CN114196791A - Epoxy-terminated hyperbranched polymer tanning agent and tanning method - Google Patents
Epoxy-terminated hyperbranched polymer tanning agent and tanning method Download PDFInfo
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- CN114196791A CN114196791A CN202111538205.1A CN202111538205A CN114196791A CN 114196791 A CN114196791 A CN 114196791A CN 202111538205 A CN202111538205 A CN 202111538205A CN 114196791 A CN114196791 A CN 114196791A
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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
- C14C3/22—Chemical tanning by organic agents using polymerisation products
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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Abstract
The invention discloses an epoxy-terminated hyperbranched polymer tanning agent and a tanning method, wherein the epoxy-terminated hyperbranched polymer tanning agent is a hyperbranched polymer containing a plurality of epoxy groups and hydroxyl groups and a derivative thereof, when tanning is carried out, pretreated animal skin is put into bath liquid containing an epoxy-terminated hyperbranched polymer tanning agent and a catalyst, the pH value of bath liquid in the step S1 is adjusted, an alkali extracting agent is added into the bath liquid, the tanned animal skin is stacked and kept stand, and leather is obtained through shaving, retanning, neutralizing, dyeing and fatliquoring.
Description
Technical Field
The invention belongs to the technical field of leather tanning, in particular to an epoxy-terminated hyperbranched polymer tanning agent and a tanning method, which can not use neutral salt, aldehyde, chromium and other substances in tanning and belong to the technical field of leather cleaning production.
Background
The leather production stabilizes collagen through a series of physical and chemical methods, so that the raw leather is converted into soft, firm and corrosion-resistant leather, and high-value utilization of biomass resources is realized. Various pollution problems are accompanied in the production process of the traditional leather. In terms of tanning, which is the most critical step in the leather-making process, chrome tanning has always taken an irreplaceable importance, because of its high thermal stability, mechanical strength and resistance to microbial corrosion of the tanned leathers. However, the chrome tanning process has the problems of low chrome absorption rate, difficult treatment of chrome-containing waste water and solid waste and the like, causes irreversible damage to the environment due to poor or improper management of chrome-rich waste and seriously harms public health. In addition, a pickling step is required before metal tanning (chrome tanning) to adjust the pH of the hide for subsequent penetration and bonding of the tanning agent, wherein a large amount of neutral salt is used to suppress the acid swelling of the skin, thereby resulting in a Cl-rich waste stream after tanning-The sewage treatment is complicated. Currently, tannery wastewater, sludge and solid waste gradually become three major technical bottlenecks of sustainable development of leather industry, and along with the continuous enhancement of environmental awareness and health awareness of people, ecological leather products will become the mainstream trend of consumption. The method adopts a cleaner process technology to implement chrome-free tanning and salt-free pickling, and the manufacture of ecological leather products is a necessary choice for the sustainable development of the leather industry and an important strategic measure for realizing transformation and upgrading of the leather industry, and the development of replaceable leather cleaning chemicals becomes an important measure for advancing the leather industry to reduce pollution from the source.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides an epoxy-terminated hyperbranched polymer tanning agent and a tanning method, which not only have high absorption performance, can well chelate ions and adsorb small molecules, improve the absorption utilization rate of metal ions such as aluminum and the like, but also meet the production requirements of a pickling-free tanning process and a salt-free pickling metal tanning process, and solve the problems of neutral salt and chromium pollution in the leather tanning process.
In order to achieve the purpose, the invention provides the following technical scheme: an epoxy-terminated hyperbranched polymer tanning agent is a hyperbranched polymer containing a plurality of epoxy groups and hydroxyl groups and a derivative thereof, and the general formula of the epoxy-terminated hyperbranched polymer tanning agent can be represented as follows:
further, the structure of R in the epoxy-terminated hyperbranched polymer tanning agent is as follows:
the structure of R' in the structure of R in the epoxy-terminated hyperbranched polymer tanning agent is as follows:
further, the structure of R in the epoxy-terminated hyperbranched polymer tanning agent is as follows
R' has the structure of
The invention provides a use method of an epoxy-terminated hyperbranched polymer tanning agent, which comprises the following specific steps:
s1, putting the pretreated animal skin into a bath solution containing an epoxy-terminated hyperbranched polymer tanning agent and a catalyst;
s2, adjusting the pH value of the bath liquid in the step S1, adding an alkali extracting agent into the bath liquid, stacking and standing the tanned animal skins, and obtaining the leather through shaving, retanning, neutralizing, dyeing and greasing.
Further, when the pickled leather is tanned, the animal leather is treated by the procedures of soaking, unhairing, liming, deliming, softening and pickling, and the specific tanning steps are as follows:
1) mixing 50-150 parts of water, 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent, 0.2-3 parts of catalyst and 5-8 parts of neutral salt at the temperature of 15-30 ℃ to obtain bath liquid, adjusting the pH value of the bath liquid to 5.0-7.5, putting 100 parts of pickled pelts into the bath liquid, and reacting for 3-6 hours;
2) adding an alkali extracting agent into the bath liquid obtained in the step 1), adjusting the pH value of the bath liquid to 7.5-9.0, supplementing 50-150 parts of water, heating to 30-40 ℃, reacting for 1-3 h, and stopping blowing overnight;
3) and after stopping the drum and standing overnight, stacking and standing for 1-2 days, and then shaving, retanning, neutralizing, dyeing and greasing to obtain the leather.
