CN1161990A - Rare-earth dyeing assistant and preparation technology thereof - Google Patents
Rare-earth dyeing assistant and preparation technology thereof Download PDFInfo
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- CN1161990A CN1161990A CN 97103855 CN97103855A CN1161990A CN 1161990 A CN1161990 A CN 1161990A CN 97103855 CN97103855 CN 97103855 CN 97103855 A CN97103855 A CN 97103855A CN 1161990 A CN1161990 A CN 1161990A
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Abstract
A rare-earth dyeing assistant is a multi-component and multi-function dyeing assistant with high-molecule rare-earth complex as the main component. It is composed of ethylenediamine, polyelhylene polyamine, trimethylamine, divinyl triamine, glycol, chloropropylene oxide, dodecyl betaine, chloroacetic acid and rare earth. It concentrates level dyeing, dye fixing and darkening into one body, may raise the binding power of dye and blank leather, increase dyeing fastness, and at the same time, may increase colour depth (saturation degree and brightness); raise the degree of dyeing and save red alum, lower Cr2O3 content in waste water, and at the same time, raise the exhausting degree of fattening agent and so save fattening agent to play the role of grease fixing. This dyeing assistant, besides used for leather, may be further used for cotton, articial cotton, fur, wool, hemp, flax and chemical fibre.
Description
Leather coloring auxiliary agent involved in the present invention is to be many components of main component with the polymer rare-earth complex, the multifunctional dyeing auxiliary agent.
Background technology of the present invention: the present used proprietary dyestuff rareness of leather industry, and acidity, direct dyeing fastness commonly used are poor, tone is not full, and dye dosage is big during dyeing, cost is high, chroma in waste water is dark.Be difficult to dye dark-toned leather when particularly the crust leather after the anionic acrylic resin retanning is with anionic acidity, direct dyestuff, particularly dye the black leather.So just hindered the widespread use of acrylic resin retanning agent in leather retanning.
Purpose of design of the present invention: the one, the colouring problem that solves acrylic resin retanning crust leather.Leather agent can change the electriferous state of crust leather, improve of the absorption of resin retanning crust leather to anionic dyestuff and fatting agent, resin retanning crust leather with the rare-earth additive processing, the leather color of being dyed is pure, tone is full, bright-coloured, the colouring problem that solved acrylic resin retanning crust leather, even it is also very good to dye the black effect, reached the degree that the chrome tanning crust leather dyes black.The 2nd, improve dyefastness, reduce dye dosage, simplify production technique.Rare-earth additive is used for leather coloring, its level dyeing, the effect that increases dark and fixation are all fairly obvious, can play and prevent the look flower, the institute dye the leather color even, pure, tone is full, bright-coloured, improved the dye uptake of dyestuff, can improve dyefastness 0.5--1 level, saved dyestuff 10--25% leather, suede garment leather secondary dyeing (chromatography) can be changed into once dyeing, simplify production technique.
Design of the present invention: the present invention synthesizes the macromolecule complex body earlier, then itself and rare earth is formed title complex, composite again other material, thus synthesize the rare earth high polymer complex compound.
1, rare-earth additive help that to dye function as follows:
Synthesizing of a, macromolecule complex body:
Anionic dyestuff (acid, direct dyestuff) and crust leather fiber are mainly with the electrovalent bond combination, and the electrovalent bond bonding force is not strong; Moreover it is not the sulfonic group isoreactivity base wetting ability of dye molecule is strong, thereby water-fast.Desire improves fastness of dyeing, must improve the bonding state of dyestuff and fiber.
Sulfonic group effect among middle ortho-nitrogen ion and the D-SO3H is played tint retention, simultaneously
Can play the effect of regulating molecular weight.
Have among product (B) in reaction (2), (3), (C)-NH-,-the nitrogenous active group of NH2, under the low situation of pH value, do not show electrically; When under the high situation of pH value, thereby become-NH2-,-NH3 can react with anionic dyestuff like this and generate the color lake.
Product (B), (C) and the combination of acrylic resin retan in reaction (2), (3) increase its cation group, help like this dying on the anionic dyestuff.
HOCH2CH2OH in the reaction (4) can regulate positive charge in the molecular chain, avoids crosslinked strong excessively simultaneously, causes that grain is coarse.
