CN101870990B - Method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis - Google Patents
Method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis Download PDFInfo
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- CN101870990B CN101870990B CN201010205937A CN201010205937A CN101870990B CN 101870990 B CN101870990 B CN 101870990B CN 201010205937 A CN201010205937 A CN 201010205937A CN 201010205937 A CN201010205937 A CN 201010205937A CN 101870990 B CN101870990 B CN 101870990B
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Abstract
The invention relates to a method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis, which comprises the following steps: dissolving p-aminobenzene sulfonic acid and 2, 3-dihydroxy naphthalene-6-sodium sulfonate into de-ionized water, using a sodium bicarbonate solution for regulating the pH value of the system, and finally, obtaining the retanning dyeing auxiliary agents through co-polymerization reaction carried out under the horse radish peroxidase (HRP) catalysis. The invention uses HRP as catalysts of the polymerization reaction, and the HRP has the advantages of high efficiency, high selectivity and environment protection when being used for catalyzing the polymerization. The invention has the advantages that phenols or arylamines can carry out polymerization in ortho positions or para positions of hydroxide groups and amino groups for forming a polymer with directly connected C-C structures and large pi conjugated systems, the formaldehyde pollution in the traditional synthesized retanning agents is avoided, and at the same time, the products with the conjugated systems contain a large number of auxochromic groups such as -NH2, -OH and -SO3H and the like. Retanning leather is full and soft, and the dye absorption rate is higher than 99 percent, and in addition, the retanning dyeing auxiliary agents have obvious dyeing aid effect.
Description
Technical field
The present invention relates to a kind of preparation method of high molecular retanning dyeing auxiliary agents, particularly adopt the method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis.
Background technology
In leather chemicals; Be referred to as synthetic tanning agent to the condenses of phenol and formaldehyde; Because formaldehyde is to contain formaldehyde in one of raw material and the product, can produce formaldehyde in the time of in production, use and pollute, traditional in recent years synthetic tanning agent is limited or bans use of; Therefore develop the focus that formaldehydeless green leather synthetic tanning agent becomes research, formaldehyde-free leather synthetic tanning agent has the very big market requirement and economic benefit.Leather coloring can make leather obtain pure color, and bright in colour, evenly, fastness is high.In recent years, market to leather coloring require increasingly high, except that require color and luster evenly, also to the plumpness of color and luster, anti-ly do, wet rubbing property, photostabilization and water-wash resistance etc. have proposed requirement.Therefore, except using the New-type leather dyestuff and improving the staining technique, use suitable dyeing auxiliary also significant.At HRP/H
2O
2Under the catalysis 2; Have low, the characteristics such as reaction conditions is gentle, technology uniqueness of power consumption in 3-dihydroxy naphthlene-6-sodium sulfonate and the Sulphanilic Acid copolymer process; Product has good tanning, filling properties, can significantly improve the absorption intensity and the dye uptake of dyestuff simultaneously, and the leather products of using this product tanning is soft plentiful; Grain is fine and smooth, uniform coloring.Therefore, can be widely used in the leather industry production.Employed catalyzer horseradish peroxidase (horseradish peroxidase in synthetic; HRP) be a kind of green enzymatic polymerization catalyzer with special performance; It can be single-minded catalysis phenols, arylamine class, monomeric Raolical polymerizable (Tawaki Shin-Ichiro such as vinyl-based; Uchida Yugo, Maeda Yasushi, Ikeda Isao.HRP-catalyzed polymerization of sugar-based phenols in aqueous organic solvents ［ J ］ .Carbohydrate Polymer; 2005,59:71-74; Kalra Bhanu; Gross R A.HRP-mediated polymerization of acrylamide and sodium acrylate ［ J ］ .American Chemical Society; Polymer Preprints; Division of Polymer Chemistry, 2000,41 (2): 1828-1829; Chul H L, Young J Y.Synthesis of ortho-directed polyaniline using horseradish peroxidase ［ J ］ .Process Biochemistry, 2000,36:233-241).At present, research aspect green leather tanning agent, many is vinyl-based tanning agent, organic phosphine tanning agent and improved plant tanning agent etc.In addition, the research of dyeing auxiliary also develop to environmental protection, low toxicity, low formaldehyde or formaldehydeless direction (Dan Zhihua, Shao Shuanxi. the exploitation prospect ［ J ］ of China's cleaning tanning industry material. fine chemistry industry, 2006,23 (10): 1001-1006; Masoud R A.Anoptimization study of the graft polymerization of HEMA onto leather ［ J ］ .Joural of the Society of Leather Technologists and Chemists; 2003,87 (4): 159-161; Qian Yiping, Liu are the research ［ J ］ of .PT such as Zhao Shuai organic phosphonium salt tanning agent flexibility and application art thereof. Chinese leather, 2006,35 (19): 19-22; Zhou Guoquan, Gao Haoqi, Wu Haiping etc. nanometer SiO
2Composite tanning agent progress ［ J ］. leather science and engineering, 2009,19 (4): 37-39; Chapter is outstanding. the opportunity to develop of China's dyeing and printing auxiliary and new and innovative ways ［ J ］. and printing and dyeing, 2009, (21): 41-45).But at present the reasonable green retanning dyeing auxiliary agents of application performance is more rare, and excellent performance, the product that can be mass-produced are also among research.