Further, when the softened leather is tanned, the animal leather is treated by the procedures of soaking, unhairing, liming, deliming, softening and pickling, and the specific tanning steps are as follows:
1) mixing 50-150 parts of water, 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent and 0.2-3 parts of catalyst at the temperature of 15-30 ℃ to obtain bath liquid, adjusting the pH value of the bath liquid to 5.0-7.5, putting 100 parts of softened pelts into the bath liquid, and reacting for 3-6 h;
2) adding an alkali extracting agent into the bath liquid obtained in the step 1), adjusting the pH value of the mixed liquid to 7.5-9.0, supplementing 50-150 parts of water, heating to 30-40 ℃, reacting for 1-3 h, and stopping blowing overnight;
further, when the combined tanning of the salt-free pickling-metal tanning agent is carried out, the specific tanning steps are as follows after the animal skin is subjected to the procedures of soaking, unhairing, liming, deliming, softening and pickling:
1) mixing 50-150 parts of water, 5-10 parts of epoxy-terminated hyperbranched polymer tanning agent and 0.2-2 parts of catalyst at the temperature of 15-30 ℃ to obtain bath liquid, adjusting the pH value of the bath liquid to 6.0-7.5, putting 100 parts of softened pelts into the bath liquid, and reacting for 3-6 h;
2) adding an alkali extracting agent into the bath liquid obtained in the step 1), adjusting the pH value of the mixed liquid to 7.5-8.5, supplementing 50-150 parts of water, heating to 30-40 ℃, reacting for 1-3 h, and stopping blowing overnight;
3) standing the tanned crust leather for 1-2 days, performing a salt-free pickling aluminum tanning process, stopping the drum for overnight, standing the tanned crust leather for 1-2 days, shaving, retanning, neutralizing, dyeing and greasing to obtain the leather.
Further, in the step 1), during tanning, adding an epoxy-terminated hyperbranched polymer tanning agent into water to obtain bath liquid, adjusting the pH value of the bath liquid, putting the pretreated animal skin into the bath liquid, reacting for 1-3 h, adding a catalyst, reacting for 3-5 h, and keeping the rest steps unchanged;
or
In the step 1), during tanning, firstly adding a catalyst into water, putting the pretreated animal skin into bath liquid, reacting for 1-3 h, then adding an epoxy-terminated hyperbranched polymer tanning agent, adjusting the pH value of the bath liquid, and reacting for 3-5 h, wherein the rest steps are unchanged.
Further, in step S1, the catalyst is urotropin, and the catalyst is added to the solvent before, after or simultaneously with the epoxy-terminated hyperbranched polymer tanning agent.
Further, in step S2, the alkali extracting agent is at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide; the mass ratio of the sodium carbonate to the sodium bicarbonate is 1 (1-3).
Compared with the prior art, the invention has at least the following beneficial effects:
the invention provides an epoxy-terminated hyperbranched polymer tanning agent which is an epoxy-terminated hyperbranched polymer containing a plurality of epoxy groups and hydroxyl groups, wherein the tanning agent has a high-degree branched structure in molecules, so that molecular chains are less wound, good water solubility is provided, and the ratio of reaction raw materials can be controlled during the preparation of the epoxy-terminated hyperbranched polymer so that the molecular weight is controllable, thereby meeting the size requirement of cross-linking of the tanning agent molecules among multi-level collagen fibers and the requirements of different animal skins; the hyperbranched polymer has unique internal micropores which can chelate and adsorb small molecules, and hydroxyl on the molecules can further generate coordination with subsequent metal ions to enhance the tanning property, thereby improving the absorption and utilization rate of the metal tanning agent.
The epoxy-terminated hyperbranched polymer tanning agent has relatively considerable molecular weight, can improve the fullness and physical and mechanical properties of tanned leather, achieves the similar retanning effect, and realizes the main retanning integration of a tanning process.
The tanning method of the invention utilizes the characteristic that epoxy groups on the epoxy-terminated hyperbranched polymer tanning agent have low reaction activity under neutral condition and acidic condition, can be carried out under weak acid or neutral condition in the initial tanning stage, and can realize the direct tanning of conventional pickled skins or softened skins; the catalyst is added, the pH value is increased at the later stage to promote the reaction process, and the reaction of epoxy groups and collagen amino groups is promoted to generate the tanning effect.
