CN115807137B - Preparation method of hydrogen bond-based fluorine-containing retanning agent for chrome-free tanning - Google Patents
Preparation method of hydrogen bond-based fluorine-containing retanning agent for chrome-free tanning Download PDFInfo
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- CN115807137B CN115807137B CN202111076172.3A CN202111076172A CN115807137B CN 115807137 B CN115807137 B CN 115807137B CN 202111076172 A CN202111076172 A CN 202111076172A CN 115807137 B CN115807137 B CN 115807137B
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 56
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 33
- 239000011737 fluorine Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 18
- 239000001257 hydrogen Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 60
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 60
- 239000004814 polyurethane Substances 0.000 claims abstract description 55
- 229920002635 polyurethane Polymers 0.000 claims abstract description 55
- 239000010985 leather Substances 0.000 claims abstract description 54
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims abstract description 49
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 34
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 19
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- AQYSYJUIMQTRMV-UHFFFAOYSA-N hypofluorous acid Chemical compound FO AQYSYJUIMQTRMV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000001816 cooling Methods 0.000 claims description 26
- 238000003756 stirring Methods 0.000 claims description 22
- 239000012153 distilled water Substances 0.000 claims description 16
- CERQOIWHTDAKMF-UHFFFAOYSA-N alpha-methacrylic acid Natural products CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 15
- 239000003513 alkali Substances 0.000 claims description 12
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 10
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 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 claims description 3
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 39
- 230000000694 effects Effects 0.000 abstract description 21
- 239000000835 fiber Substances 0.000 abstract description 18
- 125000000129 anionic group Chemical group 0.000 abstract description 14
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011068 loading method Methods 0.000 abstract description 6
- -1 carboxyl ions Chemical class 0.000 abstract description 5
- 238000001338 self-assembly Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 17
- 239000007787 solid Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 230000035699 permeability Effects 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 231100000693 bioaccumulation Toxicity 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BYEAHWXPCBROCE-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-ol Chemical compound FC(F)(F)C(O)C(F)(F)F BYEAHWXPCBROCE-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000004043 dyeing Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000013622 meat product Nutrition 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Treatment And Processing Of Natural Fur Or Leather (AREA)
Abstract
The invention discloses a preparation method of a hydrogen bond-based fluorine-containing retanning agent for chrome-free tanning. Firstly, polyethylene glycol monomethyl ether reacts with diisocyanate, then short-chain fluoro alcohol is added to obtain nonionic short fluorocarbon chain polyurethane, and then the nonionic short fluorocarbon chain polyurethane is compounded with the prepared (methyl) acrylic resin according to a proportion to obtain the hydrogen bond-based chrome-free tanning fluorine-containing retanning agent. The short fluorocarbon chain polyurethane has low biotoxicity and can endow a composite system with high surface activity, promote the permeation of (methyl) acrylic resin, and the nonionic block can shield part of carboxyl ions of the acrylic resin, so that the loading rate of anionic dye and fatliquor during retanning is improved; the pH control system is regulated to realize hydrogen bond self-assembly during fixing, so that the pH control system and the fiber are selectively filled in the fiber, and the mechanical property of the finished leather can be remarkably improved; and simultaneously, the carbamate chain of the short fluorocarbon chain polyurethane can react with formaldehyde in an energy-saving way, so that the free formaldehyde content of the finished leather can be reduced. The method provided by the invention is simple and convenient to operate, and accords with the design concept of environmental friendliness of chrome-free tanning.
Description
Technical Field
The invention relates to a preparation method of a hydrogen bond-based fluorine-containing retanning agent for chrome-free tanning, in particular to a preparation method of a hydrogen bond-based self-assembled fluorine-containing retanning agent for chrome-free tanning by two-block non-ionic short fluorocarbon chain polyurethane and (methyl) acrylic resin, belonging to the field of retanning of chrome-free tanning.
