CN101565588B - Organic attapulgite water-borne polyurethane nano composite leather coating agent and preparation method thereof - Google Patents
Organic attapulgite water-borne polyurethane nano composite leather coating agent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic attapulgite water-borne polyurethane nano composite leather coating agent and a preparation method thereof. The method firstly uses acid for conducting purification and dispersion treatment to crude attapulgite, then conducts organic modification on the attapulgite by quaternary ammonium salt, organic amine, a coupling agent, a polyisocyanate monomer or amino acid to prepare organic attapulgite and then uses a latex blending or in-situ polymerization method for dispersing the organic attapulgite in the base material of water-borne polyurethane in a nano level, thus obtaining the organic attapulgite water-borne polyurethane nano composite leather coating agent. In the invention, acid is selected to treat the crude attapulgite, thus improving the purity anddispersity of the attapulgite and increasing ion exchange capacity thereof; the quaternary ammonium salt, the organic amine, the coupling agent, the polyisocyanate or the amino acid is adopted to con duct organic modification on the attapulgite, thus improving the surface microenvironment of a chained silicate sheet layer on an attapulgite clay layer, increasing the dispersity of the attapulgite in a macromolecular solution and the compatibility thereof with an organic macromolecular phase and being beneficial to improving the performance of a composite material. By the latex blending or in-situ polymerization method, one-dimensional nano rod crystals are led into the base material of the water-borne polyurethane, thus remarkably improving the mechanical property, thermal stability, rub-resistant strength, water resistance and water vapor permeability of the coating material. The coating agent is used as leather coating material in leather coating, has remarkable effects in improving the mechanical strength, thermal stability and rub-resistant strength of coatings and also exerts positive effect on the water resistance, sanitary property and the like of the coatings.
Description
Technical field
The present invention relates to nano composite material research field and polyurethane leather coating and decorating material development field, be specifically related to a kind of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent and preparation method thereof.
Background technology
Nano composite material originates from the phase at the beginning of the eighties in last century, people such as Roy and Kormaneni has proposed the notion of nano composite material (nanocomposite) first in 1984, the solid phase size that it is meant two or more at least on the one dimension direction less than the matrix material of 100nm.Nanotechnology and nano composite material have become the focus of scientific research and developing material in recent years, are penetrated into the every field of Materials science research, and become the frontier of interdisciplinary development.
Because little, the specific surface area of nanoclay particles size is big, surface energy and surface tension sharply increase with the decline of particle diameter, shows small-size effect, surface effects, quantum size effect and macro quanta tunnel effect etc.As the properties-correcting agent of macromolecular material, toughener etc., can improve the mechanical property, heat-resistant stability of matrix material etc., the high workability of nanoparticle has been improved Drawing abillity simultaneously, makes material surface smooth, and frictional coefficient diminishes, and wear resistance strengthens.Nanoparticle has great specific surface area, and the effectively pseudo-plasticity of controlled liq polymkeric substance and thixotropic property can be used as thickening material, strengthening agent, rheological agent of high-grade paint, tackiness agent, seal gum etc. etc.Utilize characteristics such as the special light of nanoparticle, electricity, magnetic, can prepare macromolecular material with specific function.These research and development and upgradings that are characterized as material provide new thinking, have caused the very big interest of scientific and technological circle and industrial community, and in a very long time from now on, nanotechnology must produce tremendous influence to world economy.
Attapulgite (attapulgite) soil has another name called polygorskite (palygorskite), be a kind of layer of chain transition structure to contain the natural clay mineral of Shuifu County's zeopan, on mineralogy, be under the jurisdiction of sepiolite group.1940, Brandley proposed the ideal crystal structure of recessed soil, its chemical formula Mg according to the X-diffraction analysis
5(Si
4O
10)
2(OH)
2(H
2O)
44H
2O and layered crystal structure pattern also gain public acceptance.Attapulgite belongs to 2:1 type clay mineral, and promptly two-layer silicon-oxy tetrahedron folder one deck magnesia octahedron holds dorsad thirty years of age therebetween every four silicon-oxy tetrahedrons, axially is laminate structure along b, c; The c direction of principal axis is the parallel fibers direction, is made up of two pyroxene chains, and interchain is linked up by the Sauerstoffatom of dividing equally each other, because the interchain bonding force is less than the chain internal bond, so make it have tangible one to the fiber crystal habit of extending.The attapulgite crystal habit is bar-shaped or fibrous, the most 10～100nm of single crystal diameter, and length is 0.1～1 μ m, so it has very big length-to-diameter ratio, constitutional features belongs to the 1-dimention nano particle.Attapulgite clay has sliding sense, light weight, water-absorbent is strong, chance water does not expand, have characteristics such as stickiness and plasticity-when wetting.Because the special construction of itself, recessed soil is used widely in fields such as building materials, mining, chemical fertilizer, food, agricultural chemicals, printing and dyeing, environmental protection, have the title of " using soil for thousand ".
