CN108929924B - Preparation method of carboxymethyl cellulose leather retanning and filling agent - Google Patents
Preparation method of carboxymethyl cellulose leather retanning and filling agent Download PDFInfo
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- CN108929924B CN108929924B CN201811176252.4A CN201811176252A CN108929924B CN 108929924 B CN108929924 B CN 108929924B CN 201811176252 A CN201811176252 A CN 201811176252A CN 108929924 B CN108929924 B CN 108929924B
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- carboxymethyl cellulose
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- 229920002134 Carboxymethyl cellulose Polymers 0.000 title claims abstract description 118
- 239000001768 carboxy methyl cellulose Substances 0.000 title claims abstract description 118
- 235000010948 carboxy methyl cellulose Nutrition 0.000 title claims abstract description 117
- 239000008112 carboxymethyl-cellulose Substances 0.000 title claims abstract description 117
- 239000010985 leather Substances 0.000 title claims abstract description 83
- 239000000945 filler Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000007864 aqueous solution Substances 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 40
- 239000003795 chemical substances by application Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 150000004696 coordination complex Chemical class 0.000 claims description 25
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- DSHWASKZZBZKOE-UHFFFAOYSA-K chromium(3+);hydroxide;sulfate Chemical group [OH-].[Cr+3].[O-]S([O-])(=O)=O DSHWASKZZBZKOE-UHFFFAOYSA-K 0.000 claims description 12
- 229910000356 chromium(III) sulfate Inorganic materials 0.000 claims description 12
- 239000011696 chromium(III) sulphate Substances 0.000 claims description 12
- 235000015217 chromium(III) sulphate Nutrition 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 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 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 5
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 5
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052804 chromium Inorganic materials 0.000 abstract description 13
- 239000011651 chromium Substances 0.000 abstract description 13
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 description 12
- 102000008186 Collagen Human genes 0.000 description 6
- 108010035532 Collagen Proteins 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 6
- 239000001913 cellulose Substances 0.000 description 6
- 229920001436 collagen Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- -1 chromium Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000005406 washing 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
- C14C3/08—Chemical tanning by organic agents
- C14C3/22—Chemical tanning by organic agents using polymerisation products
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention relates to the field of leather chemical industry, in particular to a preparation method of a carboxymethyl cellulose leather retanning and filling agent. The carboxymethyl cellulose leather retanning and filling agent prepared by the invention is applied to retanning of chrome tanned leather, and can greatly reduce the content of metal chromium and the like in waste liquid after tanning, thereby reducing the pollution of the metal chromium and the like to the environment, improving the fullness of the leather after retanning, reducing the position difference of the leather and improving the quality of the leather.
Description
Technical Field
The invention relates to the field of leather chemical industry, in particular to a preparation method of carboxymethyl cellulose leather retanning and filling agent.
Background
Tanning is a process of metamorphism which converts hides into leather, while chemical materials which can convert skins into leather are called tanning agents, and among the tanning agents which can be used in the process of leather production are inorganic tanning agents, organic tanning agents and the like. As for the metal complex inorganic tanning agent, particularly the chrome tanning agent, the tanned leather has excellent properties such as softness, fullness, elasticity, water washing resistance and the like, and becomes one of the important tanning agents which are difficult to replace at present, but with the deep understanding of people, people find that the chrome tanning agent causes great harm to the environment due to incomplete chromium absorption in the tanning process, and therefore, the improvement of the metal absorption rate in the metal tanning agent becomes an important research direction and development trend in the leather chemical industry field.
