CN109536036B - Preparation method of silicon-containing condensation tannin extract with polyethylene polyamine cross-linked structure - Google Patents
Preparation method of silicon-containing condensation tannin extract with polyethylene polyamine cross-linked structure Download PDFInfo
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- CN109536036B CN109536036B CN201811199984.5A CN201811199984A CN109536036B CN 109536036 B CN109536036 B CN 109536036B CN 201811199984 A CN201811199984 A CN 201811199984A CN 109536036 B CN109536036 B CN 109536036B
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- tannin extract
- polyethylene polyamine
- silicon
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- crosslinked structure
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- 239000000284 extract Substances 0.000 title claims abstract description 148
- 229920001864 tannin Polymers 0.000 title claims abstract description 113
- 239000001648 tannin Substances 0.000 title claims abstract description 113
- 235000018553 tannin Nutrition 0.000 title claims abstract description 112
- -1 polyethylene Polymers 0.000 title claims abstract description 59
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 58
- 229920000768 polyamine Polymers 0.000 title claims abstract description 58
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 58
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 43
- 239000010703 silicon Substances 0.000 title claims abstract description 43
- 238000009833 condensation Methods 0.000 title claims abstract description 32
- 230000005494 condensation Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920002770 condensed tannin Polymers 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 27
- 238000001291 vacuum drying Methods 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 25
- 239000002243 precursor Substances 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 239000000706 filtrate Substances 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 230000008859 change Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 5
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 229960001124 trientine Drugs 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- DJEHXEMURTVAOE-UHFFFAOYSA-M potassium bisulfite Chemical compound [K+].OS([O-])=O DJEHXEMURTVAOE-UHFFFAOYSA-M 0.000 claims description 2
- 229940099427 potassium bisulfite Drugs 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000010259 potassium hydrogen sulphite Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 2
- 235000019252 potassium sulphite Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 3
- 238000001035 drying Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 5
- 210000000051 wattle Anatomy 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 description 3
- 235000013311 vegetables Nutrition 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 235000013479 Amaranthus retroflexus Nutrition 0.000 description 1
- 240000005674 Ceanothus americanus Species 0.000 description 1
- 235000014224 Ceanothus americanus Nutrition 0.000 description 1
- 235000001904 Ceanothus herbaceus Nutrition 0.000 description 1
- 244000276331 Citrus maxima Species 0.000 description 1
- 235000001759 Citrus maxima Nutrition 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- 241000218671 Ephedra Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 235000007270 Gaultheria hispida Nutrition 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 241000218652 Larix Species 0.000 description 1
- 235000005590 Larix decidua Nutrition 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 235000009134 Myrica cerifera Nutrition 0.000 description 1
- 244000269152 Myrica pensylvanica Species 0.000 description 1
- 235000012851 Myrica pensylvanica Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 235000019606 astringent taste Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
- C09F1/04—Chemical modification, e.g. esterification
-
- C—CHEMISTRY; METALLURGY
- C14—SKINS; HIDES; PELTS; LEATHER
- C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
- C14C3/00—Tanning; Compositions for tanning
- C14C3/02—Chemical tanning
- C14C3/08—Chemical tanning by organic agents
- C14C3/10—Vegetable tanning
- C14C3/12—Vegetable tanning using purified or modified vegetable tanning agents
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compounds Of Unknown Constitution (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of tanning chemistry and engineering, and provides a preparation method of a silicon-containing condensation tannin extract with a polyethylene polyamine cross-linked structure, wherein an organic silicon group is introduced into the condensation tannin extract by the preparation method, and the water solubility of the tannin extract is improved by introducing the organic silicon group, so that the use amount of inorganic salts required by a sulfitation treatment process is reduced, and the problem of excessive water insoluble substances in a solution in the existing sulfitation modified tannin extract is solved; the tannin extract modified by the preparation method of the invention has a polyethylene polyamine cross-linked structure, thus solving the problem that the existing sulfitation modified tannin extract has overhigh content of tannin extract micromolecules; the leather is manufactured by using the silicon-containing condensation tannin extract with the polyethylene polyamine crosslinked structure prepared by the preparation method disclosed by the invention, and the obtained leather has excellent softness and fullness.
