CN104073575A - Fur tanning agent based on isocyanate and preparation method of fur tanning agent - Google Patents
Fur tanning agent based on isocyanate and preparation method of fur tanning agent Download PDFInfo
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Abstract
The invention discloses a fur tanning agent based on isocyanate and a preparation method of the fur tanning agent. According to the process, diisocyanate molecules are adopted to perform end-capping on two ends of fat-diol or polyether glycols in a mixed solution under the condition of catalysis, and prepolymer with high selectivity and high conversion rate is obtained; then, hydrosulphite is adopted to protect isocyanate groups on two ends of the prepolymer, the water solubility of the compound is increased, and the tanning agent is obtained finally. The molecular weight of the tanning agent can be controlled, thereby being applicable to tanning of furs with different fibrous textures; during the tanning process, the fur tanning agent can effectively permeate to the position among the fur collagen; hydrosulphite decomposes under the condition of raised temperature and raised alkali, the tanning agent molecule expose the isocyanate group to cause the isocyanate group to react with the amino group on the collagen molecule, crosslinking of the fur collagen is realized, and the purpose of tanning is achieved; only neutral salt is released during the entire process, heavy metal ions or free aldehyde groups are not generated, the process is simplified, the fur tanning agent is environment friendly, the price is low, the fur tanning agent is very suitable for fur, especially tanning of rabbit fur with light color.
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 isocyanic ester and preparation method thereof.Belong to the ecological tanning agent technical field of the fur that contains specific functional groups.
Background technology
In recent years, China's fur industry presents the situation of sound development gradually, and fur manufacturing and goods trade thereof occupy very important status in the world.But the technology barriers that face in recent years and ecological index require also further strict, thereby limit the outlet of China's furs product.Therefore the tanning agent that cleans that meets environment and human health requirement is needed exploitation badly.
Tradition fur tanning mainly adopts chrome tanning agent and organic aldehydes tanning agent.When the former tanning, can produce a large amount of heavy metal chromiums, and formaldehyde, oxalic dialdehyde, the product Free Aldehyde base content of the aldehydes tanning agent tanning such as alkanoic is higher.These hazardous and noxious substances not only can be larger to human consumer's healthy generation threat, also can give follow-up environmental treatment bring very large difficulty, increase Financial cost.The countries such as European Union classify formaldehyde as 3 carcinogenss such as grade as, require the leather free formaldehyde content of direct and skin contact must not exceed 75mg/kg, and leather free formaldehyde content direct and skin contact must not exceed 150mg/kg.These green standards are strict with enterprises and are controlled leather fur product Free Aldehyde base and chromic content, and exploitation to environment-friendly type tanning agent and the cleaner production of fur propose higher requirement.
For fear of use formaldehyde in tanning, the people such as Wang Quanjie have carried out modification as leather retanning agent (leather glutaraldehyde and modified glutaraldehyde to glutaraldehyde, [J] Chinese leather, 2011,40 (3): 27-31.), reaction conditions is gentleer when modified glutaraldehyde tanning, finished product pliability and fullness ratio are better, but still exist expensive raw material price, store and transport difficulty, and produce the problem of free aldehyde.Oxazolidine tanning agent is the good chrome-free tanning agent of a kind of flexibility, the people such as Shi Bi have openly invented a kind of bicyclo oxazolidine tanning agent (extremely preparation method of a kind of bicyclo oxazolidine tanning agent, 2009, publication number: CN101367773A), this tanning agent is prepared from by methylol amine, polyhydroxy-alcohol and fatty aldehyde, can reach chrome-tanned shrinkage temperature with vegetable tanning agent combination tanned leather.But this tanning agent is still kept away the problem of unavoidable leather goods Free Aldehyde base.For this reason, Li Yao etc. have studied organophosphorated salt, and as fur tanning agent, (organic phosphonium salt tanning rabbit Performance Ratio, [J] leather and chemical industry, 2011,28 (6): 5-7.), research is found not contain heavy metal ion in organic phosphonium salt tanning agent tanning waste liquid, be easy to reach sewage discharge index, and the higher flexibility of finished product shrinkage temperature is better after processing.But when this tanning agent tanning fur, need be oxidized, thereby make the impaired fleece that causes of hair scale sheet micro-rubescent, glossiness declines.Therefore, a kind of tanning agent that does not produce free aldehyde and have a better process hides effect is urgently developed.
Organic tanning agent is one of study hotspot, wherein isocyanic ester and the purposes as tanning agent thereof have been studied and have been gained public acceptance, as " with isocyanic ester tanning " (German) the 1st and 2 parts at US-A 2 923 594 " process for tanning ", US-A 4 413 997 " based on the tanning agent of vulcabond " and H. Tr ubel, leather (Das Leder), all statements to some extent in 1977, the 150 pages of ff and 181 pages of ff.
