CN102911526B - turquoise blue reactive dye and preparation method thereof - Google Patents
turquoise blue reactive dye and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of Turquoise blue reactive dye and preparation method thereof, the Turquoise blue reactive dye, with following structural formula：
Description
Technical field
The present invention relates to a kind of reactive dye and preparation method thereof, especially a kind of Turquoise blue reactive dye and its preparation side
Method.
Background technology
Reactive dye also known as chemically-reactive dyes, in molecule contain chemically active group, can in aqueous with cotton,
The fiber-reactives such as fiber crops, hair form the dyestuff of covalent bond, and reactive dye can be obtained with economical dyeing and simple dying operation
Obtain high-caliber every strong performance and be particularly wet fastness.The chromatogram of reactive dye is wide, lovely luster, excellent performance, applicability
By force, the requirement of its form and aspect and performance substantially with market to fiber and dress material is adapted.
In reactive dye, the Turquoise blue reactive dye with CuPc as parent is of less types.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of brand-new molecular structure, lovely luster, full turquoise blue
Reactive dye and preparation method thereof, it is adaptable to the dyeing of the fiber such as cotton, fiber crops, hair, are particularly suited for ink-jet printed.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of Turquoise blue reactive dye, with such as
Lower general structure（Ⅰ）
CuPc represents CuPc in formula
R is-SO2NH-C2H4OCOCH3Or-SO2NH-C2H4OSO2NH2
Present invention also offers a kind of structure above（Ⅰ）The preparation method of Turquoise blue reactive dye, comprises the following steps：
A, chlorosulfonation
To adding chlorosulfonic acid in retort（No. CAS： 7790-94-5 ）, control 40~50 DEG C of temperature.Time-consuming 2 hours will
CuPc（No. CAS： 147-14-8 ）110~140 DEG C of temperature of adjustment is added, 110~140 DEG C of temperature is maintained, reacted 4 hours,
65~70 DEG C of temperature of adjustment, maintains 65~70 DEG C of temperature, time-consuming to add thionyl chloride within 2 hours, maintains 65~70 DEG C of temperature, instead
Answer 2 hours, adjust 90 DEG C of temperature, maintain 90~95 DEG C of temperature, react 1 hour, 105 DEG C of temperature of adjustment, maintenance temperature 105~
110 DEG C, react 1 hour, obtain chlorosulfonation feed liquid；
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added into the retort equipped with frozen water
In, 0~20 DEG C of temperature is maintained, stir 1 hour, gained feed liquid is carried out into separation of solid and liquid, filter cake to filter is washed with -5~5 DEG C of cold water
Liquid pH=4~5, collect filter cake；
B, esterification
To adding monoethanolamine in retort（No. CAS：141-43-5）, 15~20 DEG C of temperature is controlled, in 45~60 minutes
It is interior by glacial acetic acid（No. CAS：64-19-7）Add, add sulfuric acid（No. CAS：7664-93-9）, stir, under backflow, adjustment
120~150 DEG C of temperature, maintains 120~150 DEG C of temperature, reacts 5 hours, adjusts 5~10 DEG C of temperature, standby；
C, condensation
By in a steps resulting material addition b step resulting materials, 5~10 DEG C of temperature is adjusted with frozen water, with 10~40% hydrogen
Sodium oxide molybdena（No. CAS：1310-73-2）Solution maintains pH=9~12, and stirring reaction 1~3 hour adjusts 35~50 DEG C of temperature, dimension
Hold 35~50 DEG C of temperature, pH=9~12, stirring reaction 1~3 hour.
D, neutralization reaction
The reaction solution of step c is adjusted to pH=6~7.5 with 30% hydrochloric acid solution；
E, post processing
Feed liquid that Step d is obtained is refined, dry after be finished product dyestuff.
Further, ammoniacal liquor is added in c the step of the above method.
As another embodiment of the present invention：Structure above（Ⅰ）The preparation method of Turquoise blue reactive dye, including such as
Lower step：
A, chlorosulfonation
To chlorosulfonic acid is added in retort, 40~50 DEG C of temperature is controlled.It is time-consuming to add CuPc within 2 hours, adjust temperature
100~120 DEG C, 100~120 DEG C of temperature is maintained, reacted 1 hour, adjust 120~140 DEG C of temperature, maintain temperature 120~140
DEG C, react 3~6 hours, obtain chlorosulfonation feed liquid；
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added into the retort equipped with frozen water
In.0~20 DEG C of temperature is maintained, is stirred 1 hour, gained feed liquid is carried out into separation of solid and liquid, filter cake to filter is washed with -5~5 DEG C of cold water
Liquid pH=4~5；Collect filter cake.
