CN108047085A - Hair mothproof Naphthaquinone Pigments and preparation method thereof and application method - Google Patents
Hair mothproof Naphthaquinone Pigments and preparation method thereof and application method Download PDFInfo
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- CN108047085A CN108047085A CN201711353824.7A CN201711353824A CN108047085A CN 108047085 A CN108047085 A CN 108047085A CN 201711353824 A CN201711353824 A CN 201711353824A CN 108047085 A CN108047085 A CN 108047085A
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- 0 CC*C(C(C)=NNC(C(C(CCC=C1)=C1C1=[U])=[U])=C1Cl)=[U] Chemical compound CC*C(C(C)=NNC(C(C(CCC=C1)=C1C1=[U])=[U])=C1Cl)=[U] 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/72—Hydrazones
- C07C251/74—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C251/76—Hydrazones having doubly-bound carbon atoms of hydrazone groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C245/00—Compounds containing chains of at least two nitrogen atoms with at least one nitrogen-to-nitrogen multiple bond
- C07C245/02—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides
- C07C245/04—Azo compounds, i.e. compounds having the free valencies of —N=N— groups attached to different atoms, e.g. diazohydroxides with nitrogen atoms of azo groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
- C07D231/46—Oxygen atom in position 3 or 5 and nitrogen atom in position 4
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/0018—Monoazo dyes prepared by diazotising and coupling from diazotized aminopolycyclic rings
- C09B29/0022—Monoazo dyes prepared by diazotising and coupling from diazotized aminopolycyclic rings from diazotized aminoanthracene
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/32—Monoazo dyes prepared by diazotising and coupling from coupling components containing a reactive methylene group
-
- 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
- C09B29/00—Monoazo dyes prepared by diazotising and coupling
- C09B29/34—Monoazo dyes prepared by diazotising and coupling from other coupling components
- C09B29/36—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds
- C09B29/3604—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom
- C09B29/3647—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms
- C09B29/3652—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles
- C09B29/366—Monoazo dyes prepared by diazotising and coupling from other coupling components from heterocyclic compounds containing only a nitrogen as heteroatom containing a five-membered ring with two nitrogen atoms as heteroatoms containing a 1,2-diazoles or hydrogenated 1,2-diazoles containing hydroxy-1,2-diazoles, e.g. pyrazolone
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- 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
- D06M13/325—Amines
-
- 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
- D06M13/352—Heterocyclic compounds having five-membered heterocyclic rings
-
- 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
- D06P1/02—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 azo dyes
- D06P1/04—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 azo dyes not containing metal
-
- 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
- D06P3/02—Material containing basic nitrogen
- D06P3/04—Material containing basic nitrogen containing amide groups
- D06P3/14—Wool
-
- 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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/10—Animal fibres
- D06M2101/12—Keratin fibres or silk
Abstract
The present invention provides the naphthoquinone derivatives of the structure as shown in Formulas I or Formula II, are the mothproof Naphthaquinone Pigments of hair.The hair of the present invention has both dyeing and mothproof performance with mothproof Naphthaquinone Pigments.The present invention is improved the water solubility and dyeability of NQ FH or NQ FP, the rear dye-uptake of washing of NQ FP can be made to reach 57.34%, adsorption rate reaches 81.54% using " ethyl alcohol solubilising " colouring method processing wool fabric.And moth erosion broken hole grade 1 grade and visible surface damage level 1 grade of the casting skin moth to wool fabric can be improved, it is more than 70% to reduce fabric weight-loss ratio, with certain mothproof effect while dyeing.
Description
Technical field
The present invention relates to hair technical field of dye, and in particular to a kind of Naphthaquinone Pigments with mothproof performance.
Background technology
The protein fibres such as wool are high-grade textile raw materials, but easily generate and go mouldy and damaged by worms.According to relevant department
Consumer survey, the accident rate that textile is subject to moth to invade food in use are only second to change colour, fade, stain, contracting
Water and arrange residence the 5th.In recent years, as the high-grade product such as fur garment, cashmere product, pure wool woollen blanket, feather cushion is into general
Long and deep friendship between two families front yard, more efficient, the safer new mothproofing agent of exploitation are just particularly important.
At the mothproof aspect of health, natural camphor and lavender oil are healthy and safe, but price is relatively high.Naphthalene is synthesized due to it
Toxicity and carcinogenesis worldwide forbid using.Paracide is by the World Health Organization (WHO) and international cancer
" dubiety mankind carcinogenic compound " is confirmed as in research center (IARC), according to standard GB/T 13690-2009, paracide
Belong to the carcinogenicity article in " health risk " major class, but still sell and circulate in the domestic market.Just implement《Clothing is mothproof
Agent》(QB/T 4367-2012) standard, is only applicable to the clothes moth-proof agent using paracide as active ingredient, therefore there are still phases
When safe limitation.
