CN104762423A - Preparation and application of carboxyl-containing carbamyl sulfonate chrome tanning assistant - Google Patents
Preparation and application of carboxyl-containing carbamyl sulfonate chrome tanning assistant Download PDFInfo
- Publication number
- CN104762423A CN104762423A CN201510134109.9A CN201510134109A CN104762423A CN 104762423 A CN104762423 A CN 104762423A CN 201510134109 A CN201510134109 A CN 201510134109A CN 104762423 A CN104762423 A CN 104762423A
- Authority
- CN
- China
- Prior art keywords
- chrome tanning
- carbamyl
- sulfonates
- carboxylic
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 title claims abstract description 13
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 title abstract 3
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000005554 pickling Methods 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002671 adjuvant Substances 0.000 claims description 50
- 150000003871 sulfonates Chemical class 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000006210 lotion Substances 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 10
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 238000010790 dilution Methods 0.000 claims description 8
- 239000012895 dilution Substances 0.000 claims description 8
- 239000008393 encapsulating agent Substances 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000013589 supplement Substances 0.000 claims description 6
- 229940095064 tartrate Drugs 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 4
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Chemical group 0.000 claims description 4
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical group [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- DQFBYFPFKXHELB-UHFFFAOYSA-N Chalcone Natural products C=1C=CC=CC=1C(=O)C=CC1=CC=CC=C1 DQFBYFPFKXHELB-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- 235000005513 chalcones Nutrition 0.000 claims description 2
- 229960002725 isoflurane Drugs 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 abstract description 5
- 102000008186 Collagen Human genes 0.000 abstract description 3
- 108010035532 Collagen Proteins 0.000 abstract description 3
- 229920001436 collagen Polymers 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 abstract 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 1
- 235000011941 Tilia x europaea Nutrition 0.000 abstract 1
- 125000005442 diisocyanate group Chemical group 0.000 abstract 1
- 239000004571 lime Substances 0.000 abstract 1
- 238000002791 soaking Methods 0.000 abstract 1
- 239000010985 leather Substances 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 8
- 150000001299 aldehydes Chemical class 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 239000002699 waste material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 241000502561 Acacia irrorata Species 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- NIGWMJHCCYYCSF-UHFFFAOYSA-N Fenclonine Chemical compound OC(=O)C(N)CC1=CC=C(Cl)C=C1 NIGWMJHCCYYCSF-UHFFFAOYSA-N 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- -1 carbamyl Sulfonates Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
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
- C14C3/28—Multi-step processes
-
- 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
-
- 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
- C14C3/04—Mineral tanning
-
- 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
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
The invention relates to preparation and application of a carboxyl-containing carbamyl sulfonate chrome tanning assistant. The preparation method comprises the following steps: reacting carboxyl dibasic alcohol with diisocyanate, and closing free NCO with sulfite to obtain the carboxyl-containing carbamyl sulfonate chrome tanning assistant. The application method comprises the following steps: pretanning, pickling and finally chrome tanning. When being used for treating pelt softened by normal lime soaking, the chrome tanning assistant can avoid the use of neutral salts in the subsequent pickling and chrome tanning procedures, lower the discharge of chloride ions in wastewater and greatly enhance the absorptivity of the collagen for the chrome tanning agent.
Description
Technical field
The present invention relates to chrome tanning adjuvant technical field, be specifically related to a kind of preparations and applicatio of carboxylic carbamyl Sulfonates chrome tanning adjuvant.