Description
Technical Field
The invention relates to the technical field of leather-making chemistry and engineering, in particular to a preparation method of a silicon-containing condensation tannin extract with a polyethylene polyamine cross-linked structure.
Background
Tannin extract is a substance with main component of plant polyphenol extracted from plants. Plant polyphenols including plant tannins and tannin precursor compounds and tannin polymers are natural macromolecular compounds widely present in plants and having a polyhydric phenolic hydroxyl structure, and are present in contents inferior to cellulose, hemicellulose and lignin. At present, the research on plant polyphenol relates to a plurality of fields such as tanning, oil exploitation, daily chemicals, medicines, foods, agriculture, environmental protection and the like. Because vegetable tanning has the characteristics of good fullness and formability, stiff and firm leather body, wear resistance, good air permeability and the like, the vegetable tanning method is still the basic tanning method for producing heavy leather. However, the vegetable tanning agent has the problems of low tannin content, a lot of insoluble substances in tanning liquid, easy generation of precipitate, slow permeability, weak combination with hide collagen, poor washing resistance, poor flexibility, difficult coloring at a dye filling section and the like, and brings great difficulty to the tanning production.
At present, in order to solve the aforesaid technical problems, the current methods are to slightly sulfitate the tannin extract, i.e. to treat the tannin extract solution with sulfite, then to add a suitable amount of acid to obtain sulfitated tannin extract; although the tannin extract after sulfitation modification has stronger astringency, filling property and water solubility, a large amount of tannin extract micromolecules still exist in the solution, and the viscosity value, the chromatic value and the salting-out value are not obviously reduced. In addition, although the mild sulfitation can be improved moderately by adopting the high-degree sulfitation, the problem of increased anionic property exists, so that the tannin extract has obvious color losing phenomenon when being used in a leather-making re-dyeing section, and because the use amount of the sulfite is too large, the ash content of the tannin extract is too high, and the tannin content is too low.
Disclosure of Invention
Therefore, aiming at the problems, the invention provides a preparation method of a silicon-containing condensed tannin extract with a polyethylene polyamine crosslinking structure, and by the preparation method, an organic silicon group is introduced into the condensed tannin extract, so that the water solubility of the tannin extract is improved, the use amount of inorganic salts required by a sulfitation treatment process is reduced, and the problem of excessive water insoluble substances in a solution in the existing sulfitation modified tannin extract is solved; the tannin extract modified by the preparation method of the invention has a polyethylene polyamine cross-linked structure, thus solving the problem that the existing sulfitation modified tannin extract has overhigh content of tannin extract micromolecules; the leather is manufactured by using the silicon-containing condensation tannin extract with the polyethylene polyamine crosslinked structure prepared by the preparation method disclosed by the invention, and the obtained leather has excellent softness and fullness.
In order to realize the technical problem, the solution scheme adopted by the invention is as follows: a preparation method of a silicon-containing condensed tannin extract with a polyethylene polyamine crosslinked structure sequentially comprises the following procedures of selecting condensed tannin extract → tannin treatment → tannin modification → sulfitation treatment; the tannin extract modification is to react tannin extract treated by tannin extract with a silane coupling agent and then to perform a crosslinking reaction with polyethylene polyamine to obtain a silicon-containing condensation tannin extract precursor with a polyethylene polyamine crosslinking structure.
Further, the condensed tannin extract is at least one of a wattle tannin extract, a quebracho tannin extract, a larch tannin extract, a shaddock tannin extract, a waxberry tannin extract, a red root tannin extract, an ephedra tannin extract, a cortex magnoliae officinalis tannin extract and a acacia tannin extract.
