CN116083660B - Light-resistant bio-based polyurethane composite retanning agent and application thereof - Google Patents
Light-resistant bio-based polyurethane composite retanning agent and application thereof Download PDFInfo
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- CN116083660B CN116083660B CN202310246826.5A CN202310246826A CN116083660B CN 116083660 B CN116083660 B CN 116083660B CN 202310246826 A CN202310246826 A CN 202310246826A CN 116083660 B CN116083660 B CN 116083660B
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- based polyurethane
- bio
- resistant
- sulfone
- tannin
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 36
- 239000004814 polyurethane Substances 0.000 title claims abstract description 36
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims abstract description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000003457 sulfones Chemical class 0.000 claims abstract description 39
- 235000018553 tannin Nutrition 0.000 claims abstract description 39
- 229920001864 tannin Polymers 0.000 claims abstract description 39
- 239000001648 tannin Substances 0.000 claims abstract description 39
- 238000004383 yellowing Methods 0.000 claims abstract description 30
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 29
- 239000002028 Biomass Substances 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 14
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 10
- 239000010985 leather Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 29
- 238000006482 condensation reaction Methods 0.000 claims description 27
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 19
- 230000018044 dehydration Effects 0.000 claims description 19
- 238000006297 dehydration reaction Methods 0.000 claims description 19
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000006277 sulfonation reaction Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- 229920005610 lignin Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 3
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 claims description 3
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 claims description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 3
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005770 Eugenol Substances 0.000 claims description 3
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 3
- 229960002217 eugenol Drugs 0.000 claims description 3
- 229940074391 gallic acid Drugs 0.000 claims description 3
- 235000004515 gallic acid Nutrition 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000001816 cooling Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 9
- 238000000967 suction filtration Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000001105 regulatory effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000008719 thickening Effects 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 102000008186 Collagen Human genes 0.000 description 3
- 108010035532 Collagen Proteins 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- 229920001436 collagen Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- PAUHLEIGHAUFAK-UHFFFAOYSA-N 1-isocyanato-1-[(1-isocyanatocyclohexyl)methyl]cyclohexane Chemical compound C1CCCCC1(N=C=O)CC1(N=C=O)CCCCC1 PAUHLEIGHAUFAK-UHFFFAOYSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 235000019766 L-Lysine Nutrition 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- QORUGOXNWQUALA-UHFFFAOYSA-N N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 Chemical compound N=C=O.N=C=O.N=C=O.C1=CC=C(C(C2=CC=CC=C2)C2=CC=CC=C2)C=C1 QORUGOXNWQUALA-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 210000001161 mammalian embryo Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000909 polytetrahydrofuran Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Classifications
-
- 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
- C14C3/22—Chemical tanning by organic agents using polymerisation products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of tanning, in particular to a light-resistant bio-based polyurethane composite retanning agent and application thereof. The invention provides a light-resistant bio-based polyurethane composite retanning agent, which comprises the following components in percentage by mass (3-5): (20-28) yellowing-resistant sulfone tannin and bio-based polyurethane resin; the preparation raw materials of the yellowing-resistant sulfone tannin comprise p-hydroxy phenol, 4' -dihydroxydiphenyl sulfone, urea and formaldehyde; the preparation raw materials of the bio-based polyurethane resin comprise polyalcohol, biomass raw materials and polyisocyanate. The light-resistant bio-based polyurethane composite retanning agent has good light resistance and filling property.
Description
Technical Field
The invention relates to the technical field of tanning, in particular to a light-resistant bio-based polyurethane composite retanning agent and application thereof.
Background
Retanning is a critical process in leather production, is known as "point golden" in leather production, and the same leather embryo can be made into solid vamp leather by adopting different retanning methods, and also can be used for producing soft and plump clothing leather, and the retanning agent has important influence on leather forming performance and plays a role in quality and grade.
Phenolic synthetic retanning agent contains hydroxyl groups, can be combined with collagen to have tanning property, and leather after retanning is soft and plump. The conventional phenolic syntans have weak binding with collagen molecules, so that the light fastness and heat resistance are general, which limits their application in white or light-colored skins. White leather and light-colored leather products have been favored in recent years. Therefore, the development of a phenolic synthetic retanning agent with good light resistance is significant.
