CN104357593A - Water-soluble sulfonated resorcinol calixarene tanning agent applied to tannage of leather and preparation method of tanning agent - Google Patents
Water-soluble sulfonated resorcinol calixarene tanning agent applied to tannage of leather and preparation method of tanning agent Download PDFInfo
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- CN104357593A CN104357593A CN201410684034.7A CN201410684034A CN104357593A CN 104357593 A CN104357593 A CN 104357593A CN 201410684034 A CN201410684034 A CN 201410684034A CN 104357593 A CN104357593 A CN 104357593A
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- tanning agent
- tanning
- resorcinol
- calixarene
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- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/06—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with sulfuric acid or sulfur trioxide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
- C07C303/04—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups
- C07C303/08—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof by substitution of hydrogen atoms by sulfo or halosulfonyl groups by reaction with halogenosulfonic acids
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a water-soluble sulfonated resorcinol calixarene tanning agent applied to tannage of leather and a preparation method of the tanning agent. A chrome tanning agent is used as a main tanning agent in a plurality of leather making enterprises due to the characteristics of being simple in operation and excellent in leather performance; no tanning agent can be used for fully replacing the chrome tanning agent at present. The preparation method of the tanning agent comprises the following steps: mixing resorcinol, a solvent and o-hydroxybenzaldehyde under the condition of ice water bath, magnetically stirring and dissolving, introducing N2 and discharging air, dropwise adding an inorganic strong acid catalyst under the protection of N2, heating and reacting, cooling, carrying out suction filtration, washing and drying to obtain resorcinol calixarene, and adding a sulfonating agent into the resorcinol calixarene for reacting to obtain the water-soluble sulfonated resorcinol calixarene tanning agent. The water-soluble sulfonated resorcinol calixarene tanning agent is used as a chrome-free tanning agent; the chrome residue of the leather making process is reduced; when the water-soluble sulfonated resorcinol calixarene tanning agent is applied to tannage of goat skin, the shrinkage temperature of the raw skin is increased to 80 DEG C; and the breaking elongation ratio of a skin blank is 120%, the tensile strength is 23N/mm<2> and the tearing strength is 69.3N/mm, all of which are superior to those of the skin blank subjected to conventional chrome tanning.
Description
Technical field
the present invention relates to a kind of leather retanning agent, be specifically related to a kind of leather tanning water soluble sulfonated Resorcinol calixarene tanning agent and preparation method thereof.
Background technology
Leather retanning agent is that a class can form chemical bonded refractory with materials with hide glue fibril generation chemical reaction and merges the chemical substance producing crosslinking structure, and tanned skin becomes leather.The advantages such as the finished leather performance that chrome tanning agent is simple to operate with it, excellent are come out top in tanning industry, so far also can substitute chromium tanning agent completely without any a kind of tanning agent.But in conventional chrome tanning process, there is a large amount of chromium residues in waste tanning liquor, with Cr
2o
3count concentration up to 3 ~ 8g/L, Cr under certain condition
3+cr can be transformed into
6+, and Cr
6+it is strong carcinogenic substance.Within 2014, EU Committee issues Official Journal, and revision leatherware sexavalent chrome restriction order requires directly and in the leatherware of contact human skin, content of 6-valence Cr ions more than 3mg/kg, therefore must not strictly should control chromium discharge.
Calixarene is a class by the material of phenols and aldehyde material cyclic condensation, exactly likes Greece's Holy grail and gains the name.Calixarene lower edge has a large amount of phenolic hydroxyl group, can to give again that it is good water-soluble after sulfonic group when introducing, phenolic hydroxyl group can with the group effect such as the amino on collagen, carboxyl, guanidine radicals, play tanning effect.Water soluble sulfonated Resorcinol calixarene building-up process is simple, it can be used as chrome-free tanning agent to be feasible for process hides tanning processes.Water soluble sulfonated Resorcinol calixarene is a kind of novel chrome-free tanning agent, can reduce chromium consumption, reduces pollution of chromium, realizes the cleanly production of process hides tannery.
