CN107217116B - A kind of full constituent, more aldehyde radical organic tanning agents of wide distribution and preparation method thereof - Google Patents
A kind of full constituent, more aldehyde radical organic tanning agents of wide distribution and preparation method thereof Download PDFInfo
- Publication number
- CN107217116B CN107217116B CN201710546396.3A CN201710546396A CN107217116B CN 107217116 B CN107217116 B CN 107217116B CN 201710546396 A CN201710546396 A CN 201710546396A CN 107217116 B CN107217116 B CN 107217116B
- Authority
- CN
- China
- Prior art keywords
- tanning
- parts
- aldehyde radical
- sodium
- added
- 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.)
- Active
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
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C1/00—Chemical treatment prior to tanning
- C14C1/08—Deliming; Bating; Pickling; Degreasing
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
A kind of full constituent, wide distribution the preparation methods of more aldehyde radical organic tanning agents retain whole components its main feature is that carrying out hydroformylation to more carbohydrates and their derivatives under optimum conditions with periodate first；Then will contain iodine compound Efficient Conversion with inorganic reducing agent to be solid-state elemental iodine and be recovered by filtration, hydroformylation product filtrate is further heat-treated, so that residual iodine is steamed in vapour form and is absorbed and recycled with NaOH solution, finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution.The technical issues of present invention is able to solve existing hydroformylation polysaccharide tanning agent or molecular weight distribution is narrow, and tanning performance is poor, or contains and contain iodine compound, and leather comprehensive performance is influenced after tanning.Gained tanning agent component is complete, and molecular weight distribution is wide, and the shrinkage temperature of hides/skins is up to 85-90 DEG C after tan, and leather body is pure white, plentiful softness.
Description
Technical field
The invention belongs to the preparation methods of a kind of leather, fur tanning agent, are distributed more particularly to a kind of full constituent, width more
Aldehyde radical organic tanning agent and preparation method thereof.
Background technique
Tanning is a vital link in leather and fur manufacturing.Tanning agent is in the multilevel structure of materials with hide glue fibril
New cross-bond is formed, so that the hydrothermal stability of hides/skins, intensity and porosity increase, the bonding between materials with hide glue fibril
Degree reduces, to assign hides/skins with excellent service performance and organoleptic properties.Currently, leather and most of fur master
Chrome tanning tanning is used, the chromate waste water of generation and the processing difficulty of solid waste containing chromium are larger.With national environmental protection regulation
It is increasingly stringent, the use of chrome tanning has become the bottleneck for restricting development of China leather industry development.Therefore, the excellent nothing of research and development flexibility
Chrome tanning agent simultaneously promotes implementation chrome-free tanning technology, and eliminating pollution of chromium from source is necessarily becoming for leather industry sustainable and healthy development
Gesture.More carbohydrates and their derivatives are one of the primary raw materials of modern organic chemical industry and macromolecule chemical industry, be widely used in food,
The industries such as medicine and chemical industry, and the tanning or retanning that leather will be can also be used for after polysaccharide progress chemical modification.
Hydroformylation polysaccharide can be prepared using selective oxidation of the periodate to vicinal diamines on polysaccharide structures unit.Based on aldehyde
Tan mechanism, such hydroformylation polysaccharide can be used for leather tanning.But when being used using the hydroformylation polysaccharide of prior art preparation as tanning agent
It is primarily present two problems.First problem is that the molecular weight distribution of hydroformylation polysaccharide is excessively concentrated, in intradermal collagen multi-layer knot
Structure (is followed successively by tropocollagen molecule → microfibril → fibrinogen → base fiber → fibre bundle, made of assembling step by step from small to large
Supramolecular structure) in distributed pole it is uneven, cause the shrinkage temperature of tan leather to be normally no higher than 80 DEG C, show poor
Tanning performance, strongly limit the post-production and use of leather.Kanth et al. aoxidizes seaweed with sodium metaperiodate at room temperature
Hydroformylation product plus salt are precipitated after reaction, are centrifugally separating to obtain solid-state hydroformylation product, then dissolve again by sour 24 h of sodium,
The macromolecular components in hydroformylation product are precipitated out with the tert-butyl alcohol, dry obtained molecular weight is high and is distributed the hydroformylation sea concentrated very much
Mosanom tanning agent, and the components such as hydroformylation polysaccharide and hydroformylation oligosaccharides compared with small molecule are then dissolved in waste liquid and are finally separated
It removes, causes molecular weight of product distribution narrow.When the tanning agent is used for leather tanning, the contraction temperature of tan leather with optimal conditions
Degree is also less than 80 DEG C, reflects bad (Kanth, S. V., Madhan, B., Philo, M. J., the et al. of its flexibility
Tanning with natural polymeric materials part I: Ecofriendly tanning using
dialdehyde sodium alginate [J]. Journal of the Society of Leather
Technologists and Chemists, 2007,91 (6): 252-259).A kind of Chinese patent CN104087688A " skin
Leather modification rice dialdehyde starch retanning filler and preparation method thereof " disclose it is a kind of use sodium metaperiodate to rice starch into
Row hydroformylation is modified, solid-state hydroformylation product is then obtained by filtration, and alternately washed with dehydrated alcohol and water, it is double that re-dry obtains rice
The method of starch aldehyde.It can be seen that being also that alternately washing remains solid macromolecular hydroformylation by filtering and ethanol/water in the technology
Polysaccharide component, and eliminate molten/water-soluble small molecule component of alcohol.Although the technology has then carried out sour drop to hydroformylation product again
Solution, further reduced molecular weight, but its polydispersity coefficient (pdi is shown in Figure of description) illustrates molecular weight between 1 ~ 1.15
Distribution is still too narrow, and flexibility is poor.So modification rice dialdehyde starch obtained can only be used as retanning filler, and not conduct
Tanning agent uses.Chinese patent CN102020719B " a kind of preparation method of modified starch tanning agent " disclose it is a kind of first degrade, then
Degradation has been placed on the first step by graft modification, then the method for obtaining the modified starch tanning agent with aldehyde radical with periodate oxidation, unified
The molecular weight for reducing starch, is then modified again.But the technology does not solve the problem of narrow molecular weight distribution, leather after tan still
Shrinkage temperature be only 75 ~ 80 DEG C, it is seen that its flexibility is still bad.