Background
Meat products contain a large amount of nutrients required by human bodies, and if the animal skin remained in the production of the meat products is not reused, not only is the waste of resources caused, but also serious environmental pollution is caused, so that the leather is prepared into leather, and the leather is an measure conforming to the requirement of sustainable development. At present, about 90% of raw leather is used for producing light leather, and more than 90% of the light leather is produced by chrome tanning, but hexavalent chromium is inevitably produced in the production and use process of chrome tanning, and is extremely harmful to human bodies and the environment (Qiao Huan, qiangxi, cui Lu, and the like). Solid waste such as chromium-containing sludge, waste leather scraps and the like generated by chrome tanning can be basically only treated by incineration at present, the chromium-containing wastewater is extremely difficult to treat, the treatment cost of the chromium-containing sludge and the waste leather scraps is high, and the development of the leather industry is severely limited.
In the production of chrome-free tanned light leather, aldehyde tannage is often used as the main tannage. Aldehyde tanning avoids hexavalent chromium pollution, but the aldehyde tanning is flat and thin and has poor mechanical properties, so that the application range of the aldehyde tanning is greatly limited. Thus, the fullness and mechanical strength of aldehyde tanned leather must be improved and increased more by retanning after aldehyde tanning. The retanning agent most commonly used in conventional retanning of chrome tanning in the tanning industry is an acrylic resin retanning agent, the preparation and application processes are mature, and meanwhile, the retanning agent has the advantages of multiple active groups, good structural adjustability and the like, and the properties of finished leather can be improved in multiple aspects after retanning. However, the presence of a large amount of carboxyl ions in the conventional acrylic resin retanning agent can generate an anion rejection effect, and the dyeing and fatting effects of the subsequent anionic dye and fatting agent are seriously reduced, so that the practical application effect of the acrylic resin in aldehyde tanning is greatly influenced. Meanwhile, in view of the fact that metal ions are not contained in aldehyde tannage, an anionic acrylic resin retanning agent is difficult to permeate and fix in leather fibers through interaction of positive and negative ions (the method is a normal permeation and fixing mode of the anionic acrylic resin retanning agent in conventional chrome tannage), in order to ensure a retanning effect of aldehyde tannage, the addition amount of the acrylic resin retanning agent is generally large, the surface of finished leather is possibly oversanning, the hand feeling of leather products is seriously influenced, and the commercial value of the leather products is further reduced (Gao Xiaozhong, li Xia. The reason for the hard production of leather boards and improvement method [ J ]. Beijing leather, 2021, 46 (05): 48-51.). And the aldehyde tanning can release a certain amount of free formaldehyde in the use process, so that the harm to human bodies is great, and the release amount of the free formaldehyde in leather is regulated by the industry standard in countries around the world (Li Xinxin, wang Yanan, zhang Wenhua, and the like). Therefore, the anionic rejection effect of the acrylic resin retanning agent is reduced, so that the dyeing and fatting effects of the anionic dye and the fatting agent are improved, the anionic dye and the fatting agent are effectively permeated and fixed in aldehyde tanned leather fibers, good retanning effects are obtained, the free formaldehyde content in aldehyde tanned leather can be reduced, and the method has great significance in developing clean tanneries and widening commercial application of the clean tanneries.
There have been studies (Journal of Cleaner Production, 2018 (175): 199-206) on the problem of poor penetration and fixation of acrylic resin by compounding nonionic amphiphilic polyurethane with acrylic resin and using it as a leather retanning agent. Because the nonionic amphiphilic polyurethane contains carbamate groups, hydrogen bonds can be generated with the leather fibers, so that the retanning agent can be well assisted to be fixed in the leather fibers. The nonionic amphiphilic polyurethane introduced in the research is essentially a surfactant, however, the amphiphilic polyurethane surfactant is a hydrocarbon surfactant and has general surface activity, so that the permeability of the acrylic resin retanning agent is improved only limitedly, and the improvement of the mechanical properties of the leather lining fiber is obviously influenced. Among the surfactants, the fluorosurfactant has the lowest surface energy and the highest surface activity (Langmuir, 2006, 22 (10): 4643-4648.). However, conventional fluorosurfactants are usually constructed based on long fluorocarbon chains, which are highly biotoxic and bioaccumulative, and their introduction, while significantly improving the penetration properties, presents significant environmental risks, which are contrary to the concept of developing clean tanning, and do not meet the design initiative of chrome-free tanning. Therefore, the chrome-free tanning agent for cleaning and retanning is designed to perfectly improve the permeability of the acrylic resin, ensure the fixing effect of the acrylic resin and not destroy the green design concept, and has milestone significance for the development of the chrome-free tanning agent.
