CN104232809B - Collagen-modified negatively charged ion retanning agent of a kind of magnetic and preparation method thereof - Google Patents
Collagen-modified negatively charged ion retanning agent of a kind of magnetic and preparation method thereof Download PDFInfo
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- 239000000725 suspension Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 239000004160 Ammonium persulphate Substances 0.000 claims description 7
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Substances OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 5
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 5
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- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
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- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 6
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The present invention relates to collagen-modified negatively charged ion retanning agent of a kind of magnetic and preparation method thereof, mainly with process hides waste collagen albumen for raw material, be combined with magnetic fluid and be prepared from.Beneficial effect of the present invention: preparation magneticsubstance being used for skin material, is used for the separation of residual skin material in waste leather-making liquid, has innovated tanning sewage tupe, for tanning production prevention and cure of pollution propose new thinking and approach by magnetic separation technique.Achieve the recycling of tanning waste, decrease tanning production pollutant emission.Magnetic collagen hydrolysate through grafting, copolymerization and modification, modified product have good filling properties, with chrome tanned leather collegen filament bonding properties.
Description
(1) technical field
The invention belongs to magnetic organic polymer composite preparation field, be specifically related to collagen-modified negatively charged ion retanning agent of a kind of magnetic and preparation method thereof.
(2) background technology
Tanning industry lives with people to contact light industrial segment closely, and China is leather producing country important in the world.Tanning production is also the more serious industrial production of environmental pollution, and only have the collagen of 22%-30% to become leather in tanning industry, remaining is all thrown away as process hides solid waste.According to statistics, China's tanning industry solid waste produced every year based on collagen protein is about 1,400,000 tons.The a considerable amount of solid waste of tanning industry is landfilled or natural degradation in the environment, not only causes serious environment water and soil pollution, also wastes collagen protein resource greatly.Tanning production not only produces the solid waste of enormous amount, also produces a large amount of industrial sewages.Tanning production water consumption is large, and a large amount of skin material used can not be completely absorbed utilization, and in tanning production, the skin material be difficult to again not absorbing is separated, and therefore, leather making integrated sewage pollution load is high, complicated.At present, China's leather industry produces waste water 1.6 hundred million tons every year, wherein COD about 40.4 ten thousand tons.
Make full use of the refuse of tanning production, collagen protein is converted into the edible product, medical products, makeup etc. of high added value or large Chemicals, solve China's tanning production solid waste pollution, realize the only way of tanning industry Sustainable development, tanning industry is produced and steps into " atom economy " pattern.Late 1920s, people begin one's study tanning waste process, recovery and utilization, and Chinese scholars has carried out extensive research in decades, obtains a large amount of achievements in research in fields such as food, feed, makeup, fertilizer and tanning agents.China natural resources utilizes the collagen protein in tanning waste to start from late 1980s, and mainly for the production of manufacture feed, fertilizer, gelatin etc., added value is low, is unfavorable for the popularization of tanning waste application technology as the second resource.
The skin material remained in waste leather-making liquid is difficult to be separated, and being all pooled in composite wastewater, is cause tanning sewage pollution load weight, the reason that pollutant kind is many.Tanning sewage process generally adopts the pattern focused on, and makes tanning sewage complex treatment process, is difficult to steady running, and effluent quality fluctuating range is large, and restriction is produced and normally carried out.The pollution load reducing tanning industry sewage is the fundamental way solving tanning sewage contaminate environment.Isolating the skin material remained in waste leather-making liquid is reduce tanning sewage pollution load effective means.But do not have good method to isolate not by skin material that collagen absorbs at present.
Retanning agent is the skin material that a class has auxiliary tanning effect, plays vital effect to physical and mechanical properties, the use properties making leather.Collagen protein partial hydrolysate is similar to collagen structure in leather, intermiscibility is good.Take collagen protein as raw material, through retanning agent prepared by proper method modification, be easy to diffuse and penetrate into leather collagen fiber inside, and can be combined with leather collagen fabric by ionic linkage, hydrogen bond etc., play tanning and filling effect, overcome other kind retanning agents to make to make leather surface and tightly harden, remove from office the deficiencies such as body is stiff, improve colored leather performance, improve resultant leather quality processed.