But these compounds are because having the characteristic of toxicity, high-vapor-pressure and low water solubility, and cannot in conventional tanning equipment, use.What in addition, the isocyanic ester in the aqueous solution can be very fast pass through, and intermediate carboxylamine and amine form the polyureas that there is no tanning function.Therefore, can utilize the temporary blocked isocyanate of blocking group functional group, effectively to bring into play the tanning effect of isocyanide ester.
Preparing formamyl Sulfonates tanning agent based on isocyanic ester is one of improved route, and this type of tanning agent can not only effectively be brought into play tanning effect, in process hides process, only discharges neutral salt simultaneously, does not produce heavy metal and free aldehyde, has ecological free of contamination feature.EP-A 0 690 135 is by obtaining having under water surrounding again the tanning agent based on isocyanic ester of inertia with bisulfite reaction after isocyanide ester is reacted with Aethoxy Sklerol.But the isocyanic ester tanning agent before sulfonate modified adopts single solvent and catalyst-free preparation in this patent, have that cost is high, synthesis step mainly with and the high defect of by-products content.Because single solvent must preferably not suppress the solvent of viscosity, this kind solvent price general charged is high, and needs extra synthesis step.Under catalyst-free condition, prepare, the reaction times is longer, and side reaction is more.
EP-A-1647563 has announced and has comprised that at least one contains the compound of the alcoxylates of carbamyl sulfonate ester group and at least one alcohol.These chemicals have good tanning effect.But its compound (as 30 DEG C-40 DEG C) under intensification environment can experience one be separated, and is irreversible.Therefore, its compound is unfavorable for storing, and needs extra storage cost in commercial use.
Under this background, a kind of technique is simple, cost is low, effect is good and the method for the fur tanning agent of eco-friendly preparation based on isocyanic ester is urgently developed.
Summary of the invention
One of object of the present invention is the deficiency for existing fur tanning agent based on isocyanic ester and preparation method thereof, by improving synthetic technology and preparation technology, provide a kind of fur tanning agent based on isocyanic ester and the preparation method that a kind of technique is simple, cost is low and effect is good thereof:
By molar weight part, first 1 part of aliphatic dialcohol or polyether glycol are dissolved in organic solvent, then add 2-4 part vulcabond to react with alcoholic extract hydroxyl group, under being 0-100 DEG C and catalyzer condition, temperature reacts, and the reaction times is 1-10 hour.Under reduced pressure, organic solvent is removed in evaporation, obtains the not tanning agent of end-blocking of vulcabond.Above-mentioned tanning agent is dissolved in the water, and adding molar weight part is the hydrosulphite of vulcabond 2-4 part, under normal temperature, reacts 2-12 hour, obtains the tanning agent solution of hydrosulphite protection, solution clear.
Organic solvent described in preparation process is acetone, tetrahydrofuran (THF), ethyl acetate, butylacetate, benzene, the above any two kinds of mixed solvents of toluene, is preferably the mixed solvent that toluene and ethyl acetate volume ratio are 1:1.Mixed solvent select the single solvent that does not suppress viscosity that can avoid alternative costs high, and omitted extra synthesis step and saved cost.
The carbonatoms of aliphatic dialcohol described in preparation process is preferably 1-18, and polyether glycol carbonatoms is preferably 1-50.Adopt the few polyether glycol of backbone c atoms number, as polyoxyethylene glycol, the tanning agent molecular weight obtaining, is applicable to tanning materials with hide glue fibril fur closely, as beaver rabbit skin; And the large tanning agent of molecular weight is because of poor permeability, is not suitable for tanning materials with hide glue fibril fur closely, and is applicable to the loose fur of tanning materials with hide glue fibril, as family's rabbit.Utilize aliphatic dialcohol and the polyether glycol of preferred carbonatoms to prepare the fur tanning agent as described in claim 1-10, can meet the tanning of and fur that materials with hide glue fibril loose tight to materials with hide glue fibril simultaneously.Tanning agent taking aliphatic dialcohol as main chain has harder chain structure than the tanning agent taking Aethoxy Sklerol as main chain, and the leather of institute's tanning also has higher shrinkage temperature.But aliphatic dialcohol has hydrophobicity, between materials with hide glue fibril, tend to shrink, and Aethoxy Sklerol is hydrophilic, is difficult for shrinking.Therefore the carbonatoms of preferred fat glycol will lack (<18), and the carbonatoms of preferred, polyethers alcohol can reach 50.
