WO2022023736A1 - Composés de triazine - Google Patents

Composés de triazine Download PDF

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Publication number
WO2022023736A1
WO2022023736A1 PCT/GB2021/051937 GB2021051937W WO2022023736A1 WO 2022023736 A1 WO2022023736 A1 WO 2022023736A1 GB 2021051937 W GB2021051937 W GB 2021051937W WO 2022023736 A1 WO2022023736 A1 WO 2022023736A1
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Prior art keywords
carbons
alkyl
formula
acid
triazine compound
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PCT/GB2021/051937
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English (en)
Inventor
David Lewis
Christopher Carr
Muriel RIGOUT
Peter Broadbent
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University Of Leeds
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Publication of WO2022023736A1 publication Critical patent/WO2022023736A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B11/00—Preparation of cellulose ethers
    • C08B11/02—Alkyl or cycloalkyl ethers
    • C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
    • C08B11/14—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals with nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J1/00—Modifying the structure or properties resulting from a particular structure; Modifying, retaining, or restoring the physical form or cross-sectional shape, e.g. by use of dies or squeeze rollers
    • D02J1/22—Stretching or tensioning, shrinking or relaxing, e.g. by use of overfeed and underfeed apparatus, or preventing stretch
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02J—FINISHING OR DRESSING OF FILAMENTS, YARNS, THREADS, CORDS, ROPES OR THE LIKE
    • D02J13/00—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass
    • D02J13/005—Heating or cooling the yarn, thread, cord, rope, or the like, not specific to any one of the processes provided for in this subclass by contact with at least one rotating roll
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/35—Heterocyclic compounds
    • D06M13/355—Heterocyclic compounds having six-membered heterocyclic rings
    • D06M13/358—Triazines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
    • D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
    • D06P1/5278—Polyamides; Polyimides; Polylactames; Polyalkyleneimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
    • D06P1/64—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing low-molecular-weight organic compounds without sulfate or sulfonate groups
    • D06P1/642—Compounds containing nitrogen
    • D06P1/645—Aliphatic, araliphatic or cycloaliphatic compounds containing amino groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/58—Material containing hydroxyl groups
    • D06P3/60—Natural or regenerated cellulose
    • D06P3/66—Natural or regenerated cellulose using reactive dyes
    • 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
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • 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
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/02—Chemical after-treatment of artificial filaments or the like during manufacture of cellulose, cellulose derivatives, or proteins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/30—Flame or heat resistance, fire retardancy properties

Definitions

  • the invention relates to triazine compounds, in particular to functionalised triazine compounds which can be used in the textiles industry.
  • Lyocell technology in particular, developed by Courtaulds and Lenzing, offers a closed loop process in which cellulosic fibres are produced from wood pulp. This process is not only low in water consumption relative to other textile production processes, but also provides a product, lyocell, which satisfies the consumer demand for the "comfort" of cotton-type fibres. Specifically, following extraction from wood pulp (a renewable resource), cellulose is dissolved directly into the solvent N-methylmorpholine-N-oxide (NMMO).
  • NMMO N-methylmorpholine-N-oxide
  • NMMO N-methylmorpholine-N-oxide
  • Lyocell fibres (sold in the UK under the tradename Tencel ® ) have a better wet and dry strength than viscose. However, the fibres have a higher degree of crystallinity and orientation, which results in fibrillation (i.e. formation of fibrils on the fibre and fabric surface). During wet processing, such as dyeing and laundering, such fibrils can pose a problem, as they can result in surface defects, such as pills and result in a dulling of the fabric colour. To combat these issues, cross-linked versions of lyocell have been fabricated, such as Lyocell Axis A-100 and Tencel LF, which are more resistant to fibrillation.
  • Lyocell Axis A-100 and Tencel LF offer an improvement to dyeing capabilities and more environmentally friendly wet processing procedures, there is a continuous need for a more environmentally friendly cellulosic dyeing processes and better dye fixation.
  • the invention is intended to overcome or ameliorate at least some aspects of the above problems.