Adopt proper method by Fe
3o
4magnetic fluid is combined with the protein modified material of process hides waste collagen prepares retanning agent, gives retanning agent by magnetic, and retanning waste liquid can be isolated through magnetic field not by retanning agent that leather absorbs.The existing good retanning performance of the collagen-modified retanning agent of such magnetic, being conducive to again separating remaining in retanning agent in retanning waste liquid, reducing the pollution load of leather making integrated sewage.
(3) summary of the invention
The present invention, in order to make up the deficiencies in the prior art, provides collagen-modified negatively charged ion retanning agent of a kind of magnetic and preparation method thereof, the present invention proposes with waste collagen albumen for raw material, through in conjunction with Fe
3o
4magnetic fluid, grafting, copolymerization and modification prepare magnetic retanning agent, with the method utilizing the action of a magnetic field to isolate residual retanning agent in retanning waste liquid, the existing good retanning performance of the collagen-modified retanning agent of such magnetic, being conducive to again separating remaining in retanning agent in retanning waste liquid, reducing the pollution load of leather making integrated sewage.
The present invention is achieved through the following technical solutions:
The collagen-modified negatively charged ion retanning agent of a kind of magnetic, its special character is: main with process hides waste collagen albumen for raw material, be combined with magnetic fluid and be prepared from.
A preparation method for the collagen-modified negatively charged ion retanning agent of magnetic described in basis, comprises the following steps: with process hides waste collagen albumen for raw material, through hydrolysis, in conjunction with obtaining the collagen-modified negatively charged ion retanning agent of magnetic after magnetic fluid, graft copolymerization.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, comprises the following steps:
(1) process hides scrap leather bits hydrolysis:
Appropriate process hides scrap leather bits are joined in reactor, adds scurf quality 20-50 water doubly, be warming up to 60-100 DEG C, hydrolysis reaction, obtain collagen hydrolyzed solution;
(2) magnetic collagen hydrolysate preparation:
In above-mentioned collagen hydrolyzed solution, add scurf quality 20-50% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring, adds the Fe of scurf quality 10-40% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse, then slowly adds scurf quality 10-30 Virahol doubly under rapid stirring state, then ultrasonic disperse, and add glutaraldehyde water solution, wherein glutaraldehyde quality is the 25-125% of scurf quality, then rapid stirring, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate, suspension after Magneto separate, the solid of acquisition with washed with isopropyl alcohol for several times, for subsequent use after dry at 20-50 DEG C of temperature;
(3) graft copolymerization:
Appropriate MALEIC ANHYDRIDE is joined in reactor, add MALEIC ANHYDRIDE quality 5-10 water doubly, at room temperature be stirred to dissolving, appropriate vinylformic acid is taken in MALEIC ANHYDRIDE and vinylformic acid mol ratio 1:1-5 ratio, take the initiator of MALEIC ANHYDRIDE and vinylformic acid total mass 2-10%, join in reactor after dissolving by suitable quantity of water, be warming up to 50-90 DEG C, vinylformic acid is slowly added drop-wise in reactor, after vinylformic acid dropwises, continue reaction, take MALEIC ANHYDRIDE and vinylformic acid total mass 10-50% magnetic collagen hydrolysate joins in beaker, add magnetic collagen hydrolysate quality 5-10 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving, then MALEIC ANHYDRIDE and vinylformic acid reaction system are warming up to 60-100 DEG C, magnetic collagen hydrolysate solution is slowly joined in above-mentioned reaction system, after magnetic collagen hydrolysate solution adds, continue reaction, be 6-10 by aqueous sodium hydroxide solution adjust ph, obtain the collagen-modified negatively charged ion retanning agent of magnetic.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, in step (1), is warming up to 60-100 DEG C, adds the acid of scurf quality 1-5%, stirring reaction, and adjust ph is or close to 7, obtains collagen hydrolyzed solution.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, in step (2), the mass concentration of glutaraldehyde water solution is 25%, and the addition of this glutaraldehyde water solution is scurf quality 1-5 times.