CN104419305A - Synthetic leather coating having strong adsorption capacity and preparation method thereof - Google Patents

Synthetic leather coating having strong adsorption capacity and preparation method thereof Download PDF

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Publication number
CN104419305A
CN104419305A CN201310379768.XA CN201310379768A CN104419305A CN 104419305 A CN104419305 A CN 104419305A CN 201310379768 A CN201310379768 A CN 201310379768A CN 104419305 A CN104419305 A CN 104419305A
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synthetic leather
ionic liquid
parts
hydrotalcite
preparation
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宋波
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Qingdao Lannonggu Agricultural Products Research and Development Co Ltd
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Qingdao Lannonggu Agricultural Products Research and Development Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a synthetic leather coating having strong adsorption capacity and a preparation method thereof. The synthetic leather coating is characterized by being prepared from the following raw materials in parts by weight: 15-30 parts of above 98% polyurethane resin, 5-10 parts of diisocyanate, 10-20 parts of a carboxyl functionalized ionic liquid/hydrotalcite-like compound composite material, 15-30 parts of carbon powder, 5-10 parts of methyl isobutyl ketone, 10-20 parts of polytetrahydrofuran diol and 10-15 parts of nanometer titanium dioxide. The carboxyl functionalized ionic liquid is loaded on the surface of the hydrotalcite-like compound by virtue of a co-precipitation method so as to form the carboxyl functionalized ionic liquid/hydrotalcite-like compound composite material, the composite material is combined with raw materials such as carbon powder, the adsorption effect is given full play so that the synthetic leather is clean and environmentally friendly and the damage to the human health can be avoided. Stains on the surface of the synthetic leather obtained in the invention are easy to clean and the surface of the synthetic leather has no residue of the stains and has the characteristics of high abrasion resistance and good weather resistance.

Description

Synthetic leather coating that a kind of adsorptive power is strong and preparation method thereof
Technical field
The present invention relates to synthetic leather paint field, particularly relate to strong synthetic leather coating of a kind of adsorptive power and preparation method thereof.
Background technology
Synthetic leather is the Nomenclature Composition and Structure of Complexes of simulation natural leather and can be used as the plastics of its substitute material.Usually with through dipping non-woven fabrics for reticular layer, microporous polyurethane layer as grain layer obtain.Its positive and negative are all quite similar with leather, and have certain ventilation property, than the general population fabricate-leather closer to natural leather.Be widely used in and make footwear, boots, case and bag and ball etc.
In existing synthetic leather manufactures, polyurethane resin, wood powder or other packing material is added through dilution, process infiltration levelling, froth breaking, the technological process of solidifying, according to the performance of polyurethane resin, point wet method and dry method two kinds of methods can be adopted to produce leather, obtain good effect, also achieve abundant return and benefit.But existing synthetic leather manufacture needs in producing to use a large amount of chemical substances, therefore creates very large hazardness to environmental protection and HUMAN HEALTH.Along with progress and the growth in the living standard of society, material requirement is also along with raising, and healthy and environmental protection proposes new requirement to synthetic leather product.
Charcoal is a kind of porous material, has large specific surface area, has very strong adsorption-decomposition function, damping, purification, deodorizing, far infrared rays and negative ion usefulness.Charcoal is used as health care now, decoration, the fields such as packaging, because adjustment is put in the suction of charcoal to moisture, suppress temperature rise and mould, microorganism procreation, play mildew-resistant, adjustment temperature effect, the negative ion interaction energy of charcoal comfortable pleasant, make people's ataraxia, charcoal is again a kind of fabulous electrical conductor simultaneously, can block electromagnetic radiation, be conducive to health.How the above-mentioned functions of charcoal and synthetic leather are combined, make the essential function of charcoal obtain abundant rhythm and play, significant.
