CN102199365B - NK-BB red dye special for nylon, and preparation method thereof - Google Patents
NK-BB red dye special for nylon, and preparation method thereof Download PDFInfo
- Publication number
- CN102199365B CN102199365B CN201110072479.6A CN201110072479A CN102199365B CN 102199365 B CN102199365 B CN 102199365B CN 201110072479 A CN201110072479 A CN 201110072479A CN 102199365 B CN102199365 B CN 102199365B
- Authority
- CN
- China
- Prior art keywords
- solution
- milliliters
- add
- grams
- adjust
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to a NK-BB red dye special for nylon, and a preparation method thereof. The NK-BB red dye special for the nylon is a compound having a structure represented by the following general formula (I), wherein R1 in the general formula (I) is selected from H, alkyl, alkoxy or -SO3M; R2 in the general formula (I) is selected from H, alkyl or alkoxy; R3 in the general formula (I) is selected from H or -COCHBrCH2Br; Z in the general formula (I) is selected from -SO2C2H4OSO3M or a condensation compound of monochlorotriazinyl; M in the general formula (I) is selected from H or an alkali metal. According to the present invention, environmental pollution is reduced. The NK-BB red dye special for the nylon and the preparation method thereof have advantages of low cost of raw materials, high solubility, bright color, excellent application performance and convenient operation. In addition, the NK-BB red dye special for the nylon has strong applicability.
Description
Technical field
The present invention relates to a kind of nylon active dye well its preparation method, particularly relate to a kind of NK-BB red dye special for nylon and preparation method thereof.
Technical background
Generally dye now nylon dyestuff used and be matching stain, acid mordant dye and metallized dye.Due to the material dying by these kinds of dyes, fastness is all not good enough, and coloured light is not bery gorgeous, but also can cause trouble to environmental protection.Enter 21 century, due to the restriction of environmental ecology, more and more higher for the requirement of dye uptake, degree of fixation and dyeing waste-water.Matching stain can not meet the development in epoch again.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of NK-BB red dye special for nylon, this NK-BB red dye special for nylon is the compound with following general formula (I) structure:
Wherein: R
1for H, alkyl, alkoxyl group or-SO
3m;
R
2for H, alkyl or alkoxyl group;
R
3for H ,-COCHBrCH
2br;
Z is-SO
2c
2h
4oSO
3m,
M is H or basic metal.
Preferably, wherein alkyl is-CH
3or-CH
2cH
3, alkoxyl group is-OCH
3or-OCH
2cH
3, M is basic metal;
More preferably, alkyl is-CH
3, alkoxyl group is-OCH
3, M is Na metal;
The present invention adopts following technical scheme to achieve these goals:
NK-BB red dye special for nylon, is characterized in that: this NK-BB red dye special for nylon is the compound with following general formula (I) structure:
Wherein: R
1for H, alkyl, alkoxyl group or-SO
3m;
R
2for H, alkyl or alkoxyl group;
R
3for H ,-COCHBrCH
2br;
Z is-SO
2c
2h
4oSO
3m,
M is H or basic metal.
Described dyestuff, wherein alkyl is-CH
3or-CH
2cH
3, alkoxyl group is-OCH
3or-OCH
2cH
3, M is basic metal.
Described dyestuff, wherein alkyl is-CH
3, alkoxyl group is-OCH
3, M is Na metal.
