CN103232604B - Epoxy resin modification hydrolytic collagen and retanning filler prepared therefrom and their preparation method - Google Patents
Epoxy resin modification hydrolytic collagen and retanning filler prepared therefrom and their preparation method Download PDFInfo
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- CN103232604B CN103232604B CN201310126021.3A CN201310126021A CN103232604B CN 103232604 B CN103232604 B CN 103232604B CN 201310126021 A CN201310126021 A CN 201310126021A CN 103232604 B CN103232604 B CN 103232604B
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Abstract
Epoxy resin modification hydrolytic collagen disclosed by the invention be by water-soluble epoxy resin 10��25 parts and powdery hydrolytic collagen 100 parts in deionized water and organic solvent stirring reaction and obtain, then add 20��60 parts of inorganic filler stirring reactions more wherein and namely obtain epoxy resin modification hydrolytic collagen retanning filler. The preparation method that the invention also discloses them. Owing to modified hydrolyzed collagen protein provided by the invention adopts epoxy resin to carry out, and composite on this basis obtain corresponding retanning filler with inorganic filler, thus not only avoid prior art Problems existing, and also biodegradable, also use the leather of this retanning filler tanning to obtain the technique effect of excellence in absorbability, fillibility, plumpness, flexibility, position difference size etc. simultaneously. The present invention provides method simple to operation, and raw material is easily obtained, it is simple to industrialized production, and product stores convenient, good stability.
Description
Technical field
The invention belongs to modified collagen albumen and retanning filler prepared therefrom and preparing technical field, be specifically related to epoxy resin modification hydrolytic collagen and retanning filler prepared therefrom and their preparation method.
Background technology
It is one important procedure in modern leather industry that retanning is filled, and its Main Function is to improve leather lex primaria, fullness and flexibility, corrects leather loose side, improves feel and the position difference etc. of leather. At present, the main organic/inorganic substance of retanning filler, tannic extract, acrylic resin, amino resins class, protide retanning filler etc. Wherein retanning-filling agent is compared with other retanning fillers, more can keep the kishke feel of leather, more can play the sanitation performance of leather vapor pervious. In addition, protein is again natural Amphiphatic high polymer, both having there is positively charged amino ion in molecule, and there is again electronegative carboxylic ions, it not only facilitates the dyeing of leather, and the COD (COD) in wastewater treatment and Biochemical oxygen demand (BOD) can also be reduced, (grandson waits quietly, the general introduction of Techniques of Protein Filling Agents, Chinese leather to improve environment, 2002,31 (5): 26-27). Retanning-filling agent is mainly by protein carrying out graft modification or polymerization and prepared, and collagen protein, animal hair hydrolyzed protein and soybean protein etc. all can as the raw materials producing retanning-filling agent.
Owing to the operation of split, deburring and shaving will inevitably produce substantial amounts of scrap leather slag in leather making process, the main component of this scrap leather slag is collagen protein, accounts for the 80-90% of total amount, and is the protein resource of a kind of high-quality. Therefore, hydrolytic collagen can be obtained after scrap leather pulp water solution, after chemical modification, further prepare into collagen retanning-filling agent.
About utilizing collagen protein to prepare the existing relevant report of retanning filler, but substantially all adopt acrylic resin (Li Manni etc., the scurf containing chromium prepares leather retanning filler, Chinese leather, 2001,30 (19): 12-14;) and amino resins class collagen protein is carried out graft modification (patent publication No. is CN1687463A), or by collagen protein by phenol sulfonation and aldehydes condensation and modification (Cheng Haiming etc., LB type Protein Tanning Agent application and research, leather science and engineering, 2002,12 (6): 19-23). But no matter which kind of modifiies, gained retanning filler all ubiquities can make the resin sense of leather strengthen and lose colour effect or store the problems such as unstable containing free formaldehyde, product after using, cause Leather Properties bad or content of formaldehyde exceeds standard.
