CN116102681B - Preparation method of amphoteric wet finishing material with retanning, fatliquoring and dyeing functions - Google Patents
Preparation method of amphoteric wet finishing material with retanning, fatliquoring and dyeing functions Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000004043 dyeing Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 19
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 14
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims abstract description 14
- XJHABGPPCLHLLV-UHFFFAOYSA-N benzo[de]isoquinoline-1,3-dione Chemical class C1=CC(C(=O)NC2=O)=C3C2=CC=CC3=C1 XJHABGPPCLHLLV-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000000243 solution Substances 0.000 claims description 31
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 22
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 10
- DTUOTSLAFJCQHN-UHFFFAOYSA-N 4-bromo-1,8-naphthalic anhydride Chemical compound O=C1OC(=O)C2=CC=CC3=C2C1=CC=C3Br DTUOTSLAFJCQHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 238000000502 dialysis Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004440 column chromatography Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 230000003213 activating effect Effects 0.000 claims description 2
- 239000010985 leather Substances 0.000 abstract description 34
- 238000011049 filling Methods 0.000 abstract description 7
- 238000007730 finishing process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 description 13
- 239000000178 monomer Substances 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 102000008186 Collagen Human genes 0.000 description 6
- 108010035532 Collagen Proteins 0.000 description 6
- 229920001436 collagen Polymers 0.000 description 6
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 4
- 239000012986 chain transfer agent Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- -1 F-90 Chemical compound 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
-
- 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
- C14C11/00—Surface finishing of leather
- C14C11/003—Surface finishing of leather using macromolecular compounds
-
- 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
- C14C15/00—Apparatus for chemical treatment or washing of hides, skins, or leather
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Coloring (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a preparation method of an amphoteric wet finishing material with retanning, fatliquoring and dyeing functions, which takes acrylic acid, dimethyl diallyl ammonium chloride and dodecyl acrylate as raw materials to prepare an amphoteric polymer pADD through free radical polymerization; the naphthalimide derivative is adopted to graft pADD side chain, so as to synthesize the amphoteric wet finishing material pADD-DMENA. The amphoteric wet finishing material pADD-DMENA prepared by the invention can endow leather with excellent softness, filling property and mechanical property. The material can effectively combine retanning, fatliquoring and dyeing processes in wet finishing processes into one, realizes retanning-fatliquoring-dyeing integrated operation, shortens processing time, improves production efficiency and reduces environmental pollution.
Description
Technical Field
The invention belongs to the technical field of leather chemical preparation, and particularly relates to a preparation method of an amphoteric wet finishing material with retanning, fatliquoring and dyeing functions.
Background
At present, the domestic and foreign leather processing still adopts a chrome tanning method, and chromium-containing wastewater, chromium-containing sludge and chromium-containing solid waste generated by the chrome tanning method possibly cause ecological environment pollution, and the factors gradually become technical bottlenecks for restricting sustainable development of the leather making industry. Based on this, ecological and environment-friendly organic chrome-free tanning agents become research hot spots, and organic phosphorus, F-90, TWS and other tanning agents have been developed primarily, and can basically replace chrome tanning agents. However, as the tanning agent molecules react with the amino groups of the leather collagen, the electropositivity of the leather collagen is weakened, so that the absorption and combination of the tanned leather to the anionic wet finishing material are obviously reduced, the physical and mechanical properties, softness and dyeing properties of the finished leather are directly influenced, the development requirements of the leather production process cannot be met, and further, the development of a high-performance amphoteric wet finishing material matched with the leather can be urgently required, so that the development of the clean manufacturing technology of the ecological chromium-free tanned leather is promoted.
The leather wet finishing process mainly comprises the working procedures of retanning, fatliquoring, dyeing and the like, the actual processing process is complex in operation, and the addition of different leather chemicals makes the leather-making wastewater component complex, so that the difficulty and cost of wastewater treatment are increased. Therefore, if an amphoteric polymer can be designed and has retanning, fatliquoring and dyeing functions, the complicated procedures of wet finishing of leather can be reduced, the expenditure cost of leather materials with different functions can be reduced, and the emission of pollutants in leather-making wastewater can be reduced.