Further, the tannin extract treatment specifically comprises the following steps: adding the condensed tannin extract into an alkali solution, wherein the concentration of the condensed tannin extract in the alkali solution is 0.1-10g/L, soaking for 6-36h at 0-40 ℃, filtering out filter residue after full reaction, adding the alkali solution into filtrate, stirring for 6-36h at 40-80 ℃, filtering out the filter residue, carrying out vacuum drying (the vacuum drying temperature is 30-100 ℃, and the drying time is 12-72h) on the filtrate, and grinding to obtain the alkali-treated condensed tannin extract.
Wherein the alkali solution is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate solution.
Wherein the mass fraction of the alkali solution is 1-10%.
Further, the tannin extract modification specifically comprises the following steps: adding the condensed tannin extract treated by tannin extract, epoxy chloropropane and a catalyst into a solvent, wherein the concentration of the condensed tannin extract treated by tannin extract in the solvent is 500-2000g/L, the concentration of the epoxy chloropropane in the solvent is 25-150g/L, and the concentration of the catalyst in the solvent is 25-150 g/L; uniformly stirring at 25-50 ℃, adding a silane coupling agent, heating to 60-90 ℃, and reacting for 3-9 hours, wherein the concentration of the silane coupling agent in the solvent is 50-250 g/L; when the reaction is finished, adding a polyethylene polyamine crosslinking agent, and controlling the temperature change of the solution in a segmented manner to obtain a reaction mixed solution, wherein the concentration of the polyethylene polyamine in the solvent is 0.2-2 g/L; and (3) carrying out centrifugal treatment on the reaction mixed solution (the centrifugal rate is 1500-5000r/min, and the centrifugal time is 15-90min) to obtain solid powder, and carrying out vacuum drying on the solid powder (the vacuum drying temperature is 30-100 ℃, and the drying time is 12-72h) and grinding to obtain the silicon-containing condensation tannin extract precursor with the polyethylene polyamine cross-linked structure.
Wherein the solvent is at least one of deionized water, absolute ethyl alcohol, acetone and toluene.
Wherein the catalyst is at least one of potassium persulfate and sodium persulfate.
Wherein the silane coupling agent is at least one of 3-chloropropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3- (2,3 glycidoxy) propyltriethoxysilane and triethoxysilane.
Wherein the polyethylene polyamine is at least one of ethylenediamine, diethylenetriamine, triethylene tetramine and tetraethylenepentamine.
Wherein, the temperature change of the solution is controlled in a sectional way as follows: the reaction is controlled at 90-110 ℃ for 1-8h, and then at 120-140 ℃ for 0-8 h.
Further, the sulfitation treatment comprises the following steps: mixing the precursor of the silicon-containing condensation tannin extract with the polyethylene polyamine crosslinked structure, sulfite and sulfuric acid, reacting for 1-24h at 60-170 ℃, then carrying out vacuum drying (the vacuum drying temperature is 30-100 ℃, and the drying time is 12-72h) and grinding to obtain the silicon-containing sulfitation condensation tannin extract with the polyethylene polyamine crosslinked structure.
Wherein the sulfite is at least one of sodium sulfite, sodium bisulfite, potassium sulfite and potassium bisulfite.
Wherein the mass fraction of the sulfuric acid is 70-98%.
Wherein the sulfitation treatment is a light sulfitation treatment: based on the mass of the silicon-containing condensation tannin extract precursor with the polyethylene polyamine crosslinked structure, the usage amount of sulfite is 1-10%, and the usage amount of sulfuric acid is 0-30%. .
Or, the sulfitation treatment is a high-degree sulfitation treatment: based on the mass of the silicon-containing condensation tannin extract precursor with the polyethylene polyamine crosslinked structure, the usage amount of sulfite is 30-70 percent, and the usage amount of sulfuric acid is 0-50 percent.
