CN1063799C - Tannin extract type amphoteric retanning agent and method for preparing same - Google Patents
Tannin extract type amphoteric retanning agent and method for preparing same Download PDFInfo
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- CN1063799C CN1063799C CN98111821A CN98111821A CN1063799C CN 1063799 C CN1063799 C CN 1063799C CN 98111821 A CN98111821 A CN 98111821A CN 98111821 A CN98111821 A CN 98111821A CN 1063799 C CN1063799 C CN 1063799C
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Abstract
The present invention relates to a tannin extract type amphoteric retanning agent and a preparing method thereof. When the pH of a water solution of the tannin extract type amphoteric retanning agent is less than 1.5, the water solution is not precipitated within 24 hours, and when the pH is from 2.0 to 11.0, an isoelectric point can be generated; the water solution has viscosity increment or generates precipitation within the range of the isoelectric point. The preparing method of the tannin extract type amphoteric retanning agent orderly comprises the following technological steps: preparing a tannin extract solution and a sulfonating agent solution; generating high-sulfitation reaction; generating cationizing reaction; pumping vacuum; regulating the pH. The tannin extract type amphoteric retanning agent has the advantage of good selective filling; compared with the existing tannin extract retanning agent, the permeation rate of the tannin extract type amphoteric retanning agent is enhanced more than one time, and the affinity for a greasing agent and dye is obviously enhanced.
Description
The invention belongs to process hides retanning agent and preparation method thereof, particularly a kind of amphoteric retanning agent and preparation method thereof.
Tannin extract is the polyphenol compound with flexibility that extracts from the plant materials that is rich in tannin, is divided into condensing class and hydrolysis class, and its charge property is an electronegativity.Owing to have flexibility, be used as the leather retanning material and used, because electronegative property, the defective of existing tannin extract retanning agent is the electronegativity that can increase leather after the retanning, weaken the avidity of leather, thereby influence absorption and the dyeing concentration of leather fatting agent to fatting agent and dyestuff.
About the improvement of tannin extract retanning agent, prior art is embodied in following two aspects: the one, increase the water-soluble of tannin extract by sulfited reaction, and (Soviet Union monograph SU1178767 sees before to improve its infiltration rate in leather/pelt; " vegetable tanning agent " " leather chemical industry ", 1986 the 2nd phases; " black wattle plant and utilization thereof ", China Forest press, in June, 1991), but the application side of this kind method overweights and guarantees higher flexibility at present, therefore the maximum consumption of sulphite is controlled at below 8%, makes water-soluble and perviousness improves not quite, is difficult to satisfy the requirement of light leather.This kind method also can not change the electronegativity of tannin extract retanning agent and the defective that electronegativity is brought.The 2nd, in tannin extract, introduce cation group to improve its charge property, its method is to utilize the Mannich reaction to introduce thanomin (diethanolamine) compound by formaldehyde on the tannin extract molecule [to see " external tannin extract technology ", the chief editor of China Forest scientific information institute, China Forest press publishes, in December, 1981; " preparation of amphimixis tanning agent and the research of flexibility thereof ", " Chinese leather ", 1997 26 (10)], the weak point of this kind method is: 1. reaction conversion ratio is lower; 2. introducing a positive electricity group
The time, also introduced two electronegativity groups and (OH), improved little the overall charge character of tannin extract; 3. the molecular weight of tannin extract increases, and the seepage velocity in leather further reduces.
The objective of the invention is to overcome the deficiencies in the prior art, a kind of tannin extract type amphoteric retanning agent and preparation method thereof is provided, this kind tannin extract type amphoteric retanning agent is when having good retanning fillibility, the convergency milder, infiltration rate is faster, and have tangible cationic, not only can the stuffing and the dyeing of leather not had a negative impact after the retanning, and can promote the absorption of fatting agent and dyestuff.
The object of the present invention is achieved like this:
1. break through the idea that traditionally the sulphonating agent consumption is limited to below 8%, adopt height sulphiting technical scheme, the consumption of sulphonating agent is up to 15-30%, can not only in the tannin extract molecule, introduce water-soluble sulfonic group like this, and can make the tannin extract molecule that to a certain degree degraded takes place, so that the convergency gentleness, water-soluble and perviousness improves greatly.
2. select for use dimethylamine as cationic reagent, when introducing cation group, can not introduce the electronegativity group, the cationization degree is improved.
3. uses of will height sulphiting technology connect with the cationization technology, cationization takes place and reacts in tannin extract again after appropriateness is degraded, thereby makes product both have the convergency of gentleness, has cationic again.