B, graft reaction
Connect branch
After, product (E), (F) more help the chromium in the chrome tanned leather to carry out coordination, are simultaneously and rare earth ion increase complex ability.
The complex reaction of c and rare earth ion
More than each product can with rare earth ion generation complex reaction, thereby form rare-earth complex.The hapto that complexing takes place is-NH2 ,-OH ,-COOH isoreactivity group.
Like this, delocalization effect takes place with dyestuff, the crosslinked multicomponent system of having formed of fiber in rare-earth complex, so maximum system energy descends, absorbing wavelength moves to long wave, and hyperchromic effect takes place.Moreover increase the dyestuff binding site, and increasing the dyestuff dye uptake, absorption peak strengthens, and makes color and luster dense.The rare earth complex ion causes the dyestuff absorption spectrum to narrow down simultaneously, makes the finished leather tone full, pure.
Composite other tensio-active agent Pluronic.
Law of compound according to tensio-active agent adds Pluronic in its system, improve perviousness and level-dyeing property.
2, detailed proportioning
Rare-earth dyeing assistant is made up of quadrol, polyethylene polyamine, Trimethylamine 99, diethylenetriamine, ethylene glycol, epoxy chloropropane, empgen BB, Mono Chloro Acetic Acid, sodium hydroxide, mixed chlorinated rare earth, citric acid or Glacial acetic acid.Quadrol (NH2-CH2CH2-NH2) is 0.05--0.4mol, Cui 0.36mol, and polyethylene polyamine NH2 (CH2CH2NH) mCH2CH2NH2 is 0.4--0.9mol, Cui 0.82mol, Trimethylamine 99
Be 0.02--0.2, Cui 0.18mol, diethylenetriamine (NH2CH2CH2NHCH2CH2NH2) is 0.01-0.1mol, Cui 0.08mol, ethylene glycol (OH-CH2CH2OH) is 0.02--0.2mol, Cui 0.175mol, epoxy chloropropane
Be 0.25--3.0mol, Cui 0.285mol, empgen BB
Be 0.02--0.15mol, Cui 0.12mol, Mono Chloro Acetic Acid (CICH2COOH) is 0.05--0.4mol, Cui 0.35mol, sodium hydroxide NaOH is 0.065--0.6mol, Cui 0.5mol, mixed chlorinated rare earth (content is 30%--50%) is the 40--50% of total solid amount, Cui 45%.
3, preparation technology
A, in reactor, add monomer quadrol, polyethylene polyamine, ethylene glycol, Trimethylamine 99, diethylenetriamine and a certain amount of water, stir 15--30 minute (reaction density 60--80%), heat up 40--60 ℃ then, add epoxy chloropropane, divide at 30--60 to add, and temperature control should not be higher than 60 ℃, in 15--30 minute, be warming up to then in the 75--95 ℃ of scope, be incubated 3--4 hour, be cooled to 40--50 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 0～5 ℃ of scope, drips NaOH and Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add empgen BB, add rare earth chloride again and carry out complex reaction, obtain product C like this;
D, add tensio-active agent Pluronic (polychloroprene or polyoxyethylene block copolymer), obtain rare-earth dyeing assistant like this by the 6--30% of product C weight.
E, product C and lanthanum concentrate rare earth chloride are carried out complexing, can be used for helping of network retan and dye.Lanthanum concentrate rare earth chloride accounts for the mixed chlorinated rare earth 30--40% of solid amount always.
F, product C and few europium rare earth chloride are carried out complexing, can be used for helping of velour and dye.Few europium rare earth chloride accounts for the mixed chlorinated rare earth 1--2% of solid amount always.
G, product C and pure Neodymium trichloride are carried out complexing, can be used for helping of fur and dye.Pure Neodymium trichloride accounts for the mishmetal 10--20% of solid amount always.
The present invention compares with background technology, its collection level dyeing, fixation, increases and is deeper than one, can improve the bonding force of dyestuff and crust leather, increases fastness of dyeing; Simultaneously can increase color depth (saturation ratio, lightness); Improve the colourity of dye uptake, saving dyestuff, reduction waste water.In addition, can be used as the chromium absorbing agent of leather chrome tanning, save arsenic, reduce the Cr2O3 content in the waste liquid.Simultaneously, improve the clean absorption rate of fatting agent, save fatting agent, play fixedly grease effect.This rare-earth additive except be used for leather help dye, can also be applied to cotton, artificial cotton, fur, hair, fiber crops, flax, helping of chemical fibre and dye.
