CN104073575B - Fur tanning agent based on isocyanates and preparation method thereof - Google Patents
Fur tanning agent based on isocyanates and preparation method thereof Download PDFInfo
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- CN104073575B CN104073575B CN201410338162.6A CN201410338162A CN104073575B CN 104073575 B CN104073575 B CN 104073575B CN 201410338162 A CN201410338162 A CN 201410338162A CN 104073575 B CN104073575 B CN 104073575B
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- tanning agent
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Abstract
The invention discloses a kind of fur tanning agent based on isocyanates and preparation method thereof.Its process is to utilize diisocyanate molecules under catalytic condition and in mixed solution, aliphatic glycol or PTMEG carried out two ends sealed, obtains the high selective and performed polymer of high conversion；Then with bisulfites, the isocyanate groups at performed polymer two ends is protected, improve the water solubility of compound, finally give tanning agent.This tanning agent molecular size range is controlled, it is adaptable to the fur that tanning fibre structure is different.Tannery can penetrate between collagen effectively, under the conditions of a liter gentleness carries alkali bisulfites decompose, the most exposed isocyanate groups of tanning agent molecule thus and tropocollagen molecule on amino react, crosslinking collagen to reach the purpose of tanning.Whole process only has the release of neutral salt, does not produce heavy metal ion and free aldehyde, simplifies decontamination procedure, and environmental friendliness is cheap, is very suitable for fur, particularly the tanning of light color rabbit.
Description
Technical field
The present invention relates to a kind of fur tanning agent, be specifically related to a kind of fur tanning agent based on isocyanates and preparation side thereof
Method.Belong to the fur ecology tanning agent technical field containing specific functional groups.
Background technology
In recent years, China's fur industry gradually presents the situation of sound development, fur manufacturing and goods trade thereof in the world
On occupy very important status.But the technology barriers faced in recent years and ecological index require the strictest, thus limit
The outlet of Zhi Liao China peltry product.Therefore exploitation needed badly by the tanning agent that cleans meeting environment and human health requirement.
Tradition fur tanning mainly uses chrome tanning agent and organic aldehydes tanning agent.Substantial amounts of heavy metal can be produced during the former tanning
Chromium, and in the product of the aldehydes tanning agent tannings such as formaldehyde, glyoxal, fatty aldehyde, free aldehyde group content is higher.These venomous injurants
Matter not only can be bigger to the healthy generation of consumer threat, also can give follow-up environmental treatment bring the biggest difficulty,
Increase financial cost.The countries such as European Union are classified as formaldehyde as 3 carcinogenic substances such as grade, it is desirable to the direct and leather free formaldehyde of skin contact
Content must not exceed 75mg/kg, and not direct and skin contact leather free formaldehyde content must not exceed 150mg/kg.These are green
Colour standard is strict with enterprise and is controlled free aldehyde and chromic content in leather fur product, and opens environment-friendly type tanning agent
Send out and the cleaning of fur produces the requirement that proposition is higher.
Modified as leather retanning agent (skin in order to avoid using formaldehyde, Wang Quanjie et al. that glutaraldehyde has been carried out in tanning
Leather glutaraldehyde and modified glutaraldehyde, [J] Chinese leather, 2011,40 (3): 27-31.), during modified glutaraldehyde tanning, react bar
Part is gentleer, and finished product pliability and richness are preferable, but there are still expensive raw material price, store and transport difficult, and produce
The problem of free aldehyde.Oxazolidine tanning agent is a kind of preferable chrome-free tanning agent of flexibility, and stone is green et al. open has invented a kind of dicyclo
Oxazolidine tanning agent (a kind of dicyclo oxazolidine tanning agent extremely preparation method, 2009, publication number: CN101367773A), this tanning agent by
Methylol amine, polyhydroxy-alcohol and aliphatic aldehyde are prepared from, and can reach chrome-tanned contraction with vegetable tanning agent combination tanned leather
Temperature.But this tanning agent is still not fee from the problem of free aldehyde in leather goods.To this end, Li Yao etc. have studied organophosphorated salt as hair
Skin tanning agent (organic phosphonium salt tanning rabbit Performance comparision, [J] leather and chemical industry, 2011,28 (6): 5-7.), research finds organic phosphine
Without heavy metal ion in salt tanning agent waste tanning liquor, easily reach sewage discharge index after process, and finished product shrinkage temperature is higher
Flexibility is preferable.But need to aoxidize during this tanning agent tanning fur, cause fleece micro-rubescent, under glossiness so that hair scale sheet is impaired
Fall.Therefore, a kind of do not produce free aldehyde and there is the tanning agent of preferable process hides effect urgently develop.