For example, chinese patent (CN 109627376B) discloses an amphoteric polymer auxiliary agent, a preparation method and application thereof, which is obtained by blending acrylic acid monomers and quaternary ammonium salt monomers and then reacting with ammonium persulfate, and can avoid the 'color-losing' effect generated by too much anion content in acrylic resin retanning agent to a certain extent, thereby improving the absorption rate of retanning leather to anionic dye, but has no lifting effect on the permeation of retanning agent, is easy to cause problems of surface oversanning and 'heart generation', and the application thereof is greatly limited.
For example, chinese patent (CN 104531916 a) discloses a preparation method of a retanning agent for chrome-free tanning constructed based on hydrogen bond self-assembly, which is formed by compounding (meth) acrylic resin and triblock non-ionic amphiphilic polyurethane resin, and can significantly promote fixation of the retanning agent in leather fibers, however, only by introducing non-ions to shield carboxyl groups, the improvement of the permeability of acrylic resin is limited, and the problems of surface oversanning, low dye-uptake of anionic dye and the like cannot be comprehensively solved, so that the application effect is poor.
With the increasing use of fluorine-containing materials, researchers have found that short fluorocarbon chain materials having less than or equal to four carbon atoms have very little bioaccumulation and also have high surface activity (Journal of Colloid and Interface Science,2014, 428:276-285), and thus the use of short fluorocarbon chain materials meets the original aim of being environmentally friendly.
The invention relates to a preparation method of a fluorine-containing retanning agent for chrome-free tanning based on hydrogen bonds, which comprises the steps of reacting diisocyanate with polyethylene glycol monomethyl ether, introducing short-chain fluorohydrin to prepare two-block non-ionic short-fluorocarbon-chain polyurethane, reacting (methyl) acrylic acid, acrylamide, vinyl acetate and maleic anhydride, adding alkali to adjust pH to obtain (methyl) acrylic resin, and finally mixing the two-block non-ionic short-fluorocarbon-chain polyurethane with the prepared (methyl) acrylic resin. The polyurethane introduced by the fluorine-containing retanning agent for chrome-free tanning contains nonionic blocks, can effectively shield carboxyl ions in (methyl) acrylic resin, improves the permeability of the polyurethane, improves the loading rate of widely used anionic dye and fatliquor in retanned leather, and widens the application range of the polyurethane. The pH is adjusted during fixing to control the two-block non-ionic short fluorocarbon chain polyurethane and the (methyl) acrylic resin to carry out hydrogen bond self-assembly, so that the two can be selectively filled in the leather fiber, and the mechanical property of the chrome-free tanning leather after retanning can be obviously improved; meanwhile, due to the fact that short fluorocarbon chain polyurethane is introduced, the surface activity of a composite system is greatly improved, the permeability of (methyl) acrylic resin is greatly enhanced, the filling property of the (methyl) acrylic resin is improved, the finished leather is plump and compact, the addition amount of a retanning agent is reduced, and the problems of surface oversanning and the like are avoided. The short fluorocarbon chain polyurethane can more fully penetrate into the leather fiber, so that the retention amount in the leather core is increased, a large number of carbamate chain links capable of reacting with formaldehyde exist in the leather fiber, the content of free formaldehyde in aldehyde tanning can be greatly reduced through the reaction of the carbamate chain links and aldehyde groups, the retanning effect is improved and enhanced, and the integral mechanical property of the finished leather is further improved. The invention also considers that the fluorine-containing long-chain material has high biotoxicity and bioaccumulation and has great harm to the environment after being abandoned, so the invention adopts the short fluorocarbon chain material with greatly reduced biotoxicity and bioaccumulation, and accords with the clean and green design concept of chrome-free tanning. The material prepared by the invention is applied to the retanning field of chrome-free tanning, the fullness and mechanical property of finished leather retanning by adopting the material and the loading rate of anionic dye and fatting agent are improved, and meanwhile, the free formaldehyde content in aldehyde tanning can be reduced, so that the design concept of chrome-free tanning environmental friendliness is well shown.
