US3390948A - Quaternized fluorindine compounds and textile materials dyed therewith - Google Patents

Quaternized fluorindine compounds and textile materials dyed therewith Download PDF

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Publication number
US3390948A
US3390948A US499079A US49907965A US3390948A US 3390948 A US3390948 A US 3390948A US 499079 A US499079 A US 499079A US 49907965 A US49907965 A US 49907965A US 3390948 A US3390948 A US 3390948A
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compounds
fluorindine
formula
blue
compound
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US499079A
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English (en)
Inventor
James M Straley
Raymond C Harris
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Eastman Kodak Co
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Eastman Kodak Co
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Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US499079A priority Critical patent/US3390948A/en
Priority to ES0331243A priority patent/ES331243A1/es
Priority to BE688337D priority patent/BE688337A/xx
Priority to DE19661619442 priority patent/DE1619442A1/de
Priority to GB46702/66A priority patent/GB1168461A/en
Priority to CH1509566A priority patent/CH471197A/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B17/00—Azine dyes
    • C09B17/06—Fluorindine or its derivatives
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/92—Synthetic fiber dyeing
    • Y10S8/927—Polyacrylonitrile fiber

Definitions

  • This invention relates to quaternary salts of compounds of the fluorindine series and their use particularly as dyes for acrylic polymer textile materials.
  • the compounds are quaternary salts of fiuorindines having the general formula wherein the R groups are the same or different and each represents lower alkyl or substituted lower alkyl and X and Y are the same or different and each represents an ortho-phenylene group, a 1,2-naphthylene group, or a 2,3- naphthylene group.
  • the quaternary salts are prepared by quaternizing the above fluorindines so as to obtain either mono-quaternary or di-qu'aternary salts of the formulas i t a, R
  • each R represents lower alkyl or benzyl
  • R, X and Y are as defined above
  • Z represents an anion derived from qu-aternization, e.g. C1 Br CH S 3,390,948 Patented July 2, 1968 sulfonate, ethyl p-toluene sulfonate, n-propyl p-toluene sulfonate and n-butyl p-toluene sulfonate.
  • fluorindines which are quaternized to obtain the quaternary salts of the invention: fluorindine, 5,12-dimethylfiuorindine, 5,12-diethylfluorindine, 5,12 diisopropylfiuorindine, 2,5,9,12 tetram'ethylfluorindine, 3,10-bis(trifiuoromethyl)-5,12-dimethylfluorindine, 2,9-dibromo-5,12-dimethylfluorindine, 2,9- dinitro 5,12 dimethylfluorindine, 5,l2-di(B-cyanoethyl) fluorindine, 5,12-di(fi-hydroxyethyl)fluorindine, 5,12-dibutylfiuon'ndine, 2,5-dimethyl-l2-ethylfiuorindine, 2,5-dimethylfluorindine, 12-ethylfluorindine, 2,9-'bis(s)
  • the unsymmetrical fluorindines described above Where the R groups are different are prepared as described in our above patent application by reaction of a hydroxyphenazinone as illustrated in the examples below.
  • the quaternized fluorindine compounds are especially useful as dyes for acrylic polymer textile materials such as those containing acrylonitrile units yielding blue and green dyeings having good fastness, for example to light, washing, perspiration, gas (atmospheric fumes), and sublimation.
  • the fiuorindines can also be expected to respond favorably to other tests as textile dyes when tested by methods such as described in the A.A.T.C.C. Technical Manual, 1964 Edition.
  • the degree of utility varies, for example, depending upon the textile material being dyed and the formula of the particular fluorindine in use. Thus, all of the quaternary fluorindine compounds will not have the same degree of utility for the same textile material.
  • the described quaternary fluorindine compounds generally have better light-fastness and wet-fastness properties than do the corresponding non-quaternary flnorindines. They can be expected to show less cross-staining when dyeing mixtures of acrylic fibers with other fibers.
  • the substituents attached to the alkyl or aryl groups R of the above formula, and to the ortho-phenylene groups represented by X and Y can be varied widely and function primarily as auxochrome groups to control the color of the fluorindine compound.
  • the substituted alkyl groups represented by R includes hydroxyal'kyl, e.g. hydroxyethyl, polyhydroxyalkyl, e.g. 2,3-dihydroxypropyl; alkoxyalkyl, e.g. methoxyethyl; cyanoalkyl, e.g. B- cyanoethyl; cyanoal-koxyalkyl, e.g.