Houghite (writing a Chinese character in simplified form LDH) is a class two-dimensional nanometer anionic clay, and its composition general formula can be expressed as [M 1-x 2+m x 3+(OH) 2] x+(A n-) x/nmH 2o, wherein M 2+refer to divalent metal, M 3+refer to trivalent metal cation, x is M 2+with M 3+mol ratio, A n- for the negatively charged ion that interlayer Absorbable organic halogens exists; there is hydrotalcite layered structure; because its lamella is elementary composition and electric density is adjustable, interlayer guest molecule, crystalline size are controlled; and the advantage such as bio-toxicity is low, present good application prospect at numerous areas such as organic catalysis, polymeric additive, biological medicine, environment protection.Be worth it is emphasized that because of laminate upper part M 2+by M 3+replace and the superfluous positive charge of generation, can attract interlayer anion object to balance, the mode also by ion-exchange inserts other anionic guest molecules.Therefore, houghite is having geneogenous advantage in anionic species Adsorption.But in actual use, houghite itself is easily reunited, its absorption property is declined, especially for some non-ionic type guest species, be difficult to enter between houghite laminate, it can only be adsorbed by intermolecular hydrogen bonding by limited functional group, and non-ionic type guest molecule and layer ineface consistency poor, thus greatly limit its practical application in pollutant removal.
Ionic liquid (Ionic Liquid, IL) salt that is liquid, that be made up of zwitterion is completely presented under referring to room temperature or low temperature, also referred to as low temperature molten salt, have special solvability, almost without vapour pressure, have the features such as higher thermostability and chemical stability, be a class environmentally friendly " green " solvent of current widespread use.Functionalized ion liquid (Functionalized Ionic Liquid, FIL) refer to by negatively charged ion or (with) cationic moiety introduces structural functionality group, and the class formed has the ionic liquid of specific physics, chemical property.When adopting functionalized ion liquid to modify inorganic materials, functionalization group by hydrogen bond formation load in inorganic materials, will have stronger bonding force, and functionalized ion liquid is not easy to run off.But yet there are no the hydrotalcite-like composite material of load Carboxyl-functional Ionic Liquid and stain the report in thing Adsorption at phenols.Here employing coprecipitation method is prepared Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material by us, and tentatively examines or check it to the absorption property of phenolic comp ' ds pollution.
Most synthetic leather surface is difficult to normal household cleaners clean clean after being stained with spot in the market, for energy clean surface spot, people can clean repeatedly with strong stain remover, while result causes spot to be eliminated, synthetic leather surface is also destroyed, light then haze changes, heavy then synthetic leather surface layer damaged, and causing needs to change synthetic leather.
Most synthetic leather all contains objectionable impurities and gas in the market, be unfavorable for the health of environmental protection and workman, how carbon dust and Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material are well added in synthetic leather, give full play to adsorption, synthetic leather is made to avoid HUMAN HEALTH impaired, make synthetic leather possess antifouling, scratch resistance, weather-proof feature, be the technical problem to be solved in the present invention simultaneously.
Summary of the invention
For the demand of the deficiencies in the prior art and this area investigation and application, the object of this invention is to provide strong synthetic leather coating of a kind of adsorptive power and preparation method thereof, it is characterized in that, be prepared from by weight by following raw material: urethane resin 15-30 part of content more than 98%; Vulcabond 5-10 part; Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material 10-20 part; Powdered carbon 15-30 part; Mibk 5-10 part; Polytetrahydrofuran diol 10-20 part; Nano titanium oxide 10-15 part.
Synthetic leather coating that above-mentioned a kind of adsorptive power is strong and preparation method thereof, it is characterized in that, described preparation method is: raw material stirring is even, selects 110-120 object treatment wheel, adopts the method for intaglio printing synthetic leather treatment agent to be overlayed on synthetic leather surface 15-18g/m 2.Then through baking oven, control temperature 125-135 DEG C, dries 3-4min.
Synthetic leather coating that above-mentioned a kind of adsorptive power is strong and preparation method thereof, is characterized in that, the making method of described Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material comprises following concrete steps:
A () prepares 1-methyl-3-propyloic imidazoles Bromide
Under condition of ice bath, get a certain amount of N-Methylimidazole in round-bottomed flask, equimolar bromoacetic acid is constantly stirred down and is slowly added drop-wise to the isopyknic dehydrated alcohol of N-Methylimidazole, reaction solution stirs 3-4h under returning to normal temperature, after filtration, wash product 3-5 time with dehydrated alcohol, obtain intermediate 1-methyl-3-propyloic imidazoles Bromide;
B () prepares 1-methyl-3-propyloic tetrafluoroborate
Sodium tetrafluoroborate is taken by equimolar ratio, slowly join in the ethanol solution of above-mentioned gained IL intermediate under continuous stirring, stir 48 hours under normal temperature, reaction terminates rear mistake and filters inorganic salt, filtrate adopts rotary distillation process, remains ethanol, again filter in removing filtrate, the NaBr generated during removing exchanges, obtains brown viscous liquid;
C () prepares Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material
By divalent metal salt Mg (NO 3) 2with trivalent metal salt Al (NO 3) 3mixing salt solution is made into by certain mol proportion, total concentration of metal ions is 0.6 mol/L, again the ionic liquid 1-methyl-3-propyloic tetrafluoroborate that step b is obtained is added in mixing salt solution by certain mol proportion, by above-mentioned mixing solutions and basic solution titration simultaneously, control pH is between 7-8, vigorous stirring, aging 15-18h at 40-50 DEG C; Gained slurries distilled water wash 3-5 time, suction filtration, dry 24 h at filter cake 60 DEG C, obtain Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material of the present invention.
