CN108003656A - It is a kind of suitable for dark blue reactive dye of llama and preparation method thereof - Google Patents

It is a kind of suitable for dark blue reactive dye of llama and preparation method thereof Download PDF

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Publication number
CN108003656A
CN108003656A CN201711376865.8A CN201711376865A CN108003656A CN 108003656 A CN108003656 A CN 108003656A CN 201711376865 A CN201711376865 A CN 201711376865A CN 108003656 A CN108003656 A CN 108003656A
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reaction
acid
obtains
sodium
added
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张兴华
郝津来
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Tianjin Dek Chemical Co Ltd
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Tianjin Dek Chemical Co Ltd
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Priority to CN201711376865.8A priority Critical patent/CN108003656A/en
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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
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
    • C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
    • C09B62/507—Azo dyes
    • C09B62/513—Disazo or polyazo dyes

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  • Organic Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of suitable for dark blue reactive dye of llama and preparation method thereof, it has such as following formula (I) or formula (II) structural formula；The obtained dark blue reactive dye of the present invention has higher stability, and excellent solubility, has bright-coloured beautiful coloured light, it is fast light, weather resistance is fabulous, the characteristics of dyestuff used has higher washable, perspiration resistance, color fastness to light, and degree of fixation is high, every fastness is excellent.

Description

It is a kind of suitable for dark blue reactive dye of llama and preparation method thereof
Technical field
The present invention relates to a kind of reactive dye, especially a kind of dark blue reactive dye and its system suitable for llama Preparation Method.
Background technology
Reactive dye because it is bright in colour, chromatography is complete, using the advantages that easy, of low cost, fastness is good, it has also become The fabrics such as cotton, fiber crops, wool, cashmere, nylon dye most important a class of dyes.Soda ash is used during dyeing as color fixing agent, Need to wash remaining alkaline agent with a large amount of clear water after dyeing.Therefore the raising to dye fixing rate in recent years, to alkaline agent Reduce the heat subject for becoming and complying with environmental requirement harsh now.
The object of the present invention is to provide a kind of dark blue reactive dye, have the reactive dye of double different active groups not only can be with The coloration requirements of corresponding different types of fabric, there is provided performance possessed by single kind active group different from the past, for dye The raising of material dye uptake and degree of fixation has positive effect.And for blended fabric, it is thus only necessary to which simple coloured light adjustment is just Dyeing demand can be competent at, avoid two or more reactive dye blendings caused by various problems, especially dyestuff is matched somebody with somebody The strict demand of 5 property.
The content of the invention
The present invention is dyeing problem of the current dark blue reactive dye of solution for blended fabric, there is provided a kind of polyazo is lived Property dyestuff, not only dye uptake and degree of fixation have an excellent behavior to the dyestuff, and every fastness index can also be met or exceeded There is product.
Technical solution provided by the present invention is：
A kind of dark blue reactive dye, it has such as following formula (I) or formula (II) structural formula：
Present invention also offers the preparation method of above-mentioned formula (I) reactive dye, include the following steps：
1), the dissolving of 2,4- diamino benzene sulfonic acids sodium
2,4- diamino benzene sulfonic acid sodium is dissolved in water, obtains 2,4- diamino benzene sulfonic acid sodium solutions；
2), condensation reaction
2,3-, bis- bromo propionyl chloros are added in 2, the 4- diamino benzene sulfonic acid sodium solutions that step 1) obtains, while add and tie up Sour agent, maintains 0~10 DEG C of temperature, pH=6.5~8, react to obtain condensation product solution；
3), diazo-reaction
30% hydrochloric acid is added in the condensation product solution obtained to step 2), is stirred evenly, adds frozen water, adjustment temperature to 5 ~15 DEG C, under conditions of reaction solution ensures pH ＜ 2, sodium nitrite is added, maintains 5~15 DEG C of temperature, when reaction 2 is small, is used Sulfamic acid eliminates excessive nitrite sodium；
4), the dissolving of H acid
H acid is dissolved in water, obtains H acid solutions；
5) a, coupling reaction
The H acid solutions that step 4) obtains are rapidly joined in the diazol that step 3) obtains, maintain 10~20 DEG C of temperature, are protected When temperature reaction 15~20 is small, pH to 6.5 is adjusted with acid binding agent, it is spare, obtain a conjugates solution；
6), para-ester diazo-reaction
Para-ester is added into beaker, frozen water, stirs evenly, and adds 30% hydrochloric acid, and adjustment temperature is being reacted to 0~5 DEG C Under conditions of solution ensures pH ＜ 2, sodium nitrite is rapidly joined, 0~5 DEG C of temperature is maintained, when reaction 2 is small；Use sulfamic acid Eliminate excessive nitrite sodium.