Background technology
In Chrome Tanning Process, collegen filament are mainly combined with chromic salts coordination by side chain carboxyl group, to produce tanning effect.Therefore, start with from the process of tanning, for improving collegen filament to the binding ability of chromic salts, one of effective way is exactly utilize chrome tanning adjuvant to carry out modification to collagen, and namely its object is the effective carboxyl-content increasing collegen filament.Such as: Qiang Xihuai (Qiang Xihuai, Li Wenxin, Yu Congzheng, Deng. the research [J] of oxoethanoic acid auxiliary tanning agent application art. Chinese leather, 2003,31 (7): 26-30.) etc. people adds oxoethanoic acid when pickling, finds that more conventional pickling is compared salt consumption and can be reduced about 25%, from blue skin state, during tanning, chromium powder consumption can reduce 40%-50%; Fan Haojun (Fan Haojun, Fan Chaoyun. the development [J] of Novel Aldehydic Acid Tanning Agent. Chinese leather, 1998,27 (2): 11-13) etc. people has carried out modification with containing the organic acid of-H and formaldehyde to glutaraldehyde, obtains a kind of novel aldehyde acid tanning agent; Li Guoying (Li Guoying, Luo Yi. high-absorption chrome tanning mechanism and Technology (III) [J] thereof. Chinese leather, 2000,29 (23): 23-26) etc. people have developed a kind of novel LL-1 aldehydic acid auxiliary tanning agent, it does raw material with aldehyde and ester, the final product under base catalysis condition; White clouds Xiang (white clouds Xiang, Wang Hongru. the structure of half aldehyde type chrome tanning adjuvant SYY and applied research [J]. Chinese leather, 2002,20 (4): 12-17) etc. people adopts aldehyde, ammonia and acid to do raw material, under weakly acidic condition, have developed a kind of multi-functional SYY aldehydic acid auxiliary tanning agent, this material is the compound with multiple aldehyde radical and carboxyl, for in chrome tanning process, the utilization ratio of chromium reaches more than 95%, and in waste tanning liquor, the concentration of chromium sesquioxide is lower than 0.3g/L; Duan Zhenji (Duan Zhenji. the research and apply [J] of auxiliary tanning agent. leather science and engineering, 1992,2 (4): 7-19) etc. people have developed a kind of excellent property, representational polymer chrome tanning adjuvant PCPA, adopt common process, in waste liquid, chromic oxide content can be down to 0.1g/L, and chromium absorptivity can reach 95%.
But just current research, report about chrome tanning adjuvant is the serial reaction based on aldehyde and acid mostly, owing to being that raw material reacts with aldehyde, finished leather Free Aldehyde class content is raised, and various countries and relevant industries do strict restriction to finished leather Free-formaldehyde content.Therefore, very necessary to the research of no-aldehyde chrome tanning adjuvant, and significant especially to the exploitation of salt-free pickling chrome tanning adjuvant.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparations and applicatio of carboxylic carbamyl Sulfonates chrome tanning adjuvant, in pickling process, avoiding the use of neutral salt, improve the specific absorption of chrome tanning agent.
In order to achieve the above object, the technical solution adopted in the present invention is:
A preparation method for carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) dibasic alcohol of 27-36 part band carboxyl is dissolved in first solvent of 80-120 part, be added drop-wise to the speed of 1/s in 1h in the there-necked flask of the band stirring filling 75-144 part vulcabond, temperature be 75-80 DEG C, under the condition of condensing reflux, reaction 3-5h;
2) massfraction of NCO group in above-mentioned reactant is measured by Di-n-Butyl Amine method, until NCO group massfraction remains unchanged close to theoretical value; Then reactant is cooled to 20-30 DEG C, adds and neutralize with the alkaline matter X of carboxyl equimolar amount;
3) be the aqueous solution of the encapsulant A of 30% or the massfraction of 57-76 part by the massfraction of 60-80 part second solvent and 62.4-83.2 part be added to there-necked flask after the aqueous solution of the encapsulant B of 15%; temperature 20-30 DEG C; reaction 2-3h; discharging obtains carboxylic carbamyl Sulfonates chrome tanning adjuvant; the thick white shape liquid of the effective content of carboxylic carbamyl Sulfonates chrome tanning adjuvant to be 33%-39%, pH be 6.0-6.5, described number is mass fraction.
The dibasic alcohol of described band carboxyl is tartrate.
The first described solvent, the second solvent are DMF (DMF).
Described vulcabond be in tolylene diisocyanate (TDI), isoflurane chalcone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), 4,4-dicyclohexyl methane diisocyanates (HMDI) or hexamethylene diisocyanate (HDI) wherein one or more.
Described alkaline matter X is triethylamine.
Described encapsulant A is sodium bisulfite.
Described encapsulant B is Sodium Pyrosulfite.