Disclosure of Invention
The invention aims to provide a light-resistant bio-based polyurethane composite retanning agent and application thereof, wherein the light-resistant bio-based polyurethane composite retanning agent has good light resistance and filling property.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a light-resistant bio-based polyurethane composite retanning agent, which comprises the following components in percentage by mass (3-5): (20-28) yellowing-resistant sulfone tannin and bio-based polyurethane resin;
the preparation raw materials of the yellowing-resistant sulfone tannin comprise p-hydroxy phenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde;
the preparation raw materials of the bio-based polyurethane resin comprise polyalcohol, biomass raw materials and polyisocyanate.
Preferably, the pH value of the light-resistant bio-based polyurethane composite retanning agent is 5-7.
Preferably, the preparation process of the yellowing-resistant sulfone tannin comprises the following steps:
mixing p-hydroxyphenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde, and performing condensation reaction to obtain the yellowing-resistant sulfone tannin.
Preferably, the mass ratio of the p-hydroxy phenol, the 4,4' -dihydroxydiphenyl sulfone, the water, the urea and the formaldehyde is (20-30): (10-20): (20-50): (10-20): (20-30).
Preferably, the temperature of the condensation reaction is 70-110 ℃ and the time is 4-6 h.
Preferably, the preparation method of the 4,4' -dihydroxydiphenyl sulfone comprises the following steps:
mixing phenol and concentrated sulfuric acid, carrying out sulfonation reaction, and then sequentially carrying out dehydration and recrystallization to obtain the 4,4' -dihydroxydiphenyl sulfone;
the mass concentration of the concentrated sulfuric acid is 98%.
Preferably, the mass ratio of the phenol to the concentrated sulfuric acid is (10-25): (7.5-12.5);
the dehydration temperature is 150-200 ℃ and the dehydration time is 3-4 h.
Preferably, the preparation method of the bio-based polyurethane resin comprises the following steps:
and mixing the polyalcohol and biomass raw materials for grafting liquefaction reaction, adding polyisocyanate for polymerization reaction, and obtaining the bio-based polyurethane resin.
Preferably, the molar ratio of biomass feedstock, polyol and polyisocyanate is 1: (1-6): (0.5-8);
the biomass raw material comprises one or more of cellulose, lignin, tannin extract, gallic acid, eugenol, abietic acid and vegetable oil cardanol.
The invention also provides application of the light-resistant bio-based polyurethane composite retanning agent in the leather manufacturing field.
The invention provides a light-resistant bio-based polyurethane composite retanning agent which comprises (3-5): (20-28) yellowing-resistant sulfone tannin and bio-based polyurethane resin in a mass ratio; the preparation raw materials of the yellowing-resistant sulfone tannin comprise p-hydroxy phenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde; the preparation raw materials of the bio-based polyurethane resin comprise polyalcohol, biomass raw materials and polyisocyanate. The invention adopts the molecular design principle, and 4,4' -dihydroxydiphenyl sulfone is introduced into the yellowing-resistant sulfone tannin to enhance the heat resistance and the light resistance of the product; by adding urea, the content of free phenol in the product is greatly reduced, and the environmental protection is improved; the yellowing-resistant sulfone tannin is combined with the bio-based polyurethane resin tanning agent, and the gaps of the leather collagen fiber bundles are reasonably filled by utilizing the volume effect of the tanning agent, so that leather crust is plump and has moderate hand feeling. The light-resistant bio-based polyurethane composite retanning agent has good light resistance and strong filling performance, and can eliminate the difference of fullness of all parts of leather; can improve the softness and fullness of the leather and give the leather a bubble feel. The product has good light resistance, and can be used for retanning white skin and light-colored skin.
Detailed Description
The invention provides a light-resistant bio-based polyurethane composite retanning agent, which comprises the following components in percentage by mass (3-5): (20-28) yellowing-resistant sulfone tannin and bio-based polyurethane resin;
the preparation raw materials of the yellowing-resistant sulfone tannin comprise p-hydroxy phenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde;
the preparation raw materials of the bio-based polyurethane resin comprise polyalcohol, biomass raw materials and polyisocyanate.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
In the invention, the mass ratio of the yellowing-resistant sulfone tannin to the bio-based polyurethane resin is (3-5): (20 to 28), preferably (3.5 to 4.5): (21 to 27), more preferably (3.8 to 4.2): (23-25). In the present invention, the pH of the light-resistant bio-based polyurethane syntan is preferably 5 to 7, more preferably 6 to 7.