Organic tanning agent is one of study hotspot, and wherein isocyanates and the purposes as tanning agent thereof have been studied and obtained
Generally acknowledge, as at US-A 2 923 594 " process for tanning ", US-A 4 413 997 " tanning agent based on diisocyanate " and H.
" with isocyanates tanning " (German) the 1st and 2 part of Tr ubel, leather (Das Leder), page 1977,150
Ff and page 181 ff has stated.
But, these compounds, and cannot be in conventional tanning because having the characteristic of toxicity, high-vapor-pressure and low aqueous solubility
Equipment uses.It addition, the isocyanates in the aqueous solution quickly can be formed by intermediate carbamic acid and amine and not have tanning
The polyureas of function.Therefore, it can to utilize blocking group temporary blocked isocyanate functional group, effectively to play isocyanide ester
Tanning effect.
Preparing carbamoyl sulphonate class tanning agent based on isocyanates is one of improved route, and this type of tanning agent can not only have
Effect plays tanning effect, simultaneously in leather making process, only discharges neutral salt, does not produce heavy metal and free aldehyde, have ecology
Free of contamination feature.EP-A 0 690 135 is by obtaining with bisulfite reaction after being reacted with Aethoxy Sklerol by isocyanide ester again
To having inert tanning agent based on isocyanates under water environment.But the isocyanates before sulfonate modified in this patent
Tanning agent uses single solvent and prepares without catalyst, has the defect that cost is high, synthesis step is many and by-products content is high.Cause
Must be preferably without the solvent of suppression viscosity for single solvent, this kind solvent price general charged is high, and needs extra synthesis to walk
Suddenly.Without preparing under catalysts conditions, the reaction time is longer, and side reaction is more.
EP-A-1647563 discloses and includes that at least one contains the alkane of carbamyl sulfonate ester group and at least one alcohol
The compound of epoxide compound.These chemicals have good tanning effect.But, its compound under elevated temp (as 30 DEG C-
40 DEG C) a kind of being separated can be experienced, and be irreversible.Therefore, its compound is unfavorable for storing, and needs volume in commercial use
Outer storage cost.
In this context, a kind of technique is simple, low cost, excellent effect and eco-friendly preparation based on isocyanates
The method of fur tanning agent is urgently developed.
Summary of the invention
An object of the present invention is the deficiency for existing fur tanning agent based on isocyanates and preparation method thereof,
By improving synthetic technology and preparation technology, it is provided that a kind of fur tanning agent based on isocyanates and a kind of technique is simple, become
This low and preparation method of excellent effect:
Based on mole part, first 1 part of aliphatic glycol or PTMEG are dissolved in organic solvent, are subsequently adding 2-4 part two
Isocyanates reacts with alcoholic extract hydroxyl group, is 0-100 DEG C in temperature and reacts under catalysts conditions, and the reaction time is that 1-10 is little
Time.Evaporating organic solvent under reduced pressure, obtains the tanning agent that diisocyanate is uncapped.Above-mentioned tanning agent is dissolved in the water,
Add the bisulfites that mole part is diisocyanate 2-4 part, react 2-12 hour under normal temperature, obtain bisulfites and protect
The tanning agent solution protected, solution clear.
Organic solvent described in preparation process is that acetone, oxolane, ethyl acetate, butyl acetate, benzene, toluene are to take up an official post
What two kinds of mixed solvent, preferably toluene and ethyl acetate volume ratio are the mixed solvent of 1:1.The selection of mixed solvent can keep away
Exempt from the single solvent not suppressing viscosity that alternative costs are high, and eliminate extra synthesis step and saved cost.
Aliphatic glycol carbon number described in preparation process is preferably 1-18, and PTMEG carbon number is preferably 1-50.