In terms of mothproof finish, sulfonamides and phoxim class mothproofing agent are the most effective mothproof finish sides of wool textile
Method can be handled with hair with one-bath dyeing, and mothproof effect is lasting, but disabled at present.Chlorophenothane (DDT) Yi Jishi prevents
Moth agent etc. is equally disabled.Pyrethroid mothproofing agent is quickly grown.Domestic commerce pyrethroid mothproofing agent produces
Product majority is applicable to dyeing and mothproof same bath process, the mothproof technique of final finishing or spraying insect moth technique such as decis, chlorine
Chrysanthemum ester, tetramethrin, empenthrin etc..But although pyrethroid coumpound generally has high-efficiency low-toxicity, low-residual
The advantages such as amount, easily biological-degradable, according to Environmental Protection Agency (EPA) pesticide for having assessed carcinogenic possibility announced in 2008
With chemicals register, multiclass pyrethroid is appeared on the list of successful candidates.At present, plan deinsectization can be remained really in wool and other textiles
Pyrethrin pesticide if selecting pyrethroid mothproofing agent improper, will will certainly generate the potential hazard of bigger.For directly with
The wool textile of human contact, European Union have strictly detected the residual quantity of chemical mothproofing agent, import cashmere product have been disabled
Including part pyrethroid mothproofing agent.State Environmental Protection Administration implemented in approval in 2005《Antitermite agent standard》(HJ/T
2172005) in, the qualified foundation for the toxicological assessment that the pyrethroid that product uses is provided also it has been distinctly claimed.
Various plants source naphthoquinones and its derivative have certain antibiotic property, mildew resistance, mite property of going out, pesticidal or dyeability
Naphthoquinones and its derivative Deng, synthesis also have different bioactivity.Existing research shows that naphthoquinones parent introduces substituent group
Type, quantity or position etc., can influence to synthesize some specific insecticidal activities of naphthoquinones, nitrogenous or sulfur heterocyclic ring to some extent
The insecticidal activity synergy of naphthoquinones is notable, but mothproof relatively limited with the report of Study on dyeing applied to wool.
The content of the invention
The object of the present invention is to provide a kind of new hairs with mothproof Naphthaquinone Pigments, have both dyeing and mothproof effect.
Another object of the present invention is to provide preparation method of the above-mentioned hair with mothproof Naphthaquinone Pigments.
The method for carrying out dyeing mothproof finish with mothproof Naphthaquinone Pigments it is also another object of the present invention to provide above-mentioned hair.
In order to achieve the above object, technical scheme is as follows：
The present invention provides a kind of mao of mothproof Naphthaquinone Pigments of use, have the structure as shown in Formulas I or Formula II：
The present invention also provides the hair preparation methods of mothproof Naphthaquinone Pigments of above-mentioned Formulas I structure, comprise the following steps：
(1) chloro- 1.4 naphthoquinones of 2- amino -3- and nitrite under strong acid media are subjected to diazo-reaction, generate diazonium
Salt；
(2) diazol that step (1) obtains and trifluoroacetic ethyl acetoacetate are in the presence of pH value 4~4.5, polarity Organic Alcohol
Coupling reaction is carried out, obtains the mothproof Naphthaquinone Pigments NQ-FH of the hair of structure shown in Formulas I.
Preferably, in step (1), the strong acid media is inorganic acid, and the pH value of the strong acid media is less than 2.0.
Preferably, the molar ratio of chloro- 1.4 naphthoquinones of the 2- amino -3- and nitrite is 1:1~1.3, the 2- ammonia
The molar ratio of the chloro- 1.4 naphthoquinones diazols obtained by the reaction of base -3- and the trifluoroacetic ethyl acetoacetate is 1:1~1.3.
Preferably, in step (2), the pH value is adjusted with sodium acetate, the sodium acetate and the trifluoroacetyl acetic acid second
The weight ratio of ester is 1~6:1.
Preferably, the reaction temperature of the diazo-reaction in the step (1) and the coupling reaction in step (2) is independently
For 0~5 DEG C.
Preferably, further included after coupling reaction：It is 1 by the product volume ratio of the coupling reaction:9~11 acetic acid second
Ester and water are washed or are 1 with volume ratio:9~11 ethyl acetate and ethyl alcohol is washed, and obtains structure shown in Formulas I
Hair with mothproof Naphthaquinone Pigments.