Described catalyzer is organic tin catalyzer, comprises dibutyl tin laurate, maleic anhydride dibutyl tin, dibutyltin diacetate, dilauryl mercaptan dibutyl tin etc., is preferably dibutyl tin laurate.Add catalyzer and be conducive to accelerated reaction process, the catalytic condition transformation efficiency of lower 2 hours can reach and not add the catalyzer transformation efficiency of 10 hours; Under catalytic condition, higher temperature of reaction (>60 DEG C) is conducive to further Reaction time shorten, and does not have the appearance of by product; Under catalyst-free condition, higher temperature of reaction (>60 DEG C) easily produces by product.This tanning agent is to be prepared from by aliphatic dialcohol or polyether glycol, vulcabond and hydrosulphite, and outward appearance is shallow white clarification thick liquid.First this tanning agent utilizes diisocyanate molecules, under catalytic condition He in mixing solutions, aliphatic dialcohol or polyether glycol are carried out to two ends sealed, obtains the performed polymer of highly selective and high conversion; Then protect with the isocyanate groups at bisulfite salt pair performed polymer two ends, and improve the water-soluble of tanning agent.The molecular size range of this tanning agent is controlled in building-up process, to be applicable to the different fur of fibrous texture, and better infiltration crosslinked combination between materials with hide glue fibril.This tanning agent can effectively be penetrated between collagen in tannery, heating up and carrying hydrosulphite under alkali condition and decompose, thereby tanning agent molecule again exposed isocyanate groups reacts with the amino on tropocollagen molecule, and crosslinked collagen is to reach the object of tanning.Whole process only has the release of neutral salt, does not produce heavy metal ion and free aldehyde, has simplified the purifying treatment program of follow-up discharge, very friendly and cheap to environment.The tanning of very applicable fur, particularly light rabbit.
Another object of the present invention is to provide the fur tanning agent based on isocyanic ester of preparing under this method.This tanning agent is prepared from by aliphatic dialcohol or polyether glycol, vulcabond and hydrosulphite, and before hydrosulphite end-blocking, tanning agent chemical structure of general formula is (1) or (2):
（1）
（2）
m1=1-18；m2=1-50.
Described aliphatic dialcohol and polyether glycol are respectively (3) and (4):
（3）
（4）
Vulcabond OCN-R-NCO is: hexamethylene diisocyanate (HDI); Isoflurane chalcone diisocyanate (IPDI); Methylene phenylene diisocyanate (TDI); Ditan-4 ' 4-vulcabond (MDI); PPDI (PPDI); 1,5-naphthalene diisocyanate (NDI); Between stupid two methylene vulcabond (XDI); Dimethyl diphenyl vulcabond (TODI);
After hydrosulphite end-blocking, the chemical structure of general formula of tanning agent is (5) or (6):
（5）
（6）?
Wherein R
1for Na or K
After hydrosulphite end-blocking, in tanning agent water soluble, outward appearance is shallow white transparent liquid, under Elevated Temperature Conditions, is hydrolyzable, discharges hydrosulphite, by out exposed the isocyanate groups of protection.
This tanning agent can be for the tanning of the tanning of all kinds of furs, particularly light fur.
Tool of the present invention has the following advantages:
1. the preparation method of the fur tanning agent based on isocyanic ester provided by the invention, preparation technology is simple, mild condition, by introducing catalyzer and mixed organic solvents, can avoid the high single solvent that does not suppress viscosity of alternative costs, control the viscosity of polymerization system, omitted again extra synthesis step and saved cost, can also control level of response simultaneously.Organic tin catalyzer can increase reactive behavior and the selectivity of aliphatic dialcohol and polyether glycol on the one hand, can improve on the other hand reaction efficiency and shorten reaction duration.The organic solvent mixing by a certain percentage can ensure that reaction system viscosity under higher polymerization temperature is unlikely excessive, can form hydrogen bond with hydroxyl again and produce shielding effect, is conducive to that preparation process is gentleer carries out, and controllability is stronger, and the dispersiveness of product is better.Therefore operability is stronger, has very large market competition advantage.
2. the molecular weight of the fur tanning agent based on isocyanic ester provided by the invention is controlled; after hydrosulphite protection, can be penetrated between collagen controlled and uniformly; after carrying alkali through heating up, slough hydrosulphite, produce tanning effect thereby can be cross-linked equably collagen.Compared with existing like product preparation method, preparation method's sintetics provided by the invention, because its reaction is tending towards completely, occurs without side reaction, and solid content and purity are higher, and stability is better.Preparation process is lower to the requirement of temperature, and reaction conditions is gentleer.When tan leather, the soft grain of finished leather is careful.When tanning fur, especially light fur, fleece can keep not yellowing of primary colors, dermatotome shrinkage temperature >75 DEG C, tearing toughness is high.Tanning agent provided by the invention is more suitable for the processing of fur product, has the advantage of producing ecological fur.
