WO2014009479A1 - Composés de stilbène - Google Patents

Composés de stilbène Download PDF

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Publication number
WO2014009479A1
WO2014009479A1 PCT/EP2013/064695 EP2013064695W WO2014009479A1 WO 2014009479 A1 WO2014009479 A1 WO 2014009479A1 EP 2013064695 W EP2013064695 W EP 2013064695W WO 2014009479 A1 WO2014009479 A1 WO 2014009479A1
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WO
WIPO (PCT)
Prior art keywords
formula
group
compounds
groups
branched
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Application number
PCT/EP2013/064695
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English (en)
Inventor
Carlo Seccomandi
Massimo FABBI
Ferruccio Berte'
Patrick ALBORGHETTI
Original Assignee
3V Sigma S.P.A.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 3V Sigma S.P.A. filed Critical 3V Sigma S.P.A.
Publication of WO2014009479A1 publication Critical patent/WO2014009479A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/614—Optical bleaching or brightening in aqueous solvents
    • D06L4/621—Optical bleaching or brightening in aqueous solvents with anionic brighteners

Definitions

  • the present invention relates to novel hydrated compounds of the tertiary alkanolamine salts of a specific compound based on 4,4'-di- triazinylamino-2,2'-disulphostilbene, characterised by their hydration water content, their crystalline forms, the preparation process of the novel hydrates, and the use of the novel hydrates for the preparation of concentrated aqueous formulations thereof.
  • whitening agents to impart a higher degree of whiteness to products like paper, cardboard, fabrics and non-woven fabrics.
  • the whitening agents most commonly used in the paper and cardboard industry are derivatives of 4,4'-bis-[l ,3,5-triazinyl]-diaminostilbene-2,2'- disulphonic acid, substituted at the triazine ring with anilino and alkanolamino groups.
  • the anilino groups can in turn contain other sulphonic groups, but as they increase the water solubility of the corresponding molecules, they reduce the affinity of said molecules for the cellulose fibres constituting paper, leading to lower performance in terms of whiteness.
  • said whitening agents to be supplied in the fluid liquid forms of an aqueous dispersion or, much more preferably, of aqueous solutions which are stable for at least a few months at temperatures ranging from 5 to 40°C.
  • stilbene whitening agents deriving from 4,4'-bis-[l ,3,5- triazinyl]-diaminostilbene-2,2'-disulphonic acid substituted at the triazine ring with anilino groups and alkanolamino groups which are preferred by this industry are not readily water-soluble, the production of the corresponding concentrated, stable aqueous solutions used to require the addition of significant amounts (up to 30% and over) of solubilising additives such as urea, caprolactam, ethylene glycol and polyglycols.
  • solubilisers added do not have great affinity for cellulose, and do not contribute significantly to the performance of the product, so that at the end of the paper manufacturing process, they constitute undesirable pollutants.
  • whitening agents in solution formulated with urea, a high additional pollutant content based on nitrogenous by-products and ammonia are present in the process liquid effluents.
  • a further problem derives from the inevitable presence in the whitening agent solutions of inorganic chlorides such as sodium chloride, which derive from the whitening agent synthesis processes.
  • inorganic chlorides such as sodium chloride
  • all industrial processes for the production of stilbene whitening agents substituted with triazine involve the use of cyanuryl chloride as reagent, whose reaction in successive steps with the various necessary amino products unavoidably gives rise to large amounts of inorganic chlorides which are difficult to remove.
  • US 3012971 discloses paper whitening compositions consisting of concentrated aqueous solutions of 4,4'-bis-[2-phenylamino-4-diethanolamino- l ,3,5-triazinyl]-diaminostilbene-2,2'-disulphonic acid or a salt thereof mixed with alkanolamines, wherein the weight ratio of the alkanolamines to the whitening agents ranges from 0.5: 1 to 3.0: 1. As the molecular weight of alkanolamines is much lower than that of the whitening agents, said interval reflects a great excess of alkanolamine over the whitening agent. However, such large amounts of alkanolamines, compared with the whitening power of the composition, are unacceptable from the ecological standpoint.
  • WO2005/028749 describes aqueous compositions comprising stilbene whitening agents and alkanolamines. Said document does not describe any example of a composition containing a tertiary alkanolamine. Moreover, the problem of the effect of inorganic chlorides on the stability of the solution is not mentioned.