Disclosure of Invention
The invention aims to provide a preparation method of an amphoteric wet finishing material with retanning, fatliquoring and dyeing functions, which solves the problem of poor binding force between the traditional anionic wet finishing material and crust leather.
The technical scheme adopted by the invention is that the preparation method of the amphoteric wet finishing material with retanning, fatliquoring and dyeing functions is implemented according to the following steps:
step 1: mixing acrylic acid, dimethyl diallyl ammonium chloride and dodecyl acrylate with absolute ethyl alcohol to dissolve the acrylic acid, adding n-dodecyl mercaptan, stirring, heating the solution, dripping azo-diisobutyronitrile serving as an initiator, carrying out heat preservation reaction, cooling to room temperature, dialyzing the copolymer in the absolute ethyl alcohol, and carrying out rotary evaporation and drying to remove solvent ethanol to obtain an amphoteric polymer pADD;
step 2: preparing a naphthalimide derivative DMENA;
step 3: dissolving pADD in absolute ethyl alcohol to form pADD solution; and dissolving the DMENA, the N-hydroxysuccinimide and the 1-ethyl- (3-dimethylaminopropyl) -carbodiimide in absolute ethyl alcohol, reacting and activating to obtain a DMENA mixed solution, slowly dripping the DMENA mixed solution into the pADD solution, carrying out reflux reaction, cooling to room temperature after the reaction is finished, evaporating the solvent, and purifying the product by using column chromatography to obtain the amphoteric wet finishing material.
The present invention is also characterized in that,
in the step 1, the temperature is raised to 60-75 ℃, the reaction time is kept for 5-7 h, and the dialysis time is 24-36 h.
In the step 1, the molar ratio of the acrylic acid to the dimethyl diallyl ammonium chloride to the dodecyl acrylate is 1:2.0 to 5.0:1.
in step 2, specifically:
step 2.1: dissolving 4-bromo-1, 8-naphthalene dicarboxylic anhydride in a mixed solution of dimethylamine aqueous solution and DMF, and adding CuSO 4 ·5H 2 O, carrying out reflux stirring reaction, cooling to room temperature, washing a product with deionized water, filtering a precipitate, and drying the precipitate in a vacuum drying oven to obtain DMNA;
step 2.2: dispersing DMNA in 1, 4-dioxane to form a mixed solution, mixing ethylenediamine and 1, 4-dioxane, heating until reflux liquid is generated, dropwise adding the mixed solution into the reflux liquid, carrying out heat preservation reaction for 1-3 h, and evaporating a solvent after the reaction is finished to obtain a yellow powdery product, namely naphthalimide Derivative (DMENA);
in the step 2.1, the reaction temperature is 90-110 ℃ and the reaction time is 2-4 h.
In step 2.1, 4-bromo-1, 8-naphthalenedicarboxylic anhydride, dimethylamine aqueous solution and CuSO 4 ·5H 2 The molar ratio of O is 0.5-1:2.5-5:0.025-0.05.
In the step 3, the molar ratio of pADD to DMENA is 2-4: 0.5 to 1.
In the step 3, the activation time is 30min; the reflux reaction temperature is 60-75 ℃, and the reflux reaction time is 12-24 h.
The beneficial effects of the invention are as follows:
acrylic acid, dimethyl diallyl ammonium chloride and dodecyl acrylate are used as basic raw materials, an amphoteric polymer pADD is prepared through free radical polymerization, wherein carboxyl groups in the acrylic acid and quaternary ammonium ions in the dimethyl diallyl ammonium chloride respectively provide anionic groups and cationic groups for the polymer, so that pADD has zwitterionic properties, permeation and combination of the pADD in leather fibers can be promoted by adjusting charge proportions in practical application, and in addition, long carbon chains in the dodecyl acrylate can play a role in softening and filling in leather collagen, and excellent retanning and fatting effects can be given to leather. The naphthalimide derivative is grafted in the polymer pADD, so that the amphoteric wet finishing material has a retanning and fatliquoring effect, and meanwhile, a dyeing function is added, and the wet finishing process is further simplified.
