CN103232604A - An epoxy resin-modified hydrolyzed collagen, a retanning filler prepared from the epoxy resin-modified hydrolyzed collagen, and method for preparing both - Google Patents
An epoxy resin-modified hydrolyzed collagen, a retanning filler prepared from the epoxy resin-modified hydrolyzed collagen, and method for preparing both Download PDFInfo
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- CN103232604A CN103232604A CN2013101260213A CN201310126021A CN103232604A CN 103232604 A CN103232604 A CN 103232604A CN 2013101260213 A CN2013101260213 A CN 2013101260213A CN 201310126021 A CN201310126021 A CN 201310126021A CN 103232604 A CN103232604 A CN 103232604A
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Abstract
The invention discloses an epoxy resin-modified hydrolyzed collagen. The epoxy resin-modified hydrolyzed collagen is obtained by stirring and reacting 10 to 25 parts of water-soluble epoxy resin with 100 parts of hydrolyzed collagen powder in deionized water and an organic solvent, and then adding 20 to 60 parts of an inorganic filler, stirring and reacting to obtain an epoxy resin-modified hydrolyzed collagen retanning filler. The invention also discloses methods for preparing the epoxy resin-modified hydrolyzed collagen and the retanning filler prepared. The modified hydrolyzed collagen of the invention is modified by using the epoxy resin, and the corresponding retanning filler is obtained by compounding the inorganic filler on the basis of the modified hydrolyzed collagen, so the problems of the prior art are prevented, and the obtained epoxy resin-modified hydrolyzed collagen and retanning filler are biodegradable; and leather prepared by using the retanning filler achieves excellent technical effects in absorbility, filling ability, fullness flexibility, softness, the size of location difference, etc. According to the present invention, the method provided is simple and easy to operate and raw materials are easy to obtain, so industrial production is facilitated; and products are convenient for storage and good in 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 Collagen Hydrolysate and retanning filler prepared therefrom and their preparation method.
Background technology
It is one important procedure in the modern tanning industry that retanning is filled, and it mainly acts on is to improve leather lex primaria, fullness and flexibility, corrects the leather loose side, improves the feel of leather and position difference etc.At present, retanning filler mainly contains inorganics, tannin extract, acrylic resin, aminoresin class, protein retanning filler etc.Wherein the albumen retanning filler is compared with other retanning fillers, more can keep the kishke feel of leather, more can bring into play the sanitation performance of leather vapor pervious.In addition, protein is again natural Amphiphatic high polymer, both had positively charged amino ion in the molecule, and had electronegative carboxylic ions again, it not only helps the dyeing of leather, and can also reduce chemical oxygen demand (COD) (COD) and biochemical oxygen demand (BOD) (BOD) in the wastewater treatment, (grandson waits quietly, Summary on protein filling agent, Chinese leather to improve environment, 2002,31 (5): 26-27).The albumen retanning filler is mainly by carrying out graft modification to protein or polymerization makes, and collagen protein, animal hair protolysate and soybean protein etc. all can be used as the raw material of producing the albumen retanning filler.
Because split, deburring and shaving operation will inevitably produce a large amount of scrap leather slags, the main component of this scrap leather slag is collagen protein, accounts for the 80-90% of total amount, and is a kind of protein resource of high-quality in the process hides process.Therefore, can will obtain Collagen Hydrolysate after the scrap leather pulp water solution, further be prepared into the collagen protein retanning filler through after the chemical modification again.
About utilizing collagen protein to prepare the existing relevant report of retanning filler, (Li Manni etc. contain the chromium scurf and prepare leather retanning filler, Chinese leather, 2001,30 (19): 12-14 but substantially all adopt acrylic resin; ) and the aminoresin class collagen protein is carried out graft modification (patent publication No. is CN1687463A), or with collagen protein by phenol sulfonation and aldehydes condensation and modification (Cheng Haiming etc., the research of LB type Protein Tanning Agent application performance, leather science and engineering, 2002,12 (6): 19-23).But no matter which kind of modification, the gained retanning filler can make after all ubiquity uses the resin sense of leather strengthen and the effect or contain problems such as free formaldehyde, product stock instability of losing colour, and causes the bad or formaldehyde content of leather performance to exceed standard.