7), secondary coupling reaction
The diazol that step 6) is obtained is added in the conjugates solution that step 5) obtains, and maintains temperature 10~15 DEG C, maintain pH=7~8.5, when reaction 2~4 is small, to obtain secondary conjugates solution.
8) auxiliary agent, is added
30% hydrochloric acid of the secondary conjugates solution that step 7) obtains is adjusted into pH to 6~6.5.
According to the weight for obtaining solution 1~5% by anhydrous sodium sulphate, mixed phosphate, calgon, EDTA, NNO One or more add；Stir evenly；
9) insoluble matter, is dispelled, that is, formula (I) reactive dye are made.
Specifically, the preparation method of formula (I) reactive dye, includes the following steps：
1), the dissolving of 2,4- diamino benzene sulfonic acids sodium
22 parts of 2,4- diamino benzene sulfonic acids sodium, 150 parts of water are added into beaker；Stir evenly, to material dissolution, clarify, Frozen water is added, adjustment temperature adjusts mass percentage concentration m/m to 10% to 0~10 DEG C；It is molten to obtain 2,4- diamino benzene sulfonic acid sodium Liquid；
2), condensation reaction
It is interior when 0.5~1.5 is small, by 2,3-, bis- bromo propionyl chloros, 27.6 parts of 2,4- diaminobenzenes for being added to step 1) and obtaining In sodium sulfonate solution, 0~10 DEG C of temperature is maintained, while adds acid binding agent, maintains pH=6.5~8,2,3- bis- bromo propionyl chloros are complete After addition, 0~10 DEG C of temperature is maintained, pH=6.5~8, when reaction 2 is small, obtain condensation product solution；
3), diazo-reaction
32 parts of 30% hydrochloric acid is added in the condensation product solution obtained to step 2), is stirred evenly, adds frozen water, adjusts temperature To 5~15 DEG C, mass percentage concentration m/m to 5% is adjusted；Under conditions of reaction solution ensures pH ＜ 2, by sodium nitrite 7.4 Part add in three times, add the 1/3 of total amount every time, be 15 minutes per time interval between twice, maintain 5~15 DEG C of temperature, instead Answer 2 it is small when, with sulfamic acid eliminate excessive nitrite sodium；
4), the dissolving of H acid
32.4 parts of H acid is added in beaker, 150 parts of water, stirs evenly, and adds acid binding agent adjustment pH to 6.5, treats that material is molten Solution, adds frozen water, and adjustment temperature adjusts mass percentage concentration m/m to 15%, obtain H acid solutions to 10~20 DEG C；
5) a, coupling reaction
The H acid solutions that step 4) obtains are rapidly joined in the diazol that step 3) obtains, maintain 10~20 DEG C of temperature, are protected When temperature reaction 15~20 is small, frozen water is added, adjustment temperature adjusts pH to 6.5 to 5~15 DEG C, with acid binding agent, spare, obtains once even Polymer solution；
6), para-ester diazo-reaction
28.1 parts of para-ester is added into beaker, 300 parts of frozen water, stirs evenly, and adds 13.4 parts of 30% hydrochloric acid, adjustment temperature Degree adjusts mass percentage concentration m/m to 5% to 0~5 DEG C.Under conditions of reaction solution ensures pH ＜ 2, by 7 parts of sodium nitrite Rapidly join, 0~5 DEG C of temperature is maintained, when reaction 2 is small；Excessive nitrite sodium is eliminated with sulfamic acid.
7), secondary coupling reaction
The diazol that step 6) is obtained is added in the conjugates solution that step 5) obtains, while is tieed up with acid binding agent Hold pH=7~8.5；10~15 DEG C of temperature is maintained, maintains pH=7~8.5, when reaction 2~4 is small, to obtain secondary conjugates solution.