Summary of the invention
The object of this invention is to provide a kind of leather tanning water soluble sulfonated Resorcinol calixarene tanning agent and preparation method thereof, obtained water soluble sulfonated Resorcinol calixarene tanning agent uses as chrome-free tanning agent, decreases the chromium residues of process for tanning.
The technical solution adopted in the present invention is:
The water soluble sulfonated Resorcinol calixarene tanning agent of leather tanning, is characterized in that:
Be made up of following component:
Resorcinol calixarene 3.0-5.0g;
Sulphonating agent 9-40mL.
Described sulphonating agent is selected from the vitriol oil, the chlorsulfonic acid that massfraction is 98%.
Described Resorcinol calixarene is made up of following component:
Resorcinol 2.75g;
Solvent 25mL;
Salicylaldhyde 2.5-3.5g;
Strong inorganic acid catalyst 3-7mL.
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is (1:4)-(4:1).
Described strong inorganic acid catalyst be selected from massfraction be 37% hydrochloric acid, massfraction be 65% nitric acid, massfraction be the sulfuric acid of 98%.
As described in the leather tanning preparation method of water soluble sulfonated Resorcinol calixarene tanning agent, it is characterized in that:
Realized by following steps:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 2.5-3.5g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, inflated with nitrogen emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 3-7mL of protection;
After being added dropwise to complete, be warming up to 60-80 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation;
Step 2: take Resorcinol calixarene 3.0-5.0g, add sulphonating agent 9-40mL, sulfonation temperature 70-80 DEG C, sulfonation 2-4h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
In step one:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is (1:4)-(4:1);
Described strong inorganic acid catalyst be selected from massfraction be 37% hydrochloric acid, massfraction be 65% nitric acid, massfraction be the sulfuric acid of 98%;
In step 2:
Sulphonating agent is selected from the vitriol oil, the chlorsulfonic acid that massfraction is 98%.
The present invention has the following advantages:
The present invention for raw material, prepares Resorcinol calixarene by single stage method with Resorcinol, salicylaldhyde, and preparation method's simple possible is well water-soluble after sulfonation.This water soluble sulfonated Resorcinol calixarene tanning agent is used for playing tanning effect to materials with hide glue fibril in leather tanning, after being applied to goatskin tanning, rawhide shrinkage temperature can be increased to 80 DEG C, test skin base physical and mechanical properties, elongation at break 120%, tensile strength 23N/mm
2, tear strength 69.3N/mm, is all better than conventional chrome tanning.And good hand feeling, softness, thicken rate obvious.Therefore the application thinks and can chrome tanning agent be replaced to be used in process hides tanning processes water soluble sulfonated Resorcinol calixarene, reduces chromium powder consumption, reduces pollution of chromium, realize the cleanly production of leather making process.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
The water soluble sulfonated Resorcinol calixarene tanning agent of the leather tanning that the present invention relates to, is a kind of novel chrome-free tanning agent, is obtained by following steps:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 2.5-3.5g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, and fills N
2emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 3-7mL of protection;
After being added dropwise to complete, be warming up to 60-80 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation.
Wherein:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is (1:4)-(4:1);
Described strong inorganic acid catalyst be selected from massfraction be 37% hydrochloric acid, massfraction be 65% nitric acid, massfraction be the sulfuric acid of 98%.
Step 2: take Resorcinol calixarene 3.0-5.0g, add sulphonating agent 9-40mL, sulfonation temperature 70-80 DEG C, sulfonation 2-4h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
Wherein:
Sulphonating agent is selected from the vitriol oil, the chlorsulfonic acid that massfraction is 98%.
Embodiment 1:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 2.5g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, and fills N
2emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 7mL of protection;
After being added dropwise to complete, be warming up to 60 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation.
Wherein:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is 4:1;
Described strong inorganic acid catalyst chooses the hydrochloric acid that massfraction is 37%.