Disclosure of Invention
The invention relates to a preparation method of a fluorine-containing retanning agent for chrome-free tanning based on hydrogen bonds, which comprises the steps of reacting diisocyanate with polyethylene glycol monomethyl ether, introducing short-chain fluoroalcohol to prepare two-block nonionic short fluorocarbon chain polyurethane, reacting (methyl) acrylic acid, acrylamide, vinyl acetate and maleic anhydride, adding alkali to adjust pH to obtain (methyl) acrylic resin, and finally mixing the two-block nonionic short fluorocarbon chain polyurethane and the (methyl) acrylic resin.
The hydrogen bond-based fluorine-containing retanning agent for chrome-free tanning provided by the invention is characterized in that:
1. the polyurethane introduced by the fluorine-containing retanning agent for chrome-free tanning contains nonionic blocks, can effectively shield carboxyl ions in (methyl) acrylic resin, improves the permeability of the polyurethane, improves the loading rate of widely used anionic dye and fatliquor in retanned leather, and widens the application range of the polyurethane.
2. The fluorine-containing retanning agent for chrome-free tanning controls the two-block non-ionic short fluorocarbon chain polyurethane and (methyl) acrylic resin to carry out hydrogen bond self-assembly by regulating the pH value during fixation, so that the two can be selectively filled in leather fibers, and the mechanical property of the chrome-free tanning after retanning can be obviously improved; meanwhile, due to the fact that short fluorocarbon chain polyurethane is introduced, the surface activity of a composite system is greatly improved, the permeability of (methyl) acrylic resin is greatly enhanced, the filling property of the (methyl) acrylic resin is improved, the finished leather is plump and compact, the addition amount of a retanning agent is reduced, and the problems of surface oversanning and the like are avoided.
3. The short fluorocarbon chain polyurethane contained in the fluorine-containing retanning agent for chrome-free tanning can more fully permeate into leather fibers, so that the retention amount in the leather fibers is increased, a large number of carbamate chain links capable of reacting with formaldehyde exist in the leather fibers, the content of free formaldehyde in the aldehyde tanning can be greatly reduced through the reaction of the carbamate chain links and aldehyde groups, the retanning effect is improved and enhanced, and the integral mechanical property of finished leather is further improved; meanwhile, the application of the short fluorocarbon chain material with greatly reduced biotoxicity and bioaccumulation is also in accordance with the clean and green design concept of chrome-free tanning.
The invention aims at realizing the following technical scheme:
the invention relates to a preparation method of a hydrogen bond-based fluorine-containing retanning agent for chrome-free tanning, which is characterized in that diisocyanate and polyethylene glycol monomethyl ether are reacted, short-chain fluoroalcohol is introduced to prepare two-block nonionic short fluorocarbon chain polyurethane, then (methyl) acrylic acid, acrylamide, vinyl acetate and maleic anhydride are reacted, alkali is added to adjust pH to obtain (methyl) acrylic resin, and finally the two-block nonionic short fluorocarbon chain polyurethane and the (methyl) acrylic resin are mixed to prepare the fluorine-containing retanning agent. Wherein the proportion of the two components in the total mass is as follows:
30-50% of two-block nonionic short fluorocarbon chain polyurethane
50-70% of (methyl) acrylic resin
Wherein the two-block nonionic short fluorocarbon chain polyurethane comprises the following components in percentage by mass:
2-5% of diisocyanate
Polyethylene glycol monomethyl ether 10-25
2.5 to 5.0 portions of short-chain fluoroalcohol
0.05 to 0.15 percent of catalyst
Distilled water 100-500
The two-block nonionic short fluorocarbon chain polyurethane is synthesized by the following specific method:
performing reduced pressure distillation on polyethylene glycol monomethyl ether at 100-120 ℃ and a vacuum degree of 0.09MPa for 6-9 h, and removing water;
adding the dried molecular sieve into short-chain fluoroalcohol, sealing overnight, and removing water;
drying the four-necked bottle, the stirrer and the feeding tube for 2-4 hours at 110-130 ℃, and placing the four-necked bottle, the stirrer and the feeding tube in a dryer for cooling;
