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WO2012088190A1 - 2,4,5-triaminothiophénols et composés associés - Google Patents

2,4,5-triaminothiophénols et composés associés Download PDF

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WO2012088190A1
WO2012088190A1 PCT/US2011/066310 US2011066310W WO2012088190A1 WO 2012088190 A1 WO2012088190 A1 WO 2012088190A1 US 2011066310 W US2011066310 W US 2011066310W WO 2012088190 A1 WO2012088190 A1 WO 2012088190A1
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formula
composition
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alkyl
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Rajiv Dhawan
Joachim C. Ritter
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/14—Side-groups
    • C08G2261/142—Side-chains containing oxygen
    • C08G2261/1422—Side-chains containing oxygen containing OH groups
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/314—Condensed aromatic systems, e.g. perylene, anthracene or pyrene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/324—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed
    • C08G2261/3246—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain condensed containing nitrogen and sulfur as heteroatoms
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/34—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain
    • C08G2261/344—Monomer units or repeat units incorporating structural elements in the main chain incorporating partially-aromatic structural elements in the main chain containing heteroatoms

Definitions

  • the disclosure relates to new compositions based on 2 , 4 , 5-triaminothiophenols , which are then used in the manufacture of high-performance heterocyclic aromatic polymers.
  • Aromatic amines and phenols are useful as monomers for high performance polymers such as aramid polymers and polybenzarenazoles .
  • the structure of the specific monomer used greatly impacts polymer
  • triaminothiophenols and related compounds processes for the preparation of such triaminothiophenols and related compounds, processes for the preparation of products into which such triaminothiophenols and related compounds can be converted, and the products obtained and obtainable by such processes.
  • triaminothiophenol salt or "[specific triaminothiophenol name or formula reference] salt," e.g., "Formula (II) salt” or "TATHIO salt” where TATHIO means 2 , 4 , 5-triaminothiophenol , denotes a compound formed by reaction of a
  • triaminothiophenol with "n” equivalents of an acid (“A”) such as HC1, acetic acid, H 2 S0 4 , or H 3 P0 4 .
  • A an acid
  • HC1 acetic acid
  • H 2 S0 4 acetic acid
  • H 3 P0 4 H 3 P0 4
  • TATHIO- 2HC1 TATHIO- 2HC1
  • the salt may also be a hydrate; one such example is TATHIO ⁇ 3HC1 ⁇ x3 ⁇ 40.
  • the acid name may also be incorporated into the name of the salt, so that, e.g., TATHIO ⁇ nHCl can be referred to as "2,4,5- triaminothiophenol hydrochloride salt" or "TATHIO hydrochloride.” Where n is known, it can be
  • TATHIO- 3HC1 can also be referred to as "2 , 4 , 5-triaminothiophenol
  • triaminothiophenol complex or "[specific triaminothiophenol name] [diacid source name] complex denotes a compound formed by reaction of a triaminothiophenol with a diacid source.
  • the complex is to be used as a monomer in a polymerization, it can also be referred to as a
  • TATHIO- TA triaminothiophenol complex
  • TATHIO 2,4,5- triaminothiophenol
  • TA terephthalic acid
  • diacid source refers to the diacid HOOC-Q-COOH itself, a disodium salt of HOOC-Q-COOH, a dipotassium salt of HOOC-Q-COOH, or mixtures thereof, wherein Q is a Ci to C2 0
  • an acid (A) useful in the practice of the present invention can be an acid or a diacid as described above, or a mixture of diacids with other acids .
  • XYTA denotes 2-X- 5-Y-terephthalic acid, where X and Y are each
  • M 2 XYTA
  • the term "oleum” denotes fuming sulfuric acid, which is anhydrous and is formed by dissolving excess sulfur trioxide (SO 3 ) into
  • weak base denotes a base having a base dissociation constant (also referred to as "ionization constant") K b that is less than 1 at 25°C.
  • K b base dissociation constant
  • Some examples are acetate ion CHsCOO-, ammonia, and bicarbonate ion, HC03 ⁇ .
  • net yield of P denotes the actual, in-hand yield, i.e., the product of the formula
  • purity denotes what percentage of an in-hand, isolated sample is actually the specified substance.
