CN107119154A - The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution - Google Patents
The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution Download PDFInfo
- Publication number
- CN107119154A CN107119154A CN201710546223.1A CN201710546223A CN107119154A CN 107119154 A CN107119154 A CN 107119154A CN 201710546223 A CN201710546223 A CN 201710546223A CN 107119154 A CN107119154 A CN 107119154A
- Authority
- CN
- China
- Prior art keywords
- polysaccharide
- tanning agent
- tanning
- weight
- polyfunctional group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/18—Oxidised starch
- C08B31/185—Derivatives of oxidised starch, e.g. crosslinked oxidised starch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0084—Guluromannuronans, e.g. alginic acid, i.e. D-mannuronic acid and D-guluronic acid units linked with alternating alpha- and beta-1,4-glycosidic bonds; Derivatives thereof, e.g. alginates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a kind of preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of wide distribution, it is characterized in that polysaccharide, at high temperature under high pressure through hydrogen peroxide oxidation, retains whole components, the polysaccharide ylidene ligands rich in aldehyde radical and carboxyl of wide distribution is made；Then non-chromium metal salt is added in above-mentioned polysaccharide ylidene ligands, complex tanning agent is obtained after complexation reaction.The complex tanning agent can be uniformly distributed in each hierarchical structure of collagen, be reacted by coordinate bond and covalent bond with collagen, so as to assign the excellent hydrothermal stability of hides/skins and organoleptic properties.
Description
Technical field
The invention belongs to the preparation method of leather, fur tanning agent, more particularly to a kind of polyfunctional group polysaccharide-based of wide distribution
The preparation method of ligand-metal complex tanning agent.
Background technology
Chrome tanning still occupies leading position in leather industry.But, the discharge and the processing of the solid waste containing chromium of chromate waste water
Limited by extremely harsh.Therefore, research and develop chrome-free tanning agent and carry out without chrome tanning, it is leather work to eliminate pollution of chromium from source
Industry realizes the active demand of sustainable development.Application of the non-chromium metal tanning agents such as aluminium salt, zirconates, titanium salt in leather industry has
Long history.Compared to organic tanning agent, the tanning properties and chrome tanning agent of non-chromium metal tanning agents are closest, and with existing process hides
Technique and dyeing and finishing match materials are good, are considered as substituting the ideal chose of chrome tanning agent.But, non-chromium metal tanning agents coordination
Effect is strong, is easily deposited on leather surface, causes surface to cross tan, causes its distributed pole in the leather uneven.In addition, aluminium salt
Combination stability etc. non-chromium metal tanning agents and collagen is weaker, and easily come off tempering after washing and tan in dyeing and finishing process.On
State reason and ultimately result in that finished leather hydrothermal stability is low, feel is stiff, and organoleptic properties are poor.Tartaric acid, lemon are commonly incorporated under study for action
The smaller ligands such as acid are combined as the masking agent of non-chromium metal tanning agents with the coordination and surface that slow down metal salt, but by
Too small in part, its improvement degree to tanning performance is very faint.Therefore, still failed promote should so far for non-chromium metal tanning agents
With.
The functional groups such as aldehyde radical, carboxyl can be introduced after polysaccharide is oxidized in sugar unit.At present, aldehyde radical is introduced in sugar unit
Topmost method is by sodium periodate oxidation, by the hydroxyl selective oxidation on sugar unit C-2 and C-3 positions into two aldehyde
Base, covalent cross-linking reaction can occur with the amino on collagen, leather tanning and retanning is directly used in.But lack in the oxidation of polysaccharides
The carboxyl that weary same non-chromium metal tanning agents are coordinated, coordination ability is weak, is not suitable for use in the part of non-chromium metal tanning agents.By double
Oxygen water, nitric acid etc. can introduce carboxyl compared with strong oxidizer oxidation in sugar unit, and now there are some researches show the oxidation of polysaccharides has necessarily
Coordination property, available for non-chromium metal tannery.Wherein, it can be obtained simultaneously containing aldehyde radical and carboxyl with hydrogen peroxide oxidation
Formed and be crosslinked between collagen after oxidized starch, its carboxyl and metal salt coordination, aldehyde radical then directly occurs altogether with collagen amino
Covalent reaction（The cooperative effect Chinese leathers of the beautiful different rigidities module of Chen Hui, Dan Zhihua, Wang Ya, 2006,35 (11)：7-
10.）.But, one defect of oxidation of polysaccharides generally existing made from prior art, i.e., due to using organic solvent after oxidation reaction
The isolated oxidation of polysaccharides product of the operation such as precipitation, centrifugation, filtering so that molecular weight of product distribution is narrow.Such as Chinese patent
CN102747173B " a kind of preparation method of aluminium-oxidized starch complex compound tanning agent " discloses one kind and first formed sediment with concentrated nitric acid oxidation
Powder, after extracting, washing through organic solvent, then the method for being mixed with aluminum sulfate complex compound tanning agent, in organic solvent deposit and
The HMW oxidation of polysaccharides component of solid-state is remained in washing process, and has given up the oxygen of molten/water miscible low molecule amount of alcohol
Change the component such as polysaccharide and oxidation oligosaccharides.Document（Feng Guotao, Chen Hui, single will China hydrogen peroxide is on grinding that starch oxidation degree influences
Study carefully leather sciences and engineering, 2005,15 (2)：46-50. Li Kai, Chen Hui, the preparation of single will China oxidized starch and characteristic are ground
Study carefully Chinese leathers, 2007,36 (9)：6-8.）Report the method with hydrogen peroxide oxidation starch, also passed through after oxidation centrifugation,
The operations such as separation, washing have obtained oxidized starch product, and size exclusion chromatography analysis result shows that molecular weight of product distribution is equal
One.When this narrow ditribution oxidation of polysaccharides as part in use, the size of non-chromium metal complex is more single, it is many in collagen
Distributed pole in hierarchical structure is uneven, shows poor tanning performance and finished leather organoleptic properties.And real effective tanning
The molecular dimension wider distribution of range request tanning agent is crossed, macromolecular components are crosslinked and are filled in fibre gap in fiber interfascicular, in
Equimolecular component is crosslinked in base fiber level, is crosslinked compared with small molecule component in fibrillation level, more small molecule group
Dividing can be even crosslinked between tropocollagen molecule, only in this way can just make tanning uniform, tanning effect is good.