B, condensation
To addition Sulfamic acid, 2-aminoethyl ester in retort（H2NCH2CH2OSO2NH2;No. CAS：
10042-77-0）, a steps resulting material is added, 5~10 DEG C of temperature is adjusted with frozen water, with 10~40% NaOH（CAS
Number：1310-73-2）Solution maintenance pH=9~12, stirring reaction 1~3 hour, 35~50 DEG C of temperature of adjustment, maintenance temperature 35~
50 DEG C, pH=9~12, stirring reaction 1~3 hour；
C, neutralization reaction
The reaction solution of b step is adjusted to pH=6~7.5 with 30% hydrochloric acid solution.
D, post processing
Feed liquid that step c is obtained is refined, dry after be finished product.
Further, ammoniacal liquor is added in b the step of the above method.
Present invention also offers application performance of structure above (I) dyestuff in dyeing.
The sodium hydroxide solution that Summary of the present invention and embodiment part are mentioned, involved by hydrochloric acid solution, ammoniacal liquor
Percent concentration be mass percent concentration.
The present invention is had the advantage that：
Obtained Turquoise blue reactive dye of the invention is applied to the dyeing of the fibers such as cotton, fiber crops, hair, is particularly suited for ink-jet print
Flower.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but does not limit protection scope of the present invention.
Embodiment 1
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
A, chlorosulfonation
To 1750 kilograms of chlorosulfonic acid is added in retort, 40~50 DEG C of temperature is controlled.Time-consuming 2 hours public by CuPc 350
Jin adds 128 DEG C of temperature of adjustment, maintains 128~130 DEG C of temperature, reacts 4 hours.65~70 DEG C of temperature of adjustment, maintains temperature 65
~70 DEG C, 2 hours are taken by 595 kilograms of additions of thionyl chloride.65~70 DEG C of temperature is maintained, is reacted 2 hours.Adjustment temperature 90
DEG C, 90~95 DEG C of temperature is maintained, react 1 hour.105 DEG C of temperature of adjustment.105~110 DEG C of temperature is maintained, is reacted 1 hour, obtain chlorine
Sulfonation feed liquid.
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added into the retort equipped with frozen water
In.0~20 DEG C of temperature is maintained, is stirred 1 hour.Gained feed liquid is carried out into separation of solid and liquid.Filter cake to filter is washed with -5~5 DEG C of cold water
Liquid pH=5.Collect filter cake；
B, esterification
Lower the temperature to 73.1 kilograms of monoethanolamine, circulating water is added in retort.15~20 DEG C of temperature of control, in 45~60
By 71.9 kilograms of additions of glacial acetic acid in minute, 3 kilograms of 98% sulfuric acid is added, stirred, under backflow, adjust temperature 120~150
DEG C, 120~150 DEG C of temperature is maintained, react 5 hours.5~10 DEG C of temperature of adjustment, it is standby；
C, condensation
By in a steps resulting material addition b step resulting materials, 5~10 DEG C of temperature is adjusted with frozen water, use 20% hydroxide
Sodium solution maintains pH=9~10, stirring reaction 3 hours.35~40 DEG C of temperature of adjustment, 35~40 DEG C of temperature of maintenance, pH=9~10,
Stirring reaction 3 hours.
D, neutralization reaction
The reaction solution of step c is adjusted to pH=6~6.5 with 30% hydrochloric acid solution.
E, post processing
Feed liquid that Step d is obtained is refined, dry after be finished product.Obtain formula Turquoise blue reactive dye.
Embodiment 2
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
Step a, b is with step a, b of embodiment 1
C, condensation
By in a steps resulting material addition b step resulting materials, 5~10 DEG C of temperature is adjusted with frozen water, add 25% ammoniacal liquor
(No. CAS：1336-21-6) 83 kilograms, pH=9~10, stirring reaction 3 hours are maintained with 10% sodium hydroxide solution.Adjustment temperature
35~50 DEG C, maintain 35~50 DEG C of temperature, pH=9~10, stirring reaction 3 hours.