  • X comprises a cellulosic material
  • Ri and R are independently selected from -ONR'R", -NR'R", or -Y; wherein R' and R" are independently selected from H, alkyl having 1 to 18 carbons, alkoxy having 1 to 18 carbons, alkenyl having 2 to 18 carbons, wherein in the alkyl, alkoxy and alkenyl at least one carbon atom may be replaced with O, N, S, or combinations thereof; or wherein the alkyl, alkoxy or alkenyl may be substituted with at least one acid selected from a carboxylic acid, phosphonic acid, and sulfonic acid, an amino acid moiety, a compound of formula I or formula II, and a straight or branched chain alkylpolyamine, wherein one or more of the carbons in the alkylpolyamine may be replaced by a heteroatom selected from N, O or S; or wherein R' and R" comprise a saturated or unsaturated cyclic moiety comprising 4,
  • the triazine compounds according to the first aspect of the invention provide a reactive cellulosic fibre, which can offer performance improvements in a wide range of sectors in the textile industry, including colouration, colour fastness, odour control (for instance through the provision of fibres with antimicrobial and/or antiviral properties) and flame reta rdancy.
  • cellulosic fibres comprising the triazine compounds of the invention can be generated with minimal changes to current production processes.
  • textile fibres comprising the triazine compound of the invention can be prepared on a large scale, using existing production facilities, allowing rapid uptake of the technology.
  • Ri and R2 may be the same or different; and each substituent thereof may be the same of different.
  • Ri or R2 are selected from -NR'R", it is often the case that at least one of R' or R" are hydrogen or an alkyl group, often both R' and R" are hydrogen, such that Ri and/or R2 may be ammonia.
  • R' or R" is an alkyl group, it will often have 1 to 5 carbon atoms, often 1 to 3 carbon atoms. It may be the case that one or more carbons in the alkyl group will be replaced with O, N or S, often with O or N.
  • Ri and/or R2 are ammonia, methanolamine or ethanolamine.
  • Ri and/or R2 are selected from -ONR'R", it is often the case that at least one of R' or R" is hydrogen or an alkyl group, often both R' and R" are hydrogen.
  • R' or R" is an alkyl group, it will often have 1 to 5 carbon atoms, often 1 to 3 carbon atoms. It may be the case that one or more carbons in the alkyl group will be replaced with O, N or S, often O or N.
  • Ri or R2 are hydroxy la mine. The presence of hydroxylamine in the triazine compounds of the invention (and other -ONR'R" functionalities) is believed to provide for potent urease inhibition, offering odour control in fibres comprising the inventive compounds.
  • alkyl is intended to take its usual meaning and covers linear, branched and cyclic saturated hydrocarbons having a carbon length in the range Ci to Cis- Often the alkyl group will be linear or branched, typically linear. Whilst the exact length of the alkyl group may vary, it is typically the case that the alkyl group has a carbon length in the range Ci to Cis, more typically Ci to C12, or Ci to C 6 , and most typically Ci to C3.
  • Typical alkyl groups are selected from, but not limited to: methyl, ethyl, propyl, isopropyl, butyl or tertiary butyl.
  • alkoxy is intended to carry its usual meaning i.e. this term is identical to "alkyl” described above with the exception that said alkyl group is covalently bonded to the triazine skeleton via an oxygen atom (as would be familiar to one skilled in the art).
  • alkenyl is also intended to take its usual meaning and covers linear, branched and cyclic partially saturated hydrocarbons having a carbon length in the range C2 to Cis-
  • the alkenyl group will be linear or branched, typically linear. Whilst the exact length of the alkenyl group may vary, it is typically the case that the alkenyl group has a carbon length in the range C2 to Cis, more typically C2 to C12, and most typically C2 to C 6 -
  • Typical alkenyl groups are selected from, but not limited to: vinyl, propenyl, isopropenyl or butenyl.
  • a dialkenyl may be formed.
  • polyamine is intended to cover organic compounds having two or more amino groups.
  • the polyamine may be an alkyl or alkenylpolyamine, often however alkylpolyamines will be used.
