CN109371182A - A kind of leather chemicals production purification characterization processes - Google Patents
A kind of leather chemicals production purification characterization processes Download PDFInfo
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- CN109371182A CN109371182A CN201811080607.XA CN201811080607A CN109371182A CN 109371182 A CN109371182 A CN 109371182A CN 201811080607 A CN201811080607 A CN 201811080607A CN 109371182 A CN109371182 A CN 109371182A
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- 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
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
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Abstract
The invention discloses a kind of leather chemicals to produce purification characterization processes, it is characterized by comprising following steps: the production of retanning agent: according to parts by weight, mixing is stirred at room temperature in 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water, and adjusting pH value is 7.5~8.5, reacts 0.5~2.5h under 50~70 °C then up to containing the polyhydroxy or simultaneously amino monomers prepolymer containing polyhydroxy and aldehyde radical.The present invention dispels free existing formaldehyde by the production process in product, in the product and in retanning finished leather formaldehydeless generation a possibility that, and the Hydrolyzed Collagen molecule introduced has the ability of lasting capture free formaldehyde, thus the product, which can also reduce, uses other Retanning Materials bring Formaldehydes, and the raw material that this product uses in process of production is all from a wealth of sources, cheap, production method is simple, can be widely to marketing.
Description
Technical field
The present invention relates to leather chemicals processing technology field, specially a kind of leather chemicals production purification detection work
Skill.
Background technique
Leather chemicals are exactly used during the Animal Skins such as ox, pig, sheep are processed into attractive and durable leather
Chemical materials.Retanning agent is used for the chemical materials of leather retanning, also known as tanning material, can combine with hide protein (collagen), and make
Its substance for being changed into leather, retanning occupy considerable position in modern leather industry, are most crucial in tanning production
Process, " Golden Touch " is described as by leather circle, especially for light leather, same leather embryo both may be used by using different retanning methods
Solid upper leather is made, soft and full clothing leather can also be produced, the quality of Retanning Materials determines the good of retanning effect
It is bad, not only there is great influence to finished leather performance, but also very important effect is also played to its quality and grade.Therefore, closely
Various retanning agents have all obtained large development over year.
Amino resins with good leather filling capacity and the better dyeability of imparting due to being widely used
In leather industry, amino resins be usually by the emulsion stabilities such as melamine, dicyandiamide, urea and aldehyde material (mainly
Formaldehyde) condensation product, since emulsion stability and formaldehyde reacting under alkaline condition are reversible, in such product
Or inevitably there is a certain amount of free formaldehyde in product use process, the presence of formaldehyde will seriously endanger the body of people
Body health proposes more Determination of Formaldehyde in Leather as people's lives level constantly improves and the needs of environmental protection
Stringent limitation standard, common amino resins retanning agent are no longer satisfied requirement of the people to high-quality leather, therefore, newly
The formaldehydeless amino resins retanning agent gesture exploitation of type is imperative.
Summary of the invention
The purpose of the present invention is to provide a kind of leather chemicals to produce purification characterization processes, has the excellent of Environmental Safety
Point solves common amino resins retanning agent and inevitably there is a certain amount of free formaldehyde in product use process,
Be no longer satisfied the problem of people are to high-quality leather requirement.
To achieve the above object, the invention provides the following technical scheme: a kind of production of leather chemicals purifies characterization processes,
It is characterized by comprising following steps:
A, the production of retanning agent
(1) according to parts by weight, by 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water in room temperature
Be stirred, and adjust pH value be 7.5~8.5, then under 50~70 °C react 0.5~2.5h contain to obtain the final product polyhydroxy or
Amino monomers prepolymer containing polyhydroxy and aldehyde radical simultaneously；
(2) 120~220 parts of water, 50~90 parts of sulfonated reagents, then under 70~95 °C are added in above-mentioned amino monomers prepolymer
1.0~3.5h is kept the temperature to get the amino monomers prepolymer of sulfonation；
(3) the amino monomers prepolymer of above-mentioned sulfonation is cooled to 50~60 °C, the hydrolysis of 80~150 parts of different molecular weights is added
Collagen solution adjusts pH to 4.0~7.0, then in 50~60 °C of lower 0.5~3.5h of insulation reaction, be cooled to 50 °C hereinafter,
Adjust pH to neutral up to formaldehydeless amino resins retanning agent product.