Embodiment 1:a, in reactor, add 0.3mol monomer quadrol, 0.75mol polyethylene polyamine, 0.15mol ethylene glycol, 0.15mol Trimethylamine 99,0.05mol diethylenetriamine and a certain amount of water, stir 20 minutes (reaction density 70%), heat up 50 ℃ then, add the 0.25mol epoxy chloropropane, added at 35 minutes, and temperature control should not be higher than 60 ℃, in 20 minutes, be warming up in 80 ℃ of scopes then, be incubated 3 hours, be cooled to 45 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 2 ℃ of scopes, drips 0.39molNaOH and 0.3mol Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add the 0.08mol empgen BB, add 40% rare earth chloride again and carry out complex reaction, obtain product C like this;
D, add tensio-active agent Pluronic (polychloroprene or polyoxyethylene block copolymer), obtain rare-earth dyeing assistant like this by 10% of product C weight.
Embodiment 2:a, in reactor, add 0.36mol monomer quadrol, 0.82mol polyethylene polyamine, 0.175mol ethylene glycol, 0.18mol Trimethylamine 99,0.08mol diethylenetriamine and a certain amount of water, stir 25 minutes (reaction density 75%), heat up 55 ℃ then, add the 0.285mol epoxy chloropropane, added at 45 minutes, and temperature control should not be higher than 60 ℃, in 26 minutes, be warming up in 85 ℃ of scopes then, be incubated 3.5 hours, be cooled to 45 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 3 ℃ of scopes, drips 0.5molNaOH and 0.35mol Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add the 0.12mol empgen BB, add 45% rare earth chloride again and carry out complex reaction, obtain product C like this;
D, add tensio-active agent Pluronic (polychloroprene or polyoxyethylene block copolymer), obtain rare-earth dyeing assistant like this by 16% of product C weight.
Embodiment 3:a, in reactor, add 0.4mol monomer quadrol, 0.9mol polyethylene polyamine, 0.2mol ethylene glycol, 0.2mol Trimethylamine 99,0.1mol diethylenetriamine and a certain amount of water, stir 30 minutes (reaction density 80%), heat up 60 ℃ then, add the 0.3mol epoxy chloropropane, added at 60 minutes, and temperature control should not be higher than 60 ℃, in 15 minutes, be warming up to then in 95 ℃ of scopes, be incubated 4 hours, be cooled to 50 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 5 ℃ of scopes, drips 0.6molNaOH and 0.4mol Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add the 0.15mol empgen BB, add 50% rare earth chloride again and carry out complex reaction, obtain product C like this;
D, add tensio-active agent Pluronic (polychloroprene or polyoxyethylene block copolymer), obtain rare-earth dyeing assistant like this by 30% of product C weight.
Embodiment 4:a, in reactor, add 0.05mol monomer quadrol, 0.4mol polyethylene polyamine, 0.02mol ethylene glycol, 0.02mol Trimethylamine 99,0.01mol diethylenetriamine and a certain amount of water, stir 15 minutes (reaction density 60%), heat up 40 ℃ then, add the 0.25mol epoxy chloropropane, added at 30 minutes, and temperature control should not be higher than 60 ℃, in 10 minutes, be warming up in 75 ℃ of scopes then, be incubated 3 hours, be cooled to 40 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 0 ℃ of scope, drips 0.65molNaOH and 0.05mol Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add the 0.02mol empgen BB, add 40% rare earth chloride again and carry out complex reaction, obtain product C like this;
D, add tensio-active agent Pluronic (polychloroprene or polyoxyethylene block copolymer), obtain rare-earth dyeing assistant like this by 6% of product C weight.
Embodiment 5:a, in reactor, add 0.36mol monomer quadrol, 0.82mol polyethylene polyamine, 0.175mol ethylene glycol, 0.18mol Trimethylamine 99,0.08mol diethylenetriamine and a certain amount of water, stir 25 minutes (reaction density 75%), heat up 55 ℃ then, add the 0.285mol epoxy chloropropane, added at 45 minutes, and temperature control should not be higher than 60 ℃, in 26 minutes, be warming up in 85 ℃ of scopes then, be incubated 3.5 hours, be cooled to 45 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 3 ℃ of scopes, drips 0.5molNaOH and 0.35mol Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add the 0.12mol empgen BB, add 45% rare earth chloride again and carry out complex reaction, obtain product C like this;
D, product C and lanthanum concentrate rare earth chloride are carried out complexing, can be used for helping of network retan and dye.Lanthanum concentrate rare earth chloride accounts for the 30--40% of the always solid amount of mixed chlorinated rare earth, Cui 33%.