  • Ri and R2 are -NR'R", and at least one of R' and R" may be selected from alkyl, wherein in the alkyl at least one carbon atom may be replaced with N or with O. Where at least one carbon atom (for instance a -CH2- group) is replaced by N, often two or more carbon atoms will be replaced by N.
  • Typical alkylpolyamines include ethyleneamines comprising 2 to 5 nitrogens, such as diethylenetriamine or triethylenetetramine; or polyethyleneimines which can be straight chain or branched chain or additionally dendritic. Often the polyethyleneimines will be branched, and often functionalised. In some cases polyethyleneimines such as Lupasol P (BASF) will be used.
  • Polyethyleneimines will often be of molecular weight in the range 500 - 50,000, often 20,000 - 30,000.
  • the polyethyleneimines and alkylpolyamines offer excellent dye uptake and fixation. Without being bound by theory this is believed to be as a result of the protonation of the amines promoting exhaustion of the anionic dyes on to the positively charged Lyocell fibre and where reactive dyes are applied improved nucleophilic addition or substitution reactions with reactive groups on the dyes, particularly where the dyes are sulfonated reactive dyes.
  • Processes of this type have the potential to reduce the environmental impact of the dyeing process by reducing the levels of salt required to fix the dye, and hence reducing the salination of freshwater courses when the waste water is released from the dyeing process.
  • the chelator may be, for instance, an acid chelator, for instance a carboxylic acid chelator, such as a di-carboxylic acid (e.g. maleic acid or glutamic acid), tri carboxylic acid (e.g. citric acid) or tetra -carboxylic acid (e.g. EDTA).
  • a carboxylic acid chelator such as a di-carboxylic acid (e.g. maleic acid or glutamic acid), tri carboxylic acid (e.g. citric acid) or tetra -carboxylic acid (e.g. EDTA).
  • Ri and R2 are -NR'R", and an alkylpolyamine is formed, it may be the case that at least one -CH2- unit in the alkylpolyamine backbone will be replaced by O, such that, for instance, diamines of polyethylene glycol can be formed.
  • amino acid is intended to take its usual meaning, and relates organic compounds containing amine and carboxyl functional groups.
  • the amino acid is often selected from cysteine, cysteamine, glycine, tyrosine, lysine, taurine, glutamic acid, arginine or combinations thereof. It may be the case that the amino acid moiety is a poly(amino acid) or amino acid polymer.
  • poly(amino acid) or “amino acid polymer” are used interchangeably, and relate to a polymer in which the monomer units are amino acids.
  • amino acid polymers include, but are not limited to, functional proteins, polypeptides, peptides, and polymers derived from amino acids, such as poly(P-alanine) and poly(lysine). It may be the case that the amino acid moiety is poly(lysine). It has been found that these amino acid functionalities, when incorporated into the triazine compounds of the invention can provide fibres and fabrics which have the ability to control odour through urease inhibition. Of these, glycine and taurine have been found to be particularly effective.
  • poly(lysine) functionality when incorporated into the triazine compounds of the invention, can provide fibres and fabric with excellent dye uptake, but which also have antimicrobial properties, such that the fibres kill and/or inhibit the growth of microorganisms including bacteria, fungi, algae, protozoa, viruses and sub-viral agents.
  • microorganism or "microbe" is intended to take its usual meaning, and relates to microscopic organisms that are unicellular, multicellular, or exist as a cell cluster.
  • poly(lysine) due to the cationic nature of poly(lysine), it exhibits such antimicrobial behaviour by either damaging or disrupting the cell membranes of microbial cells, protein denaturation, inhibiting DNA replication, inhibiting synthesis of mRNA, or preventing protein synthesis from taking place.
  • amino acids may be connected together in a sequence, forming protein residues, this can provide the urease inhibition of amino acids together with other biochemical and physiological benefits depending on the protein selected.
  • a "cyclic moiety" is a cyclic hydrocarbon, in which the carbon chain forms a ring, typically the ring is 5- or 6-membered, often the atoms in the ring will be primarily if not entirely carbon atoms; however, these may be substituted with one or more heteroatoms such as N, O or S, often N or O. Often the cyclic moiety will be a 5- membered ring, often substituted with N, often at more than one carbon, such that a 5- membered ring with one or two nitrogens within the ring may be formed.