B, it purifies
(1) after above-mentioned preparation process, amino resins retanning agent product formaldehydeless in container is put into a centrifuge, with
1500r/min is centrifuged 10~20min, collects supernatant and takes 50~60 portions of supernatants, 12~17 parts according to parts by weight
EDC.HCL, 5~10 parts of I-hydroxybenzotriazoles and 1~5 part of Raney's nickel, are first put into band for supernatant, EDC.HCL and Raney's nickel
In the three-necked flask for having blender and thermometer, using nitrogen protection, 15~30min is stirred with 120r/min；
(2) after above-mentioned stirring, three-necked flask is placed in water-bath, set temperature is 35~505 °C, by above-mentioned weight
I-hydroxybenzotriazole in number is put into three-necked flask, continues 2.5~6h of stirring, subsequent cooled to room temperature, to three
Mixture in mouthful flask is filtered, and collects filtered fluid, and filtered fluid is put into be concentrated into concentration tank original volume 60~
80%, concentrate is collected, it is spare；
(3) attapulgite is taken to be put into calcining furnace, set temperature is 800~1200 °C, calcines 0.5~2h, cools to room with the furnace
Calcined material taking-up is put into pulverizer and crushes, crosses 150 meshes by temperature, collects sieving particle A, according to parts by weight, in mass ratio
Alkyl phenol polyoxyethylene ether, humic acid and sieving particle A are put into milling tank by 1:5:15,1.5 are milled with 200r/min~
3h is sieved with 100 mesh sieve, and collects sieving particle；
(4) according to parts by weight, the spare concentrate of 40~60 parts of steps (2), 20~30 parts of above-mentioned sieving particles, 15~25 parts are taken
Step (2) spare concentrate is uniformly mixed by maleic anhydride and 8~15 parts of diethanol amine with above-mentioned sieving particle first,
It is filtered after standing 20~50min, collects filter residue and filtrate respectively, filtrate, maleic anhydride and diethanol amine are put into reaction
In kettle, set temperature is 60~80 °C, stirs 1.0~1.5h with 150r/min, then be cooled to 30~50 °C, adds filter residue,
It is stirred to react 5~8.5h, discharging collects out material, that is, completes the work of withdrawing deposit of retanning agent.
C, it detects
A, viscosity measurements:
Fly DV2T viscosimeter tested viscosity by the formaldehydeless amino resins retanning agent product constant temperature of synthesis and 25 °C, and with rich power；
B, relative molecular mass detects:
A certain amount of sample is taken, it is characterized using GPC and counts uniform relative molecular weight and its distribution coefficient；
C, rate detection is thickened:
For the antimere of retanning experiment leather base, three points are taken from ridge line to ventral direction, the thickness after testing its retanning
Degree, calculating thicken rate.
Preferably, the amino monomers are melamine, urea, any one in dicyandiamide.
Preferably, the sulfonated reagent in retanning agent preparation is sodium sulfite, sodium hydrogensulfite, in sodium pyrosulfite
It is any.
Preferably, the Hydrolyzed Collagen molecular weight in purification step be 2000~6000,8000~15000 or
15000~40000.
Compared with prior art, beneficial effects of the present invention are as follows: the present invention is by the production process in product to free
Existing formaldehyde is dispelled, in the product and in retanning finished leather formaldehydeless generation a possibility that, and the hydrolysis glue introduced
Former protein molecular has the ability of lasting capture free formaldehyde, thus the product can also be reduced and be brought using other Retanning Materials
Formaldehyde, and the raw material that uses in process of production of this product is all from a wealth of sources, cheap, production method letter
It is single, it can be widely to marketing.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution in the embodiment of the present invention is clearly and completely retouched
It states, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the present invention
In embodiment, every other implementation obtained by those of ordinary skill in the art without making creative efforts
Example, shall fall within the protection scope of the present invention.