The preparation method of described NK-BB red dye special for nylon, is characterized in that comprising the following steps:
(1) dissolving of gamma acid
In beaker, add water, then add 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarify, adjust the volume of solution, the gamma acid solution that the quality volume fraction that makes solution is 15%;
(2) condensation reaction
Directly with ice and water, adjust gamma acid solution temperature to 5-7 ℃, adjusting solution quality volume fraction is 10%, then with sodium bicarbonate, maintain pH=6-6.5, directly use ice holding temperature 5-10 ℃, used time 40-60 minute, by 100%2,3-bis-bromo propionyl chloros and acetone mixed solution add, and wherein gamma acid is 1 with the ratio of acylate and acetone: 1-1.1: 0.1-0.11, holding temperature 5-10 ℃ and pH value 6-6.5, reaction 1-3 hour, obtains condensated liquid;
(3) diazotization reaction
In beaker, add water, then add the compound of following structural formula (II), stir 10-20 minute; 30% hydrochloric acid soln is added, directly with ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, adds 30% sodium nitrite solution fast, wherein structure (II) is 1 with the ratio of Sodium Nitrite: 1-1.02, holding temperature 0-5 ℃, reaction 1-3 hour, eliminates excessive nitrous acid with thionamic acid, obtain diazo liquid
R wherein
1, R
2with the implication of Z with the definition in claim 1;
(4) coupled reaction
The diazo liquid that (3) step is obtained joins in the condensated liquid that (2) step obtains, and with sodium carbonate, adjusts pH=7, is warmed up to 10 ℃, and holding temperature 10-30 ℃, maintains pH=5-8, reaction 3-5 hour;
(5) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 10-20 minute;
(6) dry
The look liquid of step (5) is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dryly, obtain product.
In such scheme, gamma acid is the abbreviation of 2-amido-8-naphthol-6-sulfonic acid, and its structural formula is as follows:
The compound of said structure formula (II) is position ester, Ke Lixiding para-ester, sulfonation para-ester, 2,5-dimethoxy para-ester or a chloro-s-triazine condenses between para-ester, a position ester, O-methoxy.
Particularly, the compound of said structure formula (II) is respectively:
Para-ester claims again (beta-sulfuric ester ethyl sulfonyl) aniline, vinyl sulfone(RemzaolHuo Xingranliaohuoxingjituan) sulfuric ester, and 4-sulfovinic acid sulfuryl aniline, p-beta-hydroxy second sulfone aniline sulfuric ester or p-beta-hydroxy second sulfone aniline sulfuric ester, its structural formula is as follows:
Between position ester be between the abbreviation of (beta-sulfuric ester ethyl sulfonyl base) aniline, its structural formula is as follows:
Between O-methoxy, the chemistry of position ester its structural formula of 2-methoxyl group-4-β-ethyl sulfuryl sulfate ester aniline by name is as follows:
The CAS number of boarding of Ke Lixiding para-ester (Para Cresidine Base) is 21635-69-8.
Chemistry 4-β-ethyl sulfuryl sulfate ester aniline-2-sulfonic acid by name of sulfonation para-ester, its structural formula is as follows:
Chemistry 2,5-dimethoxy-4 '-β-ethyl sulfuryl sulfate ester aniline by name of 2,5-dimethoxy para-ester, the CAS number of boarding is 26672-24-2, structural formula is as follows:
One chloro-s-triazine condenses, structural formula is as follows
In the method for aforesaid method and below embodiment, the unit of quality volume fraction is grams per milliliter (g/ml) or kg/liter (kg/L).
Advantage of the present invention:
The invention provides one and can reduce environmental pollution, desired raw material cost is low, and product solubility is high, and bright in colour, and application performance is excellent, easy to use, red reactive dye for wool that suitability is strong and preparation method thereof.
Embodiment
Embodiment 1
(1) dissolving of gamma acid
In 500 ml beakers, add 120 milliliters, water, then add 23.9 grams of 100% gamma acid, stir lower to 30% sodium hydroxide solution tune pH=6.5-7.0, make material dissolution, clarification, the volume of adjusting solution is 160 milliliters, making the quality volume fraction of solution is 15%, obtains gamma acid solution.
(2) condensation reaction
Direct ice and water are adjusted gamma acid solution temperature to 5-7 ℃, adjusting solution quality volume fraction is 10%, then follow 96% sodium bicarbonate to maintain pH=6-6.5, with direct ice holding temperature 5-10 ℃, 50 minutes used times, by 100% 2,32.6 grams of 3-bis-bromo propionyl chloros and acetone mixed solution add, holding temperature 5-10 ℃ and pH value 6-6.5, react 2 hours to obtain condensated liquid.
(3) diazotization reaction
In 800 ml beakers, add 200 milliliters, water, then 28.1 grams of 100% para-esters are added, stir 15 minutes.Again 15.8 gram of 30% hydrochloric acid soln added, by direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantee that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast, holding temperature 0-5 ℃, react 2 hours, with thionamic acid, eliminate excessive nitrous acid, obtain diazo liquid
(4) coupled reaction
The diazo liquid that step (3) is obtained joins in the condensated liquid that step (2) obtains, and with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(5) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(6) dry
The look liquid of step (5) is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure.