On the other hand, although prior art aoxidizes out carboxyl on polysaccharide, for the part of non-chromium metal tanning agents,
It can co-ordinating functionality quantity it is still inadequate so that the coordination ability of oxidation of polysaccharides is limited, and the tanning performance of complex is still
It is not good.Such as document（Wang Xuechuan, Li Feihu, strong torrential preparation for waiting high oxidized starchs and the application in process hides tanning
Leather science and engineering, 2013,23 (2)：5-8.）The use of the carboxyl-content of high oxidized starch obtained by concentrated nitric acid is only 13.9%
（Equivalent 3.09 mmol/g）, and because concentrated nitric acid oxidation is strong and is free of aldehyde radical.In addition, when making oxidant with hydrogen peroxide, protecting
Oxidation obtains also obtaining aldehyde radical while carboxyl on card polysaccharide, it is thus possible to strengthen the combination energy of complex tanning agent and collagen
Power, so as to improve tanning performance.But the aldehyde radical and carboxyl-content of prior art products are all too low, such as document（Li Kai, Chen Hui,
The preparation of single will China oxidized starch and characteristic research Chinese leathers, 2007,36 (9)：6-8.）The oxidized starch aldehyde radical of preparation
Content is 0.83%（Equivalent 0.29 mmol/g）, carboxyl-content is 0.75%（Equivalent 0.17 mmol/g）, therefore to tanning performance
Raising effect it is very limited.The reason for causing prior art products carboxyl and low aldehyde group content is mainly hydrogen peroxide oxidation temperature and set
Put too low, be below 70 DEG C.Those skilled in the art it is believed that when hydrogen peroxide makees oxidant, reaction temperature can not be too high, because
Easily decomposed at high temperature for hydrogen peroxide, oxidisability can be reduced.
The content of the invention
The technical problems to be solved by the invention are to be distributed narrow, carboxylic for oxidation of polysaccharides ligand molecular amount in the prior art
There is provided a kind of preparation side of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of wide distribution for base and the low shortcoming of aldehyde group content
Method, is characterized in that polysaccharide ylidene ligands have the aldehyde radical and carboxyl and range of molecular weight distributions of sufficient amount wide, matches somebody with somebody with non-chromium metal salt
Position after promote complex tanning agent being uniformly distributed in each hierarchical structure of collagen, and strengthen tanning agent with collagen combine it is steady
It is qualitative.
The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent for the wide distribution that the present invention is provided, this method
Processing step and condition it is as follows：
Concentration is placed in reactor for 5-50 wt% polysaccharide solution with the catalyst for accounting for polysaccharide weight 0.05-1 wt ‰, dripped
Plus polysaccharide weight 40-100 wt% hydrogen peroxide is accounted for, pass through one-pot oxidation in 120-160 DEG C of temperature, pressure 0.2-0.6 MPa
0.5-4 h are reacted, the liquid polyfunctional group polysaccharide ylidene ligands of wide distribution are obtained；After alkali lye regulation part pH to 2-6, addition is accounted for
Polysaccharide weight 180-300 wt% non-chromium metal salt, stirring reaction 0-24 h obtain the polyfunctional group polysaccharide ylidene ligands gold of wide distribution
Metal complex tanning agent.
The polysaccharide is any of starch, sodium alginate and sodium carboxymethyl starch.
The catalyst is at least one of copper sulphate, ferrous sulfate and ferric sulfate.
The alkali lye is selected from NaOH, Na2CO3And NaHCO3At least one of the aqueous solution.
The aldehyde group content of the polyfunctional group polysaccharide ylidene ligands is 2.0-6.6 mmol/g, and carboxyl-content is 8.4-14.7
Mmol/g, weight average molecular weight is 1000-6000 g/mol, and polydispersity coefficient is 1.5-5.0.
The non-chromium metal salt is at least one of aluminum sulfate, zirconium sulfate and titanium sulfate.