  • Typical cyclic and/or aromatic moieties include imidazole, pyrrole, pyrazole, oxazole, benzimidazole, pyridine, pyrimidine, phenol, aniline and furan. Often the cyclic/aromatic moiety will include pyrimidine, phenol, aniline, or imidazole.
  • Ri and R 2 are both -NR'R", and R' and R" may independently comprise a saturated or unsaturated cyclic moiety comprising 4, 5 or 6 carbons, wherein one or more of the carbons in the cyclic moiety may be replaced by a heteroatom selected from N, O or, on occasion, S.
  • the cyclic moiety will be imidazole, although together with the other cyclic moieties listed here, it is believed that the use of imidazole will provide for a fabric with excellent dye uptake and exhaustion.
  • phenol or "phenolic moiety” are intended to take their usual meaning, and cover a compound consisting of a hydroxyl group bonded directly to a six-membered aromatic hydrocarbon group.
  • the phenolic moiety is selected from phenol, di-hydroxy phenol or tri-hydroxy phenol, although often the moiety will be phenol (-C 6 H 4 OH).
  • Ri and R 2 may independently be -Y, wherein Y is a phenolic moiety which may be substituted at one or more sites with -OH or - (CH 2 ) X OH where x may be 1 - 5.
  • x will be 5, such that a six-membered "phenol” ring is formed.
  • sulphur-containing moiety is intended to cover any functional group which comprises sulphur.
  • the sulphur-containing moiety is selected from sulphates, sulphites, and sulfonic acids.
  • the sulphur-containing moiety may be selected from cysteamine, cysteine, sulphide, inorganic sulphite, inorganic thiosulphate (such as sodium thiosulphate), bisulphite, or thiocyanate.
  • sulphite or thiosulphate are present, such that optionally, Ri and R2 are independently -Y, wherein Y may be selected from sulphite or thiosulphate.
  • the sulphur containing triazine compounds are believed to be advantageous in reducing textile odour, as sulfonic acid acts to inhibit urease breakdown preventing the release of ammonia and the associated unpleasant smells.
  • sulfonic acid acts to inhibit urease breakdown preventing the release of ammonia and the associated unpleasant smells.
  • functionalities include bisulphite, sulfonic acid, or thiosulphate. Bisulphite functionalities have been found to be particularly effective in odour control due to an unexpected selective binding to urease.
  • Ri and R2 are -NR'R", and at least one of R' and R" may be selected from an alkyl, wherein the alkyl may be substituted with at least one acid selected from a carboxylic acid (such as ethanoic acid), phosphonic acid, and sulphonic acid. It is often the case that the at least one acid is phosphonic acid or carboxylic acid. It may be the case that the acid comprises more than one acid group, for instance the acid may be a chelator as described above with multiple acid groups, for instance it could be a diacid, such as maleic acid or glutamic acid, a tri-acid such as citric acid, or a tetra-acid such as EDTA.
  • Ri and R2 are -NR'R", and at least one of R' and R" may be selected from an alkyl, alkenyl or alkoxy, wherein the alkyl, alkenyl or alkoxy may be substituted with at least one conjugate base of an acid selected from a carboxylic acid (i.e. a carboxylate), phosphonic acid (i.e. phosphonate), and sulphonic acid (i.e. sulphonate), or sulphuric acid (i.e. sulphate).
  • a carboxylic acid i.e. a carboxylate
  • phosphonic acid i.e. phosphonate
  • sulphonic acid i.e. sulphonate
  • sulphuric acid i.e. sulphate
  • virus is intended to take its usual meaning and includes any infectious agent that is only capable of growth and multiplication in living cells. Without being bound by theory, it is believed that conjugate bases are able to complex with active functionalities in microbial and viral enzymes.
  • the at least one acid is phosphonic acid
  • the phosphonic acid is (aminomethyl)phosphonic acid.