When the salt-free pickling and metal tanning agent are combined for tanning, the hydroxyl on the epoxy-terminated hyperbranched polymer tanning agent can be subjected to coordination and complexation with a subsequent metal tanning agent, so that the uniform tanning is realized, the absorption and utilization rate of metal ions is improved, and the emission pollution of heavy metals is reduced
The invention provides a high-efficiency tanning method taking an epoxy-terminated hyperbranched polymer as a tanning agent, which is directly applied to tanning pickled skins and softened skins as a main tanning agent and can obtain soft and white leather with the shrinkage temperature close to 82 ℃ (a shrinkage temperature determinator (QB/T2713) 2005); the leather serving as the salt-free pickling auxiliary agent for pretanning and softening the leather realizes the combination tanning of the salt-free pickling and non-chromium metal tanning agent, can obtain soft and plump leather with the shrinkage temperature close to 85 ℃ (a shrinkage temperature tester (QB/T2713-.
Drawings
FIGS. 1-6 are schematic molecular structure diagrams of epoxy and hydroxyl terminated hyperbranched polymer tanning agents of examples 1-15.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
The invention provides an epoxy-terminated hyperbranched polymer tanning agent, which is a hyperbranched polymer containing a plurality of epoxy groups and hydroxyl groups and a derivative thereof, and the general formula of the hyperbranched polymer tanning agent can be expressed as follows:
the structure of R in the epoxy-terminated hyperbranched polymer tanning agent is as follows:
the R' structure in the R structure in the epoxy-terminated hyperbranched polymer tanning agent is as follows:
preferably, the epoxy-terminated hyperbranched polymer tanning agent has the structure R
R' has the structure of
The invention provides a using method of an epoxy-terminated hyperbranched polymer tanning agent, which comprises the following specific steps:
(1) the polymer tanning agent is applied to acid leather tanning of the traditional tanning process to realize chromium-free processing of white wet leather:
(a) animal skins such as sheepskin, cowhide, pigskin and the like which are used as leather-making raw material skins are tanned according to the following steps after being treated by conventional procedures of soaking, unhairing, liming, deliming, softening and pickling:
(b) under the condition of 15-30 ℃, adding 50-150 parts of water, 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent, 0.2-3 parts of catalyst and 5-8 parts of neutral salt into a rotary drum, transferring for 10min to obtain bath liquid, putting 100 parts (by mass of hide) of pickling naked skin into the bath liquid, transferring for 3-6 h, adding a proper amount of alkali extracting agent for multiple times, adjusting the pH value of the bath liquid to be 7.5-9.0 stably, replenishing 50-150 parts of water, heating to 30-40 ℃, continuing to rotate for 1-3 h, and stopping the drum for overnight.
Or in the operation, adding 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent and 5-8 parts of neutral salt into water to obtain bath liquid, adjusting the pH value of the bath liquid, turning for 1-3 h, then putting the pickled bare skin into the bath liquid, adding 0.2-3 parts of catalyst into the rotary drum after the tanning agent is basically permeated into the skin, turning for 2-5 h, and keeping other operations unchanged.
Or in the operation, firstly adding 0.2-3 parts of catalyst and 5-8 parts of neutral salt into water to obtain bath liquid, putting the pickled pelts into the bath liquid, rotating for 1-3 hours, then adding 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent into the rotary drum, adjusting the pH value of the bath liquid, and continuing rotating for 2-5 hours, wherein other operation procedures are kept unchanged. And taking out after 20min of next day, stacking and standing for 1-2 days, and then carrying out subsequent procedures of shaving, retanning, neutralizing, dyeing, fatliquoring and the like.
(2) The polymer tanning agent is applied to the softening leather tanning of the traditional tanning process to realize the neutral salt-free and chromium-free processing of the white wet leather:
(a) the animal skins such as sheepskin, cowhide, pigskin and the like which are used as leather-making raw material skins are tanned according to the following steps after being treated by conventional procedures of soaking, unhairing, liming, deliming and softening:
(b) under the condition of 15-30 ℃, adding 50-150 parts of water, 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent and 0.2-3 parts of catalyst into a rotary drum for transferring for 10min to obtain bath liquid, adding acid to adjust the pH value of the bath liquid to be 5.0-7.5, putting 100 parts (by mass of grey skin) of softened naked skin into the bath liquid, adding a proper amount of alkali extracting agent for 3-6 h, adjusting the pH value of the bath liquid to be stable within the range of 7.5-9.0, replenishing 50-150 parts of water, heating to 30-40 ℃, continuing to rotate for 1-3 h, and stopping the drum for overnight.
Or in the operation, firstly adding 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent into water to obtain bath liquid, adjusting the pH value of the bath liquid, putting the softened pelts into the bath liquid, rotating for 1-3 hours, adding 0.2-3 parts of catalyst into the rotary drum after the tanning agent is basically permeated into the pelts, and rotating for 2-5 hours, wherein other operations are kept unchanged.
Or in the operation, 0.2-3 parts of catalyst is added into water to obtain bath liquid, the softened pelts are put into the bath liquid, after 1-3 hours of rotation, 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent is added into the rotary drum, the pH value of the bath liquid is adjusted, the rotary drum continues to rotate for 2-5 hours, and other operation procedures are kept unchanged. And taking out after 20min of next day, stacking and standing for 1-2 days, and then carrying out subsequent procedures of shaving, retanning, neutralizing, dyeing, fatliquoring and the like.