The hair preparation method of mothproof Naphthaquinone Pigments of the above-mentioned Formula II structure of the present invention, comprises the following steps：
Above-mentioned compound of formula I and hydrazine hydrate are subjected to cyclization under organic polar solvent environment, obtained Formula II knot
The mothproof Naphthaquinone Pigments NQ-FP of the hair of structure, the temperature of the cyclization is 15~25 DEG C, when the reaction time is 12~20 small.
The present invention also provides the method for carrying out dyeing mothproof finish with mothproof Naphthaquinone Pigments using above-mentioned hair, by the hair
It is dissolved in by the use of mothproof Naphthaquinone Pigments in the mixed liquor of second alcohol and water as dye liquor, fiber dye using the dye liquor mothproof whole
Reason.
Preferably, the volume ratio of the second alcohol and water is 1:2~5, the pH value of the dye liquor is 3.5~4.0, and the hair is used
Mothproof Naphthaquinone Pigments weigh 0.9~1.1o.w.f% compared with fiber.
Compared with prior art, the present invention has the following advantages：
The present invention using 2-amino-3-chloro-1,4-naphthoquinone as raw material, selection with certain bioactivity fluorine-containing acylhydrazone and
Pyrazolone modification structure by the synergy of active component, is prepared and has both dyeing and mothproof effect to wool fabric
The fluorine-containing acylhydrazone of the mothproof pigment of target naphthoquinones (NQ-FH) and pyrazolone (NQ-FP) realize dyeing and mothproof dual work(
Energy.
The fluorine-containing acylhydrazone of the mothproof pigment of naphthoquinones (NQ-FH) and pyrazolone (NQ-FP) of the present invention is due to lacking water solubility
Group or reactive group, it is impossible to which the directly upper dyeing wool as reactive dye or acid dyes, the present invention is using " ethyl alcohol increases
It is molten " colouring method processing wool fabric, the water solubility and dyeability of NQ-FH or NQ-FP are improved, after the washing of NQ-FP can be made
Dye-uptake reaches 57.34%, and adsorption rate reaches 81.54%.
The NQ-FH or NQ-FP of the present invention can improve casting skin moth to 1 grade of the moth of wool fabric erosion broken hole grade and visible
1 grade of surface damage grade, it is more than 70% to reduce fabric weight-loss ratio, with certain mothproof effect while dyeing.
Description of the drawings
Fig. 1 is the chemical structural drawing of NQ-FH；
Fig. 2 is the chemical structural drawing of NQ-FP；
Fig. 3 is the infrared spectrum of NQ-FH；
Fig. 4 is the infrared spectrum of NQ-FP；
Fig. 5 is the mothproof one-pass bath method for dyeing treatment process graphs of NQ-FH of the present invention or NQ-FP；
Fig. 6 is the ultraviolet and visible spectrogram of NQ-FH and NQ-FP；
Fig. 7 is the digital photograph of wool fabric after mothproof performance test, wherein, (a) NQ-FH processing, (b) NQ-FP processing.
Specific embodiment
The present invention provides the naphthoquinone derivatives of new construction, have both dyeing and mothproof performance.The mothproof naphthalene of the hair of the present invention
Quinochrome has the structure as shown in Formulas I or Formula II：
The present invention also provides the preparation method of said structure compound, using 2-amino-3-chloro-1,4-naphthoquinone as raw material,
Selection has the fluorine-containing acylhydrazone of certain bioactivity and pyrazolone modification structure, obtains the NQ-FH of Formulas I structure and Formula II knot
The NQ-FP of structure.
The method of the NQ-FH of structure, comprises the following steps shown in formula I of the present invention：
(1) chloro- 1.4 naphthoquinones of 2- amino -3- and nitrite under strong acid media are subjected to diazo-reaction, generate diazonium
Salt；
(2) diazol that step (1) obtains and trifluoroacetic ethyl acetoacetate are in the presence of pH 4~4.5, polarity Organic Alcohol
Carry out coupling reaction, obtained yellow solid for Formulas I structure hair with mothproof Naphthaquinone Pigments NQ-FH.
In the present invention, the strong acid media of diazo-reaction is preferably inorganic acid, such as hydrochloric acid, sulfuric acid inorganic acid.This
Invention concrete operations use, preferably chloro- 1.4 naphthoquinones of 2- amino -3- is dissolved in the aqueous solution of inorganic acid, then with nitrite into
Row reaction.The dosage of inorganic acid of the present invention is added in right amount according to the pH value of reaction solution.The pH value of diazo-reaction of the present invention is excellent
Choosing is less than 2.0, more preferably less than 1.5, and therefore, the dosage of inorganic acid is adjusted according to above-mentioned pH value.