Summary of the invention
The objective of the invention is at the deficiencies in the prior art, a kind of Collagen Hydrolysate through epoxy resin modification at first is provided.
Another object of the present invention provides a kind of preparation method of above-mentioned Collagen Hydrolysate through epoxy resin modification.
The 3rd purpose of the present invention provides the retanning filler of the Collagen Hydrolysate preparation of the above-mentioned epoxy resin modification of a kind of usefulness.
The Collagen Hydrolysate that the 4th purpose of the present invention provides the above-mentioned epoxy resin modification of a kind of usefulness prepares the method for retanning filler.
Epoxy resin modification Collagen Hydrolysate provided by the invention, this Collagen Hydrolysate are to be got through stirring reaction by the following component by mass parts:
Wherein the structural formula of gained epoxy resin modification Collagen Hydrolysate is as follows:
R in the formula
1For:
Contained water-soluble epoxy resin is any in glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or the ethylene glycol diglycidylether in the above Collagen Hydrolysate, preferred glycerol triglycidyl ether; Preferred 10～20 parts of its contained mass parts.
Contained powdery Collagen Hydrolysate is any in ox-hide, pigskin, the sheepskin Collagen Hydrolysate in the above Collagen Hydrolysate, its molecular weight distribution is 3000-6000Da or 7000-12000Da, preferably use the Collagen Hydrolysate that extracts from the scrap leather slag, more preferably utilizing number of patent application is the Collagen Hydrolysate that 201210536906.6 disclosed methods are extracted from contain chromium scrap leather slag.
Contained organic solvent is any in ethanol, acetone or the tetrahydrofuran (THF) in the above Collagen Hydrolysate, preferred alcohol.
The preparation method of above-mentioned epoxy resin modification Collagen Hydrolysate provided by the invention, this method is that first water-soluble epoxy resin with 10～25 mass parts adds in the 100 mass parts deionized waters, under 40～70 ℃ of temperature, stir, and then adding 100 mass parts powdery Collagen Hydrolysates and 5～20 mass parts organic solvents successively, 40～80 ℃ of following stirring reaction 2～6h get final product in temperature.
Above method provided by the invention is to react generation by water-soluble epoxy resin and Collagen Hydrolysate under alkaline condition, and its reaction equation is as follows:
In the formula, wherein R is:
Or
Be the Resins, epoxy molecular structural formula;
H
2N-P-COO
-Be the Collagen Hydrolysate molecular structural formula, wherein P is
R
1For
Or
Used water-soluble epoxy resin is any in glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or the ethylene glycol diglycidylether in the above method, preferred glycerol triglycidyl ether; Preferred 10～20 parts of its used mass parts.
Used powdery Collagen Hydrolysate is any in ox-hide, pigskin, the sheepskin Collagen Hydrolysate in the above method, its molecular weight distribution is 3000-6000Da or 7000-12000Da, preferably use the Collagen Hydrolysate that extracts from the scrap leather slag, more preferably utilizing number of patent application is the Collagen Hydrolysate that 201210536906.6 disclosed methods are extracted from contain chromium scrap leather slag.
Used organic solvent is any in ethanol, acetone or the tetrahydrofuran (THF) in the above method, preferred alcohol.
The retanning filler of above-mentioned epoxy resin modification Collagen Hydrolysate preparation provided by the invention, this retanning filler is to be mixed through stirring reaction by following component in mass parts:
10～25 parts of water-soluble epoxy resins
100 parts of powdery Collagen Hydrolysates
100 parts of deionized waters
5～20 parts of organic solvents
20～60 parts of mineral fillers.