8) auxiliary agent, is added
30% hydrochloric acid of the secondary conjugates solution that step 7) obtains is adjusted into pH to 6~6.5.
According to the weight for obtaining solution 1~5% by anhydrous sodium sulphate, mixed phosphate, calgon, EDTA, NNO One or more add；Stir evenly；
9) insoluble matter, is dispelled
The solution that step 8) is obtained is added in equipment for separating liquid from solid, carries out separation of solid and liquid, is washed filter residue, is dispelled insoluble Thing, while feed liquid is collected in clean beaker；The unified recycling of filter residue is destroyed, that is, formula (I) reactive dye are made.
Present invention also offers the preparation method of above-mentioned formula (II) reactive dye, include the following steps：
1), para-ester diazo-reaction
Para-ester is added into beaker, frozen water, stirs evenly, and adds 30% hydrochloric acid, and adjustment temperature is being reacted to 0~5 DEG C Under conditions of solution ensures pH ＜ 2, sodium nitrite is rapidly joined, 0~5 DEG C of temperature is maintained, when reaction 2 is small；Use sulfamic acid Eliminate excessive nitrite sodium；
2), the dissolving of H acid
H acid is dissolved in water, obtains H acid solutions；
3) a, coupling reaction
The H acid solutions that step 2) obtains are rapidly joined in the para-ester diazol that step 1) obtains, maintenance temperature 10~ 20 DEG C, when insulation reaction 10~16 is small, pH to 6.5 is adjusted with acid binding agent, obtains a conjugates solution, it is spare；
4), the dissolving of 2,4- diamino benzene sulfonic acids sodium
2,4- diamino benzene sulfonic acid sodium is dissolved in water, obtains 2,4- diamino benzene sulfonic acid sodium solutions；
5), condensation reaction
2,3-, bis- bromo propionyl chloros are added in 2, the 4- diamino benzene sulfonic acid sodium solutions that step 4) obtains, while add and tie up Sour agent, maintains 0~10 DEG C of temperature, pH=6.5~8, react to obtain condensation product solution；
6), diazo-reaction
30% hydrochloric acid is added in the condensation product solution obtained to step 5), is stirred evenly, adds frozen water, adjustment temperature to 5 ~15 DEG C, under conditions of reaction solution ensures pH ＜ 2, sodium nitrite is added, maintains 5~15 DEG C of temperature, when reaction 2 is small, is used Sulfamic acid eliminates excessive nitrite sodium；
7), secondary coupling reaction
The diazol that step 6) is obtained is added in the conjugates solution that step 3) obtains, while is tieed up with acid binding agent PH=7~8.5 are held, maintain 10~20 DEG C of temperature, pH=7~8.5 are maintained, when reaction 2~4 is small；Obtain secondary conjugates solution；
8) auxiliary agent, is added
30% hydrochloric acid of the secondary conjugates solution that step 7) obtains is adjusted into pH to 6~6.5；
According to the weight for obtaining solution 1~5% by anhydrous sodium sulphate, mixed phosphate, calgon, EDTA, NNO One or more add, and stir evenly；
9) insoluble matter, is dispelled, that is, formula (II) reactive dye are made.