adding diisocyanate, a catalyst and polyethylene glycol monomethyl ether into a four-necked bottle containing a thermometer, stirring and heating to 70-90 ℃, and reacting for 5-7 h;
cooling to 50-70 ℃, adding short-chain fluoroalcohol, and reacting for 6-12 h;
cooling to 40 ℃, adding distilled water, and stirring for 30min to obtain two-block nonionic short fluorocarbon chain polyurethane resin;
the (methyl) acrylic resin comprises the following components in parts by mass:
(meth) acrylic acid 50 to 68
15-30% of acrylamide
10-25 of vinyl acetate
Maleic anhydride 5-15
5-10% of alkali
Distilled water 100-550
0.05 to 0.15 of water-soluble initiator
The (meth) acrylic resin is synthesized by the following specific method:
adding alkali into distilled water to prepare 15% -35% alkali solution;
adding distilled water, (methyl) acrylic acid, acrylamide, vinyl acetate and maleic anhydride into the four-necked bottle, and stirring for 5-25 min;
adding a water-soluble initiator, and stirring for 5-25 min;
heating to 70-90 ℃ and reacting for 3-7 h;
cooling to 30 ℃, adding an alkali solution to adjust the pH of the system to 6.0-7.5, and obtaining (methyl) acrylic resin;
the fluorine-containing retanning agent for chrome-free tanning is synthesized by the following specific method:
adding (methyl) acrylic resin into the four-necked bottle, heating to 40-60 ℃, and stirring for 15-35 min;
dropwise adding two-block nonionic short fluorocarbon chain polyurethane within 30min, and then stirring for 1h at 40-60 ℃;
and cooling to room temperature to obtain the fluorine-containing retanning agent for chrome-free tanning.
Wherein the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and homologs thereof; polyethylene glycol monomethyl ether is one of 600, 800, 1000 and 1500 in number average molecular weight; the short-chain fluoroalcohol is one of fluoroalcohols with fluorocarbon chain length less than or equal to 4 carbon atoms; the catalyst is one of dibutyl tin dilaurate and bismuth isooctanoate; the alkali is one of sodium hydroxide, potassium carbonate and triethanolamine; the water-soluble initiator is one of potassium persulfate and ammonium persulfate.
The invention has the advantages that: the polyurethane introduced by the fluorine-containing retanning agent for chrome-free tanning contains nonionic blocks, can effectively shield carboxyl ions in (methyl) acrylic resin, improves the permeability of the polyurethane, improves the loading rate of widely used anionic dye and fatliquor in retanned leather, and widens the application range of the polyurethane. The pH is regulated during fixing to control the two-block non-ionic short fluorocarbon chain polyurethane and (methyl) acrylic resin to carry out hydrogen bond self-assembly, so that the two can be selectively filled in the leather fiber, and the mechanical property of the chrome-free tanning leather after retanning can be obviously improved; meanwhile, due to the short fluorocarbon chain polyurethane, the surface activity of the composite system is greatly improved, the permeability of the (methyl) acrylic resin is obviously enhanced, the filling property of the (methyl) acrylic resin is improved, the finished leather is plump and compact, the addition amount of the retanning agent is reduced, and the problems of surface oversanning and the like are avoided. The short fluorocarbon chain polyurethane can more fully penetrate into the leather fiber, so that the retention amount in the leather center is increased, a large number of carbamate chain links capable of reacting with formaldehyde exist in the leather fiber, the content of free formaldehyde in aldehyde tanning can be greatly reduced through the reaction of the carbamate chain links and aldehyde groups, the retanning effect is improved and enhanced, and the integral mechanical property of the finished leather is further improved; meanwhile, the short fluorocarbon chain material with greatly reduced biotoxicity and bioaccumulation is also a clean and green design concept conforming to chrome-free tanning. The material prepared by the invention is applied to the retanning field of chrome-free tanning, the fullness and mechanical property of finished leather retanning by adopting the material and the loading rate of anionic dye and fatting agent are improved, and meanwhile, the free formaldehyde content in aldehyde tanning can be reduced, so that the design concept of chrome-free tanning environmental friendliness is well shown.
