CN101880470A - Benzotriazole reactive dye for resisting ultraviolet radiation and preparation method thereof - Google Patents
Benzotriazole reactive dye for resisting ultraviolet radiation and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a benzotriazole reactive dye for resisting ultraviolet radiation and a preparation method thereof, aiming at solving the technical problems of ensuring that the wavelength range for resisting the ultraviolet radiation is wider and the effects are better. The dye is a compound as shown in a general formula (I), is a mixed bifunctional reactive dye, comprises a reactive dye mother body D, a connecting bridge group (cyanuric chloride group) and an ultraviolet absorbing group (benzotriazole group) and belongs to the mixed bifunctional reactive dye. The preparation method comprises the following steps of: (1) primarily condensing; (b) diazo coupling; (c) secondarily condensing; and (d) obtaining dye power by salting out or directly spraying dry.
Description
Technical field
The present invention relates to a kind of organic dye, specifically is reactive dyestuffs of wide wavelength region ultra-violet radiation resisting and preparation method thereof.
Background technology
As everyone knows, the intensive ultraviolet ray shines on the skin for a long time can cause very big injury to skin, such as the formation erythema, and skin aging etc., serious also can cause skin carcinoma.In ultraviolet ray stronger summer, clothes, umbrella (cap) etc. are the main barriers of human body antiultraviolet, but it is not enough only depending on fiber to come shielding ultraviolet rays, and the textiles that only has ultra-violet radiation resisting could protect human body to avoid ultraviolet injury effectively.At present, the ultra-violet radiation resisting effect of raising fiber mainly contains ultraviolet light screener and the two kinds of methods of uv-absorbing agent used.In fiber, add the snugness of fit of ultraviolet screening agent, bigger influence is arranged such as ventilation property, pliability etc. to fabric.And the ultraviolet screening agent that adds since be physical attachment on fiber, be easy to be cleaned and remove from lining, this just makes the ability of fiber ultra-violet radiation resisting reduce greatly, even disappears.The application UV light absorber improves ultra-violet radiation resisting and need through dyeing and putting two steps in order, increase cost and discharge of wastewater, but also can influence whiteness and the colour fastness performance that is organized fabric dying preceding or dying the back fabric is carried out anti UV finishing.
Therefore the ultra-violet radiation resisting ability that adopts these two kinds of methods to improve fiber can not obtain satisfied result, press for the ultra-violet radiation resisting performance that a kind of new approach can improve fabric, do not influence the snugness of fit of fabric again, can not increase treatment step simultaneously yet.
Chinese patent literature CN101177543A discloses a kind of " reactive dyestuffs that contain ultraviolet absorbing groups ", and it compares the deficiency that has the ultra-violet radiation resisting wavelength region narrow with the present invention.
Summary of the invention
The technical issues that need to address of the present invention are, a kind of new mixing double-active radical dye with ultra-violet radiation resisting function is provided, and make the ultra-violet radiation resisting wavelength region wideer, better effects if.
Reactive dye for resisting ultraviolet radiation of the present invention is a kind of mixing double-active radical dye, and its structure comprises the reactive dyestuffs mother body D, connects abutment (cyanuric chloride base), ultraviolet absorption group (benzotriazole base) three parts, belongs to the mixed type double-active radical dye.It is characterized in that its structure is shown in general formula (Ι):
Wherein, X is a halogen;
Y is H, the alkyl of C1～C6, the alkoxyl group of C1～C8 or-SO
3M, wherein M=H or alkali metal atom;
D is selected from compound shown in the following formula (color bodies structure):
Wherein, A is
,
R
1For-C
2H
4OSO
3M ,-C
2H
4SSO
3M or-CH=CH
2,
R
2For-H ,-SO
3M or-OR
4,
R
3For-the alkane of H, C1～C4 or-OR
4,
R
4Be the alkane of C1～C4,
M is H or alkali metal atom.
The described compound of above-mentioned general formula (Ι), its structure optimization is:
(I-7)，
Or
In the said structure, M is preferably H or Na.