In the prior art, Ding et al. uses sodium periodate oxidation sodium alginate, is prepared for the hydroformylation sea of wider distribution
Mosanom, crosslinking (Ding W., Zhou J. F., Zeng Y. H., the et al. Preparation for collagenous fibres
of oxidized sodium alginate with different molecular weights and its
application for crosslinking collagen fiber [J]. Carbohydrate Polymers, 2017,
157:1650-1656.).But when oxidized sodium alginate made from the technology is used for leather tanning, it may appear that mentioned above
Second Problem, i.e., the iodine compound contained in hydroformylation product remain in the leather, in post-production, storage and use process
It can be converted into iodine, lead to problems such as leather occur darkening, strength reduction, seriously affect the organoleptic properties and object of leather
Rationality energy.In addition, the program, which will also result in periodate, cannot regenerate and reuse, cause tanning agent preparation cost high, it is difficult
With practical application.Chinese patent CN102020719B " a kind of preparation method of modified starch tanning agent " equally has and deposits containing iodine compound
The problem of being in tanning agent, not being effectively separated.The mode that alcohol precipitation or dialysis can be used in the prior art is removed containing iodate conjunction
Object, but the technology can be such that a large amount of small molecule component is lost, and molecular weight of product distribution is narrow, i.e., occurs above-mentioned first again and ask
Topic.In addition the technology needs to consume a large amount of organic solvent (alcohol) and cumbersome, and time-consuming for separation process, low efficiency.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of full constituent, wide distribution and the organic tans of more aldehyde radicals for being free of iodine
The preparation method of agent, to overcome existing hydroformylation polysaccharide tanning agent or only retain constituent part, molecular weight distribution is narrow, tanning performance
Difference, or contain iodine compound, after tanning the shortcomings that influence leather comprehensive performance.
A kind of full constituent provided by the invention, wide distribution more aldehyde radical organic tanning agents, be by the original of following weight
Material is made: 10 parts of more carbohydrates and their derivatives, 6 ~ 12 parts of periodate, 200 ~ 500 parts of water, 4 ~ 14 parts of inorganic reducing agent.
Further, more carbohydrates and their derivatives be selected from sodium alginate, tower draw polysaccharide, xanthan gum, sodium carboxymethyl starch,
At least one of sodium carboxymethylcellulose, hydroxyethyl cellulose.
Further, the periodate is at least one of sodium metaperiodate, potassium metaperiodate.
Further, the inorganic reducing agent is at least one of sodium hydrogensulfite, sodium nitrite, sulfur dioxide.
Further, the weight average molecular weight of more aldehyde radical organic tanning agents is 4000 ~ 30000 g/mol and continuously distributed,
Polydispersity coefficient is 6 ~ 18.
Further, the aldehyde group content of more aldehyde radical organic tanning agents is 5 ~ 9 mmol/g.
The present invention also provides the preparation methods of full constituent, more aldehyde radical organic tanning agents of wide distribution, comprising the following steps:
By weight, carbohydrates and their derivative more than 10 parts and 6 ~ 12 parts of periodates are added in 200 ~ 500 parts of water, are controlled
System temperature processed is 10 ~ 30 DEG C, and pH is 7.5 ~ 9.5, is protected from light 0.5 ~ 6 h of stirring, obtains the hydroformylation polysaccharide of full constituent, wide distribution
Solution；4 ~ 14 parts of inorganic reducing agents are added into above-mentioned solution, continues that 10 min of reaction are sufficiently stirred, iodine compound reduction will be contained
For elemental iodine, be separated by filtration recycling solid-state iodine, filtrate stir at 80 ~ 100 DEG C then and is heat-treated 1 ~ 2 h, make residual iodine with
Vaporous form steams and is absorbed and recycled with NaOH solution, finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution.