  • alkyl is used to denote a univalent group derived from an alkane by removing a hydrogen atom from any carbon atom: -C n H 2n+ i where n ⁇ 1 ; as used herein, the term “alkyl” includes both substituted and unsubstituted groups.
  • aryl is used to denote a univalent group whose free bonding site is to a carbon atom of an aromatic ring; as used herein, the term “aryl” includes both substituted and unsubstituted groups.
  • An example is the "phenyl” group, i.e., the C 6 H 5 radical shown below:.
  • aralkyl denotes an alkyl group which bears an aryl group; as used herein, the term “aralkyl” includes both substituted and unsubstituted groups.
  • benzyl group i.e., the C 7 H 7 radical shown below,
  • alkaryl denotes an aryl group which bears an alkyl group; as used herein, the term “alkaryl” includes both substituted and unsubstituted groups.
  • alkaryl group is the 4-methylphenyl radical, C 7 H 7i shown below:
  • acetyl is used to denote the univalent radical CH 3 CO-, i.e.,
  • novel polymer compositions comprising repeat units represented by Formula (VI) .
  • R 1 and R 2 are each independently H, alkyl, aryl, alkaryl, or aralkyl;
  • R 3 and R 4 are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;
  • R 5 and R 6 are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;
  • R 7 and R 8 are each independently H, alkyl, aryl, alkaryl, or aralkyl; or may be joined to form an aliphatic ring structure;
  • R 9 is H or acetyl
  • n 1 to 10;
  • A is an acid, e.g., HC1, acetic acid, H 2 S0 4 , or H 3 P0 4 ;
  • Q is a Ci to C20 substituted or unsubstituted monocyclic or polycyclic aromatic nucleus.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are each H.
  • This compound (Formula (VII)) is 2, 4, 5-triaminothiophenol ( "TATHIO” ) .
  • R 1 and R 2 are each
  • R 3 is H
  • R 4 is alkyl or H
  • R 5 , R 6 , R 7 , and R 8 any three are H
  • the fourth is H, alkyl, aryl, alkaryl, or aralkyl.
  • R 1 , R 2 , R 7 , and R 8 are each
  • composition represented by Formula (IX) is made by
  • each Z is independently CI or Br, by heating a suspension of the composition of Formula (X) in solvent to a temperature in the range of about 60 °C to about 140°C and contacting it with an aqueous solution of at least 2.0 equivalents HNR R to produce a composition of Formula (XI)
  • composition represented by Formula (X) may be prepared by nitration of the corresponding dihalobenzene according to the method described in copending U.S. Patent Application 12/335,959, which is hereby incorporated by reference in its entirety for all purposes; by admixing a dihalobenzene represented by the structure of Formula (XII)
  • each Z is independently CI or Br, with nitric acid, sulfuric acid, and oleum or SO 3 , to form a reaction mixture that is characterized by (i) a
  • concentration of nitric acid therein that is in the range of about 2.0 to about 2.3 moles per mole of dihalobenzene ;
  • concentration of SO 3 therein that is in the range of about 1 to about 3 moles per mole of dihalobenzene;
  • concentration of dihalobenzene therein that is in the range of about 12 to about 24 weight percent; and
  • a temperature of up to about 120°C and stirring the reaction mixture at a
  • each Z is CI and R 1 and R 2 are each H; i.e., the compound of Formula (X) is 1 , 3-dichloro-4 , 6-dinitrobenzene and the Formula (XII) dihalobenzene is 1 , 3-dichlorobenzene, which is commercially available.
  • a suspension of the composition of Formula (X) in solvent is heated to a temperature in the range of about 60°C to about 140°C, preferably about 100°C to about 135°C, and more preferably about 130°C, to dissolve the composition of Formula (X) in a solvent.
  • a suitable solvent is an organic solvent inert to the reaction such as an aliphatic dihydric alcohol, such as ethylene glycol (“glycol”) .
  • the resulting solution is contacted at that temperature with an aqueous solution of HNR 7 R 8 for approximately two to four hours close to ambient pressure; the HNR 7 R 8 solution is fed as it is consumed, as indicated by any convenient analytical technique (e.g., pH monitoring or measuring the flow rate of HNR 7 R 8 in the gas phase above the reaction mixture) .