Specifically, the preparation method of formula (II) reactive dye, includes the following steps：
1), para-ester diazo-reaction
28.1 parts of para-ester is added into beaker, 300 parts of frozen water, stirs evenly, and adds 13.4 parts of 30% hydrochloric acid, adjustment temperature Degree adjusts mass percentage concentration m/m to 5% to 0~5 DEG C, under conditions of reaction solution ensures pH ＜ 2, by 7 parts of sodium nitrite Rapidly join, maintain 0~5 DEG C of temperature, when reaction 2 is small, excessive nitrite sodium is eliminated with sulfamic acid；
2), the dissolving of H acid
32.4 parts of H acid is added in beaker, 150 parts of water, stirs evenly, and adds acid binding agent adjustment pH to 6.5, treats that material is molten Solution, adds frozen water, and adjustment temperature adjusts mass percentage concentration m/m to 15%, obtain H acid solutions to 10~20 DEG C；
3) a, coupling reaction
The H acid solutions that step 2) obtains are rapidly joined in the para-ester diazol that step 1) obtains, maintenance temperature 10~ 20 DEG C, when insulation reaction 10~16 is small, frozen water is added, adjustment temperature adjusts pH to 6.5 to 5~15 DEG C, with acid binding agent, obtains once Conjugates solution, it is spare；
4), the dissolving of 2,4- diamino benzene sulfonic acids sodium
22 parts of 2,4- diamino benzene sulfonic acids sodium, 150 parts of water are added into beaker.Stir evenly, to material dissolution, clarify, Frozen water is added, adjustment temperature adjusts mass percentage concentration m/m to 10%, it is molten to obtain 2,4- diamino benzene sulfonic acid sodium to 0~10 DEG C Liquid；
5), condensation reaction
It is interior when 0.5~1.5 is small, by 2,3-, bis- bromo propionyl chloros, 27.6 parts of 2,4- diaminobenzenes for being added to step 4) and obtaining In sodium sulfonate solution, 0~10 DEG C of temperature is maintained, while adds acid binding agent, maintains pH=6.5~8,2,3- bis- bromo propionyl chloros are complete After addition, 0~10 DEG C of temperature is maintained, pH=6.5~8, when reaction 2 is small, obtain condensation product solution；
6), diazo-reaction
32 parts of 30% hydrochloric acid is added in the condensation product solution obtained to step 5), is stirred evenly, adds frozen water, adjusts temperature To 5~15 DEG C, mass percentage concentration m/m to 5% is adjusted, under conditions of reaction solution ensures pH ＜ 2, by sodium nitrite 7.4 Part add in three times, add the 1/3 of total amount every time, be 15 minutes per time interval between twice, maintain 5~15 DEG C of temperature, instead Answer 2 it is small when, with sulfamic acid eliminate excessive nitrite sodium；
7), secondary coupling reaction
The diazol that step 6) is obtained is added in the conjugates solution that step 3) obtains, while is tieed up with acid binding agent PH=7~8.5 are held, maintain 10~20 DEG C of temperature, pH=7~8.5 are maintained, when reaction 2~4 is small；Obtain secondary conjugates solution；
8) auxiliary agent, is added
30% hydrochloric acid of the secondary conjugates solution that step 7) obtains is adjusted into pH to 6~6.5；
According to the weight for obtaining solution 1~5% by anhydrous sodium sulphate, mixed phosphate, calgon, EDTA, NNO One or more add, and stir evenly；
9) insoluble matter, is dispelled
The solution that step 8) is obtained is added in equipment for separating liquid from solid, carries out separation of solid and liquid, is washed filter residue, is dispelled insoluble Thing, while feed liquid is collected in clean beaker, the unified recycling of filter residue is destroyed, that is, formula (II) reactive dye are made.
Heretofore described acid binding agent is to contain carbonate (CO3 2-), bicarbonate radical (HCO3 -), hydroxyl (OH-) sodium Salt, different step selection acid binding agent are identical or different.
Present invention also offers a kind of dark blue reactive dye mixture, which includes formula (I) and formula (II) structure The reactive dye of formula：
Chemically-reactive dyes according to the present invention is suitable for dyeing multiple material and stamp, particularly hydroxyl or The cellulose fiber of amino-containing fibrous material, including cotton, fiber crops, paper, silk, leather, wool and cashmere, particularly all kinds Tie up material.The fibrous material is such as native cellulose fibre, such as cotton, flax and hemp and cellulose and regenerated fiber Element.The dyestuff of the present invention is also adapted to dye the fiber of hydroxyl present in blended fabric or amino.
Beneficial effect possessed by the present invention：
The obtained dark blue reactive dye of the present invention has higher stability, and excellent solubility, has bright-coloured beautiful Beautiful coloured light, fast light, weather resistance is fabulous, dyestuff used has higher washable, perspiration resistance, color fastness to light, and degree of fixation is high The characteristics of, every fastness is excellent.
Embodiment
The following examples are the explanation to technical scheme, not to technical scheme and protection Scope forms any limitation.