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, in step (2), in above-mentioned collagen hydrolyzed solution, add scurf quality 20-50% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring 30-60 minute, adds the Fe of scurf quality 10-40% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 2-10 minute, then slowly adds scurf quality 10-30 Virahol doubly under rapid stirring state, ultrasonic disperse 2-10 minute again, adding scurf quality 1-5 mass concentration is doubly the glutaraldehyde water solution of 25%, rapid stirring 30-60 minute, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, in step (3), appropriate MALEIC ANHYDRIDE is joined in reactor, add MALEIC ANHYDRIDE quality 5-10 water doubly, at room temperature be stirred to dissolving, appropriate vinylformic acid is taken in MALEIC ANHYDRIDE and vinylformic acid mol ratio 1:1-5 ratio, take the initiator of MALEIC ANHYDRIDE and vinylformic acid total mass 2-10%, join in reactor after dissolving by suitable quantity of water, be warming up to 50-90 DEG C, in 30-60 minute, vinylformic acid is slowly added drop-wise in reactor, after vinylformic acid dropwises, continue reaction 30-90 minute, take MALEIC ANHYDRIDE and vinylformic acid total mass 10-50% magnetic collagen hydrolysate joins in beaker, add magnetic collagen hydrolysate quality 5-10 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving, then MALEIC ANHYDRIDE and vinylformic acid reaction system are warming up to 60-100 DEG C, in 30-60 minute, magnetic collagen hydrolysate solution is slowly joined in above-mentioned reaction system, after magnetic collagen hydrolysate solution adds, continue reaction 2-5 hour, be 6-10 by aqueous sodium hydroxide solution adjust ph, obtain the collagen-modified negatively charged ion retanning agent of magnetic.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, in step (1), acid is the vitriol oil, concentrated hydrochloric acid and/or its mixture, is or close to 7 by aqueous sodium hydroxide solution adjust ph.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, in step (1) and step (3), aqueous sodium hydroxide solution mass concentration is 20%.
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present invention, in step (3), initiator is Potassium Persulphate, ammonium persulphate, Sulfothiorine-Potassium Persulphate initiator system, Sulfothiorine-ammonium persulphate initiator system, Sulfothiorine-hydrogen peroxide.
The present invention with process hides waste collagen albumen for raw material, after hydrolysis, with Fe
3o
4magnetic fluid combines, through graft copolymerization, and the collagen-modified negatively charged ion retanning agent of preparation magnetic.Feature of the present invention is preparation magnetic separation technique being used for leather composite tanning agent, retanning agent is made to possess magnetic, in retanning operation, can do not separated from retanning waste liquid by Magneto separate mode by leather absorption, the retanning agent remained in retanning waste liquid, the tupe of innovation tanning production sewage.Can the application of Magneto separate retanning agent, make to be easy to separate from water body by the retanning agent of stable dispersion in water, thus effectively alleviate the pollution load of leather making integrated sewage, reduce cost of sewage disposal.
The present invention for magnetic retanning agent prepared by raw material, takes full advantage of collagen protein resource with process hides waste collagen albumen, provides effective way, achieve the recycling of tanning waste for solving the discharge of process hides solid waste and piling up environmental pollution problem.
The present invention not only to consider to meet tanning production prevention and cure of pollution requirement, realize tanning waste recycling, also to consider to meet the requirement of tanning production to retanning agent performance.Collagen hydrolysate and collagen just have similar structure, are easy to enter materials with hide glue fibril inside.For improving the fillibility of collagen hydrolysate, the associativity with collagen, to combining Fe
3o
4the collagen hydrolysate of magnetic fluid has carried out grafting, copolymerization and modification, makes the collagen-modified negatively charged ion retanning agent of magnetic meet the demand of tanning production to high-performance retanning agent.
Beneficial effect of the present invention:
(1) magneticsubstance is used for the preparation of skin material, magnetic separation technique is used for the separation of residual skin material in waste leather-making liquid, has innovated tanning sewage tupe, for tanning production prevention and cure of pollution propose new thinking and approach.
(2) achieve the recycling of tanning waste, decrease tanning production pollutant emission.
(3) magnetic collagen hydrolysate is through grafting, copolymerization and modification, modified product have good filling properties, with chrome tanned leather collegen filament bonding properties.
(4) embodiment
Tanning industry is the important light industrial segment of China, and China has become the main process hides in the world and leather goods are produced and processing, skin material preparation and application country.China's tanning industry Sustainable development is govern to the pollution of environment.At present, the annual sewage effluent of China's tanning industry 1.6 hundred million tons, wherein COD about 40.4 ten thousand tons; Process hides solid waste 1,400,000 tons.Minimizing tanning sewage generation, the prevention and cure of pollution such as pollution load, recycling tanning waste reducing sewage, clearer production technology are the gordian techniquies supporting China's tanning industry Sustainable development.