  • the compound represented by Formula (XI) is l-amino-3-chloro-4 , 6-dinitrobenzene (i.e., R 1 , R 2 , R 7 , and R 8 are each H and Z is CI) . At least 2.00, preferably about 2.03 to about 2.07, equivalents of HNR 7 R 8 are required.
  • the composition of Formula (XI) thereby produced can be directly isolated from the reaction mixture since it is only sparingly soluble in suitable solvents such as glycol at temperatures below 50°C;
  • composition of Formula (XI) is filtered, typically at about 60°C, and washed with solvent. It can then be thiolated (step (b) ) .
  • the composition of Formula (XI) is slurried in ethanol and reacted in step (b) with aqueous SH ⁇ (for example, from NaSH) under mild conditions (e.g., at about 10°C to 50°C) in a molar ratio of at least 1.0 mole SH ⁇ per mole Formula (XI) composition, to form the disulfide represented by Formula (IV) .
  • aqueous SH ⁇ for example, from NaSH
  • the disulfide is bis (3, 4-diamino-6-dinitrophenyl) disulfide (“DANDS”) , represented by Formula (XIII) .
  • composition of Formula (XI) is contacted in step (b) with sulfide ion, S ⁇ 2 (e.g., from an aqueous solution of a 2 S) to produce the disulfide represented by Formula (IV) .
  • sulfide ion, S ⁇ 2 e.g., from an aqueous solution of a 2 S
  • disulfide represented by Formula (IV) can be isolated and
  • a reducing agent e.g., Zn, in acetic acid; or Sn +2 .
  • the composition of Formula (XI) is prepared as described above (step (a)) and then is contacted in step (b) with thioacetate ion (for example, from sodium thioacetate, prepared by reacting thiolacetic acid with aqueous NaOH in an oxygen-free environment) , typically under ambient conditions, in an ethanol/water mixture in a molar ratio of at least 1.0 mole thioacetate per mole Formula
  • thioacetate ion for example, from sodium thioacetate, prepared by reacting thiolacetic acid with aqueous NaOH in an oxygen-free environment
  • hydrolysis of thioacetates can occur via base or acid catalysis.
  • the thioacetate (Formula XIV) can be hydrolyzed by heating in an aqueous or alcoholic solution of 1 equivalent NaOH (e.g., at about 50°C for about 1 h) to form the sodium salt of the
  • hydrochloride of Formula (XV) which is partially soluble .
  • the dinitroaminothiophenol can be isolated and subsequently contacted with a reducing agent (e.g., Zn in acetic acid, Sn +2 , or SH ⁇ ) or it can be directly reduced without isolation to form triaminothiophenol represented by Formula (I) . Including the isolation step results in higher purity product.
  • a reducing agent e.g., Zn in acetic acid, Sn +2 , or SH ⁇
  • n 1 to 10 and A is an acid, e.g., HC1, acetic acid, H 2 SO 4 , or H 3 PO 4 .
  • the Formula (II) salt can be converted to the free base or to a novel aromatic diacid complex of the free base with a diacid source, the complex represented by Formula (III),
  • the salt may also be a hydrate; one such example is 2 , 4 , 5-triaminothiophenol ⁇ 3HC1 ⁇ x3 ⁇ 40 ("TATHIO- 3HC1 ⁇ ⁇ 2 0") .
  • a in Formula (II) is HC1 and n is 2 to 4.
  • the mixture containing the precipitated Formula (II) salt is then cooled to about 5°C to about 15°C, stirred, and filtered.
  • the Formula (II) salt is then washed. It may be washed with deaerated aqueous acid, such as HC1 (33%) , and then optionally with deaerated ethanol or methanol to produce a wet cake material.
  • aqueous acid or cold water is used as a wash, it may be possible to eliminate the ethanol or methanol wash and dry directly from aqueous wet cake or simply use the wet cake in subsequent processing. It is likely that in a commercial process one would only wash with HCl aq and, if desired, dry directly.
  • the resulting wet cake material (Formula (II) salt) can be used in subsequent processing without drying or can be dried, for example at a pressure less than 400 Torr and a temperature of about 30 °C to about 50°C, under a stream of N 2 .
  • the dried product is preferably kept under nitrogen.
  • Q is a Ci to C2 0 substituted or unsubstituted monocyclic or polycyclic aromatic nucleus.