  • fi-cyanoethoxyethyl acyloxyalkyl, e.g. acetoxyethyl; carboalkoxyalkyl, e.g. carbethoxyet-hyl; halogenoalkyl, e.-g. chloroethyl; hydroxyhalogenoalkyl, e.g. 8-hydroxyy-chloropropyl; alkylsulfonylalkyl, e.g. methylsulfonylethyl;
  • Substituents on the ortho phenylene groups represented by X and Y include alkyl e.g. methyl, alkoxy e.g. methoxy, nitro, amino, cyano, halogen, alkylsu'lfonyl e.g.
  • methylsulfonyl alkylsulfonamido e.g. methylsulfonamido, alkanoylamido e.g. acetamido, alkylthio e.g. methylthio, carbamoyl, etc.
  • R alkyl or substituted alkyl may have better affinity than compounds where R is an aryl group such as phenyl.
  • the following example illustrates one way in which the fluorindine compounds of the invention can be used to dye acrylonitrile polymer textile material. .1 gram of dye is dissolved by warming in cc. of methyl Cellosolve. A 2% aqueous solution of a non-ionic surfactant, such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product), is added slowly until a fine emulsion is obtained and then the dye mixture i brought to a volume of 200 cc. with warm water. 5 cc.
  • a non-ionic surfactant such as Igepal CA (a polymerized ethylene oxide-alkylphenol condensation product)
  • Representative acrylonitrile homopolymer and copolymer textile materials dyed by the fiuorindine compounds, especially the above 5,12-alkyl and substituted alkyl fluorindines, are characterized by containing at least about 35% combined acrylonitrile units and up to about 95% acrylonitrile units, and modified, for example, by 85-5 of vinyl pyridine units as described in US. Patents 2,990,- 393 (Re. 25,533) and 3,014,008 (Re. 25,539) or modified by 65-5% of vinylpyrrolidone units, for example, as described by US. Patent 2,970,783, or modified with 65-5 acrylic ester or acrylamide units as described in US.
  • Patents 2,879,253, 2,879,254 and 2,838,470 Similar amounts of the other polymeric modifiers mentioned above are also useful.
  • a preferred group of the copolymers readily dyeable with the fiuorindines are the modacrylic polymers such as described in US.
  • Patent 2,831,- 826 composed of a mixture of (A) 70-95% by Weight of a copolymer of from to 60% by weight of vinylidene chloride or vinyl chloride and 70-35% by weight of acrylonitrile, and (B) 305% by weight of second polymer from the group consisting of (1) homopolymers of acrylamidic monomers of the formula wherein R is selected from the group consisting of hydrogen and methyl, and R and R are selected from the group consisting of hydrogen and alkyl groups of 1-6 carbon atoms, (2) copolymers consisting of at least two of said acrylamidic monomers, and (3) cop'olymers consisting of at least 50% by weight of at least one of said acrylamidic monomers and not more than 50% by weight of a polymerizable monovinyl pyridine monomer.
  • EXAMPLE 1-5 l2 DIHYDRO 5,12 DIMETHYL- QUINOXALO [2,3 -b] PHENAZINE(5,12 DIMETH- YLFLUORINDINE) precipitate was washed with hot water, then with acetone and air-dried. The product was a dark powder, soluble in methanol and dilute mineral acids with a clear blue color. The acid solutions give a typical ruby-red fluorescence in ultraviolet light.
  • FLUORINDINE 4.8 g. of l0-ethyl-3-hydroxy-2-phenazinone and 4 g. of l-N-4-dimethyl-o-phenylenediamine dihydrochloride are added to 25 g. of 3-picoline.
  • the reaction mixture is Quaternization 4.77 g. of the above trialkylfiuorindine'in 80 ml. of dry toluene is heated to 90 C. and 6.66 g. of dimethylsulfate is added over a period of 15 minutes. The temperature is kept at 8590 C. during the addition and for 15 minutes thereafter.
  • the compound has the formula Quaternization EXAMPLE 4.5 IZ-DIMETHYL-DIBENZO [b,m] FLUORINDINE Forty-nine grams of 2-amino-3-methylaminonaphthalene dihydrochloride and 14 g. of 2,5-dihydroxybenzoquinone in 150 ml. of 3-picoline were refluxed with stirring for 3 hours. The reaction mixture was then cooled and filtered and the product thoroughlywashed with 6. warm water. The precipitate was then washed with 3% sodium hydroxide until the filtrate came through colorless. It was then washed with water until alkali-free and dried at 60 C. The material dyes acrylic fibers fast blue shades. Quaternization with dimethylsulfate gave a product which dyes acrylic and modacrylic fibers in fast, blue shades.
  • a compound having the formula 2 A compound having the formula T] N N x Y Z [in]... I i
  • X and Y are the same or difierent and each represents ortho-phenylene; ortho-phenylene substituted with lower alkyl, trifluoromethyl; halogen, hydroxy, lower alkylsulfonyl, sulfamoyl, or nitro; 1,2-naphthylene; or 2,3-
  • R represents lower alkyl
  • R represents lower alkyl
  • n and n each represent 0 or 1, the sum of m and n being 1;
  • Z represents an anion 3.
  • X and Y each represents ortho-phenylene or orthophenylene substituted with lower alkyl; R represents methyl or ethyl; and Z represents CH SO or C H SO 4.