  • textiles comprising triazine compounds of formula I or formula II, where at least one of Ri and R2 is -NR'R", and at least one of R' and R" is selected from an alkyl, wherein the alkyl may be substituted with an acid as defined above, and particularly phosphonic acid functionalities and phosphonic acid containing functionalities, display excellent flame retardant properties.
  • this chemical structure provides for the possibility of generating enhanced flame retardant textiles.
  • the sulphonic acid is aminoethanesulphonic acid (taurine).
  • taurine aminoethanesulphonic acid
  • the use of taurine provides for a textile fibre with good anti-odour properties, as it can selectively bind to urease, inhibiting urease breakdown, thereby reducing or preventing the release of ammonia and the associated unpleasant smells.
  • Ri and R2 are independently -NR'R", and at least one of R' and R" may be selected from an alkyl, wherein in the alkyl at least one carbon atom may be replaced with N, or wherein the alkyl is substituted with a straight or branched chain alkylpolyamine, wherein one or more of the carbons in the alkylpolyamine may be replaced by a heteroatom selected from N, O or S. It has been found that cellulosic fibres comprising triazine compounds of formula I or formula II, as described here, can provide for extremely high - often as high as 100% - dye exhaustion, and subsequently similarly high levels of dye fixation.
  • dye exhaustion is defined as the mass of the dye taken up by the material divided by the total initial mass of dye in the bath.
  • the protonation removes the need for high levels of sodium chloride to be present in the process, reducing costs as this additive is not needed in such high amounts, if at all, and providing a more environmentally friendly process than typical cellulosic dyeing processes, as salination of freshwater courses is reduced upon release of the wastewater from the dyeing process.
  • Ri and R2 are -NR'R", and at least one of R' and R" optionally selected from an alkyl, wherein the alkyl is substituted with a compound of formula I or formula II.
  • the substitution of the compound of formula I or formula II with a further compound of formula I or formula II provides for a strong retention of the desirable properties of, for instance, existing lyocell or viscose materials in terms of low fibrillation of the fibre, whilst providing for excellent dye retention, of up to 100% dye retention and fixation as described above.
  • the chains of compounds of formula I and/or II formed will be terminated with cellulosic material X, such that they are terminated with the cellulosic fibre forming component and in some senses encased therein.
  • the chains may comprise 1 - 5 compounds of formulae I and II.
  • R', R" and Y may independently be an alkyl, wherein in the alkyl at least two adjacent carbon atoms are replaced with O, such that a peroxide functionality is formed.
  • the alkyl comprises a peroxide group.
  • the cellulosic material comprises lyocell cellulose fibres, although viscose fibres are also often used.
  • Lyocell textiles are popular as they offer a consumer perception of comfort and softness, whilst providing the benefits of a natural cellulosic fibre.
  • lyocell production involves a closed loop production of cellulosic fibres from wood pulp, which not only reduces water consumption relative to other fabric production techniques, providing a more environmentally friendly solution to the provision of textiles to the end user.
  • a triazine compound of formula III or formula IV for use in dye fixation, the reduction of textile odour, for instance through the inhibition of urease breakdown or the provision of antimicrobial properties to fibres including the compounds, and/or as a flame retardant.
  • R' and R" are independently selected from H, alkyl having 1 to 18 carbons, alkoxy having 1 to 18 carbons, alkenyl having 2 to 18 carbons, wherein in the alkyl, alkoxy and alkenyl at least one carbon atom may be replaced with O, N, S, or combinations thereof; or wherein the alkyl, alkoxy or alkenyl may be substituted with at least one acid selected from carboxylic acid, phosphonic acid, and sulphonic acid, an amino acid moiety, a compound of formula I or formula II, and a straight or branched chain alkylpolyamine, wherein one or more of the carbons in the alkylpolyamine may be replaced by a heteroatom selected from N, O or S; or wherein R' and R" comprise a saturated or unsaturated cyclic moiety comprising 4, 5 or 6 carbons, wherein one or more of the carbons in the cyclic mo
  • a fourth aspect of the invention there is provided use of the triazine compound of the invention in dye fixation, the reduction of textile odour, for instance by the inhibition of urease breakdown or the provision of antimicrobial properties to fibres including the compounds, and/or to provide flame retardant properties.