The application of described carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) pretan: the liming skin after deliming, softening washing is dropped into rotary drum, adds the water of liming tare weight amount 100% and the carboxylic carbamyl Sulfonates chrome tanning adjuvant of 4-6%, 20-25 DEG C, rotate 1-2h; Use the alkaline matter Y after the dilution of 10 times of water in 1h by pH regulator to 8.5-9.0, be rotated further 1-2h;
2) pickling: in step 1) in body lotion gradation add the acidic substance after with 10 times of water dilutions, in 1h, regulate body lotion pH at 2.5-3.0, be rotated further 1-2h at 20-25 DEG C;
3) chrome tanning: basicity 33% chromium powder adding liming tare weight amount 5-6%, 20-25 DEG C turns 2h; Use the sodium bicarbonate of liming tare weight amount 1.8-2.2% and be mixed with concentration be 10% the aqueous solution divide 6 times to add, every minor tick 20min, regulates pH to 3.8-4.0, then rotates 1h, supplements 40 DEG C of hot water of liming tare weight amount 150%, turns 2h; Stop drum to spend the night, next day turns 0.5h, goes out drum, takes horse and leaves standstill;
Described liming skin is sheepskin, ox-hide or pigskin;
Described alkaline matter Y is sodium bicarbonate or soda ash;
Described acidic substance are formic acid or sulfuric acid.
The present invention has the following advantages:
The present invention adopts with the dibasic alcohol of carboxyl and di-isocyanate reaction, free NCO group is closed afterwards, obtain the chrome tanning adjuvant of carboxylic carbamyl Sulfonates with sulphite.Pelt after using chrome tanning adjuvant of the present invention to soften normal liming processes, and can remove the use of neutral salt in follow-up pickling chrome tanning process from, reduces the discharge of chlorion in waste water, more significantly can improve the absorption of collagen to chrome tanning agent.The shrinkage temperature of the wet blue leather prepared thus can reach more than 98 DEG C, chrome uptake rate up to more than 90%, Cr in waste liquid
2o
3content be down to below 0.6g/L.Therefore, this auxiliary agent is a kind of excellent performance and can realizes cleaning the novel chrome tanning adjuvant of chrome tanning process.
Embodiment
Below by embodiment, the present invention is specifically described, is only used to further illustrate the present invention, can not limiting the scope of the invention be interpreted as.
Embodiment one
A preparation method for carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) 27.0g tartrate is dissolved in 80gDMF, is added drop-wise in the there-necked flask that the band that fills 99.9gIPDI stirs with the speed of 1/s, temperature be 80 DEG C, under the condition of condensing reflux, reaction 3h;
2) massfraction of the NCO group in above-mentioned reactant is measured by Di-n-Butyl Amine method, until constant, the massfraction recording NCO group is 10.11%, close to theoretical value 10.96%, then reactant is cooled to 30 DEG C, adds 36.4g triethylamine and neutralize;
3) by the massfraction of 60gDMF and 62.4g be 30% sodium bisulfite aqueous solution after be added to there-necked flask; temperature 30 DEG C; reaction 2h; obtain carboxylic carbamyl Sulfonates chrome tanning adjuvant after discharging, carboxylic carbamyl Sulfonates chrome tanning adjuvant be 37.1%, thick white shape liquid that pH is 6.5.
The application of described carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) pretan: the ox-hide after deliming, softening washing is dropped into rotary drum, adds the water of ox-hide liming tare weight amount 100% and the carboxylic carbamyl Sulfonates chrome tanning adjuvant of 4.5%, 20 DEG C, rotate 1h; Soda ash after using 10 times of water to dilute by pH regulator to 8.5, is rotated further 1h in 1h;
2) pickling: in step 1) in body lotion gradation add the formic acid after with 10 times of water dilutions, in 1h, regulate body lotion pH 2.5, be rotated further 1h at 20 DEG C;
3) chrome tanning: basicity 33% chromium powder adding ox-hide liming tare weight amount 6%, 20 DEG C turn 2h; Use the sodium bicarbonate of ox-hide liming tare weight amount 2.2% and be mixed with concentration be 10% the aqueous solution divide 6 times to add, every minor tick 20min, regulates pH to 4.0, then rotates 1h, supplements 40 DEG C of hot water of ox-hide liming tare weight amount 150%, turns 2h; Stop drum to spend the night, next day turns 0.5h, goes out drum, takes horse and leaves standstill.