Embodiment 6:a, in reactor, add 0.36mol monomer quadrol, 0.82mol polyethylene polyamine, 0.175mol ethylene glycol, 0.18mol Trimethylamine 99,0.08mol diethylenetriamine and a certain amount of water, stir 25 minutes (reaction density 75%), heat up 55 ℃ then, add the 0.285mol epoxy chloropropane, added at 45 minutes, and temperature control should not be higher than 60 ℃, in 26 minutes, be warming up in 85 ℃ of scopes then, be incubated 3.5 hours, be cooled to 45 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 3 ℃ of scopes, drips 0.5molNaOH and 0.35mol Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add the 0.12mol empgen BB, add 45% rare earth chloride again and carry out complex reaction, obtain product C like this;
D, product C and few europium rare earth chloride are carried out complexing, can be used for helping of velour and dye.Few europium rare earth chloride accounts for the mixed chlorinated rare earth 1--2% of solid amount always, Cui 1.5%.
Embodiment 7:a, in reactor, add 0.36mol monomer quadrol, 0.82mol polyethylene polyamine, 0.175mol ethylene glycol, 0.18mol Trimethylamine 99,0.08mol diethylenetriamine and a certain amount of water, stir 25 minutes (reaction density 75%), heat up 55 ℃ then, add the 0.285mol epoxy chloropropane, added at 45 minutes, and temperature control should not be higher than 60 ℃, in 26 minutes, be warming up in 85 ℃ of scopes then, be incubated 3.5 hours, be cooled to 45 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in 3 ℃ of scopes, drips 0.5molNaOH and 0.35mol Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add the 0.12mol empgen BB, add 45% rare earth chloride again and carry out complex reaction, obtain product C like this;
D, product C and pure Neodymium trichloride are carried out complexing, can be used for helping of fur and dye.Pure Neodymium trichloride accounts for the 10--20% of the always solid amount of mishmetal, Cui 16%.
Claims (9)
1, a kind of rare-earth dyeing assistant is characterized in that being made up of quadrol, polyethylene polyamine, Trimethylamine 99, diethylenetriamine, ethylene glycol, epoxy chloropropane, empgen BB, Mono Chloro Acetic Acid, sodium hydroxide, mixed chlorinated rare earth, citric acid or Glacial acetic acid.
2, rare-earth dyeing assistant according to claim 1, it is characterized in that: quadrol (NH2-CH2CH2-NH2) is 0.05--0.4mol, Cui 0.36mol, and polyethylene polyamine NH2 (CH2CH2NH) mCH2CH2NH2 is 0.4--0.9mol, Cui 0.82mol, Trimethylamine 99
Be 0.02--0.2, Cui 0.18mol, diethylenetriamine (NH2CH2CH2NHCH2CH2NH2) is 0.01--0.1mol, Cui 0.08mol, ethylene glycol (OH-CH2CH2OH) is 0.02--0.2mol, Cui 0.175mol, epoxy chloropropane
Be 0.25--3.0mol, Cui 0.285mol, empgen BB
Be 0.02--0.15mol, Cui 0.12mol, Mono Chloro Acetic Acid (CICH2COOH) is 0.05--0.4mol, Cui 0.35mol, sodium hydroxide NaOH is 0.065--0.6mol, Cui 0.5mol, mixed chlorinated rare earth (content is 30%--50%) is the 40--50% of total solid amount, Cui 45%.