The specific embodiment is as follows:
embodiment one:
1. synthesis of two-block nonionic short fluorocarbon chain polyurethane
Vacuum distilling polyethylene glycol monomethyl ether at 110 deg.C under 0.09MPa for 7 hr to remove water; adding the dried molecular sieve into 2, 3-pentafluoro-1-propanol, and standing overnight to remove water; drying the four-necked bottle, the stirrer and the feeding tube for 3 hours at 110 ℃, taking out, and then putting the dried materials into a dryer for cooling; sequentially adding 12.0g of polyethylene glycol monomethyl ether with the number average molecular weight of 600, 4.446g of isophorone diisocyanate and 0.05g of dibutyltin dilaurate into a four-necked flask containing a stirrer thermometer, and stirring and reacting for 6 hours at 80 ℃; cooling to 75 ℃, adding 3.0g of dried 2, 3-pentafluoro-1-propanol, and stirring for reaction for 8 hours; cooling to 40 ℃, adding 175g of distilled water under high-speed stirring, and obtaining the two-block nonionic short fluorocarbon chain polyurethane with the solid content of 10 wt%.
2. Synthesis of (meth) acrylic resin
To a four-necked flask containing a stirrer thermometer were added 207g of distilled water, 12.9g of (meth) acrylic acid, 4.26g of acrylamide, 3.924g of vinyl acetate and 1.96g of maleic anhydride, and stirred for 25 minutes; adding 0.05g of potassium persulfate, stirring for 15min, heating to 80 ℃ and reacting for 3h; cooling to 30deg.C, adding 10wt% potassium hydroxide aqueous solution to adjust pH to 6.5 to obtain (meth) acrylic resin with solid content of 10wt%.
3. Synthesis of fluorine-containing retanning agent for chrome-free tanning
60g of (methyl) acrylic resin with the solid content of 10wt% is added into a four-necked bottle, the mixture is stirred for 30min, the temperature is raised to 50 ℃, 60g of two-block non-ionic short fluorocarbon chain polyurethane with the solid content of 10wt% is added dropwise within 30min, the mixture is stirred for 1h, and the temperature is lowered to 30 ℃ to obtain the chromium-free tanning fluorine-containing retanning agent.
Embodiment two:
1. synthesis of two-block nonionic short fluorocarbon chain polyurethane
Vacuum distilling polyethylene glycol monomethyl ether at 110 deg.C under 0.09MPa for 7 hr to remove water; adding the dried molecular sieve into 2, 3-pentafluoro-1-propanol, and standing overnight to remove water; drying the four-necked bottle, the stirrer and the feeding tube for 3 hours at 110 ℃, taking out, and then putting the dried materials into a dryer for cooling; sequentially adding 16.0g of polyethylene glycol monomethyl ether with the number average molecular weight of 800, 4.446g of isophorone diisocyanate and 0.05g of dibutyltin dilaurate into a four-necked flask containing a stirrer thermometer, and stirring and reacting for 6 hours at 80 ℃; cooling to 75 ℃, adding 3.0g of dried 2, 3-pentafluoro-1-propanol, and stirring for reaction for 8 hours; cooling to 40 ℃, adding 211g of distilled water under high-speed stirring, and obtaining the two-block nonionic short fluorocarbon chain polyurethane with the solid content of 10 wt%.
2. Synthesis of (meth) acrylic resin
To a four-necked flask containing a stirrer thermometer were added 207g of distilled water, 12.9g of (meth) acrylic acid, 4.26g of acrylamide, 3.924g of vinyl acetate and 1.96g of maleic anhydride, and stirred for 25 minutes; adding 0.05g of potassium persulfate, stirring for 15min, heating to 80 ℃ and reacting for 3h; cooling to 30deg.C, adding 10wt% potassium hydroxide aqueous solution to adjust pH to 6.5 to obtain (meth) acrylic resin with solid content of 10wt%.
3. Synthesis of fluorine-containing retanning agent for chrome-free tanning
60g of (methyl) acrylic resin with the solid content of 10wt% is added into a four-necked bottle, the mixture is stirred for 30min, the temperature is raised to 50 ℃, 60g of two-block non-ionic short fluorocarbon chain polyurethane with the solid content of 10wt% is added dropwise within 30min, the mixture is stirred for 1h, and the temperature is lowered to 30 ℃ to obtain the chromium-free tanning fluorine-containing retanning agent.
