EP0564346A1 - Finishing of textiles with compositions containing phosphinicosuccinic acid, phosphinicobissuccinic acid or a mixture thereof - Google Patents

Finishing of textiles with compositions containing phosphinicosuccinic acid, phosphinicobissuccinic acid or a mixture thereof Download PDF

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Publication number
EP0564346A1
EP0564346A1 EP93400806A EP93400806A EP0564346A1 EP 0564346 A1 EP0564346 A1 EP 0564346A1 EP 93400806 A EP93400806 A EP 93400806A EP 93400806 A EP93400806 A EP 93400806A EP 0564346 A1 EP0564346 A1 EP 0564346A1
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Prior art keywords
acid
phosphinicobissuccinic
phosphinicosuccinic
textile
finishing
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EP93400806A
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German (de)
French (fr)
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EP0564346B1 (en
Inventor
Didier Wilhelm
Antonio Gelabert
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Clariant Finance BVI Ltd
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Francaise Hoechst Ste
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244Treating 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 sulfur or phosphorus
    • D06M13/282Treating 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 sulfur or phosphorus with compounds containing phosphorus
    • D06M13/285Phosphines; Phosphine oxides; Phosphine sulfides; Phosphinic or phosphinous acids or derivatives thereof
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2369Coating or impregnation improves elasticity, bendability, resiliency, flexibility, or shape retention of the fabric
    • Y10T442/2393Coating or impregnation provides crease-resistance or wash and wear characteristics

Definitions

  • the present invention relates to a fabric finishing process, a fabric finishing bath using phosphinicosuccinic acid, phosphinicobissuccinic acid or mixtures thereof, finished textiles and the use of said acids as finishes.
  • Textile finishes are currently commonly used to impart wrinkle-resistant properties to cellulosic fabrics, but most contain free or combined formaldehyde, which is released either in the sizing workshops, or when the fabrics so finished are used.
  • Phosphinicosuccinic acid (I) as well as phosphinicobissuccinic acid (II) are described in the literature (United States patent No. 5018577). They are obtained in particular by adding an alkali metal hypophosphite such as sodium hypophosphite to maleic acid, a dialkyl maleate or maleic anhydride followed, if necessary, by acid or basic hydrolysis of the ester functions, when a dialkyl maleate is used as the starting product.
  • This addition reaction is generally catalyzed with a mineral peroxide derivative such as sodium persulfate, or an organic derivative such as 2-ethyl tert-butyl perhexanoate, TBPEH; it can also be carried out under ultraviolet radiation within acetone (French patent No. 2,356,658, United States patents 4138431, 4590014, 4632741, 5023000, 5018577, 4088678 and Beil. IV, 4th supplement, page 3497, 1959).
  • a mineral peroxide derivative such as sodium persulfate
  • organic derivative such as 2-ethyl tert-butyl perhexanoate
  • Phosphinicosuccinic acid (I) and phosphinicobissuccinic acid (II), as well as their mixtures in variable proportions, have, as has been said previously, very interesting properties of crosslinking of cellulose, which justify their application as 'textile finishes, to give cellulosic fabrics wrinkle-resistant properties.
  • the present invention therefore relates to a process for finishing textiles, characterized in that the textile to be treated is impregnated using a finishing bath comprising phosphinicosuccinic acid (I), acid phosphinicobissuccinic (II), or a mixture of these two acids. This mixture can be in variable proportions.
  • the textile dressing bath is partially neutralized with an alkali metal hydroxide in order to obtain a dressing bath having a pH of 2 to 7.
  • the finishes described above are characterized in that they do not contain any catalyst of any kind.
  • the present application also relates to a finishing bath for textiles, characterized in that it comprises a solution of phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II), or their mixture partially neutralized at pH 2 at 7 using an alkali metal hydroxide, and in particular the baths described in the examples.
  • a finishing bath for textiles characterized in that it comprises a solution of phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II), or their mixture partially neutralized at pH 2 at 7 using an alkali metal hydroxide, and in particular the baths described in the examples.
  • the above solutions are preferably aqueous solutions; they are advantageously added with a wetting agent well known from the state of the art.
  • the present application also relates to finished textiles, characterized in that they are obtained by the implementation of the process described above.
  • the present application also relates to the use, as a textile finish, of phosphinicosuccinic acid (I), of phosphinicobissuccinic acid (II), or of a mixture thereof.
  • the present application finally relates to the use of phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II) or their mixtures in variable proportions, as crosslinking agents for the cellulose contained in particular in fibers textiles, wood chips, sawdust.
  • the wrinkle test is carried out according to the AATCC 66-1972 standard on samples as they are and on samples subjected to three household washes at 60 ° C; the crease resistance is expressed by the sum of the crease angles obtained in warp direction and in weft direction.
  • the tensile strength of the samples expressed in daN in the warp direction plus in the weft direction is produced according to standard AFNOR G 07.001.
  • the yellowing of the tissues carried out on a FIXOTEST device at 200 ° C for 30 seconds and the whiteness expressed in Berger degrees, are measured with a spectrophotometer.
  • the residual formaldehyde level on tissue was determined according to the method described in Japanese law 112-1973; in the fabrics of the examples, no formaldehyde could be detected.
  • This product dosed by potentiometry, contains 15.49 meq / g of acid functions, of which 2.756 meq / g of strong acid functions, or a ratio between carboxylic acid function and phosphinic acid function of 4.62: 1 (theory 4: 1).
  • a 100% cotton poplin fabric, scalded and bleached, is impregnated with the scarf, weighing approximately 130 g per square meter with a rate of expression of 75% in an aqueous bath, the pH of which has been adjusted with soda at the value indicated in table I, containing in solution the quantities of acid, as well as 2 g per liter of ethoxylated nonylphenol with 10 moles of ethylene oxide as wetting agent.
  • the fabric is then dried for 45 seconds at 120 ° C, then it is subjected on a laboratory oar to a heat treatment for 90 seconds at 180 ° C.
  • Comparison example C1 corresponds to the untreated tissue.
  • Example 5 is repeated, replacing the sodium persulfate with an equivalent quantity of ammonium persulfate. This gives about 1464 g of a clear, colorless aqueous solution containing about 2.5 moles of phosphinicobissuccinic acid monosodium, having an acidity of 6.96 meq / g (theory 6.83 meq / g) and no longer containing maleic anhydride determined by NMR analysis of the proton and carbon thirteen.
  • This solution, designated E is used in this form in Example 9.