Summary of the invention
It is an object of the invention to, for the deficiencies in the prior art, first provide a kind of hydrolytic collagen through epoxy resin modification.
The preparation method that it is a further object of the present invention to provide a kind of above-mentioned hydrolytic collagen through epoxy resin modification.
The third object of the present invention is to provide a kind of retanning filler prepared with the hydrolytic collagen of above-mentioned epoxy resin modification.
4th purpose of the present invention is to provide a kind of method that hydrolytic collagen with above-mentioned epoxy resin modification prepares retanning filler.
Epoxy resin modification hydrolytic collagen provided by the invention, this hydrolytic collagen is to be obtained by by the agitated reaction of the following components of mass parts:
Wherein the structural formula of gained epoxy resin modification hydrolytic collagen is as follows:
R in formula1For:
OrP is1647cm in its infrared spectrum-1There is the characteristic absorption peak of amide groups at place, and at 1115cm-1There is secondary hydroxyl group in-plane bending vibration peak at place.
Water-soluble epoxy resin contained in above hydrolytic collagen is any one in glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or Ethylene glycol diglycidyl ether, it is preferable that glycerin triglycidyl ether; Its contained mass parts preferably 10��20 parts.
Powdery hydrolytic collagen contained in above hydrolytic collagen is any one in Corii Bovis seu Bubali, Corii Sus domestica, Corii Caprae seu Ovis hydrolytic collagen, its molecular weight distribution is 3000-6000Da or 7000-12000Da, preferably with the hydrolytic collagen extracted from scrap leather slag, more preferably utilizing number of patent application is that method disclosed in 201210536906.6 is from containing the hydrolytic collagen extracted chromium scrap leather slag.
Organic solvent contained in above hydrolytic collagen is any one in ethanol, acetone or oxolane, it is preferable that ethanol.
The preparation method of above-mentioned epoxy resin modification hydrolytic collagen provided by the invention, the method is first to be added by the water-soluble epoxy resin of 10��25 mass parts in 100 mass parts deionized waters, stir at temperature 40��70 DEG C, then 100 mass parts powdery hydrolytic collagen and 5��20 mass parts organic solvents, stirring reaction 2��6h at temperature 40��80 DEG C are sequentially added.
Above method provided by the invention is to be reacted generation in the basic conditions by water-soluble epoxy resin and hydrolytic collagen, and its reaction equation is as follows:
In formula, wherein R is:
OrFor epoxy molecule structural formula;
H2N-P-COO-For hydrolytic collagen molecular structural formula, wherein P isR1ForOr
Water-soluble epoxy resin used in above method is any one in glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or Ethylene glycol diglycidyl ether, it is preferable that glycerin triglycidyl ether; Its mass parts used preferably 10��20 parts.
Powdery hydrolytic collagen used in above method is any one in Corii Bovis seu Bubali, Corii Sus domestica, Corii Caprae seu Ovis hydrolytic collagen, its molecular weight distribution is 3000-6000Da or 7000-12000Da, preferably with the hydrolytic collagen extracted from scrap leather slag, more preferably utilizing number of patent application is that method disclosed in 201210536906.6 is from containing the hydrolytic collagen extracted chromium scrap leather slag.
Organic solvent used in above method is any one in ethanol, acetone or oxolane, it is preferable that ethanol.
Retanning filler prepared by above-mentioned epoxy resin modification hydrolytic collagen provided by the invention, this retanning filler is mixed by the agitated reaction of following components in mass parts:
Water-soluble epoxy resin 10��25 parts
Powdery hydrolytic collagen 100 parts
Deionized water 100 parts
Organic solvent 5��20 parts
Inorganic filler 20��60 parts.