In the present invention, the molar ratio of chloro- 1.4 naphthoquinones of the 2- amino -3- and nitrite is preferably 1:1~1.3.This hair
The bright species to nitrite does not limit, and preferably described nitrite is sodium nitrite.
Diazo-reaction of the present invention preferably carries out under ice bath, and the ice bath temperature is preferably 0~5 DEG C.Specifically, by 2-
The strong acid solution of chloro- 1.4 naphthoquinones of amino -3- stirs under ice bath, and nitrite is slowly added dropwise and carries out diazo-reaction.
The present invention judges that the chloro- 1.4 naphthoquinones diazotising of 2- amino -3- is complete whether discoloration with test paper.When Congored test paper becomes
When blue, illustrate excessive acid；When KI- starch papers become blueness, illustrate NaNO2Excessive, diazo-reaction is complete.The present invention is excellent
The diazo-reaction complete time is selected as 20~40min, more preferably 30min.
The diazol of chloro- 1.4 naphthoquinones of 2- amino -3- is obtained after diazo-reaction.The present invention is by the diazol and trifluoro
Ethyl acetoacetate carries out coupling reaction in the presence of pH value 4~4.5, polarity Organic Alcohol, and the naphthoquinones for obtaining structure shown in Formulas I spreads out
Biology.
In the present invention, the organic alcoholic solution of the polarity of trifluoroacetic ethyl acetoacetate is mixed into the solution after diazo-reaction
Row coupling reaction.Dropwise addition mode on coupling reaction do not influence.In the specific embodiment of the invention, preferably by trifluoro second
The organic alcoholic solution of polarity of ethyl acetoacetic acid ethyl ester, which is added dropwise in the solution after diazo-reaction, to be reacted.In the present invention, the 2-
The molar ratio of the diazol and the trifluoroacetic ethyl acetoacetate of the chloro- 1.4 naphthoquinones reaction generations of amino -3- is preferably 1:1~
1.3。
During the coupling reaction of the present invention, the polarity Organic Alcohol is preferably ethyl alcohol or ethylene glycol, is made in the present invention
For cosolvent, promote the progress of coupling reaction.The preferably weight ratio of polarity Organic Alcohol and trifluoroacetic ethyl acetoacetate of the invention is
(1~2)：(6~8), more preferably (1.2~1.5):(6.5~7.0).
The pH value of coupling reaction system of the present invention is 4~4.5, more preferably 4.2~4.3.Present invention strong base-weak acid salt
Adjust the pH value of solution in coupling reaction.In the specific embodiment of the invention, reaction solution preferably is adjusted to above-mentioned institute with sodium acetate
Need pH value.
Coupling reaction of the present invention preferably carries out under ice bath, and the ice bath temperature is preferably 0~5 DEG C, when there is yellow solid
During precipitation, coupling reaction terminates, and the mothproof Naphthaquinone Pigments NQ-FH crude products of the hair of Formulas I structure are obtained by filtration.
The NQ-FH crude products ethyl acetate and water or ethyl acetate or ethyl alcohol that the present invention preferably obtains coupling reaction
Mixed liquor washed, be dried in vacuo, obtain the mothproof Naphthaquinone Pigments NQ-FH sterlings of the hair of Formulas I structure.
In the present invention, ethyl acetate and water, the volume ratio of ethyl acetate and ethyl alcohol preferably stand alone as 1 in the mixed liquor:9
~11, more preferably 1:10.The present invention is not particularly limited vacuum drying mode, and use is well known to those skilled in the art
Mode.
NQ-FH and hydrazine hydrate are carried out cyclization by the present invention under organic polar solvent environment, formula II structures
NQ-FP。
In the present invention, the molal weight of the hydrazine hydrate and NQ-FH are than being preferably 1:1~1.1.The organic polar solvent
Preferably methanol or ethyl alcohol as cosolvent in cyclization, promote the progress of reaction.NQ-FH of the present invention with it is described
The mass volume ratio of organic polar solvent is (0.1~1) g:(5~15) ml, more preferably (0.2~0.6) g:(7~10) ml.
Cyclization of the present invention carries out at room temperature, and preferable reaction temperature is 15~25 DEG C, and more preferably 18~22
℃。
The pH value of cyclization of the present invention is preferably 10.5~11.0.In the present invention, it is preferred to use dilute ammonia solution
Cyclisation reaction system is adjusted to above-mentioned pH value.
It is complete that the present invention preferably tracks to cyclization with thin-layer chromatography (TLC).The present invention is excellent during thin-layer chromatography
Choosing is using FeCl3The chromogenic reaction for generating purple complex in alkaline conditions with ethyl acetoacetate judges the trifluoro of NQ-FH
Whether the reaction was complete for ethyl acetoacetate group.If being generated without purple complex, judge that the cyclization is reached home.This
Invent the cyclization required reaction time completely for 12~20 it is small when, more preferably 17~18 it is small when.