The pollution load of tanning sewage is low primarily of the utilization ratio of skin material, the reason such as wide variety, good water solubility causes.In addition, leather-making technology numerous and complicated, according to the change of finished leather performance various processes greatly, is difficult to realize sewage separation and divides and rules.The flocculation deposition seperation of leather making integrated sewage can not effectively reduce sewage pollution load, is unfavorable for that continuous biochemical treatment is efficient, steady running.The skin material residued in process waste liquor is separated the pollution load that effectively can reduce leather making integrated sewage.Skin material is combined with magneticsubstance, gives skin material magnetic, high efficiency separation can go out skin material residual in process waste liquor under the action of a magnetic field, effectively reduce the pollution load of leather making integrated sewage, reduce cost of sewage disposal.
Tanning industry solid waste, mainly the process of collagen protein is same with application technology as the second resource governs tanning industry Sustainable development.Collagen protein partial hydrolysate is similar to collagen structure in leather.Take collagen protein as retanning agent excellent property prepared by raw material, good penetrability, is easily combined with leather collagen fabric.Tanning waste being used for tanning production is the shortest industrial waste recycling approach of flow process.
The present invention proposes and prepare magnetic retanning agent with the method utilizing the action of a magnetic field to isolate residual retanning agent in retanning waste liquid.For the preparation and application of skin material, tanning production prevention and cure of pollution provide new thinking and countermeasure.
The invention provides a kind of with process hides waste collagen albumen for raw material, be combined with magnetic fluid, through proper method modification, prepare the method for the collagen-modified negatively charged ion retanning agent of magnetic.High level conversion for process hides collagen based refuse have found a feasible approach.
Embodiment 1
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present embodiment, comprising:
(1) process hides scrap leather bits hydrolysis: appropriate process hides scrap leather bits are joined in reactor, adds the water of scurf quality 20 times, be warming up to 60 DEG C, add the vitriol oil of scurf quality 1%, stirring reaction 60 minutes.Be 7 by the aqueous sodium hydroxide solution adjust ph of appropriate mass concentration 20%.
(2) magnetic collagen hydrolysate mixture preparation: in above-mentioned collagen hydrolyzed solution, add scurf quality 20%Span-80 tensio-active agent, at 40 DEG C of temperature, dispersed with stirring 30 minutes.The Fe of scurf quality 10% is added after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 2 minutes, then slowly adds the Virahol of scurf quality 10 times under rapid stirring state, then ultrasonic disperse 2 minutes.The mass concentration adding scurf quality 1 times is the glutaraldehyde water solution of 25%, rapid stirring 30 minutes, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.Suspension is after Magneto separate, and the solid washed with isopropyl alcohol several of acquisition, at 20 DEG C of temperature, drying is rear for subsequent use.
(3) graft copolymerization: join in reactor by appropriate MALEIC ANHYDRIDE, adds the water of MALEIC ANHYDRIDE quality 5 times, is at room temperature stirred to dissolving.Vinylformic acid has been taken in right amount by MALEIC ANHYDRIDE and vinylformic acid mol ratio 1:1.Take the Potassium Persulphate of MALEIC ANHYDRIDE and vinylformic acid total mass 2%, join in reactor after dissolving by suitable quantity of water.Be warming up to 50 DEG C, in 30 minutes, vinylformic acid be slowly added drop-wise in reactor.After vinylformic acid dropwises, continue reaction 30 minutes.Take MALEIC ANHYDRIDE and vinylformic acid total mass 10% magnetic collagen hydrolysate joins in beaker, add the water of magnetic collagen hydrolysate quality 5 times, at 40 DEG C of temperature, be stirred to dissolving.MALEIC ANHYDRIDE and vinylformic acid reaction system are warming up to 60 DEG C, in 30 minutes, magnetic collagen hydrolysate solution are slowly joined in above-mentioned reaction system.After magnetic collagen hydrolysate solution adds, continue reaction 2 hours.Be 6 by aqueous sodium hydroxide solution adjust ph.Obtain the collagen-modified negatively charged ion retanning agent of magnetic.
Embodiment 2
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present embodiment, comprising:
(1) process hides scrap leather bits hydrolysis: appropriate process hides scrap leather bits are joined in reactor, adds the water of scurf quality 50 times, be warming up to 100 DEG C, add the concentrated hydrochloric acid of scurf quality 5%, stirring reaction 90 minutes.Be 7 by the aqueous sodium hydroxide solution adjust ph that appropriate mass concentration is 20%.