The water-soluble epoxy resin that contains in the above retanning filler is any in glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or the ethylene glycol diglycidylether, preferred glycerol triglycidyl ether, preferred 10～20 parts of its contained mass parts; The powdery Collagen Hydrolysate that contains is any in ox-hide, pigskin, the sheepskin Collagen Hydrolysate, its molecular weight distribution is 3000-6000Da or 7000-12000Da, preferably use the Collagen Hydrolysate that extracts from the scrap leather slag, more preferably utilizing number of patent application is the Collagen Hydrolysate that 201210536906.6 disclosed methods are extracted from contain chromium scrap leather slag; The organic solvent that contains is any in ethanol, acetone or the tetrahydrofuran (THF), preferred alcohol; Used mineral filler is any in kaolin, diatomite, titanium dioxide or the white carbon black, preferred 40～50 parts of its contained mass parts.
Above retanning filler is composite with mineral filler again with gained epoxy resin modification Collagen Hydrolysate, is more abundant for the epoxy resin modification Collagen Hydrolysate is absorbed in the retanning filling work procedure of process hides, allows the organoleptic properties of leather better and design.(use M because contain a large amount of metallic elements in the mineral filler of selecting for use
N+Expression), these metallic elements have certain crosslinked action to Collagen Hydrolysate, can make the Collagen Hydrolysate molecule behind epoxy resin modification bigger, and charge property is more suitable, the energy stable bond plays good retanning filling effect after it enters in the leather smoothly.Collagen Hydrolysate 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 this method are as follows:
(1) elder generation adds the water-soluble epoxy resin of 10～25 mass parts in the 100 mass parts deionized waters, under 40～70 ℃ of temperature, stir, and then add 100 mass parts powdery Collagen Hydrolysates and 5～20 mass parts organic solvents successively, in 40～80 ℃ of following stirring reaction 2～6h of temperature;
(2) cool the temperature to 30～40 ℃, add 20～60 parts of mineral fillers, stirring reaction 0.5～3h gets final product.
Epoxy resin modification Collagen Hydrolysate retanning filler of the present invention both can be liquid, also can be with the spray-dried powdery product that obtains of liquid product.
Used water-soluble epoxy resin is any in glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or the ethylene glycol diglycidylether in the above method, preferred glycerol triglycidyl ether, preferred 10～20 parts of its used mass parts; Used powdery Collagen Hydrolysate is any in ox-hide, pigskin, the sheepskin Collagen Hydrolysate, its molecular weight distribution is 3000-6000Da or 7000-12000Da, and preferably utilizing number of patent application is the Collagen Hydrolysate that 201210536906.6 disclosed methods are extracted from contain chromium scrap leather slag; Used organic solvent is any in ethanol, acetone or the tetrahydrofuran (THF), preferred alcohol; Used mineral filler is any in kaolin, diatomite, titanium dioxide or the white carbon black, preferred 40～50 parts of its used mass parts.
The present invention compared with prior art has following beneficial effect:
1, because modified hydrolyzed collagen protein provided by the invention adopts Resins, epoxy to carry out, thereby it is the effect of not only having avoided prior art to use aminoresin and aldehyde material modification bringing of losing colour, contain problems such as free formaldehyde, product stock instability, and also biodegradable.
2, because to the invention provides retanning filler be composite mineral filler on the basis of epoxy resin modification Collagen Hydrolysate, the introducing of metal ion in the hydrophobic chain of Resins, epoxy and the mineral filler, make with the leather of this retanning filler tanning regardless of being at absorptivity, fillibility, plumpness, still aspect such as flexibility, position difference size all is better than the leather of commercially available albumen retanning filler and the tanning of unmodified leather protolysate greatly, and concrete outcome sees the following form.
