CN106609308A - Preparation method of environment-friendly chromium-free tanning agent - Google Patents
Preparation method of environment-friendly chromium-free tanning agent Download PDFInfo
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- CN106609308A CN106609308A CN201611211671.8A CN201611211671A CN106609308A CN 106609308 A CN106609308 A CN 106609308A CN 201611211671 A CN201611211671 A CN 201611211671A CN 106609308 A CN106609308 A CN 106609308A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000011787 zinc oxide Substances 0.000 claims abstract description 23
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 12
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical class [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012530 fluid Substances 0.000 claims description 9
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 150000002689 maleic acids Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 229910000077 silane Inorganic materials 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 235000010265 sodium sulphite Nutrition 0.000 claims description 6
- 239000007921 spray Substances 0.000 claims description 6
- 239000003643 water by type Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 19
- 238000000034 method Methods 0.000 abstract description 18
- 239000010985 leather Substances 0.000 abstract description 17
- 239000011651 chromium Substances 0.000 abstract description 12
- 229910052804 chromium Inorganic materials 0.000 abstract description 10
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- 239000003822 epoxy resin Substances 0.000 abstract description 2
- 230000003993 interaction Effects 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 150000007524 organic acids Chemical class 0.000 abstract description 2
- 229920000647 polyepoxide Polymers 0.000 abstract description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- 235000014692 zinc oxide Nutrition 0.000 description 17
- 230000008569 process Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 5
- 241000283898 Ovis Species 0.000 description 4
- 241001494479 Pecora Species 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RNWHGQJWIACOKP-UHFFFAOYSA-N zinc;oxygen(2-) Chemical class [O-2].[Zn+2] RNWHGQJWIACOKP-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 241000282342 Martes americana Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 210000001835 viscera Anatomy 0.000 description 1
- 238000010792 warming Methods 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
- C14C3/04—Mineral tanning
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- 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
- C14C3/22—Chemical tanning by organic agents using polymerisation products
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to a preparation method of an environment-friendly chromium-free tanning agent, and belongs to the technical field of leather tanning agents. According to the preparation method of the environment-friendly chromium-free tanning agent, nano-zinc oxide is modified through a silane coupling agent, so that the dispersing performance of the nano-zinc oxide is improved, and meanwhile, interaction between the nano-zinc oxide and a matrix is enhanced; then a silicon-aluminum complex is modified through polybasic organic acid, so that the water tolerance and hydrothermal stability of the silicon-aluminum complex are improved; and the silicon-aluminum complex and the modified nano-zinc oxide are matched and dispersed in water-borne epoxy resin to replace a chromium tanning agent, and the environment-friendly chromium-free tanning agent is prepared. The environment-friendly chromium-free tanning agent prepared through the method is nontoxic and free of pollution, crust leather is white, soft, fine in grain surface and good in extensibility, and the preparation method has broad application prospects.
Description
Technical field
The present invention relates to a kind of preparation method of environmentally friendly chrome-free tanning agent, belongs to leather retanning agent technical field.
Background technology
From initial animal skin apron, marten coat till now, leather have been passed by thousands of years along with people, and from most
First coarse warming dress ornament, fine luxurious jewelry till now then represent the development and progress of leather industry.China makees
Manufacturing center and trade centre for current World Leather Industry, leather fur and the nearly trillion yuan of manufacturing total industrial output value,
Local economic development is driven, has become an important force of China's Foreign Trade.
With the expansion of Leather Industry process scale, while bringing economic interests, the problem of environmental pollution is also brought.
The waste water produced in leather making process, garbage etc., cause different degrees of harm to environment, wherein widely people
It is well known that pollution of chromium.
In the process hides course of processing, tanning is a most key step, is the qualitative change process for making rawhide be changed into leather, and tanning agent
It is then the most important thing.The excellent hydrothermal stability of chrome leather, mechanical strength, dyeability, soft and full etc. so that chrome tanning
It is the most widely used process for tanning of current curriery.At present, chrome tanning leather accounts for 90% of leather yield or so.But use chrome tanning
During agent, the utilization rate of chromium is low, and only 60%～70%, part chrome tanning agent is had unavoidably not to be absorbed, the waste liquid containing chromium is such as
It is really untreated, can produce be difficult in a large number to administer chromate waste water, chromium-bearing sludge, chrome leather wastes, serious is caused to environment
Pollution, trivalent chromium are easily oxidized to Cr VI, and Cr VI is a kind of material of inducible mutant organism, and directly contact can be to people
Body skin causes damage, and can accumulate in internal organs after entering human body, finally induces various diseases even cancer.Therefore, few chromium
The even use of chrome-free tanning agent, the circulation of Chrome Tanning Process, cleans important directions by leather industry sustainable development is become.