(3) The polymer tanning agent is applied to a combined tanning process of a salt-free pickling-metal tanning agent, and realizes the processing of neutral-salt-free leather:
(a) the raw leather is tanned according to the following steps after being treated by the procedures of soaking, unhairing, liming, deliming and softening in the traditional process:
(b) 100 parts of softened naked leather (by mass of grey leather), 50-150 parts of water, 15-30 ℃ of temperature, 5-10 parts of end-epoxy hyperbranched polymer tanning agent and 0.2-2 parts of catalyst, wherein chemical materials are added into a rotary drum for transferring for 10min, acid is added to adjust the pH value of bath liquid to be 6.0-7.5, then leather is thrown, an appropriate amount of alkali extracting agent is added for multiple times after 3-6 h of transferring, the pH value of the bath liquid is adjusted to be stable within the range of 7.5-8.5, 50-150 parts of water is supplemented, the temperature is increased to 30-40 ℃, and after 1-3 h of continuous rotation, the drum is stopped for overnight.
Or in the operation, firstly adding 5-10 parts of epoxy-terminated hyperbranched polymer tanning agent into water to obtain bath liquid, adjusting the pH value of the bath liquid, putting the softened pelts into the bath liquid, rotating for 1-3 hours, adding 0.2-2 parts of catalyst into the rotary drum after the tanning agent basically finishes penetrating into the pelts, and rotating for 2-5 hours, wherein other operations are kept unchanged.
Or in the operation, 0.2-3 parts of catalyst is added into water to obtain bath liquid, the softened pelts are put into the bath liquid, after 1-3 hours of rotation, 5-10 parts of epoxy-terminated hyperbranched polymer tanning agent is added into the rotary drum, the pH value of the bath liquid is adjusted, the rotary drum continues to rotate for 2-5 hours, and other operation procedures are kept unchanged. Standing the tanned crust leather for 1-2 days, and then performing a salt-free pickling aluminum tanning process.
The salt-free pickling aluminum tanning process comprises the following steps: adding 0.6-1.2 parts of sulfuric acid (by mass of the ash bark), 0.3-0.8 part of formic acid and 30-150 parts of water, adjusting the temperature to 15-30 ℃, adjusting the pH to 2.5 +/-0.2, rotating for 3-4 h, and standing overnight; turning for 1-3 h the next day, adjusting the pH value to 2.8-3.2, keeping the pickle liquor to 0.3-0.5, adding 5-8 parts of metal tanning agent (reduced to Al)2O31.0-1.2 parts), rotating for 3-6 hours, adding an appropriate amount of an alkali extracting agent for multiple times, adjusting the pH value of the bath liquid to be 3.8-4.2 stably, supplementing 50-150 parts of water, heating to 35-40 ℃, continuing to rotate for 1-3 hours, and stopping blowing overnight. And taking out after 20min of next day, stacking and standing for 1-2 days, and then carrying out subsequent procedures of shaving, retanning, neutralizing, dyeing, fatliquoring and the like.
Preferably, the catalyst is urotropin.
Preferably, the mode of adding the catalyst comprises adding the catalyst before or after the hyperbranched tanning agent or simultaneously with the tanning agent,
preferably, the addition is 2 hours before the tanning agent.
Preferably, the pH value control during tanning comprises that the initial stage of tanning acid leather and softened leather is controlled to be 5.0-7.5, and the final stage is controlled to be 7.5-9.0.
Preferably, the alkali extracting agent is at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide;
preferably, sodium carbonate and sodium bicarbonate are used in a mixture (mass ratio: 1 to 3).
Preferably, the tanning temperature control comprises controlling the temperature at the initial stage of tanning at 15-30 ℃, preferably at 20-25 ℃; the temperature at the final stage of tanning is controlled to be 30-45 ℃, preferably 32-40 ℃.
In the technical scheme, the animal skin cleaning and tanning method of the epoxy-terminated hyperbranched polymer can be suitable for tanning various animal acid skins and softened skins, and realizes a chromium-free or chromium-free and neutral-salt-free cleaning leather making technology.