  • Examples of Q include without limitation:
  • One or more heteroatoms may be present in the ring(s) of Q, for example, as shown below :
  • Q is represented by the structure of Formula (XVI)
  • X and Y are each independently selected from the group consisting of H, OH, SH, SO 3 H, methyl, ethyl, F, CI, and Br.
  • (II) salt is precipitated and washed as described above, then slurried with water.
  • Base e.g., NaHCOs
  • a diacid source are then added to the slurry to form and precipitate the complex, Formula (III) .
  • diacid source refers to the diacid HOOC-Q- COOH itself, a disodium salt of HOOC-Q-COOH, a
  • aqueous potassium hydroxide in the Option A, B, or C process can cause the free base to diacid ratio in the complexes so produced to deviate from 1:1.
  • a preferred process is to dissolve the Formula (II) salt, e.g., TATHIO ⁇ 3HC1 , in water and contact that solution with the diacid source in an aqueous solution of a weak base such as aHC03 or KHCO3.
  • This process can be performed under mild conditions, e.g., from ambient temperatures to about 50°C.
  • the ratio of equivalents of the Formula (II) salt to equivalents of diacid source is between and optionally including any two of the following ratios: 1.00:1.00, 1.025:1.00, 1.05:1.00, 1.075:1.00, 1.10:1.00;
  • the ratio is from 1.025:1.00 to 1.10:1.00.
  • the base and the diacid source are most conveniently added as a single solution.
  • the Formula (II) salt in an acid solution could be introduced into a vessel containing a basic diacid source solution, or the diacid source stream could be fed into the vessel containing the Formula (II) salt in an acid solution. Which design is best for a specific situation will be evident to one of skill in the art.
  • the Formula (III) complex is recovered from the reaction mixture by filtration at a temperature in of the range of about 5°C to about 50°C, preferably about 10°C to about 15°C, and washed with water and methanol, typically at a temperature in the range of about 15°C to about 40°C, and then dried.
  • the washed and dried Formula (III) complex is kept under nitrogen to protect it from oxygen. It is of high enough quality and purity to produce heterocyclic aromatic polymer of high enough molecular weight to make high performance fibers .
  • Options B and C have fewer steps, generate less waste and also require less acid (e.g., HC1) and base (e.g., NaHCOs) , thus lessening raw material and handling costs. All
  • disclosed embodiments produce polymer grade material suitable for the manufacture of high-performance fibers .
  • Oxygen is excluded throughout all steps of the processes of making the free base, the Formula (II) salt, and the Formula (III) complex. Deaerated water and deaerated acid are used. A small amount of a reducing agent (e.g., about 0.5% tin powder) is used.
  • aqueous suspensions or aqueous solutions containing the triaminothiophenol free base, the Formula (II) salt, or the Formula (III) complex optionally added to one or more of aqueous suspensions or aqueous solutions containing the triaminothiophenol free base, the Formula (II) salt, or the Formula (III) complex during the process to reduce impurities caused by oxidation and to prevent further impurity formation by that route .
  • novel polymer compositions comprising a composition of Formula (I) as a monomer.
  • Articles comprising these polymers are also provided. Examples of such articles include without limitation fiber, film, and tape.
  • novel polymer compositions are provided comprising repeat units represented by Formula (VI) .
  • R 1 , R 2 , and R 7 are each independently H, alkyl, aryl, alkaryl, or aralkyl; and Q is a Ci to C2 0
  • Polymers comprising repeat units represented by Formula (VI) can be prepared at high molecular weight from a mixture of a triaminothiophenol salt represented by Formula (II) (e.g., TATHIO ⁇ 3HC1 ) with HOOC-Q-COOH in polyphosphoric acid, or from a complex represented by Formula (III) at temperatures from about 100°C to about 180°C.
  • a triaminothiophenol salt represented by Formula (II) e.g., TATHIO ⁇ 3HC1
  • Formula (III) e.g., TATHIO ⁇ 3HC1
  • R 1 , R 2 , and R 7 are each H and Q is 1,4- phenylene .
  • the polymer represented by Formula (XVIII) can be made by polymerizing the 1:1 monomer complex of 2,4,5- triaminothiophenol with terephthalic acid ("TATHIO- T complex”) ; or by polymerizing a mixture of a TATHIO salt (e.g., TATHIO ⁇ 3HC1 ) and terephthalic acid.
