WO2015100478A1 - Polyamide hétérocyclique fluoré - Google Patents

Polyamide hétérocyclique fluoré Download PDF

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Publication number
WO2015100478A1
WO2015100478A1 PCT/BR2014/000045 BR2014000045W WO2015100478A1 WO 2015100478 A1 WO2015100478 A1 WO 2015100478A1 BR 2014000045 W BR2014000045 W BR 2014000045W WO 2015100478 A1 WO2015100478 A1 WO 2015100478A1
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WIPO (PCT)
Prior art keywords
compounds
bonds
double
molecular weight
mol
Prior art date
Application number
PCT/BR2014/000045
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English (en)
Portuguese (pt)
Inventor
Rafael Oliveira de FIGUEIREDO
Original Assignee
Figueiredo Rafael Oliveira De
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Filing date
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Application filed by Figueiredo Rafael Oliveira De filed Critical Figueiredo Rafael Oliveira De
Publication of WO2015100478A1 publication Critical patent/WO2015100478A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/42—Polyamides containing atoms other than carbon, hydrogen, oxygen, and nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0633—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only two nitrogen atoms in the ring
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D01F6/605—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides from aromatic polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
    • D01F6/80—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides
    • D01F6/805—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyamides from aromatic copolyamides

Definitions

  • the present invention relates to a novel high molecular weight polymer with characteristics which, as well as similar aramidic compounds, are desirable, such as high resistance to mechanical impact as well as stability when exposed to high temperatures.
  • aramids and para-aramids such as for example US 3484183-A which refers to thermo-resistant black fibers that are produced by metal phosphate rayon impregnation and thermochemical transformation of the corresponding rayon fiber, US 309451 1 which refers to a high molecular weight polymer with melting point of 300 ° C to 350 ° C and high tensile capacity, Kevlar, which is an example of aramid having high resistance to impacts, deformation and temperature variations, having applications in the most diverse areas of industry and commerce, being used from bulletproof vests to bicycle tires, cables, covers for phones, tarpaulins, brakes, shoes and etc.
  • Nylon compound which is employed in all types of clothing, ropes, gears, screws, suturing, parachute and many other uses of this material which as well as other aramids have. Great resistance to chemicals, tensioning and good stretching ability.
  • the high molecular weight chemical compounds of this invention include three having the molecular formula C10H14N6F4O2 and C10H6N6F4O2, of which two of the three presented have the same molecular formula (C10H6N6F4O2), so the molecular weight of two of the three compounds is approximately 318,192g / mol and the remainder 326,256g / mol have the nomenclature 6 - [(6- Amino-4,5-difluoro-1,2-dihydropyridazine-3-ylamino) carbonyl] -4,5-difluoro - 1, 2-dihydropyridazine-3-carbaldehyde (Figl .The) 6 - [(6- Amino - 4,5 difluoro - 1 4 ⁇ , 2 ⁇ 4 - -pyridazinilamino 3) carb Onila] -4,5 - difluoro-4 la, 2a -3-4 pirid
  • the compounds specified in this patent use the intermolecular interactions that occur between their monomers (Fig. 4. D) to form strong " intermolecular bonds, enabling their exceptional characteristics. These compounds differ from other polymer in structure and characteristics that resemble it. , poly (1,4-phenyleneterephthalamide), having in their molecular structure two nitrogen atoms constituting their heterocyclic ring and two fluorine atoms attached to carbons 2 and 3 of the heterocyclic ring (Fig 1A), this configuration allows both rings to gain a dipole moment resulting, in addition to, of course, the other intermolecular forces originated by other organic functions of the compound.
  • 6 - [(6-Amino-4,5-difluoro-4 lA, 2A -3-4 pyridazinilamino) carbonyl] -4,5-difluoro-4 la, 4 2A - 3-pyridazinacarbaldehyde (Fig.2.B) has special features that deserve attention, firstly it has a flat geometric structure, secondarily, the three double bonds in each aromatic ring give the compound resonance structures that are not only much more stable than simple cyclo rings but are also subject to a carbon-halogen bond strengthening, wherein the resonance structure gives the ring-bound fluorine atoms a double bond character and hence an even more stable structure.
