WO2015100478A1

WO2015100478A1 - Fluorinated heterocyclic polyamide

Info

Publication number: WO2015100478A1
Application number: PCT/BR2014/000045
Authority: WO
Inventors: Rafael Oliveira de FIGUEIREDO
Original assignee: Figueiredo Rafael Oliveira De
Priority date: 2014-01-06
Filing date: 2014-01-27
Publication date: 2015-07-09

Abstract

The high molecular weight compounds of the present invention have a molecular formula that varies from C₁₀H₁₄N₆F₄O₂ to C₁₀H₆N₆F₄O₂ and a molecular weight in the range of approximately 318.192 g/mol to 326.256 g/mol, wherein all of said compounds have one or more double bonds or single bonds between ring carbon atoms as indicated in the structural formula of figures 5.E and 6.F, wherein bonds marked with dashed lines indicate that each carbon atom of each heterocyclic ring can form at most one double bond and two single bonds, or at least four single bonds, wherein the species can have a corresponding conformational isomer shown in figures 5.E and 6.F and/or a geometric isomer, depending on the degree of saturation of the ring, and are polymer compounds with intermolecular bonding forces and exceptional features.

Description

Fluorinated Heterocyclic Polyamide

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.

Various types of polymeric compounds have been produced for decades and are used in the form of fibers and fabrics for the most diverse applications thanks to their unique characteristics including high resistance to deformation, abrasives, mechanical impacts, action of organic solvents and the ability to maintain their stability. integrity at high temperatures. Many of these were first introduced in the 1960s onwards and are generally divided into 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.

Another commonly used polymer of great commercial and industrial importance is the popularly 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.

It is the object of this invention to have a material which has potential characteristics superior or as satisfactory as other polymeric materials, such as tensioning, flexibility, chemical stability, thermal and abrasive resistance.

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 λ, 2λ ⁴ - -pyridazinilamino 3) carb Onila] -4,5 - ^difluoro-4 la, 2a ^-3-4 piridazinacarbaldeído (Fig.2.B) and 6 - [(6-amino-4,5-difluoroperidropirazina-3-ylamino) carbonyl] -4,5-3-carbaldehyde difluoroperidropirazina (Fig. 3.C), of course, in addition to the nomenclatures derived from the cis / trans geometric isomerism of the compound listed in Figure 3.C. The other compounds included in this invention have molecular formula and molecular weight ranging from the values of the three compounds presented above and their structural formulas are shown generally in Figures 5.E and 6.F and, as a result of possible variations in the level of heterocyclic ring saturation may have cis / trans isomerism as well as the compound of Figure 3.C. Also shown in Figures 5.E and 6.F are conformational isomers and dotted bonds may indicate a single or double bond and black stripes at the ends of the compound indicate continuity of the polymeric chain.

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. Among the various compounds reinvindicados, in particular one, 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 μ fluorine holds 3.98 μ, 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. First, 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. In fact, this weak interaction of carbon-fluorine bonds with their monomers in planes Parallels is a beneficial factor due to the large molecular mass of the compound provided by the molar mass of the four fluorine atoms in the structure, where, by way of comparison, the molecular mass of aramid on the market that most closely resembles it, poly (1,4-phenyleneterephthalamide) is 238g / mol, representing compounds with a 33% to 36% higher mass, so if the compound in question had a strong attraction with its monomers positioned parallel to it instead From a weak interaction, the material would become extremely rigid and dense on its transverse axis when macromolecular scale, limiting its possible applications in various sectors, so even weak repulsion guarantees the material a low transverse resistance capacity, providing flexibility and at the same time a strong longitudinal resistance that is mainly due to the strong covalent bonds and intermole interactions. in the fiber direction and a weak interaction in the transverse direction.

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). This results in a powerful tensile strength, mechanical strength and higher thermal strength than many similar aramid materials due to their higher molecular weight and enhanced stability of their intermolecular forces. 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). There is also a strong polarization in the bond that occurs between the nitrogen atoms that make up the aromatic ring and their respective bonding hydrogen atoms, where the dipole moment created between them is approximately 3.97D (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.