  • TATHIO- T complex 2,4,5- triaminothiophenol with terephthalic acid
  • TATHIO- T complex 2,4,5- triaminothiophenol with terephthalic acid
  • R 1 , R 2 , and R 7 are each H and Q is 2 , 5-dihydroxy- 1 , 4 -phenylene .
  • the polymer represented by Formula (XIX) can be made by polymerizing the 1:1 monomer complex of 2,4,5- triaminothiophenol with 2 , 5-dihydroxyterephthalic acid ("TATHIO ⁇ DHTA complex"); or by polymerizing a mixture of a TATHIO salt (e.g., TATHIO ⁇ 3HC1 ) and 2,5- dihydroxyterephthalic acid.
  • TATHIO ⁇ DHTA complex a mixture of a TATHIO salt (e.g., TATHIO ⁇ 3HC1 ) and 2,5- dihydroxyterephthalic acid.
  • the polymerization of the monomer complex is typically carried out in a reactor suitably equipped with connections for purging with inert gas, applying a vacuum, heating and stirring.
  • Monomer complex, P 2 O 5 , polyphosphoric acid (“PPA”) and powdered metal are typically added to the reactor.
  • the reactor is typically purged, heated and mixed to effect polymerization.
  • PPA polyphosphoric acid
  • powdered metal for example, tin or iron metal
  • tin or iron metal about 10 parts of P 2 O 5 , 100 parts of PPA, and about 0.1 parts tin or iron metal are added to a suitable reactor.
  • the contents of the reactor are stirred at about 60 rpm and heated to about 100°C for about one hour under vacuum with a slight nitrogen purge.
  • the temperature is typically raised to at least 110°C, preferably at least about 120°C, and preferably not more than 140°C for a few more hours, preferably about four hours.
  • the temperature is then raised and held at a higher temperature, at least about 130°C, more typically at least about 140°C, and preferably at about 150 °C for about an hour, more preferably about three hours.
  • the temperature is subsequently then raised and held at a higher temperature, at least about 150°C, more typically at least about 170°C, and
  • the reactor is typically flushed with nitrogen and a sample of the polymer solution is taken for viscosity determination.
  • the polymers so produced from monomer complexes are polybenzarenazoles that are characterized as providing a polymer solution having an inherent viscosity of at least about 8 dL/g at 30°C at a polymer concentration of 0.05 g/dL in methanesulfonic acid.
  • the metal powder is present in an amount of about 0.1 to about 0.5 weight percent based on monomer complex.
  • the reaction mixture includes polyphosphoric acid having an equivalent P 2 O 5 content of at least about 81 percent after
  • the reaction mixture includes polyphosphoric acid having an equivalent P 2 O 5 content of at least about 81 percent after contacting, in polyphosphoric acid, the monomer complex with metal powder, the metal powder added in an amount of from about 0.05 to about 0.9 weight percent, based on the total monomer weight and polymerizing the monomers in polyphosphoric acid to form the polymer solution.
  • triaminothiophenol to the diacid source is at least about 1.00:1.00, at least 1.025:1.00, at least
  • a solution of such polymers at about 10 to about 30 wt% in polyphosphoric acid can be used to prepare high strength fiber, films, and tapes, which can be used, for example, as reinforcement materials for thermoplastic and thermoset matrices. Fibers may also be cut and used as staple fiber or, when
  • Useful articles comprising the polybenzarenazole polymers described herein include without limitation: protective apparel (e.g., body armor, industrial gloves, flame retardant apparel) ; aircraft applications (e.g., components of aircraft cabin, flooring and interiors, landing gear doors;
  • ACDNB means l-chloro-3-amino-4 , 6-dinitrobenzene
  • Cm means centimeter ( s )
  • d means density
  • DDNB means 1 , 3-diamino-4 , 6-dinitrobenzene
  • DANDS means bis (3,4- diamino- 6-dinitrophenyl ) disulfide
  • DCDNB means 1,3- dichloro-4 , 6-dinitrobenzene
  • DHTA means 2,5- dihydroxyterephthalic acid
  • DL means deciliter ( s )
  • DMAC means dimethylacetamide
  • equiv means
  • ACDNB 100 g was added to 250 mL water to form a yellow slurry.