Abstract

Process for finishing a textile in which the textile to be treated is impregnated using a finishing bath containing phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II) or a mixture of phosphinicosuccinic acid (I) and phosphinico-bissuccinic acid (II), finishing bath, finished textile and use of previously-mentioned acids as textile finishes or as cross-linking agents for cellulose.

Description

La présente invention concerne un procédé d'apprêtage de textiles, un bain d'apprêtage pour textiles utilisant de l'acide phosphinicosuccinique, de l'acide phosphinicobissuccinique ou leurs mélanges, des textiles apprêtés et l'utilisation desdits acides comme apprêts.The present invention relates to a fabric finishing process, a fabric finishing bath using phosphinicosuccinic acid, phosphinicobissuccinic acid or mixtures thereof, finished textiles and the use of said acids as finishes.

Les apprêts textiles sont actuellement couramment utilisés pour conférer aux tissus cellulosiques des propriétés d'infroissabilité, mais la plupart contiennent du formaldéhyde libre ou combiné, qui se libère soit dans les ateliers d'apprêtage, soit lors de l'utilisation des tissus ainsi apprêtés.Textile finishes are currently commonly used to impart wrinkle-resistant properties to cellulosic fabrics, but most contain free or combined formaldehyde, which is released either in the sizing workshops, or when the fabrics so finished are used.

Or, le formaldéhyde est aujourd'hui considéré comme un produit nocif dont certaines réglementations nationales limitent les doses d'exposition à de très faibles valeurs. On recherche donc activement des apprêts textiles exempts de toute trace de formaldéhyde. Au cours de ces recherches, la demanderesse a découvert avec étonnement, que l'acide phosphinicosuccinique (I) et l'acide phosphinicobissuccinique (II) présentent de très intéressantes propriétés de réticulation de la cellulose, justifiant leur utilisation comme apprêt textile.

Figure imgb0001
However, formaldehyde is today considered to be a harmful product for which certain national regulations limit the exposure doses to very low values. So we are actively looking for textile finishes free of any trace of formaldehyde. During this research, the Applicant discovered with astonishment, that phosphinicosuccinic acid (I) and phosphinicobissuccinic acid (II) have very interesting properties of crosslinking of cellulose, justifying their use as a textile finish.
Figure imgb0001

L'acide phosphinicosuccinique (I) ainsi que l'acide phosphinicobissuccinique (II) sont décrits dans la littérature (brevet des Etats Unis d'Amérique N°5018577). Ils sont notamment obtenus par addition d'un hypophosphite de métal alcalin tel que l'hypophosphite de sodium sur l'acide maléique, un maléate de dialkyle ou l'anhydride maléique suivie, si nécessaire, d'une hydrolyse acide ou basique des fonctions esters, lorsqu'un maléate de dialkyle est utilisé comme produit de départ. Cette réaction d'addition est généralement catalysée avec un dérivé péroxydique minéral tel que le persulfate de sodium, ou organique tel que l'éthyl-2 perhexanoate de tertiobutyle, TBPEH ; elle peut être également effectuée sous un rayonnement ultraviolet au sein de l'acétone (brevet français N° 2356658, brevets des Etats Unis d'Amérique 4138431, 4590014, 4632741, 5023000, 5018577, 4088678 et Beil. IV, 4ème suppl., page 3497, 1959).Phosphinicosuccinic acid (I) as well as phosphinicobissuccinic acid (II) are described in the literature (United States patent No. 5018577). They are obtained in particular by adding an alkali metal hypophosphite such as sodium hypophosphite to maleic acid, a dialkyl maleate or maleic anhydride followed, if necessary, by acid or basic hydrolysis of the ester functions, when a dialkyl maleate is used as the starting product. This addition reaction is generally catalyzed with a mineral peroxide derivative such as sodium persulfate, or an organic derivative such as 2-ethyl tert-butyl perhexanoate, TBPEH; it can also be carried out under ultraviolet radiation within acetone (French patent No. 2,356,658, United States patents 4138431, 4590014, 4632741, 5023000, 5018577, 4088678 and Beil. IV, 4th supplement, page 3497, 1959).