In the invention, the preparation process of the yellowing-resistant sulfone tannin preferably comprises the following steps of:
mixing p-hydroxyphenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde, and performing condensation reaction to obtain the yellowing-resistant sulfone tannin.
In the present invention, the preparation method of 4,4' -dihydroxydiphenyl sulfone preferably comprises the steps of: mixing phenol and concentrated sulfuric acid, carrying out sulfonation reaction, and then sequentially carrying out dehydration and recrystallization to obtain the 4,4' -dihydroxydiphenyl sulfone; the mass concentration of the concentrated sulfuric acid is 98%.
In the invention, the mass ratio of the phenol to the concentrated sulfuric acid is preferably (10-25): (7.5 to 12.5), more preferably (12 to 20): (8-10.5).
In the present invention, the temperature of the sulfonation reaction is preferably 80 to 100 ℃, more preferably 85 to 95 ℃, and most preferably 88 to 92 ℃; the time is preferably 2 to 6 hours, more preferably 3 to 5 hours, most preferably 3.5 to 4.5 hours.
In the present invention, the dehydration temperature is 150 to 200 ℃, more preferably 160 to 190 ℃, and most preferably 170 to 180 ℃; the time is preferably 3 to 4 hours, more preferably 3.5 to 3.8 hours.
After the dehydration is completed, the present invention also preferably includes cooling, and the cooling process is not limited in any way, and may be performed by a process well known to those skilled in the art.
In the present invention, the organic solvent used for the recrystallization preferably includes one or more of toluene, acetone, ethanol-water solution, ethyl acetate and petroleum ether; the volume concentration of ethanol in the ethanol-water solution is preferably 30%; when the organic solvent is two or more of the above specific choices, the present invention is not limited in particular to the ratio of the above specific substances, and may be mixed in any ratio. In the present invention, the mass of the organic solvent is 1 to 5 times, more preferably 1 to 3 times the mass of the reactant. In the present invention, the temperature of dissolution in the recrystallization process is preferably 70 to 100 ℃, more preferably 80 to 90 ℃; the temperature of crystallization during the recrystallization is preferably 20 to 55 ℃, more preferably 30 to 50 ℃.
After the recrystallization is finished, the invention also preferably comprises suction filtration, and the suction filtration is preferably vacuum suction filtration; the vacuum filtration process is not particularly limited, and may be performed by a process known to those skilled in the art.
In the present invention, the mass ratio of the p-hydroxyphenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde is preferably (20 to 30): (10-20): (20-50): (10-20): (20 to 30), more preferably (22 to 28): (12-18): (25-45): (12-18): (23 to 29), most preferably (24 to 26): (14-16): (30-40): (14-16): (25-26).
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the temperature of the condensation reaction is preferably 70 to 110 ℃, more preferably 80 to 100 ℃, and most preferably 85 to 95 ℃; the time is preferably 4 to 6 hours, more preferably 4.5 to 5.5 hours, most preferably 4.8 to 5.2 hours.
After the condensation reaction is completed, the invention also preferably includes spray drying; the spray drying process is not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art.
In the present invention, the preparation method of the bio-based polyurethane resin preferably includes the steps of:
and mixing the polyalcohol and biomass raw materials for grafting liquefaction reaction, adding polyisocyanate for polymerization reaction, and obtaining the bio-based polyurethane resin.
In the present invention, the polyhydric alcohol preferably includes one or more of ethylene glycol, pentaerythritol, and diethylene glycol; when the polyhydric alcohol is two or more of the above specific choices, the present invention is not limited to any particular ratio of the above specific substances, and may be mixed in any ratio.
In the invention, the biomass raw material preferably comprises one or more of cellulose, lignin, tannin extract, gallic acid, eugenol, abietic acid and vegetable oil cardanol; when the biomass raw material is two or more of the above specific choices, the invention does not have any special limitation on the ratio of the above specific substances, and the biomass raw material is mixed according to any ratio.