Use the PTMEG that backbone c atoms number is few, such as polyethylene glycol, the tanning agent molecular weight obtained, be suitable for tanning hide glue fibril
Tie up close fur, such as beaver rabbit skin；And the big tanning agent of molecular weight is because of poor permeability, is not suitable for the close hair of tanning materials with hide glue fibril
Skin, and it is suitable for the fur that tanning materials with hide glue fibril is loose, such as family's rabbit.Utilize aliphatic glycol and the polyethers two of preferred carbon number
Alcohol preparation fur tanning agent as described in claim 1-10, can meet tight to materials with hide glue fibril simultaneously and materials with hide glue fibril is loose
The tanning of fur.Tanning agent with aliphatic glycol as main chain has harder chain structure than the tanning agent with Aethoxy Sklerol as main chain, institute
The leather of tanning also has higher shrinkage temperature.But, aliphatic glycol has hydrophobicity, tends to receive between materials with hide glue fibril
Contracting, and Aethoxy Sklerol is hydrophilic, is difficult to shrink.Therefore the carbon number of preferred fat glycol to lack (< 18), and preferred, polyethers
The carbon number of alcohol can reach 50.
Described catalyst is organic tin catalyst, including dibutyl tin laurate, maleic anhydride dibutyl tin, diethyl
Acid dibutyl tin, dilauryl dibutyltin mercaptide etc., preferably dibutyl tin laurate.Add catalyst to be conducive to accelerating
Course of reaction, the catalytic condition conversion ratio of lower 2 hours can reach not add the catalyst conversion ratio of 10 hours；Under catalytic condition,
Higher reaction temperature (> 60 DEG C) be conducive to shortening the reaction time further, and do not have the appearance of accessory substance；Without catalyst
Under the conditions of, higher reaction temperature (> 60 DEG C) easily produce accessory substance.This tanning agent is by aliphatic glycol or PTMEG, two different
Cyanate and bisulfites are prepared from, and outward appearance is shallow white clarification thick liquid.This tanning agent is first with diisocyanate
Molecule and carries out two ends sealed to aliphatic glycol or PTMEG in mixed solution under catalytic condition, obtains high selective and high
The performed polymer of conversion ratio；Then with bisulfites, the isocyanate groups at performed polymer two ends is protected, and improve tan
The water solubility of agent.The molecular size range of this tanning agent is controlled in building-up process, in order to be applicable to the hair that fibre structure is different
Skin, preferably permeates between materials with hide glue fibril and cross-links combination.This tanning agent can penetrate into collagen in tannery effectively
Between, under the conditions of a liter gentleness carries alkali, bisulfites decomposes, the most exposed isocyanate groups of tanning agent molecule thus and collagen
Amino on molecule reacts, and crosslinking collagen is to reach the purpose of tanning.Whole process only has the release of neutral salt, does not produces
Raw heavy metal ion and free aldehyde, simplify the purified treatment program of follow-up emission, the most friendly to environment and price is low
Honest and clean.It is very suitable for fur, particularly the tanning of light color rabbit.
It is a further object to provide the fur tanning agent based on isocyanates prepared under such an approach.This tanning agent
It is prepared from by aliphatic glycol or PTMEG, diisocyanate and bisulfites, tanning agent chemistry before bisulfites end-blocking
General structure is (1) or (2):
(1)
(2)
m1=1-18；m2=1-50.
Described aliphatic glycol and PTMEG are respectively (3) and (4):
(3)(4)
Diisocyanate OCN-R-NCO is: 1, hexamethylene-diisocyanate (HDI)；Isoflurane chalcone diisocyanate
(IPDI)；Methylene phenylene diisocyanate (TDI)；Diphenyl methane-4 ' 4-diisocyanate (MDI)；PPDI
(PPDI)；1,5-naphthalene diisocyanate (NDI)；Between stupid two methylene diisocyanate (XDI)；Dimethyl diphenyl diisocyanate
(TODI)；
After bisulfites end-blocking, the chemical structure of general formula of tanning agent is (5) or (6):
(5)
(6)
Wherein R1For Na or K
After bisulfites end-blocking, in tanning agent water soluble, outward appearance is shallow white clear liquid, gets final product water under Elevated Temperature Conditions
Solve, discharge bisulfites, by exposed out for the isocyanate groups of protection.
This tanning agent may be used for the tanning of all kinds of fur, the particularly tanning of light color fur.
Present invention have the advantage that
1. the preparation method of the fur tanning agent based on isocyanates that the present invention provides, preparation technology is simple, condition temperature
With, by introducing catalyst and mixed organic solvents, the single solvent not suppressing viscosity that alternative costs are high can be avoided,
Control the viscosity of polymerization system, eliminate again extra synthesis step and saved cost, the extent of reaction can also be controlled simultaneously.