(2) magnetic collagen hydrolysate mixture preparation: in above-mentioned collagen hydrolyzed solution, add scurf quality 50%Span-40 tensio-active agent, at 70 DEG C of temperature, dispersed with stirring 60 minutes.The Fe of scurf quality 40% is added after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 10 minutes, then slowly adds the Virahol of scurf quality 30 times under rapid stirring state, then ultrasonic disperse 10 minutes.The mass concentration adding scurf quality 5 times is the glutaraldehyde water solution of 25%, rapid stirring 60 minutes, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.Suspension is after Magneto separate, and the solid washed with isopropyl alcohol several of acquisition, at 50 DEG C of temperature, drying is rear for subsequent use.
(3) graft copolymerization: join in reactor by appropriate MALEIC ANHYDRIDE, adds the water of MALEIC ANHYDRIDE quality 10 times, is at room temperature stirred to dissolving.Vinylformic acid has been taken in right amount by MALEIC ANHYDRIDE and vinylformic acid mol ratio 1:5.Take the Sulfothiorine of MALEIC ANHYDRIDE and vinylformic acid total mass 10%, dissolve by suitable quantity of water and join in reaction system.Be warming up to 90 DEG C, in 60 minutes, vinylformic acid be slowly added drop-wise in reactor.Take the Potassium Persulphate identical with Sulfothiorine molar weight, dissolve by suitable quantity of water, join in reactor with vinylformic acid simultaneously.After vinylformic acid and potassium persulfate solution dropwise, continue reaction 90 minutes.Take MALEIC ANHYDRIDE and vinylformic acid total mass 50% magnetic collagen hydrolysate joins in beaker, add the water of magnetic collagen hydrolysate quality 10 times, at 70 DEG C of temperature, be stirred to dissolving.MALEIC ANHYDRIDE and vinylformic acid reaction system are warming up to 100 DEG C, in 60 minutes, magnetic collagen hydrolysate solution are slowly joined in above-mentioned reaction system.After magnetic collagen hydrolysate solution adds, continue reaction 5 hours.Be 10 by aqueous sodium hydroxide solution adjust ph.Obtain the collagen-modified negatively charged ion retanning agent of magnetic.
Embodiment 3
Initiator is ammonium persulphate, and other are identical with embodiment 1.
Embodiment 4
Initiator is Sulfothiorine and ammonium persulphate oxidation-reduction trigger system, and wherein, the mol ratio of Sulfothiorine and ammonium persulphate is 1:1, and other are identical with example 2.
Embodiment 5
Initiator is Sulfothiorine and hydrogen peroxide oxidation-reduction initiating system, and wherein, the mol ratio of Sulfothiorine and hydrogen peroxide is 1:1, and other are identical with example 2.
Embodiment 6
The preparation method of the collagen-modified negatively charged ion retanning agent of magnetic of the present embodiment, comprising:
(1) process hides scrap leather bits hydrolysis: appropriate process hides scrap leather bits are joined in reactor, adds the water of scurf quality 35 times, be warming up to 80 DEG C, add the vitriol oil of scurf quality 2%, the concentrated hydrochloric acid of scurf quality 1%, stirring reaction 75 minutes.Be 30% aqueous sodium hydroxide solution adjust ph by appropriate mass concentration be 7.
(2) magnetic collagen hydrolysate mixture preparation: in above-mentioned collagen hydrolyzed solution, add scurf quality 35%Span-80 tensio-active agent, at 55 DEG C of temperature, dispersed with stirring 45 minutes.The Fe of scurf quality 25% is added after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 6 minutes, then slowly adds the Virahol of scurf quality 20 times under rapid stirring state, then ultrasonic disperse 6 minutes.The mass concentration adding scurf quality 3 times is the glutaraldehyde water solution of 25%, rapid stirring 45 minutes, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.Suspension is after Magneto separate, and the solid washed with isopropyl alcohol several of acquisition, at 35 DEG C of temperature, drying is rear for subsequent use.