A kind of leather chemicals production purification characterization processes, characterized by the following steps:
A, the production of retanning agent
(1) according to parts by weight, by 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water in room temperature
Be stirred, and adjust pH value be 7.5~8.5, then under 50~70 °C react 0.5~2.5h contain to obtain the final product polyhydroxy or
Amino monomers prepolymer containing polyhydroxy and aldehyde radical simultaneously；
(2) 120~220 parts of water, 50~90 parts of sulfonated reagents, then under 70~95 °C are added in above-mentioned amino monomers prepolymer
1.0~3.5h is kept the temperature to get the amino monomers prepolymer of sulfonation；
(3) the amino monomers prepolymer of above-mentioned sulfonation is cooled to 50~60 °C, the hydrolysis of 80~150 parts of different molecular weights is added
Collagen solution adjusts pH to 4.0~7.0, then in 50~60 °C of lower 0.5~3.5h of insulation reaction, be cooled to 50 °C hereinafter,
Adjust pH to neutral up to formaldehydeless amino resins retanning agent product.
B, it purifies
(1) after above-mentioned preparation process, amino resins retanning agent product formaldehydeless in container is put into a centrifuge, with
1500r/min is centrifuged 10~20min, collects supernatant and takes 50~60 portions of supernatants, 12~17 parts according to parts by weight
EDC.HCL, 5~10 parts of I-hydroxybenzotriazoles and 1~5 part of Raney's nickel, are first put into band for supernatant, EDC.HCL and Raney's nickel
In the three-necked flask for having blender and thermometer, using nitrogen protection, 15~30min is stirred with 120r/min；
(2) after above-mentioned stirring, three-necked flask is placed in water-bath, set temperature is 35~505 °C, by above-mentioned weight
I-hydroxybenzotriazole in number is put into three-necked flask, continues 2.5~6h of stirring, subsequent cooled to room temperature, to three
Mixture in mouthful flask is filtered, and collects filtered fluid, and filtered fluid is put into be concentrated into concentration tank original volume 60~
80%, concentrate is collected, it is spare；
(3) attapulgite is taken to be put into calcining furnace, set temperature is 800~1200 °C, calcines 0.5~2h, cools to room with the furnace
Calcined material taking-up is put into pulverizer and crushes, crosses 150 meshes by temperature, collects sieving particle A, according to parts by weight, in mass ratio
Alkyl phenol polyoxyethylene ether, humic acid and sieving particle A are put into milling tank by 1:5:15,1.5 are milled with 200r/min~
3h is sieved with 100 mesh sieve, and collects sieving particle；
(4) according to parts by weight, the spare concentrate of 40~60 parts of steps (2), 20~30 parts of above-mentioned sieving particles, 15~25 parts are taken
Step (2) spare concentrate is uniformly mixed by maleic anhydride and 8~15 parts of diethanol amine with above-mentioned sieving particle first,
It is filtered after standing 20~50min, collects filter residue and filtrate respectively, filtrate, maleic anhydride and diethanol amine are put into reaction
In kettle, set temperature is 60~80 °C, stirs 1.0~1.5h with 150r/min, then be cooled to 30~50 °C, adds filter residue,
It is stirred to react 5~8.5h, discharging collects out material, that is, completes the work of withdrawing deposit of retanning agent.
C, it detects
A, viscosity measurements:
Fly DV2T viscosimeter tested viscosity by the formaldehydeless amino resins retanning agent product constant temperature of synthesis and 25 °C, and with rich power；
B, relative molecular mass detects:
A certain amount of sample is taken, it is characterized using GPC and counts uniform relative molecular weight and its distribution coefficient；
C, rate detection is thickened:
For the antimere of retanning experiment leather base, three points are taken from ridge line to ventral direction, the thickness after testing its retanning
Degree, calculating thicken rate
Embodiment one:
A, the production of retanning agent
First according to parts by weight, by 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water in room
Temperature is stirred, and adjust pH value be 7.5~8.5, then under 50~70 °C react 0.5~2.5h contain to obtain the final product polyhydroxy or
Then person's amino monomers prepolymer containing polyhydroxy and aldehyde radical simultaneously is added 120~220 parts in above-mentioned amino monomers prepolymer
Then water, 50~90 parts of sulfonated reagents keep the temperature 1.0~3.5h to get the amino monomers prepolymer of sulfonation, most under 70~95 °C
The amino monomers prepolymer of above-mentioned sulfonation is cooled to 50~60 °C afterwards, the hydrolytic collagen of 80~150 parts of different molecular weights is added
Protein solution adjusts pH to 4.0~7.0, then in 50~60 °C of lower 0.5~3.5h of insulation reaction, is cooled to 50 °C hereinafter, adjusting pH
To neutral up to formaldehydeless amino resins retanning agent product.
