromatic rings containing two or more aromatic rings
    • C08G63/187—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings
    • C08G63/189—Acids containing aromatic rings containing two or more aromatic rings containing condensed aromatic rings containing a naphthalene ring
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6856—Dicarboxylic acids and dihydroxy 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/914—Polymers modified by chemical after-treatment derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/916—Dicarboxylic acids and dihydroxy compounds

Definitions

  • the present disclosure relates to new aromatic oligomers suitable for use in the production of useful polymers.
  • Such oligomers comprise versatile functionality that enable the synthesis of useful polymers in various forms and by multiple processing techniques.
  • the reaction of these new molecules with various difunctional comonomers can produce thermoplastic-like linear or branched polymers while homopolymerization or polymerization with multifunctional comonomers can produced crosslinked thermoset structures.
  • thermoplastic and thermoset materials find applications in many industries, including the aviation, automotive, and marine industries. Such materials also find applications in the areas of health, medicine, and biotechnology, which is a rapidly developing domain based largely on known materials but moving to designed and engineered polymers, as well as information and communications, which is an emerging field for polymers significantly based on their electronic properties.
  • Articles and parts comprising polymeric materials are made by a variety of manufacturing processes, including, for example, extrusion, injection molding, thermoforming, liquid resin casting, additive manufacturing, such as 3D printing, and the like.
  • manufacturing processes including, for example, extrusion, injection molding, thermoforming, liquid resin casting, additive manufacturing, such as 3D printing, and the like.
  • challenges in the manufacturing of polymeric articles and parts For example, one such challenge is that the nature of the polymeric material and the process used to manufacture articles and parts from it must be considered, as heating causes expansion, and the following cooling process can cause shrinkage and warping. These phenomena can affect the strength and integrity of the final product.
  • Such features must also be balanced with the properties required for the product being made, such as mechanical and electrical properties, to name a few.
  • thermoplastics and thermosets are described.
  • processing methods such as, for example, extrusion, injection molding, thermoforming, liquid resin casting, additive manufacturing, such as 3D printing, etc.
  • new and inventive oligomers including the use of such oligomers in the production of useful polymers, are described.
  • the present disclosure relates to an oligomer represented by formula wherein
  • R7, Rs, and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation; and n is an integer from 1 to 30.
  • the present disclosure relates to a process for producing the oligomer described herein, the process comprising: a) reacting a compound represented by formula II: wherein
  • R a and Rb are each, independently H, alkyl, typically C1-C6 alkyl, more typically methyl, or M + , wherein M + is a monovalent cation; with a compound represented by formula III:
  • R7 is alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation;
  • Rs and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation.
  • the present disclosure relates to a polymer comprising a repeating unit derived from the oligomer described herein or derived from the oligomer produced by the process described herein.
  • the present disclosure relates to a process for producing a polymer described herein, the process comprising: reacting the oligomer described herein or the oligomer produced by the process described herein with a compound comprising one or more, typically two or more, thiol or amine groups, with a compound comprising one or more acrylate or methacrylate groups, with a compound comprising one or more vinyl ether groups, or with a compound comprising one or more maleimide groups.
  • the present disclosure relates to an article comprising the polymer described herein or polymer produced according to a process described herein.
  • the terms “a”, “an”, or “the” means “one or more” or “at least one” and may be used interchangeably, unless otherwise stated.
  • the term “and/or” used in a phrase in the form of “A and/or B” means A alone, B alone, or A and B together.
  • the term “comprises” includes “consists essentially of” and “consists of.”
  • the term “comprising” includes “consisting essentially of” and “consisting of.”
  • “Comprising”, which is synonymous with “including,” “containing,” or “characterized by,” is intended to be inclusive or open-ended and does not exclude additional, unrecited elements or steps.
  • the transitional phrase “consisting essentially of” is inclusive of the specified materials or steps and those that do not materially affect the basic characteristic or function of the composition, process, method, or article of manufacture described.
  • the transitional phrase “consisting of” excludes any element, step, or component not specified.
  • the term “about” or “approximately” means an acceptable error for a particular value as determined by one of ordinary skill in the art, which depends in part on how the value is measured or determined.
  • the term “about” or “approximately” means within 1 , 2, 3, or 4 standard deviations. In certain embodiments, the term “about” or “approximately” means within 50%, 20%, 15%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, 1 %, 0.5%, or 0.05% of a given value or range.