  • a textile product, sanitary product or flame retardant textile comprising the triazine compound of the invention.
  • the textile product is generally a cellulosic product, often viscose or lyocell, most often lyocell.
  • Such products benefiting from the enhanced dyeing, in particular dye uptake and fixation, which is offered by selecting the functionalisation of the triazine compounds as described above, in particular by providing amine functionalities.
  • the sanitary product may be a nappy, sanitary towel, incontinence pad or similar, such products benefiting from reduced odour production either because of antimicrobial properties imbued to the textile fibres by virtue of the functionalisation of the compound of formula I and/or II (for instance peroxide), or because the functionalisation imparts the fibres containing the claimed compounds with the ability to inhibit urease breakdown, such that sweat or urine in contact with the textile do not release ammonia, and so the unpleasant smell associated with urease breakdown is either eliminated or greatly reduced.
  • the urease inhibition is particularly associated with glycine, taurine and thiosulphate, or chelator-functionalised polyamines, such as maleic acid polyethylene imine.
  • the flame retardant textile may be used in a wide variety of ways, including home and public space furnishings such as sofas, curtains, carpets, bedding, insulation to provide fire barriers etc. Such products benefit from improved flame retardancy when certain functionalities are present in the compounds of formulae I or II as described above. In particular aminomethylphosphonate. According to further aspects, there is provided an antimicrobial agent and antiviral agent comprising the triazine compound of the invention.
  • Figure 2 is a photograph of untreated Lyocell Axis A-100 (Figure 2a) and Lyocell Axis A- 100 treated with diethylene triamine ( Figure 2b) after treatment with 2% Remazol Brilliant Red 3B (2% o.m.f.) at 90°C for a period of 30 minutes (zero salt addition and neutral pH conditions).
  • Lyocell Axis A-100 supplied by Lenzing
  • TAHT 1,3,5-triacryloylhexahydro-s-triazine
  • Lupasol P ® supplied by BASF
  • Remazol Brilliant Red 3B ® (C.I. Reactive Red 23, supplied by DyStar) - sulphato- ethylsulphone reactive dye
  • Example 1 Preparation of Axis A100 Lyocell using 1,3,5-triacryloylhexahvdro-s-triazine (TAHT ’ )
  • TAHT is a tri-functional cross-linker that is commonly used to generate Lyocell Axis A- 100.
  • Lyocell Axis A-100 was produced by application of TAHT continuously to the Lyocell tow by a pad-steam process (J-Box) using an alkali mix of sodium hydroxide and tri sodium phosphate. If all three acryloyl residues in the TAHT undergo Michael addition with Cell-O , then the fully cross-linked cellulose has the structure X.
  • Example 2 Activation of Lyocell Axis A-100 by alkali catalysed b-elimination of cross- linked cellulose
  • Example 3 Dyeing Results of Lvocell A-100 with amines to deliver salt-free, 100% fixation reactive dve coloration
  • Lyocell Axis A-100 possessing some free acryloyl residues (scheme 1) was reacted following after-treatment with amines to form structures C and D according to the following scheme;
  • Example 5 Dve exhaustion and fixation efficiency of modified Lyocell A-100 fibre
  • Table 1 below indicates the dye exhaustion and total fixation efficiency are close to 100% for the modified Lyocell A-100 fibre, and significantly better than the dyeing of Lyocell Axis A-100 using the "eco-unfriendly" conventional dyeing process ("untreated"). This indicates that the combination of high dye fixation coupled to zero salt addition and neutral pH conditions offers significant economic and environmental benefits over current commercial cellulosic dyeing processes.
  • Lyocell Axis A-100 knitted fabric was treated (40 minutes, 20°C, pH 11.5) with a 2.5% w/w solution of diethylene triamine, ethanolamine or imidazole. The treated fabric was washed in running water to remove unreacted amine and then dried.