The content of the invention
The technical problem to be solved：For using during chrome tanning agent, the utilization rate of chromium is low, and contains at present
Environmental pollution and chromium that chromium waste liquid is easily caused have the problem of carcinogenecity, the invention provides a kind of preparation of environmentally friendly chrome-free tanning agent
Method, the present invention are modified by Nano-zinc Oxide by Silane Coupling Agents, so as to lift the dispersive property of nano zine oxide, together
Shi Zengqiang its interaction between matrix, then sial coordination compound is modified by multicomponent organic acid, improve which water-fast
Property and hydrothermal stability, then itself and modified nano zinc oxide are dispersed in aqueous epoxy resins with merging, replace chrome tanning agent,
Environmental protection chrome-free tanning agent is obtained.Environmentally friendly chrome-free tanning agent prepared by the present invention, nontoxic, pollution-free, crust leather color is white, soft, grain is careful,
Good-extensibility, has broad application prospects.
To solve above-mentioned technical problem, the technical solution used in the present invention is：
（1）25～30g nano zine oxides are weighed, in adding 600～720mL deionized waters, disperses 20 with 120W ultrasonic echographies
～30min, obtains nano zinc oxide fluid dispersion, in nano zinc oxide fluid dispersion add 12.5～15.0g silane coupling As-
151,2～3h is reacted at 80～90 DEG C, is proceeded to after being cooled to room temperature in centrifuge, in 5000～6000r/min centrifugations
10～12min, collects precipitation, is washed with deionized precipitation 2～3 times, precipitation is placed in lyophilizing in freeze drying box subsequently, is obtained
Modified nano zinc oxide, it is standby；
（2）Weigh 20～25g citric acids, 25～30g maleic acids, 20～25g oxalic acid, 18～20g malonic acid mix homogeneously
Afterwards, in adding 200～300mL mass fractions to be 2% sulfuric acid solution, 20～30min is stirred with 300～400r/min, subsequently with
2mL/min 150～200mL of Deca mass fractions are 1% sodium silicate solution, continue stirring until completion of dropping, obtain Ludox；
（3）To in above-mentioned Ludox with 2mL/min 150～200mL of Deca mass fractions as 4% liquor alumini chloridi, with 300～
400r/min is uniformly mixed, then with mass fraction be 10% sodium acetate solution adjust pH of mixed be 1.5～2.0, continue to stir
1～2h of reaction is mixed, is dried in being subsequently filled into spray dryer, is obtained modified silicon aluminum complex；
（4）Weigh 10～20g steps（1）The modified nano zinc oxide of preparation, the above-mentioned modified silicon aluminum complexes of 15～30g are added
During 300～500mL mass fractions are 1% sodium sulfite solution, 20～30min is disperseed with 100W ultrasonic echographies, 60 are heated to
While 200～300mL of Deca is containing the mixing that mass fraction is 10% methacrylic acid and 8% allyl glycidyl ether after～70 DEG C
Monomer solution and 200～300mL mass fractions are 2% ammonium persulfate solution, and 3～5h of insulation reaction after completion of dropping is cooled to room
Temperature discharging, obtains environmentally friendly chrome-free tanning agent.
The present invention application process be：By intact sheep pelt, Jing after mechanical fleshing, softened according to common process
After washing, the environmentally friendly chrome-free tanning agent tanning prepared using the present invention, consumption are 8～10%, at 35～45 DEG C, tanning 3～
5h, you can.After testing, the Corii Caprae seu Oviss shrinkage temperature of tanning is 90～95 DEG C, and tearing strength is 20.85～21.32Nmm-1Fracture
Percentage elongation 83.73～85.65%, 18.59～19.15Nmm of tensile strength-2, rate is thickened for 23.7～24.5%.
The method have the benefit that：
（1）The environmentally friendly chrome-free tanning agent for preparing of the invention is nontoxic, pollution-free, crust leather color is white, soft, grain is careful, good-extensibility；
（2）For Trend of Chrome-free process hides processing industry sustainable development direction, environmentally friendly chrome-free tanning agent prepared by the present invention has wide
Application prospect.