  • any numerical range recited herein is intended to include all sub-ranges subsumed therein.
  • a range of “1 to 10” is intended to include all sub-ranges between and including the recited minimum value of 1 and the recited maximum value of 10; that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.
  • the disclosed numerical ranges are continuous, they include every value between the minimum and maximum values.
  • the various numerical ranges specified in this application are approximations.
  • various publications may be incorporated by reference. Should the meaning of any language in such publications incorporated by reference conflict with the meaning of the language of the present disclosure, the meaning of the language of the present disclosure shall take precedence, unless otherwise indicated.
  • (Cx-Cy) or “Cx-Cy” in reference to an organic group, wherein x and y are each integers, means that the group may contain from x carbon atoms to y carbon atoms per group.
  • aryl refers to a 5- or 6-membered carbocyclic ring having a delocalized, conjugated IT system, with a number of IT electrons that is equal to 4n+2, where n is 0 or a positive integer, or an arrangement of 2 or more of such rings in which the rings are connected by bonds and/or share one or more sides, i.e. , are fused.
  • One or more of the ring members may be a heteroatom, typically selected from oxygen, nitrogen, and sulfur, and one or more of the ring members may possess non-hydrogen substituents, typically selected from alkyl, alkoxyl, hydroxyalkyl, cycloalkyl, alkoxyalkyl, haloalkyl, aryl, alkaryl, and aralkyl.
  • aryl groups include, but are not limited to, those derived from benzene, biphenyl, furan, pyridine, imidazole, thiophene, acridine, cinnoline, quinoline, phenazine, naphthalene, anthracene, phenanthrene, acenaphthylene, pyrene, perylene, and the like.
  • radicals described herein may be bivalent, i.e., two hydrogen atoms may be replaced by chemical bonds. Such groups are often modified by an “-ene” ending herein.
  • alkylene means an alkyl radical with an additional hydrogen replaced by a chemical bond.
  • arylene means an aryl radical with an additional hydrogen replaced by a chemical bond.
  • aromatic means that the organic compound comprises one or more aryl or arylene moieties as defined herein.
  • Any substituent or radical described herein may optionally be substituted at one or more carbon atoms with one or more, same or different, substituents described herein.
  • an aryl group may be further substituted with another aryl group or an alkyl group.
  • Any substituent or radical described herein may also optionally be substituted at one or more carbon atoms with one or more substituents selected from the group consisting of halogen, such as, for example, F, Cl, Br, and I; nitro (NO2), cyano (CN), and hydroxy (OH).
  • the present disclosure relates to an oligomer represented by formula I: wherein
  • A1, A2, and A3 are each, independently, -(CH2)m-, -(CH2CH2O) P CH2CH2-, or -
  • R1 and R2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20;
  • R4, Rs, and Re are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl;
  • R7, Rs, and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation; and n is an integer from 1 to 30, typically 2 to 15.
  • Suitable C6-C14 arylene groups include, but are not limited to, those derived from benzene, biphenyl, furan, pyridine, imidazole, thiophene, acridine, cinnoline, quinoline, phenazine, naphthalene, anthracene, phenanthrene, acenaphthylene, pyrene, perylene, and the like.
  • An and Ar2 are each, independently, a C6-C14 arylene group, typically selected from the group consisting of those derived from benzene, naphthalene, biphenyl, anthracene, and phenanthrene.
  • An and Ar2 are each, independently, selected from the group consisting of:
  • the two bonds connecting the carbonyl carbons to An and Ar2 are not limited and may be on the same ring or on different rings.
  • An and Ar2 are each, independently, selected from the group consisting of:
  • Suitable C6-C14 arylene groups are those described hereinabove.
  • Ar a and Arb are each, independently, selected from the group consisting of:
  • Ai, A2, and A3 provide functionalities that act as flexible spacers in polymers made from the oligomer of formula I.
  • A1 , A2, and A3 are each, independently, -(CH2)m-, - (CH2CH2O) P CH2CH2-, or -(SiRi R2O) q SiRiR2-, wherein R1 and R2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20.
  • A1 , A2, and A3 are each, independently, -(CH2)m-, wherein each occurrence of m is an integer from 5 to 20, typically 10 to 15.
  • A1 , A2, and A3 are each, independently, - (CH2CH2O) P CH2CH2-, wherein each occurrence of p is an integer from 2 to 10, typically 3 to 8.