Summary of the invention
The object of the present invention is to provide the method for a kind of low pollution, dynamical synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis, the pollution of having avoided formaldehyde to produce in leather industry.Retan is plentiful, soft, and has to help significantly and dye effect, and dye absorption rate is greater than 99%.
For achieving the above object, the technical scheme that the present invention adopts is:
With 8 ~ 13 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 2.4 ~ 5.3 gram Sulphanilic Acid are dissolved in 30 ~ 40 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7 ~ 8; Add concentration again and be that to drip massfraction behind 3 ~ 6 milliliters of the HRP solution of 0.5 grams per liter again be 30% superoxol 6.2 ~ 7.4 grams; Control is 1 ~ 2 hour the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.5 ~ 3 hours.
The present invention has introduced phenolic hydroxyl group, amino and the sulfonic group etc. that have the tanning effect and help the look effect through copolymerization in product structure.The products therefrom relative molecular mass is moderate, good penetrability, and specific absorption is high, can significantly improve the absorption intensity and the dye uptake of dyestuff simultaneously, is a kind of green non-pollution high molecular retanning dyeing auxiliary agents.Preparing method's technology involved in the present invention is unique, and tanning, the filling properties of products therefrom are good, is fit to retanning dyeing, selects filling properties remarkable; The good hand feeling of leather is soft after the retanning, and grain is fine and smooth, thickens obviously; Can significantly improve the absorption intensity and the dye uptake of dyestuff during dyeing, make colored leather even, strong.
Embodiment
Embodiment 1: with 8 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 5.3 gram Sulphanilic Acid are dissolved in 32 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.6; Add concentration again and be that to drip massfraction behind 3 milliliters of the HRP solution of 0.5 grams per liter again be 30% superoxol 6.8 grams; Control is 1.5 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 3 hours.
Embodiment 2: with 9 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 4.2 gram Sulphanilic Acid are dissolved in 36 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.4; Add concentration again and be that to drip massfraction behind 4 milliliters of the HRP solution of 0.5 grams per liter again be 30% superoxol 6.2 grams; Control is 1.8 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.5 hours.
Embodiment 3: with 10 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 3.3 gram Sulphanilic Acid are dissolved in 38 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.8; Add concentration again and be that to drip massfraction behind 5 milliliters of the HRP solution of 0.5 grams per liter again be 30% superoxol 7 grams; Control is 1.5 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.8 hours.
Embodiment 4: with 11 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 3.1 gram Sulphanilic Acid are dissolved in 34 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.2; Add concentration again and be that to drip massfraction behind 5 milliliters of the HRP solution of 0.5 grams per liter again be 30% superoxol 6.7 grams; Control is 1.6 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 3 hours.
Embodiment 5: with 12 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 2.9 gram Sulphanilic Acid are dissolved in 30 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 8.0; Add concentration again and be that to drip massfraction behind 6 milliliters of the HRP solution of 0.5 grams per liter again be 30% superoxol 7.1 grams; Control is 1 hour the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.7 hours.
Embodiment 6: with 13 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 2.4 gram Sulphanilic Acid are dissolved in 40 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.5; Add concentration again and be that to drip massfraction behind 4 milliliters of the HRP solution of 0.5 grams per liter again be 30% superoxol 7.4 grams; Control is 2 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 3 hours.
Claims (7)
1. the method for a synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis is characterized in that:
With 8～13 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 2.4～5.3 gram Sulphanilic Acid are dissolved in 30～40 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7～8; Add concentration again and be that to drip massfraction behind 3～6 milliliters of the horseradish peroxidase solution of 0.5 grams per liter again be 30% superoxol 6.2～7.4 grams; Control is 1～2 hour the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.5～3 hours.