B, it purifies
First after above-mentioned preparation process, amino resins retanning agent product formaldehydeless in container is put into a centrifuge, with
1500r/min is centrifuged 10~20min, collects supernatant and takes 50~60 portions of supernatants, 12~17 parts according to parts by weight
EDC.HCL, 5~10 parts of I-hydroxybenzotriazoles and 1~5 part of Raney's nickel, are first put into band for supernatant, EDC.HCL and Raney's nickel
In the three-necked flask for having blender and thermometer, using nitrogen protection, 15~30min is stirred with 120r/min, then above-mentioned
After stirring, three-necked flask is placed in water-bath, set temperature is 35~505 °C, by the 1- hydroxyl in above-mentioned parts by weight
Base benzotriazole is put into three-necked flask, continues 2.5~6h of stirring, subsequent cooled to room temperature, to mixed in three-necked flask
It closes object to be filtered, collects filtered fluid, and filtered fluid is put into and is concentrated into the 60~80% of original volume in concentration tank, collect concentration
Liquid, it is spare, then attapulgite is taken to be put into calcining furnace, set temperature is 800~1200 °C, calcines 0.5~2h, furnace cooling
To room temperature, calcined material taking-up is put into pulverizer and is crushed, 150 meshes are crossed, sieving particle A is collected, according to parts by weight, by matter
Alkyl phenol polyoxyethylene ether, humic acid and sieving particle A are put into milling tank than 1:5:15 by amount, mill 1.5 with 200r/min
~3h, sieves with 100 mesh sieve, collect sieving particle, finally according to parts by weight, take the spare concentrate of 40~60 parts of steps (2), 20~
30 parts of above-mentioned sieving particles, 15~25 parts of maleic anhydrides and 8~15 parts of diethanol amine, first by step (2) spare concentration
Liquid is uniformly mixed with above-mentioned sieving particle, is filtered after standing 20~50min, filter residue and filtrate is collected respectively, by filtrate, maleic
Dicarboxylic anhydride and diethanol amine are put into reaction kettle, and set temperature is 60~80 °C, stir 1.0~1.5h with 150r/min, then drop
Temperature adds filter residue to 30~50 °C, is stirred to react 5~8.5h, and discharging collects out material, that is, completes the work of withdrawing deposit of retanning agent
Make.
C, it detects
Viscosity measurements are carried out first:
Fly DV2T viscosimeter tested viscosity by the formaldehydeless amino resins retanning agent product constant temperature of synthesis and 25 °C, and with rich power,
Then it carries out relative molecular mass detection: taking a certain amount of sample, it is characterized using GPC and counts uniform relative molecular mass and divides
Cloth coefficient finally carries out thickening rate detection: for the antimere of retanning experiment leather base, taking three from ridge line to ventral direction
A, after testing its retanning thickness, calculating thicken.
Embodiment two:
In example 1, following processes are added:
Amino monomers are melamine, urea, any one in dicyandiamide.
A, the production of retanning agent
First according to parts by weight, by 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water in room
Temperature is stirred, and adjust pH value be 7.5~8.5, then under 50~70 °C react 0.5~2.5h contain to obtain the final product polyhydroxy or
Then person's amino monomers prepolymer containing polyhydroxy and aldehyde radical simultaneously is added 120~220 parts in above-mentioned amino monomers prepolymer
Then water, 50~90 parts of sulfonated reagents keep the temperature 1.0~3.5h to get the amino monomers prepolymer of sulfonation, most under 70~95 °C
The amino monomers prepolymer of above-mentioned sulfonation is cooled to 50~60 °C afterwards, the hydrolytic collagen of 80~150 parts of different molecular weights is added
Protein solution adjusts pH to 4.0~7.0, then in 50~60 °C of lower 0.5~3.5h of insulation reaction, is cooled to 50 °C hereinafter, adjusting pH
To neutral up to formaldehydeless amino resins retanning agent product.