Embodiment 1
A kind of dark blue reactive dye, the dyestuff have formula (I) structural formula：
The preparation method of formula (I) dark blue reactive dye, includes the following steps：
1st, the dissolving of 2,4- diamino benzene sulfonic acids sodium
22 parts of 2,4- diamino benzene sulfonic acids sodium, 150 parts of water are added into beaker.Stir evenly, to material dissolution, clarification. Frozen water is added, adjustment temperature adjusts mass percentage concentration m/m to 10% to 0 DEG C.
2nd, condensation reaction
It is interior when 0.5~1.5 is small, by 2,3-, bis- bromo propionyl chloros, 27.6 parts of 2,4- diaminobenzenes for being added to step 1 and obtaining In sodium sulfonate solution, 0~5 DEG C of temperature is maintained.Acid binding agent is added at the same time, maintains pH=6.5~8.2,3 dibromo propionyl chloride is complete After addition, 0~5 DEG C of temperature, pH=6.5~8, when reaction 2 is small are maintained.
3rd, diazo-reaction
32 parts of 30% hydrochloric acid is added in the condensation product solution obtained to step 2, is stirred evenly, adds frozen water, adjusts temperature To 5 DEG C, mass percentage concentration m/m to 5% is adjusted.Under conditions of reaction solution ensures pH ＜ 2, by 7.4 parts points of sodium nitrite Add three times, add the 1/3 of total amount every time, be 15 minutes per time interval between twice.5~10 DEG C of temperature is maintained, reaction 2 is small When.Excessive nitrite sodium is eliminated with sulfamic acid.
4th, the dissolving of H acid
32.4 parts of H acid, 150 parts of water are added in beaker.Stir evenly, add acid binding agent adjustment pH to 6.5, treat that material is molten Solution, adds frozen water, and adjustment temperature adjusts mass percentage concentration m/m to 15% to 10~15 DEG C.
5th, a coupling reaction
The H acid solutions that step 4 obtains are rapidly joined in the diazol that step 3 obtains, maintain 10~15 DEG C of temperature, insulation When reaction 15~20 is small.Frozen water is added, adjustment temperature adjusts pH to 6.5 to 5~10 DEG C, with acid binding agent, spare.
6th, para-ester diazo-reaction
28.1 parts of para-ester is added into beaker, 300 parts of frozen water, stirs evenly, and adds 13.4 parts of 30% hydrochloric acid.Adjustment temperature Degree adjusts mass percentage concentration m/m to 5% to 0 DEG C.It is under conditions of reaction solution ensures pH ＜ 2,7 parts of sodium nitrite is fast Speed adds.0~5 DEG C of temperature is maintained, when reaction 2 is small.Excessive nitrite sodium is eliminated with sulfamic acid.
7th, secondary coupling reaction
The diazol that step 6 is obtained is added in the conjugates solution that step 5 obtains, while is maintained with acid binding agent PH=7~7.5.10~15 DEG C of temperature is maintained, pH=7~7.5 are maintained, when reaction 2~4 is small.
8th, auxiliary agent is added
30% hydrochloric acid of the secondary conjugates solution that step 7 obtains is adjusted into pH to 6~6.5.
2% according to the weight for obtaining solution adds auxiliary agent, and the auxiliary agent is 1 for mass ratio:1 anhydrous sodium sulphate and EDTA's is mixed Compound；Stir evenly.
9th, insoluble matter is dispelled
The solution that step 8 is obtained is added in equipment for separating liquid from solid, carries out separation of solid and liquid, is washed filter residue, is dispelled insoluble Thing, while feed liquid is collected in clean beaker.The unified recycling of filter residue is destroyed.
Embodiment 2
A kind of dark blue reactive dye, the reactive dye have the structural formula of formula (II)：
The preparation method of formula (II) dark blue reactive dye, includes the following steps：
1st, para-ester diazo-reaction
28.1 parts of para-ester is added into beaker, 300 parts of frozen water, stirs evenly, and adds 13.4 parts of 30% hydrochloric acid.Adjustment temperature Degree adjusts mass percentage concentration m/m to 5% to 0 DEG C.It is under conditions of reaction solution ensures pH ＜ 2,7 parts of sodium nitrite is fast Speed adds.0~5 DEG C of temperature is maintained, when reaction 2 is small, excessive nitrite sodium is eliminated with sulfamic acid.