3, a kind of preparation technology of rare-earth dyeing assistant is characterized in that:
A, in reactor, add monomer quadrol, polyethylene polyamine, ethylene glycol, Trimethylamine 99, diethylenetriamine and a certain amount of water, stir 15--30 minute (reaction density 60 to 80%), heat up 40--60 ℃ then, add epoxy chloropropane, divide at 30--60 to add, and temperature control should not be higher than 60 ℃, in 10--30 minute, be warming up to then in the 75--95 ℃ of scope, be incubated 3--4 hour, be cooled to 40--50 ℃, naturally cool to normal temperature, can obtain product A like this;
B, product A is inserted in another reactor, frozen water is cooled in the 0--5 ℃ of scope, drips NaOH and Mono Chloro Acetic Acid (ICH2COOH) respectively, such product B;
C, product B is regulated PH4--6 with citric acid or acetic acid, add empgen BB, add rare earth chloride again and carry out complex reaction, obtain product C like this;
D, add tensio-active agent Pluronic (polychloroprene or polyoxyethylene block copolymer), obtain rare-earth dyeing assistant like this by the 6--30% of product C weight.
4, according to claim 1 or 3 described rare-earth dyeing assistants, it is characterized in that: product C and lanthanum concentrate rare earth chloride are carried out complexing, can be used for helping of network retan and dye.
5, according to claim 1 or 3 described rare-earth dyeing assistants, it is characterized in that: product C and few europium rare earth chloride are carried out complexing, can be used for helping of velour and dye.
6, according to claim 1 or 3 described rare-earth dyeing assistants, it is characterized in that: product C and pure Neodymium trichloride are carried out complexing, can be used for helping of fur and dye.
7, according to claim 1 or 4 described rare-earth dyeing assistants, it is characterized in that: lanthanum concentrate rare earth chloride accounts for the mixed chlorinated rare earth 30--40% of solid amount always.
8, rare-earth dyeing assistant according to claim 1 or 5 is characterized in that: few europium rare earth chloride accounts for the mixed chlorinated rare earth 1--2% of solid amount always.
9, according to claim 1 or 6 described rare-earth dyeing assistants, it is characterized in that: pure Neodymium trichloride accounts for the mishmetal 10--20% of solid amount always.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97103855 CN1161990A (en) | 1997-04-01 | 1997-04-01 | Rare-earth dyeing assistant and preparation technology thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97103855 CN1161990A (en) | 1997-04-01 | 1997-04-01 | Rare-earth dyeing assistant and preparation technology thereof |
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| Publication Number | Publication Date |
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| CN1161990A true CN1161990A (en) | 1997-10-15 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 97103855 Pending CN1161990A (en) | 1997-04-01 | 1997-04-01 | Rare-earth dyeing assistant and preparation technology thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560736B (en) * | 2009-03-19 | 2011-05-25 | 宁波新科纺织助剂有限公司 | Accelerant for textile dyeing, preparation method and applications thereof |
| CN103030991A (en) * | 2003-09-23 | 2013-04-10 | 联合色料制造公司 | Organic solvent soluble metal complex azo dyes |
| CN106012600A (en) * | 2016-05-31 | 2016-10-12 | 太仓协大申泰羊毛衫有限公司 | Wool fabric dyeing assistant |
| CN107558257A (en) * | 2017-09-20 | 2018-01-09 | 安徽省无为县永昌鬃刷制造有限公司 | One kind improves bristles pliability coloring agent |
| CN109281200A (en) * | 2018-09-26 | 2019-01-29 | 深圳市裕农科技股份有限公司 | A kind of dyeing auxiliary and preparation method thereof |
-
1997
- 1997-04-01 CN CN 97103855 patent/CN1161990A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103030991A (en) * | 2003-09-23 | 2013-04-10 | 联合色料制造公司 | Organic solvent soluble metal complex azo dyes |
| CN103030991B (en) * | 2003-09-23 | 2016-01-20 | 联合色料制造公司 | organic solvent soluble metal complex azo dyes |
| CN101560736B (en) * | 2009-03-19 | 2011-05-25 | 宁波新科纺织助剂有限公司 | Accelerant for textile dyeing, preparation method and applications thereof |
| CN106012600A (en) * | 2016-05-31 | 2016-10-12 | 太仓协大申泰羊毛衫有限公司 | Wool fabric dyeing assistant |
| CN107558257A (en) * | 2017-09-20 | 2018-01-09 | 安徽省无为县永昌鬃刷制造有限公司 | One kind improves bristles pliability coloring agent |
| CN109281200A (en) * | 2018-09-26 | 2019-01-29 | 深圳市裕农科技股份有限公司 | A kind of dyeing auxiliary and preparation method thereof |
| CN109281200B (en) * | 2018-09-26 | 2020-11-13 | 深圳市裕农科技股份有限公司 | Dyeing auxiliary and preparation method thereof |
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