Drawings
FIG. 1 is a diagram showing the synthesis of an amphoteric wet finishing material pADD-DMENA according to the present invention;
FIG. 2 is a graph showing the particle size distribution of the amphoteric polymer pADD prepared in the example;
fig. 3 is a graph of softness versus thickening ratio data for leather samples prepared using the amphoteric wet finishing material of example 1.
Fig. 4 is an optical photograph of the bath solution under natural light and ultraviolet lamp before and after the leather sample prepared using the amphoteric wet finishing material of example 1.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description,
the invention relates to a preparation method of an amphoteric wet finishing material (pADD-DMENA) with retanning, fatliquoring and dyeing functions, which is shown in figure 1 and is specifically implemented according to the following steps:
step 1: synthesis of ampholytic polymers (pADD);
the method comprises the following steps: mixing acrylic acid, dimethyl diallyl ammonium chloride and dodecyl acrylate with absolute ethyl alcohol to dissolve the acrylic acid, adding a chain transfer agent n-dodecyl mercaptan, continuously stirring the mixture fully, heating the solution to 60-75 ℃, dropwise adding an initiator azo diisobutyronitrile AIBN, carrying out heat preservation stirring reaction for 5-7 h to obtain a pale yellow copolymer, cooling the pale yellow copolymer to room temperature, dialyzing the copolymer in the absolute ethyl alcohol for 24-36 h (dialysis bag MD-44, molecular weight cutoff is 500), removing unreacted monomers, and removing solvent ethanol after dialysis, and obtaining an amphoteric polymer (pADD) by rotary evaporation and drying;
the molar ratio of acrylic acid to dimethyl diallyl ammonium chloride to dodecyl acrylate is 1:2.0 to 5.0:1, a step of;
step 2: the synthesis of the DMENA comprises the following steps:
step 2.1: dissolving 4-bromo-1, 8-naphthalene dicarboxylic anhydride in a mixed solution of dimethylamine aqueous solution and DMF, and adding CuSO to the mixed solution 4 ·5H 2 O, carrying out reflux stirring reaction, cooling to a room after the reaction is completed, washing a product with deionized water, filtering a precipitate, and drying the precipitate in a vacuum drying oven to obtain DMNA;
the reaction temperature is 90-110 ℃ and the reaction time is 2-4 h;
4-bromo-1, 8-naphthalenedicarboxylic anhydride, dimethylamine aqueous solution and CuSO 4 ·5H 2 The molar ratio of O is 0.5-1:2.5-5:0.025-0.05;
step 2.2: dispersing DMNA in 1, 4-dioxane to form a mixed solution, mixing ethylenediamine and 1, 4-dioxane, heating until reflux liquid is generated, dropwise adding the mixed solution into the reflux liquid, carrying out heat preservation reaction for 1-3 h, and evaporating a solvent after the reaction is finished to obtain a yellow powdery product, namely naphthalimide Derivative (DMENA);
step 3: synthesis of amphoteric wet finishing Material (pADD-DMENA);
dissolving pADD in absolute ethyl alcohol to form pADD solution; then, dissolving the DMENA, N-hydroxysuccinimide (NHS) and 1-ethyl- (3-dimethylaminopropyl) -carbodiimide (EDC) in absolute ethyl alcohol, carrying out reaction and activation for 30min to obtain a DMENA mixed solution, then slowly dripping the DMENA mixed solution into pADD solution, carrying out reflux reaction for 12-24 h at 60-75 ℃, cooling the reaction solution to room temperature after the reaction is finished, evaporating the solvent, and purifying the product by using column chromatography to obtain the amphoteric wet finishing material (pADD-DMENA).