(3) graft copolymerization: join in reactor by appropriate MALEIC ANHYDRIDE, adds the water of MALEIC ANHYDRIDE quality 7 times, is at room temperature stirred to dissolving.Vinylformic acid has been taken in right amount by MALEIC ANHYDRIDE and vinylformic acid mol ratio 1:3.Take the Potassium Persulphate of MALEIC ANHYDRIDE and vinylformic acid total mass 6%, join in reactor after dissolving by suitable quantity of water.Be warming up to 70 DEG C, in 45 minutes, vinylformic acid be slowly added drop-wise in reactor.After vinylformic acid dropwises, continue reaction 60 minutes.Take MALEIC ANHYDRIDE and vinylformic acid total mass 30% magnetic collagen hydrolysate joins in beaker, add the water of magnetic collagen hydrolysate quality 7 times, at 55 DEG C of temperature, be stirred to dissolving.MALEIC ANHYDRIDE and vinylformic acid reaction system are warming up to 80 DEG C, in 45 minutes, magnetic collagen hydrolysate solution are slowly joined in above-mentioned reaction system.After magnetic collagen hydrolysate solution adds, continue reaction 3 hours.Be 8 by aqueous sodium hydroxide solution adjust ph.Obtain the collagen-modified negatively charged ion retanning agent of magnetic.
Embodiment 7
In step (2), the mass concentration adding scurf quality 3 times is the glutaraldehyde water solution of 30%, and other are identical with embodiment 6.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.
The method for hydrolysis of collagen described in the present invention is the acid-hydrolysis method adopting concentrated hydrochloric acid, the vitriol oil; for the acid hydrolysis collagen adopting other kind; without departing from the inventive concept of the premise; the collagen-modified negatively charged ion retanning agent of preparation magnetic, should be considered as belonging to protection scope of the present invention.
The method for hydrolysis of collagen described in the present invention is acid-hydrolysis method; employing alkaline process, enzyme process, enzyme process are combined with acid system, method is hydrolyzed collagen to enzyme process with alkaline process is combined etc.; without departing from the inventive concept of the premise; the collagen-modified negatively charged ion retanning agent of preparation magnetic, should be considered as belonging to protection scope of the present invention.
Modified monomer described in the present invention is MALEIC ANHYDRIDE, vinylformic acid; for other monomer of employing; the monomers such as such as methyl acrylate, butyl acrylate, vinylbenzene, sodium p styrene sulfonate, 2-acrylamide-2-methyl propane sulfonic participate in graft copolymerization; without departing from the inventive concept of the premise; the collagen-modified negatively charged ion retanning agent of preparation magnetic, should be considered as belonging to protection scope of the present invention.
Collagen described in the present invention derives from process hides solid waste; for the collagen taking from the generation of other production departments; without departing from the inventive concept of the premise, the collagen-modified negatively charged ion retanning agent of preparation magnetic, should be considered as belonging to protection scope of the present invention.
Claims (8)
1. the collagen-modified negatively charged ion retanning agent of magnetic, is characterized in that: main with process hides waste collagen albumen for raw material, be combined with magnetic fluid and be prepared from,
The preparation method of the collagen-modified negatively charged ion retanning agent of described magnetic, comprises the following steps: with process hides waste collagen albumen for raw material, through hydrolysis, in conjunction with obtaining the collagen-modified negatively charged ion retanning agent of magnetic after magnetic fluid, graft copolymerization,
Specifically comprise the following steps:
(1) process hides scrap leather bits hydrolysis:
Appropriate process hides scrap leather bits are joined in reactor, adds scurf quality 20-50 water doubly, be warming up to 60-100 DEG C, hydrolysis reaction, obtain collagen hydrolyzed solution;
(2) magnetic collagen hydrolysate preparation:
In above-mentioned collagen hydrolyzed solution, add scurf quality 20-50% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring, adds the Fe of scurf quality 10-40% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse, then slowly adds scurf quality 10-30 Virahol doubly under rapid stirring state, then ultrasonic disperse, and add glutaraldehyde water solution, wherein glutaraldehyde quality is the 25-125% of scurf quality, then rapid stirring, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate, suspension after Magneto separate, the solid of acquisition with washed with isopropyl alcohol for several times, for subsequent use after dry at 20-50 DEG C of temperature;
(3) graft copolymerization:
Appropriate MALEIC ANHYDRIDE is joined in reactor, add MALEIC ANHYDRIDE quality 5-10 water doubly, at room temperature be stirred to dissolving, appropriate vinylformic acid is taken in MALEIC ANHYDRIDE and vinylformic acid mol ratio 1:1-5 ratio, take the initiator of MALEIC ANHYDRIDE and vinylformic acid total mass 2-10%, join in reactor after dissolving by suitable quantity of water, be warming up to 50-90 DEG C, vinylformic acid is slowly added drop-wise in reactor, after vinylformic acid dropwises, continue reaction, take MALEIC ANHYDRIDE and vinylformic acid total mass 10-50% magnetic collagen hydrolysate joins in beaker, add magnetic collagen hydrolysate quality 5-10 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving, then MALEIC ANHYDRIDE and vinylformic acid reaction system are warming up to 60-100 DEG C, magnetic collagen hydrolysate solution is slowly joined in above-mentioned reaction system, after magnetic collagen hydrolysate solution adds, continue reaction, be 6-10 by aqueous sodium hydroxide solution adjust ph, obtain the collagen-modified negatively charged ion retanning agent of magnetic.