The Mg of divalent metal salt described in above-mentioned steps c (NO 3) 2with trivalent metal salt Al (NO 3) 3mol ratio be 3:2.
The Mg of divalent metal salt described in above-mentioned steps c (NO 3) 22:0.3,2:0.5,2:0.8,2:1.0 is respectively with the mol ratio that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate;
The Mg of divalent metal salt described in above-mentioned steps c (NO 3) 22:0.8 is preferably with the mol ratio that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate.
Basic solution described in above-mentioned steps c is ammoniacal liquor or sodium hydroxide solution or its mixture.
Synthetic leather coating that above-mentioned a kind of adsorptive power is strong and preparation method thereof, is characterized in that, Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material in described step c, and its median size is 110-140 nm, and the polydispersity index of particle diameter is 0.122-0.220.
The instrument that data determination of the present invention adopts is:
Rigaku D/max-rA type X-ray diffractometer and Vertex70 type Fourier infrared spectrograph (German Bruker company) carry out qualitative analysis to sample;
Adopt JEM-2000EX type transmission electron microscope (TEM) pattern to sample to rise to characterize;
Zetasizer Nano-ZS90 type nanometer dynamics analyser is adopted to analyze the particle diameter of sample and dispersiveness.
Beneficial effect of the present invention:
Adopt coprecipitation method that Carboxyl-functional Ionic Liquid is carried on houghite surface, Carboxyl-functional Ionic Liquid and houghite define Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material by chemical bonds, its interpolation creates the unexpected technique effect of 1+1 > 2 to the adsorption effect of phenolic comp ' ds pollution in synthetic leather and clearance thereof, no matter product of the present invention is to compared with the eliminating rate of absorption of phenolic comp ' ds pollution in synthetic leather with houghite or functionalized ion liquid to the eliminating rate of absorption of phenolic comp ' ds pollution in synthetic leather, all there is the difference of significance.Add raw material to be combined with carbon dust, give full play to adsorption, the synthetic leather clean environment firendly making to obtain, HUMAN HEALTH can be avoided impaired.Its surface blot of the synthetic leather that the present invention obtains is easy to cleaning, noresidue.Even stain, also can remove clean with conventional family expenses treatment agent.Simultaneously also to have wear resistance high on surface, and weather-proof good feature, can allow user reduce by the stained replacement cost caused.
accompanying drawing explanation:
Fig. 1 is infrared (IR) spectrogram of houghite (a), embodiment 1-4 gained Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material (b-e) and Carboxyl-functional Ionic Liquid (f).
Fig. 2 is the XRD diffractogram of houghite (a), embodiment 1-4 gained Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material (b-e).
Fig. 3 is the transmission electron microscope picture of embodiment 1-4 gained Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material (a-d).
Embodiment
Embodiment 1
Under condition of ice bath, get a certain amount of N-Methylimidazole in round-bottomed flask, equimolar bromoacetic acid is constantly stirred down and is slowly added drop-wise to the isopyknic dehydrated alcohol of N-Methylimidazole, reaction solution stirs 3h under returning to normal temperature, after filtration, wash product 3 times with dehydrated alcohol, obtain intermediate 1-methyl-3-propyloic imidazoles Bromide; Sodium tetrafluoroborate is taken by equimolar ratio, slowly join in the ethanol solution of above-mentioned gained IL intermediate under continuous stirring, stir 48 hours under normal temperature, reaction terminates rear mistake and filters inorganic salt, filtrate adopts rotary distillation process, remains ethanol, again filter in removing filtrate, the NaBr generated during removing exchanges, obtains brown viscous liquid; By divalent metal salt Mg (NO 3) 2with trivalent metal salt Al (NO 3) 3in molar ratio for 3:2 is made into mixing salt solution, total concentration of metal ions is 0.6 mol/L, then the ionic liquid 1-methyl-3-propyloic tetrafluoroborate that step b is obtained is pressed divalent metal salt Mg (NO 3) 2add in mixing salt solution with the mol ratio 2:0.3 that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate, by the titration simultaneously of above-mentioned mixing solutions and ammonia soln, control pH between 7-8, vigorous stirring, aging 15h at 40 DEG C; Gained slurries distilled water wash 3 times, suction filtration, dry 24 h at filter cake 60 DEG C, obtain Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material of the present invention.
By Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material 20 parts; The urethane resin of content more than 98% 15 parts; Vulcabond 10 parts; Powdered carbon 30 parts; Mibk 5 parts; Polytetrahydrofuran diol 10 parts; Nano titanium oxide 10 parts stirs, and selects 110 object treatment wheel, adopts the method for intaglio printing synthetic leather treatment agent to be overlayed on synthetic leather surface 15g/m 2.Then through baking oven, control temperature 125 DEG C, dries 3min.
Embodiment 2
Under condition of ice bath, get a certain amount of N-Methylimidazole in round-bottomed flask, equimolar bromoacetic acid is constantly stirred down and is slowly added drop-wise to the isopyknic dehydrated alcohol of N-Methylimidazole, reaction solution stirs 4h under returning to normal temperature, after filtration, wash product 5 times with dehydrated alcohol, obtain intermediate 1-methyl-3-propyloic imidazoles Bromide; Sodium tetrafluoroborate is taken by equimolar ratio, slowly join in the ethanol solution of above-mentioned gained IL intermediate under continuous stirring, stir 48 hours under normal temperature, reaction terminates rear mistake and filters inorganic salt, filtrate adopts rotary distillation process, remains ethanol, again filter in removing filtrate, the NaBr generated during removing exchanges, obtains brown viscous liquid; By divalent metal salt Mg (NO 3) 2with trivalent metal salt Al (NO 3) 3in molar ratio for 3:2 is made into mixing salt solution, total concentration of metal ions is 0.6 mol/L, then the ionic liquid 1-methyl-3-propyloic tetrafluoroborate that step b is obtained is pressed divalent metal salt Mg (NO 3) 2add in mixing salt solution with the mol ratio 2:0.5 that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate, by the titration simultaneously of above-mentioned mixing solutions and ammonia soln, control pH between 7-8, vigorous stirring, aging 18h at 50 DEG C; Gained slurries distilled water wash 5 times, suction filtration, dry 24 h at filter cake 60 DEG C, obtain Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material of the present invention.
By Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material 20 parts; The urethane resin of content more than 98% 15 parts; Vulcabond 10 parts; Powdered carbon 30 parts; Mibk 5 parts; Polytetrahydrofuran diol 10 parts; Nano titanium oxide 10 parts stirs, and selects 120 object treatment wheel, adopts the method for intaglio printing synthetic leather treatment agent to be overlayed on synthetic leather surface 15g/m 2.Then through baking oven, control temperature 125 DEG C, dries 3min.
Embodiment 3
Under condition of ice bath, get a certain amount of N-Methylimidazole in round-bottomed flask, equimolar bromoacetic acid is constantly stirred down and is slowly added drop-wise to the isopyknic dehydrated alcohol of N-Methylimidazole, reaction solution stirs 4h under returning to normal temperature, after filtration, wash product 5 times with dehydrated alcohol, obtain intermediate 1-methyl-3-propyloic imidazoles Bromide; Sodium tetrafluoroborate is taken by equimolar ratio, slowly join in the ethanol solution of above-mentioned gained IL intermediate under continuous stirring, stir 48 hours under normal temperature, reaction terminates rear mistake and filters inorganic salt, filtrate adopts rotary distillation process, remains ethanol, again filter in removing filtrate, the NaBr generated during removing exchanges, obtains brown viscous liquid; By divalent metal salt Mg (NO 3) 2with trivalent metal salt Al (NO 3) 3in molar ratio for 3:2 is made into mixing salt solution, total concentration of metal ions is 0.6 mol/L, then the ionic liquid 1-methyl-3-propyloic tetrafluoroborate that step b is obtained is pressed divalent metal salt Mg (NO 3) 2add in mixing salt solution with the mol ratio 2:0.8 that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate, by the titration simultaneously of above-mentioned mixing solutions and sodium hydroxide solution, control pH between 7-8, vigorous stirring, aging 18h at 50 DEG C; Gained slurries distilled water wash 5 times, suction filtration, dry 24 h at filter cake 60 DEG C, obtain Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material of the present invention.
By Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material 20 parts; The urethane resin of content more than 98% 15 parts; Vulcabond 10 parts; Powdered carbon 30 parts; Mibk 5 parts; Polytetrahydrofuran diol 10 parts; Nano titanium oxide 10 parts stirs, and selects 120 object treatment wheel, adopts the method for intaglio printing synthetic leather treatment agent to be overlayed on synthetic leather surface 18g/m 2.Then through baking oven, control temperature 125 DEG C, dries 3min.
Embodiment 4
Under condition of ice bath, get a certain amount of N-Methylimidazole in round-bottomed flask, equimolar bromoacetic acid is constantly stirred down and is slowly added drop-wise to the isopyknic dehydrated alcohol of N-Methylimidazole, reaction solution stirs 4h under returning to normal temperature, after filtration, wash product 5 times with dehydrated alcohol, obtain intermediate 1-methyl-3-propyloic imidazoles Bromide; Sodium tetrafluoroborate is taken by equimolar ratio, slowly join in the ethanol solution of above-mentioned gained IL intermediate under continuous stirring, stir 48 hours under normal temperature, reaction terminates rear mistake and filters inorganic salt, filtrate adopts rotary distillation process, remains ethanol, again filter in removing filtrate, the NaBr generated during removing exchanges, obtains brown viscous liquid; By divalent metal salt Mg (NO 3) 2with trivalent metal salt Al (NO 3) 3in molar ratio for 3:2 is made into mixing salt solution, total concentration of metal ions is 0.6 mol/L, then the ionic liquid 1-methyl-3-propyloic tetrafluoroborate that step b is obtained is pressed divalent metal salt Mg (NO 3) 2add in mixing salt solution with the mol ratio 2:1.0 that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate, by the titration simultaneously of above-mentioned mixing solutions and sodium hydroxide solution, control pH between 7-8, vigorous stirring, aging 18h at 50 DEG C; Gained slurries distilled water wash 5 times, suction filtration, dry 24 h at filter cake 60 DEG C, obtain Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material of the present invention.
By Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material 20 parts; The urethane resin of content more than 98% 15 parts; Vulcabond 10 parts; Powdered carbon 30 parts; Mibk 5 parts; Polytetrahydrofuran diol 10 parts; Nano titanium oxide 10 parts stirs, and selects 120 object treatment wheel, adopts the method for intaglio printing synthetic leather treatment agent to be overlayed on synthetic leather surface 18g/m 2.Then through baking oven, control temperature 135 DEG C, dries 3min.
Embodiment 5
By the urethane resin 30 parts of content more than 98%; Vulcabond 10 parts; Powdered carbon 30 parts; Mibk 5 parts; Polytetrahydrofuran diol 15 parts; Nano titanium oxide 10 parts stirs, and selects 120 object treatment wheel, adopts the method for intaglio printing synthetic leather treatment agent to be overlayed on synthetic leather surface 15g/m 2.Then through baking oven, control temperature 125 DEG C, dries 3min.
Fig. 1 is houghite, embodiment 1-4 gained Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material and Carboxyl-functional Ionic Liquid infrared (IR) spectrogram.In figure in curve a-e all at 3443 cm -1there is the contracting vibration peak of crystal water and the hydrogen bond stretching vibration peak of surface hydroxyl, at 452 cm in left and right -1there is the charateristic avsorption band of houghite M – O and O – M – O key in place, 1384 cm -1the stretching vibration peak of the carbanion that place occurs is the cause because carbonic acid gas in preparation process does not eliminate; Except the characteristic absorption band of houghite, Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material compared to houghite, also at 788 cm -1there is the absorption peak of imidazole ring, 1090 cm in left and right -1there is strong B-H vibration absorption peak at left and right place, and Carboxyl-functional Ionic Liquid is at 1760 cm -1the strong absorption peak of C=O that place occurs, disappears in the composite, goes out Carboxyl-functional Ionic Liquid of the present invention with the form load of hydrogen bond on hydrotalcite-like materials, define matrix material by above result deducibility.