The shrinkage temperature that the present embodiment records wet blue leather is 99 DEG C, and chrome uptake rate is 91.2%, waste liquid Cr
2o
3content is 0.53g/L.
Embodiment two
A preparation method for carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) 36.0g tartrate is dissolved in 120gDMF, is added drop-wise in the there-necked flask that the band that fills 50.4gHDI and 52.4gHMDI stirs with the speed of 1/s, temperature be 75 DEG C, under the condition of condensing reflux, reaction 4h;
2) measure the massfraction of the NCO group in above-mentioned reactant by Di-n-Butyl Amine method, the massfraction recording NCO group is 8.21%, close to theoretical value 8.44%, until constant, then reactant is cooled to 20 DEG C, adds 48.5g triethylamine and neutralizes;
3) by the massfraction of 80g DMF and 60.3g be 30% sodium bisulfite aqueous solution after be added to there-necked flask, temperature 20 DEG C, reaction 3h, obtain carboxylic carbamyl Sulfonates chrome tanning adjuvant after discharging, carboxylic carbamyl Sulfonates chrome tanning adjuvant be 34.0%, thick white shape liquid that pH is 6.3;
The application of described carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) pretan: the sheepskin after deliming, softening washing is dropped into rotary drum, adds the water of sheepskin liming tare weight amount 100% and the carboxylic carbamyl Sulfonates chrome tanning adjuvant of 6%, 25 DEG C, rotate 1.5h; Sodium bicarbonate after using 10 times of water to dilute by pH regulator to 8.8, is rotated further 1.5h in 1h;
2) pickling: gradation adds the sulfuric acid after with 10 times of water dilutions in above-mentioned body lotion, regulates body lotion pH 2.8, be rotated further 1.5h at 25 DEG C in 1h;
3) chrome tanning: basicity 33% chromium powder adding sheepskin liming tare weight amount 6%, 25 DEG C turn 2h; Use the sodium bicarbonate of sheepskin liming tare weight amount 2.0% and be mixed with concentration be 10% the aqueous solution divide 6 times to add, every minor tick 20min, regulates pH to 4.0, then rotates 1h, supplements 40 DEG C of hot water of sheepskin liming tare weight amount 150%, turns 2h; Stop drum to spend the night, next day turns 0.5h, goes out drum, takes horse and leaves standstill.
The shrinkage temperature that the present embodiment records wet blue leather is 98 DEG C, and chrome uptake rate is 90.4%, waste liquid Cr
2o
3content is 0.58g/L.
Embodiment three
A preparation method for carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) 30.0g tartrate is dissolved in 100gDMF, is added drop-wise in the there-necked flask that the band that fills 87.0gTDI stirs with the speed of 1/s, temperature be 75 DEG C, under the condition of condensing reflux, reaction 4h;
2) measure the mass content of NCO group in above-mentioned reactant by Di-n-Butyl Amine method, the massfraction recording NCO group is 11.49%, close to theoretical value 11.61%, until constant, then reactant is cooled to 20 DEG C, adds 40.4g triethylamine and neutralizes;
3) by the massfraction of 70gDMF and 57.0g be 30% Sodium Pyrosulfite aqueous solution after be added to there-necked flask, temperature 20 DEG C, reaction 3h, obtain carboxylic carbamyl Sulfonates chrome tanning adjuvant after discharging, carboxylic carbamyl Sulfonates chrome tanning adjuvant be 33.6%, thick white shape liquid that pH is 6.0;
The application of described carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) pretan: the ox-hide after deliming, softening washing is dropped into rotary drum, adds the water of ox-hide liming tare weight amount 100% and the carboxylic carbamyl Sulfonates chrome tanning adjuvant of 4%, 25 DEG C, rotate 2h; Soda ash after using 10 times of water to dilute by pH regulator to 9.0, is rotated further 2h in 1h;
2) pickling: in step 1) in body lotion gradation add the sulfuric acid after with 10 times of water dilutions, in 1h, regulate body lotion pH 3.0, be rotated further 1h at 25 DEG C;
3) chrome tanning: basicity 33% chromium powder adding ox-hide liming tare weight amount 5%, 25 DEG C turn 2h; Use the sodium bicarbonate of ox-hide liming tare weight amount 1.8% and be mixed with concentration be 10% the aqueous solution divide 6 times to add, every minor tick 20min, regulates pH to 3.8, then rotates 1h, supplements 40 DEG C of hot water of ox-hide liming tare weight amount 150%, turns 2h; Stop drum to spend the night, next day turns 0.5h, goes out drum, takes horse and leaves standstill.