On the one hand organic tin catalyst can increase aliphatic glycol and the reactivity of PTMEG and selectivity, on the other hand can improve
Reaction efficiency shortens reaction duration.The organic solvent mixed by a certain percentage both can guarantee that reaction system was under higher polymerization temperature
Viscosity will not be excessive, can form hydrogen bond with hydroxyl again and produce that shielding action, beneficially preparation process are gentleer carries out, and controllability is more
By force, the dispersiveness of product is more preferably.Therefore operability is higher, has the biggest market competition advantage.
2. the molecular weight of the fur tanning agent based on isocyanates that the present invention provides is controlled, can after bisulfites protection
With controlled and penetrate into uniformly between collagen, after heating up and carrying alkali, slough bisulfites, it is possible to cross-link hide glue equably
Former thus produce tanning effect.Compared with existing like product preparation method, the preparation method sintetics that the present invention provides
Because its reaction tends to complete, occurring without side reaction, solid content and purity are higher, and stability is more preferable.Temperature is wanted by preparation process
Asking lower, reaction condition is gentleer.During tan leather, finished leather softness grain is careful.During tanning fur, especially light color fur,
Fleece can keep primary colors not yellowing, dermatotome shrinkage temperature > 75 DEG C, tearing toughness is high.The tanning agent that the present invention provides is more suitable for
The processing of fur product, has the advantage producing ecological fur.
3. the fur tanning agent based on isocyanates prepared due to the present invention only discharges bisulfite in tannery
Salt, will not produce the pollution of heavy metal and free aldehyde, and human health also will not be produced and threaten by fur goods, it is possible to meet hair
The export requirement of leathercraft.
Accompanying drawing explanation
Accompanying drawing 1 is the infrared spectrogram of the fur tanning agent based on isocyanates of embodiment 1 preparation.
Accompanying drawing 2 is the tanning schematic diagram of the fur tanning agent application example 1 based on isocyanates of preparation in embodiment 1.
It is embodied as example
Invention is further described below in conjunction with instantiation.Authority described in the invention comprise following instance but not only
Being limited only to following instance, any content relevant with the present invention is all within the scope of the protection of usage right of the present invention.It is necessary
This is pointed out that the present embodiment to be served only for the present invention and is further described, it is impossible to be interpreted as the limit to scope
System, the person skilled in the art in this field can make some nonessential improvement and adjustment according to same in the invention described above.
Embodiment 1
0.05 mol polyethylene glycol (Mn=400) is dissolved in the toluene and ethyl acetate that 80 mL mix, and is subsequently adding
0.11 mol IPDI and 1-2 drips dibutyltin dilaurate catalyst, reacts 3 h at 40 DEG C.After reaction terminates, decompression is revolved
Steam and toluene and ethyl acetate solvent are steamed, obtain intermediate product, and be dissolved in ethanol solution.Sulfurous containing 0.11 mol
Acid hydrogen sodium water solution added in above-mentioned ethanol solution, 5 DEG C of isothermal reactions 2 hours.Rotation is evaporated off ethanol again, obtains target tan
The aqueous solution of agent product.
Embodiment 2
0.05 mol propane diols is dissolved in the acetone and toluene that 80 mL mix, be subsequently adding 0.11 mol MDI and
1-2 drips dibutyltin dilaurate catalyst, reacts 3 h at 40 DEG C.Reaction terminates rear vacuum rotary steam by molten to acetone and toluene
Agent steams, and obtains intermediate product, and is dissolved in ethanol solution.Aqueous solution of sodium bisulfite containing 0.11 mol adds above-mentioned
In ethanol solution, 5 DEG C of isothermal reactions 2 hours.Rotation is evaporated off ethanol again, obtains the aqueous solution of target tanning agent product.
Embodiment 3
0.05 mol polyethylene glycol (Mn=1000) is dissolved in 80 mL tetrahydrofuran solvents, is subsequently adding 0.11 mol
HDI and 1-2 drips dibutyltin dilaurate catalyst, reacts 3 h at 40 DEG C.Reaction terminates rear vacuum rotary steam by tetrahydrochysene furan
Solvent of muttering steams, and obtains intermediate product, and is dissolved in ethanol solution.Bisulfite aqueous solutions of potassium containing 0.11 mol adds
In above-mentioned ethanol solution, 5 DEG C of isothermal reactions 2 hours.Rotation is evaporated off ethanol again, obtains the aqueous solution of target tanning agent product.