Performance index are the sensory evaluation that veteran process hides slip-stick artist gives in the last table, and wherein "+" is more many, illustrate that these product performance are more good.Absorptivity and the fillibility of unmodified Collagen Hydrolysate are very poor, can not enter intracutaneous substantially and play the retanning filling effect, and mainly be attached to the surface of skin, cause leather stiff inflexible, are the resin sense; Though commercially available albumen retanning filler is better than unmodified Collagen Hydrolysate, but comparing with the epoxy resin modification Collagen Hydrolysate retanning filler that the present invention is prepared, its absorptivity, fillibility, plumpness, flexibility, all still is far short of what is expected to reducing position difference effect.
3, it is simple to operation to the invention provides method, and raw material is easy to obtain, and is convenient to suitability for industrialized production, and product stock is convenient, good stability.
4, because method provided by the invention can scrap leather bits Collagen Hydrolysate be raw material, thereby recycling and the energy-saving and emission-reduction of tanning industry biomass resource all had active effect.
Description of drawings
Fig. 1 is the epoxy resin modification Collagen Hydrolysate (a) of preparation in the embodiment of the invention 1 and the infrared spectrum of unmodified Collagen Hydrolysate (b), 1647cm among the figure
-1Be the charateristic avsorption band of amide group, (a) (b) weakens by force at the peak herein, and at 1115cm
-1(a) peak, place is strong obviously to be strengthened, and is secondary hydroxyl group in-plane bending vibration peak herein, can prove on the cross linking of epoxy resin Collagen Hydrolysate.
Fig. 2 is the epoxy resin modification protolysate of preparation in the embodiment of the invention 4 and the thermogravimetric curve figure of unmodified Collagen Hydrolysate.
Fig. 3 is the epoxy resin modification protolysate of preparation in the embodiment of the invention 4 and the differential thermogravimetric graphic representation of unmodified Collagen Hydrolysate.
In the comparison diagram 2,3 both thermogravimetrics and differential thermogravimetric graphic representation as can be known, the thermostability of the Collagen Hydrolysate behind epoxy resin modification increases, and has further specified on the cross linking of epoxy resin Collagen Hydrolysate.
Embodiment
Carry out concrete description below by the present invention of embodiment; be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified; can not be interpreted as 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.
In addition, what deserves to be explained is 1) umber of the used material of following examples is mass parts; 2) to utilize number of patent application be that 201210536906.6 disclosed methods are extracted from contain chromium scrap leather slag to the used Collagen Hydrolysate of following examples.
Earlier 15 parts of glycerol triglycidyl ether and 100 parts of deionized waters addings are had in the closed reactor of cooling and reflux device, under 50 ℃ of temperature, stir, and then powdery ox-hide Collagen Hydrolysate and 5 parts of ethanol that to add 100 parts of molecular weight successively be 7000-12000Da, in 70 ℃ of following stirring reaction 3h of temperature; Close cooling and reflux device, cool the temperature to 35 ℃, add 40 parts of kaolin, stirring reaction 2h can obtain liquid epoxy resin modification Collagen Hydrolysate retanning filler.
Earlier 20 parts of ethylene glycol diglycidylethers and 100 parts of deionized waters addings are had in the closed reactor of cooling and reflux device, under 70 ℃ of temperature, stir, and then powdery pigskin Collagen Hydrolysate and 20 parts of acetone that to add 100 parts of molecular weight successively be 3000-6000Da, in 40 ℃ of following stirring reaction 2h of temperature; Close cooling and reflux device, cool the temperature to 38 ℃, add 30 parts of diatomite, stirring reaction 3h can obtain liquid epoxy resin modification Collagen Hydrolysate retanning filler.
Earlier 10 parts of trihydroxymethylpropanyltri diglycidyl ethers and 100 parts of deionized waters addings are had in the closed reactor of cooling and reflux device, under 60 ℃ of temperature, stir, and then powdery sheepskin Collagen Hydrolysate and 15 parts of ethanol that to add 100 parts of molecular weight successively be 3000-6000Da, in 50 ℃ of following stirring reaction 6h of temperature; Close cooling and reflux device, cool the temperature to 32 ℃, add 60 parts of titanium dioxides, stirring reaction 0.5h can obtain liquid epoxy resin modification Collagen Hydrolysate retanning filler.