In the present invention, the polyisocyanate preferably includes a diisocyanate and/or a triisocyanate; the diisocyanate preferably comprises one or more of toluene diisocyanate, methylene diphenyl diisocyanate, hexamethylene diisocyanate, methylene dicyclohexyl diisocyanate and isophorone diisocyanate; the triisocyanate preferably comprises one or more of 4,4' -triphenylmethane triisocyanate, triphenylmethane triisocyanate and L-lysine triisocyanate; when the polyisocyanate is two or more of the above specific choices, the present invention is not limited in particular to the ratio of the above specific substances, and may be mixed in any ratio.
In the present invention, the molar ratio of the biomass feedstock, polyol and polyisocyanate is preferably 1: (1-6): (0.5 to 8), more preferably 1: (2-5): (1 to 5), most preferably 1: (3-4): (2-3).
The mixing of the polyol and biomass feedstock in the present invention is not particularly limited and may be carried out by processes well known to those skilled in the art.
In the present invention, the temperature of the graft liquefaction reaction is preferably 90 to 150 ℃, more preferably 100 to 140 ℃, and most preferably 120 to 130 ℃; the time is preferably 2 to 8 hours, more preferably 3 to 6 hours, and most preferably 4 to 5 hours.
In the present invention, the temperature of the polymerization reaction is preferably 30 to 90 ℃, more preferably 45 to 80 ℃, and most preferably 50 to 60 ℃; the time is preferably 8 to 18 hours, more preferably 10 to 15 hours. In the present invention, the temperature at which the polyisocyanate is added and the temperature of the polymerization reaction are preferably the same.
In the present invention, the preparation method of the light-resistant bio-based polyurethane composite retanning agent preferably comprises the following steps: and mixing the yellowing-resistant sulfone tannin with the bio-based polyurethane resin, and then adjusting the pH value to obtain the light-resistant bio-based polyurethane composite.
The mixing process is not particularly limited, and may be performed by a process well known to those skilled in the art.
In the present invention, the reagent used for adjusting the pH is preferably sodium hydroxide.
The invention also provides application of the light-resistant bio-based polyurethane composite retanning agent in the leather manufacturing field. The method of the present invention is not particularly limited, and may be carried out by methods known to those skilled in the art.
The light-resistant bio-based polyurethane syntan and the use thereof according to the present invention are described in detail with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 10 parts by weight of phenol and 7.5 parts by weight of concentrated sulfuric acid with the mass concentration of 98% for sulfonation reaction (the temperature of the sulfonation reaction is 85 ℃ and the time is 3.5 h), heating to 170 ℃ for dehydration (the time of dehydration is 3.5 h), then sequentially cooling, adding ethanol-water solution with the ethanol concentration of 30vol% and the addition amount of 3 times of the weight of the reactants, maintaining 80 ℃, fully stirring and dissolving, then discharging into a crystallization tank for cooling to 30 ℃, and obtaining 4,4' -dihydroxydiphenyl sulfone through vacuum suction filtration;
mixing 20 parts by weight of p-hydroxyphenol, 10 parts by weight of 4,4' -dihydroxydiphenyl sulfone, 30 parts by weight of water, 10 parts by weight of urea and 20 parts by weight of formaldehyde to perform condensation reaction (the temperature of the condensation reaction is 80 ℃ and the time is 4 hours), and performing spray drying to obtain yellowing-resistant sulfone tannin;
mixing 10 parts by weight of polypropylene glycol and 12 parts by weight of biomass raw material (tannin extract), reacting for 4 hours at 100 ℃, cooling to 60 ℃, adding 15 parts by weight of toluene diisocyanate, and performing condensation reaction (the temperature of the condensation reaction is 60 ℃ and the time is 10 hours) to obtain tannin extract-based polyurethane resin;
and 5 parts by weight of the yellowing-resistant sulfone tannin and 25 parts by weight of the tannin extract-based polyurethane resin are mixed, and then the pH value is regulated to 6 by sodium hydroxide, so that the light-resistant bio-based polyurethane compound retanning agent is obtained.