  • A1 , A2, and A3 are each, independently, -(SiRi R2O) q SiRiR2-, wherein R1 and R2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, and each occurrence of q is an integer from 2 to 18.
  • A1 , A2, and A3 are unsubstituted.
  • R’ and R” provide the reactive functionality used for producing polymers from the oligomer of formula I.
  • R7, Rs, and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation.
  • R’ and R” are each, independently,
  • R4 is H or alkyl, typically Ci-Ce alkyl, more typically methyl.
  • R’ and R” are each , wherein R4 is H or alkyl, typically C1-C6 alkyl, more typically methyl.
  • the present disclosure relates to a process for producing the oligomer described herein, the process comprising: a) reacting a compound represented by formula II:
  • R a and Rb are each, independently H, alkyl, typically C1-C6 alkyl, more typically methyl, or M + , wherein M + is a monovalent cation; with a compound represented by formula III:
  • R7 is alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation;
  • Rs and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation.
  • Suitable C6-C14 arylene groups are those already described hereinabove.
  • Ar is a C6-C14 arylene group, typically selected from the group consisting of those derived from benzene, naphthalene, biphenyl, anthracene, and phenanthrene.
  • Ar is selected from the group consisting of:
  • the two bonds connecting the carbonyl carbons to Ar are not limited and may be on the same ring or on different rings.
  • Ar is selected from the group consisting of:
  • Suitable C6-C14 arylene groups are those described hereinabove.
  • Ar a and Arb are each, independently, selected from the group consisting of:
  • A is -(CH 2 )m- -(CH2CH 2 O) P CH2CH2- or -(SiRi R 2 O) q SiRi R 2 -, wherein Ri and R 2 are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl, each occurrence of m is an integer from 1 to 20, each occurrence of p is an integer from 1 to 10, and each occurrence of q is an integer from 1 to 20.
  • A is -(CH 2 )m-, wherein each occurrence of m is an integer from 5 to 20, typically 10 to 15.
  • the compounds of formula III are alkanediols. Suitable alkanediols include, but are not limited to, 1 ,2-ethanediol, 1 ,3- propanediol, 1 ,4-butanediol, 1 ,5-pentanediol, 1 ,6-hexanediol, 1 ,7-heptanediol, 1 ,8- octanediol, 1 ,9-nonanediol, 1 ,10-decanediol, 1 ,11 -undecanediol, 1 ,12-dodecanediol, and so on.
  • A is -(CH 2 CH2O)pCH 2 CH2-, wherein each occurrence of p is an integer from 2 to 10, typically 3 to 8.
  • the compounds of formula III are polyethylene glycols produced from the polymerization of ethylene oxide. Suitable polyethylene glycols include, but are not limited to, diethylene glycol, triethylene glycol, tetraethylene glycol, and so on.
  • A is -(SiRiR2O) q SiRiR2-, wherein Ri and R2 are each, independently, H or alkyl, typically C1-C6 alkyl, more typically methyl, and each occurrence of q is an integer from 2 to 18.
  • the compounds of formula III are polysiloxanes.
  • An exemplary polysiloxane is polydimethylsiloxane.
  • A1 , A2, and A3 are unsubstituted.
  • the compounds of formula II and III may be obtained from commercial sources or synthesized according to published methods.
  • the reaction between the compound of formula II with the compound of formula III is an apparent transesterification reaction in which ester linkages are formed between the compound of formula II and the compound of formula III.
  • esterification reaction between the compound of formula II and the compound of formula III is conducted in the presence of a titanium compound, typically a titanium(IV) compound, more typically a titanium(IV) alkoxide.
  • titanium tetraisopropoxide is used.
  • the reaction conditions are not particularly limited.
  • the reaction is conducted at a temperature in the range of 150 °C to 250 °C, typically 200 °C to 240 °C. In an embodiment, the reaction is conducted under inert atmosphere and/or vacuum.
  • R4, Rs, and Re are each, independently, H or alkyl, typically Ci-Ce alkyl, more typically methyl;
  • R7 is alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation;
  • Rs and R9 are each, independently, H, alkyl, typically Ci-Ce alkyl, more typically methyl, or M + , wherein M + is a monovalent cation.
  • the product from step a) of the process is reacted with one or more reagents to convert one or more pendent hydroxyl groups into a moiety selected from the group consisting of
  • R4 is H or alkyl, typically C1-C6 alkyl, more typically methyl.