The molar ratio of pADD to DMENA is 2-4: 0.5 to 1;
the amphoteric wet finishing material based on the acrylic acid polymer system synthesizes an amphoteric polymer pADD by taking Acrylic Acid (AA), dimethyl diallyl ammonium chloride (DMDAAC) and Dodecyl Acrylate (DA) as raw materials, and the amphoteric polymer can endow TWS tannage with excellent retanning and fatliquoring performances. In order to further simplify the process, the amphoteric wet finishing material has a dyeing effect, and is finally synthesized into the amphoteric wet finishing material (pADD-NADE) by adopting naphthalimide Derivatives (DMENA) to modify pADD, and the material can effectively ' three retanning, fatliquoring and dyeing processes ' into one ' in the wet finishing process, so that retanning-fatliquoring-dyeing integrated operation is realized, the processing time is shortened, the production efficiency is improved, and the environmental pollution is reduced. In addition, the leather is endowed with bright color while the softness, physical and mechanical properties and filling property of the leather are ensured, and the application value of the leather is increased.
Example 1
The invention discloses a preparation method of an amphoteric wet finishing material with retanning, fatliquoring and dyeing functions, which is implemented according to the following steps:
step 1: synthesis of the amphoteric Polymer pADD
2.16g of acrylic acid, 9.7g of dimethyldiallylammonium chloride, 7.2g of dodecyl acrylate monomer were dissolved in an absolute ethanol solution, and then transferred to a three-necked flask to be mixed, and the mixed solution was stirred at a speed of 220 r/min. After the solution is stirred uniformly, adding 0.22g of chain transfer agent n-dodecyl mercaptan, continuously stirring fully, filling an initiator AIBN ethanol solution with the mass concentration of 1wt% relative to the total monomer into a constant pressure dropping funnel, after the temperature is raised to 70 ℃, dropwise adding the initiator into the constant pressure dropping funnel, keeping the total monomer accounting for 30% of the absolute ethanol, reacting for 6 hours to obtain a bright yellow copolymer with certain viscosity, cooling to room temperature, dialyzing the copolymer in the absolute ethanol for 24 hours, removing unreacted monomers, ending the dialysis, steaming and drying to remove solvent ethanol, and obtaining the amphoteric polymer pADD.
Step 2: synthesis of DMENA
Step 2.1: 5.0g of 4-bromo-1, 8-naphthalenedicarboxylic anhydride was dissolved in a mixed solution of 12mL of dimethylamine aqueous solution and 30mL of DMF, and 0.22g of CuSO was added to the mixed solution 4 ·5H 2 And O, transferring the mixture into a 250mL three-neck flask with a condensing and stirring device, heating to 110 ℃, preserving heat and reacting for 3 hours, washing a product with deionized water after the reactant is cooled to room temperature, filtering and precipitating, and drying the precipitate in a vacuum drying oven after washing for three times, thereby obtaining the DMNA after the precipitate is completely dried.
Step 2.2: adding 1.5mL of ethylenediamine and 30mL of 1, 4-dioxane into a 250mL three-neck flask, heating until the mixed solution has reflux phenomenon, dispersing the product DMNA (1.0 g) synthesized in the step 2.1 into 10mL of 1, 4-dioxane, dropwise adding into the reflux solution, carrying out heat preservation reaction for 1h, evaporating the solvent, purifying the product by using a gradient silica gel column, and obtaining a yellow powdery product, namely the DMENA.