Specific embodiment
25～30g nano zine oxides are weighed, in adding 600～720mL deionized waters, disperses 20 with 120W ultrasonic echographies
～30min, obtains nano zinc oxide fluid dispersion, in nano zinc oxide fluid dispersion add 12.5～15.0g silane coupling As-
151,2～3h is reacted at 80～90 DEG C, is proceeded to after being cooled to room temperature in centrifuge, in 5000～6000r/min centrifugations
10～12min, collects precipitation, is washed with deionized precipitation 2～3 times, precipitation is placed in lyophilizing in freeze drying box subsequently, is obtained
Modified nano zinc oxide；Weigh 20～25g citric acids, 25～30g maleic acids, 20～25g oxalic acid, 18～20g malonic acid
After mix homogeneously, in adding 200～300mL mass fractions to be 2% sulfuric acid solution, 20～30min is stirred with 300～400r/min,
Subsequently with 2mL/min 150～200mL of Deca mass fractions as 1% sodium silicate solution, completion of dropping is continued stirring until, silicon is obtained molten
Glue；To in above-mentioned Ludox with 2mL/min 150～200mL of Deca mass fractions as 4% liquor alumini chloridi, with 300～400r/
Min is uniformly mixed, then is that to adjust pH of mixed be 1.5～2.0 to 10% sodium acetate solution with mass fraction, continues stirring anti-
1～2h is answered, is dried in being subsequently filled into spray dryer, is obtained modified silicon aluminum complex；Weigh the above-mentioned modified Nano oxidations of 10～20g
Zinc, the above-mentioned modified silicon aluminum complexes of 15～30g, in adding 300～500mL mass fractions to be 1% sodium sulfite solution, with
100W ultrasonic echographies disperse 20～30min, while 200～300mL of Deca is 10% containing mass fraction after being heated to 60～70 DEG C
The mixed monomer solution and 200～300mL mass fractions of methacrylic acid and 8% allyl glycidyl ether is 2% Ammonium persulfate.
Solution, 3～5h of insulation reaction after completion of dropping are cooled to room temperature discharging, obtain environmentally friendly chrome-free tanning agent.
Example 1
25g nano zine oxides are weighed, in adding 600mL deionized waters, 20min is disperseed with 120W ultrasonic echographies, nano oxygen is obtained
Change zinc dispersion liquid, 12.5g silane coupling A -151 are added in nano zinc oxide fluid dispersion, 2h is reacted at 80 DEG C, is cooled to
Proceed to after room temperature in centrifuge, in 5000r/min centrifugation 10min, collect precipitation, be washed with deionized and precipitate 2 times, with
Precipitation is placed in into lyophilizing in freeze drying box afterwards, modified nano zinc oxide is obtained；Weigh 20g citric acids, 25g maleic acids, 20g
Oxalic acid, after 18g malonic acid mix homogeneously, in adding 200mL mass fractions to be 2% sulfuric acid solution, stirs 20min with 300r/min,
Subsequently with 2mL/min Deca 150mL mass fraction as 1% sodium silicate solution, completion of dropping is continued stirring until, Ludox is obtained；Upwards
State in Ludox with 2mL/min Deca 150mL mass fraction as 4% liquor alumini chloridi, be uniformly mixed with 300r/min, then
It is 1.5 pH of mixed to be adjusted for 10% sodium acetate solution with mass fraction, continues stirring reaction 1h, is subsequently filled into spray dryer
Middle drying, obtains modified silicon aluminum complex；The above-mentioned modified nano zinc oxides of 10g are weighed, the above-mentioned modified silicon aluminum complexes of 15g are added
300mL mass fractions be 1% sodium sulfite solution in, with 100W ultrasonic echographies disperse 20min, after being heated to 60 DEG C while
Deca 200mL is containing the mixed monomer solution and 200mL matter that mass fraction is 10% methacrylic acid and 8% allyl glycidyl ether
Amount fraction be 2% ammonium persulfate solution, insulation reaction 3h after completion of dropping, be cooled to room temperature discharging, obtain environmentally friendly chrome-free tanning agent.
The present invention application process be：By intact sheep pelt, Jing after mechanical fleshing, softened according to common process
After washing, the environmentally friendly chrome-free tanning agent tanning prepared using the present invention, consumption is 8%, at 35 DEG C, tanning 3h, you can.Jing is examined
Survey, the Corii Caprae seu Oviss shrinkage temperature of tanning is 90 DEG C, and tearing strength is 20.85Nmm-1Elongation at break 83.73%, tensile strength
18.59N·mm-2, rate is thickened for 23.7%.