Example 2
Mixing 10 parts by weight of phenol and 8.5 parts by weight of concentrated sulfuric acid with the mass concentration of 98% for sulfonation reaction (the temperature of the sulfonation reaction is 88 ℃ and the time is 3.5 h), heating to 175 ℃ for dehydration (the dehydration time is 3.5 h), sequentially cooling, adding 30% of ethanol-water solution, keeping the adding amount to be 3 times of the weight of the reactants, fully stirring and dissolving, discharging into a crystallization tank, cooling to 30 ℃, and carrying out vacuum suction filtration to obtain 4,4' -dihydroxydiphenyl sulfone;
mixing 20 parts by weight of p-hydroxyphenol, 12 parts by weight of 4,4' -dihydroxydiphenyl sulfone, 30 parts by weight of water, 12 parts by weight of urea and 22 parts by weight of formaldehyde to perform condensation reaction (the temperature of the condensation reaction is 90 ℃ C., the time is 4 hours) to obtain yellowing-resistant sulfone tannin;
mixing 12 parts by weight of polypropylene glycol and 12 parts by weight of biomass raw material (cellulose), reacting for 4.5 hours at 100 ℃, cooling to 60 ℃, adding 15 parts by weight of methylene diphenyl diisocyanate, and performing condensation reaction (the temperature of the condensation reaction is 60 ℃ and the time is 12 hours) to obtain cellulose-based polyurethane resin;
and 5 parts by weight of the yellowing-resistant sulfone tannin and 26.5 parts by weight of the cellulose-based polyurethane resin are mixed, and then the pH value is regulated to 6.5 by sodium hydroxide, so that the light-resistant bio-based polyurethane compound retanning agent is obtained.
Example 3
Mixing 12.5 parts by weight of phenol and 8.5 parts by weight of concentrated sulfuric acid with the mass concentration of 98% for sulfonation (the temperature of the sulfonation is 90 ℃ and the time is 4 hours), heating to 190 ℃ for dehydration (the time of dehydration is 3.5 hours), then sequentially cooling, adding ethyl acetate, keeping the adding amount to be 3 times of the weight of the reactants, maintaining 85 ℃, fully stirring and dissolving, then discharging to a crystallization tank for cooling to 45 ℃, and obtaining 4,4' -dihydroxydiphenyl sulfone through vacuum suction filtration;
mixing 25 parts by weight of p-hydroxyphenol, 15 parts by weight of 4,4' -dihydroxydiphenyl sulfone, 30 parts by weight of water, 15 parts by weight of urea and 25.5 parts by weight of formaldehyde to perform condensation reaction (the temperature of the condensation reaction is 90 ℃ C., the time is 4 hours) to obtain yellowing-resistant sulfone tannin;
mixing 15 parts by weight of polytetrahydrofuran glycol and 15 parts by weight of biomass raw material (castor oil), reacting for 5 hours at 120 ℃, cooling to 50 ℃, adding 22.5 parts by weight of toluene diisocyanate, and performing condensation reaction (the temperature of the condensation reaction is 55 ℃ and the time is 15 hours) to obtain castor oil-based polyurethane resin;
and 5 parts by weight of the yellowing-resistant sulfone tannin and 25 parts by weight of the castor oil-based polyurethane resin are mixed, and then the pH value is regulated to 6.5 by sodium hydroxide, so that the light-resistant bio-based polyurethane compound retanning agent is obtained.
Example 4
Mixing 15 parts by weight of phenol and 12.5 parts by weight of concentrated sulfuric acid with the mass concentration of 98% for sulfonation reaction (the temperature of the sulfonation reaction is 90 ℃ and the time is 3.5 h), heating to 200 ℃ for dehydration (the dehydration time is 4 h), then sequentially cooling, adding 20% of ethanol-water solution, keeping the addition amount to be 4 times of the weight of the reactants, fully stirring and dissolving, then discharging to a crystallization tank for cooling to 45 ℃, and obtaining 4,4' -dihydroxydiphenyl sulfone through vacuum suction filtration;
mixing 20 parts by weight of p-hydroxyphenol, 12 parts by weight of 4,4' -dihydroxydiphenyl sulfone, 30 parts by weight of water, 15 parts by weight of urea and 24 parts by weight of formaldehyde to perform condensation reaction (the temperature of the condensation reaction is 85 ℃ C., the time is 6 hours) to obtain yellowing-resistant sulfone tannin;
mixing 15 parts by weight of polypropylene glycol and 12 parts by weight of biomass raw material (tannin extract), reacting for 5 hours at 100 ℃, cooling to 60 ℃, adding 15 parts by weight of isophorone diisocyanate, and performing condensation reaction (the temperature of the condensation reaction is 60 ℃ and the time is 4.5 hours) to obtain tannin extract-based polyurethane resin;
and (3) mixing 4 parts by weight of the yellowing-resistant sulfone tannin and 26 parts by weight of the tannin extract-based polyurethane resin, and then regulating the pH value to 7 by using sodium hydroxide to obtain the light-resistant bio-based polyurethane composite retanning agent.