Embodiment 2
(1) dissolving of gamma acid
In 500 ml beakers, add 120 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 160 milliliters.The quality volume fraction that makes solution is 15%
(2) condensation reaction
With direct ice and water, adjust gamma acid solution temperature to 5-7 ℃, adjusting solution quality volume fraction is 10%, then follow 96% sodium bicarbonate to maintain pH=6-6.5, with direct ice holding temperature 5-10 ℃, 50 minutes used times, by 100% 2,32.6 grams of 3-bis-bromo propionyl chloros and acetone mixed solution add, holding temperature 5-10 ℃ and pH value 6-6.5, react 2 hours to obtain condensated liquid.
(3) diazotization reaction
In 800 ml beakers, add 200 milliliters, water, then 28.1 grams of 100% position esters are added, stir 15 minutes.Again 15.8 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.Holding temperature 0-5 ℃, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid
(4) coupled reaction
The diazo liquid that step (3) is obtained joins in the condensated liquid that step (2) obtains, and with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(5) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(6) dry
The look liquid of step (5) is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
Embodiment 3
(1) dissolving of gamma acid
In 500 ml beakers, add 120 milliliters, water, then add 23.9 grams of 100%H acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 160 milliliters.The quality volume fraction that makes solution is 15%
(2) condensation reaction
With direct ice and water, adjust gamma acid solution temperature to 5-7 ℃, adjusting solution quality volume fraction is 10%, then follow 96% sodium bicarbonate to maintain pH=6-6.5, with direct ice holding temperature 5-10 ℃, 50 minutes used times, by 100% 2,32.6 grams of 3-bis-bromo propionyl chloros and acetone mixed solution add, holding temperature 5-10 ℃ and pH value 6-6.5, react 2 hours to obtain condensated liquid.
(3) diazotization reaction
In 800 ml beakers, add 200 milliliters, water, then 31.1 grams of 100%2-methoxyl group-4-β-ethyl sulfuryl sulfate ester anilines are added, stir 15 minutes.Again 15.8 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.Holding temperature 0-5 ℃, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid
(4) coupled reaction
The diazo liquid that step (3) is obtained joins in the condensated liquid that step (2) obtains, and with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(5) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(6) dry
The look liquid of step (5) is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
Embodiment 4
(1) dissolving of gamma acid
In 500 ml beakers, add 120 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 160 milliliters.The quality volume fraction that makes solution is 15%
(2) condensation reaction
With direct ice and water, adjust gamma acid solution temperature to 5-7 ℃, adjusting solution quality volume fraction is 10%, then follow 96% sodium bicarbonate to maintain pH=6-6.5, with direct ice holding temperature 5-10 ℃, 50 minutes used times, by 100% 2,32.6 grams of 3-bis-bromo propionyl chloros and acetone mixed solution add, holding temperature 5-10 ℃ and pH value 6-6.5, react 2 hours to obtain condensated liquid.
(3) diazotization reaction
In 800 ml beakers, add 200 milliliters, water, then 32.5 grams of 100% Ke Lixiding para-esters are added, stir 15 minutes.Again 15.8 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.Holding temperature 0-5 ℃, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid
(4) coupled reaction
The diazo liquid that step (3) is obtained joins in the condensated liquid that step (2) obtains, and with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(5) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(6) dry
The look liquid of step (5) is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
Embodiment 5
(1) dissolving of gamma acid
In 500 ml beakers, add 120 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 160 milliliters.The quality volume fraction that makes solution is 15%
(2) condensation reaction
With direct ice and water, adjust gamma acid solution temperature to 5-7 ℃, adjusting solution quality volume fraction is 10%, then follow 96% sodium bicarbonate to maintain pH=6-6.5, with direct ice holding temperature 5-10 ℃, 50 minutes used times, by 100% 2,32.6 grams of 3-bis-bromo propionyl chloros and acetone mixed solution add, holding temperature 5-10 ℃ and pH value 6-6.5, react 2 hours to obtain condensated liquid.