The invention further relates to the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution in leather or fur tanning
In application, including following technique：
The pickled pelt that routinely technique is obtained is placed in rotary drum, adds the leaching that 80-200 wt% are calculated as with pickled pelt weight
The complex tanning agent of acid solution and 5-25 wt%（In terms of solid content）, turn after 2-4 h, carried with magnesia alkali to pH be 3.0, Ran Houyong
It is 3.4-4.2 that sodium bicarbonate, which carries alkali to pH, and temperature adjustment continues to turn 2 h, obtain tan leather to 40 DEG C；
Or
The Pickled skin that routinely technique is obtained is placed in rotary drum or paddle-tumble, and addition is calculated as 400-600 with Pickled skin weight
Wt% pickling liquid and to add the complex tanning agent that the volume of water is calculated as 15-38 g/L（In terms of solid content）, rotate or stroke 2-
After 6 h, it is 3.0 that alkali is carried with magnesia to pH, and it is 3.4-4.2 that alkali is then carried with sodium bicarbonate to pH, and temperature adjustment is rotated further to 40 DEG C
Or the h of stroke 2, obtain tanning fur.
The polysaccharide ylidene ligands that are prepared by hydrogen peroxide oxidation of the present invention, which are not centrifuged, separated, wash etc., to be separated
Operation, remains whole components of oxidation product, molecular weight distribution is wider.In tannery, the chi of complex tanning agent of the present invention
Very little more horn of plenty, being more evenly distributed in collagen multi-level structure, macromolecular components are crosslinked and are filled in fiber interfascicular
In fibre gap, medium molecule component is crosslinked in base fiber level, is handed over compared with small molecule component in fibrillation level
Connection, more small molecule component is crosslinked between can even entering tropocollagen molecule, significantly improves tanning uniformity and tanning effect.
Therefore, the tanning performance of complex tanning agent of the present invention（Leather hydrothermal stability and metal tanning agents binding ability）And organoleptic properties
（Pliability etc.）It is substantially better than the complex tanning agent that other oxidation of polysaccharides are formed with non-chromium metal.In addition, the polysaccharide of the present invention
Method for oxidation employs high-temperature and high-pressure conditions, and hydrogen peroxide fast decoupled can be promoted to produce peroxylradicals, improves free radical and exists
The mass transfer rate of polysaccharide emulsion, and the viscosity and surface tension of polysaccharide emulsion are reduced, the speed of oxidation reaction is significantly improved, and
Improve the content of carboxyl and aldehyde radical in the degree of oxidation of polysaccharide, i.e. oxidation of polysaccharides.
The present invention compared with prior art, has the advantages that：
（1）The polysaccharide ylidene ligands preparation method that the present invention is provided, remains whole components of oxidation of polysaccharides（Raw material complete utilization）, point
Son amount distribution is wide, and the complex tanning agent with the formation of non-chromium metal salt can be respectively enterd in each level structure of materials with hide glue fibril and
Even distribution, is remarkably improved the organoleptic properties such as the tanning performance and pliability of hides/skins.
（2）The polysaccharide method for oxidation of the present invention employs high-temperature and high-pressure conditions, and having broken hydrogen peroxide oxidation polysaccharide need to be low
Warm condition（Less than 70 DEG C）It is lower to obtain the technology prejudice of higher oxygen degree, the oxidation journey in oxidation of polysaccharides greatly improved
The total amount of degree, aldehyde radical and carboxyl has reached 10.4-21.3 mmol/g, and this is that current existing polysaccharide oxidation technology can not be realized,
Therefore polysaccharide ylidene ligands of the present invention have excellent coordination ability with non-chromium metal salt, and its aldehyde radical can be sent out with collagen amino
Raw covalent reaction, so that the tanning function admirable such as hydrothermal stability and metal tanning agents binding ability of hides/skins.
Brief description of the drawings
The distribution schematic diagram of metal zirconium in Fig. 1 tan leathers.
Embodiment
The present invention is specifically described below by example, it is necessary to it is pointed out here that be the present embodiment be served only for this
Invention is further illustrated, it is impossible to be interpreted as limiting the scope of the invention, and the person skilled in the art in the field can basis
The content of the invention described above makes some nonessential modifications and adaptations.
In following examples and comparative example, the molecular weight distribution of polysaccharide ylidene ligands（Polydispersity coefficient）Using gel infiltration color
Spectrometry is measured, and aldehyde group content is determined using hydroxyamine hydrochloride, and carboxyl-content is determined using acid base neutralization titration method.Non-chromium gold
The assay method that is distributed in the leather of category tanning agent is：Use freezing-microtome by the uniform subdivision of tan leather for grain layer, centre
Layer and flesh noodles layer, drying, the metal salt concentration in each layer sample is determined after clearing up with ICP-OES.The contraction temperature of tan leather
Degree（Characterize hydrothermal stability）It is measured using standard shrinkage temperature instrument.Base is routinely made after technique dyeing and finishing for tan leather
Leather, the pliability of crust leather is determined using softness instrument.
Embodiment 1：
By weight, 30 parts of starch, 100 parts of water and 0.015 part of copper sulphate are placed in reactor, 18 parts of peroxidating is added dropwise
Hydrogen, reacts 2 h by one-pot oxidation in 120 DEG C of temperature, the MPa of pressure 0.2, obtains the liquid polyfunctional group starch of wide distribution
Ylidene ligands；After NaOH solution regulation part pH to 2,90 parts of zirconium sulfates are added, the h of stirring reaction 12 obtains many officials of wide distribution
Starch ylidene ligands zirconium complex tanning agent can be rolled into a ball.
The pickled pelt that routinely technique is obtained is placed in rotary drum, and addition is calculated as 200 wt%'s with pickled pelt weight
The complex tanning agent of pickling liquid and 25 wt%（In terms of solid content）, turn 3 h after, carried with magnesia alkali to pH be 3.0, then with small
It is 3.8 that soda, which carries alkali to pH, and temperature adjustment continues to turn 2 h, obtain tan leather to 40 DEG C.