B, it purifies
First after above-mentioned preparation process, amino resins retanning agent product formaldehydeless in container is put into a centrifuge, with
1500r/min is centrifuged 10~20min, collects supernatant and takes 50~60 portions of supernatants, 12~17 parts according to parts by weight
EDC.HCL, 5~10 parts of I-hydroxybenzotriazoles and 1~5 part of Raney's nickel, are first put into band for supernatant, EDC.HCL and Raney's nickel
In the three-necked flask for having blender and thermometer, using nitrogen protection, 15~30min is stirred with 120r/min, then above-mentioned
After stirring, three-necked flask is placed in water-bath, set temperature is 35~505 °C, by the 1- hydroxyl in above-mentioned parts by weight
Base benzotriazole is put into three-necked flask, continues 2.5~6h of stirring, subsequent cooled to room temperature, to mixed in three-necked flask
It closes object to be filtered, collects filtered fluid, and filtered fluid is put into and is concentrated into the 60~80% of original volume in concentration tank, collect concentration
Liquid, it is spare, then attapulgite is taken to be put into calcining furnace, set temperature is 800~1200 °C, calcines 0.5~2h, furnace cooling
To room temperature, calcined material taking-up is put into pulverizer and is crushed, 150 meshes are crossed, sieving particle A is collected, according to parts by weight, by matter
Alkyl phenol polyoxyethylene ether, humic acid and sieving particle A are put into milling tank than 1:5:15 by amount, mill 1.5 with 200r/min
~3h, sieves with 100 mesh sieve, collect sieving particle, finally according to parts by weight, take the spare concentrate of 40~60 parts of steps (2), 20~
30 parts of above-mentioned sieving particles, 15~25 parts of maleic anhydrides and 8~15 parts of diethanol amine, first by step (2) spare concentration
Liquid is uniformly mixed with above-mentioned sieving particle, is filtered after standing 20~50min, filter residue and filtrate is collected respectively, by filtrate, maleic
Dicarboxylic anhydride and diethanol amine are put into reaction kettle, and set temperature is 60~80 °C, stir 1.0~1.5h with 150r/min, then drop
Temperature adds filter residue to 30~50 °C, is stirred to react 5~8.5h, and discharging collects out material, that is, completes the work of withdrawing deposit of retanning agent
Make.
C, it detects
Viscosity measurements are carried out first:
Fly DV2T viscosimeter tested viscosity by the formaldehydeless amino resins retanning agent product constant temperature of synthesis and 25 °C, and with rich power,
Then it carries out relative molecular mass detection: taking a certain amount of sample, it is characterized using GPC and counts uniform relative molecular mass and divides
Cloth coefficient finally carries out thickening rate detection: for the antimere of retanning experiment leather base, taking three from ridge line to ventral direction
A, after testing its retanning thickness, calculating thicken.
Embodiment three:
In example 2, following processes are added:
A, the production of retanning agent
First according to parts by weight, by 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water in room
Temperature is stirred, and adjust pH value be 7.5~8.5, then under 50~70 °C react 0.5~2.5h contain to obtain the final product polyhydroxy or
Then person's amino monomers prepolymer containing polyhydroxy and aldehyde radical simultaneously is added 120~220 parts in above-mentioned amino monomers prepolymer
Then water, 50~90 parts of sulfonated reagents keep the temperature 1.0~3.5h to get the amino monomers prepolymer of sulfonation, most under 70~95 °C
The amino monomers prepolymer of above-mentioned sulfonation is cooled to 50~60 °C afterwards, the hydrolytic collagen of 80~150 parts of different molecular weights is added
Protein solution adjusts pH to 4.0~7.0, then in 50~60 °C of lower 0.5~3.5h of insulation reaction, is cooled to 50 °C hereinafter, adjusting pH
To neutral up to formaldehydeless amino resins retanning agent product.