  • US2010/0159763 discloses aqueous compositions of fluorescent whitening agents, substituted at the triazine rings with propionamide amino groups, having the following formula:
  • IT 1356016 discloses a fluorescent paper whitening method using substantially aqueous suspensions of the compound with the following formula:
  • M and Mi represent hydrogen, an alkali metal, an alkaline earth metal or ammonium.
  • X is an -HN + RiR 2 R 3 group wherein R R 2 and R 3 are selected from the group consisting of straight or branched Ci-C 6 alkyl groups, C 3 -C 6 cycloalkyl groups, straight or branched Ci-C 6 hydroxyalkyl groups and C 3 -C 6 hydroxycycloalkyl groups, and wherein at least one of R l 5 R 2 and R 3 is a straight or branched Ci-C 6 hydroxyalkyl group, and the number of moles of hydration water n is an integer from 1 to 80.
  • the compounds of the invention are able to produce concentrated, stable aqueous solutions useful to improve the whiteness of a high number of substrates, including textiles and paper. They can also be easily formulated in detergents so that they impart an improved degree of whiteness to the products washed.
  • the solutions obtainable are stable even in the presence of significant amounts of salts, especially sodium chloride. Said solutions are stable regardless of the presence of specific stabilisers or solubilisers.
  • This property allows the manufacturing process to be simplified by eliminating the final steps of purification of the whitening agent from salts, such as osmosis.
  • the hydrates according to the present invention comprise the compounds of formula (I):
  • R is hydrogen or the -CH 2 CH 2 OH group
  • X is an -HN + RiR 2 R 3 group wherein R R 2 and R 3 are selected from the group consisting of straight or branched Ci-C 6 alkyl groups, C 3 -C 6 cycloalkyl groups, straight or branched Ci-C 6 hydroxyalkyl groups and C 3 -C 6 hydroxycycloalkyl groups, and wherein at least one of R l 5 R 2 and R 3 is a straight or branched Ci-C 6 hydroxyalkyl group, and the number of moles of hydration water n is an integer from 1 to 80.
  • the compounds of formula (I) are preferably those wherein R is a -CH 2 CH 2 OH group.
  • the compounds of formula (I) are preferably hydrates of salts with 2-(dimethylamino)ethanol wherein X is HN + (CH 3 ) 2 (CH 2 CH 2 OH).
  • n is preferably an integer from 10 to 70, more preferably from 15 to 65.
  • the compounds of formula (I) are hydrates represented by the compounds of formula (II):
  • X is HN + (CH 3 ) 2 (CH 2 CH 2 OH) and n ranges from 15 to 80.
  • the compounds of the present invention can be prepared by reacting cyanuryl chloride with 4,4'-diamino stilbene disulphonic acid and aniline in succession in an aqueous medium, optionally combined with polar solvents such as acetone and/or methyl ethyl ketone, to obtain a compound of formula (III):
  • the compound of formula (III) is then reacted with at least 2 moles of diethanolamine or monoethanolamine, adjusting the pH between 9 and 12 with a suitable amount of bases such as sodium or potassium hydroxide, bicarbonate or carbonate.
  • bases such as sodium or potassium hydroxide, bicarbonate or carbonate.
  • the reaction mixture is heterogeneous, and when heated separates the sodium or potassium salt of the fluorescent whitening agent which is treated with a solution of strong acid, preferably hydrochloric or sulphuric acid, in an at least stoichiometric amount to the sulphonic groups present.
  • the result is the acid form of the fluorescent whitening agent.
  • the temperatures of said processes range from -20°C to 100°C and the pressures from 0 to 10 bars, more preferably from 0 to 3 bars.
  • the invention relates to a concentrated aqueous solution of the hydrates of the present invention, comprising:
  • the aqueous solution of the hydrates of the invention can also include a tertiary alkanolamine excess compared with the fluorescent whitening agent of formula (I). It is stable for a long time even in the absence of stabilising agents, and also in the presence of inorganic chlorides deriving from the manufacturing process of the stabilising agent.
  • the aqueous solutions of the hydrates of the invention can also include further ingredients such as further whitening agents, inorganic salts, surfactants, preservatives, solubilising agents or organic solvents.
  • optical whitening agents are optical tetra- and/or hexasulphonated stilbene brighteners.
  • inorganic salts are sodium chloride, sodium sulphate, ammonium chloride and potassium chloride.
  • surfactants are sodium polynaphthalene sulphonates and ethoxylated fatty alcohols.
  • preservatives examples include glutaraldehyde, isothiazolinones and 2-bromo-2-nitropropano- 1 ,3-diol.