In this step, the polydispersity coefficient of starch ylidene ligands aldehyde radical and carboxyl-content and molecular weight is determined, and is surveyed
The shrinkage temperature of tan leather and the pliability of crust leather after dyeing and finishing are determined（It the results are shown in Table 1）.Analyze simultaneously golden in tan leather
Belong to tanning agent distribution situation（As shown in Figure 1）.
Comparative example 1：
By weight, 30 parts of starch, 100 parts of water and 0.015 part of copper sulphate are placed in reactor, 18 parts of peroxidating is added dropwise
Hydrogen, in 120 DEG C of temperature, the h of 0.2 MPa oxidation reactions of pressure 2, into obtained solution, addition ethanol precipitates constituent part, mistake
Continuation is washed with ethanol to precipitation after filter, is then dissolved with distilled water, is obtained the starch ylidene ligands of narrow ditribution；It is molten with NaOH
After liquid regulation part pH to 2,90 parts of zirconium sulfates are added, the h of stirring reaction 12 obtains the starch ylidene ligands zirconium complex of narrow ditribution
Tanning agent.
The application process and Testing index be the same as Example 1 of the complex tanning agent.
Comparative example 2：
By weight, 30 parts of starch, 100 parts of water and 0.015 part of copper sulphate are placed in reactor, 18 parts of peroxidating is added dropwise
Hydrogen, reacts 2 h by one-pot oxidation under temperature 70 C, condition of normal pressure, obtains liquid starch ylidene ligands；Adjusted with NaOH solution
Save after part pH to 2, add 90 parts of zirconium sulfates, the h of stirring reaction 12 obtains starch ylidene ligands zirconium complex tanning agent.
The application process and Testing index be the same as Example 1 of the complex tanning agent.
As shown in Table 1, polydispersity coefficient, aldehyde radical and the carboxyl-content for the polysaccharide ylidene ligands that the present invention is provided are far above use
Part made from the method that comparative example is provided, thus it can occur effective coordination, uniformly penetrating point with non-chromium metal tanning agents
It is distributed in into intracutaneous（Fig. 1）And full cross-linked combination is carried out between the multilevel hierarchy of materials with hide glue fibril so that tan leather/fur
Shrinkage temperature is greatly improved, and shows more preferable organoleptic properties.
Embodiment 2：
By weight, 5 parts of sodium alginates, 100 parts of water and 0.00025 part of ferrous sulfate are placed in reactor, 2 parts of mistakes is added dropwise
Hydrogen oxide, reacts 0.5 h, the liquid for obtaining wide distribution is multifunctional in 140 DEG C of temperature, the MPa of pressure 0.4 by one-pot oxidation
Group's sodium alginate ylidene ligands；After NaOH solution regulation part pH to 4,12 parts of aluminum sulfate are added, the h of stirring reaction 24 obtains width
The polyfunctional group sodium alginate ylidene ligands aluminum complex tanning agent of distribution.
The Pickled skin that routinely technique is obtained is placed in rotary drum, and addition is calculated as 500 wt%'s with Pickled skin weight
Pickling liquid and to add the complex tanning agent that the volume of water is calculated as 26 g/L（In terms of solid content）, turn after 6 h, alkali carried with magnesia
It is 3.0 to pH, it is 3.4 that alkali is then carried with sodium bicarbonate to pH, and temperature adjustment continues to turn 2 h, obtain tanning fur to 40 DEG C.
Sodium alginate ylidene ligands aldehyde group content is 6.1 mmol/g in the present embodiment；Carboxyl-content content is 8.4 mmol/
g；The polydispersity coefficient of molecular weight is 4.8；The shrinkage temperature of tanning fur is 81.2oC；The pliability of dermatotome is 7.3 mm.Together
When learnt by analyzing metallic aluminium distribution situation in tanning fur, tanning agent uniformly penetrating is distributed in into intracutaneous and in materials with hide glue fibril
Multilevel hierarchy between carry out full cross-linked combination.
Embodiment 3：
By weight, 50 parts of sodium carboxymethyl starches, 100 parts of water and 0.05 part of ferric sulfate are placed in reactor, are added dropwise 50 parts
Hydrogen peroxide, reacts 4 h, the liquid for obtaining wide distribution is multifunctional in 160 DEG C of temperature, the MPa of pressure 0.6 by one-pot oxidation
Group's sodium carboxymethyl starch part；After NaOH solution regulation part pH to 4,90 parts of titanium sulfates are added, does not stir and directly obtains width
The polyfunctional group sodium carboxymethyl starch part titanium complex tanning agent of distribution.
The pickled pelt that routinely technique is obtained is placed in rotary drum, adds the leaching that 80 wt% are calculated as with pickled pelt weight
The complex tanning agent of acid solution and 5 wt%（In terms of solid content）, turn after 2 h, it is 3.0 that alkali is carried with magnesia to pH, then uses little Su
It is 3.4 to beat and carry alkali to pH, and temperature adjustment continues to turn 2 h, obtain tan leather to 40 DEG C.
Sodium carboxymethyl starch part aldehyde group content is 2.0 mmol/g in the present embodiment；Carboxyl-content content is 13.5
mmol/g；The polydispersity coefficient of molecular weight is 2.8；The shrinkage temperature of tan leather is 83.7oC；The pliability of crust leather after dyeing and finishing
For 6.8 mm.Simultaneously learnt by analyzing Titanium distribution situation in tan leather, tanning agent uniformly penetrating be distributed in into it is intracutaneous simultaneously
Full cross-linked combination is carried out between the multilevel hierarchy of materials with hide glue fibril.