The shrinkage temperature that the present embodiment records wet blue leather is 105 DEG C, and chrome uptake rate is 94.9%, waste liquid Cr
2o
3content is 0.26g/L.
Embodiment four
A preparation method for carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) 33.0g tartrate is dissolved in the DMF of 110g, is added drop-wise in the there-necked flask that the band that fills 137.5gMDI stirs with the speed of 1/s, temperature be 80 DEG C, under the condition of condensing reflux, reaction 5h;
2) measure the massfraction of NCO group in above-mentioned reactant by Di-n-Butyl Amine method, the massfraction recording NCO group is 9.72%, close to theoretical value 9.88%, until constant, then reactant is cooled to 25 DEG C, adds 44.4g triethylamine and neutralizes;
3) by the massfraction of 65gDMF and 66.5g be 30% Sodium Pyrosulfite aqueous solution after be added to there-necked flask, temperature 25 DEG C, reaction 2.5h, obtain carboxylic carbamyl Sulfonates chrome tanning adjuvant after discharging, carboxylic carbamyl Sulfonates chrome tanning adjuvant be 38.8%, thick white shape liquid that pH is 6.1;
The application of described carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) pretan: the pigskin after deliming, softening washing is dropped into rotary drum, adds the water of pigskin liming tare weight amount 100% and the carboxylic carbamyl Sulfonates chrome tanning adjuvant of 5%, 20 DEG C, rotate 1.5h; Sodium bicarbonate after using 10 times of water to dilute by pH regulator to 9.0, is rotated further 1.5h in 1h;
2) pickling: in step 1) in body lotion gradation add the formic acid after with 10 times of water dilutions, in 1h, regulate body lotion pH 2.5, be rotated further 2h at 20 DEG C;
3) chrome tanning: basicity 33% chromium powder adding pigskin liming tare weight amount 6%, 20 DEG C turn 2h; Use pigskin liming tare weight amount 2.2% sodium bicarbonate and be mixed with concentration be 10% the aqueous solution divide 6 times to add, every minor tick 20min, regulates pH to 4.0, then rotates 1h, supplements pigskin liming tare weight amount 150%40 DEG C of hot water, turns 2h; Stop drum to spend the night, next day turns 0.5h, goes out drum, takes horse and leaves standstill.
The shrinkage temperature that the present embodiment records wet blue leather is 101 DEG C, and chrome uptake rate is 93.9%, waste liquid Cr
2o
3content is 0.31g/L.
Claims (8)
1. a preparation method for carboxylic carbamyl Sulfonates chrome tanning adjuvant, is characterized in that, comprise the following steps:
1) dibasic alcohol of 27-36 part band carboxyl is dissolved in first solvent of 80-120 part, be added drop-wise to the speed of 1/s in 1h in the there-necked flask of the band stirring filling 75-144 part vulcabond, temperature be 75-80 DEG C, under the condition of condensing reflux, reaction 3-5h;
2) massfraction of NCO group in above-mentioned reactant is measured by Di-n-Butyl Amine method, until the massfraction of NCO group remains unchanged close to theoretical value; Then reactant is cooled to 20-30 DEG C, adds and neutralize with the alkaline matter X of carboxyl equimolar amount;
3) be the aqueous solution of the encapsulant A of 30% or the massfraction of 57-76 part by the massfraction of 60-80 part second solvent and 62.4-83.2 part be added to there-necked flask after the aqueous solution of the encapsulant B of 15%; temperature 20-30 DEG C; reaction 2-3h; discharging obtains carboxylic carbamyl Sulfonates chrome tanning adjuvant; the thick white shape liquid of the effective content of carboxylic carbamyl Sulfonates chrome tanning adjuvant to be 33%-39%, pH be 6.0-6.5, described number is mass fraction.