It is also interesting to note that some consequences cited here would not occur if other halogens were substituted for fluorine, for example, the use of another halogen atom would greatly increase the density of the compound by its molar mass, larger bonding radius and To a lesser extent, because they have a larger atomic radius, and have a smaller modulus dipolar moment, the replacement of fluorine by a hydroxyl group (-OH) in turn could be almost as effective as, however, the fact that oxygen still has two electron pairs capable of hydrogen bonding and together having a COH valence angle of 112 ° entails the risk of hydrogen bond interaction with parallel monomer hydroxyls and possibly a denser crystalline structure, inflexible and brittle. In place of nitrogen, it is not possible to use more electronegative atoms such as fluorine because it forms only a single bond and oxygen is only able to form two covalent bonds in the +0 oxidation state. In addition, a component for the formation of compounds such as 1,2-dioxane is poorly synthesized, difficult to oxidize and not capable of performing a resonance structure. Indeed, both fluorine and nitrogen demonstrate exceptional specific characteristics for their respective purposes in this invention.

It should be noted that thanks to its potential characteristics such as crystalline structure, transverse flexibility and longitudinal strength the compound, as well as various aramids and polymers, is capable of being woven into fibers in the most varied weft configurations that are applied to this material modality like the configurations used in kevlar, nylon and many others. The foregoing description and associative figures will make the invention well understood.

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. Synthesis Method:

The method proposed below is only one of several possibilities of synthesis, being only for the purpose of demonstrating the feasibility of synthesis of the material. 6 - [(6-Amino-4,5-difluoro-1,2-dihydropyridazin-3-yl-amino) carbonyl] -4,5-difluoro-1,2-dihydropyridazine-3-carbaldehyde was chosen for representation. .

The theoretical method adopted uses two copolymers for the synthesis: 4,5-difluoro-1,2-dihydropyridazine-3,6-diamine and 4,5-difluoro-1,2-dihydropyridazine-3,6-dicarbonyl. dichloride.

For 4,5-difluoro-1,2-dihydropyridazine-3,6-diamine 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 . All that is left is the addition of 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. With fluoroboric acid, precipitation of the arenodiazonium fluoroborate occurs which is heated to decomposition and subsequent obtaining of the desired copolymer.

For 4,5-difluoro-1,2-dihydropyridazine-3,6-dicarbonyl dichloride, as in the case of its 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 ηη4 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. with the addition of a concentrated fluoride solution or a fluorination method such as the diazotization cited above. With both polymer constituents, it can be synthesized by a hexamethylphosphoramide or methylpyrrolidone / calcium chloride solution or any other method that serves the final polymerization step.

Again, the intention is only to demonstrate the possibility of synthesis of the material, and many chemical techniques and procedures that do not follow the mentioned procedures are probably more industrially interesting because they have fewer steps or more economically viable constituents, as may be the case. for example, the fluorination techniques employed such as the Simons Process and electrophilic fluorination with compounds such as selectfluor, NFSI, NFOBS and others.

Claims

CLAIM

1 - High molecular weight polymers that, as well as similar polymeric compounds, have high mechanical impact resistance and stability when exposed to high and low temperatures, having qualitative improvements over existing materials such as tensile capacity, flexibility. , chemical stability, thermal and abrasion resistance, characterized by _^ fact of having molecular formulas ranging from C10H14N6F4O2 the C10H6N6F4O2, characterized by the fact that all compounds containing one or more double or single covalent bonds between the carbon atoms as shown in The structural formula of Figures 5E and 6F, wherein the dotted bonds indicate that each carbon of each heterocyclic ring can make at most one single double covalent bond and two single covalent bonds or at least four single bonds are claimed, as well as compounds having the atoms those of the heterocyclic ring nitrogen capable of making three to four single covalent bonds or one double and two single covalent bonds.

Compounds according to claim 1, characterized in that all claimed species have a corresponding conformational isomer as shown in Figures 5E and 6F and / or a cis / trans geometric isomer depending on the saturation level of the heterocyclic rings in that both isomeric forms of all compounds are characterized in that they are polymeric compounds capable of performing various intermolecular bonds and having chemical characteristics similar to or equal to their isomers, thus they are included in this invention.

Compounds according to claims 1 and 2, characterized in that according to Fig. 4 D, the intermolecular interactions occurring only between two monomers are represented, where the dotted lines indicate the intermolecular interactions and, despite representing a compound in Specifically, the interactions depicted occur in all compounds claimed in this invention.

These compounds according to claims 1, 2, 3 and 4 characterized in that two of the claimed compounds have the same molecular formula, C10 H6 N6 F402, differing only from each other by having a different number of double bonds as indicated in the above. 1A and 2B and have a molecular weight of approximately 318, 192g / mol. The third compound has molecular formula C 1 OH 14 N 6 F 402 and molecular weight of approximately 326.256 g / mol represented by having the structural formula listed in Figure 3.C.