Embodiment 4：
By weight, by 30 parts of sodium carboxymethyl starches, 100 parts of water, 0.0003 part of copper sulphate, 0.0006 part of ferrous sulfate and
0.0006 part of ferric sulfate and it is placed in reactor, 18 parts of hydrogen peroxide is added dropwise, a step is passed through in 120 DEG C of temperature, the MPa of pressure 0.2
The h of method oxidation reaction 2, obtains the liquid polyfunctional group sodium carboxymethyl starch part of wide distribution；Use Na2CO3Solution regulation part pH
To after 2,45 parts of aluminum sulfate and 45 parts of zirconium sulfates, the h of stirring reaction 12 are added, the polyfunctional group CMS of wide distribution is obtained
Sodium ligand aluminum zirconium complex tanning agent.
The Pickled skin that routinely technique is obtained is placed in rotary drum, and addition is calculated as 400 wt%'s with Pickled skin weight
Pickling liquid and to add the complex tanning agent that the volume of water is calculated as 15 g/L（In terms of solid content）, turn after 6 h, alkali carried with magnesia
It is 3.0 to pH, it is 4.2 that alkali is then carried with sodium bicarbonate to pH, and temperature adjustment continues to turn 2 h, obtain tanning fur to 40 DEG C.
Sodium carboxymethyl starch part aldehyde group content is 4.1 mmol/g in the present embodiment；Carboxyl-content content is 10.2
mmol/g；The polydispersity coefficient of molecular weight is 4.1；The shrinkage temperature of tanning fur is 84.7oC；The pliability of dermatotome is：7.8
mm.Learnt simultaneously by analyzing metallic aluminium in tan leather, zirconium distribution situation, tanning agent uniformly penetrating is distributed in into intracutaneous and in skin
Full cross-linked combination is carried out between the multilevel hierarchy of collagenous fibres.
Embodiment 5：
By weight, by 50 parts of sodium alginates, 0.02 part of copper sulphate, 0.005 part of ferrous sulfate and 100 parts of water are placed in reactor
In, 30 parts of hydrogen peroxide are added dropwise, 2 h are reacted by one-pot oxidation in 120 DEG C of temperature, the MPa of pressure 0.2, wide distribution is obtained
Liquid polyfunctional group sodium alginate ylidene ligands；Use Na2CO3After solution regulation part pH to 6,150 parts of zirconium sulfates are added, stirring is anti-
12 h are answered, the polyfunctional group sodium alginate ylidene ligands zirconium complex tanning agent of wide distribution is obtained.
The pickled pelt that routinely technique is obtained is placed in rotary drum, and addition is calculated as 150 wt%'s with pickled pelt weight
The complex tanning agent of pickling liquid and 20 wt%（In terms of solid content）, turn 3 h after, carried with magnesia alkali to pH be 3.0, then with small
It is 3.8 that soda, which carries alkali to pH, and temperature adjustment continues to turn 2 h, obtain tan leather to 40 DEG C.
Sodium alginate ylidene ligands aldehyde group content is 4.0 mmol/g in the present embodiment；Carboxyl-content content is 11.1 mmol/
g；The polydispersity coefficient of molecular weight is 4.1；The shrinkage temperature of tan leather is 93.2oC；The pliability of crust leather is 8.0 after dyeing and finishing
mm.Learnt simultaneously by analyzing metal zirconium distribution situation in tan leather, tanning agent uniformly penetrating is distributed in into intracutaneous and in hide glue
Full cross-linked combination is carried out between the multilevel hierarchy of fibrillation.
Embodiment 6：
By weight, by 5 parts of starch, 0.0002 part of copper sulphate, 0.00005 part of ferrous sulfate and 100 parts of water are placed in reactor
In, 2 parts of hydrogen peroxide are added dropwise, 3 h are reacted by one-pot oxidation in 140 DEG C of temperature, the MPa of pressure 0.4, wide distribution is obtained
Liquid polyfunctional group starch ylidene ligands；Use Na2CO3And NaHCO3After solution regulation part pH to 4,9 parts of aluminum sulfate are added, are not stirred
Mix the polyfunctional group starch base part aluminum complex tanning agent for directly obtaining wide distribution.
The Pickled skin that routinely technique is obtained is placed in rotary drum, and addition is calculated as 500 wt%'s with Pickled skin weight
Pickling liquid and to add the complex tanning agent that the volume of water is calculated as 15 g/L（In terms of solid content）, turn after 6 h, alkali carried with magnesia
It is 3.0 to pH, it is 4.2 that alkali is then carried with sodium bicarbonate to pH, and temperature adjustment continues to turn 2 h, obtain tanning fur to 40 DEG C.
Starch ylidene ligands aldehyde group content is 6.6 mmol/g in the present embodiment；Carboxyl-content content is 8.4 mmol/g；Point
The polydispersity coefficient of son amount is 5.0；The shrinkage temperature of tanning fur is 79.6oC；The pliability of dermatotome is 7.4 mm.Lead to simultaneously
Cross metallic aluminium distribution situation in analysis tan leather to learn, tanning agent uniformly penetrating is distributed in into intracutaneous and in many of materials with hide glue fibril
Full cross-linked combination is carried out between level structure.