By adopting the technical scheme, the invention has the beneficial effects that: according to the preparation method of the silicon-containing condensation tannin extract with the polyethylene polyamine crosslinked structure, the organic silicon group is introduced into the condensation tannin extract, and the water solubility of the tannin extract is improved due to the introduction of the organic silicon group, so that the use amount of inorganic salts required by a sulfitation treatment process is reduced, the water insoluble substance in the tannin extract solution prepared by the preparation method is lower than 5%, the tannin content is higher than 70%, and the problem that the water insoluble substance in the solution is excessive in the existing sulfitation modified tannin extract is solved; the tannin extract modified by the preparation method of the invention has a polyethylene polyamine cross-linked structure, thus solving the problem that the existing sulfitation modified tannin extract has overhigh content of tannin extract micromolecules; the softness and fullness of the finished leather are improved by more than 15 percent by using the silicon-containing condensation tannin extract with the polyethylene polyamine crosslinked structure prepared by the preparation method of the invention.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, so that how to apply technical means to solve technical problems and achieve technical effects can be fully understood and implemented, and it should be noted that the embodiments are only used for further description of the present invention and should not be construed as limiting the scope of the present invention, and those skilled in the art can make modifications and adjustments according to the above disclosure.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. Various procedures and methods not described in detail are conventional methods well known in the art, and the source, trade name, and if necessary, the constituents of the reagents used are indicated at the first appearance.
Example 1
A preparation method of a silicon-containing condensed tannin extract with a polyethylene polyamine cross-linked structure sequentially comprises the following working procedures:
(1) selecting condensed tannin extracts: the condensed tannin extract is wattle tannin extract;
(2) treating tannin extract: adding a condensed tannin extract into an alkali solution (a sodium hydroxide solution with the mass fraction of 5%), wherein the concentration of the condensed tannin extract in the alkali solution is 6g/L, soaking for 18h at 20 ℃, filtering out filter residue after full reaction, adding the alkali solution into filtrate, stirring for 18h at 60 ℃, filtering out the filter residue, carrying out vacuum drying (the vacuum drying temperature is 60 ℃, and the drying time is 36h) on the filtrate, and grinding to obtain the alkali-treated condensed tannin extract;
(3) and tannin extract modification: adding the condensed tannin extract subjected to tannin extract treatment, epichlorohydrin and a catalyst (sodium persulfate) into a solvent (deionized water), wherein the concentration of the condensed tannin extract subjected to tannin extract treatment in the solvent is 500g/L, the concentration of the epichlorohydrin in the solvent is 25g/L, and the concentration of the catalyst in the solvent is 25 g/L; after stirring uniformly at 40 ℃, adding a silane coupling agent, heating to 80 ℃, and reacting for 6 hours, wherein the concentration of the silane coupling agent (3-chloropropyltriethoxysilane) in the solvent is 150 g/L; at the end of the reaction, adding a polyethylene polyamine crosslinking agent, and controlling the temperature change of the solution in stages (firstly controlling the reaction at 100 ℃ for 6 hours and then controlling the reaction at 120 ℃ for 4 hours) to obtain a reaction mixed solution, wherein the concentration of the polyethylene polyamine (triethylene tetramine) in the solvent is 2 g/L; centrifuging the reaction mixed solution (the centrifugation speed is 2000r/min, the centrifugation time is 60min) to obtain solid powder, and carrying out vacuum drying (the vacuum drying temperature is 60 ℃, and the drying time is 36h) on the solid powder and grinding to obtain a silicon-containing condensation tannin extract precursor with a polyethylene polyamine cross-linked structure;
(4) sulfitation treatment, wherein the mass of the silicon-containing condensation tannin extract precursor with the polyethylene polyamine crosslinked structure is as follows: mixing a silicon-containing condensation tannin extract precursor with a polyethylene polyamine crosslinking structure, 5% of sulfite (sodium sulfite) and 15% of sulfuric acid (the mass fraction is 80%), reacting for 12 hours at 120 ℃, and then performing vacuum drying (the vacuum drying temperature is 60 ℃, and the drying time is 36 hours) and grinding to obtain the silicon-containing sulfitation condensation tannin extract with the polyethylene polyamine crosslinking structure.