The invention further relates to application of the tanning agent in leather or fur tanning, include the following steps:
Pickled pelt is placed in rotary drum, be added be calculated as with pickled pelt weight 50% ~ 200% pickling liquid and 4% ~ 12%
More aldehyde radical organic tanning agents (in terms of solid content) simultaneously start turning, and it is 7.5 ~ 8.2 that sodium bicarbonate, which is added, and adjusts the pH of owse, and temperature is
25 ~ 40 DEG C, rotation total time is 120 ~ 420 min, obtains tan leather；
Or
Softening skin is placed in rotary drum, is added and 100% water and 2% ~ 6% organic tan of more aldehyde radicals is calculated as with liming tare weight amount
Agent (in terms of solid content) simultaneously starts turning at 25 ~ 40 DEG C, and rotation total time is 120 ~ 420 min, obtains tan leather；
Or
Into rotary drum or paddle-tumble, addition is calculated as 500% water with Pickled skin weight, is calculated as 4 ~ 10 so that the volume of water is added
More aldehyde radical organic tanning agents (in terms of solid content) of g/L and the sodium chloride of 40 g/L simultaneously start turning or stroke, then put into pickling
Fur, be added sodium bicarbonate adjust owse pH be 7.5 ~ 8.2, temperature be 25 ~ 40 DEG C, rotation or stroke total time be 120 ~
420 min obtain tanning fur.
The present invention do not precipitated by more aldehyde radical organic tanning agents that periodate oxidation is prepared, is centrifuged, filtered,
The lock out operation such as washing, remain whole components of hydroformylation product, i.e., the polysaccharide or widow that different number of sugar unit is formed by connecting
The hydroformylation product of sugar, molecular weight distribution are wide.In tannery, each component in tanning agent of the present invention can respectively enter collagen
Tanning effect is crosslinked in the multilevel structure of fiber, as macromolecular components are crosslinked in fiber interfascicular and are filled in fibre gap
In, medium molecule component is in base fiber level, and compared with small molecule component in fibrinogen level, more small molecule component even can be into
Enter and be crosslinked between tropocollagen molecule, so that tanning uniformity and tanning degree significantly improve.Therefore, the tanning of tanning agent of the present invention
Other hydroformylation polyoses can be substantially better than.In addition, the inorganic reducing agent used can incite somebody to action in iodine reclaimer operation of the invention
It is converted into elemental iodine containing iodine compound, while not being reacted again with hydroformylation polysaccharide, therefore tanning agent flexibility will not be reduced.Since iodine is in tanning agent
There is certain solubility in solution, so the subsequent mode with heating steams residual iodine in vapour form.The iodine of recycling is available
In regeneration sodium metaperiodate.
Compared with the prior art, the present invention has the following beneficial effects:
(1) preparation method of more aldehyde radical organic tanning agents provided by the invention, remains whole components of hydroformylation polysaccharide, molecule
Amount distribution is wide, can respectively enter in each level structure of materials with hide glue fibril and be uniformly distributed, play the role of good crosslinking tanning,
The shrinkage temperature of leather and fur can be greatly improved to 85-90 DEG C, this is that current any single organic tanning agent tanning cannot achieve
, therefore more aldehyde radical organic tanning agents of the invention show excellent tanning performance.
(2) preparation method of more aldehyde radical organic tanning agents provided by the invention can will contain iodine compound and efficiently divide from tanning agent
From recycling, and tanning agent active principle is not lost, to assign tanning agent good service performance, so that tan leather/fur leather
Body is pure white, and good hand feeling is soft, be not in the processing and use process in later period darken, intensity decline the problems such as.
Method of the invention simultaneously facilitates the regeneration and reuse of periodate, the preparation cost of tanning agent is greatly reduced, and avoid
A large amount of uses of organic solvent have good environment friendly.
Specific embodiment
The present invention is specifically described combined with specific embodiments below, it is necessary to which indicated herein is that the present embodiment is only used
In invention is further explained, it should not be understood as limiting the scope of the invention, the people that is skilled in technique in the field
Member can make some nonessential modifications and adaptations according to the content of aforementioned present invention.
In embodiment, the weight average molecular weight of tanning agent is measured using gel permeation chromatography, and aldehyde group content uses salt
Sour azanol potentiometric titration is measured.
Embodiment 1:
By weight, 10 parts of sodium alginates and 10 parts of sodium metaperiodates are added in 500 parts of water, control system temperature is
30 DEG C, pH 9.5,2 h of stirring are protected from light, obtain the hydroformylation polysaccharide solution of full constituent, wide distribution；12 are added into above-mentioned solution
Part sodium hydrogensulfite continues that 10 min of reaction are sufficiently stirred, will contain iodine compound and be reduced to elemental iodine, and be separated by filtration recycling solid-state
Iodine, filtrate stir 1.5 h of heat treatment at 100 DEG C, residual iodine are made to steam in vapour form and be absorbed and returned with NaOH solution
It receives, finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 18065 g/mol, and polydispersity coefficient 15, aldehyde group content is 8.5 mmol/g；
Into rotary drum, addition is calculated as 500% water with Pickled skin weight, is calculated as the above-mentioned of 10 g/L so that the volume of water is added
The sodium chloride of more aldehyde radical organic tanning agents (in terms of solid content) and 40 g/L simultaneously start turning, and then put into Pickled skin, and carbon is added
The pH that sour hydrogen sodium adjusts owse is 8.2, and temperature is 25 DEG C, and rotation total time is 420 min, obtains tanning fur.The tanning hair
Leather body is pure white, and good hand feeling is soft, and do not occur in the processing and use process in later period darkening, intensity decline etc. is asked
Topic.