Tannin extract type amphoteric retanning agent provided by the invention is that the compound of following three kinds of forms is formed by structural formula mainly.
Wherein,
Expression sulfonation vegatable tannin.Its pH value of aqueous solution is less than 1.5 o'clock, do not precipitate in 24 hours; Its pH value of aqueous solution an iso-electric point can occur between 2.0～11.0, this iso-electric point is 0.5～4 pH value scope, and in the iso-electric point scope, viscosity in aqueous solution increases or has precipitation to produce.Its product both can be solid-state, also can be the aqueous solution of any concentration.
The preparation method of above-mentioned retanning agent, be made up of following two portions content:
1. raw material and prescription thereof (weight part)
100 parts of tannin extracts
15～30 parts of sulphonating agents
20～70 parts of dimethylamine (concentration 40%)
22～80 parts in formaldehyde (concentration 37%)
The acid add-on reaches 2.0～6.0 with the pH value of product and exceeds
2. processing step and processing parameter
Comprise following processing step successively:
(1) tannin extract solution, sulphonating agent formulations prepared from solutions
The tannin extract formulations prepared from solutions is that 100 parts of tannin extracts are dissolved in 150～300 parts of water, and under agitation is warming up to 55～95 ℃, and the sulphonating agent formulations prepared from solutions is that sulphonating agent is soluble in water, is mixed with concentration and is 20% the aqueous solution.
(2) height sulfited reaction
The sulphonating agent drips of solution for preparing is added the tannin extract solution for preparing, 55～95 ℃ of sustained reactions 5～10 hours.
(3) the cationization skin should
The cationization reaction is carried out in two steps.The first step is that the solution behind the sulfited reaction is cooled to 15～45 ℃, adds dimethylamine, splashes into formaldehyde and 15～45 ℃ of sustained reactions 0.5～3.0 hour.Second step was that the first step reacted solution is warming up to 50～75 ℃, this thermotonus 0.5～2.0 hour.
(4) vacuumize
Vacuumized 0.5～2.0 hour at 50～75 ℃, vacuum degree control is at-0.05～0.09MPa.
(5) adjust pH
Solution after vacuumizing is cooled to 15～45 ℃, adds sour adjust pH and get liquid product, the pH value is controlled at 2.0～6.0.
If need make solid phase prod, then liquid product can be carried out spraying drying.
Employed raw material in the aforesaid method, tannin extract both can be that condensing class is (as the wattle extract of South Africa and Brazil, the larch extract of China, myrica extract), also can be hydrolysis class (as the valonex of China, external Ke Zi, chestnut extract), if select condensed tannin extracts for use, then the prescription of sulphonating agent, dimethylamine, formaldehyde should be limit on the upper side, if select hydrolysable tannin extracts for use, then the prescription of sulphonating agent, dimethylamine, formaldehyde should be partial to lower limit.
The raw material that uses in the aforesaid method, sulphonating agent can be selected S-WAT or sodium bisulfite or Sodium Pyrosulfite for use, and the used acid of adjust pH can be selected hydrochloric acid or sulfuric acid or formic acid or their mixture for use.
The present invention has the following advantages and positively effect:
1. product of the present invention has been owing to reached the balance of rational molecular weight and cationization degree, the excellent stability in water, and the pH value is 0.5～8.5, concentration reaches at 20% o'clock and can be in the uniform dissolution state, can satisfy the requirement of various leather-making technology working conditionss.
2. compare with existing tannin extract retanning agent, product rate of permeation of the present invention is enhanced about more than once, and can permeate 1.5 millimeters blue skins in 1 hour.
3. product of the present invention shows good selection fillibility, can make leather vest portion thicken 4～5%, and the part between the ribs and the hips position, limit thickens 11～13%, thereby can improve the utilization ratio of leather.
4. product of the present invention is used for leather retanning can improve the affinity of leather to fatting agent and dyestuff, thereby the fatting agent consumption can reduce about 20%, and dye dosage can reduce 30～35%.
5. product of the present invention, its price are not higher than existing tannin extract retanning agent, but make the quality of finished leather improve a class.
6. method technology of the present invention is simple, and raw material is wide, and can improve the comprehensive utilization ratio of China's Forest Resources.
Fig. 1 is the process flow sheet of method provided by the invention.
Embodiment 1:
The raw material of present embodiment and prescription thereof:
100 parts of larch extracts (in homemade)
25 parts of S-WATs
50 parts of dimethylamine (concentration 40 %)
60 parts in formaldehyde (concentration 37%)
The hydrochloric acid add-on reaches 4.0 with the pH value of product
Limit
The processing step of present embodiment and processing parameter:
(1) tannin extract solution, sulphonating agent formulations prepared from solutions
100 parts of larch extracts are dissolved in 250 parts of water, and under agitation heat up 70 ℃; S-WAT is soluble in water, be mixed with concentration and be 20% the aqueous solution.