(3) diazotization reaction
In 800 ml beakers, add 200 milliliters, water, then 36.1 grams of 100% sulfonation para-ester are added, stir 15 minutes.Again 15.8 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.Holding temperature 0-5 ℃, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid.
(4) coupled reaction
The diazo liquid that step (3) is obtained joins in the condensated liquid that step (2) obtains, and with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(5) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(6) dry
The look liquid of step (5) is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
Embodiment 6
(1) dissolving of gamma acid
In 500 ml beakers, add 120 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 160 milliliters.The quality volume fraction that makes solution is 15%
(2) condensation reaction
With direct ice and water, adjust gamma acid solution temperature to 5-7 ℃, adjusting solution quality volume fraction is 10%, then follow 96% sodium bicarbonate to maintain pH=6-6.5, with direct ice holding temperature 5-10 ℃, 50 minutes used times, by 100% 2,32.6 grams of 3-bis-bromo propionyl chloros and acetone mixed solution add, holding temperature 5-10 ℃ and pH value 6-6.5, react 2 hours to obtain condensated liquid.
(3) diazotization reaction
In 800 ml beakers, add 200 milliliters, water, then 34.1 grams of 100%2,5-dimethoxy para-esters are added, stir 15 minutes.Again 15.8 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.0～5 ℃ of holding temperature, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid
(4) coupled reaction
The diazo liquid that step (3) is obtained joins in the condensated liquid that step (2) obtains, and with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(5) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(6) dry
The look liquid of step (5) is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
Embodiment 7
(1) dissolving of contraposition fat
In 500 ml beakers, add 200 milliliters, water, then add 28.1 grams, 100% contraposition fat, under stirring, with 15% sodium carbonate solution, adjust pH=4, make material dissolution, clarification.The volume of adjusting solution is 281 milliliters.The quality volume fraction that makes solution is 10%.
(2) condensation reaction
To in 1000 ml beakers with 200 milliliters of frozen water, 19.2 grams of cyanuric chlorides, pull an oar 30 minutes.Then in pH value, be less than 3; Temperature, under the condition of 0-5 ℃, adds contraposition lipoprotein solution.Holding temperature 0-5 ℃; Maintain pH=2.5-5, react 4 hours.
(3) dissolving of Ursol D ortho-sulfonic acid
In 500 ml beakers, add 150 milliliters, water, then add 18.8 grams of 100% Ursol D ortho-sulfonic acids, under stirring, with sodium carbonate, adjust pH=7.5-8, make material dissolution, clarification.The volume of adjusting solution is 188 milliliters.The quality volume fraction that makes solution is 10%.
(4) consecutive condensation
(3) step solution is joined in the condensated liquid that (2) step obtains, with 15% sodium carbonate, adjust pH=6, be warmed up to 20 ℃, holding temperature 20-30 ℃, maintains pH=6-6.5, reacts 1 hour.
(5) diazotization reaction
Under stirring, 30.4 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.Holding temperature 0-5 ℃, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid.
(6) dissolving of gamma acid
In 500 ml beakers, add 180 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 239 milliliters.The quality volume fraction that makes solution is 10%.
(7) coupled reaction
The diazo liquid that (5) step is obtained joins in the gamma acid solution of (6) step, with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(8) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(9) dry
The look liquid of (8) step is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
Embodiment 8
(1) dissolving of position fat between
In 500 ml beakers, add 200 milliliters, water, then add 28.1 grams, 100% position fat, under stirring, with 15% sodium carbonate solution, adjust pH=7, make material dissolution, clarification.The volume of adjusting solution is 281 milliliters.The quality volume fraction that makes solution is 10%.
(2) condensation reaction
To in 1000 ml beakers with 200 milliliters of frozen water, 19.2 grams of cyanuric chlorides, pull an oar 30 minutes.Then in pH value, be less than 3; Temperature, under the condition of 0-5 ℃, adds contraposition lipoprotein solution.Holding temperature 0-5 ℃; Maintain pH=2.5-5, react 4 hours.