The water-soluble epoxy resin contained in above retanning filler is any one in glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or Ethylene glycol diglycidyl ether, preferred glycerin triglycidyl ether, its contained mass parts preferably 10��20 parts; The powdery hydrolytic collagen contained is any one in Corii Bovis seu Bubali, Corii Sus domestica, Corii Caprae seu Ovis hydrolytic collagen, its molecular weight distribution is 3000-6000Da or 7000-12000Da, preferably with the hydrolytic collagen extracted from scrap leather slag, more preferably utilizing number of patent application is that method disclosed in 201210536906.6 is from containing the hydrolytic collagen extracted chromium scrap leather slag; The organic solvent contained is any one in ethanol, acetone or oxolane, it is preferable that ethanol; Inorganic filler used is any one in Kaolin, kieselguhr, titanium dioxide or white carbon, its contained mass parts preferably 40��50 parts.
Above retanning filler is composite with inorganic filler again by gained epoxy resin modification hydrolytic collagen, is more abundant in order to make epoxy resin modification hydrolytic collagen absorb in the retanning filling work procedure of process hides, allows the organoleptic properties of leather better design. Because the inorganic filler selected (uses M containing substantial amounts of metallic elementn+Represent), hydrolytic collagen is had certain crosslinked action by these metallic elements, and the hydrolytic collagen molecule after epoxy resin modification can be made bigger, and charge property is more suitable, enter energy stable bond after in leather smoothly at it, play good retanning filling effect. Hydrolytic collagen retanning filler molecular structure after composite is as follows:
The preparation method of above-mentioned retanning filler provided by the invention, processing step and the condition of the method are as follows:
(1) first the water-soluble epoxy resin of 10��25 mass parts is added in 100 mass parts deionized waters, stir at temperature 40��70 DEG C, then 100 mass parts powdery hydrolytic collagen and 5��20 mass parts organic solvents, stirring reaction 2��6h at temperature 40��80 DEG C are sequentially added;
(2) cool the temperature to 30��40 DEG C, add 20��60 parts of inorganic fillers, stirring reaction 0.5��3h.
Epoxy resin modification hydrolytic collagen retanning filler of the present invention, both can be liquid, it is also possible to obtain powdery product by spray-dried for liquid product.
Water-soluble epoxy resin used in above method is any one in glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or Ethylene glycol diglycidyl ether, it is preferable that glycerin triglycidyl ether, its mass parts used preferably 10��20 parts; Powdery hydrolytic collagen used is any one in Corii Bovis seu Bubali, Corii Sus domestica, Corii Caprae seu Ovis hydrolytic collagen, its molecular weight distribution is 3000-6000Da or 7000-12000Da, it is preferable that utilizing number of patent application is that method disclosed in 201210536906.6 is from containing the hydrolytic collagen extracted chromium scrap leather slag; Organic solvent used is any one in ethanol, acetone or oxolane, it is preferable that ethanol; Inorganic filler used is any one in Kaolin, kieselguhr, titanium dioxide or white carbon, its mass parts used preferably 40��50 parts.
The present invention compared with prior art, has the advantages that
1, owing to modified hydrolyzed collagen protein provided by the invention adopts epoxy resin to carry out, thus not only avoid prior art use amino resins and aldehyde material modified bring effect of losing colour, store the problems such as unstable containing free formaldehyde, product, and also biodegradable.
2, owing to the present invention provides retanning filler to be composite inorganic filler on the basis of epoxy resin modification hydrolytic collagen, the introducing of metal ion in the hydrophobic chain of epoxy resin and inorganic filler, make no matter the leather with this retanning filler tanning is at absorbability, fillibility, plumpness, or the aspects such as flexibility, position difference size are all significantly better than commercially available retanning-filling agent and the leather of unmodified leather hydrolyzed protein tanning, and concrete outcome is shown in following table.
In upper table, performance indications are the sensory evaluation that veteran process hides engineer gives, wherein "+" more many, illustrate that these properties of product are more good. Absorbability and the fillibility of unmodified hydrolytic collagen are very poor, substantially can not enter Intradermal and play retanning filling effect, and are mainly attached to the surface of skin, cause leather stiff inflexible, in resin sense; Although commercially available retanning-filling agent is better than unmodified hydrolytic collagen, but compared with the epoxy resin modification hydrolytic collagen retanning filler prepared by the present invention, its absorbability, fillibility, plumpness, flexibility, to reduce position difference effect all still far short of what is expected.