Example 1: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 50kg of water, the temperature of 15 ℃, 0.2kg of urotropine and 5kg of neutral salt are added into a rotary drum for transferring for 10min, the acid pelts are added after chemical materials are basically dissolved, 8kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 1) is added after 1h of rotation, the pH value of bath liquid is adjusted to be about 5.0, a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water for dissolution, the mass ratio of sodium carbonate to sodium bicarbonate is 1:3) is added after 3h of rotation, the pH value of the bath liquid is slowly adjusted to be 7.5 +/-and 150kg of 50 ℃ water is added, the temperature is increased to 30 ℃, and the drum is stopped for overnight after 1h of rotation. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 70 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 2: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 100kg of water, the temperature of which is 20 ℃, 0.5kg of urotropine and 8kg of neutral salt are added into a rotary drum for transferring for 10min, the acid pelts are added after chemical materials are basically dissolved, 10kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 2) is added after 2h of transfer, the pH value of bath liquid is adjusted to be about 7.0, the bath liquid is continuously transferred for 4h, a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:2) is added at intervals of 20min, the pH value of the bath liquid is slowly adjusted to be 8.5 +/-and 100kg of water with the temperature of 50 ℃ is supplemented, the temperature is increased to 35 ℃, and the drum is stopped for overnight after 2h of continuous transfer. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 80 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 3: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 150kg of water, the temperature of 30 ℃, 3kg of urotropine and 7kg of neutral salt are added into a rotary drum for transferring for 10min, the acid pelts are added after chemical materials are basically dissolved, 15kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 3) is added after 3h of transfer, the pH value of bath foam is adjusted to be about 7.5, the bath foam is continuously transferred for 5h, a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:1) is added at intervals of 20min, the pH value of the bath foam is slowly adjusted to be 9.0, 50kg of water at +/-50 ℃ is added, the temperature is increased to 40 ℃, the drum is stopped for 3h of continuous rotation, and the drum is kept overnight. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 82 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 4: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 100kg of water, the temperature of 30 ℃, 0.5kg of urotropine, 7kg of neutral salt and 12kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 4) are added into a rotary drum for transferring for 10min, the pelts are added into the rotary drum after chemical materials are basically dissolved, the pH value of bath liquid is adjusted to be about 6.5, a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:1) is added into the rotary drum for transferring for 20min, the pH value of the bath liquid is slowly adjusted to be 9.0 +/-and 50kg of water with the temperature of 50 ℃ is supplemented, the temperature is increased to 40 ℃, the rotary drum is stopped for overnight after continuing to rotate for 3 h. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 72 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 5: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 100kg of water, the temperature of 30 ℃, 0.5kg of urotropine, 7kg of neutral salt and 12kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 5) are added into a rotary drum for transferring for 10min, the pelts are added into the rotary drum after chemical materials are basically dissolved, the pH value of bath liquid is adjusted to be about 6.5, a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:1) is added into the rotary drum at intervals of 20min after 3h of rotation, the pH value of the bath liquid is slowly adjusted to be 9.0 +/-and 50kg of water at the temperature of 50 ℃ is supplemented, the temperature is raised to 40 ℃, the rotary drum is stopped for overnight after continuing to rotate for 3 h. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 70 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 6: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated by the mass of the pelts), 100kg of water, the temperature of 30 ℃, 0.5kg of urotropine, 7kg of neutral salt and 12kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6) are added into a rotary drum for transferring for 10min, the pelts are added into the rotary drum after chemical materials are basically dissolved, the pH of bath liquid is adjusted to be about 6.5, a proper amount of mixed solution of potassium carbonate and potassium bicarbonate is added into the rotary drum at intervals of 20min after 6h of transfer, the pH value of the bath liquid is slowly adjusted to be 9.0 +/-and 50kg of water at the temperature of 50 ℃ is supplemented, the temperature is increased to 40 ℃, the rotary drum is stopped for overnight after continuing to rotate for 3 h. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 70 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 7: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 100kg of water, the temperature of 30 ℃, 7kg of neutral salt and 12kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6) are added into a rotary drum for transferring for 10min, the pelts are added after chemical materials are basically dissolved, the pH of bath liquid is adjusted to be about 6.5, 1kg of urotropine is added after 1h of transfer, a proper amount of sodium hydroxide solution is added after 3h of transfer and at intervals of 20min, the pH value of the bath liquid is slowly adjusted to be 9.0 +/-and 50kg of water at the temperature of 50 ℃ is supplemented, the temperature is increased to 35 ℃, the pelts are stopped from being blown overnight after 2h of transfer. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 78 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 8: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 100kg of water, the temperature of 30 ℃, 7kg of neutral salt and 12kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6) are added into a rotary drum for transferring for 10min, the pelts are added after chemical materials are basically dissolved, the pH of bath liquid is adjusted to be about 6.5, 1kg of urotropine is added after 2h of transfer, a proper amount of potassium hydroxide solution is added after 4h of transfer at intervals of 20min, the pH value of the bath liquid is slowly adjusted to be 9.0 +/-and 50kg of water at the temperature of 50 ℃ is supplemented, the temperature is increased to 35 ℃, the pelts are stopped from being blown overnight after 2h of transfer. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 80 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 9: tanning of sheep acid skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening, pickling and the like according to the conventional process. 100kg of pickled pelts (calculated according to the mass of the pelts), 100kg of water, the temperature of 30 ℃, 7kg of neutral salt and 12kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6) are added into a rotary drum for transferring for 10min, the pelts are added after chemical materials are basically dissolved, the pH of bath liquid is adjusted to be about 6.5, 1kg of urotropine is added after 2h of transfer, a proper amount of mixed solution of sodium carbonate and potassium bicarbonate is added after 5h of transfer is continued and at intervals of 20min, the pH value of the bath liquid is slowly adjusted to be 9.0 +/-and 50kg of water at the temperature of 50 ℃ is supplemented, the temperature is increased to 35 ℃, the pelts are rotated for 2h, and the pelts are stopped to be used for overnight. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 80 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 10: tanning of sheep softened skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening and the like according to the conventional process.