Embodiment 7：
By weight, by 5 parts of sodium carboxymethyl starches, 0.0025 part of ferrous sulfate and 100 parts of water are placed in reactor, are added dropwise 2
Part hydrogen peroxide, reacts 3 h by one-pot oxidation in 140 DEG C of temperature, the MPa of pressure 0.4, obtains many officials of liquid of wide distribution
Sodium carboxymethyl starch part can be rolled into a ball；Use Na2CO3After NaOH solution regulation part pH to 6,15 parts of zirconium sulfates, stirring reaction are added
24 h, obtain the polyfunctional group sodium carboxymethyl starch part zirconium complex tanning agent of wide distribution.
The pickled pelt that routinely technique is obtained is placed in rotary drum, and addition is calculated as 200 wt%'s with pickled pelt weight
The complex tanning agent of pickling liquid and 25 wt%（In terms of solid content）, turn 4 h after, carried with magnesia alkali to pH be 3.0, then with small
It is 3.8 that soda, which carries alkali to pH, and temperature adjustment continues to turn 2 h, obtain tan leather to 40 DEG C.
Sodium carboxymethyl starch part aldehyde group content is 4.7 mmol/g in the present embodiment；Carboxyl-content content is 13.5
mmol/g；The polydispersity coefficient of molecular weight is 4.7；The shrinkage temperature of tan leather is 94.7oC；The pliability of crust leather after dyeing and finishing
For 8.3 mm.Simultaneously learnt by analyzing metal zirconium distribution situation in tan leather, tanning agent uniformly penetrating be distributed in into it is intracutaneous simultaneously
Full cross-linked combination is carried out between the multilevel hierarchy of materials with hide glue fibril.
Embodiment 8：
By weight, by 30 parts of sodium alginates, 0.03 part of copper sulphate and 100 parts of water are placed in reactor, and 30 parts of peroxides are added dropwise
Change hydrogen, 4 h are reacted by one-pot oxidation in 160 DEG C of temperature, the MPa of pressure 0.6, obtain the liquid polyfunctional group sea of wide distribution
Mosanom ylidene ligands；Use NaHCO3After solution regulation part pH to 2,18 parts of titanium sulfates, 18 parts of aluminum sulfate and 18 parts of sulfuric acid are added
Zirconium, the polyfunctional group sodium alginate ylidene ligands aluminium zirconium titanium complex tanning agent for directly obtaining wide distribution is not stirred.
The Pickled skin that routinely technique is obtained is placed in paddle-tumble, and addition is calculated as 600 wt%'s with Pickled skin weight
Pickling liquid and to add the complex tanning agent that the volume of water is calculated as 38 g/L（In terms of solid content）, after the h of stroke 6, carried with magnesia
Alkali is 3.0 to pH, and it is 4.2 that alkali is then carried with sodium bicarbonate to pH, and temperature adjustment continues the h of stroke 2, obtain tanning fur to 40 DEG C.
Sodium alginate ylidene ligands aldehyde group content is 2.8 mmol/g in the present embodiment；Carboxyl-content content is 14.7 mmol/
g；The polydispersity coefficient of molecular weight is 1.5；The shrinkage temperature of tanning fur is 91.2oC；The pliability of dermatotome is 7.8 mm.Together
When learnt by analyzing Titanium in tan leather, aluminium, zirconium distribution situation, tanning agent uniformly penetrating is distributed in into intracutaneous and in hide glue
Full cross-linked combination is carried out between the multilevel hierarchy of fibrillation.
Embodiment 9：
By weight, by 50 parts of starch, 0.05 part of ferrous sulfate and 100 parts of water are placed in reactor, and 50 parts of peroxidating are added dropwise
Hydrogen, reacts 4 h by one-pot oxidation in 160 DEG C of temperature, the MPa of pressure 0.6, obtains the liquid polyfunctional group starch of wide distribution
Ylidene ligands；Use NaHCO3After solution regulation part pH to 6,60 parts of titanium sulfates and 60 parts of aluminum sulfate, the h of stirring reaction 24 are added, is obtained
To the polyfunctional group starch base ligand aluminum titanium complex tanning agent of width distribution.
The pickled pelt that routinely technique is obtained is placed in rotary drum, and addition is calculated as 100 wt%'s with pickled pelt weight
The complex tanning agent of pickling liquid and 5 wt%（In terms of solid content）, turn 2 h after, carried with magnesia alkali to pH be 3.0, then with small
It is 3.4 that soda, which carries alkali to pH, and temperature adjustment continues to turn 2 h, obtain tan leather to 40 DEG C.
Starch ylidene ligands aldehyde group content is 3.7 mmol/g in the present embodiment；Carboxyl-content content is 12.4 mmol/g；Point
The polydispersity coefficient of son amount is 3.7；The shrinkage temperature of tan leather is 83.2oC；The pliability of crust leather is 7.5 mm after dyeing and finishing.
Learnt simultaneously by analyzing Titanium in tan leather, aluminium distribution situation, tanning agent uniformly penetrating is distributed in into intracutaneous and in hide glue
Full cross-linked combination is carried out between the multilevel hierarchy of fibrillation.