After cyclization of the present invention, by the liquid cooling after reaction, filtering obtains brown solid crude product.
The present invention preferably carries out column chromatography to obtained brown solid crude product, obtains the mothproof naphthoquinones of the hair of Formula II structure
Pigment NQ-FP.The column solvent is preferably the volume ratio of the mixture of ethyl acetate and alkane, the ethyl acetate and alkane
For 1:10~15, more preferably 1:12~13.Alkane of the present invention is preferably the alkane of short straight chain, more preferably n-hexane,
N-propane or normal butane.
Present invention invention additionally provides the dyeing mothproof finish method of above-mentioned NQ-FH and NQ-FP.Due to NQ-FH or NQ-FP
Containing trifluoromethyl and lack water soluble group, influence the dyeability using water as medium, it is of the invention by NQ-FH or NQ-FP
It is dissolved in the mixed liquor of second alcohol and water as dye liquor, dyeing mothproof finish is carried out to fiber, improves adsorption rate and dye-uptake.
In the present invention, the ratio of the second alcohol and water is preferably 1:2~5, more preferably 1:3~4.
The pH value of dye liquor of the present invention is preferably 3.5~4.0.The present invention preferably adjusts the pH of dye liquor with acetic acid.
In dye liquor of the present invention, the weight of NQ-FH or NQ-FP be preferably fibre weight to be contaminated 0.9~
1.1o.w.f%, more preferably 1.0o.w.f%.
In dyeing mothproof finish method of the present invention, dye is entered at preferably 35~45 DEG C, bath raio is preferably 1：30~55,90
50~70min is dyed at~100 DEG C, is cleaned, drying.More preferably 40 DEG C enter dye, bath raio 1:50,95 DEG C of dyeing 60min, room
Temperature cleaning, drying.
Understand to make the object, technical solutions and advantages of the present invention clearer, with reference to embodiment to the present invention into
Row detailed description, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
The preparation of NQ-FH：
Solution A：In conical flask by the chloro- 1.4 naphthoquinones 2.076g of 2- amino -3- of 10mmol with 3.7mL concentrated hydrochloric acids with
The mixed liquor dissolving of 10mL distilled water, is subsequently placed in 0~5 DEG C of ice-water bath and stirs 10min, be slowly added dropwise 12.6mmol's
NaNO20.86g carries out diazo-reaction 30min, and pH value during reaction is 1.5.
B solution：It by the trifluoroacetic ethyl acetoacetate 1.84g of 10mmol, is uniformly mixed with 31mL ethyl alcohol, adds in 55.4mmol
Sodium acetate solution 4.55g, make B solution pH value be 4-4.5.
In 0~5 DEG C of ice-water bath, B solution is slowly added dropwise into solution A, continues to stir 2h, until there is yellow solid
It is precipitated, the crude product of filtering is with V (ethyl acetate):V (pure water) is 1:10 washings, vacuum drying obtain product NQ-FH, yield
90.2%.
Embodiment 2
The preparation of NQ-FH：
Solution A：It is in conical flask that the chloro- 1.4 naphthoquinones 1g of 2- amino -3- of 10mmol is molten in 25mL dilute hydrochloric acid solutions
Solution, is subsequently placed in 0~5 DEG C of ice-water bath and stirs 10min, is slowly added to the NaNO that solid content is 4.5g2Solution carries out diazonium
Change reaction 20min, pH value during reaction is 2.0.
B solution：It by the trifluoroacetic ethyl acetoacetate 1.84g of 10mmol, is uniformly mixed, adds in 37mL ethylene glycol
The sodium acetate solution 4.55g of 55.4mmol, the pH value for making B solution are 4-4.5.
In 0~5 DEG C of ice-water bath, B solution is slowly added dropwise into solution A, continues to stir 3h, until there is yellow solid
It is precipitated, the crude product of filtering is with V (ethyl acetate):V (ethyl alcohol) is 1:10 washings, vacuum drying obtain product NQ-FH, yield
89.5%.
Infrared spectrum (Fig. 3), proton magnetic and mass spectral analysis are carried out to the NQ-FH being prepared, to determine the chemical combination of NQ-FH
Object structure, is shown in Fig. 1.
NQ-FH：IR(KBr)ν:3299.49,3409.94(NH),2166.89(COOC),1685.43(Ar),1604.38,
1558.40 (C=O), 1273.21 (CF3),1334.46,1304.87(Ar-NH),1003.46(Cl),931.69(COC)；NQ-
FH is located at 2166.89cm-1And 894.48cm-1Ethyl acetate base absworption peak disappear.