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  • Organic Chemistry (AREA)
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US499079A 1965-10-20 1965-10-20 Quaternized fluorindine compounds and textile materials dyed therewith Expired - Lifetime US3390948A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US499079A US3390948A (en) 1965-10-20 1965-10-20 Quaternized fluorindine compounds and textile materials dyed therewith
ES0331243A ES331243A1 (es) 1965-10-20 1966-09-15 Un procedimiento para la preparacion de sales cuaternarias de compuesto de fluorindina.
BE688337D BE688337A (enrdf_load_html_response) 1965-10-20 1966-10-17
DE19661619442 DE1619442A1 (de) 1965-10-20 1966-10-19 Verwendung von quaternaeren Salzen von Fluorindinen zum Faerben von Faeden und Fasern aus Acrylnitrilpolymeren
GB46702/66A GB1168461A (en) 1965-10-20 1966-10-19 Quaternized Fluorindine Dyestuffs for Textile Fibers
CH1509566A CH471197A (fr) 1965-10-20 1966-10-19 Procédé de préparation de sels quaternaires de fluorindines

Applications Claiming Priority (1)

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US499079A US3390948A (en) 1965-10-20 1965-10-20 Quaternized fluorindine compounds and textile materials dyed therewith

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BE (1) BE688337A (enrdf_load_html_response)
CH (1) CH471197A (enrdf_load_html_response)
DE (1) DE1619442A1 (enrdf_load_html_response)
ES (1) ES331243A1 (enrdf_load_html_response)
GB (1) GB1168461A (enrdf_load_html_response)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3534040A (en) * 1965-10-20 1970-10-13 Eastman Kodak Co 5,12-dialkyl fluorindine compounds
FR2864782A1 (fr) * 2004-01-07 2005-07-08 Oreal Utilisation pour la teinture des fibres keratiniques d'une composition tinctoriale comprenant au moins un compose fluorindine et composition tinctoriale le comprenant
US20050188475A1 (en) * 2004-01-07 2005-09-01 Alain Lagrange Dyeing composition comprising at least one fluorindine compound for the dyeing of keratinic fibers, dyeing process comprising the composition and compound

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3534040A (en) * 1965-10-20 1970-10-13 Eastman Kodak Co 5,12-dialkyl fluorindine compounds
FR2864782A1 (fr) * 2004-01-07 2005-07-08 Oreal Utilisation pour la teinture des fibres keratiniques d'une composition tinctoriale comprenant au moins un compose fluorindine et composition tinctoriale le comprenant
EP1552813A1 (fr) * 2004-01-07 2005-07-13 L'oreal Composition tinctoriale capillaire comprenant au moins un composé fluorindinium
US20050188475A1 (en) * 2004-01-07 2005-09-01 Alain Lagrange Dyeing composition comprising at least one fluorindine compound for the dyeing of keratinic fibers, dyeing process comprising the composition and compound
US7294152B2 (en) * 2004-01-07 2007-11-13 L'oreal S.A. Dyeing composition comprising at least one fluorindine compound for the dyeing of keratinic fibers, dyeing process comprising the composition and compound

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Publication number Publication date
BE688337A (enrdf_load_html_response) 1967-03-31
DE1619442A1 (de) 1971-03-11
CH471197A (fr) 1969-04-15
GB1168461A (en) 1969-10-29
ES331243A1 (es) 1967-12-01

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