Claims (9)
1. a kind of preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of wide distribution, it is characterised in that this method
Comprise the following steps：
Concentration is placed in reactor for 5-50 wt% polysaccharide solution with the catalyst for accounting for polysaccharide weight 0.05-1 wt ‰, dripped
Plus polysaccharide weight 40-100 wt% hydrogen peroxide is accounted for, pass through one-pot oxidation in 120-160 DEG C of temperature, pressure 0.2-0.6 MPa
0.5-4 h are reacted, the liquid polyfunctional group polysaccharide ylidene ligands of wide distribution are obtained；After alkali lye regulation part pH to 2-6, addition is accounted for
Polysaccharide weight 180-300 wt% non-chromium metal salt, stirring reaction 0-24 h obtain the polyfunctional group polysaccharide ylidene ligands gold of wide distribution
Metal complex tanning agent.
2. according to the method described in claim 1, it is characterised in that the polysaccharide is starch, sodium alginate and sodium carboxymethyl starch
Any of.
3. according to the method described in claim 1, it is characterised in that the catalyst is in copper sulphate, ferrous sulfate and ferric sulfate
At least one.
4. according to the method described in claim 1, it is characterised in that the alkali lye is selected from NaOH, Na2CO3And NaHCO3It is water-soluble
At least one of liquid.
5. according to the method described in claim 1, it is characterised in that the aldehyde group content of the polyfunctional group polysaccharide ylidene ligands is
2.0-6.6 mmol/g, carboxyl-content is 8.4-14.7 mmol/g, and weight average molecular weight is 1000-6000 g/mol, and polydispersion
Coefficient is 1.5-5.0.
6. according to the method described in claim 1, it is characterised in that the non-chromium metal salt is aluminum sulfate, zirconium sulfate and titanium sulfate
At least one of.
7. the polyfunctional group polysaccharide-based ligand metal of the wide distribution obtained by the method described in claim any one of 1-6 coordinates
Thing tanning agent.
8. application of the complex tanning agent in leather tanning described in claim 7.
9. application according to claim 8, it is characterised in that the leather or fur tanning comprise the following steps：
The pickled pelt that routinely technique is obtained is placed in rotary drum, adds the leaching that 80-200 wt% are calculated as with pickled pelt weight
The complex tanning agent of acid solution and 5-25 wt%（In terms of solid content）, turn after 2-4 h, carried with magnesia alkali to pH be 3.0, Ran Houyong
It is 3.4-4.2 that sodium bicarbonate, which carries alkali to pH, and temperature adjustment continues to turn 2 h, obtain tan leather to 40 DEG C；
Or
The Pickled skin that routinely technique is obtained is placed in rotary drum or paddle-tumble, and addition is calculated as 400-600 with Pickled skin weight
Wt% pickling liquid and to add the complex tanning agent that the volume of water is calculated as 15-38 g/L（In terms of solid content）, rotate or stroke 2-
After 6 h, it is 3.0 that alkali is carried with magnesia to pH, and it is 3.4-4.2 that alkali is then carried with sodium bicarbonate to pH, and temperature adjustment is rotated further to 40 DEG C
Or the h of stroke 2, obtain tanning fur.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546223.1A CN107119154B (en) | 2017-07-06 | 2017-07-06 | The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546223.1A CN107119154B (en) | 2017-07-06 | 2017-07-06 | The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107119154A true CN107119154A (en) | 2017-09-01 |
| CN107119154B CN107119154B (en) | 2019-04-26 |
Family
ID=59731317
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710546223.1A Active CN107119154B (en) | 2017-07-06 | 2017-07-06 | The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107119154B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747299A (en) * | 2019-11-04 | 2020-02-04 | 四川大学 | Method for preparing aluminum zirconium complex tanning agent based on microcrystalline cellulose |
| CN112279927A (en) * | 2020-11-04 | 2021-01-29 | 暨南大学 | Carboxyl nano-cellulose, preparation method and application thereof |
| CN112831617A (en) * | 2021-02-08 | 2021-05-25 | 四川大学 | Light-colored polycarboxyl oxidized polysaccharide tanning agent and preparation method and application thereof |
| CN113999943A (en) * | 2021-11-15 | 2022-02-01 | 陕西科技大学 | Polysaccharide-based hydrotalcite nano composite tanning agent and preparation method and application thereof |
| CN114478810A (en) * | 2022-01-21 | 2022-05-13 | 中国皮革制鞋研究院有限公司 | Bio-based organic tanning agent and preparation method and application thereof |
| US20220251672A1 (en) * | 2021-02-08 | 2022-08-11 | Sichuan University | Light-colored polycarboxylated polysaccharide tanning agent, and preparation method and use thereof |
| US20240263257A1 (en) * | 2022-02-24 | 2024-08-08 | Sichuan University | Chrome-free tanning process of ecological leather |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705314A (en) * | 2009-10-27 | 2010-05-12 | 宁波工程学院 | Plant biomass-metal in-situ leather combining-tanning method |
| CN102747173A (en) * | 2012-07-02 | 2012-10-24 | 陕西科技大学 | Preparation method of aluminum-oxidized starch complex tanning agent |
| CN103451328A (en) * | 2013-09-29 | 2013-12-18 | 四川大学 | Regeneration plant tanning agent and preparation method thereof |
-
2017
- 2017-07-06 CN CN201710546223.1A patent/CN107119154B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101705314A (en) * | 2009-10-27 | 2010-05-12 | 宁波工程学院 | Plant biomass-metal in-situ leather combining-tanning method |