Comparative example 1:
By weight, 10 parts of sodium alginates and 10 parts of sodium metaperiodates are added in 500 parts of water, control system temperature is
30 DEG C, pH 9.5,2 h of stirring are protected from light, hydroformylation polysaccharide solution is obtained；Ethyl alcohol is added into above-mentioned solution makes the portion of hydroformylation polysaccharide
It is grouped fractional precipitation, precipitating is washed with distilled water and ethyl alcohol after filtering, the more aldehyde radicals for being then dried to obtain narrow ditribution are organic
Tanning agent；
The application method of the tanning agent is the same as embodiment 1.
Embodiment 2:
By weight, polysaccharide and 8 parts of sodium metaperiodates is drawn to be added in 200 parts of water in 10 parts of towers, control system temperature is
20 DEG C, pH 7.5,4 h of stirring are protected from light, obtain the hydroformylation polysaccharide solution of full constituent, wide distribution；10 are added into above-mentioned solution
Part sodium hydrogensulfite continues that 10 min of reaction are sufficiently stirred, will contain iodine compound and be reduced to elemental iodine, and be separated by filtration recycling solid-state
Iodine, filtrate stir 1.5 h of heat treatment at 95 DEG C, residual iodine are made to steam in vapour form and be absorbed and recycled with NaOH solution,
Finally obtain more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 14870 g/mol, and polydispersity coefficient 13, aldehyde group content is 8.0 mmol/g；
Into rotary drum, addition is calculated as 500% water with Pickled skin weight, is calculated as the above-mentioned of 10 g/L so that the volume of water is added
The sodium chloride of more aldehyde radical organic tanning agents (in terms of solid content) and 40 g/L simultaneously start turning, and then put into Pickled skin, and carbon is added
The pH that sour hydrogen sodium adjusts owse is 7.8, and temperature is 30 DEG C, and rotation total time is 240 min, obtains tanning fur.The tanning hair
Leather body is pure white, and good hand feeling is soft, and do not occur in the processing and use process in later period darkening, intensity decline etc. is asked
Topic.
Comparative example 2:
By weight, polysaccharide and 8 parts of sodium metaperiodates is drawn to be added in 200 parts of water in 10 parts of towers, control system temperature is
20 DEG C, pH 7.5,4 h of stirring are protected from light, hydroformylation polysaccharide solution is obtained；Ethyl alcohol is added into above-mentioned solution makes the portion of hydroformylation polysaccharide
It is grouped fractional precipitation, precipitating is washed with distilled water and ethyl alcohol after filtering, the more aldehyde radicals for being then dried to obtain narrow ditribution are organic
Tanning agent；
The application method of the tanning agent is the same as embodiment 2.
Embodiment 3:
By weight, 10 parts of sodium carboxymethylcelluloses and 12 parts of sodium metaperiodates are added in 400 parts of water, control system
Temperature is 10 DEG C, pH 9.5, is protected from light 6 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；Into above-mentioned solution
14 parts of sodium hydrogensulfites are added, continues that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to elemental iodine, be separated by filtration back
Solid-state iodine is received, filtrate stirs 2.0 h of heat treatment at 100 DEG C, steams residual iodine in vapour form and absorbed with NaOH solution
And recycle, finally obtain more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 4000 g/mol, and polydispersity coefficient 18, aldehyde group content is 9.0 mmol/g；
Pickled pelt is placed in rotary drum, be added with pickled pelt weight be calculated as 200% pickling liquid and 10% it is above-mentioned more
Aldehyde radical organic tanning agent (in terms of solid content) simultaneously starts turning, and it is 8.0 that sodium bicarbonate, which is added, and adjusts the pH of owse, and temperature is 40 DEG C,
Rotation total time is 420 min, obtains tan leather.Tan leather leather body is pure white, and good hand feeling is soft, and adding in the later period
Do not occur the problems such as darkening, intensity decline in work and use process.
Comparative example 3:
By weight, 10 parts of sodium carboxymethylcelluloses and 12 parts of sodium metaperiodates are added in 400 parts of water, control system
Temperature is 10 DEG C, pH 9.5, is protected from light 6 h of stirring, obtains hydroformylation polysaccharide solution；Ethyl alcohol is added into above-mentioned solution keeps hydroformylation more
The constituent part precipitating of sugar, washs precipitating with distilled water and ethyl alcohol after filtering, is then dried to obtain more aldehyde of narrow ditribution
Base organic tanning agent；
The application method of the tanning agent is the same as embodiment 3.
The polydispersity coefficient for the more aldehyde radical organic tanning agents being prepared using the above method and the contraction of tanning fur/leather
Temperature is as shown in table 1.It is made as can be seen that the polydispersity coefficient of tanning agent of the present invention is much higher than using method provided by comparative example
Tanning agent, thus its can be uniformly distributed in intradermal and multilevel structure in materials with hide glue fibril between carry out full cross-linked combination, make
Tanning fur/leather shrinkage temperature greatly improves, and shows excellent tanning performance.In addition, present invention gained tanning fur/
Leather leather body is pure white, and good hand feeling is soft, and storage stability is good.And processing of the tanning fur/leather in the later period obtained by comparative example
With occur darkening in use process, intensity decline the problems such as.