(3) dissolving of Ursol D ortho-sulfonic acid
In 500 ml beakers, add 150 milliliters, water, then add 18.8 grams of 100% Ursol D ortho-sulfonic acids, under stirring, with sodium carbonate, adjust pH=7.5-8, make material dissolution, clarification.The volume of adjusting solution is 188 milliliters.The quality volume fraction that makes solution is 10%.
(4) consecutive condensation
(3) step solution is joined in the condensated liquid that (2) step obtains, with 15% sodium carbonate, adjust pH=6, be warmed up to 20 ℃, holding temperature 20-30 ℃, maintains pH=6-6.5, reacts 1 hour.
(5) diazotization reaction
Under stirring, 30.4 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.0～5 ℃ of holding temperature, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid.
(6) dissolving of gamma acid
In 500 ml beakers, add 180 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 239 milliliters.The quality volume fraction that makes solution is 10%.
(7) coupled reaction
The diazo liquid that (5) step is obtained joins in the gamma acid solution of (6) step, with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(8) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(9) dry
The look liquid of (8) step is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
Embodiment 9
(1) dissolving of position fat between
In 500 ml beakers, add 200 milliliters, water, then add between 100%N-ethyl 30.9 grams, position fat, stir and with 15% sodium carbonate solution, adjust pH=7 down, makes material dissolution, clarify.The volume of adjusting solution is 309 milliliters.The quality volume fraction that makes solution is 10%.
(2) condensation reaction
To in 1000 ml beakers with 200 milliliters of frozen water, 19.2 grams of cyanuric chlorides, pull an oar 30 minutes.Then in pH value, be less than 3; Temperature, under the condition of 0-5 ℃, adds contraposition lipoprotein solution.Holding temperature 0-5 ℃; Maintain pH=2.5-5, react 4 hours.
(3) dissolving of Ursol D ortho-sulfonic acid
In 500 ml beakers, add 150 milliliters, water, then add 18.8 grams of 100% Ursol D ortho-sulfonic acids, under stirring, with sodium carbonate, adjust pH=7.5-8, make material dissolution, clarification.The volume of adjusting solution is 188 milliliters.The quality volume fraction that makes solution is 10%.
(4) consecutive condensation
(3) step solution is joined in the condensated liquid that (2) step obtains, with 15% sodium carbonate, adjust pH=6, be warmed up to 20 ℃, holding temperature 20-30 ℃, maintains pH=6-6.5, reacts 1 hour.
(5) diazotization reaction
Under stirring, 30.4 gram of 30% hydrochloric acid soln added.By direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantees that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast.Holding temperature 0-5 ℃, reacts 2 hours, with thionamic acid, eliminates excessive nitrous acid, obtains diazo liquid.
(6) dissolving of gamma acid
In 500 ml beakers, add 180 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification.The volume of adjusting solution is 239 milliliters.The quality volume fraction that makes solution is 10%.
(7) coupled reaction
The diazo liquid that (5) step is obtained joins in the gamma acid solution of (6) step, with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours.
(8) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes.
(9) dry
The look liquid of (8) step is joined in feed liquid preheater, adjust 90 ℃ of spray tower inlet temperatures and spray dry.Obtain the orchil of following formula structure:
The red reactive dye for wool application performance of the embodiment of the present invention 1 preparation is as shown in the table:
Compound of the present invention and preparation method thereof is described by specific embodiment.Those skilled in the art can use for reference the links such as content appropriate change raw material of the present invention, processing condition and realize corresponding other object, its relevant change does not all depart from content of the present invention, within all similar replacements and change will become apparent to those skilled in the art that and be all deemed to be included in scope of the present invention.