1H NMR(CDCl3, 400MHz) and δ：7.70~8.20 (m, 4H, ArH), 7.00 (s, 1H, NH), 5.50 (q, 2H,
CH2),1.30(t,3H,CH3)；
MS(70eV,EI)m/z:402.02 (100.0%), 404.02 (32.1%), 403.03 (17.6%), 405.02
(5.8%), 404.03 (2.5%)；Molecular formula：C16H10ClF3N2O5.Detected value is 402.71, calculated value 402.02；Element
Analysis:C,47.72；H,2.50；Cl,8.80；F,14.15；N,6.96；O,19.86.
Embodiment 3
In 50mL conical flasks, add in NQ-FH (0.393g, 1mmol), methanol 8mL and hydrazine hydrate (0.05g,
1mmol), the room temperature at 25 DEG C, pH value are ring-closure reaction under conditions of 11.0, stir 15h.Suitable reaction solution is pipetted to beaker
In be diluted, then add in a certain amount of FeCl3Solution finds do not there is any color change, explanation into diluted reaction solution
The reaction was complete by NQ-FH so that the elementary reaction is reached home.After completion of the reaction, ice water is added in reactant, filters, obtains yellow
Brown solid crude product.Column chromatography, column chromatography solvent are carried out to obtained solid crude product：V (n-hexane):V (ethyl acetate) is
15:1, obtain product NQ-FP, yield 85.6%.
Embodiment 4
In 50mL conical flasks, add in NQ-FH (0.393g, 1mmol), absolute ethyl alcohol 10mL and hydrazine hydrate (0.6g,
1.2mmol), the room temperature at 15 DEG C, pH value are ring-closure reaction under conditions of 10.5, stir 20h.Suitable reaction solution is pipetted to burning
It is diluted in cup, then adds in a certain amount of FeCl3Solution finds there is not any color change into diluted reaction solution, says
The reaction was complete by bright NQ-FH so that the elementary reaction is reached home.After completion of the reaction, ice water is added in reactant, filters, obtains
Brown solid crude product.Column chromatography, column chromatography solvent are carried out to obtained solid crude product：V (normal butane):V (ethyl acetate)
For 12:1, obtain product NQ-FP, yield 87.2%.
Infrared spectrum (Fig. 4), proton magnetic and mass spectral analysis are carried out to the NQ-FP being prepared, to determine the chemical combination of NQ-FP
Object structure, is shown in Fig. 2.
NQ-FP：IR(KBr)ν：3429.39 (NH-NH), 1678.55 (Ar), 1614.97,1572.13,1502.08 (C=
O),1277.96(CF3),1436.87,1390.72(Ar-NH),1019.11(Cl)；There is position compared with NQ-FH, NQ-FP
In 3427.39cm-1Pyrrazole structure-NH-the absworption peak at place, while naphthalene ring ,-CF3The peak position class of ,-Cl, C ═ O
Seemingly, it is that intensity is slightly different.
1HNMR(DMSO-d6,400MHz)δ：7.50~8.00 (m, 4H, ArH), 7.50 (d, 1H, NH), 2.5 (d, 1H,
NH)；
MS(70eV,EI)m/z:370.01 (100.0%), 372.01 (33.9%), 371.01 (16.8%), 373.01
(4.9%)；Molecular formula：C14H6ClF3N4O3, detected value 370.67, calculated value 370.01；Elemental analysis:C,45.36；H,
1.63；Cl,9.56；F,15.38；N,15.12；O,12.95.
Embodiment 5
The dyeing of NQ-FH and mothproof finish
The NQ-FH of the structure is carried out at mothproof one-pass bath method for dyeing wool fabric as hair with mothproof Naphthaquinone Pigments
Reason, dye is entered at 40 DEG C, and prescription is following (dosage/o.w.f)：Hair mothproof Naphthaquinone Pigments 1.0%, 33% hydrotropy of ethyl alcohol, CH3COOH
2.0% adjusting solution ph is 3.5~4.0, and surplus is water.Enter dye, bath raio 1 at 40 DEG C:50th, 95 DEG C of dyeing 60min, have been handled
Cheng Houyong room temperatures clear water washs, and is baked to.Process curve is as shown in Figure 3.
Embodiment 6
The NQ-FP of the structure is carried out at mothproof one-pass bath method for dyeing wool fabric as hair with mothproof Naphthaquinone Pigments
Reason.Processing method is the same as embodiment 5.