The preparation method of a kind of benzotriazole ultra-violet radiation resisting mixed type double-active radical dye of the present invention is characterized in that, when D was D1～D3 in the general formula (Ι), its preparation comprised the steps:
A) primary condensation: be preferably 400～450 to 350～500() mole ice and water are to add 0.95～1.05 mole of cyanuric chloride in the mixture of arbitrary proportion, pull an oar 0.5～2 hour at 0～5 ℃; In addition 1 mole of D ' is dissolved in 350～500 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=1.6～4.0(preferred 2 ~ 3.5), obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point; Wherein D ' is selected from compound shown in D1 ', D2 ' or the D3 ':
(D1’)，
(D2’)，
(D3’)；
B) diazo coupling: in 350～500 moles of ice and water are the mixture of arbitrary proportion, add 0.95～1.05 mole of A ', add 800 milliliters of concentrated hydrochloric acids after 0.5～2 hour 0 ℃ of making beating; Be preferably 1.0～1.1 with 100 mole of water dissolvings, 1.0～1.5(simultaneously) behind the mole Sodium Nitrite, it slowly is added drop-wise in the solution of A ', after 0～15 ℃ (being preferably 5～10 ℃) reacted 0.5～3 hour, and detected no amino substance, eliminate excessive Sodium Nitrite with thionamic acid; Then it is added drop-wise in the primary condensation liquid, regulates pH=5.5～7.5(and be preferably 6.5～7.0), 0～15 ℃ of reaction; Detect no diazonium salt and exist for reaction end, obtain coupling solution; Wherein A ' is the compound shown in the following formula:
C) secondary condensation: in above-mentioned coupling solution, add 0.90～1.1(and be preferably 0.95～1.05) powder of mole U ', be warming up to 40～55 ℃ (being preferably 40～45 ℃), regulate pH=5.5～7.5(and be preferably 6.5～7.0), react 3～6 hours must dye solution; Wherein U ' is the compound shown in the following formula
D) saltout then or directly spray the dried dye powder that obtains.
The preparation method of another kind of benzotriazole ultra-violet radiation resisting mixed type double-active radical dye of the present invention is characterized in that, when D was D4 in the general formula (Ι), its preparation comprised the steps:
A) diazo coupling: in 350～500 moles of ice and water are the mixture of arbitrary proportion, add 0.95～1.05 mole of A ', add 800 milliliters of concentrated hydrochloric acids after 0.5～1 hour 0～10 ℃ of making beating; Simultaneously with behind 1.0～1.5 moles of Sodium Nitrites of 100 mole of water dissolving, it slowly is added drop-wise in the solution of A ', after 0～15 ℃ (being preferably 5～10 ℃) reacted 0.5～3 hour, and detected no amino substance, eliminate the diazonium liquid that excessive Sodium Nitrite obtains A ' with thionamic acid; After so being dissolved in 350～500 mole of water fully with NaOH solution 1 mole of D1 ', slowly be added drop-wise in the diazonium liquid of A ', regulate pH=2～3.0,0～10 ℃ of reaction; Detect no diazonium salt and exist for reaction end, obtain coupling solution one time;
Wherein A ' is the compound shown in the following formula
(A '),
Compound shown in the sour following formula of D1 '
(D1 ');
B) primary condensation: be preferably 400～450 to 350～500() mole ice and water are to add 0.95～1.05 mole of cyanuric chloride in the mixture of arbitrary proportion, pull an oar 0.5～2 hour at 0～5 ℃; In addition 1 mole of D3 ' acid is dissolved in 350～500 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=1.6～4.0(and be preferably 2 ~ 3.5), obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point;
C) secondary condensation: in above-mentioned primary condensation liquid, add the powder of 0.90～1.1 mole of U ', be warming up to 40～55 ℃, regulate pH=5.5～7.5, react 3～6 hours must secondary condensation solution; Wherein U ' is the compound shown in the following formula
(U ');
D) secondary diazo coupling: secondary condensation solution cooling back is added 800 milliliters of concentrated hydrochloric acids; Simultaneously with behind 1.0～1.5 moles of Sodium Nitrites of 100 mole of water dissolving, it slowly is added drop-wise in the secondary condensation solution, 0～10 ℃ of reaction 1～2 hour, after detecting no amino substance, eliminate excessive Sodium Nitrite with thionamic acid, so it is added drop-wise in coupling solution, regulates pH=6.5～7.0, obtained dye solution in 3～6 hours in 0～15 ℃ (being preferably 5～10 ℃) reaction;
E) saltout then or directly spray the dried dye powder that obtains.
Reaction conditions of the present invention is not made special restriction, only otherwise influencing goal of the invention of the present invention gets final product.The selection that those skilled in the art can more optimize above-mentioned various reaction conditionss by limited experiment according to prior art.