Claims (1)
1. a preparation method for NK-BB red dye special for nylon, is characterized in that:
(1) dissolving of para-ester
In 500 ml beakers, add 200 milliliters, water, then add 28.1 grams of 100% para-esters, under stirring, with 15% sodium carbonate solution, adjust pH=4, make material dissolution, clarification, the volume of adjusting solution is 281 milliliters, the quality volume fraction that makes solution is 10%;
(2) condensation reaction
To in 1000 ml beakers with 200 milliliters of frozen water, 19.2 grams of cyanuric chlorides, pull an oar 30 minutes, then in pH value, are less than 3; Temperature, under the condition of 0-5 ℃, adds para-ester solution holding temperature 0-5 ℃; Maintain pH=2.5-5, react 4 hours;
(3) dissolving of Ursol D ortho-sulfonic acid
In 500 ml beakers, add 150 milliliters, water, then add 18.8 grams of 100% Ursol D ortho-sulfonic acids, under stirring, with sodium carbonate, adjust pH=7.5-8, make material dissolution, clarification, the volume of adjusting solution is 188 milliliters, the quality volume fraction that makes solution is 10%;
(4) consecutive condensation
(3) step solution is joined in the condensated liquid that (2) step obtains, with 15% sodium carbonate, adjust pH=6, be warmed up to 20 ℃, holding temperature 20-30 ℃, maintains pH=6-6.5, reacts 1 hour;
(5) diazotization reaction
Under stirring, 30.4 gram of 30% hydrochloric acid soln added, by direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantee that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast, holding temperature 0-5 ℃, react 2 hours, with thionamic acid, eliminate excessive nitrous acid, obtain diazo liquid;
(6) dissolving of gamma acid
In 500 ml beakers, add 180 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification, the volume of adjusting solution is 239 milliliters, the quality volume fraction that makes solution is 10%;
(7) coupled reaction
The diazo liquid that (5) step is obtained joins in the gamma acid solution of (6) step, with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours;
(8) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes;
(9) dry
The look liquid of (8) step is joined in feed liquid preheater, adjusts 90 ℃ of spray tower inlet temperatures and spray dryly, obtain the orchil of following formula structure:
2. a preparation method for NK-BB red dye special for nylon, is characterized in that:
(1) dissolving of position ester between
In 500 ml beakers, add 200 milliliters, water, then add 28.1 grams of 100% position esters, under stirring, with 15% sodium carbonate solution, adjust pH=7, make material dissolution, clarification, the volume of adjusting solution is 281 milliliters, the quality volume fraction that makes solution is 10%;
(2) condensation reaction
To in 1000 ml beakers with 200 milliliters of frozen water, 19.2 grams of cyanuric chlorides, pull an oar 30 minutes, then in pH value, are less than 3; Temperature, under the condition of 0-5 ℃, adds para-ester solution holding temperature 0-5 ℃; Maintain pH=2.5-5, react 4 hours;
(3) dissolving of Ursol D ortho-sulfonic acid
In 500 ml beakers, add 150 milliliters, water, then add 18.8 grams of 100% Ursol D ortho-sulfonic acids, under stirring, with sodium carbonate, adjust pH=7.5-8, make material dissolution, clarification, the volume of adjusting solution is 188 milliliters, the quality volume fraction that makes solution is 10%;
(4) consecutive condensation
(3) step solution is joined in the condensated liquid that (2) step obtains, with 15% sodium carbonate, adjust pH=6, be warmed up to 20 ℃, holding temperature 20-30 ℃, maintains pH=6-6.5, reacts 1 hour;
(5) diazotization reaction
Under stirring, 30.4 gram of 30% hydrochloric acid soln added, by direct ice, adjust solution temperature and be less than 0 ℃, adjusting quality volume fraction is 5.5%, at reaction soln, guarantee that pH value is less than under 2 condition, by 7.04 grams of 100% Sodium Nitrites, is made into 30% sodium nitrite solution and adds fast, 0～5 ℃ of holding temperature, react 2 hours, with thionamic acid, eliminate excessive nitrous acid, obtain diazo liquid;
(6) dissolving of gamma acid
In 500 ml beakers, add 180 milliliters, water, then add 23.9 grams of 100% gamma acid, under stirring, with 30% sodium hydroxide solution, adjust pH=6.5-7, make material dissolution, clarification, the volume of adjusting solution is 239 milliliters, the quality volume fraction that makes solution is 10%;