  • solubilising agents are polyethylene glycols, urea and caprolactam.
  • organic solvents examples include ethylene and propylene glycols.
  • solutions containing the hydrates of the invention are obtained by dissolving the fluorescent agent of formula (I) and preferably the compound of formula (II) in water or a mixture of water and another solvent miscible with water, optionally subjecting the solution to heating and stirring.
  • solutions of the hydrates of the invention can be used to whiten natural, semisynthetic or synthetic fibres or paper.
  • solutions containing the hydrates of the invention are particularly effective in pulp slurry or mass treatment and surface treatment of paper and cardboard (size press and coating).
  • the hydrates of the invention can also be used in the formulation of detergents able to improve the whiteness of textiles and other products.
  • the invention will be illustrated by reference to the following examples.
  • the number of moles of hydration water "n" in formulae (I) and (II) of the compounds of the invention was determined by subtracting the value of the water content that freezes, obtainable with differential scanning calorimetry measurements, from the value of the total water content, obtainable by calculating the weight difference after drying, or by the Karl Fischer method.
  • the CIE whiteness (D65/10 0 ) of products treated with the hydrates of the invention was determined with an Elrepho LWE450-X Datacolor reflectometer according to standard ISO 1 1475.
  • the temperature was maintained at 80-85 °C under stirring until the solid was transformed into an oily organic phase.
  • the temperature was maintained at 80-85 °C under stirring until the solid was transformed to an oily organic phase.
  • aqueous solutions of the hydrates of examples 1 and 2 were evaluated applicatively on paper in pulp slurry, coating and size press and in a detergent, and compared with the results obtained with the same system in the absence of the compounds according to the present invention. In all cases the whiteness of the products obtained with the treatments in the presence of the hydrated compounds according to the present invention was much greater.
  • a fibrous mixture was prepared according to the following recipe:
  • PCC precipitated calcium carbonate
  • the application yield of the whitening agents is quantifiable as the increase in the whiteness of the paper compared with the reference whiteness.
  • Demineralised water up to a final dry residue of 70%.
  • each sample was applied to the backing paper with a laboratory doctor blade; at the end of the application the specimens were dried at ambient temperature for one hour.
  • the application yield of the whitening agents is quantifiable by the increase in the whiteness of the paper compared with the reference whiteness.
  • each sample was applied to the "Fabriano 2 smooth 1 10 g/m 2 " backing paper with a laboratory doctor blade; at the end of the application the specimens were dried at ambient temperature for one hour.
  • Example IB The sample of Example IB was formulated at the concentration of 0.52% (specific extinction 1 16) in a liquid detergent (heavy-duty liquid, table 4) designed for washing fabrics.
  • Table 4 composition of heavy-duty liquid
  • the detergent formulation was evaluated for whitening power conducting repeated washes on two different types of standard fabric:
  • the fabrics were repeatedly washed with the same formulation, assessing the degree of whitening power by reading the surface of the fabric on the colorimeter.
  • the colorimeter reading was performed before washing and after 3 and 5 consecutive washes.
  • Whitening power was expressed on the Berger scale.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)
  • Paper (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des hydrates de sels d'alcanolamine tertiaire de formule (I) : dans laquelle R représente hydrogène ou un groupe CH2CH2OH, X représente -HN+R1R2R3, R1, R2 et R3 étant sélectionnés dans le groupe constitué par les groupes C1-C6-alkyle linéaires ou ramifiés, les groupes C3-C6-cycloalkyle, les groupes C1-C6-hydroxyalkyle linéaires ou ramifiés et les groupes C3-C6-hydroxycycloalkyle, et au moins un parmi R1, R2 et R3 représentant un groupe C1-C6-hydroxyalkyle linéaire ou ramifié, et le nombre de moles d'eau d'hydratation n est un entier de 1 à 80. Les composés selon l'invention, en particulier leurs solutions aqueuses, sont utiles comme agents de blanchiment.
PCT/EP2013/064695 2012-07-12 2013-07-11 Composés de stilbène WO2014009479A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT001220A ITMI20121220A1 (it) 2012-07-12 2012-07-12 Composti stilbenici
ITMI2012A001220 2012-07-12