Cellulose is a natural high-molecular organic polymer which is most widely dispersed and contains most in nature, is mainly synthesized by photosynthesis of plants, has the advantages of huge earth reserve, biodegradability, easiness in modification, no toxicity, no pollution, good biocompatibility, renewability and the like, is a common linear macromolecular polysaccharide, and is mainly used in some traditional industries such as papermaking, medicine, textile, fine chemical industry and other production departments at present. Carboxymethyl cellulose (CMC), also called sodium carboxymethyl cellulose because of its sodium salt is commonly used in production, is the most widely used cellulose variety in the application field in the world today, is a cellulose derivative with a glucose degree of polymerization of 100-2000-obtained by chemical modification of cellulose molecules, and is in the form of white fibrous or granular powder. Has good water solubility, no odor and odor, and hygroscopicity, and is insoluble in organic solvent. At present, carboxymethyl cellulose is used for preparing inorganic coordination compound tanning agents, and few researches are carried out, and related documents and patents are few.
Disclosure of Invention
The invention provides a preparation method of a carboxymethyl cellulose leather retanning and filling agent, which aims to make up for the defects of the prior art.
The invention is realized by the following technical scheme:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of carboxymethyl cellulose into a reaction vessel, then continuously adding water into the reaction vessel, stirring to prepare a carboxymethyl cellulose aqueous solution with the mass concentration of 1%, and then continuously stirring for 30-40 minutes at the temperature of 30-35 ℃;
(2) adjusting the pH value: adjusting the pH value of the carboxymethyl cellulose aqueous solution prepared in the step (1) to 3.0-5.0, and controlling the temperature to be 25-35 ℃;
(3) adding a metal complex inorganic tanning agent: adding 50-200 parts by mass of metal complex inorganic tanning agent into the carboxymethyl cellulose aqueous solution adjusted in the step (2) under continuous stirring, and reacting for 20-50 minutes;
(4) standing: and (4) standing the solution prepared in the step (3) for 24-48 hours to obtain the carboxymethyl cellulose leather retanning and filling agent.
Further, an acidic solution is adopted for adjusting the pH value in the step (2); preferably, the acidic solution is sulfuric acid or hydrochloric acid or formic acid or acetic acid.
Preferably, in the step (3), the metal complex inorganic tanning agent is basic chromium sulfate or basic chromium chloride or aluminum sulfate or zirconium sulfate or titanium sulfate or iron sulfate.
The carboxyl in the carboxymethyl cellulose is coordinated and combined with chromium, aluminum, zirconium, iron, titanium and the like in the metal complex inorganic tanning agent, and when the chromium, the aluminum, the zirconium, the iron, the titanium and the like in the metal complex inorganic tanning agent are coordinated and combined with the carboxyl on the leather collagen, the carboxymethyl cellulose is also fixed on the leather collagen, so that more cross-links are formed, the shrinkage temperature and the strength of the leather are improved, and meanwhile, the fullness and the compactness of the leather can be improved, thereby forming the novel tanning agent.
The coordination and combination of metal complex inorganic tanning agents such as complexes of chromium, aluminum, zirconium, iron, titanium and the like and leather collagen are good, usually, carboxyl on the leather collagen enters the inner boundary of the metal complex tanning agent to coordinate with metal ions, the quality of leather can be improved, and the shrinkage temperature reaches more than 85 ℃. The novel tanning agent is used for retanning chrome tanned leather, not only can be coordinated and combined with carboxyl on leather collagen, but also can utilize the carboxyl which is not combined on carboxymethyl cellulose to be coordinated and combined with a metal complex which is in single-point combination on the collagen, so that the single-point combination is converted into multi-point combination, and the shrinkage temperature and the mechanical strength of the finished leather can be obviously increased. Because the cellulose molecules are relatively large, the cellulose is filled among leather fibers to have a good filling effect on leather, particularly the loose parts of the leather during retanning, so that the plumpness of the leather can be improved, the position difference of the leather is reduced, and the quality and the performance of the leather are improved. In addition, the carboxyl which is not combined on the carboxymethyl cellulose and a metal complex which is free in the skin such as basic chromium sulfate can form coordination combination, so that the chromium content in finished leather can be increased, the chromium content in waste liquid after tanning can be reduced, and the environmental pollution caused by chromium is reduced.