3. the fur tanning agent based on isocyanic ester of preparing due to the present invention only discharges hydrosulphite in tannery, can not produce the pollution of heavy metal and free aldehyde, fur goods also can not produce and threaten human health, can meet the export requirement of fur goods.
Brief description of the drawings
The infrared spectrogram of the fur tanning agent based on isocyanic ester that accompanying drawing 1 is prepared for embodiment 1.
Accompanying drawing 2 is the tanning schematic diagram of the fur tanning agent application example 1 based on isocyanic ester of preparation in embodiment 1.
the concrete example of implementing
Further describe invention below in conjunction with specific examples.Authority described in the invention comprises following instance but is not only confined to following instance, and any content relevant with the present invention is all within protection of usage right scope of the present invention.Be necessary to be pointed out that at this present embodiment is only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can be according to interior same make some nonessential improvement and adjustment of the invention described above.
Embodiment 1
0.05 mol polyoxyethylene glycol (Mn=400) is dissolved in the toluene and ethyl acetate that 80 mL mix, and then adds 0.11 mol IPDI and 1-2 to drip dibutyltin dilaurate catalyst, reacts 3 h at 40 DEG C.Reaction finishes rear vacuum rotary steam toluene and ethyl acetate solvent is steamed, and obtains intermediate product, and is dissolved in ethanolic soln.The aqueous solution of sodium bisulfite that contains 0.11 mol added in above-mentioned ethanolic soln, 5 DEG C of isothermal reactions 2 hours.Again revolve to steam and remove ethanol, obtain the aqueous solution of target tanning agent product.
Embodiment 2
0.05 mol propylene glycol is dissolved in the acetone and toluene that 80 mL mix, and then adds 0.11 mol MDI and 1-2 to drip dibutyltin dilaurate catalyst, reacts 3 h at 40 DEG C.Reaction finishes rear vacuum rotary steam acetone and toluene solvant is steamed, and obtains intermediate product, and is dissolved in ethanolic soln.The aqueous solution of sodium bisulfite that contains 0.11 mol added in above-mentioned ethanolic soln, 5 DEG C of isothermal reactions 2 hours.Again revolve to steam and remove ethanol, obtain the aqueous solution of target tanning agent product.
Embodiment 3
0.05 mol polyoxyethylene glycol (Mn=1000) is dissolved in 80 mL tetrahydrofuran solvents, then adds 0.11 mol HDI and 1-2 to drip dibutyltin dilaurate catalyst, reacts 3 h at 40 DEG C.Reaction finishes rear vacuum rotary steam tetrahydrofuran solvent is steamed, and obtains intermediate product, and is dissolved in ethanolic soln.The bisulfite aqueous solutions of potassium that contains 0.11 mol added in above-mentioned ethanolic soln, 5 DEG C of isothermal reactions 2 hours.Again revolve to steam and remove ethanol, obtain the aqueous solution of target tanning agent product.
Embodiment 4
0.05 mol ethylene glycol is dissolved in 80 mL toluene, then adds 0.11 mol TDI and 1-2 to drip dibutyltin dilaurate catalyst, reacts 3 h at 40 DEG C.Reaction finishes rear vacuum rotary steam toluene solvant is steamed, and obtains intermediate product, and is dissolved in ethanolic soln.The aqueous solution of sodium bisulfite that contains 0.11 mol added in above-mentioned ethanolic soln, 5 DEG C of isothermal reactions 2 hours.Again revolve to steam and remove ethanol, obtain the aqueous solution of target tanning agent product.
The independent tanning rabbit of the fur tanning agent of application example 1 based on isocyanic ester
Raw material: pickling rabbit (adopting liquor ratio 20:1)
Disacidify: water 2L, salt 50g/L, normal temperature turns 5min; Sodium bicarbonate 2g/L, adds after ten times of water dissolution at twice, adjusts pH to 6 left and right.
Tanning: be warming up to 30 DEG C, the ecological fur tanning agent of 8g/L (water dissolution) turns 5min/60min × 4
Carry alkali: be warming up to 35 DEG C, magnesium oxide 3g/L, turns 5min/30min × N, (each 0.5g/L, repeats this step), adjusts pH to 8 left and right, stops drum and spends the night.Turn 30min next day, washes out skin, takes horse.