L'acide phosphinicosuccinique (I) et l'acide phosphinicobissuccinique (II), ainsi que leurs mélanges en proportions variables, présentent comme on l'a dit précédemment, de très intéressantes propriétés de réticulation de la cellulose, qui justifient leur application à titre d'apprêts textiles, pour donner aux tissus cellulosiques des propriétés d'infroissabilité.Phosphinicosuccinic acid (I) and phosphinicobissuccinic acid (II), as well as their mixtures in variable proportions, have, as has been said previously, very interesting properties of crosslinking of cellulose, which justify their application as 'textile finishes, to give cellulosic fabrics wrinkle-resistant properties.

La présente invention a donc pour objet un procédé pour apprêter les textiles caractérisé en ce que l'on imprègne le textile à traiter à l'aide d'un bain d'apprêtage comprenant de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II), ou un mélange de ces deux acides. Ce mélange peut être en proportions variables.The present invention therefore relates to a process for finishing textiles, characterized in that the textile to be treated is impregnated using a finishing bath comprising phosphinicosuccinic acid (I), acid phosphinicobissuccinic (II), or a mixture of these two acids. This mixture can be in variable proportions.

Dans des conditions préférentielles de mise en oeuvre de l'invention, le bain apprêtage des textiles est partiellement neutralisé avec un hydroxyde de métal alcalin afin d'obtenir un bain d'apprêtage présentant un pH de 2 à 7.Under preferential conditions for implementing the invention, the textile dressing bath is partially neutralized with an alkali metal hydroxide in order to obtain a dressing bath having a pH of 2 to 7.

Dans d'autres conditions préférentielles, les apprêts ci-dessus décrits sont caractérisés en ce qu'il ne renferment pas de catalyseur, de quelque nature que ce soit.In other preferential conditions, the finishes described above are characterized in that they do not contain any catalyst of any kind.

La présente demande a aussi pour objet un bain d'apprêtage pour textiles, caractérisé en ce qu'il comprend une solution d'acide phosphinicosuccinique (I), d'acide phosphinicobissuccinique (II), ou de leur mélange partiellement neutralisé à pH 2 à 7 à l'aide d'un hydroxyde de métal alcalin, et notamment les bains décrits dans les exemples.The present application also relates to a finishing bath for textiles, characterized in that it comprises a solution of phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II), or their mixture partially neutralized at pH 2 at 7 using an alkali metal hydroxide, and in particular the baths described in the examples.

Les solutions ci-dessus sont de préférence des solutions aqueuses ; elles sont avantageusement additionnées d'un agent mouillant bien connu de l'état de la technique.The above solutions are preferably aqueous solutions; they are advantageously added with a wetting agent well known from the state of the art.

La présente demande a aussi pour objet les textiles apprêtés, caractérisés en ce qu'ils sont obtenus par la mise en oeuvre du procédé ci-dessus décrit.The present application also relates to finished textiles, characterized in that they are obtained by the implementation of the process described above.

La présente demande a aussi pour objet l'utilisation, à titre d'apprêt textile, de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II), ou d'un de leurs mélanges.The present application also relates to the use, as a textile finish, of phosphinicosuccinic acid (I), of phosphinicobissuccinic acid (II), or of a mixture thereof.

La présente demande a enfin pour objet l'utilisation de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II) ou de leurs mélanges en proportions variables, à titre d'agents de réticulation de la cellulose contenue notamment dans des fibres textiles, des copeaux de bois, de la sciure de bois.The present application finally relates to the use of phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II) or their mixtures in variable proportions, as crosslinking agents for the cellulose contained in particular in fibers textiles, wood chips, sawdust.

Les exemples suivants sont donnés à titre indicatif ; ils permettent de mieux comprendre l'invention, mais ils n'en limitent pas la portée. Sauf indications contraires, les parties et pourcentages sont donnés en poids. Le test de défroissabilité est réalisé selon la norme AATCC 66-1972 sur des échantillons tels quels et sur des échantillons soumis à trois lavages ménagers à 60°C ; la défroissabilité est exprimée par la somme des angles de défroissement obtenus en sens chaîne et en sens trame. La résistance à la traction des échantillons exprimée en daN en sens chaîne plus en sens trame est réalisée selon la norme AFNOR G 07.001. Le jaunissement des tissus, réalisé sur un appareil FIXOTEST à 200°C pendant 30 secondes et les blancheurs exprimées en degrés Berger, sont mesurés avec un spectrophotomètre. Le taux de formaldéhyde résiduel sur tissu a été déterminé selon la méthode décrite dans la loi japonaise 112-1973 ; dans les tissus des exemples, on n'a pas pu déceler de formaldéhyde.The following examples are given for information only; they allow a better understanding of the invention, but they do not limit its scope. Unless otherwise indicated, parts and percentages are given by weight. The wrinkle test is carried out according to the AATCC 66-1972 standard on samples as they are and on samples subjected to three household washes at 60 ° C; the crease resistance is expressed by the sum of the crease angles obtained in warp direction and in weft direction. The tensile strength of the samples expressed in daN in the warp direction plus in the weft direction is produced according to standard AFNOR G 07.001. The yellowing of the tissues, carried out on a FIXOTEST device at 200 ° C for 30 seconds and the whiteness expressed in Berger degrees, are measured with a spectrophotometer. The residual formaldehyde level on tissue was determined according to the method described in Japanese law 112-1973; in the fabrics of the examples, no formaldehyde could be detected.