The preparation method of the carboxymethyl cellulose leather retanning and filling agent has the advantages of simple operation and easily obtained raw materials, and after the carboxymethyl cellulose leather retanning and filling agent is used for retanning and filling leather, the leather has excellent performances in the aspects of cracking, breaking and shrinkage temperature increase, and has better performances on the fullness of finished leather and higher tearing strength than chrome retanning leather. In addition, the carboxymethyl cellulose leather retanning and filling agent ensures that the finished leather is plumper, can reduce the using amount of the chromium complex tanning agent, reduce the pollution of chromium to the environment and save the cost for recovering and treating metals such as chromium, is suitable and environment-friendly, and the synthesized tanning agent has good selective filling effect, thereby reducing the position difference of the finished leather.
After the leather is retanned by the carboxymethyl cellulose leather prepared by the method and treated by the filler, the color is light, the grain surface is fine, and according to standards of QBT2706-2005 leather chemical, physical, mechanical and color fastness test sampling parts and QBT2713-2005 leather physical and mechanical test shrinkage temperature determination, the shrinkage temperature of the leather is increased by 15-21 ℃ and the area of the leather is increased by 4-16 percent compared with that before retanning; according to the standard of QB/T2709-2005 leather physical and mechanical test thickness determination, the thickness of the leather is increased by 1% -5% compared with that before retanning; according to standards of QBT2706-2005 leather chemical, physical, mechanical and color fastness test sampling positions and standards of QB/T2710-2005 leather physical and mechanical test tensile strength and elongation, the tensile strength can be improved by 30% -50% compared with pure chromium retanning.
Detailed Description
The following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 40 minutes at 30 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted formic acid solution, and the temperature was controlled at 30 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 50 parts by weight of accurately weighed basic chromium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 30 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 2:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 30 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 4.0 with a diluted sulfuric acid solution, and the temperature was controlled at 35 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 100 parts by weight of accurately weighed basic chromium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 30 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 3:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 40 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted formic acid solution, and the temperature was controlled at 35 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 150 parts by weight of accurately weighed basic chromium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 30 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 4:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 40 minutes at 30 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.5 with a diluted formic acid solution, and the temperature was controlled at 25 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 150 parts by weight of accurately weighed basic chromium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 30 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 5:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 35 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 5.0 with a diluted hydrochloric acid solution, and the temperature was controlled at 35 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 100 parts by weight of accurately weighed basic chromium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 20 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 6:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 40 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted acetic acid solution, and the temperature was controlled at 25 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 100 parts by weight of accurately weighed basic chromium chloride into the solution obtained in the step (2), continuously stirring while adding, and reacting for 30 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 7:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 30 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted sulfuric acid solution, and the temperature was controlled at 30 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 200 parts by weight of accurately weighed basic chromium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 50 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 8:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 30 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted hydrochloric acid solution, and the temperature was controlled at 25 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 150 parts by weight of accurately weighed aluminum sulfate into the solution in the step (2), continuously stirring while adding, and reacting for 50 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 9:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 30 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.5 with a diluted formic acid solution, and the temperature was controlled at 30 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 200 parts by weight of accurately weighed basic chromium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 50 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 10:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 40 minutes at 30 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted formic acid solution, and the temperature was controlled at 30 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 100 parts by weight of accurately weighed zirconium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 50 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 11:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 35 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted sulfuric acid solution, and the temperature was controlled at 30 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 100 parts by weight of accurately weighed ferric sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 45 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
Example 12:
a preparation method of carboxymethyl cellulose leather retanning and filling agent comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of accurately weighed carboxymethyl cellulose into a reaction vessel, adding water, continuously stirring, preparing a carboxymethyl cellulose aqueous solution with the mass concentration of 1% by using the carboxymethyl cellulose as a solute and the water as a solvent, and continuously stirring for 35 minutes at 35 ℃.
(2) Adjusting the pH value: the pH of the aqueous solution of carboxymethyl cellulose of step (1) was adjusted to 3.0 with a diluted acetic acid solution, and the temperature was controlled at 25 ℃.