Example 2
28g nano zine oxides are weighed, in adding 680mL deionized waters, 25min is disperseed with 120W ultrasonic echographies, nano oxygen is obtained
Change zinc dispersion liquid, 13.0g silane coupling A -151 are added in nano zinc oxide fluid dispersion, 2.4h is reacted at 85 DEG C, cooled down
Proceed to room temperature in centrifuge, in 5500r/min centrifugation 11min, collect precipitation, be washed with deionized and precipitate 2 times,
Precipitation is placed in into lyophilizing in freeze drying box subsequently, modified nano zinc oxide is obtained；Weigh 22g citric acids, 28g maleic acids,
22g oxalic acid, after 19g malonic acid mix homogeneously, in adding 250mL mass fractions to be 2% sulfuric acid solution, is stirred with 350r/min
25min, subsequently with 2mL/min Deca 180mL mass fraction as 1% sodium silicate solution, continues stirring until completion of dropping, obtains silicon molten
Glue；To in above-mentioned Ludox with 2mL/min Deca 170mL mass fraction as 4% liquor alumini chloridi, mixed with 350r/min stirrings
Uniformly, it is 1.8 then to adjust pH of mixed for 10% sodium acetate solution with mass fraction, continues stirring reaction 1.5h, is subsequently filled into spray
It is dried in mist exsiccator, obtains modified silicon aluminum complex；The above-mentioned modified nano zinc oxides of 15g are weighed, the above-mentioned modified sial of 19g coordinates
Thing, in adding 400mL mass fractions to be 1% sodium sulfite solution, disperses 25min with 100W ultrasonic echographies, is heated to 65 DEG C
Afterwards simultaneously Deca 25mL containing the mixed monomer solution that mass fraction is 10% methacrylic acid and 8% allyl glycidyl ether and
250mL mass fractions be 2% ammonium persulfate solution, insulation reaction 4h after completion of dropping, be cooled to room temperature discharging, obtain environmentally friendly Chrome-free
Tanning agent.
The present invention application process be：By intact sheep pelt, Jing after mechanical fleshing, softened according to common process
After washing, the environmentally friendly chrome-free tanning agent tanning prepared using the present invention, consumption is 9%, at 39 DEG C, tanning 4h, you can.Jing is examined
Survey, the Corii Caprae seu Oviss shrinkage temperature of tanning is 92 DEG C, and tearing strength is 21.12Nmm-1Elongation at break 84.65%, tensile strength
18.95N·mm-2, rate is thickened for 23.9%.
Example 3
30g nano zine oxides are weighed, in adding 720mL deionized waters, 30min is disperseed with 120W ultrasonic echographies, nano oxygen is obtained
Change zinc dispersion liquid, 15.0g silane coupling A -151 are added in nano zinc oxide fluid dispersion, 3h is reacted at 90 DEG C, is cooled to
Proceed to after room temperature in centrifuge, in 6000r/min centrifugation 12min, collect precipitation, be washed with deionized and precipitate 3 times, with
Precipitation is placed in into lyophilizing in freeze drying box afterwards, modified nano zinc oxide is obtained；Weigh 25g citric acids, 30g maleic acids, 25g
Oxalic acid, after 20g malonic acid mix homogeneously, in adding 300mL mass fractions to be 2% sulfuric acid solution, stirs 30min with 400r/min,
Subsequently with 2mL/min Deca 200mL mass fraction as 1% sodium silicate solution, completion of dropping is continued stirring until, Ludox is obtained；Upwards
State in Ludox with 2mL/min Deca 200mL mass fraction as 4% liquor alumini chloridi, be uniformly mixed with 400r/min, then
It is 2.0 pH of mixed to be adjusted for 10% sodium acetate solution with mass fraction, continues stirring reaction 2h, is subsequently filled into spray dryer
Middle drying, obtains modified silicon aluminum complex；The above-mentioned modified nano zinc oxides of 20g are weighed, the above-mentioned modified silicon aluminum complexes of 30g are added
500mL mass fractions be 1% sodium sulfite solution in, with 100W ultrasonic echographies disperse 30min, after being heated to 70 DEG C while
Deca 300mL is containing the mixed monomer solution and 300mL matter that mass fraction is 10% methacrylic acid and 8% allyl glycidyl ether
Amount fraction be 2% ammonium persulfate solution, insulation reaction 5h after completion of dropping, be cooled to room temperature discharging, obtain environmentally friendly chrome-free tanning agent.