German Bayer company took the lead in having developed water-based PU hide finishes in 1972, and PU compares with solvent-borne type, water-based PU in building-up process with water as solvent, reduced the volatilization and the danger of building-up process kind organic solvent; Nontoxic during use, pollution-free, do not burn, inexpensive, have the performance of common solvent type PU, be a kind of application prospect " green material " widely.Along with the progress of industrial technology, people increase day by day to the performance requriements of material, and material is carried out modification to improve its performance or to increase the trend that specific function becomes commercial exploitation and research.In view of the advantage of above-mentioned attapulgite as the 1-dimention nano particle, attapulgite is dispersed in the polymkeric substance with 0.1%～20% of polymer solids level, it is existed with one dimension Nano structure in aqueous polyurethane matrix.Because characteristics such as the great specific surface area of attapulgite clay nano material, good thermostability and dimensional stability, it is entrained in can make matrix material have excellent more performance than conventional material in the polymkeric substance, for example high physical strength, high-modulus, heat-resistant stability are good, have certain electro-optical performance.
Because attapulgite clay has good water-swelling, dispersiveness is not good in organic phase, and is relatively poor with the organic macromolecule consistency, so often carry out organically-modified to attapulgite clay.The organically-modified microenvironment that can improve attapulgite clay layer interchain surface makes Attapulgite layer chain surface become hydrophobic state by hydrophilic nmature, thus improve its dispersed of organic phase and with the consistency of organic phase, help improving the performance of material.
Summary of the invention
The object of the invention is to provide a kind of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent and preparation method.
Technical scheme mainly comprises following step:
A kind of organic attapulgite clay-water-borne polyurethane nano composite leather coating agent is characterized in that by the emulsion blending of aqueous polyurethane emulsion and organic attapulgite soil aqueous dispersions or the method preparation of in-situ polymerization.
The emulsion blending preparation method of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent is as follows:
1) with a certain amount of organic attapulgite soil and distilled water according to mass ratio (0.005～0.2): 1, add abundant swelling in the container, low whipping speed is under the condition of 100～2000rpm, stir 30～150min, be ultra-sonic dispersion 30～120min in the ultrasonic wave of 40～100Hz in frequency then, make organic attapulgite soil aqueous dispersions, standby;
2) mol ratio with isocyanate group and hydroxyl is (1.05～2): 1 polyisocyanates and polymer polyatomic alcohol add in the reaction vessel simultaneously, under 40～150 ℃, and stirring reaction 2～5h;
3) in above-mentioned reaction vessel, add be (0.05～1) with the mol ratio of reactive group and polymer polyatomic alcohol hydroxyl: 1 chainextender, under 25～90 ℃, stir chain extending reaction 1～4h;
4) in reaction vessel, add the aqueous solution of a certain amount of neutralizing agent behind the chain extending reaction, in temperature is that 25～60 ℃ and stirring velocity are that neutralization disperses 1～3h under the condition of 500～2000rpm, obtain aqueous polyurethane emulsion, and to make aqueous polyurethane emulsion pH value be 4～9;
5) according to the dry weight of organic attapulgite soil and urethane than (0.005～0.1): add the native aqueous dispersions of scattered organic attapulgite in 1 hydrotropisms's polyaminoester emulsion,, obtain reaction product at 60～90 ℃ of following dispersed with stirring 2～6h;
6) reaction product being concentrated to solid content is 25%～30%, leaves standstill to be cooled to below 40 ℃.