Step 3: synthesis of amphoteric wet finishing Material pADD-DMENA
16g pADD was added to 50mL absolute ethanol and stirred until completely dissolved. After 0.5g of DMENA, 0.23g of NHS and 0.38g of EDC were dissolved in absolute ethanol and activated for 30min, the DMENA solution was slowly added dropwise to pADD solution, the temperature of the reaction solution was raised to 60℃and the reaction was refluxed for 24h. After the completion of the reaction, the reaction mixture was cooled to room temperature, and after evaporating the solvent, the product was purified by column chromatography to obtain an amphoteric wet finishing material (pADD-DMENA).
The synthesized amphoteric wet finishing material is applied to an organic chrome-free tanning leather wet finishing procedure, and a specific operation flow of pADD-DMENA applied to chrome-free tanning is shown in table 1;
table 1 organic chrome-free tanning wet finishing process
FIG. 2 is a graph showing the particle size distribution of pADD prepared in example 1, wherein the pADD particle size is concentrated and distributed between 100 nm and 2000nm, and the pADD particle size is normally distributed, which shows that the amphoteric polymer pADD particle size under the system is completely applicable to leather retanning and fatting, wherein emulsion particles with larger size easily enter loose parts of leather to realize combination with collagen, and the micro emulsion particles penetrate into compact parts of gaps of collagen fibers to lubricate and fill collagen fibers.
The figure 3 shows the thickening rate, softness and physical and mechanical property data of the leather, and from the figure, it can be seen that the softness and thickening rate of the leather after pADD and pADD-DMENA treatment are obviously improved compared with that of a blank, so that pADD can play a role in retanning and filling TWS tanned leather.
FIG. 4 is an optical photograph of pADD-DMENA treated leather and bath liquid, and it can be seen from the figure that the leather sample is bright yellow, and the pADD-DMENA structure contains fluorescent group naphthalimide derivatives, so that the leather sample can be different colors under natural light and ultraviolet lamp, and the aesthetic value of the leather is increased.
Example 2
The invention discloses a preparation method of an amphoteric wet finishing material with retanning, fatliquoring and dyeing functions, which is implemented according to the following steps:
step 1: synthesis of the amphoteric Polymer pADD
Three monomers of 2.16g of acrylic acid, 14.55g of dimethyldiallylammonium chloride and 7.2g of dodecyl acrylate were dissolved in an absolute ethanol solution, transferred to a three-necked flask, and mixed, and the mixed solution was stirred at a speed of 220 r/min. After the solution was stirred well, 0.47g of the chain transfer agent n-dodecyl mercaptan was added and stirring continued well. And (3) filling an initiator AIBN ethanol solution with the mass concentration of 1wt% relative to the total monomers into the constant-pressure dropping funnel, dropwise adding the initiator into the constant-pressure dropping funnel after the temperature is raised to 70 ℃, wherein the total monomers account for 30% of absolute ethanol. And (3) maintaining the temperature and stirring for reaction for 6 hours to obtain the bright yellow copolymer with certain viscosity. After cooling to room temperature, the copolymer was dialyzed in absolute ethanol for 24 hours, unreacted monomers were removed, and solvent ethanol was removed by spin drying after the dialysis was completed, to obtain amphoteric polymer pADD.
Step 2: synthesis of DMENA
Step 2.1: 5.0g of 4-bromo-1, 8-naphthalenedicarboxylic anhydride was dissolved in a mixed solution of 12mL of dimethylamine aqueous solution and 30mL of DMF, and 0.22g of CuSO was added to the mixed solution 4 ·5H 2 O, transferring the mixture into a 250mL three-neck flask with a condensing and stirring device, heating to 110 ℃, and preserving heat for 3h. After the reaction is completed, after the reactants are cooled to room temperature, the products are washed by deionized water, the precipitates are filtered, and after the precipitates are washed for three times, the precipitates are placed in a vacuum drying oven to be dried, and the DMNA is obtained after the precipitates are completely dried.