  • Lyocell Axis A-100 fabric was boiled for 1 hour in a 5% w/w sodium thiosulphate solution with pH adjusted to pH 5, the TAHT derivative electrophilic double bond adds to the nucleophilic sodium thiosulphate to form the Lyocell Axis A-100 Bunte salt modified fabric.
  • the pH of the treatment solution rose from 5 to 8 as the Bunte salt formation reaction proceeded
  • the performance of the modified lyocell fabric 5 was determined using a Limiting Oxygen Index Tester, Vertical Strip Flammability testing and Kawabata Evaluation System for Fabrics (Fabric handle).
  • the modified fabric showed evidence of reduced flammability.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Microbiology (AREA)
  • Emergency Medicine (AREA)
  • Manufacturing & Machinery (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

L'invention concerne un composé triazine de formule I ou de formule II : x comprenant un matériau cellulosique ; R1 et R2 étant indépendamment sélectionnés parmi -ONR'R', -NR'R'', ou -Y, R' et R'' étant indépendamment sélectionnés parmi H, un alkyle ayant 1 à 18 atomes de carbone, un alcoxy ayant 1 à 18 atomes de carbone, un alcényle ayant 2 à 18 atomes de carbone, au moins un atome de carbone pouvant être remplacé par O, N, S, ou des combinaisons de ceux-ci dans l'alkyle, l'alcoxy et l'alcényle ; ou l'alkyle, l'alcoxy ou l'alcényle pouvant être substitué par au moins un acide sélectionné parmi l'acide carboxylique, l'acide phosphonique, et l'acide sulfonique, une fraction acide aminé, un composé de formule I ou de formule II, et une alkylpolyamine à chaîne droite ou ramifiée, un ou plusieurs des carbones dans l'alkylpolyamine pouvant être remplacés par un hétéroatome choisi parmi N, O ou S ; ou R' et R'' comprennent une fraction cyclique saturée ou insaturée comprenant de 4 à 6 atomes de carbone, un ou plusieurs des carbones dans la fraction cyclique pouvant être remplacés par un hétéroatome sélectionné parmi N, O ou S ; et Y étant une fraction contenant du soufre sélectionnée parmi la cystéamine, la cystéine, le sulfure, le sulfite, le bisulfite et le thiosulfate, -S=C=N-, ou -N=C=S, un alkyle ayant 1 à 18 atomes de carbone, un alcoxy ayant 1 à 18 atomes de carbone, un alcényle ayant de 2 à 18 atomes de carbone, au moins un atome de carbone pouvant être remplacé par O, N, S ou des combinaisons de ceux-ci dans l'alkyle, l'alcoxy et l'alcényle, ou une fraction phénolique qui peut être substituée en un ou plusieurs sites avec – OH ou (CH2)xOH, x pouvant être de 1 à 5. L'invention concerne également des procédés de fabrication, des intermédiaires et leurs utilisations ; et un produit textile, un produit sanitaire et un textile ignifuge comprenant ledit composé de triazine.
PCT/GB2021/051937 2020-07-29 2021-07-28 Composés de triazine WO2022023736A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994009191A1 (fr) * 1992-10-21 1994-04-28 Courtaulds Fibres (Holdings) Limited Traitement de fibres
WO1995028516A1 (fr) * 1994-04-15 1995-10-26 Courtaulds Fibres (Holdings) Limited Traitement pour fibres

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1994009191A1 (fr) * 1992-10-21 1994-04-28 Courtaulds Fibres (Holdings) Limited Traitement de fibres
WO1995028516A1 (fr) * 1994-04-15 1995-10-26 Courtaulds Fibres (Holdings) Limited Traitement pour fibres

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RIM C ET AL: "Facile and efficient synthesis of star-shaped oligomers from a triazine core", TETRAHEDRON LETTERS, ELSEVIER, AMSTERDAM , NL, vol. 50, no. 28, 15 July 2009 (2009-07-15), pages 4161 - 4163, XP026158753, ISSN: 0040-4039, [retrieved on 20090505], DOI: 10.1016/J.TETLET.2009.04.132 *

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