Embodiment 7
NQ-FH and NQ-FP dyeing and mothproof performance test
1st, chroma characteristic is dyed
Fig. 6 represents the ultraviolet and visible spectrum of NQ-FH and NQ-FP, respectively using chloroform or DMSO as solvent.With NQ-FH phases
Than NQ-FP conjugated chains are longer, and molecule coplanarity is stronger, therefore can make absworption peak that apparent red shift occur.For the purple of NQ-FP
External spectrum, it should the naphthoquinones that 257nm occurs the red shift of phenyl ring absworption peak to 264nm, the naphthoquinones that in addition should occur in 335nm
Quinone ring absworption peak red shift go out ultraviolet region；In visible light part, the λ of NQ-FHmaxFor 438nm, displaing yellow, and the λ of NQ-FPmax
For 502nm, show orange red.
Colorimetric parameter：Table 1 handles the colorimetric parameter of wool fabric for NQ-FH or NQ-FP.Compared with NQ-FH, NQ-FP makes
More than 50%, wool fabric is yellow by feux rouges for the reduction of the lightness L* and chroma C* and chromaticity coordinate a* and b* of wool fabric
Discoloration is dark purple dark reddish brown.Compare Fig. 1 and Fig. 2 understand, the naphthoquinones condensed ring of NQ-FH has been distorted, and with trifluoroacetyl acetic acid second
Ester formed acylhydrazone coplanarity it is very poor, influence its to the absorption of visible ray and and wool macromolecular combination.And NQ-FP is total to
Yoke and molecule coplanarity are relatively preferable, are more suitable for the dyeing to fiber.
Table 1NQ-FH or NQ-FP handle the colorimetric parameter of wool fabric
| Fabric | L* | a* | b* | X | Y | Z | C* |
| NQ-FH processing | 71.3 | 11.8 | 28.6 | 44.2 | 42.5 | 24.3 | 30.9 |
| NQ-FP processing | 31.6 | 4.2 | -7.4 | 7.0 | 6.9 | 9.6 | 8.6 |
| Slip/% | 55.7 | 64.4 | 125.9 | 84.2 | 83.8 | 60.5 | 72.2 |
2nd, dyeing and performance evaluation
Dyeability is tested：K/S values are according to GB/T 23976.2-2009《The measure and color of dyestuff one bath dyeing
Deep value measuring method》.Dye-uptake is according to GB/T2391-2003《The measure of reactive dye dye-uptake and degree of fixation》.
Dyefastness is tested：Fastness to soaping is according to GB/T 3921-2008《Textile color stability tests resistance to color of soaping
Fastness》Grading；Colour fastness to rubbing is according to GB/T 3920-2008《Textile color stability tests colour fastness to rubbing》Grading.
Apparent dye level K/S values, the adsorption rate of NQ-FH and NQ-FP is listed in table 2 with washing rear dye-uptake.It can by table 2
Know, the coloring handled by " ethyl alcohol increase-volume method " is preferable.Compared with NQ-FH, this 3 of NQ-FP processing wool fabrics refer to
For target amplification more than 50%, this is closely related with the molecular structure of NQ-FP.
Table 2NQ-FH or NQ-FP handle the dyeability of wool fabric
Table 3 handles the dyefastness of wool fabric for NQ-FH or NQ-FP.As can be seen from Table 3, NQ-FH and NQ-FP are equal
There is preferable dyefastness, the dyefastness of NQ-FH is compared with the fastness to soaping of NQ-FP processing wool fabrics and rub resistance color jail
Degree improves at least 1 grade, and wherein cotton staining fastness is improved more than 1 grade.
Table 3NQ-FH or NQ-FP handle the dyefastness of wool fabric
3rd, mothproof assessment of performance：According to GB/T29776-2013/ISO 3998:1977《The survey of textile Anti-moth-eating performance
It is fixed》It is tested.It is straight according to indexs such as attagenus piceus lethality, fabric weight-loss ratio, visible surface damage and moth erosion broken hole grades
It connects or the mothproof performance of Indirect evaluation wool fabric.Wherein, the calculating of weight-loss ratio r is as follows:
In formula：M0For example weight, g；M1For the weight that sample loses, g.