Step d, e obtains formula Turquoise blue reactive dye with step d, e of embodiment 1.
Embodiment 3
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
A, chlorosulfonation
To 2100 kilograms of chlorosulfonic acid is added in retort, 40~50 DEG C of temperature is controlled.Time-consuming 2 hours public by CuPc 350
Jin adds 118 DEG C of temperature of adjustment, maintains 118~120 DEG C of temperature, reacts 1 hour.138 DEG C of temperature of adjustment, maintenance temperature 138~
140 DEG C, react 4 hours, obtain chlorosulfonation feed liquid.
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added into the retort equipped with frozen water
In.0~20 DEG C of temperature is maintained, is stirred 1 hour.Gained feed liquid is carried out into separation of solid and liquid.Filter cake to filter is washed with -5~5 DEG C of cold water
Liquid pH=4.Collect filter cake.
B, condensation
To 166 kilograms of Sulfamic acid, 2-aminoethyl ester is added in retort, by a step gains
Material is added, and 5~10 DEG C of temperature is adjusted with frozen water, and pH=9~10, stirring reaction 3 hours are maintained with 10% sodium hydroxide solution.Adjustment
35~40 DEG C of temperature, maintains 35~40 DEG C of temperature, pH=9~10, stirring reaction 3 hours.
C, neutralization reaction
The reaction solution of b step is adjusted to pH=6~6.5 with 30% hydrochloric acid solution.
D, post processing
Feed liquid that step c is obtained is refined, dry after be finished product.Obtain formula orange Turquoise blue reactive dye.
Embodiment 4
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
The step of step a is with embodiment 3 a
B, condensation
To Sulfamic acid, 2-aminoethyl ester166 kilogram are added in retort, by a step resulting materials
Add, 5~10 DEG C of temperature is adjusted with frozen water, add 83 kilograms of 25% ammoniacal liquor, pH=9~10 are maintained with 10% sodium hydroxide solution, stir
Mix reaction 3 hours.35~40 DEG C of temperature of adjustment, maintains 35~40 DEG C of temperature, pH=9~10, stirring reaction 3 hours.
The step of step c, d is with embodiment 3 c, d, obtain formula Turquoise blue reactive dye.
Embodiment 5
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
A, chlorosulfonation
To 1750 kilograms of chlorosulfonic acid is added in retort, 40~50 DEG C of temperature is controlled.Time-consuming 2 hours public by CuPc 350
Jin adds 110 DEG C of temperature of adjustment, maintains 110~115 DEG C of temperature, reacts 4 hours.65~70 DEG C of temperature of adjustment, maintains temperature 65
~70 DEG C, 2 hours are taken by 595 kilograms of additions of thionyl chloride.65~70 DEG C of temperature is maintained, is reacted 2 hours.Adjustment temperature 90
DEG C, 90~95 DEG C of temperature is maintained, react 1 hour.105 DEG C of temperature of adjustment.105~110 DEG C of temperature is maintained, is reacted 1 hour, obtain chlorine
Sulfonation feed liquid.
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added into the retort equipped with frozen water
In.0~20 DEG C of temperature is maintained, is stirred 1 hour.Gained feed liquid is carried out into separation of solid and liquid.Filter cake to filter is washed with -5~5 DEG C of cold water
Liquid pH=5.Collect filter cake.
B, esterification
Lower the temperature to 36.6 kilograms of monoethanolamine, circulating water is added in retort.15~20 DEG C of temperature of control, in 45~60
By 36. kilograms of additions of glacial acetic acid in minute, 1.5 kilograms of 98% sulfuric acid is added, stirred, under backflow, adjust temperature 140~150
DEG C, 140~150 DEG C of temperature is maintained, react 5 hours.5~10 DEG C of temperature of adjustment.
C, condensation
By in a steps resulting material addition b step resulting materials, 5~10 DEG C of temperature is adjusted with frozen water, use 20% hydroxide
Sodium solution maintains pH=11~12, stirring reaction 1 hour.45~50 DEG C of temperature of adjustment, 45~50 DEG C of temperature of maintenance, pH=11~
12, stirring reaction 1 hour.
D, neutralization reaction
The reaction solution of step c is adjusted to pH=6~6.5 with 30% hydrochloric acid solution.