3, the present invention provides method simple to operation, and raw material is easily obtained, it is simple to industrialized production, and product stores convenient, good stability.
4, owing to method provided by the invention can scrap leather bits hydrolytic collagen be raw material, thus the recycling and energy-saving and emission-reduction to leather industry biomass resource all has positive role.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of epoxy resin modification hydrolytic collagen (a) and the unmodified hydrolytic collagen (b) prepared in the embodiment of the present invention 1,1647cm in figure-1For the characteristic absorption peak of amide groups, (a) relatively (b) peak weakens by force herein, and at 1115cm-1(a) peak, place is remarkably reinforced by force, here for secondary hydroxyl group in-plane bending vibration peak, it is possible to proved on cross linking of epoxy resin hydrolytic collagen.
Fig. 2 is the thermogravimetric curve figure of epoxy resin modification hydrolyzed protein and the unmodified hydrolytic collagen prepared in the embodiment of the present invention 4.
Fig. 3 is the differential thermogravimetric curve chart of epoxy resin modification hydrolyzed protein and the unmodified hydrolytic collagen prepared in the embodiment of the present invention 4.
Both thermogravimetric and differential thermogravimetric curve chart in comparison diagram 2,3, it can be seen that the heat stability of hydrolytic collagen after epoxy resin modification increases, have further illustrated on cross linking of epoxy resin hydrolytic collagen.
Detailed description of the invention
By the examples below the present invention is specifically described; be necessary it is pointed out here that be that the present embodiment is served only for the present invention is further described; it is not intended that limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
It addition, what deserves to be explained is, 1) number of material used by following example is mass parts; 2) hydrolytic collagen used by following example utilizes number of patent application to be that method disclosed in 201210536906.6 is extracted from containing chromium scrap leather slag.
Embodiment 1
First 15 parts of glycerin triglycidyl ethers and 100 parts of deionized waters are added with in the closed reactor of cooling and reflux device, stir under temperature 50 C, then powdery Corii Bovis seu Bubali hydrolytic collagen and 5 parts of ethanol, stirring reaction 3h under temperature 70 C that 100 parts of molecular weight are 7000-12000Da are sequentially added;Close cooling and reflux device, cool the temperature to 35 DEG C, add 40 parts of Kaolin, stirring reaction 2h, liquid epoxy resin modification hydrolytic collagen retanning filler can be obtained.
Embodiment 2
First 20 parts of Ethylene glycol diglycidyl ethers and 100 parts of deionized waters are added with in the closed reactor of cooling and reflux device, stir under temperature 70 C, then powdery Corii Sus domestica hydrolytic collagen and 20 parts of acetone, stirring reaction 2h at temperature 40 DEG C that 100 parts of molecular weight are 3000-6000Da are sequentially added; Close cooling and reflux device, cool the temperature to 38 DEG C, add 30 parts of kieselguhr, stirring reaction 3h, liquid epoxy resin modification hydrolytic collagen retanning filler can be obtained.
Embodiment 3
First 10 parts of trihydroxymethylpropanyltri diglycidyl ethers and 100 parts of deionized waters are added with in the closed reactor of cooling and reflux device, stir under temperature 60 C, then powdery Corii Caprae seu Ovis hydrolytic collagen and 15 parts of ethanol, stirring reaction 6h under temperature 50 C that 100 parts of molecular weight are 3000-6000Da are sequentially added; Close cooling and reflux device, cool the temperature to 32 DEG C, add 60 parts of titanium dioxides, stirring reaction 0.5h, liquid epoxy resin modification hydrolytic collagen retanning filler can be obtained.