Publications (1)

Publication Number Publication Date
WO2014009479A1 true WO2014009479A1 (fr) 2014-01-16

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IT (1) ITMI20121220A1 (fr)
WO (1) WO2014009479A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016142955A1 (fr) 2015-03-10 2016-09-15 Deepak Nitrite Limited Solutions d'azurants optiques présentant une bonne stabilité au stockage
CN109776757A (zh) * 2019-01-15 2019-05-21 陕西科技大学 一种含二苯甲酮的纸张表面聚氨酯荧光增白乳液的制备方法及其应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3012971A (en) 1959-04-07 1961-12-12 Du Pont Whitening composition for paper
US6153122A (en) 1997-05-23 2000-11-28 Ciba Specialty Chemicals Corporation Triazinylaminostilbene compounds
WO2002055646A1 (fr) * 2001-01-10 2002-07-18 Clariant International Ltd Compositions d'azurants optiques, production et utilisation desdites compositions
WO2005028749A1 (fr) 2003-09-19 2005-03-31 Ciba Specialty Chemicals Holding Inc. Solutions aqueuses d'agents blanchissants fluorescents
WO2009074548A2 (fr) * 2007-12-12 2009-06-18 Clariant International Ltd Solutions d'azurants optiques stables au stockage
US20100159763A1 (en) 2005-08-04 2010-06-24 John Martin Farrar "Storage Stable Solutions of Optical Brighteners"

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3012971A (en) 1959-04-07 1961-12-12 Du Pont Whitening composition for paper
US6153122A (en) 1997-05-23 2000-11-28 Ciba Specialty Chemicals Corporation Triazinylaminostilbene compounds
WO2002055646A1 (fr) * 2001-01-10 2002-07-18 Clariant International Ltd Compositions d'azurants optiques, production et utilisation desdites compositions
WO2005028749A1 (fr) 2003-09-19 2005-03-31 Ciba Specialty Chemicals Holding Inc. Solutions aqueuses d'agents blanchissants fluorescents
US20100159763A1 (en) 2005-08-04 2010-06-24 John Martin Farrar "Storage Stable Solutions of Optical Brighteners"
WO2009074548A2 (fr) * 2007-12-12 2009-06-18 Clariant International Ltd Solutions d'azurants optiques stables au stockage

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016142955A1 (fr) 2015-03-10 2016-09-15 Deepak Nitrite Limited Solutions d'azurants optiques présentant une bonne stabilité au stockage
CN109776757A (zh) * 2019-01-15 2019-05-21 陕西科技大学 一种含二苯甲酮的纸张表面聚氨酯荧光增白乳液的制备方法及其应用
CN109776757B (zh) * 2019-01-15 2021-06-08 陕西科技大学 一种含二苯甲酮的纸张表面聚氨酯荧光增白乳液的制备方法及其应用

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