E, post processing
Feed liquid that Step d is obtained is refined, dry after be finished product.Obtain formula Turquoise blue reactive dye.
Embodiment 6
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
Step a, b is with step a, b of embodiment 5
C, condensation
By in a steps resulting material addition b step resulting materials, 5~10 DEG C of temperature is adjusted with frozen water, add 25% ammoniacal liquor
41.5 kilograms, pH=11~12, stirring reaction 1 hour are maintained with 20% sodium hydroxide solution.45~50 DEG C of temperature of adjustment, maintains temperature
45~50 DEG C of degree, pH=11~12, stirring reaction 1 hour.
Step d, e obtains formula Turquoise blue reactive dye with step d, e of embodiment 5.
Embodiment 7
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
A, chlorosulfonation
To 2100 kilograms of chlorosulfonic acid is added in retort, 40~50 DEG C of temperature is controlled.Time-consuming 2 hours public by CuPc 350
Jin adds 100 DEG C of temperature of adjustment, maintains 100~102 DEG C of temperature, reacts 1 hour.120 DEG C of temperature of adjustment, maintenance temperature 120~
122 DEG C, react 4 hours, obtain chlorosulfonation feed liquid.
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added into the retort equipped with frozen water
In.0~20 DEG C of temperature is maintained, is stirred 1 hour.Gained feed liquid is carried out into separation of solid and liquid.Filter cake to filter is washed with -5~5 DEG C of cold water
Liquid pH=5.Collect filter cake.
B, condensation
To Sulfamic acid, 2-aminoethyl ester83 kilogram are added in retort, by a step resulting materials
Add, 5~10 DEG C of temperature is adjusted with frozen water, pH=11~12, stirring reaction 1 hour are maintained with 40% sodium hydroxide solution.Adjustment
45~50 DEG C of temperature, maintains 45~50 DEG C of temperature, pH=11~12, stirring reaction 1 hour.
C, neutralization reaction
The reaction solution of b step is adjusted to pH=6~6.5 with 30% hydrochloric acid solution.
D, post processing
Feed liquid that step c is obtained is refined, dry after be finished product.Obtain formula Turquoise blue reactive dye
Embodiment 8
A kind of preparation method of Turquoise blue reactive dye, comprises the following steps：
Step a is with the step a of embodiment 7
B, condensation
To 83 kilograms of Sulfamic acid, 2-aminoethyl ester is added in retort, by a step resulting materials
Add, with frozen water adjust 5~10 DEG C of temperature, add 41.5 kilograms of 25% ammoniacal liquor, with 40% sodium hydroxide solution maintain pH=11~
12, stirring reaction 1 hour.45~50 DEG C of temperature of adjustment, maintains 45~50 DEG C of temperature, pH=11~12, stirring reaction 1 hour.
Step c, d obtains formula Turquoise blue reactive dye with step c, d of embodiment 7
Turquoise blue reactive dye dye hair prepared by the present invention（Pad dyeing）Application performance table
Product of the invention and method are described by specific embodiment.Those skilled in the art can borrow
The links such as mirror present disclosure appropriate feed change, process conditions realize corresponding other purposes, and its correlation change all do not have
There is disengaging present disclosure, all similar replacements and change are it will become apparent to those skilled in the art that all
It is deemed to be included within the scope of the present invention.