Example 5
Mixing 15 parts by weight of phenol and 12.5 parts by weight of concentrated sulfuric acid with the mass concentration of 98% for sulfonation reaction (the temperature of the sulfonation reaction is 92 ℃ and the time is 4 hours), heating to 170 ℃ for dehydration (the time of dehydration is 3.5 hours), then sequentially cooling, adding 20% of ethanol-water solution, keeping the adding amount to be 4 times of the weight of the reactant, fully stirring and dissolving, then discharging to a crystallization tank for cooling to 35 ℃, and obtaining 4,4' -dihydroxydiphenyl sulfone through vacuum suction filtration;
mixing 25 parts by weight of p-hydroxyphenol, 18 parts by weight of 4,4' -dihydroxydiphenyl sulfone, 30 parts by weight of water, 16 parts by weight of urea and 30 parts by weight of formaldehyde to perform condensation reaction (the temperature of the condensation reaction is 90 ℃ C., the time is 4 hours) to obtain yellowing-resistant sulfone tannin;
mixing 10 parts by weight of polypropylene glycol and 12 parts by weight of biomass raw material (lignin), reacting for 5 hours at 120 ℃, cooling to 60 ℃, adding 16.5 parts by weight of 4,4' -triphenylmethane triisocyanate, and performing condensation reaction (the temperature of the condensation reaction is 60 ℃ and the time is 15 hours) to obtain lignin-based polyurethane resin;
and 3 parts by weight of the yellowing-resistant sulfone tannin and 28 parts by weight of the lignin-based polyurethane resin are mixed, and then the pH value is regulated to 6.5 by sodium hydroxide, so that the light-resistant bio-based polyurethane compound retanning agent is obtained.
Test case
The properties of the lightfast bio-based polyurethane syntan described in examples 1 to 5 were tested, and the test items included softness, thickening ratio, tear strength and lightfast properties.
(1) Method for measuring softness:
the test uses GT-300 leather softness, and the tester measures leather softness, wherein 9 different points are selected for each leather, and the average value is taken as the softness of the leather.
(2) Method for measuring thickening ratio:
the thickness of the leather washed before and after fatliquoring and the thickness of the leather washed after fatliquoring are respectively measured by a leather thickness meter, 5 different points are selected and measured for each piece of leather, the thickness (mm) is read after 5 seconds, the average value is obtained, and the thickening rate is calculated. The calculation formula is shown in formula 1:
in formula 1:
delta: a thickening ratio of 100%;
b 1 : the average thickness of crust leather before fatliquoring is mm;
b 2 : the average thickness of crust leather after fatliquoring is mm.
(3) Determination of tear Strength:
the leather after fatliquoring is manufactured into the specification of 50X 25mm 2 The test results were averaged over four samples in the transverse and longitudinal directions, and the maximum load number (also referred to as tearing force) of the test sample during the breaking process was measured by placing the test sample on a multifunctional leather tester. The calculation formula is shown as the following formula 2:
in formula 2:
p: tear strength, N/mm;
f: maximum load number, N;
d: sample thickness (thickness of one side of the tear, if both sides are broken at the same time, calculate average thickness at two points A, B, mm.)