Fig. 2 is the XRD diffractogram of houghite, embodiment 1-4 gained Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material.All the characteristic diffraction peak that houghite 003,006 and 009 crystal face three peak types are sharp-pointed has been there is at low 2 θ places in all samples.Gained matrix material presents the higher and sharp-pointed peak shape of intensity, and interpret sample all maintains than more complete LDH structure, and degree of crystallinity is higher.The d of all hybrids 003all be stabilized in about 0.76 nm, show due to CO in preparation process 2do not drain, ten million interlayer is negatively charged ion is carbonate, but not nitrate radical, this is consistent with infrared results.But along with the increase of the ionic liquid scale of construction, the d of all matrix materials 003diffraction peak width at half height does not present regular change.The results are shown in Table 1, wherein houghite is that sample a, embodiment 1-4 gained Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material is respectively sample.
Table 1: the XRD structural parameter of houghite and Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material
Sample a Sample b Sample c Sample d Sample e
d 003/? 7.726 7.624 7.567 7.628 7.596
d 110/? 1.507 1.504 1.535 1.506 1.504
a/? 3.013 3.017 3.077 3.018 3.013
c/? 5.555 5.246 5.014 5.246 5.196
003 crystallographic plane diffraction peak peak width at half height (°) 0.503 0.377 0.518 0.407 0.507
110 crystallographic plane diffraction peak peak width at half heights (°) 0.320 0.295 0.344 0.316 0.359
Fig. 3 is the transmission electron microscope picture of embodiment 1-4 gained Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material, obviously can find out, although load has the hydrotalcite-like composite material of ionic liquid to maintain the laminated structure of houghite, but the original hexagonal structure of houghite has suffered destruction, prove that ionic liquid has been combined in houghite surface, and along with the increase of the ionic liquid scale of construction, the median size of matrix material is reducing gradually, a, b, c, the median size of d is respectively 133, 121, 108 and 103 nm, (138 are respectively with dynamic light scattering the data obtained is basically identical, 123, 1218 and 118 nm), the increase along with the ionic liquid scale of construction can also be found from picture, the nanoparticulate dispersed of matrix material is raising trend, the polydispersity index of dynamic light scattering institute particle is respectively 0.220, 0.187, 0.141 and 0.122.
The product that subjects: embodiment 1-5 is obtained, synthetic leather;
Test objective: the product that investigation embodiment of the present invention 1-4 obtains is to the Adsorption effect of the phenolic comp ' ds pollution in synthetic leather.
Test grouping:
Test 1 group: the product B that embodiment 1 is obtained;
Test 2 groups: the products C that embodiment 2 is obtained;
Test 3 groups: the product D that embodiment 3 is obtained;
Test 4 groups: the product E that embodiment 4 is obtained;
Simultaneous test group: the product A that embodiment 5 is obtained.
Test method:
Subjects of the present invention is measured the Pollutant levels contained by it, and often group test is in triplicate, and measures the clearance of its product obtained by relative embodiment 5, averages, test-results:
Table 2 product of the present invention is to the adsorption Removal result of phenolic comp ' ds pollution
Remarks: *compared with simultaneous test group, P<0.05,
aMP.AMp.Ampcompared with test 1 group, 2 groups, 4 groups corresponding products B, C, E, P<0.05.
Brief summary: can be found out by the test-results of table 2:
On the one hand, when adding same amount, the each experimental group of the present invention (testing 1,2,3,4 group) has significant difference with simultaneous test group compared with the Adsorption effect of phenolic comp ' ds pollution and clearance, the Adsorption successful of visible product Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material of the present invention to phenolic comp ' ds pollution is better than houghite, achieves unexpected technique effect compared with houghite simultaneous test group.
On the other hand, in each group of the test of product of the present invention, the most outstanding to test 3 groups for the treatment of effects, its with test 1 group, test 2 groups and test compared with 4 groups of Adsorption effects to phenolic comp ' ds pollution and clearance, there is significant difference.

Claims (8)

1. synthetic leather coating that an adsorptive power is strong and preparation method thereof, is characterized in that, be prepared from by weight by following raw material:
Urethane resin 15-30 part of content more than 98%;
Vulcabond 5-10 part;
Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material 10-20 part;
Powdered carbon 15-30 part;
Mibk 5-10 part;
Polytetrahydrofuran diol 10-20 part;
Nano titanium oxide 10-15 part.