Table 4 is the mothproof performance of wool fabric after mothproof performance test, as follows：
Table 4NQ-FH or NQ-FP handle the mothproof performance of wool fabric
From table 4 and Fig. 7, the wool fabric moth erosion broken hole degree handled through NQ-FH and NQ-FP is below unprocessed
Wool fabric, grade improves a class.The wool fabric of NQ-FH and NQ-FP processing, after the moth erosion of attagenus piceus larva,
There is the hole that a little yarn is broken by moth in surface, is rated as moderate 3 grades of damages.Intensity level is prevented for highest is belonged to
Other moth attagenus piceus, on the fabric handled through NQ-FH or NQ-FP, the weightlessness of the wool fabric after the moth erosion of attagenus piceus larva
Rate r decrease beyond 70%.Therefore, the wool fabric handled through NQ-FH or NQ-FP, because playing inhibitory action to attagenus piceus larva
And with certain mothproof effect, and NQ-FP has more preferably mothproof effect than NQ-FH.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. the mothproof Naphthaquinone Pigments of mao use, which is characterized in that there is the structure as shown in Formulas I or Formula II：
2. the preparation method of the mothproof Naphthaquinone Pigments of the hair of Formulas I structure described in claim 1, which is characterized in that including following step
Suddenly：
(1) chloro- 1.4 naphthoquinones of 2- amino -3- and nitrite under strong acid media are subjected to diazo-reaction, generate diazol；
(2) diazol that step (1) obtains is carried out with trifluoroacetic ethyl acetoacetate in the presence of pH value 4~4.5, polarity Organic Alcohol
Coupling reaction obtains the mothproof Naphthaquinone Pigments of the hair of structure shown in Formulas I.
3. preparation method according to claim 2, which is characterized in that in step (1), the strong acid media is inorganic strong
Acid, the pH value of the strong acid media are less than 2.0.
4. preparation method according to claim 2, which is characterized in that chloro- 1.4 naphthoquinones of the 2- amino -3- and nitrous acid
The molar ratio of salt is 1:1~1.3, the chloro- 1.4 naphthoquinones diazols obtained by the reaction of 2- amino -3- and the trifluoroacetyl second
The molar ratio of acetoacetic ester is 1:1~1.3.
5. preparation method according to claim 2, which is characterized in that in step (2), the pH value is adjusted with sodium acetate.
6. preparation method according to claim 2, which is characterized in that diazo-reaction and step in the step (1)
(2) reaction temperature of the coupling reaction in independently is 0~5 DEG C.
7. preparation method according to claim 2, which is characterized in that further included after the coupling reaction：By the coupling
The product volume ratio of reaction is 1:9~11 ethyl acetate and water is washed or is 1 with volume ratio:9~11 acetic acid
Ethyl ester and ethyl alcohol are washed, and obtain the mothproof Naphthaquinone Pigments of the hair of structure shown in Formulas I.
8. the preparation method of the mothproof Naphthaquinone Pigments of the hair of Formula II structure described in claim 1, which is characterized in that including following step
Suddenly：
Compound of formula I described in claim 1 and hydrazine hydrate under organic polar solvent environment are subjected to cyclization, obtain Formula II
The mothproof Naphthaquinone Pigments of the hair of structure, the temperature of the cyclization is 15~25 DEG C, when the reaction time is 12~20 small.
9. the method for dyeing mothproof finish is carried out with mothproof Naphthaquinone Pigments using hair described in claim 1, which is characterized in that by institute
It states the mothproof Naphthaquinone Pigments of hair to be dissolved in the mixed liquor of second alcohol and water as dye liquor, it is anti-to carry out dyeing to fiber using the dye liquor
Moth arranges.
10. according to the method described in claim 9, it is characterized in that, the volume ratio of the second alcohol and water is 1:2~5, the dye
The pH value of liquid is 3.5~4.0, and the hair weighs 0.9~1.1o.w.f% with mothproof Naphthaquinone Pigments compared with fiber.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321454A (en) * | 2020-11-25 | 2021-02-05 | 湖南华腾制药有限公司 | Elotriporpa intermediate, preparation method thereof and method for preparing Elotriporpa by using intermediate |
| CN113788838A (en) * | 2020-09-18 | 2021-12-14 | 南京合谷生命生物科技有限公司 | Red natural pigment compound and preparation method and application thereof |
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| US4118186A (en) * | 1976-05-13 | 1978-10-03 | Hoechst Aktiengesellschaft | Process for the fixation of organic dyestuffs on materials having a fibrous structure |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4118186A (en) * | 1976-05-13 | 1978-10-03 | Hoechst Aktiengesellschaft | Process for the fixation of organic dyestuffs on materials having a fibrous structure |
Non-Patent Citations (1)
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| 陈诚，贾丽霞，张初阳: "毛用防蛀萘醌色素的合成与性能评价", 《纺织学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113788838A (en) * | 2020-09-18 | 2021-12-14 | 南京合谷生命生物科技有限公司 | Red natural pigment compound and preparation method and application thereof |
| CN112321454A (en) * | 2020-11-25 | 2021-02-05 | 湖南华腾制药有限公司 | Elotriporpa intermediate, preparation method thereof and method for preparing Elotriporpa by using intermediate |
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