(7) coupled reaction
The diazo liquid that (5) step is obtained joins in the gamma acid solution of (6) step, with 96% sodium carbonate, adjusts pH=7, is warmed up to 20 ℃, and holding temperature 20-30 ℃, maintains pH=7-7.5, reacts 4 hours;
(8) neutralization reaction
Coupled reaction liquid is adjusted to pH=6-6.5 with 30% hydrochloric acid soln, stirs 15 minutes;
(9) dry
The look liquid of (8) step is joined in feed liquid preheater, adjusts 90 ℃ of spray tower inlet temperatures and spray dryly, obtain the orchil of following formula structure:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110072479.6A CN102199365B (en) | 2011-03-25 | 2011-03-25 | NK-BB red dye special for nylon, and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110072479.6A CN102199365B (en) | 2011-03-25 | 2011-03-25 | NK-BB red dye special for nylon, and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102199365A CN102199365A (en) | 2011-09-28 |
| CN102199365B true CN102199365B (en) | 2014-01-29 |
Family
ID=44660369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110072479.6A Expired - Fee Related CN102199365B (en) | 2011-03-25 | 2011-03-25 | NK-BB red dye special for nylon, and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102199365B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104031409B (en) * | 2014-06-16 | 2016-01-20 | 湖北华丽染料工业有限公司 | A kind of active deep red look dye well its preparation method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1106839A (en) * | 1977-11-02 | 1981-08-11 | Ernst Hoyer | Water-soluble dyestuffs |
| CN101575457A (en) * | 2009-05-25 | 2009-11-11 | 安徽省凤阳染料化工有限公司 | Reactive acid red dye for nylon and preparation method thereof |
| CN101735651A (en) * | 2009-11-16 | 2010-06-16 | 天津德凯化工股份有限公司 | Red reactive dye for wool and preparation method thereof |
-
2011
- 2011-03-25 CN CN201110072479.6A patent/CN102199365B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1106839A (en) * | 1977-11-02 | 1981-08-11 | Ernst Hoyer | Water-soluble dyestuffs |
| CN101575457A (en) * | 2009-05-25 | 2009-11-11 | 安徽省凤阳染料化工有限公司 | Reactive acid red dye for nylon and preparation method thereof |
| CN101735651A (en) * | 2009-11-16 | 2010-06-16 | 天津德凯化工股份有限公司 | Red reactive dye for wool and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102199365A (en) | 2011-09-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101215425B (en) | Red reactive dyestuffs and preparation method thereof | |
| CN101705014B (en) | Orange reactive dye for wool and preparation method thereof | |
| CN101418136A (en) | Blue reactive dyes for wool and preparation method thereof | |
| CN102190906B (en) | Nylon orange active dye and preparation method thereof | |
| CN102199365B (en) | NK-BB red dye special for nylon, and preparation method thereof | |
| CN111100478B (en) | Preparation method and application of blue dye with three active groups | |
| CN101735651B (en) | Red reactive dye for wool and preparation method thereof | |
| CN101942215A (en) | Orange reactive dye for wool and preparation method thereof | |
| CN101705019B (en) | Red reactive dye for wool and preparation method thereof | |
| CN101942214A (en) | Orange degreased reactive dye for wool and preparation method thereof | |
| CN101481523A (en) | Red reactive dye for fur and preparation thereof | |
| CN101735655B (en) | Red reactive dye for wool and preparation method thereof | |
| CN101735652B (en) | Red reactive dye and preparation method thereof | |
| CN101735653B (en) | Red reactive dye for wool and preparation method thereof | |
| CN101705015B (en) | Orange active dye and preparation method thereof | |
| CN101735656B (en) | Red reactive dye for wool | |
| CN101705017B (en) | Orange reactive dye for wool and preparation method thereof | |
| CN101481528A (en) | Red reactive dye for fur and preparation thereof | |
| CN101481527A (en) | Red reactive dye for fur and preparation thereof | |
| CN101792613B (en) | Yellow reactive dye for wool and preparation method and application thereof | |
| CN101906256A (en) | Orange reactive dye and preparation method thereof | |
| CN101705018B (en) | Orange reactive dye for wool | |
| CN101735654B (en) | Reactive dye for wool and preparation method thereof | |
| CN101724292B (en) | Wool orange reactive dye and preparation method thereof | |
| CN101705016B (en) | Orange reactive dye for wool and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140129 Termination date: 20140325 |