EXEMPLE 1EXAMPLE 1

On introduit goutte à goutte, en 150 minutes, sous agitation, une solution constituée par :

  • 150 g (1 mole) de maléate de diméthyle à 96%,
  • 2 g (9,2 mmoles) d'éthyl-2 perhexanoate de tertiobutyle,
  • 99 g d'éthanol absolu,

dans une solution maintenue à 80°C et constituée par :
  • 44 g (0,485 mole) d'hypophosphite de sodium à 97%,
  • 60 g d'eau distillée,
  • 99 g d'éthanol absolu,

puis on abandonne le milieu réactionnel deux heures sous agitation à 80°C. La solution réactionnelle est ensuite concentrée à 80% environ sous pression réduite, puis elle est diluée avec 300 g d'eau et enfin, elle est lavée 2 fois avec 150 g d'oxyde de diéthyle, et les phases éthérées réunies sont lavées une fois avec 50 g d'eau. Les phases aqueuses sont ensuite réunies puis concentrées à sec sous pression réduite. On obtient ainsi 197,2 g d'une pâte visqueuse contenant principalement le sel de sodium de l'acide phosphinicobissuccinate de diméthyle (environ 95%) et les traces d'hypophosphite de sodium et du sel de sodium de l'acide phosphinicosuccinate de diméthyle.A solution consisting of: dropwise introduced over 150 minutes, with stirring
  • 150 g (1 mole) of 96% dimethyl maleate,
  • 2 g (9.2 mmol) of 2-ethyl tert-butyl perhexanoate,
  • 99 g of absolute ethanol,

in a solution maintained at 80 ° C and consisting of:
  • 44 g (0.485 mole) 97% sodium hypophosphite,
  • 60 g of distilled water,
  • 99 g of absolute ethanol,

then the reaction medium is left for two hours with stirring at 80 ° C. The reaction solution is then concentrated to approximately 80% under reduced pressure, then it is diluted with 300 g of water and finally, it is washed twice with 150 g of diethyl ether, and the combined ethereal phases are washed once with 50 g of water. The aqueous phases are then combined and then concentrated to dryness under reduced pressure. This gives 197.2 g of a viscous paste containing mainly the sodium salt of dimethyl phosphinicobissuccinate acid (about 95%) and the traces of sodium hypophosphite and the sodium salt of dimethyl phosphinicosuccinate acid .

Ce produit est ensuite chauffé à l'ébullition dans 555 g d'eau distillée et 216 g d'acide chlorhydrique concentré, d = 1,19, tout en éliminant le méthanol formé par distillation. Après 5 heures de chauffage, il n'y a plus de formation de méthanol, le milieu réactionnel est alors concentré à sec, sous pression réduite. On obtient ainsi 185 g d'une pâte visqueuse que l'on dissout à chaud dans 350 g d'acide acétique. La solution chaude ainsi obtenue est traitée avec 1 g de charbon actif, puis elle est filtrée et ensuite concentrée à sec sous pression réduite. On obtient ainsi 143,7 g d'un produit cristallisé blanc, soit un rendement de 99,4% de la théorie calculée par rapport à l'hypophosphite de sodium mis en oeuvre. Ce produit, dosé par potentiométrie, contient 15,49 meq/g de fonctions acides dont 2,756 meq/g de fonctions acides fortes, soit un rapport entre fonction acide carboxylique et fonction acide phosphinique de 4,62:1 (théorie 4:1).This product is then heated to boiling in 555 g of distilled water and 216 g of concentrated hydrochloric acid, d = 1.19, while removing the methanol formed by distillation. After 5 hours of heating, there is no more methanol formation, the reaction medium is then concentrated to dryness, under reduced pressure. 185 g of a viscous paste are thus obtained which are dissolved hot in 350 g of acetic acid. The hot solution thus obtained is treated with 1 g of activated carbon, then it is filtered and then concentrated to dryness under reduced pressure. 143.7 g of a white crystallized product are thus obtained, ie a yield of 99.4% of the theory calculated relative to the sodium hypophosphite used. This product, dosed by potentiometry, contains 15.49 meq / g of acid functions, of which 2.756 meq / g of strong acid functions, or a ratio between carboxylic acid function and phosphinic acid function of 4.62: 1 (theory 4: 1).