2nd, the dissolving of H acid
32.4 parts of H acid, 150 parts of water are added in beaker.Stir evenly, add acid binding agent adjustment pH to 6.5, treat that material is molten Solution, adds frozen water, and adjustment temperature adjusts mass percentage concentration m/m to 15% to 10~15 DEG C.
3rd, a coupling reaction
The H acid solutions that step 2 obtains are rapidly joined in the para-ester diazol that step 1 obtains, maintain temperature 10~15 DEG C, when insulation reaction 12 is small；Frozen water is added, adjustment temperature adjusts pH to 6.5 to 5~10 DEG C, with acid binding agent, spare.
4th, the dissolving of 2,4- diamino benzene sulfonic acids sodium
22 parts of 2,4- diamino benzene sulfonic acids sodium, 150 parts of water are added into beaker.Stir evenly, to material dissolution, clarification. Frozen water is added, adjustment temperature adjusts mass percentage concentration m/m to 10% to 0 DEG C.
5th, condensation reaction
It is interior when 0.5~1.5 is small, by 2,3-, bis- bromo propionyl chloros, 27.6 parts of 2,4- diaminobenzenes for being added to step 4 and obtaining In sodium sulfonate solution, 0~5 DEG C of temperature is maintained.Acid binding agent is added at the same time, maintains pH=6.5~7.2,3 dibromo propionyl chloride is complete After addition, 0~5 DEG C of temperature, pH=6.5~7, when reaction 2 is small are maintained.
6th, diazo-reaction
32 parts of 30% hydrochloric acid is added in the condensation product solution obtained to step 5, is stirred evenly, adds frozen water, adjusts temperature To 5 DEG C, mass percentage concentration m/m to 5% is adjusted.Under conditions of reaction solution ensures pH ＜ 2, by 7.4 parts points of sodium nitrite Add three times, add the 1/3 of total amount every time, be 15 minutes per time interval between twice.5~10 DEG C of temperature is maintained, reaction 2 is small When.Excessive nitrite sodium is eliminated with sulfamic acid.
7th, secondary coupling reaction
The diazol that step 6 is obtained is added in the conjugates solution that step 3 obtains, while is maintained with acid binding agent PH=7.5~8.10~15 DEG C of temperature is maintained, pH=7.5~8 are maintained, when reaction 2~4 is small.
8th, auxiliary agent is added
30% hydrochloric acid of the secondary conjugates solution that step 7 obtains is adjusted into pH to 6~6.5.
2% according to the weight for obtaining solution adds auxiliary agent, and the auxiliary agent is 1 for mass ratio:1 anhydrous sodium sulphate and EDTA's is mixed Compound；Stir evenly.
9th, insoluble matter is dispelled
The solution that step 8 is obtained is added in equipment for separating liquid from solid, carries out separation of solid and liquid, is washed filter residue, is dispelled insoluble Thing, while feed liquid is collected in clean beaker.The unified recycling of filter residue is destroyed.
Embodiment 3
A kind of dark blue reactive dye mixture, the mixture include mass ratio 1:1 formula (I) and formula (II) structural formula Reactive dye：
The preparation method of the mixture, includes the following steps：
1st, it is dry
Embodiment 1 and 2 obtained dyestuff of embodiment are stored respectively.By the dry drying of feed liquid small spraying, adjust Entrance inlet temperature is 215 DEG C, is spray-dried with 100 DEG C of outlet temperature.After the drying of 1 gained dyestuff of embodiment, thoroughly Washe-dryer, then carries out the drying of 2 gained dyestuff of embodiment, to avoid pollution again.
2nd, the adjustment of coloured light and intensity
The dried dye that step 1 is obtained carries out UV intensity detections respectively, and dyes respectively.According to coloration result, according to UV intensity, 2 obtained dyestuff each 1 of Example 1 and embodiment:1, blending is carried out, adjusts coloured light.Contaminated further according to blending is completed The UV intensity of material is proportionally added into glucose and anhydrous sodium sulphate carries out the adjustment of UV intensity.
3rd, product preserves
Dyestuff obtained by step 2 is sealed.