Measure shrinkage temperature and the physical strength of dermatotome.
After the fur tanning agent tanning based on isocyanic ester of preparing through employing present method, fleece is pure white submissive, and shrinkage temperature reaches 76 DEG C.The physical and mechanical properties of dermatotome is stronger, and the tensile strength recording is 17.9MPa, and tear strength is 35.49N/mm.Compared with the fur tanning agent of routine based on isocyanic ester, its physical strength is more excellent, and wear resistance is strong, and the fur goods making is prolonged endurable.
The independent tanning sheepskin of the fur tanning agent of application example 2 based on isocyanic ester
Raw material: pickling sheepskin (following materials are taking the weight of pickling sheepskin as benchmark)
Disacidify: water 50%, salt 8%, normal temperature turns 10min; Soda ash 2%, turns 10min; Sodium bicarbonate 2%, adjusts pH to 6 left and right.
Tanning: ecological fur tanning agent 8%(water dissolution), turn 30min, 5min/30min × 4
Carry alkali: be warming up to 35 DEG C, soda ash 2%, adds at twice, every minor tick 15min; Then turn 5min/30min × N, (each 0.2%, repeat this step), adjusts pH to 8 left and right, stops drum and spends the night.After the tanning of this tanning agent, become grain careful, leather body softness, shrinkage temperature reaches 78 DEG C.
Claims (10)
1. the method for the fur tanning agent of preparation based on isocyanic ester, it is characterized in that: be that aliphatic dialcohol or polyether glycol and vulcabond are dissolved in to organic solvent, then under organic tin catalyzer existence condition, carry out catalyzed reaction, get rid of after the solvent in reaction system, obtain the tanning agent based on isocyanic ester.
2. preparation method according to claim 1, is characterized in that: described organic tin catalyzer comprises dibutyl tin laurate, maleic anhydride dibutyl tin, dibutyltin diacetate, dilauryl mercaptan dibutyl tin etc.; Be preferably dibutyl tin laurate.
3. preparation method according to claim 1, is characterized in that: the functionality of described vulcabond is (2-4), and molecular weight is (being less than 400g/mol); Be preferably hexamethylene diisocyanate (HDI); Isoflurane chalcone diisocyanate (IPDI); Methylene phenylene diisocyanate (TDI); Ditan-4 ' 4-vulcabond (MDI); PPDI (PPDI); 1,5-naphthalene diisocyanate (NDI); Between stupid two methylene vulcabond (XDI); Dimethyl diphenyl vulcabond (TODI).
4. preparation method according to claim 1, is characterized in that: the time of catalyzed reaction is 1-10 hour, and temperature is 0-100 degree Celsius.
5. preparation method according to claim 1, is characterized in that: aliphatic dialcohol carbonatoms is 1-18, and polyether glycol carbonatoms is 1-50.
6. according to the preparation method described in the arbitrary claim of claim 1 to 5, it is characterized in that: also comprise the described tanning agent based on isocyanic ester is carried out to termination process, described termination process is that the tanning agent based on isocyanic ester is dissolved in water, add hydrosulphite, under normal temperature, react at least 2 hours, obtain the tanning agent based on isocyanic ester of end-blocking; Preferably, add after hydrosulphite, under normal temperature, react 2-12 hour.
7. preparation method according to claim 6, it is characterized in that: by molar weight part, aliphatic dialcohol or polyether glycol are 1 part, vulcabond is 2-4 part, hydrosulphite molar weight is 2-4 part of vulcabond, and described hydrosulphite is that described hydrosulphite is sodium bisulfite or Potassium hydrogen sulfite.
8. preparation method according to claim 7, is characterized in that: described organic solvent is at least two kinds of mixed solvents in acetone, tetrahydrofuran (THF), ethyl acetate, butylacetate, benzene, toluene; Be preferably the mixed solvent that toluene and ethyl acetate volume ratio are 1:1.
9. the fur tanning agent based on isocyanic ester that adopts claim 1-5 method gained, is characterized in that: have following general formula:
or
in formula: m1 is 1-18, m2 is 1-50.
10. the fur tanning agent based on isocyanic ester that adopts claim 6-8 method to prepare, is characterized in that: have following general formula:
or
in formula: m1 is 1-18, m2 is 1-50, and R1 is Na or K.
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| CN105803131A (en) * | 2014-12-29 | 2016-07-27 | 焦作隆丰皮草企业有限公司 | Tanning method of leather |
| CN109735668A (en) * | 2019-03-01 | 2019-05-10 | 四川大学 | A kind of tibet lamp process for tanning of the Chrome-free without aldehyde |
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| 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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