2. the preparation method of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant according to claim 1, is characterized in that: the dibasic alcohol of described band carboxyl is tartrate.
3. the preparation method of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant according to claim 1, is characterized in that: the first described solvent, the second solvent are DMF (DMF).
4. the preparation method of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant according to claim 1; it is characterized in that: described vulcabond be in tolylene diisocyanate (TDI), isoflurane chalcone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI), 4,4-dicyclohexyl methane diisocyanates (HMDI) or hexamethylene diisocyanate (HDI) wherein one or more.
5. the preparation method of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant according to claim 1, is characterized in that: described alkaline matter X is triethylamine.
6. the preparation method of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant according to claim 1, is characterized in that: described encapsulant A is sodium bisulfite.
7. the preparation method of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant according to claim 1, is characterized in that: described encapsulant B is Sodium Pyrosulfite.
8. the preparation method of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant according to claim 1, is characterized in that: the application of described carboxylic carbamyl Sulfonates chrome tanning adjuvant, comprises the following steps:
1) pretan: the liming skin after deliming, softening washing is dropped into rotary drum, adds the water of liming tare weight amount 100% and the carboxylic carbamyl Sulfonates chrome tanning adjuvant of 4-6%, 20-25 DEG C, rotate 1-2h; Use the alkaline matter Y after the dilution of 10 times of water in 1h by pH regulator to 8.5-9.0, be rotated further 1-2h;
2) pickling: in step 1) in body lotion gradation add the acidic substance after with 10 times of water dilutions, in 1h, regulate body lotion pH at 2.5-3.0, be rotated further 1-2h at 20-25 DEG C;
3) chrome tanning: basicity 33% chromium powder adding liming tare weight amount 5-6%, 20-25 DEG C turns 2h; Use the sodium bicarbonate of liming tare weight amount 1.8-2.2% and be mixed with concentration be 10% the aqueous solution divide 6 times to add, every minor tick 20min, regulates pH to 3.8-4.0, then rotates 1h, supplements 40 DEG C of hot water of liming tare weight amount 150%, turns 2h; Stop drum to spend the night, next day turns 0.5h, goes out drum, takes horse and leaves standstill;
Described liming skin is sheepskin, ox-hide or pigskin;
Described alkaline matter Y is sodium bicarbonate or soda ash;
Described acidic substance are formic acid or sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510134109.9A CN104762423B (en) | 2015-03-25 | 2015-03-25 | The preparation of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510134109.9A CN104762423B (en) | 2015-03-25 | 2015-03-25 | The preparation of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104762423A true CN104762423A (en) | 2015-07-08 |
| CN104762423B CN104762423B (en) | 2016-11-23 |
Family
ID=53644513
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510134109.9A Expired - Fee Related CN104762423B (en) | 2015-03-25 | 2015-03-25 | The preparation of a kind of carboxylic carbamyl Sulfonates chrome tanning adjuvant and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104762423B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105063253A (en) * | 2015-08-10 | 2015-11-18 | 四川大学 | Salt-free high-chrome-absorption chrome tanning method for animal skin and application of salt-free high-chrome-absorption chrome tanning method |
| CN109628662A (en) * | 2018-12-27 | 2019-04-16 | 陕西科技大学 | A kind of preparation and application of modified tannin acid chrome tanning adjuvant |
| CN112552158A (en) * | 2020-12-09 | 2021-03-26 | 南京工业大学 | Preparation and application of high-absorption chrome tanning auxiliary agent containing ketocarboxylic acid structure |
| CN112778133A (en) * | 2021-01-07 | 2021-05-11 | 南京工业大学 | high-pH-value chrome tanning auxiliary agent containing polyfunctional group structure and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7226621B2 (en) * | 2002-07-29 | 2007-06-05 | Annes Participacoes | Formulation and process for making formulation for preservation of animal and vegetable tissues |