The present invention also provides a kind of dye composite, contains the dye composition of the present invention of painted significant quantity, and other dyestuff of surplus, carrier, auxiliary agent or its combination.Described painted significant quantity is allocated according to those skilled in the art's common practise.Other dyestuff comprises one or more dye compositions of the present invention and other dye species that is suitable for.
Dye composition of the present invention exists with the form of solid or liquid usually.Wherein can add the various auxiliary agents in some commercial dyes.
Reactive dye for resisting ultraviolet radiation of the present invention is used for the dyeing of cotton, viscose fiber, silk etc. and mixed fibre thereof, can be made into the dyeing product of cotton with ultra-violet radiation resisting function, viscose fiber, silk etc. and mixed fibre thereof.
Reactive dye for resisting ultraviolet radiation of the present invention mixes with tackiness agent, thickening material with printing and dyeing, obtain the printing and dyeing slurry of ultra-violet radiation resisting, this slurry can be coated with and invest on cotton, viscose fiber, silk etc. and the mixed fibre thereof, makes the stamp product of cotton with ultra-violet radiation resisting function, viscose fiber, silk etc. and mixed fibre thereof.
The invention has the advantages that:
Benzotriazole reactive dye for resisting ultraviolet radiation of the present invention, be that the ultraviolet absorption group that can absorb the ultraviolet benzotriazole type of very wide radiation scope contains in the reactive dyestuff molecule of mixing double active base as basic being incorporated into of sealing, the dyestuff that obtains had both had very strong painted and fixing property, had the function of wide wavelength region ultra-violet radiation resisting again.
Reactive dye for resisting ultraviolet radiation of the present invention only need dye according to the ordinary method of reactive dyestuffs, just can make the dyeing substrate have the function of ultra-violet radiation resisting simultaneously, does not need to carry out the arrangement of uvioresistant secondary.
Reactive dye for resisting ultraviolet radiation of the present invention, because the active group that has two kinds of different activities degree in the molecule, this dyestuff range of application is more extensive, the degree of fixation height, good with the combination stability of dyeing substrate, can make the dyeing substrate have the function of ultra-violet radiation resisting for a long time.
Reactive dye for resisting ultraviolet radiation of the present invention, the scope of ultraviolet radiation-absorbing is very wide, has excellent ultra-violet radiation resisting performance.
Embodiment
Below by embodiment, technical scheme of the present invention is done specific description.Need explanation, protection of the present invention is not limited to this.
Reactive dyestuffs embodiment 1.As follows,
1) primary condensation: in 450 moles of mixture of ice and water, add 1 mole of cyanuric chloride, 0～5 ℃ of making beating 0.5 hour; In addition 1 mole of H acid (D1 ', raw material 1) is dissolved in 450 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=2 ~ 3.5, obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point.The structural formula of D1 '-raw material 1 is as follows:
2) diazo coupling: in 450 moles of mixture of ice and water, add 1 mole of para-ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 0.5 hour 0 ℃ of making beating; With behind 1.1 moles of Sodium Nitrites of 100 mole of water dissolvings, it slowly is added drop-wise in the solution of para-ester simultaneously, 5～10 ℃ of reactions 0.5 hour, detects no amino substance after, with the excessive Sodium Nitrite of thionamic acid elimination; Then it is added drop-wise in the primary condensation liquid, regulates pH=6.5～7.0,0～15 ℃ of reaction.Detect no diazonium salt and exist for reaction end, obtain coupling solution.The structural formula of para-ester-raw material 2 is as follows:
3) secondary condensation: in above-mentioned coupling solution, add the powder of 1 mole of raw material 3, be warming up to 40～45 ℃, regulate pH=6.5～7.0, react 6 hours must dye solution; The structural formula of raw material 3 is as follows:
；
4) saltout then or directly spray the dried dye powder that obtains.Its structural formula is
(dyestuff I-1, M=H)
Adopt high performance liquid chromatography/mass spectrum on-line system that the molecular fragment of said structure is confirmed, corresponding with the I-1 structure.
Reactive dyestuffs embodiment 2 ~ 12.
Reactive dyestuffs embodiment 2
Primary condensation: in 500 moles of ice and water are the mixture of arbitrary proportion, add 1.05 moles of cyanuric chlorides, 0～5 ℃ of making beating 2 hours; In addition 1 mole of H acid (D1 ', raw material 1) is dissolved in 450 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=2 ~ 3.5, obtain primary condensation liquid 0～10 ℃ of reaction.