The polydispersity coefficient and tanning fur/leather shrinkage temperature contrast table of more than the 1 aldehyde radical organic tanning agent of table
Embodiment 4:
By weight, 10 parts of sodium alginates and 8 parts of sodium metaperiodates are added in 250 parts of water, control system temperature is
25 DEG C, pH 8.0, it is protected from light 0.5 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；It is added into above-mentioned solution
10 parts of sodium hydrogensulfites continue that 10 min of reaction are sufficiently stirred, will contain iodine compound and be reduced to elemental iodine, it is solid to be separated by filtration recycling
State iodine, filtrate stir 1.5 h of heat treatment at 90 DEG C, residual iodine are made to steam in vapour form and be absorbed and returned with NaOH solution
It receives, finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 24543 g/mol and continuously distributed, polydispersity coefficient 11.5, aldehyde group content are
5.9 mmol/g；
Pickled pelt is placed in rotary drum, is added and 150% pickling liquid and 8% above-mentioned more aldehyde is calculated as with pickled pelt weight
Base organic tanning agent (in terms of solid content) simultaneously starts turning, and sodium bicarbonate is added under room temperature, and the pH for adjusting owse is 8.2, temperature
It is 35 DEG C, rotation total time is 360 min, obtains tan leather.The tan leather shrinkage temperature is 87 DEG C, and leather body is pure white,
Good hand feeling is soft, and does not occur the problems such as darkening, intensity decline in the processing and use process in later period.
Embodiment 5:
By weight, 6 parts of sodium alginates, 4 parts of sodium carboxymethylcelluloses and 6 parts of sodium metaperiodates are added to 500 parts of water
In, control system temperature is 30 DEG C, pH 7.5, is protected from light 3 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；To
4 parts of sulfur dioxide are added in above-mentioned solution, continues that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to elemental iodine, mistake
Filter separation and recovery solid-state iodine, filtrate stir at 80 DEG C is heat-treated 2 h, steams residual iodine in vapour form and molten with NaOH
Liquid is absorbed and is recycled, and finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 20157 g/mol, and the coefficient of dispersion 10, aldehyde group content is 5.0 mmol/g；
Pickled pelt is placed in rotary drum, is added and 50% pickling liquid and 12% above-mentioned more aldehyde is calculated as with pickled pelt weight
Base organic tanning agent (in terms of solid content) simultaneously starts turning, and sodium bicarbonate is added under room temperature, and the pH for adjusting owse is 7.5, temperature
It is 40 DEG C, rotation total time is 240 min, obtains tan leather.The tan leather shrinkage temperature is 86 DEG C, and leather body is pure white,
Good hand feeling is soft, and does not occur the problems such as darkening, intensity decline in the processing and use process in later period.
Embodiment 6:
By weight, 10 parts of sodium carboxymethyl starches and 10 parts of sodium metaperiodates are added in 500 parts of water, control system temperature
Degree is 30 DEG C, pH 8.5, is protected from light 2 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；Add into above-mentioned solution
Enter 8 parts of sodium hydrogensulfites and 3 parts of sodium nitrites, continue that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to elemental iodine,
It is separated by filtration recycling solid-state iodine, filtrate stirs 2 h of heat treatment at 90 DEG C, steams residual iodine in vapour form and use NaOH
Solution is absorbed and is recycled, and finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 27502 g/mol, and polydispersity coefficient 11, aldehyde group content is 8.1 mmol/g；
Pickled pelt is placed in rotary drum, is added and 100% pickling liquid and 4% above-mentioned more aldehyde is calculated as with pickled pelt weight
Base organic tanning agent (in terms of solid content) simultaneously starts turning, and sodium bicarbonate is added under room temperature, and the pH for adjusting owse is 8.0, temperature
It is 35 DEG C, rotation total time is 240 min, obtains tan leather.The tan leather shrinkage temperature is 85 DEG C, and leather body is pure white,
Good hand feeling is soft, and does not occur the problems such as darkening, intensity decline in the processing and use process in later period.
Embodiment 7:
By weight, 10 parts of hydroxyethyl celluloses and 8 parts of potassium metaperiodates are added in 400 parts of water, control system temperature
Degree is 15 DEG C, pH 8.0, is protected from light 6 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；Add into above-mentioned solution
Enter 10 parts of sodium hydrogensulfites, continues that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to elemental iodine, be separated by filtration recycling
Solid-state iodine, filtrate stir 2 h of heat treatment at 90 DEG C, residual iodine are made to steam in vapour form and be absorbed and returned with NaOH solution
It receives, finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 22139 g/mol, and polydispersity coefficient 9, aldehyde group content is 7.6 mmol/g；
Softening skin is placed in rotary drum, is added and 100% water and 6% above-mentioned more organic tans of aldehyde radical is calculated as with liming tare weight amount
Agent (in terms of solid content) simultaneously starts turning at 30 DEG C, and rotation total time is 240 min, obtains tan leather.The tan leather
Shrinkage temperature is 86 DEG C, and leather body is pure white, and good hand feeling is soft, and does not occur color change in the processing and use process in later period
The problems such as deep, intensity declines.