Ces contrôles montrent que la fonction acide phosphinique est partiellement salifiée avec du sodium. Ce produit est alors traité en solution dans 1 kg d'eau distillée à la température ambiante, pendant 1 heure, avec 350 ml d'une résine échangeuse de cations sous forme acide, présentant une capacité totale d'échange de 1,4 meq par ml, puis la suspension est filtré et le filtrat est concentré à sec sous pression réduite. On obtient ainsi 135 g de produit cristallisé blanc contenant 16,28 meq/g de fonctions acides (théorie 16,77 meq/g) dont 3,39 meq/g de fonctions acides présentant un pk inférieur ou égal à 1,6 (théorie 3, 35). Ce produit contient environ 97% d'acide phosphinicobissuccinique (II), il est utilisé sous cette forme en application sous la référence A ; RMN¹³C(D₂O), 25 MHz, γ 32,1 (s, CH₂), γ 32,9 (s, CH₂), γ 45,7 (d, J = 82 Hz, CH), γ 175 (2d, J = 4 Hz, CH-COOH), γ 177,4 (dd, J = 16 Hz, CH₂-COOH).These checks show that the phosphinic acid function is partially salified with sodium. This product is then treated in solution in 1 kg of distilled water at room temperature, for 1 hour, with 350 ml of a cation exchange resin in acid form, having a total exchange capacity of 1.4 meq per ml, then the suspension is filtered and the filtrate is concentrated to dryness under reduced pressure. 135 g of white crystallized product are thus obtained containing 16.28 meq / g of acid functions (theory 16.77 meq / g) of which 3.39 meq / g of acid functions having a pk less than or equal to 1.6 (theory 3, 35). This product contains approximately 97% phosphinicobissuccinic acid (II), it is used in this form in application under the reference A; RMN¹³C (D₂O), 25 MHz, γ 32.1 (s, CH₂), γ 32.9 (s, CH₂), γ 45.7 (d, J = 82 Hz, CH), γ 175 (2d, J = 4 Hz, CH- C OOH), γ 177.4 (dd, J = 16 Hz, CH₂- C OOH).

EXEMPLE 2EXAMPLE 2

On introduit goutte à goutte, sous agitation, une solution constituée par :

  • 75 g (500 mmoles) de maléate de diméthyle à 96%,
  • 2 g (9,2 mmoles) d'éthyl-2 perhexanoate de tertiobutyle,
  • 99 d'éthanol absolu,

dans une solution maintenue à 80°C et constituée par :
  • 59 g d'eau distillée,
  • 44 g (485 mmoles) d'hypophosphite de sodium à 97%,
  • 99 g d'éthanol absolu,

puis on abandonne la solution réactionnelle 3 heures à 80°C sous agitation avant de la concentrer à sec sous pression réduite. Le résidu solide ainsi obtenu, dissous dans 250 g d'eau est lavé deux fois avec 150g d'oxyde de diéthyle, puis les phases éthérées réunies sont lavées un fois avec 50 g d'eau distillée. Les phases aqueuses réunies sont ensuite concentrées à sec sous pression réduite. On obtient ainsi 118,4 g d'une pâte visqueuse que l'on dissout dans 600 g d'eau distillée. Cette solution est ensuite chauffée à l'ébullition en présence de 142 g d'acide chlorhydrique concentré, d = 1,19, tout en distillant le méthanol formé. Après 5 heures de chauffage au reflux, il ne se forme plus de méthanol. Le milieu réactionnel est alors concentré à sec sous pression réduite. On obtient 125 g de produit que l'on dissout dans 185 g d'acide acétique à chaud. Cette solution abandonne par refroidissement à la température ambiante, 6,9 g (58,5 mmoles) d'acide succinique cristallisé pur. Le filtrat obtenu après séparation de ce produit cristallisé, est concentré à sec sous pression réduite. On obtient ainsi 91 g d'un produit visqueux dont l'analyse par RMN du proton montre qu'il est constitué par un mélange en quantité sensiblement équimoléculaire d'acide succinique, d'acide phosphinicobissuccinique (II), et d'acide phosphinicosuccinique (I) RMN¹³C (D₂O), 25 MHz, γ 31,2 (s, CH₂), γ 46,9 (d, J = 77 Hz, CH), γ 174,8 (s, CH-COOH), γ 177,3 (d, J = 16 Hz, CH₂-COOH). Par dosage potentiométrique, on trouve 16,58 meq/g de fonctions acides, dont 4,56 meq/g de fonctions acides présentant un pk inférieur ou égal à 1,8. Ce produit est utilisé sous cette forme en application, sous la référence B.A solution consisting of:
  • 75 g (500 mmol) of 96% dimethyl maleate,
  • 2 g (9.2 mmol) of 2-ethyl tert-butyl perhexanoate,
  • 99 of absolute ethanol,

in a solution maintained at 80 ° C and consisting of:
  • 59 g of distilled water,
  • 44 g (485 mmol) 97% sodium hypophosphite,
  • 99 g of absolute ethanol,