Diazo coupling: to 350 moles of ice and water be add 1.05 moles in the mixture of arbitrary proportion between position ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 0.5 hour 0 ℃ of making beating; Simultaneously with behind 1.1 moles of Sodium Nitrites of 100 mole of water dissolvings, in the solution of position ester, after 2 hours, eliminate excessive Sodium Nitrite between it slowly is added drop-wise to thionamic acid 0～10 ℃ of reaction; Then it is added drop-wise in the primary condensation liquid, regulates pH=6～7, do not exist to there being diazonium salt, obtain coupling solution 0～15 ℃ of reaction.
The secondary condensation: in above-mentioned coupling solution, add the powder of 1.05 moles of raw materials 3, be warming up to 50～55 ℃, regulate pH=6～7, react 6 hours must dye solution, through oversalting or directly spray the dried dye powder that obtains.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-2, M=H).
Reactive dyestuffs embodiment 3
Primary condensation: in 350 moles of ice and water are the mixture of arbitrary proportion, add 0.95 mole of cyanuric chloride, 0～5 ℃ of making beating 0.5 hour; In addition 1 mole of H acid (D1 ', raw material 1) is dissolved in 350 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=3～4.0, obtain primary condensation liquid 0～10 ℃ of reaction.
The diazo coupling step replaces with sulfonation para-ester with raw material 2, and other is with embodiment 1.
The secondary condensation: in coupling solution, add the powder of 0.95 mole of raw material 3, be warming up to 40～45 ℃, regulate pH=6～7, react 5 hours must dye solution, through oversalting or directly spray the dried dye powder that obtains.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-3, M=H).
Reactive dyestuffs embodiment 4
The diazonium step adds 1 mole of raw material 2 in 450 moles of mixture of ice and water, add 800 milliliters of concentrated hydrochloric acids and 1.1 moles of Sodium Nitrite diazotization after 2 hours 0 ℃ of making beating, 5～10 ℃ of reactions 3 hours, detect no amino substance after, eliminate excessive Sodium Nitrite with thionamic acid, obtain diazonium liquid.Other is with embodiment 1.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-4, M=H).
Reactive dyestuffs embodiment 5
Primary condensation: in 450 moles of mixture of ice and water, add 1 mole of cyanuric chloride, 0～5 ℃ of making beating 0.5 hour; In addition 1 mole of J acid (D2 ', raw material 1) is dissolved in 450 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=2 ~ 3.5, obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point.The structural formula of D2 '-raw material 1 is as follows:
Diazo coupling: in 450 moles of mixture of ice and water, add 1 mole of para-ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 0.5 hour 0 ℃ of making beating; With behind 1.1 moles of Sodium Nitrites of 100 mole of water dissolvings, it slowly is added drop-wise in the solution of para-ester simultaneously, 0～10 ℃ of reaction 1 hour, detects no amino substance after, with the excessive Sodium Nitrite of thionamic acid elimination; Then it is added drop-wise in the primary condensation liquid, regulates pH=6.5～7.0,0～10 ℃ of reaction.Detect no diazonium salt and exist for reaction end, obtain coupling solution.
The secondary condensation: in above-mentioned coupling solution, add the powder of 1.05 moles of raw materials 3, be warming up to 40～45 ℃, regulate pH=6.5～7.0, react 6 hours must dye solution.Through oversalting or directly spray the dried dye powder that obtains.Structural formula is:
Reactive dyestuffs embodiment 6
Position ester (as shown in the formula showing) the diazonium step is replaced with raw material 2 by para-ester between, other step is with embodiment 5.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-6, M=H).
Reactive dyestuffs embodiment 7
The diazonium step replaces with sulfonation para-ester (as shown in the formula showing) with raw material 2 by para-ester, and other step is with embodiment 5.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-7, M=H).
Reactive dyestuffs embodiment 8
The diazonium step replaces with 2-methoxyl group-5-methyl para-ester (as shown in the formula showing) with raw material 2 by para-ester, and other step is with embodiment 5.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-8, M=H).
