CN108929924A - A kind of preparation method of carboxymethyl cellulose leather retanning, filler - Google Patents
A kind of preparation method of carboxymethyl cellulose leather retanning, filler Download PDFInfo
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- CN108929924A CN108929924A CN201811176252.4A CN201811176252A CN108929924A CN 108929924 A CN108929924 A CN 108929924A CN 201811176252 A CN201811176252 A CN 201811176252A CN 108929924 A CN108929924 A CN 108929924A
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- China
- Prior art keywords
- carboxymethyl cellulose
- filler
- leather
- aqueous solution
- retanning
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Links
- 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 65
- 239000000945 filler Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 45
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 18
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical group [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 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
- 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
- 239000002253 acid Substances 0.000 claims description 4
- 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 4
- 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000000126 substance 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
- 239000011651 chromium Substances 0.000 description 9
- 229910052804 chromium Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 102000008186 Collagen Human genes 0.000 description 6
- 108010035532 Collagen Proteins 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 229920001436 collagen Polymers 0.000 description 6
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 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
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement 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
- VJHCJDRQFCCTHL-UHFFFAOYSA-N acetic acid 2,3,4,5,6-pentahydroxyhexanal Chemical compound CC(O)=O.OCC(O)C(O)C(O)C(O)C=O VJHCJDRQFCCTHL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000008569 process Effects 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 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
- 230000009172 bursting Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- -1 chromium Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 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
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 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
- 238000009987 spinning Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 238000005303 weighing 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 present invention relates to leather chemical industry fields, in particular to the preparation method of a kind of carboxymethyl cellulose leather retanning, filler, it is prepared by carboxymethyl cellulose and metal complex inorganic tanning agent, metal complex inorganic tanning agent is added in carboxymethyl cellulose aqueous solution, end reaction generates a kind of carboxymethyl cellulose leather retanning, filler.The retanning that carboxymethyl cellulose leather retanning prepared by the present invention, filler are applied to chrome leather can greatly reduce the content of crome metal etc. in waste liquid after tanning, to reduce the pollution to environment such as crome metal, the fullness removed from office after retanning also can be improved, the position for reducing leather is poor, improves the quality of leather.
Description
Technical field
The present invention relates to leather chemical industry field, in particular to a kind of preparation of carboxymethyl cellulose leather retanning, filler
Method.
Background technique
Tanning is the qualitative change process for making rawhide be converted into leather, and the chemical material that skin can be changed into leather is known as tanning agent, in process hides
Workable tanning agent has inorganic tanning agent and organic tanning agent etc. in production process.For metal complex inorganic tanning agent, especially chromium
Tanning agent becomes important at present and is difficult to take since the leather suppleness of its tanning, fullness, elasticity, water-fastness etc. are had excellent performance
One of the tanning agent in generation, but with people understanding go deep into, it has been found that chrome tanning agent in tannery due to chromium absorb not exclusively,
Environment is caused great harm, therefore the absorptivity for improving metal in metal tanning agents becomes that leather chemical industry field is important to grind
Study carefully direction and development trend.
Cellulose is that the macromolecule natural organic polymeric materials most wide, content is most are spread in nature, mainly by plant
Photosynthesis synthesis, earth reserves are huge, have biodegradable, easily modified, nontoxic, pollution-free, good biocompatibility,
The advantages such as renewable are common linear macromolecule polysaccharide, are primarily used to some traditional industries such as papermaking, medicine, spinning at present
It knits, the production divisions such as fine chemistry industry.Carboxymethyl cellulose (CMC), because its sodium salt is often used in production, thus it is also known as carboxylic
Sodium carboxymethylcellulose pyce, it be in the world today with field most wide, the maximum cellulose grades of dosage, be that cellulosic molecule passes through
The cellulose derivative that the glucose polymerization degree obtained after chemical method modification is 100-2000, white threadiness or graininess
Powder.The water solubility having had, odorless, tasteless have hygroscopicity, do not dissolve in organic solvent.Carboxymethyl cellulose is used at present
The research of inorganic coordination compound tanning agent preparation is considerably less, and relevant document and patent are also fewer and fewer.