(3) Adding a metal complex inorganic tanning agent: continuously adding 50 parts by weight of accurately weighed titanium sulfate into the solution obtained in the step (2), continuously stirring while adding, and reacting for 20 minutes;
(4) standing: and (4) standing the solution obtained in the step (3) for 24-48 hours, and finishing the reaction to finally obtain the carboxymethyl cellulose leather retanning and filling agent.
The carboxymethyl cellulose, basic chromium sulfate, basic chromium chloride, aluminum sulfate, zirconium sulfate, titanium sulfate, ferric sulfate and the like weighed above refer to one hundred percent pure, if not one hundred percent pure, the carboxymethyl cellulose, the basic chromium sulfate, the basic chromium chloride, the aluminum sulfate, the zirconium sulfate, the titanium sulfate and the ferric sulfate should be converted into one hundred percent pure when being added.
The above-described embodiment is only one of the preferred embodiments of the present invention, and general changes and substitutions by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.
Claims (4)
1. A preparation method of carboxymethyl cellulose leather retanning and filling agent is characterized by comprising the following steps: the method comprises the following steps:
(1) preparation of an aqueous solution of carboxymethyl cellulose: adding 100 parts by mass of carboxymethyl cellulose into a reaction vessel, then continuously adding water into the reaction vessel, stirring to prepare a carboxymethyl cellulose aqueous solution with the mass concentration of 1%, and then continuously stirring for 30-40 minutes at the temperature of 30-35 ℃;
(2) adjusting the pH value: adjusting the pH value of the carboxymethyl cellulose aqueous solution prepared in the step (1) to 3.0-5.0, and controlling the temperature to be 25-35 ℃;
(3) adding a metal complex inorganic tanning agent: adding 50-200 parts by mass of metal complex inorganic tanning agent into the carboxymethyl cellulose aqueous solution adjusted in the step (2) under continuous stirring, and reacting for 20-50 minutes;
(4) standing: and (4) standing the solution prepared in the step (3) for 24-48 hours to obtain the carboxymethyl cellulose leather retanning and filling agent.
2. The method for preparing carboxymethyl cellulose leather retanning and filling agent according to claim 1, wherein: and (3) adopting an acidic solution for adjusting the pH value in the step (2).
3. The method for preparing carboxymethyl cellulose leather retanning and filling agent according to claim 2, wherein: the acid solution is sulfuric acid or hydrochloric acid or formic acid or acetic acid.
4. The method for preparing carboxymethyl cellulose leather retanning and filling agent according to claim 1, wherein: in the step (3), the metal complex inorganic tanning agent is basic chromium sulfate or basic chromium chloride or aluminum sulfate or zirconium sulfate or titanium sulfate or ferric sulfate.
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| CN111321260B (en) * | 2020-03-31 | 2022-01-28 | 河南中牛实业有限公司 | Environment-friendly chromium-free retanning method for leather |
| CN111320332B (en) * | 2020-03-31 | 2022-02-18 | 河南中牛实业有限公司 | Leather sewage emission reduction treatment method |
| CN115044715A (en) * | 2022-07-05 | 2022-09-13 | 徐州鸿丰高分子材料有限公司 | Cellulose-based protein compound synthesis method |
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| CN101027038A (en) * | 2004-09-24 | 2007-08-29 | 赫尔克里士公司 | High DS cationic polygalactomannan for skincare products |
| CN101250827A (en) * | 2008-02-02 | 2008-08-27 | 四川大学 | Preparation of dialdehyde carboxymethyl cellulose and method for testing aldehyde group content |
| CN107217116A (en) * | 2017-07-06 | 2017-09-29 | 四川大学 | A kind of full constituent, many aldehyde radical organic tanning agents of wide distribution and preparation method thereof |
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| CN101027038A (en) * | 2004-09-24 | 2007-08-29 | 赫尔克里士公司 | High DS cationic polygalactomannan for skincare products |
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| CN107217116A (en) * | 2017-07-06 | 2017-09-29 | 四川大学 | A kind of full constituent, many aldehyde radical organic tanning agents of wide distribution and preparation method thereof |
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