Embodiment 8:
By weight, 10 parts of xanthan gum and 8 parts of sodium metaperiodates are added in 500 parts of water, control system temperature is 20
DEG C, pH 8.0 is protected from light 4 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；10 parts of Asias are added into above-mentioned solution
Sodium bisulfate continues that 10 min of reaction are sufficiently stirred, will contain iodine compound and be reduced to elemental iodine, is separated by filtration recycling solid-state iodine,
Filtrate stirs 1.0 h of heat treatment at 95 DEG C, so that residual iodine is steamed in vapour form and is absorbed and recycled with NaOH solution, most
More aldehyde radical organic tanning agents of full constituent, wide distribution are obtained eventually；
The weight average molecular weight of the tanning agent is 24249 g/mol, and polydispersity coefficient 10, aldehyde group content is 6.9 mmol/g；
Pickled pelt is placed in rotary drum, is added and 50% pickling liquid and 4% above-mentioned more aldehyde is calculated as with pickled pelt weight
Base organic tanning agent (in terms of solid content) simultaneously starts turning, and sodium bicarbonate is added under room temperature, and the pH for adjusting owse is 7.8, temperature
It is 35 DEG C, rotation total time is 120 min, obtains tan leather.The tan leather shrinkage temperature is 86 DEG C, and leather body is pure white,
Good hand feeling is soft, and does not occur the problems such as darkening, intensity decline in the processing and use process in later period.
Embodiment 9:
By weight, polysaccharide and 8 parts of potassium metaperiodates is drawn to be added in 250 parts of water in 10 parts of towers, control system temperature is
15 DEG C, pH 8.0,2 h of stirring are protected from light, obtain the hydroformylation polysaccharide solution of full constituent, wide distribution；10 are added into above-mentioned solution
Part sodium hydrogensulfite continues that 10 min of reaction are sufficiently stirred, will contain iodine compound and be reduced to elemental iodine, and be separated by filtration recycling solid-state
Iodine, filtrate stir 2 h of heat treatment at 90 DEG C, so that residual iodine is steamed in vapour form and is absorbed and recycled with NaOH solution, most
More aldehyde radical organic tanning agents of full constituent, wide distribution are obtained eventually；
The weight average molecular weight of the tanning agent is 15437 g/mol, and polydispersity coefficient 12, aldehyde group content is 8.2 mmol/g；
Softening skin is placed in rotary drum, is added and 100% water and 6% above-mentioned more organic tans of aldehyde radical is calculated as with liming tare weight amount
Agent (in terms of solid content) simultaneously starts turning at 25 DEG C, and rotation total time is 120 min, obtains tan leather.The tan leather
Shrinkage temperature is 87 DEG C, and leather body is pure white, and good hand feeling is soft, and does not occur color change in the processing and use process in later period
The problems such as deep, intensity declines.
Embodiment 10:
By weight, 10 parts of sodium carboxymethyl starches and 6 parts of potassium metaperiodates are added in 400 parts of water, control system temperature
Degree is 10 DEG C, pH 8.5, is protected from light 6 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；Add into above-mentioned solution
Enter 6 parts of sulfur dioxide, continues that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to elemental iodine, it is solid to be separated by filtration recycling
State iodine, filtrate stir 2 h of heat treatment at 85 DEG C, residual iodine are made to steam in vapour form and be absorbed and recycled with NaOH solution,
Finally obtain more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 30000 g/mol, and polydispersity coefficient 6, aldehyde group content is 5.7 mmol/g；
Softening skin is placed in rotary drum, is added and 100% water and 2% above-mentioned more organic tans of aldehyde radical is calculated as with liming tare weight amount
Agent (in terms of solid content) simultaneously starts turning at 40 DEG C, and rotation total time is 420 min, obtains tan leather.The tan leather
Shrinkage temperature is 85 DEG C, and leather body is pure white, and good hand feeling is soft, and does not occur color change in the processing and use process in later period
The problems such as deep, intensity declines.
Embodiment 11:
By weight, 10 parts of sodium carboxymethylcelluloses and 10 parts of sodium metaperiodates are added in 250 parts of water, control system
Temperature is 20 DEG C, pH 8.0, is protected from light 4 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；Into above-mentioned solution
12 parts of sodium hydrogensulfites are added, continues that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to elemental iodine, be separated by filtration back
Solid-state iodine is received, filtrate stirs 1 h of heat treatment at 95 DEG C, and residual iodine is made to steam and be absorbed simultaneously in vapour form with NaOH solution
Recycling finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 6806 g/mol, and polydispersity coefficient 16, aldehyde group content is 8.4 mmol/g；
Into paddle-tumble, addition is calculated as 500% water with Pickled skin weight, is calculated as the above-mentioned of 4 g/L so that the volume of water is added
The sodium chloride of more aldehyde radical organic tanning agents (in terms of solid content) and 40 g/L simultaneously start stroke, then put into Pickled skin, Yu Changwen
Lower addition sodium bicarbonate, the pH for adjusting owse is 7.5, and temperature is 40 DEG C, and stroke total time is 360 min, obtains tanning hair
Skin.The tanning fur shrinkage temperature is 87 DEG C, and leather body is pure white, and good hand feeling is soft, and in the processing and use process in later period
Do not occur the problems such as darkening, intensity decline.