Summary of the invention
In order to compensate for the shortcomings of the prior art, the present invention provides a kind of carboxymethyl cellulose leather retannings, filler
Preparation method.
The present invention is achieved by the following technical solutions:
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction of carboxymethyl cellulose being added in reaction vessel, so
Be continuously added water stirring in backward reaction vessel and be made into the carboxymethyl cellulose aqueous solution that mass concentration is 1%, then 30 DEG C-
Continue stirring 30-40 minutes at a temperature of 35 DEG C；
(2) it adjusts pH value: the pH for the carboxymethyl cellulose aqueous solution that above-mentioned steps (1) is prepared being adjusted to 3.0-5.0, controls temperature
At 25 DEG C -35 DEG C；
(3) metal complex inorganic tanning agent is added: the carboxymethyl cellulose aqueous solution adjusted in step (2) adds under constant stirring
Enter 50-200 parts of metal complex inorganic tanning agents of mass fraction, reacts 20-50 minutes；
(4) it stands: by solution left standstill 24-48 hours of step (3) preparation, obtaining carboxymethyl cellulose leather retanning, filler.
Further, pH value is adjusted in the step (2) use acid solution；Preferably, the acid solution is sulfuric acid
Or hydrochloric acid or formic acid or acetic acid.
Preferably, in the step (3), metal complex inorganic tanning agent is chromium sulfate basic or basic chromic chloride or sulfuric acid
Aluminium or zirconium sulfate or titanium sulfate or ferric sulfate.
The present invention utilizes chromium, the aluminium, zirconium, iron, titanium in the carboxyl and metal complex inorganic tanning agent in carboxymethyl cellulose
It is combined Deng at coordination, when chromium, aluminium, zirconium, iron, titanium in metal complex inorganic tanning agent etc. is in conjunction with carboxyl coordination on collagen
Carboxymethyl cellulose also is secured on leather collagen, more crosslinkings is not only formed, improves the shrinkage temperature and intensity of leather, together
When, the richness and the degree of packing of leather can also be improved, to form a kind of novel tanning agent.
The complex of metal complex inorganic tanning agent such as chromium, aluminium, zirconium, iron, titanium etc. is combined preferably, usually with collagen coordination
Interior boundary and the metallic ion coordination for entering metal complex tanning agent for the carboxyl on leather collagen, can be improved the quality of leather, receive
Contracting temperature is up to 85 DEG C or more.Above-mentioned novel tanning agent is used for the retanning of chrome leather, not only can in conjunction with carboxyl coordination on collagen,
The metal complex using the carboxyl being not associated on carboxymethyl cellulose in conjunction on collagen at single-point is combined at coordination simultaneously,
So that single-point, which combines, is converted into multiple spot combination, the shrinkage temperature and mechanical strength of finished leather can be obviously increased.Due to cellulosic molecule
Relatively large, cellulose, which is full of between leather fiber, while retanning preferably the loose position of the sky of leather, particularly leather
Filling effect, the fullness of leather can be improved, the position for reducing leather is poor, to improve the quality and performance of leather.In addition,
It can also match by the carboxyl and intradermal free metal complex being not associated on carboxymethyl cellulose, such as chromium sulfate basic formation
Position combines, and can not only increase the chrome content in finished leather, and can reduce the chromium content after tanning in waste liquid, to reduce chromium to ring
The pollution in border.
Carboxymethyl cellulose leather retanning of the invention, the preparation method of filler are easy to operate, raw material is easy to get, with carboxylic first
After base cellulose leather retanning, filler fill leather retanning, the bursting apart of leather, collapse broken and shrinkage temperature promoted aspect show it is excellent
It is different, it is showed on finished leather richness preferably, tearing strength is removed from office higher than chrome retanned.In addition, using this carboxymethyl cellulose leather
Retanning, filler keep finished leather more plentiful, can reduce the dosage of chromic compound tanning agent, reduce pollution and saving of the chromium to environment
It is recycled the expense of the metals such as chromium, has not only been applicable in but also environmentally friendly, and the tanning agent synthesized has good selectivity filling effect, from
And the position that can reduce finished leather is poor.