Embodiment III:
1. synthesis of two-block nonionic short fluorocarbon chain polyurethane
Vacuum distilling polyethylene glycol monomethyl ether at 110 deg.C under 0.09MPa for 7 hr to remove water; adding the dried molecular sieve into hexafluoroisopropanol, standing overnight, and removing water; drying the four-necked bottle, the stirrer and the feeding tube for 3 hours at 110 ℃, taking out, and then putting the dried materials into a dryer for cooling; sequentially adding 12.0g of polyethylene glycol monomethyl ether with the number average molecular weight of 600, 4.446g of isophorone diisocyanate and 0.05g of dibutyltin dilaurate into a four-necked flask containing a stirrer thermometer, and stirring and reacting for 6 hours at 80 ℃; cooling to 75 ℃, adding 3.36g of dry hexafluoroisopropanol, and stirring for reaction for 8 hours; cooling to 40 ℃, adding 180g of distilled water under high-speed stirring to obtain the two-block nonionic short fluorocarbon chain polyurethane with the solid content of 10 wt%.
2. Synthesis of (meth) acrylic resin
To a four-necked flask containing a stirrer thermometer were added 207g of distilled water, 12.9g of (meth) acrylic acid, 4.26g of acrylamide, 3.924g of vinyl acetate and 1.96g of maleic anhydride, and stirred for 25 minutes; adding 0.05g of potassium persulfate, stirring for 15min, heating to 80 ℃ and reacting for 3h; cooling to 30deg.C, adding 10wt% potassium hydroxide aqueous solution to adjust pH to 6.5 to obtain (meth) acrylic resin with solid content of 10wt%.
3. Synthesis of fluorine-containing retanning agent for chrome-free tanning
60g of (methyl) acrylic resin with the solid content of 10wt% is added into a four-necked bottle, the mixture is stirred for 30min, the temperature is raised to 50 ℃, 60g of two-block non-ionic short fluorocarbon chain polyurethane with the solid content of 10wt% is added dropwise within 30min, the mixture is stirred for 1h, and the temperature is lowered to 30 ℃ to obtain the chromium-free tanning fluorine-containing retanning agent.
Embodiment four:
1. synthesis of two-block nonionic short fluorocarbon chain polyurethane
Vacuum distilling polyethylene glycol monomethyl ether at 110 deg.C under 0.09MPa for 7 hr to remove water; adding the dried molecular sieve into 2, 3-pentafluoro-1-propanol, and standing overnight to remove water; drying the four-necked bottle, the stirrer and the feeding tube for 3 hours at 110 ℃, taking out, and then putting the dried materials into a dryer for cooling; 12.0g of polyethylene glycol monomethyl ether with the number average molecular weight of 600, 3.483g of toluene diisocyanate and 0.05g of dibutyltin dilaurate are sequentially added into a four-necked flask containing a stirrer thermometer, and stirred and reacted for 6 hours at 80 ℃; cooling to 75 ℃, adding 3.0g of dried 2, 3-pentafluoro-1-propanol, and stirring for reaction for 8 hours; cooling to 40 ℃, adding 166g of distilled water under high-speed stirring, and obtaining the two-block nonionic short fluorocarbon chain polyurethane with the solid content of 10 wt%.
2. Synthesis of (meth) acrylic resin
To a four-necked flask containing a stirrer thermometer were added 207g of distilled water, 12.9g of (meth) acrylic acid, 4.26g of acrylamide, 3.924g of vinyl acetate and 1.96g of maleic anhydride, and stirred for 25 minutes; adding 0.05g of potassium persulfate, stirring for 15min, heating to 80 ℃ and reacting for 3h; cooling to 30deg.C, adding 10wt% potassium hydroxide aqueous solution to adjust pH to 6.5 to obtain (meth) acrylic resin with solid content of 10wt%.
3. Synthesis of fluorine-containing retanning agent for chrome-free tanning
60g of (methyl) acrylic resin with the solid content of 10wt% is added into a four-necked bottle, the mixture is stirred for 30min, the temperature is raised to 50 ℃, 60g of two-block non-ionic short fluorocarbon chain polyurethane with the solid content of 10wt% is added dropwise within 30min, the mixture is stirred for 1h, and the temperature is lowered to 30 ℃ to obtain the chromium-free tanning fluorine-containing retanning agent.