  • thioacetic acid 38.49 g was slowly added to a cooled solution of NaOH (47.84) in 250 mL of water. The resultant thioacetate salt was then slowly added to the ACDNB slurry. After stirring for
  • Example 7 Preparation of TATHIO ⁇ DHTA from TATHIO ⁇ 3HC1 and K 2 DHTA 11.41 g of 2 , 5-dihydroxyterephthalic acid (41.58 mmol) along with 5.50 g of sodium bicarbonate (65.489 mmol) was added to a reaction vessel. This was
  • TATHIO- DHTA monomer complex 3.9 g of P 2 0 5 , 78.51 g of PPA with a % P 2 0 5 equivalent to 85.4%, and 0.05 g Sn powder.
  • the stirrer was turned on at 100 rpm and the contents were heated to 100°C for one hour under vacuum. The temperature was raised and held at 135°C for 20 hours. The temperature was raised and held at 180°C for 3 hours.
  • the reactor was flushed with nitrogen gas ("N 2 ") and a sample of the polymer

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention concerne de nouvelles compositions de triaminothiophénol et de nouveaux composés associés, ainsi que leurs procédés de préparation et des procédés de préparation de nouveaux sels, complexes diacides et polymères à partir de ces composés. Les polymères préparés à partir de ces compositions peuvent être transformés en fibres, en pellicules et en rubans extrêmement résistants, et sont utilisés dans des applications telles que les vêtements protecteurs, les composants d'avion, d'automobile, les composants électroniques et les articles de sport.
PCT/US2011/066310 2010-12-20 2011-12-20 2,4,5-triaminothiophénols et composés associés Ceased WO2012088190A1 (fr)

Applications Claiming Priority (16)

Application Number Priority Date Filing Date Title
US201061424858P 2010-12-20 2010-12-20
US201061424818P 2010-12-20 2010-12-20
US201061424826P 2010-12-20 2010-12-20
US201061424814P 2010-12-20 2010-12-20
US201061424809P 2010-12-20 2010-12-20
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WO2019008115A1 (fr) 2017-07-07 2019-01-10 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre
WO2020053365A2 (fr) 2018-09-13 2020-03-19 Syngenta Participations Ag Composés azole-amide à action pesticide
CN113087629A (zh) * 2021-04-07 2021-07-09 中北大学 一种1,5-二氯-2,4-二硝基苯的制备方法
WO2023247360A1 (fr) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Composés hétéroaromatiques bicycliques fusionnés à action pesticide
WO2024110554A1 (fr) 2022-11-23 2024-05-30 Syngenta Crop Protection Ag Dérivés de n-[(1-[2-[6-(pyridazin-3-yl]-1,2,4-triazol-3-yl]éthyl]-quinazolin-4-amine et de n-[1-[3-(6-(pyridazin-3-yl)pyrazin-2-yl]éthyl]-8-quinazolin-4-amine utilisés en tant que pesticides
WO2025132349A1 (fr) 2023-12-19 2025-06-26 Syngenta Crop Protection Ag Composés de quinazoline à action pesticide

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019008115A1 (fr) 2017-07-07 2019-01-10 Syngenta Participations Ag Dérivés hétérocycliques à activité pesticide comportant des substituants contenant du soufre
WO2020053365A2 (fr) 2018-09-13 2020-03-19 Syngenta Participations Ag Composés azole-amide à action pesticide
CN113087629A (zh) * 2021-04-07 2021-07-09 中北大学 一种1,5-二氯-2,4-二硝基苯的制备方法
WO2023247360A1 (fr) 2022-06-21 2023-12-28 Syngenta Crop Protection Ag Composés hétéroaromatiques bicycliques fusionnés à action pesticide
WO2024110554A1 (fr) 2022-11-23 2024-05-30 Syngenta Crop Protection Ag Dérivés de n-[(1-[2-[6-(pyridazin-3-yl]-1,2,4-triazol-3-yl]éthyl]-quinazolin-4-amine et de n-[1-[3-(6-(pyridazin-3-yl)pyrazin-2-yl]éthyl]-8-quinazolin-4-amine utilisés en tant que pesticides
WO2025132349A1 (fr) 2023-12-19 2025-06-26 Syngenta Crop Protection Ag Composés de quinazoline à action pesticide

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