Embodiment 4
First 25 parts of glycerin triglycidyl ethers and 100 parts of deionized waters are added with in the closed reactor of cooling and reflux device, stir at temperature 40 DEG C, then powdery Corii Sus domestica hydrolytic collagen and 10 parts of ethanol, stirring reaction 4h at temperature 80 DEG C that 100 parts of molecular weight are 7000-12000Da are sequentially added; Close cooling and reflux device, cool the temperature to 30 DEG C, add 20 parts of white carbons, stirring reaction 1h, liquid epoxy resin modification hydrolytic collagen retanning filler can be obtained.
Embodiment 5
First 10 parts of Ethylene glycol diglycidyl ethers and 100 parts of deionized waters are added with in the closed reactor of cooling and reflux device, stir under temperature 50 C, then powdery Corii Caprae seu Ovis hydrolytic collagen and 5 parts of oxolanes, stirring reaction 5h under temperature 60 C that 100 parts of molecular weight are 3000-6000Da are sequentially added; Close cooling and reflux device, cool the temperature to 40 DEG C, add 50 parts of Kaolin, stirring reaction 1.5h, and liquid product will be obtained by obtaining the epoxy resin modification hydrolytic collagen retanning filler of solid powdery after spray drying.
Embodiment 6
First 20 parts of trihydroxymethylpropanyltri diglycidyl ethers and 100 parts of deionized waters are added with in the closed reactor of cooling and reflux device, stir at temperature 40 DEG C, then powdery Corii Bovis seu Bubali hydrolytic collagen and 10 parts of ethanol, stirring reaction 3h under temperature 50 C that 100 parts of molecular weight are 3000-6000Da are sequentially added; Close cooling and reflux device, cool the temperature to 35 DEG C, add 40 parts of kieselguhr, stirring reaction 2.5h, liquid epoxy resin modification hydrolytic collagen retanning filler can be obtained.
Application examples 1
Liquid epoxy resin modification hydrolytic collagen retanning filler prepared by embodiment 4 is used for the retanning of Corii Caprae seu Ovis wet blue. Retanning process condition is as follows:
Liquor ratio: 50%-80%(is with wet blue restatement)
Consumption: 4%-8%(is with wet blue restatement)
Temperature: 40 �� of C
Time: 40-60 minute
The absorbance of this retanning-filling agent reaches more than 95%, and Corii Caprae seu Ovis wet blue is high comprehensive performance after retanning is filled.
Application examples 2
Powder shaped epoxy resin modification hydrolytic collagen retanning filler prepared by embodiment 2 is used for the retanning of Corii Bovis seu Bubali wet blue. Retanning process condition is as follows:
Liquor ratio: 50%-80%(is with wet blue restatement)
Consumption: 2%-6%(is with wet blue restatement)
Temperature: 40 �� of C
Time: 40-60 minute
The absorbance of this retanning-filling agent reaches more than 92%, and Corii Bovis seu Bubali wet blue is high comprehensive performance after retanning is filled.
Claims (10)
1. an epoxy resin modification hydrolytic collagen, this hydrolytic collagen is to be obtained by by the agitated reaction of the following components of mass parts:
The water-soluble epoxy resin wherein contained is glycerin triglycidyl ether or trihydroxymethylpropanyltri diglycidyl ether, and the epoxy resin modification hydrolytic collagen of gained is at infrared spectrum 1647cm-1There is the characteristic absorption peak of amide groups at place, and at 1115cm-1There is secondary hydroxyl group in-plane bending vibration peak at place.
2. the preparation method of the epoxy resin modification hydrolytic collagen described in a claim 1, the method is first to be added by the water-soluble epoxy resin of 10��25 mass parts in 100 mass parts deionized waters, stir at temperature 40��70 DEG C, then 100 mass parts powdery hydrolytic collagen and 5��20 mass parts organic solvents are sequentially added, stirring reaction 2��6h at temperature 40��80 DEG C, water-soluble epoxy resin wherein used is glycerin triglycidyl ether or trihydroxymethylpropanyltri diglycidyl ether.