Its dyeability is as follows：
Dark blue reactive dye mixture prepared by the present invention is used for llama fiber applications performance table
Structure formula (I) λMAX=605nm；Structure formula (II) λMAX=596nm；λ after blendingMAX=600nm
The method of the present invention is described by specific embodiment.Those skilled in the art can use for reference this hair The links such as the appropriate feed change of bright content, process conditions realize corresponding other purposes, its correlation change all without departing from Present disclosure, all similar substitutions and modifications are it will become apparent to those skilled in the art that be considered as It is included within the scope of the present invention.

Claims (4)

  1. A kind of 1. dark blue reactive dye, it is characterised in that：It has such as following formula (I) or formula (II) structural formula：
  2. 2. the preparation method of dark blue reactive dye described in claim 1, it is characterised in that：The preparation side of formula (I) reactive dye Method, includes the following steps：
    1), the dissolving of 2,4- diamino benzene sulfonic acids sodium
    2,4- diamino benzene sulfonic acid sodium is dissolved in water, obtains 2,4- diamino benzene sulfonic acid sodium solutions；
    2), condensation reaction
    2,3-, bis- bromo propionyl chloros are added in 2, the 4- diamino benzene sulfonic acid sodium solutions that step 1) obtains, while add and tie up acid Agent, maintains 0~10 DEG C of temperature, pH=6.5~8, react to obtain condensation product solution；
    3), diazo-reaction
    30% hydrochloric acid is added in the condensation product solution obtained to step 2), is stirred evenly, adds frozen water, adjustment temperature to 5~15 DEG C, under conditions of reaction solution ensures pH ＜ 2, sodium nitrite is added, 5~15 DEG C of temperature is maintained, when reaction 2 is small, uses amino Sulfonic acid eliminates excessive nitrite sodium；
    4), the dissolving of H acid
    H acid is dissolved in water, obtains H acid solutions；
    5) a, coupling reaction
    The H acid solutions that step 4) obtains are rapidly joined in the diazol that step 3) obtains, maintain 10~20 DEG C of temperature, insulation is anti- Answer 15~20 it is small when, with acid binding agent adjust pH to 6.5, it is spare, obtain a conjugates solution；
    6), para-ester diazo-reaction
    Para-ester is added into beaker, frozen water, stirs evenly, and adds 30% hydrochloric acid, adjustment temperature is to 0~5 DEG C, in reaction solution Under conditions of ensuring pH ＜ 2, sodium nitrite is rapidly joined, 0~5 DEG C of temperature is maintained, when reaction 2 is small；Eliminated with sulfamic acid Excessive nitrite sodium.
    7), secondary coupling reaction
    The diazol that step 6) is obtained is added in the conjugates solution that step 5) obtains, and maintains 10~15 DEG C of temperature, Maintain pH=7~8.5, when reaction 2~4 is small, to obtain secondary conjugates solution.
    8) auxiliary agent, is added
    30% hydrochloric acid of the secondary conjugates solution that step 7) obtains is adjusted into pH to 6~6.5.
    According to the weight for obtaining solution 1~5% by one kind in anhydrous sodium sulphate, mixed phosphate, calgon, EDTA, NNO Or a variety of additions；Stir evenly；
    9) insoluble matter, is dispelled, that is, formula (I) reactive dye are made.