Reactive dyestuffs embodiment 9
Primary condensation: in 450 moles of mixture of ice and water, add 1 mole of cyanuric chloride, 0～5 ℃ of making beating 0.5 hour; In addition with 1 mole 2, and the 4-diamino benzene sulfonic acid (D3 ', raw material 1) be dissolved in fully in 450 mole of water with NaOH solution, slowly be added to then in the cyanuric chloride slurries; Regulate pH=2 ~ 3.5, obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point.The structural formula of D3 '-raw material 1 is as follows:
Diazo coupling: in 450 moles of mixture of ice and water, add 1 mole of para-ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 0.5 hour 0 ℃ of making beating; With behind 1.1 moles of Sodium Nitrites of 100 mole of water dissolvings, it slowly is added drop-wise in the solution of para-ester simultaneously, 5～10 ℃ of reactions 1 hour, detects no amino substance after, with the excessive Sodium Nitrite of thionamic acid elimination; Then it is added drop-wise in the primary condensation liquid, regulates pH=6.0～6.5,5～10 ℃ of reactions.Detect no diazonium salt and exist for reaction end, obtain coupling solution.
The secondary condensation: in above-mentioned coupling solution, add the powder of 1 mole of raw material 3, be warming up to 45～50 ℃, regulate pH=6.5～7.0, react 6 hours must dye solution; Saltout then or directly spray the dried dye powder that obtains.Its structural formula is
(dyestuff I-9, M=H).
Reactive dyestuffs embodiment 10
Position ester (as shown in the formula showing) the diazonium step is replaced with raw material 2 by para-ester between, other step is with embodiment 9.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-10, M=H).
Reactive dyestuffs embodiment 11
The diazonium step replaces with sulfonation para-ester (as shown in the formula showing) with raw material 2 by para-ester, and other step is with embodiment 9.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-11, M=H).
Reactive dyestuffs embodiment 12
The diazonium step replaces with 2-methoxyl group-5-methyl para-ester (as shown in the formula showing) with raw material 2 by para-ester, and other step is with embodiment 5.
Raw material 2=
, make the dye composition of following formula:
Reactive dyestuffs embodiment 13
1) diazo coupling: in 450 moles of mixture of ice and water, add 1 mole of para-ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 0.5 hour 0～10 ℃ of making beating; With behind 1.1 moles of Sodium Nitrites of 100 mole of water dissolvings, it slowly is added drop-wise in the para-ester solution simultaneously, 5～10 ℃ of reactions 0.5 hour, detects no amino substance after, obtain the diazonium liquid of para-ester with the excessive Sodium Nitrite of thionamic acid elimination; So with 1 mole of H acid (raw material 1), be dissolved in 450 mole of water fully with NaOH solution after, slowly be added drop-wise in the para-ester diazonium liquid, regulate pH=2～3.0,0～10 ℃ of reaction.Detect no diazonium salt and exist for reaction end, obtain coupling solution one time.
2) primary condensation: in 450 moles of mixture of ice and water, add 1 mole of cyanuric chloride, 0～5 ℃ of making beating 0.5 hour; With 1 mole 2, the 4-diamino benzene sulfonic acid is dissolved in 450 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries in addition; Regulate pH=2 ~ 3.5, obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point.
3) secondary condensation: in above-mentioned primary condensation liquid, add the powder of 1 mole of raw material 3, be warming up to 40～45 ℃, regulate pH=6～6.5, react 6 hours must secondary condensation solution;
4) secondary diazo coupling: secondary condensation solution cooling back is added 800 milliliters of concentrated hydrochloric acids; Simultaneously with behind 1.1 moles of Sodium Nitrites of 100 mole of water dissolving, it slowly is added drop-wise in the secondary condensation solution, 0～10 ℃ of reaction 2 hours, after detecting no amino substance, eliminate excessive Sodium Nitrite with thionamic acid, so it is added drop-wise in coupling solution, regulates pH=6.5～7.0, obtained dye solution in 6 hours 5～10 ℃ of reactions.