B, it purifies
First after above-mentioned preparation process, amino resins retanning agent product formaldehydeless in container is put into a centrifuge, with
1500r/min is centrifuged 10~20min, collects supernatant and takes 50~60 portions of supernatants, 12~17 parts according to parts by weight
EDC.HCL, 5~10 parts of I-hydroxybenzotriazoles and 1~5 part of Raney's nickel, are first put into band for supernatant, EDC.HCL and Raney's nickel
In the three-necked flask for having blender and thermometer, using nitrogen protection, 15~30min is stirred with 120r/min, then above-mentioned
After stirring, three-necked flask is placed in water-bath, set temperature is 35~505 °C, by the 1- hydroxyl in above-mentioned parts by weight
Base benzotriazole is put into three-necked flask, continues 2.5~6h of stirring, subsequent cooled to room temperature, to mixed in three-necked flask
It closes object to be filtered, collects filtered fluid, and filtered fluid is put into and is concentrated into the 60~80% of original volume in concentration tank, collect concentration
Liquid, it is spare, then attapulgite is taken to be put into calcining furnace, set temperature is 800~1200 °C, calcines 0.5~2h, furnace cooling
To room temperature, calcined material taking-up is put into pulverizer and is crushed, 150 meshes are crossed, sieving particle A is collected, according to parts by weight, by matter
Alkyl phenol polyoxyethylene ether, humic acid and sieving particle A are put into milling tank than 1:5:15 by amount, mill 1.5 with 200r/min
~3h, sieves with 100 mesh sieve, collect sieving particle, finally according to parts by weight, take the spare concentrate of 40~60 parts of steps (2), 20~
30 parts of above-mentioned sieving particles, 15~25 parts of maleic anhydrides and 8~15 parts of diethanol amine, first by step (2) spare concentration
Liquid is uniformly mixed with above-mentioned sieving particle, is filtered after standing 20~50min, filter residue and filtrate is collected respectively, by filtrate, maleic
Dicarboxylic anhydride and diethanol amine are put into reaction kettle, and set temperature is 60~80 °C, stir 1.0~1.5h with 150r/min, then drop
Temperature adds filter residue to 30~50 °C, is stirred to react 5~8.5h, and discharging collects out material, that is, completes the work of withdrawing deposit of retanning agent
Make.
C, it detects
Viscosity measurements are carried out first:
Fly DV2T viscosimeter tested viscosity by the formaldehydeless amino resins retanning agent product constant temperature of synthesis and 25 °C, and with rich power,
Then it carries out relative molecular mass detection: taking a certain amount of sample, it is characterized using GPC and counts uniform relative molecular mass and divides
Cloth coefficient finally carries out thickening rate detection: for the antimere of retanning experiment leather base, taking three from ridge line to ventral direction
A, after testing its retanning thickness, calculating thicken.
Example IV:
In the third embodiment, following processes are added:
Hydrolyzed Collagen molecular weight in purification step is 2000~6000,8000~15000 or 15000~40000.
A, the production of retanning agent
First according to parts by weight, by 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water in room
Temperature is stirred, and adjust pH value be 7.5~8.5, then under 50~70 °C react 0.5~2.5h contain to obtain the final product polyhydroxy or
Then person's amino monomers prepolymer containing polyhydroxy and aldehyde radical simultaneously is added 120~220 parts in above-mentioned amino monomers prepolymer
Then water, 50~90 parts of sulfonated reagents keep the temperature 1.0~3.5h to get the amino monomers prepolymer of sulfonation, most under 70~95 °C
The amino monomers prepolymer of above-mentioned sulfonation is cooled to 50~60 °C afterwards, the hydrolytic collagen of 80~150 parts of different molecular weights is added
Protein solution adjusts pH to 4.0~7.0, then in 50~60 °C of lower 0.5~3.5h of insulation reaction, is cooled to 50 °C hereinafter, adjusting pH
To neutral up to formaldehydeless amino resins retanning agent product.