  • the product from step a) of the process is reacted with one or more reagents to convert one or more pendent hydroxyl groups into
  • R4 is H or alkyl, typically C1-C6 alkyl, more typically methyl.
  • the present disclosure relates to a polymer comprising a repeating unit derived from the oligomer described herein or derived from the oligomer produced by the process described herein.
  • the polymer comprises 1 to 100 %, typically 20 to 95 %, more typically 50 to 90 %, still more typically 65 to 80 %, by weight of the repeating unit derived from the oligomer described herein or derived from the oligomer produced by the process described herein, relative to the weight of the polymer.
  • the polymer may be a thermoplastic or thermoplastic-like linear or branched polymer. In some cases, the polymer may be a thermoset or thermoset-like polymer, typically with crosslinked structure.
  • the polymer is a liquid crystalline polymer. As used herein, a liquid crystalline polymer, or “LCP”, refers to a type of thermoplastic polymer that exhibits properties between highly ordered solid crystalline materials and amorphous disordered liquids over a well-defined temperature range.
  • the present disclosure relates to a process for producing a polymer described herein, the process comprising: reacting the oligomer described herein or the oligomer produced by the process described herein with a compound comprising one or more, typically two or more, thiol or amine groups, with a compound comprising one or more acrylate or methacrylate groups, with a compound comprising one or more vinyl ether groups, or with a compound comprising one or more maleimide groups.
  • the polymerization reaction may be carried out according to methods known to those of ordinary skill in the art.
  • the present disclosure relates to an article comprising the polymer described hereinabove or polymer produced according to the process described hereinabove.
  • the article may be produced according to any method known to those of ordinary skill in the art, typically from the polymer or compositions comprising the polymer described herein.
  • Exemplary methods for manufacturing the article include, but are not limited, injection molding, extrusion, compression molding, thermoforming, such as sheet thermoforming, vacuum forming, pressure forming, trapped sheet forming, steam pressure forming; liquid resin casting, transfer molding, and additive manufacturing, such as 3D printing.
  • the polymer or compositions comprising the polymer used to produce the articles described herein may further comprise optional materials, such as fibers, fillers, colorants, additives, and the like, that impart beneficial properties to the final article.
  • Fibers may serve as reinforcing media and include, but are not limited to, carbon fiber, synthetic polymeric fibers, silicate fibers, such as aluminum silicate fibers, metal oxide fibers, such as alumina fibers, titania fibers, and magnesia fibers, wollastonite, rock wool fibers, silicon carbide fibers, etc.
  • Exemplary polymeric fibers include fibers formed from high temperature engineering polymers such as, for example, poly(benzothiazole), poly(benzimidazole), polyarylates, poly(benzoxazole), polyaryl ethers and the like, and may include mixtures comprising two or more such fibers.
  • high temperature engineering polymers such as, for example, poly(benzothiazole), poly(benzimidazole), polyarylates, poly(benzoxazole), polyaryl ethers and the like, and may include mixtures comprising two or more such fibers.
  • Other optional materials include glass, calcium silicate, silica, clays, such as kaolin, talc, chalk, mica, potassium titanate, and other mineral fillers; colorants, including pigments such as carbon black, titanium dioxide, zinc oxide, iron oxide, cadmium red, iron blue; and other additives such as alumina trihydrate, sodium aluminum carbonate, barium ferrite, etc.
  • the polymer or compositions comprising the polymer may further include additional additives commonly employed by those of ordinary skill in the art, such as thermal stabilizers, ultraviolet light stabilizers, oxidative stabilizers, plasticizers, lubricants, and mold release agents, such as polytetrafluoroethylene (PTFE) powder, and the like.
  • additional additives commonly employed by those of ordinary skill in the art, such as thermal stabilizers, ultraviolet light stabilizers, oxidative stabilizers, plasticizers, lubricants, and mold release agents, such as polytetrafluoroethylene (PTFE) powder, and the like.
  • PTFE polytetrafluoroethylene
  • the article is:
  • an extruded article such as a film, fiber, sheet stock, rod stock, tubing or profile ;
  • valve component or a related part thereof such as a seal ring ;
  • a friction and wear component such as a bushing, a bearing or a thrust washer
  • a glide ring a tappet, a gear, an electronically driven pad, a control valve, a pump component, a bushing or a check ball of a brake system ;
  • a pump component a gear, or a sensor of an emission system ;
  • an automotive chassis component or ⁇ a motor thrust washer or film for seat adjustment mechanisms.