  3. 3. the preparation method of dark blue reactive dye described in claim 1, it is characterised in that：The preparation side of formula (II) reactive dye Method, includes the following steps：
    1), para-ester diazo-reaction
    Para-ester is added into beaker, frozen water, stirs evenly, and adds 30% hydrochloric acid, adjustment temperature is to 0~5 DEG C, in reaction solution Under conditions of ensuring pH ＜ 2, sodium nitrite is rapidly joined, 0~5 DEG C of temperature is maintained, when reaction 2 is small；Eliminated with sulfamic acid Excessive nitrite sodium；
    2), the dissolving of H acid
    H acid is dissolved in water, obtains H acid solutions；
    3) a, coupling reaction
    The H acid solutions that step 2) obtains are rapidly joined in the para-ester diazol that step 1) obtains, maintain 10~20 DEG C of temperature, When insulation reaction 10~16 is small, pH to 6.5 is adjusted with acid binding agent, obtains a conjugates solution, it is spare；
    4), the dissolving of 2,4- diamino benzene sulfonic acids sodium
    2,4- diamino benzene sulfonic acid sodium is dissolved in water, obtains 2,4- diamino benzene sulfonic acid sodium solutions；
    5), condensation reaction
    2,3-, bis- bromo propionyl chloros are added in 2, the 4- diamino benzene sulfonic acid sodium solutions that step 4) obtains, while add and tie up acid Agent, maintains 0~10 DEG C of temperature, pH=6.5~8, react to obtain condensation product solution；
    6), diazo-reaction
    30% hydrochloric acid is added in the condensation product solution obtained to step 5), is stirred evenly, adds frozen water, adjustment temperature to 5~15 DEG C, under conditions of reaction solution ensures pH ＜ 2, sodium nitrite is added, 5~15 DEG C of temperature is maintained, when reaction 2 is small, uses amino Sulfonic acid eliminates excessive nitrite sodium；
    7), secondary coupling reaction
    The diazol that step 6) is obtained is added in the conjugates solution that step 3) obtains, while maintains pH with acid binding agent =7~8.5,10~20 DEG C of temperature is maintained, pH=7~8.5 are maintained, when reaction 2~4 is small；Obtain secondary conjugates solution；
    8) auxiliary agent, is added
    30% hydrochloric acid of the secondary conjugates solution that step 7) obtains is adjusted into pH to 6~6.5；
    According to the weight for obtaining solution 1~5% by one kind in anhydrous sodium sulphate, mixed phosphate, calgon, EDTA, NNO Or a variety of additions, stir evenly；
    9) insoluble matter, is dispelled, that is, formula (II) reactive dye are made.
  4. A kind of 4. dark blue reactive dye mixture, it is characterised in that：The mixture includes the work of formula (I) and formula (II) structural formula Property dyestuff：
CN201711376865.8A 2017-12-19 2017-12-19 It is a kind of suitable for dark blue reactive dye of llama and preparation method thereof Pending CN108003656A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233331A (en) * 2018-10-26 2019-01-18 天津德凯化工股份有限公司 One kind being suitable for digital ink-jet printed navy reactive dye for wool and preparation method thereof
CN109233330A (en) * 2018-10-26 2019-01-18 天津德凯化工股份有限公司 A kind of navy reactive dye for wool and preparation method thereof

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Publication number Priority date Publication date Assignee Title
US5989298A (en) * 1997-04-07 1999-11-23 Ciba Speciality Chemicals Corporation Mixtures of reactive dyes and their use
CN101967303A (en) * 2010-09-15 2011-02-09 天津德凯化工股份有限公司 Reactive navy blue dye and preparation method thereof
CN101967304A (en) * 2010-09-15 2011-02-09 天津德凯化工股份有限公司 Active navy blue dye and preparation method thereof
CN102115613A (en) * 2009-12-30 2011-07-06 上海雅运纺织化工有限公司 Blue reactive dye composition and dyeing application to fiber material thereof
CN102115612A (en) * 2009-12-30 2011-07-06 上海雅运纺织化工有限公司 Dark blue active dye composition and application thereof in dyeing fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5989298A (en) * 1997-04-07 1999-11-23 Ciba Speciality Chemicals Corporation Mixtures of reactive dyes and their use
CN102115613A (en) * 2009-12-30 2011-07-06 上海雅运纺织化工有限公司 Blue reactive dye composition and dyeing application to fiber material thereof
CN102115612A (en) * 2009-12-30 2011-07-06 上海雅运纺织化工有限公司 Dark blue active dye composition and application thereof in dyeing fibers
CN101967303A (en) * 2010-09-15 2011-02-09 天津德凯化工股份有限公司 Reactive navy blue dye and preparation method thereof
CN101967304A (en) * 2010-09-15 2011-02-09 天津德凯化工股份有限公司 Active navy blue dye and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109233331A (en) * 2018-10-26 2019-01-18 天津德凯化工股份有限公司 One kind being suitable for digital ink-jet printed navy reactive dye for wool and preparation method thereof
CN109233330A (en) * 2018-10-26 2019-01-18 天津德凯化工股份有限公司 A kind of navy reactive dye for wool and preparation method thereof

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Application publication date: 20180508