Embodiment 12:
By weight, it draws polysaccharide and 10 parts of sodium metaperiodates to be added in 500 parts of water in 8 parts of sodium alginates, 2 parts of towers, controls
System temperature processed is 20 DEG C, pH 8.5, is protected from light 2 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；To above-mentioned
12 parts of sodium hydrogensulfites are added in solution, continues that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to elemental iodine, filtered
Solid-state iodine is separated and recovered, filtrate stirs 2 h of heat treatment at 85 DEG C, steams residual iodine in vapour form and use NaOH solution
It absorbs and recycles, finally obtain more aldehyde radical organic tanning agents of full constituent, wide distribution；
The weight average molecular weight of the tanning agent is 19212 g/mol, and polydispersity coefficient 15, aldehyde group content is 8.5 mmol/g；
Into rotary drum, addition is calculated as 500% water with Pickled skin weight, more aldehyde that the volume of water is calculated as 8 g/L are added
The sodium chloride of base organic tanning agent (in terms of solid content) and 40 g/L simultaneously start turning, and then put into Pickled skin, add under room temperature
Enter sodium bicarbonate, the pH for adjusting owse is 8.0, and temperature is 35 DEG C, and rotation total time is 120 min, obtains tanning fur.It should
Tanning fur shrinkage temperature is 88 DEG C, and leather body is pure white, and good hand feeling is soft, and does not go out in the processing and use process in later period
Now darken, intensity decline the problems such as.
Claims (8)
1. more aldehyde radical organic tanning agents of a kind of full constituent, wide distribution, it is characterised in that: the tanning agent by following weight original
Material is made: 10 parts of more carbohydrates and their derivatives, 6 ~ 12 parts of periodate, 200 ~ 500 parts of water, 4 ~ 14 parts of inorganic reducing agent, preparation
Method the following steps are included:
By weight, carbohydrates and their derivative more than 10 parts and 6 ~ 12 parts of periodates are added in 200 ~ 500 parts of water, control volume
It is temperature is 10 ~ 30 DEG C, pH is 7.5 ~ 9.5, is protected from light 0.5 ~ 6 h of stirring, obtains the hydroformylation polysaccharide solution of full constituent, wide distribution；
4 ~ 14 parts of inorganic reducing agents are added into above-mentioned solution, continues that 10 min of reaction are sufficiently stirred, iodine compound will be contained and be reduced to iodine
Simple substance is separated by filtration recycling solid-state iodine, and then filtrate is stirred at 80 ~ 100 DEG C to 1 ~ 2 h of heat treatment, make residual iodine with steam
Form steams and is absorbed and recycled with NaOH solution, finally obtains more aldehyde radical organic tanning agents of full constituent, wide distribution.
2. tanning agent according to claim 1, it is characterised in that more carbohydrates and their derivatives draw more selected from sodium alginate, tower
At least one of sugar, xanthan gum, sodium carboxymethyl starch, sodium carboxymethylcellulose, hydroxyethyl cellulose.
3. tanning agent according to claim 1, it is characterised in that the periodate be sodium metaperiodate, in potassium metaperiodate extremely
Few one kind.
4. tanning agent according to claim 1, it is characterised in that the inorganic reducing agent be sodium hydrogensulfite, sodium nitrite,
At least one of sulfur dioxide.
5. tanning agent according to claim 1, it is characterised in that the weight average molecular weight of more aldehyde radical organic tanning agents be 4000 ~
30000 g/mol and continuously distributed, polydispersity coefficient are 6 ~ 18.
6. tanning agent according to claim 1, it is characterised in that the aldehyde group content of more aldehyde radical organic tanning agents is 5 ~ 9
mmol/g。
7. application of the tanning agent in leather or fur tanning described in claim 1-6 any one.