(2) height sulfited reaction
The sodium sulfite solution for preparing is added dropwise to the tannin extract solution for preparing, 70 ℃ of sustained reactions 5 hours.
(3) cationization reaction
Solution behind the sulfited reaction is cooled to 15 ℃, adds dimethylamine, splash into formaldehyde and, be warming up to 70 ℃ then, this thermotonus 2 hours 15 ℃ of sustained reactions 1.5 hours.
(4) vacuumize
Vacuumized 1 hour at 70 ℃, vacuum degree control is at-0.09MPa.
(5) adjust pH
Solution after vacuumizing is cooled to 30 ℃, adds the hydrochloric acid adjust pH and get liquid product, the pH value is controlled at 4.0.
(6) spraying drying
The liquid product spraying drying is got solid phase prod.
This product is all good, dark red brown in pH0.5～7.5 scope solvabilities and perviousness, should be used for the retanning of dark leather, can significantly reduce the loose side of leather, improves the dyeing and fat-liquoring effect.
Embodiment 2:
The raw material of present embodiment and prescription thereof:
100 parts of valonexs (in homemade)
15 parts of sodium bisulfites
30 parts of dimethylamine (concentration 40%)
25 parts in formaldehyde (concentration 37 %)
The sulfuric acid add-on reaches 2.5 with the pH value of product and exceeds
The processing step of present embodiment and processing parameter:
(1) tannin extract solution, sulphonating agent formulations prepared from solutions
100 parts of valonexs are dissolved in 300 parts of water, and under agitation are warming up to 60 ℃, sodium bisulfite is soluble in water, be mixed with concentration and be 20% the aqueous solution.
(2) height sulfited reaction
The sodium sulfite solution for preparing is added dropwise to the tannin extract solution for preparing, 60 ℃ of sustained reactions 9 hours.
(3) cationization reaction
Solution behind the sulfited reaction is cooled to 15 ℃, adds dimethylamine, splash into formaldehyde and, be warming up to 55 ℃ then, this thermotonus 2 hours 15 ℃ of sustained reactions 3 hours.
(4) vacuumize
Vacuumized 1.5 hours at 55 ℃, vacuum degree control is at-0.08MPa.
(5) adjust pH
Solution after vacuumizing is reduced to 30 ℃, add the sulfuric acid adjust pH and get liquid product, the pH value is controlled at 2.5.
(6) spraying drying
The liquid product spraying drying is got solid phase prod.
This product is light yellow, and viscosity increases between pH2.5～5.0, and convergency strengthens, and the retanning initial stage should be controlled at the pH value outside this scope, and the retanning later stage is adjustable 2.5～5.0 to be beneficial to combination.
Embodiment 3:
The raw material of present embodiment and prescription thereof:
100 parts of wattle extracts (South Africa product)
15 parts of Sodium Pyrosulfites
40 parts of dimethylamine (concentration 40%)
48 parts in formaldehyde (concentration 37%)
The formic acid add-on reaches 3.0 with the pH value of product
Limit
The processing step of present embodiment and processing parameter:
(1) tannin extract solution, sulphonating agent formulations prepared from solutions
100 parts of wattle extracts are dissolved in 200 parts of water, and under agitation are warming up to 80 ℃, Sodium Pyrosulfite is soluble in water, be mixed with concentration and be 20% the aqueous solution.
(2) height sulfited reaction
The sodium metabisulfite solution for preparing is added dropwise to the tannin extract solution for preparing, 80 ℃ of sustained reactions 8 hours.
(3) cationization reaction
Solution behind the sulfited reaction is cooled to 35 ℃, adds dimethylamine, splash into formaldehyde and, be warming up to 75 ℃ then, this thermotonus 1.5 hours 35 ℃ of sustained reactions 2.5 hours.
(4) vacuumize
Vacuumized 1 hour at 75 ℃, vacuum degree control is at-0.06MPa.
(5) adjust pH
Solution after vacuumizing is reduced to 40 ℃, add the formic acid adjust pH and get liquid product, the pH value is controlled at 3.0.
(6) spraying drying
The liquid product spraying drying is got solid phase prod.
This product is used for retanning, and fillibility, dyeing and fat-liquoring effect surpass existing tannin extract product both at home and abroad comprehensively, all can use in pH0.5～8.5 scopes, both can be used for dark leather, also can be used for the light color leather.