B, it purifies
First after above-mentioned preparation process, amino resins retanning agent product formaldehydeless in container is put into a centrifuge, with
1500r/min is centrifuged 10~20min, collects supernatant and takes 50~60 portions of supernatants, 12~17 parts according to parts by weight
EDC.HCL, 5~10 parts of I-hydroxybenzotriazoles and 1~5 part of Raney's nickel, are first put into band for supernatant, EDC.HCL and Raney's nickel
In the three-necked flask for having blender and thermometer, using nitrogen protection, 15~30min is stirred with 120r/min, then above-mentioned
After stirring, three-necked flask is placed in water-bath, set temperature is 35~505 °C, by the 1- hydroxyl in above-mentioned parts by weight
Base benzotriazole is put into three-necked flask, continues 2.5~6h of stirring, subsequent cooled to room temperature, to mixed in three-necked flask
It closes object to be filtered, collects filtered fluid, and filtered fluid is put into and is concentrated into the 60~80% of original volume in concentration tank, collect concentration
Liquid, it is spare, then attapulgite is taken to be put into calcining furnace, set temperature is 800~1200 °C, calcines 0.5~2h, furnace cooling
To room temperature, calcined material taking-up is put into pulverizer and is crushed, 150 meshes are crossed, sieving particle A is collected, according to parts by weight, by matter
Alkyl phenol polyoxyethylene ether, humic acid and sieving particle A are put into milling tank than 1:5:15 by amount, mill 1.5 with 200r/min
~3h, sieves with 100 mesh sieve, collect sieving particle, finally according to parts by weight, take the spare concentrate of 40~60 parts of steps (2), 20~
30 parts of above-mentioned sieving particles, 15~25 parts of maleic anhydrides and 8~15 parts of diethanol amine, first by step (2) spare concentration
Liquid is uniformly mixed with above-mentioned sieving particle, is filtered after standing 20~50min, filter residue and filtrate is collected respectively, by filtrate, maleic
Dicarboxylic anhydride and diethanol amine are put into reaction kettle, and set temperature is 60~80 °C, stir 1.0~1.5h with 150r/min, then drop
Temperature adds filter residue to 30~50 °C, is stirred to react 5~8.5h, and discharging collects out material, that is, completes the work of withdrawing deposit of retanning agent
Make.
C, it detects
Viscosity measurements are carried out first:
Fly DV2T viscosimeter tested viscosity by the formaldehydeless amino resins retanning agent product constant temperature of synthesis and 25 °C, and with rich power,
Then it carries out relative molecular mass detection: taking a certain amount of sample, it is characterized using GPC and counts uniform relative molecular mass and divides
Cloth coefficient finally carries out thickening rate detection: for the antimere of retanning experiment leather base, taking three from ridge line to ventral direction
A, after testing its retanning thickness, calculating thicken.
The present invention dispels free existing formaldehyde by the production process in product, in the product and retanning at
In leather formaldehydeless generation a possibility that, and the Hydrolyzed Collagen molecule introduced has the energy of lasting capture free formaldehyde
Power, thus the product can also be reduced using other Retanning Materials bring Formaldehydes, and this product makes in process of production
Raw material be all it is from a wealth of sources, cheap, production method is simple, can be widely to marketing.
It although an embodiment of the present invention has been shown and described, for the ordinary skill in the art, can be with
A variety of variations, modification, replacement can be carried out to these embodiments without departing from the principles and spirit of the present invention by understanding
And modification, the scope of the present invention is defined by the appended.
Claims (4)
1. a kind of leather chemicals production purification characterization processes, characterized by the following steps:
A, the production of retanning agent
According to parts by weight, 70~150 parts of amino monomers, 350~650 parts of glutaraldehydes, 200~500 parts of pure water are stirred in room temperature
Mixing is mixed, and adjusting pH value is 7.5~8.5,0.5~2.5h is then reacted under 50~70 °C and contains polyhydroxy or same to obtain the final product
The amino monomers prepolymer of Shi Hanyou polyhydroxy and aldehyde radical；
120~220 parts of water are added in above-mentioned amino monomers prepolymer, then 50~90 parts of sulfonated reagents are protected under 70~95 °C
1.0~3.5h of temperature to get sulfonation amino monomers prepolymer；
The amino monomers prepolymer of above-mentioned sulfonation is cooled to 50~60 °C, the hydrolysis glue of 80~150 parts of different molecular weights is added