Claims (4)
1. a kind of preparation method of Turquoise blue reactive dye, it is characterised in that：The reactive dye have such as following formula (I) general structure
X+y+z=2~4, x >=0, y >=0, z ＞ 0
(Ⅰ)
R is-SO2NH-C2H4OCOCH3Or-SO2NH-C2H4OSO2NH2；
The preparation method of the Turquoise blue reactive dye, it is characterised in that：Comprise the following steps：
A, chlorosulfonation
To chlorosulfonic acid is added in retort, 40~50 DEG C of temperature is controlled, it is time-consuming to add CuPc within 2 hours, adjustment temperature 110~
140 DEG C, 110~140 DEG C of temperature is maintained, reacted 4 hours, adjust 65~70 DEG C of temperature, maintain 65~70 DEG C of temperature, take 2 small
When thionyl chloride is added, maintain 65~70 DEG C of temperature, react 2 hours, adjust 90 DEG C of temperature, maintain 90~95 DEG C of temperature, instead
Answer 1 hour, adjust 105 DEG C of temperature, maintain 105~110 DEG C of temperature, react 1 hour, obtain chlorosulfonation feed liquid；
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added in the retort equipped with frozen water, ties up
0~20 DEG C of temperature is held, is stirred 1 hour, gained feed liquid is carried out into separation of solid and liquid, filter cake to filtrate pH is washed with -5~5 DEG C of cold water
=4~5, collect filter cake；
B, esterification
To monoethanolamine is added in retort, 15~20 DEG C of temperature is controlled, add glacial acetic acid in 45~60 minutes, add sulphur
Acid, stirs, and under backflow, adjusts 120~150 DEG C of temperature, maintains 120~150 DEG C of temperature, reacts 5 hours, adjusts temperature 5
It is~10 DEG C, standby；
C, condensation
By in a steps resulting material addition b step resulting material, 5~10 DEG C of temperature is adjusted with frozen water, with 10~40% hydroxides
Sodium solution maintains pH=9~12, and stirring reaction 1~3 hour adjusts 35~50 DEG C of temperature, maintains 35~50 DEG C of temperature, pH=9
~12, stirring reaction 1~3 hour；
D, neutralization reaction
The reaction solution of step c is adjusted to pH=6~7.5 with 30% hydrochloric acid solution；
E, post processing
Feed liquid that Step d is obtained is refined, dry after be finished product dyestuff.
2. a kind of preparation method of Turquoise blue reactive dye according to claim 1, it is characterised in that：Added in step c
Ammoniacal liquor.
3. a kind of preparation method of Turquoise blue reactive dye, it is characterised in that：The reactive dye have such as following formula (I) general structure
X+y+z=2~4, x >=0, y >=0, z ＞ 0
(Ⅰ)
R is-SO2NH-C2H4OCOCH3Or-SO2NH-C2H4OSO2NH2；
The preparation method of the Turquoise blue reactive dye, it is characterised in that：Comprise the following steps：
A, chlorosulfonation
To chlorosulfonic acid is added in retort, 40~50 DEG C of temperature is controlled, it is time-consuming to add CuPc within 2 hours, adjustment temperature 100~
120 DEG C, 100~120 DEG C of temperature is maintained, reacted 1 hour, adjust 120~140 DEG C of temperature, maintain 120~140 DEG C of temperature, reaction
3~6 hours, obtain chlorosulfonation feed liquid；
20~25 DEG C of temperature of adjustment, takes 2 hours, and the chlorosulfonation feed liquid of gained is added in the retort equipped with frozen water, ties up
0~20 DEG C of temperature is held, is stirred 1 hour, gained feed liquid is carried out into separation of solid and liquid, filter cake to filtrate pH is washed with -5~5 DEG C of cold water
=4~5；Collect filter cake；
B, condensation
To in retort add sulfamic acid, 2- amino-ethyl esters, by a steps resulting material add, with frozen water adjust temperature 5~
10 DEG C, pH=9~12 are maintained with 10~40% sodium hydroxide solutions, stirring reaction 1~3 hour adjusts 35~50 DEG C of temperature, dimension
Hold 35~50 DEG C of temperature, pH=9~12, stirring reaction 1~3 hour；
C, neutralization reaction
The reaction solution of b step is adjusted to pH=6~7.5 with 30% hydrochloric acid solution；
D, post processing
Feed liquid that step c is obtained is refined, dry after be finished product.
4. a kind of preparation method of Turquoise blue reactive dye according to claim 3, it is characterised in that：Added in step c
Ammoniacal liquor.
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| CN103554982B (en) * | 2013-09-29 | 2017-10-24 | 天津德凯化工股份有限公司 | A kind of Turquoise blue reactive dye and preparation method thereof |
| CN104530746B (en) * | 2014-12-23 | 2016-08-24 | 浙江劲光实业股份有限公司 | A kind of Turquoise blue water-soluble dye and preparation method thereof |
| CN105331143A (en) * | 2015-12-02 | 2016-02-17 | 天津德凯化工股份有限公司 | Turquoise blue dye and preparing method thereof |
| CN105295437A (en) * | 2015-12-02 | 2016-02-03 | 天津德凯化工股份有限公司 | Turquoise blue dye for inkjet printing and preparation method thereof |
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