Claims (6)
1. tannin extract type amphoteric retanning agent, the pH value of aqueous solution that it is characterized in that it was less than 1.5 o'clock, do not precipitate in 24 hours, its pH value of aqueous solution an iso-electric point can occur between 2.0～11.0, this iso-electric point is 0.5～4 pH value scope, in the iso-electric point scope, viscosity in aqueous solution increases or has precipitation to produce.
2. the preparation method of a tannin extract type amphoteric retanning agent is characterized in that:
(1) raw material and prescription thereof (weight part)
100 parts of tannin extracts
15～30 parts of sulphonating agents
20～70 parts of dimethylamine (concentration 40%)
22～80 parts in formaldehyde (concentration 37%)
The acid add-on reaches 2.0～6.0 with the pH value of product and exceeds
(2) processing step and processing parameter
Comprise following processing step successively:
A. tannin extract solution, sulphonating agent formulations prepared from solutions
The tannin extract formulations prepared from solutions is that 100 parts of tannin extracts are dissolved in 150～300 parts of water, and under agitation is warming up to 55～95 ℃, and the sulphonating agent formulations prepared from solutions is that sulphonating agent is soluble in water, is mixed with concentration and is 20% the aqueous solution,
B. the height sulfited reaction
The sulphonating agent drips of solution for preparing is added the tannin extract solution for preparing, 55～95 ℃ of sustained reactions 5～10 hours,
C. cationization reaction
Solution behind the sulfited reaction is cooled to 15～45 ℃, adds dimethylamine, splash into formaldehyde and, be warming up to 50～75 ℃ then 15～45 ℃ of sustained reactions 0.5～3.0 hour, this thermotonus 0.5～2.0 hour,
D. vacuumize
Vacuumized 0.5～2.0 hour at 50～75 ℃, vacuum degree control-0.05～-0.09MPa,
E. adjust pH
Solution after vacuumizing is cooled to 15～45 ℃, adds sour adjust pH and get liquid product, the pH value is controlled at 2.0～6.0.
3. preparation method according to claim 2 is characterized in that also comprising the spraying drying operation that liquid product is prepared into solid phase prod.
4. according to claim 2 or 3 described preparation methods, it is characterized in that sulphonating agent selects S-WAT or sodium bisulfite or Sodium Pyrosulfite for use.
5. according to claim 2 or 3 described preparation methods, it is characterized in that the used acid of adjust pH is hydrochloric acid or sulfuric acid or formic acid or their mixture.
6. preparation method according to claim 4 is characterized in that the used acid of adjust pH is hydrochloric acid or sulfuric acid or formic acid or their mixture.
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| Application Number | Priority Date | Filing Date | Title |
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| CN98111821A CN1063799C (en) | 1998-01-19 | 1998-01-19 | Tannin extract type amphoteric retanning agent and method for preparing same |
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| CN98111821A CN1063799C (en) | 1998-01-19 | 1998-01-19 | Tannin extract type amphoteric retanning agent and method for preparing same |
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| CN1063799C true CN1063799C (en) | 2001-03-28 |
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| TWI357086B (en) | 2008-07-03 | 2012-01-21 | Advanced Semiconductor Eng | Transformer and method for adjusting mutual induct |
| CN101831815B (en) * | 2009-03-13 | 2013-06-05 | 上海喜若飞精细化工有限公司 | Leather dye uniformly dyeing penetrating agent and preparation method thereof |
| CN103665290B (en) * | 2013-12-06 | 2015-05-13 | 上海金狮化工有限公司 | Preparation method for low-formaldehyde melamine resin retanning agent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053447A (en) * | 1990-01-16 | 1991-07-31 | 中国科学院成都有机化学研究所 | A kind of manufacture method of mehtod for auxiliary bleaching synthetic tanning agent |
| CN1070689A (en) * | 1991-09-17 | 1993-04-07 | 庆巴图 | Carbamide ring tanning agent and vegetable tanning agent are in conjunction with the method for tanning bottom leather |
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1998
- 1998-01-19 CN CN98111821A patent/CN1063799C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053447A (en) * | 1990-01-16 | 1991-07-31 | 中国科学院成都有机化学研究所 | A kind of manufacture method of mehtod for auxiliary bleaching synthetic tanning agent |
| CN1070689A (en) * | 1991-09-17 | 1993-04-07 | 庆巴图 | Carbamide ring tanning agent and vegetable tanning agent are in conjunction with the method for tanning bottom leather |
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| CN1224062A (en) | 1999-07-28 |
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