5) saltout then or directly spray the dried dye powder that obtains.Its structural formula is
Reactive dyestuffs embodiment 14
A diazo coupling: to 350 moles of ice and water be add 0.95 mole in the mixture of arbitrary proportion between position ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 0.5 hour 0～10 ℃ of making beating; Use 1.1 moles of sodium nitrite solutions after 1 hour, to eliminate excessive Sodium Nitrite simultaneously with thionamic acid 0～10 ℃ of diazonium; After so being dissolved in 500 mole of water fully with NaOH solution 1 mole of H acid (raw material 1), in the position ester diazonium liquid, regulate pH=2～3.0, between slowly being added drop-wise to 0～10 ℃ of reaction; Detect no diazonium salt and exist for reaction end, obtain coupling solution one time;
Primary condensation: in 350 moles of ice and water are the mixture of arbitrary proportion, add 0.95 mole of cyanuric chloride, 0～5 ℃ of making beating 1 hour; Slowly add 1 mole 2 then, the 4-diamino benzene sulfonic acid aqueous solution; Regulate pH=1.6～3, obtain primary condensation liquid 0～5 ℃ of reaction;
The secondary condensation: in above-mentioned primary condensation liquid, add the powder of 0.95 mole of raw material 3, be warming up to 40～45 ℃, regulate pH=6.5～7.0, react 5 hours must secondary condensation solution;
Secondary diazo coupling: behind 800 milliliters of concentrated hydrochloric acids of secondary condensation solution cooling back adding, with 1.2 moles of sodium nitrite in aqueous solution 0～10 ℃ of diazonium after 2 hours, eliminate excessive Sodium Nitrite with thionamic acid, so it is added drop-wise in coupling solution, regulate pH=6.5～7.0, obtained dye solution in 6 hours 0～10 ℃ of reaction; Saltout then or directly spray the dried dye powder that obtains.Its structural formula is
Reactive dyestuffs embodiment 15
Diazo coupling: in 350 moles of ice and water are the mixture of arbitrary proportion, add 1.05 moles of sulfonation para-ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 0.5 hour 0～10 ℃ of making beating; Use 1.1 moles of sodium nitrite solutions after 1 hour, to eliminate excessive Sodium Nitrite simultaneously with thionamic acid 0～10 ℃ of diazonium; After so being dissolved in 500 mole of water fully with NaOH solution 1 mole of H acid (raw material 1), in the position ester diazonium liquid, regulate pH=2～3.0, between slowly being added drop-wise to 0～10 ℃ of reaction; Detect no diazonium salt and exist for reaction end, obtain coupling solution one time;
Primary condensation: in 500 moles of ice and water are the mixture of arbitrary proportion, add 1.05 moles of cyanuric chlorides, 0～5 ℃ of making beating 1 hour; Slowly add 1 mole 2 then, the 4-diamino benzene sulfonic acid aqueous solution; Regulate pH=1.6～3, obtain primary condensation liquid 0～5 ℃ of reaction;
The secondary condensation: in above-mentioned primary condensation liquid, add the powder of 1.05 moles of raw materials 3, be warming up to 45～50 ℃, regulate pH=6.5～7.5, react 6 hours must secondary condensation solution;
Other step is with embodiment 13.
Raw material 2=
, make the dye composition of following formula:
Reactive dyestuffs embodiment 16
Diazo coupling: in 350 moles of ice and water are the mixture of arbitrary proportion, add 1 mole of 2-methoxyl group-5-methyl para-ester (raw material 2), add 800 milliliters of concentrated hydrochloric acids after 2 hours 0～10 ℃ of making beating; Use 1.1 moles of sodium nitrite solutions after 2 hours, to eliminate excessive Sodium Nitrite simultaneously with thionamic acid 0～10 ℃ of diazonium; After so being dissolved in 500 mole of water fully with NaOH solution 1 mole of H acid (raw material 1), in the position ester diazonium liquid, regulate pH=2～3.0, between slowly being added drop-wise to 0～10 ℃ of reaction; Detect no diazonium salt and exist for reaction end, obtain coupling solution one time;
Other step is with embodiment 13.
Raw material 2=
, make the dye composition of following formula:
(dyestuff I-16, M=H).
Reactive dyestuffs are at cotton Application of Dyeing embodiment 1.
The experiment of dyeing of selected part dyestuff, the dyestuff as shown in following table is respectively got 2 parts of dye powders and 130 parts of sodium sulfate are dissolved in 2000 parts of water, and 100 parts of cottons are put into this dye solution.Be warming up to 65 ℃ then and kept 30 minutes, in dye liquor, add 50 parts of soda ash again, continue to keep 1 hour.Cotton is taken out the back with behind the water rinse in dye liquor, the soap lye of using 1g/L was 95 ℃ of rinsings 15 minutes, and washing is dried then, obtains having the dyed cotton fabric of ultra-violet radiation resisting function.
Method according to standard GB/T18830-2002 is estimated the uvioresistant effect of fabric, the results are shown in Table 1.