8. application as claimed in claim 7, it is characterised in that the leather or fur tanning include the following steps:
Pickled pelt is placed in rotary drum, is added and 50% ~ 200% pickling liquid and 4% ~ 12% more aldehyde is calculated as with pickled pelt weight
Base organic tanning agent simultaneously starts turning, wherein in terms of the solid content of the tanning agent, sodium bicarbonate is added in the dosage of more aldehyde radical organic tanning agents
The pH for adjusting owse is 7.5 ~ 8.2, and temperature is 25 ~ 40 DEG C, and rotation total time is 120 ~ 420 min, obtains tan leather；
Or
Softening skin is placed in rotary drum, is added and 100% water and 2% ~ 6% more aldehyde radical organic tanning agents is calculated as simultaneously with liming tare weight amount
It is started turning at 25 ~ 40 DEG C, wherein the dosage of more aldehyde radical organic tanning agents is in terms of the solid content of the tanning agent, rotation total time is
120 ~ 420 min, obtain tan leather；
Or
Into rotary drum or paddle-tumble, addition is calculated as 500% water with Pickled skin weight, is calculated as 4 ~ 10 g/L's so that the volume of water is added
The sodium chloride of more aldehyde radical organic tanning agents and 40 g/L simultaneously start turning or stroke, wherein the dosage of more aldehyde radical organic tanning agents is with the tan
Then the solid content meter of agent puts into Pickled skin, it is 7.5 ~ 8.2 that sodium bicarbonate, which is added, and adjusts the pH of owse, and temperature is 25 ~ 40
DEG C, rotation or stroke total time are 120 ~ 420 min, obtain tanning fur.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546396.3A CN107217116B (en) | 2017-07-06 | 2017-07-06 | A kind of full constituent, more aldehyde radical organic tanning agents of wide distribution and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546396.3A CN107217116B (en) | 2017-07-06 | 2017-07-06 | A kind of full constituent, more aldehyde radical organic tanning agents of wide distribution and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107217116A CN107217116A (en) | 2017-09-29 |
| CN107217116B true CN107217116B (en) | 2019-04-23 |
Family
ID=59952969
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710546396.3A Active CN107217116B (en) | 2017-07-06 | 2017-07-06 | A kind of full constituent, more aldehyde radical organic tanning agents of wide distribution and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107217116B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108929924B (en) * | 2018-10-10 | 2020-11-24 | 齐鲁工业大学 | Preparation method of carboxymethyl cellulose leather retanning and filling agent |
| CN111223723A (en) * | 2018-11-27 | 2020-06-02 | 俊郎电气有限公司 | Electronic miniature circuit breaker |
| CN110218822B (en) * | 2019-06-17 | 2021-07-16 | 四川大学 | Glycosyl aldehyde tanning agent and preparation method thereof |
| CN110241270B (en) * | 2019-06-17 | 2021-07-16 | 四川亭江新材料股份有限公司 | Amination modified glycosyl aldehyde tanning agent and preparation method thereof |
| CN111088409B (en) * | 2019-11-27 | 2022-03-04 | 安徽银河皮革有限公司 | Multi-aldehyde-based macromolecular organic tanning agent for ecological leather manufacturing and preparation method thereof |
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 |
| CN102020719A (en) * | 2010-11-11 | 2011-04-20 | 陕西科技大学 | Method for preparing modified starch tanning agent |
| CN104087688A (en) * | 2014-07-10 | 2014-10-08 | 上虞兰博新材料科技有限公司 | Modified rice dialdehyde starch retanning filler for leather and preparation method of filler |
-
2017
- 2017-07-06 CN CN201710546396.3A patent/CN107217116B/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 |
| CN102020719A (en) * | 2010-11-11 | 2011-04-20 | 陕西科技大学 | Method for preparing modified starch tanning agent |
| CN104087688A (en) * | 2014-07-10 | 2014-10-08 | 上虞兰博新材料科技有限公司 | Modified rice dialdehyde starch retanning filler for leather and preparation method of filler |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107217116A (en) | 2017-09-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107217116B (en) | A kind of full constituent, more aldehyde radical organic tanning agents of wide distribution and preparation method thereof | |
| Hong et al. | Versatile acid base sustainable solvent for fast extraction of various molecular weight chitin from lobster shell | |
| JP2020518715A5 (en) | ||
| CN104619728B (en) | The method that hemicellulose and cellulose are separated from more sugar sources | |
| CA2568594C (en) | Method for producing a dissovling pulp | |
| CN105800996B (en) | A kind of method that utilization waste wool keratin prepares cement blowing agent | |
| CN105924596A (en) | Method for preparing silk-fibroin-based water-absorbing material by grafting vinyl monomer | |
| CN110746785A (en) | High-strength anti-freezing three-dimensional porous hydrogel adsorption material and preparation method thereof | |
| CN103865060A (en) | Preparation method and application of polymer retention filter aid containing phenylboronic acid functional group | |
| CN112029003A (en) | Solution type corn cationic starch and preparation method thereof | |
| CN103554247A (en) | Method for preparing collagen microfiber by use of ionic liquid mixing solvent | |
| EP3257955B1 (en) | Process for pretanning or retanning leather using carboxymethylcellulose and its salts | |
| CN113481334B (en) | Bio-based leather filler and preparation method thereof | |
| CN110218822A (en) | A kind of glycosyl aldehyde tanning agent and preparation method thereof | |
| CN110747299B (en) | Method for preparing aluminum zirconium complex tanning agent based on microcrystalline cellulose | |
| CN111560086B (en) | Method for preparing cationic hyaluronate by semidry method | |
| CN111088409B (en) | Multi-aldehyde-based macromolecular organic tanning agent for ecological leather manufacturing and preparation method thereof | |
| CN108484984A (en) | A kind of preparation method of high strength fibre element based coextruded film | |
| CN107938345A (en) | A kind of preparation method for hydrolyzing silk peptide modification viscose rayon | |
| CN1286856C (en) | Process for preparing poly saccuinimide crosslinking modified chitin material | |
| CN111286968A (en) | Anti-ultraviolet cotton fabric dyeing method with good stability | |
| CN108623759A (en) | A method of fibroin base water-absorbent material is prepared based on coupling and enzymatic graft copolymerization | |
| CN113999943B (en) | Polysaccharide-based hydrotalcite nano composite tanning agent and preparation method and application thereof | |
| CN112979831B (en) | Method for efficiently preparing raw material medicine icodextrin | |
| CN111793726B (en) | Method for preparing leather retanning agent by taking waste animal hair as raw material |
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 |