  • a dipole moment is created in the heterocyclic ring as a consequence of the high electronegativity difference between the ring-bound fluorine atoms and their respective ligands, the carbon atoms, where while carbon has a pauling of 2.55 ⁇ fluorine holds 3.98 ⁇ , the result is one of the most powerful covalent bonds in organic chemistry, in fact it is one of the bonds in this area of chemistry that require the most energy in kJ / mol because, in the case of atoms of fluorine bonded to the heterocyclic ring the amount of energy required for the bond breakage approaches 485 kJ / mol at a temperature of 298K.
  • the carbon-fluorine and nitrogen-hydrogen bonds provide a number of interesting consequences and characteristics in this particular compound.
  • the distance of fluorine to its equal partial charge monomers positioned in parallel planes does not differ much from the attraction distance that would exist with an atom.
  • hydrogen if it occupied the carbon bond in a Van Der Walls interaction with the parallel monomer while the nitrogen-hydrogen bond has no angle or distance favorable for parallel monomer interaction.
  • the intermolecular interactions provided by the fluorine atoms in the structure are the hydrogen bonds that occur between monomers, where the fluorine atoms, having negative partial charge due to covalent bond with carbon, create a great attraction force towards the atoms. positively charged hydrogen bonds bound to the nitrogen atoms positioned in the aromatic ring of the adjacent monomer (Fig 4. D) Adding this effect to the great stability created from the fluorocarbon bond results in a number of intermolecular interactions (hydrogen bonds) per monomer typically three times larger than in many traditional polymers on the market, such as poly (1,4-phenyleneterephthalamide).
  • Each aromatic ring has two fluorine atoms attached to the ring in an ortho configuration, and therefore has a dipole moment of about 2.54D (Debyes).
  • the resulting dipole moment of the structure rings can be interpreted as a magnitude that was estimated from 5.4D to 6.2D in each ring depending on its saturation level.
  • 1A represents the structural formula of one of the conformational isomeric forms of one of the compounds claimed, wherein the black ends at the ends represent the continuity of the polymeric chain.
  • Figure 2B depicts the structural formula of one of the conformational isomeric forms of one of the claimed compounds, wherein the black ends at the ends represent the continuity of the polymeric chain and the three double bonds form a resonant structure.
  • Figure 3C represents the structural formula of one of the isomeric geometric forms of one of the claimed compounds, wherein the black stripes at the ends represent the continuity of the polymeric chain.
  • Figure 4D depicts the intermolecular interactions that occur only between two coplanar monomers, where the dotted lines indicate the intermolecular interactions and, while representing a specific compound, the interactions shown occur in all compounds claimed in this invention.
  • Figure 5E indicates the general form of the claimed compounds and one of the conformational isomeric forms, wherein the dotted bonds may indicate a single or double bond and the black stripes at the ends of the compound indicate the continuity of the polymeric chain.
  • Figure 6F shows the general shape of the claimed compounds and one of the conformational isomeric forms, wherein the dotted bonds may indicate a single or double bond and the black stripes at the ends of the compound indicate the continuity of the polymeric chain.
  • the first component to be synthesized is dihydropyridazine by reacting hydrazine with 1,4-diketone, thus, the addition of the amino group to positions 1 remains. and 4 of the heterocyclic ring through the dealkylation of both methyl radicals that occupy such positions and the nitration by NO2, which usually has a combination of sulfuric and nitric acid, then remains the hydrogenation of nitrates and their consequent transformation into an amide group .
  • fluorine to the structure, which can be done by adding a concentrated fluoride solution (F-) or by adding another amide group and subsequent nitrous acid diazotization and treatment of the diazonium salt.
  • F- concentrated fluoride solution
  • fluoroboric acid precipitation of the arenodiazonium fluoroborate occurs which is heated to decomposition and subsequent obtaining of the desired copolymer.
  • the first synthesized component is dihydropyridazine by reaction of hydrazine with 1,4-diketone, leaving addition of oxygen and chlorine to the methyl radicals positioned at the ends of the heterocyclic ring which may be made by converting them to carboxylic acid under the action of ⁇ 4 and their subsequent transformation to an acyl chloride by the addition of thionyl chloride. All that remains is the addition of fluorine to the heterocyclic ring structure.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