Table 1
The result finds out from last table, the UPF value of cotton of being unstained only is 1.3, the ultra-violet radiation resisting poor ability, but the UPF value of the invention described above dyestuff is significantly improved, especially I-1 and I-13 UPF value 〉=17.5, shown good ultra-violet radiation resisting performance.
Claims (6)
1. reactive dye for resisting ultraviolet radiation is characterized in that its structure is shown in general formula (Ι):
(Ι) wherein, X is a halogen; Y is H, the alkyl of C1～C6, the alkoxyl group of C1～C8 or-SO
3M, wherein M=H or alkali metal atom; D is selected from compound shown in the following formula:
(D1),
(D2),
(D3),
(D4), wherein, A is
, R
1For-C
2H
4OSO
3M ,-C
2H
4SSO
3M or-CH=CH
2, R
2For-H ,-SO
3M or-OR
4, R
3For-the alkane of H, C1～C4 or-OR
4, R
4Be the alkane of C1～C4, M is H or alkali metal atom.
2. reactive dye for resisting ultraviolet radiation according to claim 1 is characterized in that its structure is shown below:
(I-1),
(I-2),
(I-3),
(I-4),
(I-5),
(I-6),
(I-7),
(I-8),
(I-9),
(I-10),
(I-11),
(I-12),
(I-13)
(I-14),
(I-15) or
(I-16) in the said structure, M is selected from H or Na.
3. the preparation method of a reactive dye for resisting ultraviolet radiation as claimed in claim 1 or 2 is characterized in that, when D was D1～D3 in the general formula (Ι), its preparation comprised the steps:
A) primary condensation: in 350～500 moles of ice and water are the mixture of arbitrary proportion, add 0.95～1.05 mole of cyanuric chloride, 0～5 ℃ of making beating 0.5～2 hour; In addition 1 mole of D ' is dissolved in 350～500 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=1.6～4.0, obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point; Wherein D ' is selected from compound shown in D1 ', D2 ' or the D3 ':
(D1 '),
(D2 '),
(D3 ');
B) diazo coupling: in 350～500 moles of ice and water are the mixture of arbitrary proportion, add 0.95～1.05 mole of A ', add 800 milliliters of concentrated hydrochloric acids after 0.5～2 hour 0 ℃ of making beating; With behind 1.0～1.5 moles of Sodium Nitrites of 100 mole of water dissolvings, it slowly is added drop-wise in the solution of A ' simultaneously, 0～15 ℃ of reaction 0.5～3 hour, detects no amino substance after, with the excessive Sodium Nitrite of thionamic acid elimination; Then it is added drop-wise in the primary condensation liquid, regulates pH=5.5～7.5,0～15 ℃ of reaction; Detect no diazonium salt and exist for reaction end, obtain coupling solution; Wherein A ' is the compound shown in the following formula:
(A ');
C) secondary condensation: in above-mentioned coupling solution, add the powder of 0.90～1.1 mole of U ', be warming up to 40～55 ℃, regulate pH=5.5～7.5, react 3～6 hours must dye solution; Wherein U ' is the compound shown in the following formula
(');
D) saltout then or directly spray the dried dye powder that obtains.
4. the preparation method of reactive dye for resisting ultraviolet radiation according to claim 3 is characterized in that in the step a), and ice and water are that the amount of mixture of arbitrary proportion is 400～450 moles; The pH value is adjusted to 2 ~ 3.5); Sodium Nitrite is 1.0～1.1 moles in the step b), and temperature of reaction is 5～10 ℃, and the pH value is adjusted to 6.5～7.0; The powder add-on of U ' is 0.95～1.05 in the step c), is warming up to 40～45 ℃, and the pH value is adjusted to 6.5～7.0.