100kg of softened sheep pelts (measured by the mass of the grey skin), 100kg of water, 15 ℃ and 0.2kg of urotropine, firstly adding chemical materials into a rotary drum, transferring for 10min, throwing the chemical materials into the rotary drum, transferring for 1h, adding 8kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6), adjusting the pH of bath lotion to 5.0, continuing to transfer for 3h, adding a proper amount of sodium carbonate solution at intervals of 20min, slowly adjusting the pH value of the bath lotion to be 7.5, supplementing 150kg of water with the temperature of 50 ℃, heating to 30 ℃, continuing to rotate for 3h, and stopping the drum for overnight. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 72 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 11: tanning of sheep softened skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening and the like according to the conventional process.
100kg of softened sheep pelts (measured by the mass of the pelts), 100kg of water, 25 ℃ of temperature, 10kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6) is added into a rotary drum to be transferred for 10min, the skin is thrown after chemical materials are basically dissolved, the pH value of bath liquid is adjusted to 6.5, the urotropine is added for 0.5kg after 2h of bath liquid is adjusted, the bath liquid is continuously transferred for 4h and then is added with a proper amount of potassium carbonate solution at intervals of 20min, the pH value of the bath liquid is slowly adjusted to be stable at 8.5, 100kg of water with the temperature of 50 ℃ is supplemented, the temperature is increased to 35 ℃, the drum is continuously rotated for 2h, and then the drum is stopped for overnight. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 80 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out. Example 12: tanning of sheep softened skin
The sheep raw leather is tanned after being treated by leather-making procedures such as soaking, unhairing, liming, deliming, softening and the like according to the conventional process.
100kg of softened sheep pelts (measured by the mass of the pelts), 150kg of water at the temperature of 30 ℃ and 3kg of urotropine, firstly adding chemical materials into a rotary drum, transferring for 10min, throwing skins, transferring for 3h, then adding 15kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6), adjusting the pH of bath lotion to 7.5, continuing to transfer for 6h, adding a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:1) at an interval of 20min, slowly adjusting the pH value of the bath lotion to be stable at 9.0, supplementing 150kg of 50 ℃ water, heating to 40 ℃, continuing to rotate for 1h, and stopping the drum overnight. Taking out after 20min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 82 ℃. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 13: salt-free pickling-aluminum tanning agent tanning of sheep softened skins
Pre-tanning: the sheep raw leather is subjected to tanning procedures such as soaking, unhairing, liming, deliming, softening and the like according to a conventional process, and then is subjected to pretanning by using the epoxy-terminated hyperbranched polymer tanning agent. 100kg of softened sheep pelts (measured by the mass of the pelts), 50kg of water, 15 ℃ of temperature and 0.2kg of urotropine, firstly adding chemical materials into a rotary drum, transferring for 10min, throwing skins, transferring for 1h, then adding 5kg of epoxy-terminated hyperbranched polymer tanning agent (shown in a structural formula as figure 6), adding formic acid to adjust the pH value of bath solution to 6.0, continuing to transfer for 3h, then adding a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:3) at an interval of 20min, slowly adjusting the pH value of the bath solution to be stable at 7.5, supplementing 150kg of water with the temperature of 50 ℃, heating to 30 ℃, continuing to rotate for 1h, and stopping the drum for overnight. Taking out after 20min next day, stacking and standing for 1 day, wherein the tanning shrinkage temperature can reach 75 ℃ +/-1 ℃.
Salt-free pickling-aluminum tanning: 1kg of sulfuric acid (calculated by the mass of the ash bark) (diluted by 20 times of aqueous solution), 0.3kg of formic acid (diluted by 10 times of aqueous solution), 100kg of water, 25 ℃ and 2 times of adding the adjusting bath solution with the pH value of 2.5 +/-0.2, rotating for 3-4 h and staying overnight; and on the next day, supplementing acid, adjusting the pH value to 2.8-3.2, rotating for 1-3 h, keeping the pickle liquor to be 3 times of the original pH value, adding 6kg of aluminum tanning agent, rotating for 5h, adding a proper amount of sodium bicarbonate solution at intervals of 20min, slowly adjusting the pH value of the bath foam to be in a range of 3.8-4.2, supplementing 100kg of water at 50 ℃, heating to 35-40 ℃, continuously rotating for 2h, and stopping the drum for overnight. And (3) taking out the leather from the drum after 30min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 85 ℃ +/-1. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 14: salt-free pickling-aluminum tanning agent tanning of sheep softened skins
Pre-tanning: the sheep raw leather is subjected to tanning procedures such as soaking, unhairing, liming, deliming, softening and the like according to a conventional process, and then is subjected to pretanning by using the epoxy-terminated hyperbranched polymer tanning agent. 100kg of softened sheep pelts (measured by the mass of the grey skin), 100kg of water, the temperature of 25 ℃ and 0.6kg of urotropine, firstly adding chemical materials into a rotary drum, transferring for 10min, throwing the chemical materials into the rotary drum, transferring for 1h, then adding 8kg of epoxy-terminated hyperbranched polymer tanning agent (shown in the structural formula shown in figure 6), adding formic acid to adjust the pH value of bath solution to 7.0, continuing to transfer for 4h, then adding a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:2) at an interval of 20min, slowly adjusting the pH value of the bath solution to be stable at 8.0, supplementing 100kg of water at the temperature of 50 ℃, heating to 35 ℃, continuing to rotate for 2h, and stopping the drum for overnight. Taking out after 20min next day, stacking and standing for 1 day, wherein the tanning shrinkage temperature can reach 78 ℃ +/-1 ℃.