Earlier 25 parts of glycerol triglycidyl ether and 100 parts of deionized waters addings are had in the closed reactor of cooling and reflux device, under 40 ℃ of temperature, stir, and then powdery pigskin Collagen Hydrolysate and 10 parts of ethanol that to add 100 parts of molecular weight successively be 7000-12000Da, in 80 ℃ of following stirring reaction 4h of temperature; Close cooling and reflux device, cool the temperature to 30 ℃, add 20 parts of white carbon blacks, stirring reaction 1h can obtain liquid epoxy resin modification Collagen Hydrolysate retanning filler.
Embodiment 5
Earlier 10 parts of ethylene glycol diglycidylethers and 100 parts of deionized waters addings are had in the closed reactor of cooling and reflux device, under 50 ℃ of temperature, stir, and then powdery sheepskin Collagen Hydrolysate and 5 parts of tetrahydrofuran (THF)s that to add 100 parts of molecular weight successively be 3000-6000Da, in 60 ℃ of following stirring reaction 5h of temperature; Close cooling and reflux device, cool the temperature to 40 ℃, add 50 parts of kaolin, stirring reaction 1.5h, and will obtain liquid product by obtaining the epoxy resin modification Collagen Hydrolysate retanning filler of solid powdery after the spraying drying.
Embodiment 6
Earlier 20 parts of trihydroxymethylpropanyltri diglycidyl ethers and 100 parts of deionized waters addings are had in the closed reactor of cooling and reflux device, under 40 ℃ of temperature, stir, and then powdery ox-hide Collagen Hydrolysate and 10 parts of ethanol that to add 100 parts of molecular weight successively be 3000-6000Da, in 50 ℃ of following stirring reaction 3h of temperature; Close cooling and reflux device, cool the temperature to 35 ℃, add 40 parts of diatomite, stirring reaction 2.5h can obtain liquid epoxy resin modification Collagen Hydrolysate retanning filler.
Application examples 1
Liquor ratio: 50%-80%(is with the wet blue restatement)
Consumption: 4%-8%(is with the wet blue restatement)
Temperature: 40 ° of C
Time: 40-60 minute
The specific absorption of this albumen retanning filler reaches more than 95%, and the sheepskin wet blue is high comprehensive performance after retanning is filled.
Application examples 2
Liquor ratio: 50%-80%(is with the wet blue restatement)
Consumption: 2%-6%(is with the wet blue restatement)
Temperature: 40 ° of C
Time: 40-60 minute
The specific absorption of this albumen retanning filler reaches more than 92%, and the ox-hide wet blue is high comprehensive performance after retanning is filled.
Claims (10)
1. epoxy resin modification Collagen Hydrolysate, this Collagen Hydrolysate is to be got through stirring reaction by the following component by mass parts:
The structural formula of the epoxy resin modification Collagen Hydrolysate that wherein contains is as follows:
R in the formula
1For:
2. the preparation method of the described epoxy resin modification Collagen Hydrolysate of claim 1, this method is that first water-soluble epoxy resin with 10～25 mass parts adds in the 100 mass parts deionized waters, under 40～70 ℃ of temperature, stir, and then adding 100 mass parts powdery Collagen Hydrolysates and 5～20 mass parts organic solvents successively, 40～80 ℃ of following stirring reaction 2～6h get final product in temperature.
3. the preparation method of epoxy resin modification Collagen Hydrolysate according to claim 2, used water-soluble epoxy resin is any in glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or the ethylene glycol diglycidylether in this method.
4. according to the preparation method of claim 2 or 3 described epoxy resin modification Collagen Hydrolysates, used powdery Collagen Hydrolysate is any in ox-hide, pigskin, the sheepskin Collagen Hydrolysate in this method, and its molecular weight distribution is 3000-6000Da or 7000-12000Da.