5. the preparation method of a reactive dye for resisting ultraviolet radiation as claimed in claim 1 or 2 is characterized in that, when D was D4 in the general formula (Ι), its preparation comprised the steps:
A) diazo coupling: in 350～500 moles of ice and water are the mixture of arbitrary proportion, add 0.95～1.05 mole of A ', add 800 milliliters of concentrated hydrochloric acids after 0.5～1 hour 0～10 ℃ of making beating; With behind 1.0～1.5 moles of Sodium Nitrites of 100 mole of water dissolvings, it slowly is added drop-wise in the solution of A ' simultaneously, 0～15 ℃ of reaction 0.5～3 hour, detects no amino substance after, obtain the diazonium liquid of A ' with the excessive Sodium Nitrite of thionamic acid elimination; After being dissolved in 350～500 mole of water fully with NaOH solution 1 mole of D1 ' then, slowly be added drop-wise in the diazonium liquid of A ', regulate pH=2～3.0,0～10 ℃ of reaction; Detect no diazonium salt and exist for reaction end, obtain coupling solution one time; Wherein A ' is the compound shown in the following formula
(A '), D1 ' is the compound shown in the following formula
(D1 '); B) primary condensation: in 350～500 moles of ice and water are the mixture of arbitrary proportion, add 0.95～1.05 mole of cyanuric chloride, 0～5 ℃ of making beating 0.5～2 hour; In addition 1 mole of D3 ' acid is dissolved in 350～500 mole of water fully with NaOH solution, slowly is added to then in the cyanuric chloride slurries; Regulate pH=1.6～4.0, obtain primary condensation liquid 0～10 ℃ of reaction; With amino indicator detection reaction terminal point;
C) secondary condensation: in above-mentioned primary condensation liquid, add the powder of 0.90～1.1 mole of U ', be warming up to 40～55 ℃, regulate pH=5.5～7.5, react 3～6 hours must secondary condensation solution; Wherein U ' is the compound shown in the following formula
(U ');
D) secondary diazo coupling: secondary condensation solution cooling back is added 800 milliliters of concentrated hydrochloric acids; Simultaneously with behind 1.0～1.5 moles of Sodium Nitrites of 100 mole of water dissolving, it slowly is added drop-wise in the secondary condensation solution, 0～10 ℃ of reaction 1～2 hour, after detecting no amino substance, eliminate excessive Sodium Nitrite with thionamic acid, so it is added drop-wise in coupling solution, regulates pH=6.5～7.0, obtained dye solution in 3～6 hours 0～15 ℃ of reaction;
E) saltout then or directly spray the dried dye powder that obtains.
6. the preparation method of reactive dye for resisting ultraviolet radiation according to claim 5 is characterized in that temperature of reaction is 5～10 ℃ in the step a)); Ice and water are that the amount of mixture of arbitrary proportion is 400～450 in the step b), and the pH value is adjusted to 2 ~ 3.5; Temperature of reaction is 5～10 ℃ in the step d).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054430A (en) * | 2018-09-05 | 2018-12-21 | 杭州下沙恒升化工有限公司 | A kind of preparation method of acid dye finished product |
| CN111286211A (en) * | 2020-03-30 | 2020-06-16 | 金华双宏化工有限公司 | Sun-proof blue acid dye and preparation method thereof |
| CN114560848A (en) * | 2022-01-26 | 2022-05-31 | 山东中康国创先进印染技术研究院有限公司 | Reactive light/light-perspiration resistant composite color fastness improver and preparation method thereof |
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| CN1465626A (en) * | 2002-12-25 | 2004-01-07 | 邱泽国 | Dye and photostabilizer of information recording material thereof |
| CN101177543A (en) * | 2006-11-10 | 2008-05-14 | 上海科华染料工业有限公司 | Active dye containing ultraviolet absorbing groups |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1465626A (en) * | 2002-12-25 | 2004-01-07 | 邱泽国 | Dye and photostabilizer of information recording material thereof |
| CN101177543A (en) * | 2006-11-10 | 2008-05-14 | 上海科华染料工业有限公司 | Active dye containing ultraviolet absorbing groups |
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| 《大连理工大学学报》 20090131 宫国梁等 含苯并三唑基团抗紫外辐射活性染料合成与应用性能研究 24-27 1-6 第49卷, 第1期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054430A (en) * | 2018-09-05 | 2018-12-21 | 杭州下沙恒升化工有限公司 | A kind of preparation method of acid dye finished product |
| CN111286211A (en) * | 2020-03-30 | 2020-06-16 | 金华双宏化工有限公司 | Sun-proof blue acid dye and preparation method thereof |
| CN111286211B (en) * | 2020-03-30 | 2021-02-23 | 金华双宏化工有限公司 | Sun-proof blue acid dye and preparation method thereof |
| CN114560848A (en) * | 2022-01-26 | 2022-05-31 | 山东中康国创先进印染技术研究院有限公司 | Reactive light/light-perspiration resistant composite color fastness improver and preparation method thereof |
| CN114560848B (en) * | 2022-01-26 | 2023-08-18 | 山东中康国创先进印染技术研究院有限公司 | Reactive light/sweat resistant composite color fastness improver and preparation method thereof |
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Application publication date: 20101110 |