  • the article is:
  • oligomers, polymers, methods and processes, and articles according to the present disclosure are further illustrated by the following non-limiting examples.
  • the reaction was performed in a dry two-neck 500-mL round-bottomed flask utilizing an overhead stirrer, nitrogen inlet, and distillation apparatus.
  • 2,6- naphthalenedimethyl ester 24.35 g, 0.099 mol equiv
  • tetraethylene glycol 21.95 g, 0.113 mol equiv
  • titanium tetraisopropoxide catalytic, 50 uL
  • the reaction progressed at 200 °C for 1 hour, 1 °C/min ramp from 200 °C to 225 °C, 225 °C for 1 hour, 1 °C/min ramp from 225 °C to 235 °C, 235 °C for 1 hour, and lastly 235 °C for 1 hour under a vacuum of 75-100 mmHg at a constant stirring rate of 75 rpm and N2 gas purge.
  • Methanol condensate was collected in a liquid nitrogen cooled round-bottomed flask. Once the oligomerization was completed, the reaction flask was cooled down to ambient temperature and a small aliqout was taken out for characterization, confirming the formation of the desired oligomer.
  • the desired oligomer was characterized by nuclear magnetic resonance (NMR) spectroscopy, gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and polarized optical microscopy (POM).
  • the resulting oligomer was then dissolved in 250 mL of dicholoroethane (15 wt%) and cooled down to 5 °C in an ice-water bath. Once the reaction flask was cooled, triethylamine (5.79 mL, 0.057 mol) was added and stirred for 1 hour. After an hour, acryloyl chloride (5.17 mL, 0.057 mol) was added dropwise over a period of 20 minutes and stirred for 24 hours. The cloudy solution was concentrated under reduced pressure to a solid. The resulting white solid was washed with 400 mL of cold deionized water (DI-H2O) to exhaust excess acryloyl chloride and dissolve salts. The white solid was collected by vacuum filtration and washed three times with 500 mL of cold DI-H2O. The resulting oligomer was placed to dry in a vacuum oven at room temperature (30 mmHg) for 48 hours.
  • DI-H2O cold deionized water
  • NDA-C12 was made according to the procedure of Example 1 , except that 1 ,12- dodecanediol was used instead of tetraethylene glycol.
  • BB-TEG was made according to the procedure of Example 1 , except that 4,4’- biphenyldimethyl ester was used instead of 2,6-naphthalenedimethyl ester.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne de nouveaux oligomères aromatiques à caractère inventif, notamment l'utilisation de tels oligomères dans la production de polymères utiles. De tels oligomères contiennent un noyau aromatique, des espaceurs flexibles et des fonctionnalités réactives. Ces nouveaux oligomères à caractère inventif permettent la synthèse de polymères utiles sous diverses formes et par de multiples techniques de traitement.
PCT/EP2022/081782 2021-11-30 2022-11-14 Oligomères aromatiques et polymères fabriqués à partir de ceux-ci WO2023099178A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6355738B2 (en) * 1998-02-27 2002-03-12 Mitsui Chemicals Inc Polyester and process for preparing polyester
US9790321B2 (en) * 2013-05-21 2017-10-17 Ester Industries Limited Heat resistant polyethylene terephthalate and a process for the preparation of the same
EP2931798B1 (fr) * 2012-12-14 2019-10-16 Resinate Materials Group, Inc. Produits de réaction contenant des téréphtalates d'hydroxyalkyle et leurs procédés de fabrication et d'utilisation

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6355738B2 (en) * 1998-02-27 2002-03-12 Mitsui Chemicals Inc Polyester and process for preparing polyester
EP2931798B1 (fr) * 2012-12-14 2019-10-16 Resinate Materials Group, Inc. Produits de réaction contenant des téréphtalates d'hydroxyalkyle et leurs procédés de fabrication et d'utilisation
US9790321B2 (en) * 2013-05-21 2017-10-17 Ester Industries Limited Heat resistant polyethylene terephthalate and a process for the preparation of the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"March's Advanced Organic Chemistry: Reactions, Mechanisms, and Structure", 2001, JOHN WILEY & SONS
"Protecting Groups in Organic Synthesis", 1999, JOHN WILEY & SONS

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