Leather color after carboxymethyl cellulose leather retanning prepared by the present invention, filler processing is light, and grain is careful,
According to " QBT2706-2005 leather chemistry, physics, machinery and color fastness test sampling position " and " QBT2713-2005 leather object
The measurement of reason and mechanical test shrinkage temperature " standard, it measures the shrinkage temperature removed from office compared with before retanning and improves 15 ~ 21 DEG C, leather
Area increases by 4% ~ 16%；According to " measurement of QB/T2709-2005 leather physics and mechanical test thickness " standard, measure and retanning
The preceding thickness compared to leather increases by 1% ~ 5%；According to " QBT2706-2005 leather chemistry, physics, machinery and color fastness test sampling portion
Position " standard and " measurement of QB/T2710-2005 leather physics and mechanical test tensile strength and elongation " standard, measure with it is pure
Chrome retanned can be improved 30% ~ 50% compared to tensile strength.
Specific embodiment
Specific embodiments of the present invention are given below, it should be noted that the invention is not limited to implement in detail below
Example, all equivalent transformations made on the basis of the technical solutions of the present application each fall within protection scope of the present invention.
Embodiment 1:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 40 minutes at 30 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the formic acid solution diluted,
Temperature is controlled at 30 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The chromium sulfate basic that 50 parts of mass fraction, when addition, are stirred continuously, and react 30 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 2:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 30 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 4.0 with the sulfuric acid solution diluted,
Temperature is controlled at 35 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The chromium sulfate basic that 100 parts of mass fraction, when addition, are stirred continuously, and react 30 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 3:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 40 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the formic acid solution diluted,
Temperature is controlled at 35 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The chromium sulfate basic that 150 parts of mass fraction, when addition, are stirred continuously, and react 30 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 4:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 40 minutes at 30 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.5 with the formic acid solution diluted,
Temperature is controlled at 25 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The chromium sulfate basic that 150 parts of mass fraction, when addition, are stirred continuously, and react 30 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 5:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 35 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 5.0 with the hydrochloric acid solution diluted,
Temperature is controlled at 35 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The chromium sulfate basic that 100 parts of mass fraction, when addition, are stirred continuously, and react 20 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 6:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 40 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the acetic acid solution diluted,
Temperature is controlled at 25 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The basic chromic chloride that 100 parts of mass fraction, when addition, are stirred continuously, and react 30 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 7:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 30 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the sulfuric acid solution diluted,
Temperature is controlled at 30 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The chromium sulfate basic that 200 parts of mass fraction, when addition, are stirred continuously, and react 50 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 8:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 30 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the hydrochloric acid solution diluted,
Temperature is controlled at 25 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The aluminum sulfate that 150 parts of mass fraction, when addition, are stirred continuously, and react 50 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 9:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 30 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.5 with the formic acid solution diluted,
Temperature is controlled at 30 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The chromium sulfate basic that 200 parts of mass fraction, when addition, are stirred continuously, and react 50 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 10:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 40 minutes at 30 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the formic acid solution diluted,
Temperature is controlled at 30 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The zirconium sulfate that 100 parts of mass fraction, when addition, are stirred continuously, and react 50 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 11:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 35 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the sulfuric acid solution diluted,
Temperature is controlled at 30 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The ferric sulfate that 100 parts of mass fraction, when addition, are stirred continuously, and react 45 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Embodiment 12:
A kind of preparation method of carboxymethyl cellulose leather retanning, filler, comprising steps of
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction good of carboxymethyl cellulose of precise being added anti-
It answers in container, water is then added and is stirred continuously, carboxymethyl cellulose is solute, and water is solvent, and being made into mass concentration is 1%
Then carboxymethyl cellulose aqueous solution continues stirring 35 minutes at 35 DEG C.