then the reaction solution is left for 3 hours at 80 ° C. with stirring before concentrating to dryness under reduced pressure. The solid residue thus obtained, dissolved in 250 g of water is washed twice with 150 g of diethyl ether, then the combined ethereal phases are washed once with 50 g of distilled water. The combined aqueous phases are then concentrated to dryness under reduced pressure. We thus obtain 118.4 g of a viscous paste which is dissolved in 600 g of distilled water. This solution is then heated to boiling in the presence of 142 g of concentrated hydrochloric acid, d = 1.19, while distilling off the methanol formed. After 5 hours of heating at reflux, methanol is no longer formed. The reaction medium is then concentrated to dryness under reduced pressure. 125 g of product are obtained which is dissolved in 185 g of hot acetic acid. This solution leaves, by cooling to room temperature, 6.9 g (58.5 mmol) of pure crystalline succinic acid. The filtrate obtained after separation of this crystallized product is concentrated to dryness under reduced pressure. 91 g of a viscous product are thus obtained, the analysis of which by proton NMR shows that it consists of a mixture in substantially equimolecular amount of succinic acid, phosphinicobissuccinic acid (II), and phosphinicosuccinic acid ( I) RMN¹³C (D₂O), 25 MHz, γ 31.2 (s, CH₂), γ 46.9 (d, J = 77 Hz, CH), γ 174.8 (s, CH- C OOH), γ 177 , 3 (d, J = 16 Hz, CH₂- C OOH). By potentiometric determination, there are 16.58 meq / g of acid functions, of which 4.56 meq / g of acid functions having a pk less than or equal to 1.8. This product is used in this form in application, under the reference B.

EXEMPLES 3 ET 4 ET EXEMPLE DE COMPARAISON C1EXAMPLES 3 AND 4 AND EXAMPLE OF COMPARISON C1

On imprègne au foulard un tissu de popeline 100% coton, débouilli et blanchi, d'un poids d'environ 130 g par mètre carré avec un taux d'exprimage de 75% dans un bain aqueux dont le pH a été ajusté avec de la soude à la valeur indiquée dans le tableau I, contenant en solution les quantités d'acide, ainsi que 2 g par litre de nonylphénol éthoxylé avec 10 moles d'oxyde d'éthylène comme agent mouillant. Le tissu est ensuite séché pendant 45 secondes à 120°C, puis il est soumis sur une rame de laboratoire à un traitement thermique de 90 secondes à 180°C.A 100% cotton poplin fabric, scalded and bleached, is impregnated with the scarf, weighing approximately 130 g per square meter with a rate of expression of 75% in an aqueous bath, the pH of which has been adjusted with soda at the value indicated in table I, containing in solution the quantities of acid, as well as 2 g per liter of ethoxylated nonylphenol with 10 moles of ethylene oxide as wetting agent. The fabric is then dried for 45 seconds at 120 ° C, then it is subjected on a laboratory oar to a heat treatment for 90 seconds at 180 ° C.

On détermine ensuite sur des échantillons du tissu traité après conditionnement :

  • la défroissabilité sur des échantillons tels quels et sur des échantillons soumis à trois lavages ménagers à 60°C,
  • la résistance à la traction, désignée Rt, exprimée en daN,
  • la blancheur, désignée Bl, exprimée en degrés Berger,
  • le jaunissement, désigné Ja,

les résultats obtenus sont données dans le tableau I.It is then determined on samples of the fabric treated after conditioning:
  • wrinkle resistance on samples as is and on samples subjected to three household washes at 60 ° C,
  • the tensile strength, designated Rt, expressed in daN,
  • whiteness, designated Bl, expressed in Berger degrees,
  • yellowing, designated Ja,

the results obtained are given in table I.

L'exemple de comparaison C1 correspond au tissu non traité.Comparison example C1 corresponds to the untreated tissue.

On constate que les produits selon la présente invention améliorent considérablement les qualités d'infroissabilité des tissus traités même après lavage, sans pour autant abaisser trop nettement leur résistance à la traction.It is found that the products according to the present invention considerably improve the wrinkle-resistant qualities of the treated fabrics even after washing, without however reducing their tensile strength too clearly.

EXEMPLE 5EXAMPLE 5

On mélange sous agitation, à la température ambiante, 625 g d'eau distillée, et 490,3 g (5 moles) d'anhydride maléique. La suspension obtenue est chauffée à 60°c jusqu'à l'obtention d'une solution. On introduit alors 220 g (2,5 moles) d'hypophosphite de sodium, puis en 5 heures, en maintenant l'agitation et la température à 60°C, une solution de 45,2 g (0,19 mole) de persulfate de sodium dans 78 g d'eau distillée. L'introduction terminée, on maintient la solution réactionnelle deux heures à 60°C puis on la refroidit à la température ambiante.625 g of distilled water and 490.3 g (5 moles) of maleic anhydride are mixed with stirring at room temperature. The suspension obtained is heated to 60 ° C. until a solution is obtained. Then introduced 220 g (2.5 moles) of sodium hypophosphite, then in 5 hours, maintaining stirring and temperature at 60 ° C, a solution of 45.2 g (0.19 mole) of persulfate sodium in 78 g of distilled water. When the introduction is complete, the reaction solution is kept for two hours at 60 ° C. and then cooled to ambient temperature.