5. according to the preparation method of claim 2 or 3 described epoxy resin modification Collagen Hydrolysates, used organic solvent is any in ethanol, acetone or the tetrahydrofuran (THF) in this method.
6. the preparation method of epoxy resin modification Collagen Hydrolysate according to claim 4, used organic solvent is any in ethanol, acetone or the tetrahydrofuran (THF) in this method.
7. retanning filler by the preparation of the described epoxy resin modification Collagen Hydrolysate of claim 1, this retanning filler are to be mixed and get through stirring reaction by following component in mass parts:
8. according to the retanning filler of the described epoxy resin modification Collagen Hydrolysate preparation of claim 7, the water-soluble epoxy resin that contains in this retanning filler is any in glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or the ethylene glycol diglycidylether; The powdery Collagen Hydrolysate that contains is any in ox-hide, pigskin, the sheepskin Collagen Hydrolysate, and its molecular weight distribution is 3000-6000Da or 7000-12000Da; The organic solvent that contains is any in ethanol, acetone or the tetrahydrofuran (THF); Used mineral filler is any in kaolin, diatomite, titanium dioxide or the white carbon black.
9. the preparation method of the described retanning filler of claim 7, processing step and the condition of this method are as follows:
(1) elder generation adds the water-soluble epoxy resin of 10～25 mass parts in the 100 mass parts deionized waters, under 40～70 ℃ of temperature, stir, and then add 100 mass parts powdery Collagen Hydrolysates and 5～20 mass parts organic solvents successively, in 40～80 ℃ of following stirring reaction 2～6h of temperature;
(2) cool the temperature to 30～40 ℃, add 20～60 parts of mineral fillers, stirring reaction 0.5～3h gets final product.
10. according to the preparation method of the described retanning filler of claim 9, used water-soluble epoxy resin is any in glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether or the ethylene glycol diglycidylether in this method; Used powdery Collagen Hydrolysate is any in ox-hide, pigskin, the sheepskin Collagen Hydrolysate, and its molecular weight distribution is 3000-6000Da or 7000-12000Da; Used organic solvent is any in ethanol, acetone or the tetrahydrofuran (THF); Used mineral filler is any in kaolin, diatomite, titanium dioxide or the white carbon black.
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| CN103739770A (en) * | 2013-10-18 | 2014-04-23 | 陕西科技大学 | Preparation method of carboxyl-containing epoxy resin tanning agent |
| CN104313201A (en) * | 2014-08-30 | 2015-01-28 | 齐鲁工业大学 | Magnetic collagen modified cationic retanning agent and preparation method thereof |
| CN105482103A (en) * | 2015-12-25 | 2016-04-13 | 四川达威科技股份有限公司 | Modified amino acid polymer and preparation method as well as application thereof |
| CN105586444A (en) * | 2016-01-06 | 2016-05-18 | 四川大学 | Leather retaining-filling agent prepared by means of phenolsulfonic acid hydrolysis leather-making 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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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739770A (en) * | 2013-10-18 | 2014-04-23 | 陕西科技大学 | Preparation method of carboxyl-containing epoxy resin tanning agent |
| CN103739770B (en) * | 2013-10-18 | 2016-04-06 | 陕西科技大学 | Containing the preparation method of carboxyl epoxy resin tanning agent |
| CN104313201A (en) * | 2014-08-30 | 2015-01-28 | 齐鲁工业大学 | Magnetic collagen modified cationic retanning agent and preparation method thereof |
| 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 |
| CN105482103A (en) * | 2015-12-25 | 2016-04-13 | 四川达威科技股份有限公司 | Modified amino acid polymer and preparation method as well as application 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 |
| CN105586444A (en) * | 2016-01-06 | 2016-05-18 | 四川大学 | Leather retaining-filling agent prepared by means of phenolsulfonic acid hydrolysis leather-making 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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