Former protein solution adjusts pH to 4.0~7.0, then in 50~60 °C of lower 0.5~3.5h of insulation reaction, is cooled to 50 °C hereinafter, adjusting
PH is to neutral up to formaldehydeless amino resins retanning agent product；
B, it purifies
After above-mentioned preparation process, amino resins retanning agent product formaldehydeless in container is put into a centrifuge, with
1500r/min is centrifuged 10~20min, collects supernatant and takes 50~60 portions of supernatants, 12~17 parts according to parts by weight
EDC.HCL, 5~10 parts of I-hydroxybenzotriazoles and 1~5 part of Raney's nickel, are first put into band for supernatant, EDC.HCL and Raney's nickel
In the three-necked flask for having blender and thermometer, using nitrogen protection, 15~30min is stirred with 120r/min；
After above-mentioned stirring, three-necked flask is placed in water-bath, set temperature is 35~505 °C, by above-mentioned parts by weight
I-hydroxybenzotriazole in number is put into three-necked flask, continues 2.5~6h of stirring, subsequent cooled to room temperature, to three mouthfuls
Mixture in flask is filtered, and collects filtered fluid, and filtered fluid is put into be concentrated into concentration tank original volume 60~
80%, concentrate is collected, it is spare；
Attapulgite is taken to be put into calcining furnace, set temperature is 800~1200 °C, 0.5~2h calcined, cools to room temperature with the furnace,
Calcined material taking-up is put into pulverizer and is crushed, 150 meshes are crossed, collects sieving particle A, according to parts by weight, in mass ratio 1:
Alkyl phenol polyoxyethylene ether, humic acid and sieving particle A are put into milling tank, are milled 1.5~3h with 200r/min by 5:15,
It sieves with 100 mesh sieve, collects sieving particle；
According to parts by weight, take the spare concentrate of 40~60 parts of steps (2), 20~30 parts of above-mentioned sieving particles, 15~25 parts it is suitable
Step (2) spare concentrate is uniformly mixed by anhydride maleique and 8~15 parts of diethanol amine with above-mentioned sieving particle first, quiet
It is filtered after setting 20~50min, collects filter residue and filtrate respectively, filtrate, maleic anhydride and diethanol amine are put into reaction kettle
In, set temperature is 60~80 °C, stirs 1.0~1.5h with 150r/min, then be cooled to 30~50 °C, adds filter residue, stir
5~8.5h of reaction is mixed, discharging collects out material, that is, completes the work of withdrawing deposit of retanning agent；
C, it detects
A, viscosity measurements:
Fly DV2T viscosimeter tested viscosity by the formaldehydeless amino resins retanning agent product constant temperature of synthesis and 25 °C, and with rich power；
B, relative molecular mass detects:
A certain amount of sample is taken, it is characterized using GPC and counts uniform relative molecular weight and its distribution coefficient；
C, rate detection is thickened:
For the antimere of retanning experiment leather base, three points are taken from ridge line to ventral direction, the thickness after testing its retanning
Degree, calculating thicken rate.
2. a kind of leather chemicals production purification characterization processes according to claim 1, it is characterised in that: the amino monomers
For any one in melamine, urea, dicyandiamide.
3. a kind of leather chemicals production purification characterization processes according to claim 1, it is characterised in that: the retanning agent system
Standby middle sulfonated reagent is any one of sodium sulfite, sodium hydrogensulfite, sodium pyrosulfite.
4. a kind of leather chemicals production purification characterization processes according to claim 1, it is characterised in that: used in purification step
Hydrolyzed Collagen molecular weight be 2000~6000,8000~15000 or 15000~40000.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140154A (en) * | 2011-02-21 | 2011-08-03 | 陕西科技大学 | Method for preparing chrome-containing protein filling and retanning agent by using chrome shavings as raw materials |
| CN104017920A (en) * | 2014-06-11 | 2014-09-03 | 四川德赛尔化工实业有限公司 | Formaldehyde-free amino resin retanning agent |
| CN106755629A (en) * | 2016-12-30 | 2017-05-31 | 周益铭 | A kind of preparation method of leather composite tanning agent |
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2018
- 2018-09-17 CN CN201811080607.XA patent/CN109371182A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102140154A (en) * | 2011-02-21 | 2011-08-03 | 陕西科技大学 | Method for preparing chrome-containing protein filling and retanning agent by using chrome shavings as raw materials |
| CN104017920A (en) * | 2014-06-11 | 2014-09-03 | 四川德赛尔化工实业有限公司 | Formaldehyde-free amino resin retanning agent |
| CN106755629A (en) * | 2016-12-30 | 2017-05-31 | 周益铭 | A kind of preparation method of leather composite tanning agent |
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