Example 2
A preparation method of a silicon-containing condensed tannin extract with a polyethylene polyamine cross-linked structure sequentially comprises the following working procedures:
(1) selecting condensed tannin extracts: the condensed tannin extract is wattle tannin extract.
(2) Treating tannin extract: adding the condensed tannin extract into an alkali solution (a sodium hydroxide solution with the mass fraction of 5%), wherein the concentration of the condensed tannin extract in the alkali solution is 10g/L, soaking for 6h at 40 ℃, filtering out filter residue after full reaction, adding the alkali solution into filtrate, stirring for 6h at 80 ℃, filtering out the filter residue, carrying out vacuum drying (the vacuum drying temperature is 100 ℃, and the drying time is 12h) on the filtrate, and grinding to obtain the alkali-treated condensed tannin extract.
(3) And tannin extract modification: adding the condensed tannin extract subjected to tannin extract treatment, epichlorohydrin and a catalyst (sodium persulfate) into a solvent (deionized water), wherein the concentration of the condensed tannin extract subjected to tannin extract treatment in the solvent is 2000g/L, the concentration of the epichlorohydrin in the solvent is 150g/L, and the concentration of the catalyst in the solvent is 150 g/L; after stirring uniformly at 50 ℃, adding a silane coupling agent, heating to 90 ℃, and reacting for 9 hours, wherein the concentration of the silane coupling agent (3-chloropropyltriethoxysilane) in the solvent is 250 g/L; at the end of the reaction, adding a polyethylene polyamine crosslinking agent, and controlling the temperature change of the solution in stages (firstly controlling the reaction at 100 ℃ for 6 hours and then controlling the reaction at 120 ℃ for 4 hours) to obtain a reaction mixed solution, wherein the concentration of the polyethylene polyamine (triethylene tetramine) in the solvent is 2 g/L; and (3) centrifuging the reaction mixed solution (the centrifugation speed is 2000r/min, the centrifugation time is 60min) to obtain solid powder, and carrying out vacuum drying on the solid powder (the vacuum drying temperature is 100 ℃, and the drying time is 12h) and grinding to obtain the silicon-containing condensed tannin extract precursor with the polyethylene polyamine cross-linked structure.
(4) Sulfitation treatment, wherein the mass of the silicon-containing condensation tannin extract precursor with the polyethylene polyamine crosslinked structure is as follows: mixing a silicon-containing condensation tannin extract precursor with a polyethylene polyamine cross-linked structure, 50% of sulfite (sodium sulfite) and 40% of sulfuric acid (the mass fraction is 80%), reacting for 24 hours at 170 ℃, and then performing vacuum drying (the vacuum drying temperature is 100 ℃, and the drying time is 12 hours) and grinding to obtain the silicon-containing sulfitation condensation tannin extract with the polyethylene polyamine cross-linked structure.
Example 3
A preparation method of a silicon-containing condensed tannin extract with a polyethylene polyamine cross-linked structure sequentially comprises the following working procedures:
(1) selecting condensed tannin extracts: the condensed tannin extract is wattle tannin extract.
(2) Treating tannin extract: adding the condensed tannin extract into an alkali solution (a sodium hydroxide solution with the mass fraction of 5%), wherein the concentration of the condensed tannin extract in the alkali solution is 10g/L, soaking for 36h, filtering out filter residue after full reaction, adding the alkali solution into filtrate, stirring for 36h at 40 ℃, filtering out the filter residue, carrying out vacuum drying (the vacuum drying temperature is 30 ℃, and the drying time is 72h) on the filtrate, and grinding to obtain the alkali-treated condensed tannin extract.