3. the preparation method of epoxy resin modification hydrolytic collagen according to claim 2, powdery hydrolytic collagen used in the method is any one in Corii Bovis seu Bubali, Corii Sus domestica, Corii Caprae seu Ovis hydrolytic collagen, and its molecular weight is 3000-6000Da or 7000-12000Da.
4. the preparation method of the epoxy resin modification hydrolytic collagen according to Claims 2 or 3, organic solvent used in the method is any one in ethanol, acetone or oxolane.
5. the retanning filler that prepared by epoxy resin modification hydrolytic collagen described in claim 1, this retanning filler is be obtained by mixing by the agitated reaction of following components in mass parts:
The water-soluble epoxy resin wherein contained is glycerin triglycidyl ether or trihydroxymethylpropanyltri diglycidyl ether.
6. the retanning filler that according to claim 5 prepared by epoxy resin modification hydrolytic collagen, the powdery hydrolytic collagen contained in this retanning filler is any one in Corii Bovis seu Bubali, Corii Sus domestica, Corii Caprae seu Ovis hydrolytic collagen, and its molecular weight is 3000-6000Da or 7000-12000Da.
7. the retanning filler that prepared by epoxy resin modification hydrolytic collagen according to claim 5 or 6, the organic solvent contained in this retanning filler is any one in ethanol, acetone or oxolane; The inorganic filler contained is any one in Kaolin, kieselguhr, titanium dioxide or white carbon.
8. a preparation method for retanning filler described in claim 5, processing step and the condition of the method are as follows:
(1) first the water-soluble epoxy resin of 10��25 mass parts is added in 100 mass parts deionized waters, stir at temperature 40��70 DEG C, then 100 mass parts powdery hydrolytic collagen and 5��20 mass parts organic solvents, stirring reaction 2��6h at temperature 40��80 DEG C are sequentially added;
(2) cool the temperature to 30��40 DEG C, add 20��60 parts of inorganic fillers, stirring reaction 0.5��3h,
Water-soluble epoxy resin wherein used is glycerin triglycidyl ether or trihydroxymethylpropanyltri diglycidyl ether.
9. the preparation method of retanning filler according to claim 8, powdery hydrolytic collagen used in the method is any one in Corii Bovis seu Bubali, Corii Sus domestica, Corii Caprae seu Ovis hydrolytic collagen, and its molecular weight is 3000-6000Da or 7000-12000Da.
10. the preparation method of retanning filler according to claim 8, organic solvent used in the method is any one in ethanol, acetone or oxolane; Inorganic filler used is any one in Kaolin, kieselguhr, titanium dioxide or white carbon.
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| CN103739770B (en) * | 2013-10-18 | 2016-04-06 | 陕西科技大学 | Containing the preparation method of carboxyl epoxy resin tanning agent |
| CN104313201B (en) * | 2014-08-30 | 2016-08-24 | 齐鲁工业大学 | A kind of collagen-modified cation retanning agent of magnetic and preparation method thereof |
| CN105482103B (en) * | 2015-12-25 | 2018-06-26 | 四川达威科技股份有限公司 | Modified amido acid polymer, preparation method and its application |
| CN105586444B (en) * | 2016-01-06 | 2017-12-26 | 四川大学 | A kind of leather retanning filler prepared with phenol sulfonic acid hydrolysis tanning waste |
| CN114774594A (en) * | 2022-05-05 | 2022-07-22 | 陕西科技大学 | Collagen-hyperbranched amphoteric polymer retanning agent and preparation method thereof |
| CN115011742A (en) * | 2022-06-29 | 2022-09-06 | 陕西科技大学 | Epoxy modified collagen polypeptide-based organic chromium-free tanning agent, preparation method and application |
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| CN103014191B (en) * | 2012-12-13 | 2014-11-05 | 四川大学 | Method for recovering collagen and chromium salts from chromium-containing scrap leather residues |
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