| CN101629218A (en) * | 2009-08-12 | 2010-01-20 | 成都凯特有机硅新材料科技有限公司 | Water-soluble self-emulsifying coupled modified silicone oil composite and application in pickling, tanning and dyeing of leather making |
-
2015
- 2015-03-25 CN CN201510134109.9A patent/CN104762423B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7226621B2 (en) * | 2002-07-29 | 2007-06-05 | Annes Participacoes | Formulation and process for making formulation for preservation of animal and vegetable tissues |
| CN101629218A (en) * | 2009-08-12 | 2010-01-20 | 成都凯特有机硅新材料科技有限公司 | Water-soluble self-emulsifying coupled modified silicone oil composite and application in pickling, tanning and dyeing of leather making |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105063253A (en) * | 2015-08-10 | 2015-11-18 | 四川大学 | Salt-free high-chrome-absorption chrome tanning method for animal skin and application of salt-free high-chrome-absorption chrome tanning method |
| CN109628662A (en) * | 2018-12-27 | 2019-04-16 | 陕西科技大学 | A kind of preparation and application of modified tannin acid chrome tanning adjuvant |
| CN109628662B (en) * | 2018-12-27 | 2021-08-03 | 陕西科技大学 | Preparation and application of modified tannic acid chromium tanning auxiliary |
| CN112552158A (en) * | 2020-12-09 | 2021-03-26 | 南京工业大学 | Preparation and application of high-absorption chrome tanning auxiliary agent containing ketocarboxylic acid structure |
| CN112552158B (en) * | 2020-12-09 | 2023-05-19 | 南京工业大学 | Preparation and application of high-absorption chrome tanning auxiliary agent containing ketocarboxylic acid structure |
| CN112778133A (en) * | 2021-01-07 | 2021-05-11 | 南京工业大学 | high-pH-value chrome tanning auxiliary agent containing polyfunctional group structure and preparation method and application thereof |
| CN112778133B (en) * | 2021-01-07 | 2023-06-16 | 南京工业大学 | high-pH chrome tanning auxiliary agent containing multifunctional structure, and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104762423B (en) | 2016-11-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104762423A (en) | Preparation and application of carboxyl-containing carbamyl sulfonate chrome tanning assistant | |
| CN100381582C (en) | Method for ash-free and no-sulfurizing alkaline liming treatment for making pigskin leather | |
| CN101117648B (en) | Novel process for leather retanning | |
| CN101265505A (en) | Ashless and alkali sulfide free depilation liming treatment method for preparing leather from raw sheep skin | |
| CN101265506B (en) | Ashless and alkali sulfide free depilation liming treatment method for preparing leather from goatskin | |
| CN100355907C (en) | Composition of tanning agent containing modified tara mimosa extract, and bating method without chrome | |
| CN101260443A (en) | Ashless and alkali sulfide free liming treatment method for preparing leather from cowskin | |
| CN107988443A (en) | A kind of method and its application method that few chrome tanning adjuvant is prepared using leather leftover | |
| CN114196791A (en) | Epoxy-terminated hyperbranched polymer tanning agent and tanning method | |
| CN102206717A (en) | Method for preparing zirconium-aluminum multi-metal tanning liquor | |
| CN107828924B (en) | Preparation method of environment-friendly resin tanning agent | |
| CN111961173B (en) | Preparation method of amino resin retanning agent, retanning agent and application thereof | |
| CN101671750B (en) | Tanning method of less-bath pickled high-absorption chromium salt | |
| CN104087688A (en) | Modified rice dialdehyde starch retanning filler for leather and preparation method of filler | |
| CN109628662B (en) | Preparation and application of modified tannic acid chromium tanning auxiliary | |
| CN1492057A (en) | Tanning method for fish skin and after finishing method for fish skin leather | |
| CN100537782C (en) | A kind of ecological bating method | |
| CN104726622B (en) | Salt-free pickling two-step chrome tanning process | |
| US3519378A (en) | Process for the rapid tanning of medium-weight and heavy leather | |
| JPH0488100A (en) | Tanning agent and production thereof | |
| CN104561396A (en) | Tanning method by using improved-structure chromium-free retanning agent | |
| CN100497660C (en) | Multifunctional tanning agent and preparation method thereof | |
| US3253879A (en) | Chrome-syntan pretannage followed by dry chrome tannage | |
| CN109880942B (en) | Acid-free chrome tanning agent | |
| CN106350619B (en) | The method of few chromium combination tanning after a kind of immersion of complex enzyme formulation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20161123 |