On obtient ainsi 1435 g d'une solution aqueuse limpide, légèrement colorée, contenant environ 2,5 moles d'acide phophinicobissuccinique monosodique, présentant une acidité de 7,0 meq/g (théorie 6,97 meq/g)et ne contenant plus d'anhydride maléique. Cette solution, désignée D, est utilisée sous cette forme dans l'exemple 8.1435 g of a clear, slightly colored aqueous solution are thus obtained, containing approximately 2.5 moles of phosinicobissuccinic monosodium acid, having an acidity of 7.0 meq / g (theory 6.97 meq / g) and no longer containing maleic anhydride. This solution, designated D, is used in this form in Example 8.

EXEMPLE 6EXAMPLE 6

On reproduit l'exemple 5 en remplaçant le persulfate de sodium par une quantité équivalente de persulfate d'ammonium. On obtient ainsi environ 1464 g d'une solution aqueuse, limpide, incolore, contenant environ 2,5 moles d'acide phosphinicobissuccinique monosodique, présentant une acidité de 6,96 meq/g (théorie 6,83 meq/g) et ne contenant plus d'anhydride maléique déterminée par l'analyse RMN du proton et du carbone treize. Cette solution désignée E, est utilisée sous cette forme dans l'exemple 9.Example 5 is repeated, replacing the sodium persulfate with an equivalent quantity of ammonium persulfate. This gives about 1464 g of a clear, colorless aqueous solution containing about 2.5 moles of phosphinicobissuccinic acid monosodium, having an acidity of 6.96 meq / g (theory 6.83 meq / g) and no longer containing maleic anhydride determined by NMR analysis of the proton and carbon thirteen. This solution, designated E, is used in this form in Example 9.

EXEMPLE 7EXAMPLE 7

On mélange sous agitation, à la température ambiante, 763 g d'eau distillée et 327,5 g (3,34 moles) d'anhydride maléique. La suspension obtenue est ensuite chauffée à 60°C jusqu'à l'obtention d'une solution. En maintenant l'agitation et la température de la solution à 60°C, on introduit en 3 heures, séparément et simultanément, d'une part une solution de 28,6 g (0,12 mole) de persulfate de sodium dans 52 g d'eau distillée, et d'autre part, une solution de 147 g (1,67 mole) d'hypophosphite de sodium dissous dans 300 g d'eau distillée. Les introductions terminées, on abandonne la solution réactionnelle deux heures à 60°C.763 g of distilled water and 327.5 g (3.34 moles) of maleic anhydride are mixed with stirring at room temperature. The suspension obtained is then heated to 60 ° C until a solution is obtained. Maintaining the stirring and the temperature of the solution at 60 ° C., a solution of 28.6 g (0.12 mole) of sodium persulfate in 52 g is introduced over 3 hours, separately and simultaneously distilled water, and on the other hand, a solution of 147 g (1.67 mole) of sodium hypophosphite dissolved in 300 g of distilled water. Once the introductions are complete, the reaction solution is left for two hours at 60 ° C.

Après refroidissement à la température ambiante, on obtient environ 1618 g environ d'une solution aqueuse limpide et incolore, contenant environ 1,67 mole d'acide phosphinicobissuccinique monosodique et ne contenant plus d'anhydride maléique, déterminée par analyses RMN du proton et du carbone treize. Cette solution présente une acidité de 4,11 meq/g (théorie 4,13 meq/g). Cette solution, désignée F, est utilisée sous cette forme dans l'exemple 10. TABLEAU I EXEMPLES ACIDE PH du bain Défroissabilité Nature Qté tel que après 3 lavages Rt BI. Ja. 3 A 44 2,14 250 210,5 74,3 69,4 63,3 4 B 41,3 2,17 240 212 76,2 70,8 62,5 CI 0 196 202 106,7 72 69,2 8 D 121 1,77 260 231 67,9 72 67 9 E 122 1,79 257,5 233 69,6 70,8 65,7 10 F 207 1,74 253 233 68,8 68,2 62 After cooling to room temperature, about 1618 g of a clear, colorless aqueous solution are obtained, containing approximately 1.67 mole of monosodium phosphinicobissuccinic acid and no longer containing maleic anhydride, determined by proton and NMR analyzes. carbon thirteen. This solution has an acidity of 4.11 meq / g (theory 4.13 meq / g). This solution, designated F, is used in this form in Example 10. TABLE I EXAMPLES ACID PH of the bath Wrinkle resistance Nature Qty such as after 3 washes Rt BI. Ja. 3 AT 44 2.14 250 210.5 74.3 69.4 63.3 4 B 41.3 2.17 240 212 76.2 70.8 62.5 THIS 0 196 202 106.7 72 69.2 8 D 121 1.77 260 231 67.9 72 67 9 E 122 1.79 257.5 233 69.6 70.8 65.7 10 F 207 1.74 253 233 68.8 68.2 62