Step 2.2: 1.5mL of ethylenediamine and 30mL of 1, 4-dioxane are added into a 250mL three-neck flask, the temperature is raised until the mixed solution has reflux phenomenon, then the product DMNA (1.0 g) synthesized in the step 2.1 is dispersed into 10mL of 1, 4-dioxane, and is added into the reflux solution dropwise, and after the complete addition, the reaction is carried out for 1h at a temperature. After the reaction was completed, the solvent was evaporated and the product was purified using a gradient silica gel column to give a yellow powdery product, i.e., DMENA.
Step 3: synthesis of amphoteric wet finishing Material pADD-DMENA
24g pADD was added to 70mL absolute ethanol and stirred until completely dissolved. 0.8gDMENA,0.34g NHS and 0.57g EDC were dissolved in absolute ethanol, and after 30min of reaction activation, the DMENA solution was slowly added dropwise to the pADD solution, the temperature of the reaction solution was raised to 60℃and the reaction was refluxed for 24h. After the completion of the reaction, the reaction mixture was cooled to room temperature, and after evaporating the solvent, the product was purified by column chromatography to obtain an amphoteric wet finishing material (pADD-DMENA).
Example 3
The invention discloses a preparation method of an amphoteric wet finishing material with retanning, fatliquoring and dyeing functions, which is implemented according to the following steps:
step 1: synthesis of the amphoteric Polymer pADD
Three monomers of 2.16g of acrylic acid, 24.25g of dimethyldiallylammonium chloride and 7.2g of dodecyl acrylate were dissolved in an absolute ethanol solution, transferred to a three-necked flask, and mixed, and the mixed solution was stirred at a speed of 220 r/min. After the solution was stirred well, 0.4g of the chain transfer agent n-dodecyl mercaptan was added and stirring continued well. And (3) filling an initiator AIBN ethanol solution with the mass concentration of 1wt% relative to the total monomers into a constant pressure dropping funnel, dropwise adding the initiator into the constant pressure dropping funnel when the temperature is raised to 70 ℃, wherein the percentage of the total monomers in the absolute ethanol is 30%. And (3) maintaining the temperature and stirring for reaction for 6 hours to obtain the bright yellow copolymer with certain viscosity. After cooling to room temperature, the copolymer was dialyzed in absolute ethanol for 24 hours (dialysis bag MD-44, molecular weight cut-off 500), unreacted monomers were removed, and solvent ethanol was removed by spin drying after dialysis was completed to obtain amphoteric polymer pADD.
Step 2: synthesis of DMENA
Step 2.1: 5.0g of 4-bromo-1, 8-naphthalenedicarboxylic anhydride was dissolved in a mixed solution of 12mL of dimethylamine aqueous solution and 30mL of DMF, and 0.22g of CuSO was added to the mixed solution 4 ·5H 2 O, transferring the mixture into a 250mL three-neck flask with a condensing and stirring device, heating to 110 ℃, and preserving heat for 3h. After the reaction is completed, after the reactants are cooled to room temperature, the products are washed by deionized water, the precipitates are filtered, and after the precipitates are washed for three times, the precipitates are placed in a vacuum drying oven to be dried, and the DMNA is obtained after the precipitates are completely dried.
Step 2.2, adding 1.5mL of ethylenediamine and 30mL of 1, 4-dioxane into a 250mL three-neck flask, heating until the mixed solution has a reflux phenomenon, dispersing the product DMNA (1.0 g) synthesized in the step 2.1 into 10mL of 1, 4-dioxane, dropwise adding into the reflux liquid, and carrying out heat preservation reaction for 1h after complete addition. After the reaction was completed, the solvent was evaporated and the product was purified using a gradient silica gel column to give a yellow powdery product, i.e., DMENA.
Step 3: synthesis of amphoteric wet finishing Material pADD-DMENA
40g pADD was added to 120mL absolute ethanol and stirred until completely dissolved. At the same time, 1.4g DMENA,0.57g NHS and 0.95g EDC were dissolved in absolute ethanol, and after 30min of reaction activation, the DMENA solution was slowly added dropwise to the pADD solution, the temperature of the reaction solution was raised to 60℃and the reaction was refluxed for 24 hours. After the completion of the reaction, the reaction mixture was cooled to room temperature, and after evaporating the solvent, the product was purified by column chromatography to obtain an amphoteric wet finishing material (pADD-DMENA).