Embodiment 4
0.05 mol ethylene glycol is dissolved in 80 mL toluene, is subsequently adding 0.11 mol TDI and 1-2 and drips tin dilaurate
Dibutyl tin catalyst, reacts 3 h at 40 DEG C.Reaction terminates rear vacuum rotary steam and is steamed by toluene solvant, obtains middle product
Thing, and be dissolved in ethanol solution.Aqueous solution of sodium bisulfite containing 0.11 mol adds in above-mentioned ethanol solution, at 5 DEG C
Isothermal reaction 2 hours.Rotation is evaporated off ethanol again, obtains the aqueous solution of target tanning agent product.
The independent tanning rabbit of application example 1 fur tanning agent based on isocyanates
Raw material: pickling rabbit (uses liquor ratio 20:1)
Go acid: water 2L, salt 50g/L, normal temperature turns 5min；Sodium bicarbonate 2g/L, ten times of water add at twice after dissolving, adjust
PH to about 6.
Tanning: be warming up to 30 DEG C, 8g/L ecology fur tanning agent (water dissolving) turns 5min/60min × 4
Carry alkali: be warming up to 35 DEG C, magnesia 3g/L, turn 5min/30min × N, (each 0.5g/L repeats this step), adjust
PH to about 8, stops drum overnight.Next day turns 30min, washes out skin, takes horse.
Measure shrinkage temperature and the mechanical strength of dermatotome.
After using fur tanning agent tanning based on isocyanates prepared by this method, fleece is pure white submissive, shrinkage temperature
Reach 76 DEG C.The physical and mechanical properties of dermatotome is relatively strong, and the hot strength recorded is 17.9MPa, and tearing strength is 35.49N/mm.
Compared with fur tanning agent based on isocyanates with routine, its mechanical strength is the most excellent, and wearability is strong, the fur goods warp prepared
The most endurable.
The independent tanning sheepskin of application example 2 fur tanning agent based on isocyanates
Raw material: pickling sheepskin (following materials are on the basis of the weight of pickling sheepskin)
Go acid: water 50%, salt 8%, normal temperature turns 10min；Soda ash 2%, turns 10min；Sodium bicarbonate 2%, adjusts pH to about 6.
Tanning: ecological fur tanning agent 8%(water dissolves), turn 30min, 5min/30min × 4
Carry alkali: be warming up to 35 DEG C, soda ash 2%, add at twice, every minor tick 15min；Then 5min/30min × N is turned,
(each 0.2%, repeat this step), adjusts pH to about 8, stops drum overnight.After the tanning of this tanning agent, becoming grain careful, leather body is soft
Soft, shrinkage temperature reaches 78 DEG C.
Claims (14)
1. the method preparing fur tanning agent based on isocyanates, it is characterised in that: it is by aliphatic glycol or PTMEG and two
Isocyanates is dissolved in organic solvent, then carries out catalytic reaction under organic tin catalyst existence condition, gets rid of reaction
After solvent in system, obtain tanning agent based on isocyanates；By molar amount, aliphatic glycol or PTMEG be 1 part, two different
Cyanate is 2～4 parts；Described aliphatic glycol carbon number is 1-18；Described PTMEG carbon number is 1-50；Described organic
Solvent is at least two mixed solvent in acetone, oxolane, ethyl acetate, butyl acetate, benzene, toluene.
Preparation method the most according to claim 1, it is characterised in that: described organic tin catalyst includes tin dilaurate two
Butyl tin, maleic anhydride dibutyl tin, dibutyltin diacetate, dilauryl dibutyltin mercaptide.
Preparation method the most according to claim 1 and 2, it is characterised in that: described organic tin catalyst is tin dilaurate
Dibutyl tin.
Preparation method the most according to claim 1, it is characterised in that: the degree of functionality of described diisocyanate is 2-4, molecule
Amount is less than 400g/mol.
Preparation method the most according to claim 4, it is characterised in that: described diisocyanate is 1, hexamethylene-diisocyanate
(HDI), isoflurane chalcone diisocyanate (IPDI), methylene phenylene diisocyanate (TDI), diphenyl methane-4 ' 4-bis-isocyanic acid
Ester (MDI), PPDI (PPDI), 1,5-naphthalene diisocyanate (NDI), a stupid two methylene diisocyanate (XDI),
Dimethyl diphenyl diisocyanate (TODI).