2. the preparation method of the collagen-modified negatively charged ion retanning agent of magnetic according to claim 1, is characterized in that: in step (1), be warming up to 60-100 DEG C, add the acid of scurf quality 1-5%, stirring reaction, adjust ph is 7, obtains collagen hydrolyzed solution.
3. the preparation method of the collagen-modified negatively charged ion retanning agent of magnetic according to claim 1 and 2, is characterized in that: in step (2), the mass concentration of glutaraldehyde water solution is 25%, and the addition of this glutaraldehyde water solution is scurf quality 1-5 times.
4. the preparation method of the collagen-modified negatively charged ion retanning agent of magnetic according to claim 1 and 2, it is characterized in that: in step (2), in above-mentioned collagen hydrolyzed solution, add scurf quality 20-50% tensio-active agent, at 40-70 DEG C of temperature, dispersed with stirring 30-60 minute, adds the Fe of scurf quality 10-40% after being cooled to room temperature
3o
4magnetic fluid, ultrasonic disperse 2-10 minute, then slowly adds scurf quality 10-30 Virahol doubly under rapid stirring state, ultrasonic disperse 2-10 minute again, adding scurf quality 1-5 mass concentration is doubly the glutaraldehyde water solution of 25%, rapid stirring 30-60 minute, obtained Fe
3o
4the mixture suspension of magnetic fluid and collagen hydrolysate.
5. the preparation method of the collagen-modified negatively charged ion retanning agent of magnetic according to claim 1 and 2, it is characterized in that: in step (3), appropriate MALEIC ANHYDRIDE is joined in reactor, add MALEIC ANHYDRIDE quality 5-10 water doubly, at room temperature be stirred to dissolving, appropriate vinylformic acid is taken in MALEIC ANHYDRIDE and vinylformic acid mol ratio 1:1-5 ratio, take the initiator of MALEIC ANHYDRIDE and vinylformic acid total mass 2-10%, join in reactor after dissolving by suitable quantity of water, be warming up to 50-90 DEG C, in 30-60 minute, vinylformic acid is slowly added drop-wise in reactor, after vinylformic acid dropwises, continue reaction 30-90 minute, take MALEIC ANHYDRIDE and vinylformic acid total mass 10-50% magnetic collagen hydrolysate joins in beaker, add magnetic collagen hydrolysate quality 5-10 water doubly, at 40-70 DEG C of temperature, be stirred to dissolving, then MALEIC ANHYDRIDE and vinylformic acid reaction system are warming up to 60-100 DEG C, in 30-60 minute, magnetic collagen hydrolysate solution is slowly joined in above-mentioned reaction system, after magnetic collagen hydrolysate solution adds, continue reaction 2-5 hour, be 6-10 by aqueous sodium hydroxide solution adjust ph, obtain the collagen-modified negatively charged ion retanning agent of magnetic.
6. the preparation method of the collagen-modified negatively charged ion retanning agent of magnetic according to claim 1 and 2, is characterized in that: in step (1), acid is the vitriol oil, concentrated hydrochloric acid and/or its mixture, is 7 by aqueous sodium hydroxide solution adjust ph.
7. the preparation method of the collagen-modified negatively charged ion retanning agent of magnetic according to claim 1 and 2, is characterized in that: in step (1) and step (3), aqueous sodium hydroxide solution mass concentration is 20%.
8. the preparation method of the collagen-modified negatively charged ion retanning agent of magnetic according to claim 1 and 2, it is characterized in that: in step (3), initiator is Potassium Persulphate, ammonium persulphate, Sulfothiorine-Potassium Persulphate initiator system, Sulfothiorine-ammonium persulphate initiator system, Sulfothiorine-hydrogen peroxide.
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