Step 2: take Resorcinol calixarene 3.0g, add sulphonating agent 40mL, sulfonation temperature 70 DEG C, sulfonation 4h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
Wherein:
The vitriol oil that massfraction is 98% chosen by sulphonating agent.
Embodiment 2:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 3.0g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, and fills N
2emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 5mL of protection;
After being added dropwise to complete, be warming up to 70 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation.
Wherein:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is 2:1;
Described strong inorganic acid catalyst chooses the nitric acid that massfraction is 65%.
Step 2: take Resorcinol calixarene 4.0g, add sulphonating agent 25mL, sulfonation temperature 75 DEG C, sulfonation 3h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
Wherein:
The chlorsulfonic acid that massfraction is 98% chosen by sulphonating agent.
Embodiment 3:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 3.5g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, and fills N
2emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 3mL of protection;
After being added dropwise to complete, be warming up to 80 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation.
Wherein:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is 1:4;
Described strong inorganic acid catalyst chooses the sulfuric acid that massfraction is 98%.
Step 2: take Resorcinol calixarene 5.0g, add sulphonating agent 9mL, sulfonation temperature 80 DEG C, sulfonation 2h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
Wherein:
Sulphonating agent is selected from the vitriol oil, the chlorsulfonic acid that massfraction is 98%.
Embodiment 4:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 2.5g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, and fills N
2emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 7mL of protection;
After being added dropwise to complete, be warming up to 60 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation.
Wherein:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is 4:1;
Described strong inorganic acid catalyst chooses the hydrochloric acid that massfraction is 37%.
Step 2: take Resorcinol calixarene 3.0g, add sulphonating agent 24mL, sulfonation temperature 70 DEG C, sulfonation 4h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
Wherein:
The vitriol oil that massfraction is 98% chosen by sulphonating agent.
Embodiment 5:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 3.0g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, and fills N
2emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 5mL of protection;
After being added dropwise to complete, be warming up to 70 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation.
Wherein:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is 2:3;
Described strong inorganic acid catalyst chooses the nitric acid that massfraction is 65%.
Step 2: take Resorcinol calixarene 4.0g, add sulphonating agent 25mL, sulfonation temperature 75 DEG C, sulfonation 3h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
Wherein:
The chlorsulfonic acid that massfraction is 98% chosen by sulphonating agent.
Embodiment 6:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 3.5g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, and fills N
2emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 3mL of protection;
After being added dropwise to complete, be warming up to 80 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation.
Wherein:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is 1:4;
Described strong inorganic acid catalyst chooses the sulfuric acid that massfraction is 98%.
Step 2: take Resorcinol calixarene 5.0g, add sulphonating agent 15mL, sulfonation temperature 80 DEG C, sulfonation 2h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
Wherein:
Sulphonating agent is selected from the vitriol oil, the chlorsulfonic acid that massfraction is 98%.
The present invention with Resorcinol, salicylaldhyde for raw material, by one-step synthesis method Resorcinol calixarene, preparation method's simple possible.This water soluble sulfonated Resorcinol calixarene tanning agent is used for playing tanning effect to materials with hide glue fibril in leather tanning, rawhide shrinkage temperature can be increased to 80 DEG C, replace chrome tanning agent to be used for process hides tanning processes, reduce chromium powder consumption, reduce pollution of chromium, realize the cleanly production of leather making process.
Content of the present invention is not limited to cited by embodiment, and the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.
Claims (7)
1. the water soluble sulfonated Resorcinol calixarene tanning agent of leather tanning, is characterized in that:
Be made up of following component:
Resorcinol calixarene 3.0-5.0g;
Sulphonating agent 9-40mL.
2. the water soluble sulfonated Resorcinol calixarene tanning agent of leather tanning according to claim 1, is characterized in that:
Described sulphonating agent is selected from the vitriol oil, the chlorsulfonic acid that massfraction is 98%.