The test results are shown in table 1:
table 1 properties of light-fast bio-based polyurethane syntan described in examples 1 to 5
| Examples | Softness and softness | Thickening ratio (%) | Tear strength (N/mm) |
| Example 1 | 9.13 | 14.98 | 35.66 |
| Example 2 | 9.56 | 15.56 | 35.73 |
| Example 3 | 9.61 | 14.39 | 35.53 |
| Example 4 | 9.38 | 16.07 | 36.27 |
| Example 5 | 9.38 | 15.64 | 35.98 |
(4) Testing of light resistance:
the light fastness performance test is carried out on the light fastness bio-based polyurethane composite retanning agents of examples 1 to 5 according to national standard QB/T2727-2017, and the test results are shown in Table 2:
table 2 lightfastness of lightfastness biobased polyurethane complex retanning agents described in examples 1 to 5
As can be seen from tables 1 to 2, the leather processed by the light-resistant bio-based polyurethane composite retanning agent according to examples 1 to 5 has excellent tearing strength and filling function, eliminates the difference of fullness of each part of the leather, and can improve softness and fullness of the leather; in addition, the lightfastness of the lightfastness bio-based polyurethane composite retanning agent is more than or equal to 4.5 grade, which shows that the sample has excellent lightfastness and can be used for retanning white skin and light-colored skin.
The foregoing is merely a preferred embodiment of the invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the invention, which are intended to be comprehended within the scope of the invention.
Claims (5)
1. The light-resistant bio-based polyurethane composite retanning agent is characterized by comprising the following components in percentage by mass (3-5): (20-28) yellowing-resistant sulfone tannin and bio-based polyurethane resin;
the preparation raw materials of the yellowing-resistant sulfone tannin comprise p-hydroxy phenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde;
the preparation raw materials of the bio-based polyurethane resin comprise polyalcohol, biomass raw materials and polyisocyanate;
the pH value of the light-resistant bio-based polyurethane composite retanning agent is 5-7;
the preparation process of the yellowing-resistant sulfone tannin comprises the following steps:
mixing p-hydroxyphenol, 4' -dihydroxydiphenyl sulfone, water, urea and formaldehyde, and performing condensation reaction to obtain the yellowing-resistant sulfone tannin;
the mass ratio of the p-hydroxy phenol, the 4,4' -dihydroxydiphenyl sulfone, the water, the urea and the formaldehyde is (20-30): (10-20): (20-50): (10-20): (20-30);
the preparation method of the bio-based polyurethane resin comprises the following steps:
mixing polyalcohol and biomass raw materials for grafting liquefaction reaction, adding polyisocyanate for polymerization reaction, and obtaining the bio-based polyurethane resin;
the molar ratio of the biomass raw material, the polyol and the polyisocyanate is 1: (1-6): (0.5-8);
the biomass raw material comprises one or more of cellulose, lignin, tannin extract, gallic acid, eugenol, abietic acid and vegetable oil cardanol.
2. The lightfast bio-based polyurethane syntan according to claim 1, wherein the condensation reaction is carried out at a temperature of 70 to 110 ℃ for a time of 4 to 6 hours.
3. The lightfast bio-based polyurethane syntan according to claim 1, wherein the process for preparing 4,4' -dihydroxydiphenyl sulfone comprises the steps of:
mixing phenol and concentrated sulfuric acid, carrying out sulfonation reaction, and then sequentially carrying out dehydration and recrystallization to obtain the 4,4' -dihydroxydiphenyl sulfone;
the mass concentration of the concentrated sulfuric acid is 98%.
4. A photostable bio-based polyurethane syntan according to claim 3, wherein the mass ratio of phenol to concentrated sulfuric acid is (10 to 25): (7.5-12.5);
the dehydration temperature is 150-200 ℃ and the dehydration time is 3-4 h.
5. Use of the lightfast biobased polyurethane syntan according to any of claims 1 to 4 in the field of leather manufacture.
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| CN103030769A (en) * | 2012-12-07 | 2013-04-10 | 青岛文创科技有限公司 | Polyurethane retanning filler |
| CN104450993A (en) * | 2014-12-24 | 2015-03-25 | 上海金狮化工有限公司 | Retanning agent and preparation method thereof |
| CN106478957A (en) * | 2016-10-12 | 2017-03-08 | 温州大学 | The preparation method of keratin grafting water-based polyurethane polymer leather retanning packing material |
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| CN103030769A (en) * | 2012-12-07 | 2013-04-10 | 青岛文创科技有限公司 | Polyurethane retanning filler |
| CN104450993A (en) * | 2014-12-24 | 2015-03-25 | 上海金狮化工有限公司 | Retanning agent and preparation method thereof |
| CN106478957A (en) * | 2016-10-12 | 2017-03-08 | 温州大学 | The preparation method of keratin grafting water-based polyurethane polymer leather retanning packing material |
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