The present invention application process be：By intact sheep pelt, Jing after mechanical fleshing, softened according to common process
After washing, the environmentally friendly chrome-free tanning agent tanning prepared using the present invention, consumption is 10%, at 45 DEG C, tanning 5h, you can.Jing is examined
Survey, the Corii Caprae seu Oviss shrinkage temperature of tanning is 95 DEG C, and tearing strength is 21.32Nmm-1Elongation at break 85.65%, tensile strength
19.15N·mm-2, rate is thickened for 24.5%.
Claims (1)
1. a kind of preparation method of environmentally friendly chrome-free tanning agent, it is characterised in that concrete preparation process is：
（1）25～30g nano zine oxides are weighed, in adding 600～720mL deionized waters, disperses 20 with 120W ultrasonic echographies
～30min, obtains nano zinc oxide fluid dispersion, in nano zinc oxide fluid dispersion add 12.5～15.0g silane coupling As-
151,2～3h is reacted at 80～90 DEG C, is proceeded to after being cooled to room temperature in centrifuge, in 5000～6000r/min centrifugations
10～12min, collects precipitation, is washed with deionized precipitation 2～3 times, precipitation is placed in lyophilizing in freeze drying box subsequently, is obtained
Modified nano zinc oxide, it is standby；
（2）Weigh 20～25g citric acids, 25～30g maleic acids, 20～25g oxalic acid, 18～20g malonic acid mix homogeneously
Afterwards, in adding 200～300mL mass fractions to be 2% sulfuric acid solution, 20～30min is stirred with 300～400r/min, subsequently with
2mL/min 150～200mL of Deca mass fractions are 1% sodium silicate solution, continue stirring until completion of dropping, obtain Ludox；
（3）To in above-mentioned Ludox with 2mL/min 150～200mL of Deca mass fractions as 4% liquor alumini chloridi, with 300～
400r/min is uniformly mixed, then with mass fraction be 10% sodium acetate solution adjust pH of mixed be 1.5～2.0, continue to stir
1～2h of reaction is mixed, is dried in being subsequently filled into spray dryer, is obtained modified silicon aluminum complex；
（4）Weigh 10～20g steps（1）The modified nano zinc oxide of preparation, the above-mentioned modified silicon aluminum complexes of 15～30g are added
During 300～500mL mass fractions are 1% sodium sulfite solution, 20～30min is disperseed with 100W ultrasonic echographies, 60 are heated to
While 200～300mL of Deca is containing the mixing that mass fraction is 10% methacrylic acid and 8% allyl glycidyl ether after～70 DEG C
Monomer solution and 200～300mL mass fractions are 2% ammonium persulfate solution, and 3～5h of insulation reaction after completion of dropping is cooled to room
Temperature discharging, obtains environmentally friendly chrome-free tanning agent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974518A (en) * | 2017-12-04 | 2018-05-01 | 安徽精致汽车饰件有限公司 | A kind of tanning agent for being used to produce leather car trim |
| CN109852739A (en) * | 2019-03-18 | 2019-06-07 | 河南大学 | Coated with silica zinc oxide compound nano particle/vegatable tannin compound tanning agent of size tunable and preparation method thereof |
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|---|---|---|---|---|
| US20030075289A1 (en) * | 2001-10-23 | 2003-04-24 | Stoltz Michael J. | Method and compositions for processing poultry feathers |
| CN103980304A (en) * | 2014-05-14 | 2014-08-13 | 陕西科技大学 | Chromium-free tanning agent and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030075289A1 (en) * | 2001-10-23 | 2003-04-24 | Stoltz Michael J. | Method and compositions for processing poultry feathers |
| CN103980304A (en) * | 2014-05-14 | 2014-08-13 | 陕西科技大学 | Chromium-free tanning agent and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107974518A (en) * | 2017-12-04 | 2018-05-01 | 安徽精致汽车饰件有限公司 | A kind of tanning agent for being used to produce leather car trim |
| CN109852739A (en) * | 2019-03-18 | 2019-06-07 | 河南大学 | Coated with silica zinc oxide compound nano particle/vegatable tannin compound tanning agent of size tunable and preparation method thereof |
| CN109852739B (en) * | 2019-03-18 | 2021-03-16 | 河南大学 | Silica-coated zinc oxide composite nanoparticle/vegetable tannin composite tanning agent with controllable particle size and preparation method thereof |
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