Claims (2)
1. The preparation method of the hydrogen bond-based chromium-free tanning fluorine-containing retanning agent is characterized in that the chromium-free tanning fluorine-containing retanning agent consists of two-block nonionic short fluorocarbon chain polyurethane and (methyl) acrylic resin, wherein the two components account for the following total mass ratio:
15-50% of two-block nonionic short fluorocarbon chain polyurethane
50 to 85 percent of (methyl) acrylic resin
Wherein the two-block nonionic short fluorocarbon chain polyurethane comprises the following components in percentage by mass:
the short-chain fluoroalcohol mentioned in the component ratio is one of fluoroalcohols with fluorocarbon chain length less than or equal to 4 carbon atoms;
the two-block nonionic short fluorocarbon chain polyurethane is synthesized by the following specific method:
vacuum distilling polyethylene glycol monomethyl ether at 100-120 deg.c and vacuum degree of 0.09MPa for 6-9 hr to eliminate water;
adding the dried molecular sieve into short-chain fluoroalcohol, sealing overnight, and removing water;
drying the four-necked bottle, the stirrer and the feeding tube for 2-4 hours at the temperature of 110-130 ℃, and placing the four-necked bottle, the stirrer and the feeding tube in a dryer for cooling;
adding diisocyanate, a catalyst and polyethylene glycol monomethyl ether into a four-necked bottle containing a thermometer, stirring and heating to 70-90 ℃, and reacting for 5-7 h;
cooling to 50-70 ℃, adding short-chain fluoroalcohol, and reacting for 6-12 h;
cooling to 40 ℃, adding distilled water, and stirring for 30min to obtain two-block nonionic short fluorocarbon chain polyurethane;
the (methyl) acrylic resin comprises the following components in parts by mass:
the (meth) acrylic resin is synthesized by the following specific method:
adding alkali into distilled water to prepare 15% -35% alkali solution;
distilled water, (methyl) acrylic acid, acrylamide, vinyl acetate and maleic anhydride are added into a four-necked bottle and stirred for 5 to 25 minutes;
adding a water-soluble initiator, and stirring for 5-25 min;
heating to 70-90 ℃ and reacting for 3-7 h;
cooling to 30 ℃, adding an alkali solution to adjust the pH of the system to 6.0-7.5, and obtaining (methyl) acrylic resin;
the fluorine-containing retanning agent for chrome-free tanning is synthesized by the following specific method:
adding (methyl) acrylic resin into the four-necked bottle, heating to 40-60 ℃, and stirring for 15-35 min;
dropwise adding two-block nonionic short fluorocarbon chain polyurethane within 30min, and then stirring for 1h at 40-60 ℃;
and cooling to room temperature to obtain the fluorine-containing retanning agent for chrome-free tanning.
2. The method for preparing the hydrogen bond-based fluorine-containing retanning agent for chrome-free tanned leather according to claim 1, which is characterized in that: the diisocyanate is one of isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and homologs thereof; polyethylene glycol monomethyl ether is one of 600, 800, 1000 and 1500 in number average molecular weight; the catalyst is one of dibutyl tin dilaurate and bismuth isooctanoate; the alkali is one of sodium hydroxide, potassium carbonate and triethanolamine; the water-soluble initiator is one of potassium persulfate and ammonium persulfate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104498649A (en) * | 2015-01-12 | 2015-04-08 | 四川大学 | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather |
| CN104531916A (en) * | 2015-01-12 | 2015-04-22 | 四川大学 | Method for preparing chrome-free tanning leather retanning agent based on hydrogen bond self-assembly |
| CN108586687A (en) * | 2018-03-26 | 2018-09-28 | 四川大学 | A kind of preparation method of the fluorine-containing short chain surfactants of two blocks nonionic polyurethane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104498649A (en) * | 2015-01-12 | 2015-04-08 | 四川大学 | Aldehydic high polymer retanning agent with self-assembly function for free-chrome leather |
| CN104531916A (en) * | 2015-01-12 | 2015-04-22 | 四川大学 | Method for preparing chrome-free tanning leather retanning agent based on hydrogen bond self-assembly |
| CN108586687A (en) * | 2018-03-26 | 2018-09-28 | 四川大学 | A kind of preparation method of the fluorine-containing short chain surfactants of two blocks nonionic polyurethane |
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