(3) And tannin extract modification: adding the condensed tannin extract subjected to tannin extract treatment, epichlorohydrin and a catalyst (sodium persulfate) into a solvent (deionized water), wherein the concentration of the condensed tannin extract subjected to tannin extract treatment in the solvent is 1000g/L, the concentration of the epichlorohydrin in the solvent is 100g/L, and the concentration of the catalyst in the solvent is 100 g/L; after stirring uniformly at 50 ℃, adding a silane coupling agent, heating to 90 ℃, and reacting for 9 hours, wherein the concentration of the silane coupling agent (3-chloropropyltriethoxysilane) in the solvent is 200 g/L; at the end of the reaction, adding a polyethylene polyamine crosslinking agent, and controlling the temperature change of the solution in stages (firstly controlling the reaction at 100 ℃ for 6 hours and then controlling the reaction at 120 ℃ for 4 hours) to obtain a reaction mixed solution, wherein the concentration of the polyethylene polyamine (triethylene tetramine) in the solvent is 1.5 g/L; and (3) centrifuging the reaction mixed solution (the centrifugation speed is 2000r/min, the centrifugation time is 60min) to obtain solid powder, and carrying out vacuum drying on the solid powder (the vacuum drying temperature is 30 ℃, and the drying time is 72h) and grinding to obtain the silicon-containing condensed tannin extract precursor with the polyethylene polyamine cross-linked structure.
(4) Sulfitation treatment, wherein the mass of the silicon-containing condensation tannin extract precursor with the polyethylene polyamine crosslinked structure is as follows: mixing a silicon-containing condensation tannin extract precursor with a polyethylene polyamine cross-linked structure, 30% of sulfite (sodium sulfite) and 40% of sulfuric acid (the mass fraction is 80%), reacting for 24 hours at 115 ℃, and then performing vacuum drying (the vacuum drying temperature is 30 ℃, and the drying time is 72 hours) and grinding to obtain the silicon-containing sulfitation condensation tannin extract with the polyethylene polyamine cross-linked structure.
Comparative example 1:
comparative example 1 is a preparation method of slightly sulfited modified condensation tannin extract: selecting condensed tannin extract → tannin extract alkali treatment → mild sulfitation treatment. The preparation method of the slightly sulfited modified condensation tannin extract described in the comparative example 1 is different from the preparation method of the example 1 in that: comparative example 1 does not have the tannin extract modification step treatment of example 1, and other step conditions of comparative example 1 are identical to those of example 1.
Comparative example 2:
selecting the existing slightly sulfited modified wattle tannin extract ATO (Shenzhen Fangzhen import and export Limited company).
A comparison experiment is carried out on the tannin extract containing silicon sulfitation condensation structure with the polyethylene polyamine crosslinked structure obtained in the embodiment 1 of the invention and the tannin extracts obtained in the comparative examples 1-2, and the experimental comparison evaluation items comprise eight indexes of solid content, ash content, water soluble substances, water insoluble substances, tannin content, non-tannin content, number average molecular weight (the larger the number average molecular weight, the smaller the tannin extract small molecular weight content) and the softness of finished leather obtained by leather production by adopting the tannin extract, and are shown in Table 1.