Salt-free pickling-aluminum tanning: 1kg of sulfuric acid (calculated by the mass of the ash bark) (diluted by 20 times of aqueous solution), 0.3kg of formic acid (diluted by 10 times of aqueous solution), 100kg of water, 25 ℃ and 2 times of adding the adjusting bath solution with the pH value of 2.5 +/-0.2, rotating for 3-4 h and staying overnight; and on the next day, supplementing acid, adjusting the pH value to 2.8-3.2, rotating for 1-3 h, keeping the pickle liquor to be 3 times of the original pH value, adding 6kg of aluminum tanning agent, rotating for 5h, adding a proper amount of sodium bicarbonate solution at intervals of 20min, slowly adjusting the pH value of the bath foam to be in a range of 3.8-4.2, supplementing 100kg of water at 50 ℃, heating to 35-40 ℃, continuously rotating for 2h, and stopping the drum for overnight. And (3) taking out the leather from the drum after 30min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 85 ℃ +/-1. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Example 15: salt-free pickling-aluminum tanning agent tanning of sheep softened skins
Pre-tanning: the sheep raw leather is subjected to tanning procedures such as soaking, unhairing, liming, deliming, softening and the like according to a conventional process, and then is subjected to pretanning by using the epoxy-terminated hyperbranched polymer tanning agent. 100kg of softened sheep pelts (calculated by the mass of the pelts), 150kg of water at the temperature of 30 ℃ and 2kg of urotropine, firstly adding chemical materials into a rotary drum, transferring for 10min, throwing skins, transferring for 1h, then adding 10kg of epoxy-terminated hyperbranched polymer tanning agent (the structural formula is shown in figure 6), adding formic acid to adjust the pH value of bath solution to 7.5, continuing to transfer for 4h, then adding a proper amount of mixed solution of sodium carbonate and sodium bicarbonate (10 times of water is dissolved, the mass ratio of sodium carbonate to sodium bicarbonate is 1:1) at an interval of 20min, slowly adjusting the pH value of the bath solution to be stable at 8.5, supplementing 50kg of water at the temperature of 50 ℃, heating to 40 ℃, continuing to rotate for 3h, and stopping the drum for overnight. Taking out after 20min next day, stacking and standing for 1 day, wherein the tanning shrinkage temperature can reach 80 ℃ +/-1 ℃.
Salt-free pickling-aluminum tanning: 1kg of sulfuric acid (calculated by the mass of the ash bark) (diluted by 20 times of aqueous solution), 0.3kg of formic acid (diluted by 10 times of aqueous solution), 100kg of water, 25 ℃ and 2 times of adding the adjusting bath solution with the pH value of 2.5 +/-0.2, rotating for 3-4 h and staying overnight; and on the next day, supplementing acid, adjusting the pH value to 2.8-3.2, rotating for 1-3 h, keeping the pickle liquor to be 3 times of the original pH value, adding 6kg of aluminum tanning agent, rotating for 5h, adding a proper amount of sodium bicarbonate solution at intervals of 20min, slowly adjusting the pH value of the bath foam to be in a range of 3.8-4.2, supplementing 100kg of water at 50 ℃, heating to 35-40 ℃, continuously rotating for 2h, and stopping the drum for overnight. And (3) taking out the leather from the drum after 30min next day, stacking and standing for 2 days, wherein the tanning shrinkage temperature can reach 85 ℃ +/-1. Then the subsequent procedures of shaving, retanning, neutralization, dyeing, fatliquoring and the like are carried out.
Claims (10)
1. The epoxy-terminated hyperbranched polymer tanning agent is characterized by being a hyperbranched polymer containing a plurality of epoxy groups and hydroxyl groups and derivatives thereof, and the general formula of the epoxy-terminated hyperbranched polymer tanning agent can be represented as follows:
2. the epoxy-terminated hyperbranched polymer tanning agent according to claim 1, wherein R structure in the epoxy-terminated hyperbranched polymer tanning agent is:
the structure of R' in the structure of R in the epoxy-terminated hyperbranched polymer tanning agent is as follows:
3. the epoxy-terminated hyperbranched polymer tanning agent according to claim 2, wherein R structure in the epoxy-terminated hyperbranched polymer tanning agent is
R' has the structure of
4. The use method of the epoxy-terminated hyperbranched polymer tanning agent according to any one of claims 1-3, characterized by comprising the following steps:
s1, putting the pretreated animal skin into a bath solution containing an epoxy-terminated hyperbranched polymer tanning agent and a catalyst;
s2, adjusting the pH value of the bath liquid in the step S1, adding an alkali extracting agent into the bath liquid, stacking and standing the tanned animal skins, and obtaining the leather through shaving, retanning, neutralizing, dyeing and greasing.