Les composés de masse moléculaire élevée de la présente invention possèdent une formule moléculaire variable de C10H14N6F4O2 à C10H6N6F4O2 et une masse moléculaire variable d'environ 318,192g/mol à 326,256g/mol, tous ces composés contenant une ou plusieurs liaisons doubles ou simples entre les atomes de carbone des anneaux, comme indiqué dans la formule structurale des figures 5.E et 6.F, les liaisons en traitillé indiquant que chaque carbone de chaque anneau hétérocyclique peut effectuer au maximum une seule liaison double et deux liaisons simples ou au minimum quatre liaisons simples, les espèces pouvant posséder un isomère conformationnel correspondant représenté dans les figures 5.E et 6.F et/ou un isomère géométrique selon le niveau de saturation de l'anneau, et sont des composés polymères présentant des forces de liaisons intermoléculaires et des caractéristiques exceptionnelles.
PCT/BR2014/000045 2014-01-06 2014-01-27 Polyamide hétérocyclique fluoré WO2015100478A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
BR102014000225 2014-01-06
BRBR1020140002251 2014-01-06

Publications (1)

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WO2015100478A1 true WO2015100478A1 (fr) 2015-07-09

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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3790382A (en) * 1971-04-16 1974-02-05 Minnesota Mining & Mfg Fluorinated polyamide-diazo resin coating composition
GB1458330A (en) * 1974-08-10 1976-12-15 Bayer Ag Dyeing dry-spun aromatic polyamides
US4278776A (en) * 1979-06-14 1981-07-14 Montedison S.P.A. Vulcanizable mixes based on fluoroelastomers and comprising elastomeric fluoropolyamides as processing aids
IT1209316B (it) * 1980-03-18 1989-07-16 Montedison Spa Composizioni vulcanizzabili a basedi fluoroelastomeri contenenti coadiuvanti di lavorazione.
JPH03234722A (ja) * 1990-02-09 1991-10-18 Tomoegawa Paper Co Ltd ブロック共重合体およびその製造方法
EP0523510A2 (fr) * 1991-07-17 1993-01-20 Bayer Ag Membranes en polyamides aromatiques/hétérocycliques, leur procédé de fabrication et leur utilisation
US20070041699A1 (en) * 2005-08-22 2007-02-22 Tomomi Makino Fluorinated polyamide acid resin composition for optical materials
CN101921395A (zh) * 2010-02-10 2010-12-22 中蓝晨光化工研究院有限公司 一种高性能杂环芳纶及其制备和应用
EP1564237B1 (fr) * 2002-10-31 2013-12-25 Toray Industries, Inc. Polyamides alicyliques ou aromatiques, films polyamides, elements optiques fabriques au moyen de ceux-ci et copolymeres polyamides

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3790382A (en) * 1971-04-16 1974-02-05 Minnesota Mining & Mfg Fluorinated polyamide-diazo resin coating composition
GB1458330A (en) * 1974-08-10 1976-12-15 Bayer Ag Dyeing dry-spun aromatic polyamides
US4278776A (en) * 1979-06-14 1981-07-14 Montedison S.P.A. Vulcanizable mixes based on fluoroelastomers and comprising elastomeric fluoropolyamides as processing aids
IT1209316B (it) * 1980-03-18 1989-07-16 Montedison Spa Composizioni vulcanizzabili a basedi fluoroelastomeri contenenti coadiuvanti di lavorazione.
JPH03234722A (ja) * 1990-02-09 1991-10-18 Tomoegawa Paper Co Ltd ブロック共重合体およびその製造方法
EP0523510A2 (fr) * 1991-07-17 1993-01-20 Bayer Ag Membranes en polyamides aromatiques/hétérocycliques, leur procédé de fabrication et leur utilisation
EP1564237B1 (fr) * 2002-10-31 2013-12-25 Toray Industries, Inc. Polyamides alicyliques ou aromatiques, films polyamides, elements optiques fabriques au moyen de ceux-ci et copolymeres polyamides
US20070041699A1 (en) * 2005-08-22 2007-02-22 Tomomi Makino Fluorinated polyamide acid resin composition for optical materials
CN101921395A (zh) * 2010-02-10 2010-12-22 中蓝晨光化工研究院有限公司 一种高性能杂环芳纶及其制备和应用

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