TABLE 1 results of tests on indexes of tannin extract
| Example 1 | Comparative example 1 | Comparative example 2 | |
| Solids content/% | 95.13 | 92.05 | 93.93 |
| Ash content% | 4.83 | 6.49 | 7.62 |
| Water soluble substance/%) | 92.01 | 82.01 | 84.22 |
| Water insoluble fraction% | 1.28 | 11.43 | 8.78 |
| Tannin content/% | 73.20 | 67.72 | 68.53 |
| Non-tannin content/%) | 22.19 | 25.97 | 25.38 |
| Number average molecular weight | 960 | 780 | 820 |
| Fullness of finished leather | 5 | 4 | 4 |
In the preparation method of the silicon-containing condensed tannin extract with the polyethylene polyamine crosslinked structure, the water insoluble substances in the prepared tannin extract solution are lower than 5%, the tannin content is higher than 70%, and the softness and fullness of finished leather are improved by more than 15% when the prepared tannin extract is used for leather making.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (7)
1. A preparation method of a silicon-containing condensed tannin extract with a polyethylene polyamine crosslinked structure is characterized by sequentially comprising the following procedures of selecting condensed tannin extract → tannin alkali treatment → tannin modification → sulfitation treatment;
the tannin extract is modified as follows: adding condensed tannin extract subjected to tannin extract treatment, epoxy chloropropane and a catalyst into a solvent, uniformly stirring at 25-50 ℃, adding a silane coupling agent, heating to 60-90 ℃, reacting for 3-9 hours, adding a polyethylene polyamine crosslinking agent at the end of the reaction, and controlling the temperature change of the solution in a segmented manner to obtain a reaction mixed solution; centrifuging the reaction mixed solution to obtain solid powder, and vacuum drying and grinding the solid powder to obtain a silicon-containing condensation tannin extract precursor with a polyethylene polyamine cross-linked structure;
the silane coupling agent is at least one of 3-chloropropyltriethoxysilane and 3-aminopropyltriethoxysilane;
the polyethylene polyamine is at least one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine;
the catalyst is at least one of potassium persulfate and sodium persulfate.
2. The method for preparing the silicon-containing condensed tannin extract with the polyethylene polyamine crosslinked structure according to claim 1, characterized in that the tannin extract alkali treatment is as follows: adding the condensed tannin extract into an alkali solution, soaking for 6-36h at 0-40 ℃, filtering out filter residues after full reaction, adding the alkali solution into filtrate, stirring for 6-36h at 40-80 ℃, filtering out the filter residues, and carrying out vacuum drying and grinding on the filtrate to obtain the alkali-treated condensed tannin extract.
3. The method for preparing a silicon-containing condensed tannin extract of polyethylene polyamine crosslinked structure according to claim 2, wherein the alkali solution is at least one of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate solution.
4. The method for preparing the silicon-containing condensed tannin extract with the polyethylene polyamine crosslinked structure according to claim 1, wherein the solvent is at least one of deionized water, absolute ethyl alcohol, acetone and toluene.
5. The method for preparing the silicon-containing condensed tannin extract with the polyethylene polyamine crosslinked structure according to claim 1, characterized in that the temperature change of the solution is controlled by stages as follows: the reaction is controlled at 90-110 ℃ for 1-8h, and then at 120-140 ℃ for 0-8 h.
6. The method for preparing the silicon-containing condensed tannin extract with the polyethylene polyamine crosslinked structure according to claim 1, characterized in that the sulfitation treatment is: mixing the precursor of the silicon-containing condensation tannin extract with the polyethylene polyamine crosslinked structure, sulfite and sulfuric acid, reacting for 1-24h at 60-170 ℃, and then carrying out vacuum drying and grinding to obtain the silicon-containing sulfitation condensation tannin extract with the polyethylene polyamine crosslinked structure.
7. The method for preparing the silicon-containing condensed tannin extract with the polyethylene polyamine crosslinked structure according to claim 6, characterized in that: the sulfite is at least one of sodium sulfite, sodium bisulfite, potassium sulfite and potassium bisulfite.
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| CN101294048A (en) * | 2008-06-19 | 2008-10-29 | 晋城市柿宝科技发展有限公司 | Preparation method of persimmon tannin extract |
| CN102604540A (en) * | 2012-01-12 | 2012-07-25 | 中国林业科学研究院林产化学工业研究所 | Series tannin extract raw material ultra-fine crushing preparation as well as combined and coupled preparation process and method for series tannin extract products |
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| CN101294048A (en) * | 2008-06-19 | 2008-10-29 | 晋城市柿宝科技发展有限公司 | Preparation method of persimmon tannin extract |
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