(2) it adjusts pH value: the carboxymethyl cellulose aqueous solution pH of step (1) being adjusted to 3.0 with the acetic acid solution diluted,
Temperature is controlled at 25 DEG C.
(3) metal complex inorganic tanning agent is added: and then to be continuously added precise in the solution in step (2) good
The titanium sulfate that 50 parts of mass fraction, when addition, are stirred continuously, and react 20 minutes；
(4) it stands: and then by solution left standstill 24-48 hours of step (3), reaction was completed, and finally obtained carboxymethyl cellulose skin
Remove from office retanning, filler.
Carboxymethyl cellulose, chromium sulfate basic, basic chromic chloride, aluminum sulfate, zirconium sulfate, titanium sulfate, the sulphur of above-mentioned weighing
The fingers such as sour iron are absolutely pure, pure if not a hundred percent, and absolutely pure carboxylic should be converted into when being added
Methylcellulose, chromium sulfate basic, basic chromic chloride, aluminum sulfate, zirconium sulfate, titanium sulfate, ferric sulfate.
Embodiment described above, only one kind of the present invention more preferably specific embodiment, those skilled in the art
The usual variations and alternatives that member carries out within the scope of technical solution of the present invention should be all included within the scope of the present invention.
Claims (4)
1. the preparation method of a kind of carboxymethyl cellulose leather retanning, filler, it is characterized in that: include the following steps:
(1) it prepares carboxymethyl cellulose aqueous solution: 100 parts of mass fraction of carboxymethyl cellulose being added in reaction vessel, so
Be continuously added water stirring in backward reaction vessel and be made into the carboxymethyl cellulose aqueous solution that mass concentration is 1%, then 30 DEG C-
Continue stirring 30-40 minutes at a temperature of 35 DEG C；
(2) it adjusts pH value: the pH for the carboxymethyl cellulose aqueous solution that above-mentioned steps (1) is prepared being adjusted to 3.0-5.0, controls temperature
At 25 DEG C -35 DEG C；
(3) metal complex inorganic tanning agent is added: the carboxymethyl cellulose aqueous solution adjusted in step (2) adds under constant stirring
Enter 50-200 parts of metal complex inorganic tanning agents of mass fraction, reacts 20-50 minutes；
(4) it stands: by solution left standstill 24-48 hours of step (3) preparation, obtaining carboxymethyl cellulose leather retanning, filler.
2. the preparation method of carboxymethyl cellulose leather retanning according to claim 1, filler, it is characterized in that: it is described
PH value is adjusted in step (2) uses acid solution.
3. the preparation method of carboxymethyl cellulose leather retanning according to claim 2, filler, it is characterized in that: it is described
Acid solution is sulfuric acid or hydrochloric acid or formic acid or acetic acid.
4. the preparation method of carboxymethyl cellulose leather retanning according to claim 1, filler, it is characterized in that: it is described
In step (3), metal complex inorganic tanning agent is chromium sulfate basic or basic chromic chloride or aluminum sulfate or zirconium sulfate or titanium sulfate
Or ferric sulfate.
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| CN110747299A (en) * | 2019-11-04 | 2020-02-04 | 四川大学 | Method for preparing aluminum zirconium complex tanning agent based on microcrystalline cellulose |
| CN111321260A (en) * | 2020-03-31 | 2020-06-23 | 河南中牛实业有限公司 | Environment-friendly chromium-free retanning method for leather |
| CN111320332A (en) * | 2020-03-31 | 2020-06-23 | 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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| 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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| CN110747299A (en) * | 2019-11-04 | 2020-02-04 | 四川大学 | Method for preparing aluminum zirconium complex tanning agent based on microcrystalline cellulose |
| CN110747299B (en) * | 2019-11-04 | 2021-07-23 | 四川大学 | Method for preparing aluminum zirconium complex tanning agent based on microcrystalline cellulose |
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| CN111320332A (en) * | 2020-03-31 | 2020-06-23 | 河南中牛实业有限公司 | Leather sewage emission reduction treatment method |
| 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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| CN108929924B (en) | 2020-11-24 |
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