| CN102747173A (en) * | 2012-07-02 | 2012-10-24 | 陕西科技大学 | Preparation method of aluminum-oxidized starch complex tanning agent |
| CN103451328A (en) * | 2013-09-29 | 2013-12-18 | 四川大学 | Regeneration plant tanning agent and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110747299A (en) * | 2019-11-04 | 2020-02-04 | 四川大学 | Method for preparing aluminum zirconium complex tanning agent based on microcrystalline cellulose |
| CN110747299B (en) * | 2019-11-04 | 2021-07-23 | 四川大学 | Method for preparing aluminum zirconium complex tanning agent based on microcrystalline cellulose |
| CN112279927A (en) * | 2020-11-04 | 2021-01-29 | 暨南大学 | Carboxyl nano-cellulose, preparation method and application thereof |
| CN112831617A (en) * | 2021-02-08 | 2021-05-25 | 四川大学 | Light-colored polycarboxyl oxidized polysaccharide tanning agent and preparation method and application thereof |
| CN112831617B (en) * | 2021-02-08 | 2021-11-09 | 四川大学 | Light-colored polycarboxyl oxidized polysaccharide tanning agent and preparation method and application thereof |
| US20220251672A1 (en) * | 2021-02-08 | 2022-08-11 | Sichuan University | Light-colored polycarboxylated polysaccharide tanning agent, and preparation method and use thereof |
| US11834724B2 (en) | 2021-02-08 | 2023-12-05 | Sichuan University | Light-colored polycarboxylated polysaccharide tanning agent, and preparation method and use thereof |
| CN113999943A (en) * | 2021-11-15 | 2022-02-01 | 陕西科技大学 | Polysaccharide-based hydrotalcite nano composite tanning agent and preparation method and application thereof |
| CN114478810A (en) * | 2022-01-21 | 2022-05-13 | 中国皮革制鞋研究院有限公司 | Bio-based organic tanning agent and preparation method and application thereof |
| CN114478810B (en) * | 2022-01-21 | 2023-02-24 | 中国皮革制鞋研究院有限公司 | Bio-based organic tanning agent and preparation method and application thereof |
| US20240263257A1 (en) * | 2022-02-24 | 2024-08-08 | Sichuan University | Chrome-free tanning process of ecological leather |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107119154B (en) | 2019-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107119154A (en) | The preparation method of the polyfunctional group polysaccharide-based ligand-metal complex tanning agent of width distribution | |
| CN110358877B (en) | Hydrotalcite-like nano tanning agent with layered structure and preparation method and tanning method thereof | |
| EP2824125B1 (en) | Polysaccharide and/or polypeptide based graft polymers as synthetic tannins | |
| CN104017920B (en) | Formaldehyde-free amino resin retanning agent | |
| Hao et al. | Sustainable leather making—An amphoteric organic chrome-free tanning agents based on recycling waste leather | |
| CN104789715B (en) | One kind is salt-free to exempt from pickling short route less chrome tannage method | |
| CN101240354B (en) | Acrylic resin/SiO2 nano composite tanning agent and preparation method thereof | |
| Wang et al. | Sustainable utilization of corn starch resources: a novel soluble starch-based functional chrome-free tanning agent for the eco-leather production | |
| CN102492079B (en) | Method for preparing nano composite high-absorptivity chrome tanning auxiliary agent by combining polycarboxylic acid copolymer with montmorillonite | |
| CN108929924B (en) | Preparation method of carboxymethyl cellulose leather retanning and filling agent | |
| CN105925735B (en) | One kind is salt-free to exempt from pickling short route bating method without chrome | |
| Ding et al. | Conversion of waste non-chrome metal complex tanned leather shavings to dual-functional bio-additive for the high-performance biomass-derived aldehyde tanned leather processing | |
| CN113481334B (en) | Bio-based leather filler and preparation method thereof | |
| WO2022166201A1 (en) | Light-color multi-carboxyl oxidized polysaccharide tanning agent, and preparation method therefor and use thereof | |
| WO2023159773A1 (en) | Chrome-free tanning process for eco-leather | |
| CN108034780B (en) | Tanning-assisting dyeing assistant, preparation method and application thereof | |
| CN113462824B (en) | Method for improving performance of organic chrome-free tanned leather | |
| CN114164308B (en) | Multi-carboxyl metal complex tanning agent with self-masking effect and preparation method thereof | |
| CN108264603A (en) | Environment-friendly type both sexes acrylic polymer retanning agent and preparation method thereof | |
| CN109022631B (en) | A kind of environmental protection leather production and processing technology | |
| CN1194103C (en) | Plant polyphenol reduced chrome-aluminium tanning agent and its prepn | |
| CN101759839A (en) | Method for preparing polystyrene-maleic acid fatty monoamide leather retanning fatliquor | |
| CN111635966B (en) | Vinyl polymer/nano perovskite oxide retanning agent and preparation method thereof | |
| CN115197361B (en) | Acrylic ester polymer tanning agent and preparation method thereof | |
| Zhu et al. | Fluorescent tracing of dialdehyde sodium alginate tanning agent in leather matrix |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170901 Assignee: SICHUAN TINGJIANG NEW MATERIALS Co.,Ltd. Assignor: SICHUAN University Contract record no.: X2023980034237 Denomination of invention: Preparation Method for Tanning Agents with Widely Distributed Multifunctional Group Polysaccharide Ligand Metal Complexes Granted publication date: 20190426 License type: Exclusive License Record date: 20230404 |
|
| EE01 | Entry into force of recordation of patent licensing contract |