2. synthetic leather coating that a kind of adsorptive power according to claim 1 is strong and preparation method thereof, it is characterized in that, described preparation method is: raw material stirring is even, selects 110-120 object treatment wheel, adopts the method for intaglio printing synthetic leather treatment agent to be overlayed on synthetic leather surface 15-18g/m 2.
3., then through baking oven, control temperature 125-135 DEG C, dries 3-4min.
4. synthetic leather coating that a kind of adsorptive power according to claim 1 is strong and preparation method thereof, is characterized in that, the making method of described Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material comprises following concrete steps:
A () prepares 1-methyl-3-propyloic imidazoles Bromide
Under condition of ice bath, get a certain amount of N-Methylimidazole in round-bottomed flask, equimolar bromoacetic acid is constantly stirred down and is slowly added drop-wise to the isopyknic dehydrated alcohol of N-Methylimidazole, reaction solution stirs 3-4h under returning to normal temperature, after filtration, wash product 3-5 time with dehydrated alcohol, obtain intermediate 1-methyl-3-propyloic imidazoles Bromide;
B () prepares 1-methyl-3-propyloic tetrafluoroborate
Sodium tetrafluoroborate is taken by equimolar ratio, slowly join in the ethanol solution of above-mentioned gained IL intermediate under continuous stirring, stir 48 hours under normal temperature, reaction terminates rear mistake and filters inorganic salt, filtrate adopts rotary distillation process, remains ethanol, again filter in removing filtrate, the NaBr generated during removing exchanges, obtains brown viscous liquid;
C () prepares Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material
By divalent metal salt Mg (NO 3) 2with trivalent metal salt Al (NO 3) 3mixing salt solution is made into by certain mol proportion, total concentration of metal ions is 0.6 mol/L, again the ionic liquid 1-methyl-3-propyloic tetrafluoroborate that step b is obtained is added in mixing salt solution by certain mol proportion, by above-mentioned mixing solutions and basic solution titration simultaneously, control pH is between 7-8, vigorous stirring, aging 15-18h at 40-50 DEG C; Gained slurries distilled water wash 3-5 time, suction filtration, dry 24 h at filter cake 60 DEG C, obtain Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material of the present invention.
5. synthetic leather coating that a kind of adsorptive power according to claim 2 is strong and preparation method thereof, is characterized in that, (the NO of divalent metal salt Mg described in described step c 3) 2with trivalent metal salt Al (NO 3) 3mol ratio be 3:2.
6. synthetic leather coating that a kind of adsorptive power according to claim 2 is strong and preparation method thereof, is characterized in that, (the NO of divalent metal salt Mg described in described step c 3) 22:0.3,2:0.5,2:0.8,2:1.0 is respectively with the mol ratio that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate;
Synthetic leather coating that a kind of adsorptive power according to claim 2 is strong and preparation method thereof, is characterized in that, (the NO of divalent metal salt Mg described in described step c 3) 22:0.8 is preferably with the mol ratio that ionic liquid is 1-methyl-3-propyloic tetrafluoroborate.
7. synthetic leather coating that a kind of adsorptive power according to claim 2 is strong and preparation method thereof, is characterized in that, the basic solution described in described step c is ammoniacal liquor or sodium hydroxide solution or its mixture.
8. synthetic leather coating that a kind of adsorptive power according to claim 2 is strong and preparation method thereof, it is characterized in that, Carboxyl-functional Ionic Liquid/hydrotalcite-like composite material in described step c, its median size is 110-140 nm, and the polydispersity index of particle diameter is 0.122-0.220.
CN201310379768.XA 2013-08-28 2013-08-28 Synthetic leather coating having strong adsorption capacity and preparation method thereof Pending CN104419305A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104998609A (en) * 2015-06-18 2015-10-28 青岛科技大学 Method for preparing small-grain-size ultra-thin hydrotalcite nano-sheets without surface active agents through reversed-phase microemulsion
CN108117779A (en) * 2017-12-21 2018-06-05 金华联创塑粉科技有限公司 A kind of generation negative oxygen ion environmental protection coating material and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104998609A (en) * 2015-06-18 2015-10-28 青岛科技大学 Method for preparing small-grain-size ultra-thin hydrotalcite nano-sheets without surface active agents through reversed-phase microemulsion
CN108117779A (en) * 2017-12-21 2018-06-05 金华联创塑粉科技有限公司 A kind of generation negative oxygen ion environmental protection coating material and preparation method thereof

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Application publication date: 20150318