Claims (7)
1. The preparation method of the amphoteric wet finishing material with retanning, fatliquoring and dyeing functions is characterized by comprising the following steps:
step 1: mixing acrylic acid, dimethyl diallyl ammonium chloride and dodecyl acrylate with absolute ethyl alcohol to dissolve the acrylic acid, adding n-dodecyl mercaptan, stirring, heating the solution, dripping azo-diisobutyronitrile serving as an initiator, carrying out heat preservation reaction, cooling to room temperature, dialyzing the copolymer in the absolute ethyl alcohol, and carrying out rotary evaporation and drying to remove solvent ethanol to obtain an amphoteric polymer pADD;
step 2: preparing a naphthalimide derivative DMENA; the method comprises the following steps:
step 2.1: dissolving 4-bromo-1, 8-naphthalene dicarboxylic anhydride in a mixed solution of dimethylamine aqueous solution and DMF, and adding CuSO 4 ·5H 2 O, carrying out reflux stirring reaction, cooling to room temperature, washing a product with deionized water, filtering a precipitate, and drying the precipitate in a vacuum drying oven to obtain DMNA;
step 2.2: dispersing DMNA in 1, 4-dioxane to form a mixed solution, mixing ethylenediamine and 1, 4-dioxane, heating until reflux liquid is generated, dropwise adding the mixed solution into the reflux liquid, carrying out heat preservation reaction for 1-3 h, and evaporating a solvent after the reaction is finished to obtain a yellow powdery product, namely the naphthalimide derivative DMENA;
step 3: dissolving pADD in absolute ethyl alcohol to form pADD solution; and dissolving the DMENA, the N-hydroxysuccinimide and the 1-ethyl- (3-dimethylaminopropyl) -carbodiimide in absolute ethyl alcohol, reacting and activating to obtain a DMENA mixed solution, slowly dripping the DMENA mixed solution into the pADD solution, carrying out reflux reaction, cooling to room temperature after the reaction is finished, evaporating the solvent, and purifying the product by using column chromatography to obtain the amphoteric wet finishing material.
2. The method for preparing amphoteric wet finishing material with retanning, fatliquoring and dyeing functions according to claim 1, wherein in the step 1, the temperature is raised to 60-75 ℃, the heat preservation reaction time is 5-7 h, and the dialysis time is 24-36 h.
3. The method for preparing amphoteric wet finishing material with retanning, fatliquoring and dyeing functions according to claim 1, wherein in the step 1, the molar ratio of acrylic acid, dimethyl diallyl ammonium chloride and dodecyl acrylate is 1:2.0 to 5.0:1.
4. the method for preparing amphoteric wet finishing material with retanning, fatliquoring and dyeing functions according to claim 1, wherein in the step 2.1, the reaction temperature is 90-110 ℃ and the reaction time is 2-4 h.
5. The method for preparing amphoteric wet finishing material with retanning, fatliquoring and dyeing functions according to claim 1, wherein in the step 2.1, 4-bromo-1, 8-naphthalene dicarboxylic anhydride, dimethylamine aqueous solution and CuSO 4 ·5H 2 The molar ratio of O is 0.5-1:2.5-5:0.025-0.05.
6. The method for preparing amphoteric wet finishing material with retanning, fatliquoring and dyeing functions according to claim 1, wherein in the step 3, the molar ratio of pADD to DMENA is 2-4: 0.5 to 1.
7. The method for preparing amphoteric wet finishing material with retanning, fatliquoring and dyeing functions according to claim 1, wherein in the step 3, the activation time is 30min; the reflux reaction temperature is 60-75 ℃, and the reflux reaction time is 12-24 h.
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