Preparation method the most according to claim 1, it is characterised in that: the time of catalytic reaction is 1-10 hour, and temperature is
0-100 degree Celsius.
7. according to the preparation method described in claim 1-2 and 4-6 any claim, it is characterised in that: also include institute
Stating tanning agent based on isocyanates and carry out termination process, described termination process is that tanning agent based on isocyanates is dissolved to water
In, add bisulfites, react under normal temperature at least 2 hours, obtain the tanning agent based on isocyanates of end-blocking；By mole
Meter, bisulfites mole is 2～4 parts of diisocyanate.
Preparation method the most according to claim 3, it is characterised in that: also include described tanning agent based on isocyanates is entered
Row termination process, described termination process is to be dissolved in water by tanning agent based on isocyanates, adds bisulfites, under normal temperature
React at least 2 hours, obtain the tanning agent based on isocyanates of end-blocking；By molar amount, bisulfites mole is two different
2～4 parts of cyanate.
Preparation method the most according to claim 7, it is characterised in that: the described reaction time is to add bisulfites
After, react 2-12 hour under normal temperature.
Preparation method the most according to claim 8, it is characterised in that: the described reaction time is to add bisulfites
After, react 2-12 hour under normal temperature.
11. preparation methods according to claim 7, it is characterised in that: described bisulfites is sodium hydrogensulfite or Asia
Potassium acid sulfate.
12. preparation methods according to claim 8, it is characterised in that: described bisulfites is sodium hydrogensulfite or Asia
Potassium acid sulfate.
13. preparation methods according to claim 7, it is characterised in that: described mixed solvent is toluene and ethyl acetate body
Long-pending than the mixed solvent being 1: 1.
14. preparation methods according to claim 8, it is characterised in that: described mixed solvent is toluene and ethyl acetate body
Long-pending than the mixed solvent being 1: 1.
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| CN105803131B (en) * | 2014-12-29 | 2018-05-29 | 焦作隆丰皮草企业有限公司 | A kind of process for tanning of leather |
| CN109735668B (en) * | 2019-03-01 | 2021-07-02 | 四川大学 | Chrome-free and aldehyde-free tan sheep skin tanning method |
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| US5820634A (en) * | 1996-06-21 | 1998-10-13 | Bayer Aktiengesellschaft | Process for tanning leather |
| CN101368219A (en) * | 2008-10-07 | 2009-02-18 | 四川大学 | Fragrant sustained-release type leather compound tanning agent and method of producing the same |
| CN101871023A (en) * | 2009-04-23 | 2010-10-27 | 中国科学院成都有机化学有限公司 | Method for preparing acid-resistance polyurethane-acrylic resin retanning agent |
| CN102250294A (en) * | 2010-04-20 | 2011-11-23 | 中国科学院成都有机化学有限公司 | Preparation method of masked retanning-type high-adsorption chrome tanning accessory ingredient |
| CN102296131A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院成都有机化学有限公司 | Preparation method of hydrogen bond compound (methyl) acrylic resin retanning agent for chromium-free tanning |
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2014
- 2014-07-16 CN CN201410338162.6A patent/CN104073575B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5820634A (en) * | 1996-06-21 | 1998-10-13 | Bayer Aktiengesellschaft | Process for tanning leather |
| CN101368219A (en) * | 2008-10-07 | 2009-02-18 | 四川大学 | Fragrant sustained-release type leather compound tanning agent and method of producing the same |
| CN101871023A (en) * | 2009-04-23 | 2010-10-27 | 中国科学院成都有机化学有限公司 | Method for preparing acid-resistance polyurethane-acrylic resin retanning agent |
| CN102250294A (en) * | 2010-04-20 | 2011-11-23 | 中国科学院成都有机化学有限公司 | Preparation method of masked retanning-type high-adsorption chrome tanning accessory ingredient |
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Inventor after: Zhang Zongcai Inventor after: Li Shuangli Inventor after: Liu Gongyan Inventor after: Dai Hong Inventor after: Chen Yingying Inventor before: Liu Gongyan |
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Free format text: CORRECT: INVENTOR; FROM: LIU GONGYAN TO: ZHANG ZONGCAI LI SHUANGLI LIU GONGYAN DAI HONG CHEN YINGYING |
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Granted publication date: 20160706 Termination date: 20170716 |