Claims (9)

Procédé pour apprêter un textile caractérisé en ce que l'on imprègne le textile à traiter à l'aide d'un bain d'apprêtage comprenant de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II) ou un mélange d'acide phosphinicosuccinique (I) et d'acide phosphinicobissuccinique (II).Method for finishing a textile, characterized in that the textile to be treated is impregnated using a finishing bath comprising phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II) or a mixture of phosphinicosuccinic acid (I) and phosphinicobissuccinic acid (II). Procédé selon la revendication 1, caractérisé en ce que le bain d'apprêtage a un pH de 2 à 7 obtenu à l'aide d'un hydroxyde de métal alcalin.Process according to Claim 1, characterized in that the finishing bath has a pH of 2 to 7 obtained using an alkali metal hydroxide. Procédé selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que le bain d'apprêtage ne renferme aucun catalyseur.Process according to either of Claims 1 and 2, characterized in that the finishing bath does not contain any catalyst. Bain d'apprêtage pour textiles, caractérisé en ce qu'il comprend une solution d'acide phosphinicosuccinique (I), d'acide phosphinicobissuccinique (II), ou de leur mélange partiellement neutralisé à pH 2 à 7 à l'aide d'un hydroxyde de métal alcalin.Textile finishing bath, characterized in that it comprises a solution of phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II), or their mixture partially neutralized at pH 2 to 7 using a alkali metal hydroxide. Textile apprêté, caractérisé en ce qu'il est obtenu par mise en oeuvre du procédé selon la revendication 1, 2 ou 3.Textile finish, characterized in that it is obtained by implementing the method according to claim 1, 2 or 3. Utilisation de l'acide phosphinicosuccinique (I) comme apprêt textile.Use of phosphinicosuccinic acid (I) as a textile finish. Utilisation de l'acide phosphinicobissuccinique (II) comme apprêt textile.Use of phosphinicobissuccinic acid (II) as a textile finish. Utilisation d'un mélange d'acide phosphinicosuccinique (I) et d'acide phosphinicobissuccinique (II) comme apprêt textile.Use of a mixture of phosphinicosuccinic acid (I) and phosphinicobissuccinic acid (II) as a textile finish. Utilisation à titre d'agents de réticulation de la cellulose, de l'acide phosphinicosuccinique (I), de l'acide phosphinicobissuccinique (II) ou d'un mélange d'acide phosphinicosuccinique (I) et d'acide phosphinicobissuccinique (II).Use as crosslinking agents for cellulose, phosphinicosuccinic acid (I), phosphinicobissuccinic acid (II) or a mixture of phosphinicosuccinic acid (I) and phosphinicobissuccinic acid (II).
EP93400806A 1992-04-03 1993-03-29 Finishing of textiles with compositions containing phosphinicosuccinic acid, phosphinicobissuccinic acid or a mixture thereof Expired - Lifetime EP0564346B1 (en)

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FR9204076 1992-04-03

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CN1743532B (en) * 2004-09-03 2010-05-26 株式会社岛精机制作所 Pretreatment method for fiber article dyeing, pretreatment agent, dyeing method and fiber article treated thereby
CN109137526A (en) * 2018-08-30 2019-01-04 常州大学 A kind of preparation method and application of formaldehyde-free anti-crease finish
US11149202B1 (en) 2016-12-13 2021-10-19 Ecolab Usa Inc. Tetracarboxylic acid combinations for corrosion inhibition

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US6841198B2 (en) 2001-10-18 2005-01-11 Strike Investments, Llc Durable press treatment of fabric
US6989035B2 (en) * 2001-10-18 2006-01-24 The Procter & Gamble Company Textile finishing composition and methods for using same
US7008457B2 (en) * 2001-10-18 2006-03-07 Mark Robert Sivik Textile finishing composition and methods for using same
US7018422B2 (en) 2001-10-18 2006-03-28 Robb Richard Gardner Shrink resistant and wrinkle free textiles
US7169742B2 (en) 2001-10-18 2007-01-30 The Procter & Gamble Company Process for the manufacture of polycarboxylic acids using phosphorous containing reducing agents
CN1973080B (en) * 2004-06-24 2010-08-11 陶氏环球技术公司 Stretch fabrics with wrinkle resistance
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US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
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CN1743532B (en) * 2004-09-03 2010-05-26 株式会社岛精机制作所 Pretreatment method for fiber article dyeing, pretreatment agent, dyeing method and fiber article treated thereby
US11149202B1 (en) 2016-12-13 2021-10-19 Ecolab Usa Inc. Tetracarboxylic acid combinations for corrosion inhibition
CN109137526A (en) * 2018-08-30 2019-01-04 常州大学 A kind of preparation method and application of formaldehyde-free anti-crease finish
CN109137526B (en) * 2018-08-30 2021-01-29 常州大学 Preparation method and application of formaldehyde-free crease-resistant finishing agent

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