3. the water soluble sulfonated Resorcinol calixarene tanning agent of leather tanning according to claim 2, is characterized in that:
Described Resorcinol calixarene is made up of following component:
Resorcinol 2.75g;
Solvent 25mL;
Salicylaldhyde 2.5-3.5g;
Strong inorganic acid catalyst 3-7mL.
4. the water soluble sulfonated Resorcinol calixarene tanning agent of leather tanning according to claim 3, is characterized in that:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is (1:4)-(4:1).
5. the water soluble sulfonated Resorcinol calixarene tanning agent of leather tanning according to claim 4, is characterized in that:
Described strong inorganic acid catalyst be selected from massfraction be 37% hydrochloric acid, massfraction be 65% nitric acid, massfraction be the sulfuric acid of 98%.
6. the leather tanning preparation method of water soluble sulfonated Resorcinol calixarene tanning agent as claimed in claim 5, is characterized in that:
Realized by following steps:
Step one: under ice-water bath condition, adds 2.75g Resorcinol, 25mL solvent, 2.5-3.5g salicylaldhyde in four-hole boiling flask, and magnetic agitation is dissolved, inflated with nitrogen emptying 10min, N
2the lower strong inorganic acid catalyst slowly dripping 3-7mL of protection;
After being added dropwise to complete, be warming up to 60-80 DEG C, reaction 7h;
After reaction terminates, by reaction solution cooling, hold over night, suction filtration, repeatedly washs solid to filtrate clear, colorless with distilled water, and obtain yellow solid after suction filtration completes, 60 DEG C of constant pressure and dries, obtain yellow solid powder, are the Resorcinol calixarene of preparation;
Step 2: take Resorcinol calixarene 3.0-5.0g, add sulphonating agent 9-40mL, sulfonation temperature 70-80 DEG C, sulfonation 2-4h, obtains water soluble sulfonated Resorcinol calixarene tanning agent.
7. the leather tanning according to claim 6 preparation method of water soluble sulfonated Resorcinol calixarene tanning agent, is characterized in that:
In step one:
Described solvent is ethanolic soln, and the volume ratio of dehydrated alcohol and water is (1:4)-(4:1);
Described strong inorganic acid catalyst be selected from massfraction be 37% hydrochloric acid, massfraction be 65% nitric acid, massfraction be the sulfuric acid of 98%;
In step 2:
Sulphonating agent is selected from the vitriol oil, the chlorsulfonic acid that massfraction is 98%.
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|---|---|---|---|
| CN201410684034.7A CN104357593B (en) | 2014-11-25 | 2014-11-25 | Leather tanning water soluble sulfonated resorcinol calixarenes tanning agent and preparation method thereof |
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|---|---|---|---|
| CN201410684034.7A CN104357593B (en) | 2014-11-25 | 2014-11-25 | Leather tanning water soluble sulfonated resorcinol calixarenes tanning agent and preparation method thereof |
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| WO2016037508A1 (en) * | 2014-09-12 | 2016-03-17 | 陕西科技大学 | Sulfonatocalixarene tanning agent for leather tanning and preparation method therefor |
| CN106435053A (en) * | 2016-12-12 | 2017-02-22 | 温州大学 | Complexing agent for leather chrome-free tanning process as well as preparation method and application thereof |
| CN106674141A (en) * | 2016-12-07 | 2017-05-17 | 陕西科技大学 | Preparation method of chromium-free tanning agent |
| CN112176128A (en) * | 2020-10-30 | 2021-01-05 | 陕西科技大学 | Method for synthesizing ZnZr-MOF-LDH nano tanning agent based on template-oriented method |
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Cited By (6)
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| CN112176128A (en) * | 2020-10-30 | 2021-01-05 | 陕西科技大学 | Method for synthesizing ZnZr-MOF-LDH nano tanning agent based on template-oriented method |
| CN112176128B (en) * | 2020-10-30 | 2021-11-30 | 陕西科技大学 | Method for synthesizing ZnZr-MOF-LDH nano tanning agent based on template-oriented method |
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| CN104357593B (en) | 2016-06-08 |
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