2. the method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis according to claim 1; It is characterized in that: with 8 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 5.3 gram Sulphanilic Acid are dissolved in 32 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.6; Add concentration again and be that to drip massfraction behind 3 milliliters of the horseradish peroxidase solution of 0.5 grams per liter again be 30% superoxol 6.8 grams; Control is 1.5 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 3 hours.
3. the method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis according to claim 1; It is characterized in that: with 9 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 4.2 gram Sulphanilic Acid are dissolved in 36 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.4; Add concentration again and be that to drip massfraction behind 4 milliliters of the horseradish peroxidase solution of 0.5 grams per liter again be 30% superoxol 6.2 grams; Control is 1.8 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.5 hours.
4. the method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis according to claim 1; It is characterized in that: with 10 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 3.3 gram Sulphanilic Acid are dissolved in 38 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.8; Add concentration again and be that to drip massfraction behind 5 milliliters of the horseradish peroxidase solution of 0.5 grams per liter again be 30% superoxol 7 grams; Control is 1.5 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.8 hours.
5. the method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis according to claim 1; It is characterized in that: with 11 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 3.1 gram Sulphanilic Acid are dissolved in 34 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.2; Add concentration again and be that to drip massfraction behind 5 milliliters of the horseradish peroxidase solution of 0.5 grams per liter again be 30% superoxol 6.7 grams; Control is 1.6 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 3 hours.
6. the method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis according to claim 1; It is characterized in that: with 12 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 2.9 gram Sulphanilic Acid are dissolved in 30 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 8.0; Add concentration again and be that to drip massfraction behind 6 milliliters of the horseradish peroxidase solution of 0.5 grams per liter again be 30% superoxol 7.1 grams; Control is 1 hour the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 2.7 hours.
7. the method for synthesizing high molecular retanning dyeing auxiliary agents through enzyme catalysis according to claim 1; It is characterized in that: with 13 grams 2; 3-dihydroxy naphthlene-6-sodium sulfonate and 2.4 gram Sulphanilic Acid are dissolved in 40 grams and mix and be heated to 30 ℃ in the deionized waters and use then in the sodium hydrogencarbonate and system pH to 7.5; Add concentration again and be that to drip massfraction behind 4 milliliters of the horseradish peroxidase solution of 0.5 grams per liter again be 30% superoxol 7.4 grams; Control is 2 hours the dropping time, and the reinforced continued that finishes is at 30 ℃ of insulation reaction sub-retanning dyeing auxiliary agents that secured satisfactory grades in 3 hours.
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| CN102002540B (en) * | 2010-11-11 | 2013-04-10 | 陕西科技大学 | Preparation method of modified Chinese gall tanning extract environmentally-friendly leather tanning agent |
| CN102212625B (en) * | 2011-04-19 | 2013-07-10 | 陕西科技大学 | Amphoteric vinyl copolymer retanning agent and preparation method thereof |
| CN102260762B (en) * | 2011-06-23 | 2014-08-13 | 陕西科技大学 | Novel phenolic aldehyde synthetic tanning agent and preparation method thereof |
| CN103224916A (en) * | 2013-05-10 | 2013-07-31 | 南开大学 | Artificial horseradish peroxidase and phenol substance catalytic polymerization method thereof |
| CN105133394A (en) * | 2015-09-01 | 2015-12-09 | 桐乡市濮院毛针织技术服务中心 | Dyeing auxiliary for modal-mercerized-wool blended fabric |
| CN111197062B (en) * | 2020-02-25 | 2023-04-25 | 天津市飞龙砼外加剂有限公司 | Modified plant tannin extract concrete air entraining agent and preparation method thereof |
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| CN1075559C (en) * | 1997-12-31 | 2001-11-28 | 四川联合大学 | Method of tanning leather by utilizing mixed rare-earth and plant tanning agent |
| DE602009000214D1 (en) * | 2008-04-07 | 2010-11-04 | Ntt Docomo Inc | Emotion recognition messaging system and messaging server for it |
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| 刘岗等.HRP催化淀粉与丙烯酰胺接枝共聚物的制备及性能研究.《中国皮革》.2010,第39卷(第5期), * |
| 马艳芬等.生物酶催化聚合的研究进展.《生物技术通报》.2010,(第4期),50-55. * |
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