5. The use method of the epoxy-terminated hyperbranched polymer tanning agent according to claim 4, characterized in that when the pickled leather is tanned, the concrete tanning steps are as follows after the animal leather is treated by soaking, unhairing, liming, deliming, softening and pickling processes:
1) mixing 50-150 parts of water, 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent, 0.2-3 parts of catalyst and 5-8 parts of neutral salt at the temperature of 15-30 ℃ to obtain bath liquid, adjusting the pH value of the bath liquid to 5.0-7.5, putting 100 parts of pickled pelts into the bath liquid, and reacting for 3-6 hours;
2) adding an alkali extracting agent into the bath liquid obtained in the step 1), adjusting the pH value of the bath liquid to 7.5-9.0, supplementing 50-150 parts of water, heating to 30-40 ℃, reacting for 1-3 h, and stopping blowing overnight;
3) and after stopping the drum and standing overnight, stacking and standing for 1-2 days, and then shaving, retanning, neutralizing, dyeing and greasing to obtain the leather.
6. The use method of the epoxy-terminated hyperbranched polymer tanning agent as claimed in claim 4, characterized in that when tanning softened skins, the tanning steps after the animal skins are treated by soaking, unhairing, liming, deliming, softening and pickling are as follows:
1) mixing 50-150 parts of water, 8-15 parts of epoxy-terminated hyperbranched polymer tanning agent and 0.2-3 parts of catalyst at the temperature of 15-30 ℃ to obtain bath liquid, adjusting the pH value of the bath liquid to 5.0-7.5, putting 100 parts of softened pelts into the bath liquid, and reacting for 3-6 h;
2) adding an alkali extracting agent into the bath liquid obtained in the step 1), adjusting the pH value of the mixed liquid to 7.5-9.0, supplementing 50-150 parts of water, heating to 30-40 ℃, reacting for 1-3 h, and stopping the drum overnight.
7. The method for using the epoxy-terminated hyperbranched polymer tanning agent as claimed in claim 4, wherein when the salt-free pickling-metal tanning agent is used for combined tanning, the specific tanning steps are as follows after the animal skin is subjected to the procedures of soaking, unhairing, liming, deliming, softening and pickling:
1) mixing 50-150 parts of water, 5-10 parts of epoxy-terminated hyperbranched polymer tanning agent and 0.2-2 parts of catalyst at the temperature of 15-30 ℃ to obtain bath liquid, adjusting the pH value of the bath liquid to 6.0-7.5, putting 100 parts of softened pelts into the bath liquid, and reacting for 3-6 h;
2) adding an alkali extracting agent into the bath liquid obtained in the step 1), adjusting the pH value of the mixed liquid to 7.5-8.5, supplementing 50-150 parts of water, heating to 30-40 ℃, reacting for 1-3 h, and stopping blowing overnight;
3) standing the tanned crust leather for 1-2 days, performing a salt-free pickling aluminum tanning process, stopping the drum for overnight, standing the tanned crust leather for 1-2 days, shaving, retanning, neutralizing, dyeing and greasing to obtain the leather.
8. The use method of the epoxy-terminated hyperbranched polymer tanning agent according to any one of claims 5 to 7,
in the step 1), during tanning, firstly adding an epoxy-terminated hyperbranched polymer tanning agent into water to obtain bath liquid, adjusting the pH value of the bath liquid, putting the pretreated animal skin into the bath liquid, adding a catalyst after reacting for 1-3 h, reacting for 3-5 h, and keeping the rest steps unchanged;
or
In the step 1), during tanning, firstly adding a catalyst into water, putting the pretreated animal skin into bath liquid, reacting for 1-3 h, then adding an epoxy-terminated hyperbranched polymer tanning agent, adjusting the pH value of the bath liquid, and reacting for 3-5 h, wherein the rest steps are unchanged.
9. The method for using the epoxy-terminated hyperbranched polymer tanning agent according to claim 4, wherein in the step S1, the catalyst is urotropin, and the catalyst is added into the solvent before, after or simultaneously with the epoxy-terminated hyperbranched polymer tanning agent.
10. The use method of the epoxy-terminated hyperbranched polymer tanning agent according to claim 4, wherein in the step S2, the alkali extracting agent is at least one of sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, sodium hydroxide and potassium hydroxide; the mass ratio of the sodium carbonate to the sodium bicarbonate is 1 (1-3).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114774594A (en) * | 2022-05-05 | 2022-07-22 | 陕西科技大学 | Collagen-hyperbranched amphoteric polymer retanning agent and preparation method thereof |
| CN116103451A (en) * | 2023-03-30 | 2023-05-12 | 精艺裘皮制品股份有限公司 | Multi-working-procedure effective synergistic beach sheepskin harmless tanning method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774594A (en) * | 2022-05-05 | 2022-07-22 | 陕西科技大学 | Collagen-hyperbranched amphoteric polymer retanning agent and preparation method thereof |
| CN116103451A (en) * | 2023-03-30 | 2023-05-12 | 精艺裘皮制品股份有限公司 | Multi-working-procedure effective synergistic beach sheepskin harmless tanning method |
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