The preparation method of the in-situ polymerization of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent is as follows:
1) organic attapulgite soil is (0.001～0.1) with polymer polyatomic alcohol according to mass ratio: 1 joins in the reactor, and 70～150 ℃ of following dispersed with stirring 3～6h are cooled to below 40 ℃;
2) mol ratio according to the hydroxyl of isocyanate group and polymer polyatomic alcohol is (1.05～2): 1 adds polyisocyanates in reactor, under 40～150 ℃, and stirring reaction 2～5h;
3) according to chainextender be (0.05～1) with the mol ratio of reactive group and polyvalent alcohol hydroxyl: 1 adds chainextender in reactor, stir chain extending reaction 1～4h under 25～90 ℃;
4) add the aqueous solution of neutralizing agent in reactor, low whipping speed is that 500～2000rpm and temperature are that neutralization disperses 1～3h under 25～60 ℃ the condition, and making the pH value is 4～9, obtains reaction product;
5) reaction product being concentrated to solid content is 25%～30%, leaves standstill to be cooled to below 40 ℃.
The preparation method of the organic attapulgite soil that uses in the preparation process of composite leather coating agent is as follows:
1) taking by weighing a certain amount of attapulgite, is (5～20) according to the mass ratio of acid solution and attapulgite: 1 adds acid solution, at 25～90 ℃ of following stirring reaction 12～48h, acid attapulgite solution;
2) filter acid attapulgite solution, washing leaching cake does not have acid ion to filtrate, in 90～120 ℃ of down dry 12～48h, pulverizes after the cooling afterwards, makes the acid treatment attapulgite;
3) get a certain amount of acid treatment attapulgite and add in the reaction vessel, behind swelling 1～2h, stir 30～150min, ultra-sonic dispersion 30～90min in the water;
4) in above-mentioned reactor, add modifier solution and carry out organically-modified reaction, the mass ratio of properties-correcting agent and acid treatment attapulgite is (0.01～0.8): 1, in temperature is under 50～90 ℃, stirring reaction 2～6h, cooling is afterwards filtered, washing, at 90～120 ℃ of down dry 12～48h, cooling is pulverized, and gets organic attapulgite soil.
The polymer polyatomic alcohol that uses in the composite leather coating agent preparation process is polyester polyol, polyether glycol, polybutadiene diol, Resins, epoxy or Viscotrol C, and molecular weight is 200～8000.
The chainextender that uses in the composite leather coating agent preparation process is one or several in 200～600 the polyhydric alcohol polymer as short chain small molecules polyvalent alcohol, polyamine, hydramine, alcohol amide, thionamic acid, polyhydroxy-acid, polyprotonic acid, multi-anhydride, amino or hydroxy-end capped organopolysiloxane or molecular weight.
The neutralizing agent that uses in the composite leather coating agent preparation process is inorganic neutralizing agent or organic neutralizer, and wherein inorganic neutralizing agent is one or several in ammoniacal liquor, sodium hydroxide, the potassium hydroxide; Organic neutralizer is one or several in triethylamine, tripropyl amine, diethanolamine, trolamine, the dimethylethanolamine.
Acid described in the preparation method of organic attapulgite soil is H
2SO
4, HCl, HNO
3And H
3PO
4In one or several, the concentration of acid solution is 0.5～6mol/L.
Properties-correcting agent described in the preparation method of organic attapulgite soil is one or several in quadrol, amino dodecane, stearylamine, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, double hexadecyl dimethyl brometo de amonio, hexadecyl benzyl dimethly ammonium chloride, octadecyl dihydroxy ethyl ammonio methacrylate, silane coupling agent, titanate coupling agent, aluminate coupling agent, aluminium titanium composite coupler, polyisocyanates, the amino acid.
The surperficial microenvironment of the present invention by the organically-modified layer interchain lamella that makes attapulgite by hydrophilic change into hydrophobic, increased its dispersion stabilization in polyurethane substrates, improve the consistency of itself and polyurethane molecular chain, helped the raising of the stable and material property of emulsion.Method by emulsion blending or in-situ polymerization has prepared organic attapulgite soil-water-borne polyurethane nano composite leather coating agent, organic attapulgite soil is dispersed in the polyurethane substrates with one dimension Nano structure, the performance of aqueous polyurethane hide finishes is improved, polyurethane molecular chain and organic attapulgite clay generation intercalation, twine or crosslinked action, because this effect has limited the free movement of polyurethane molecular chain, the corresponding mechanical property that has improved material and heat-resistant stability etc.: the synergistic effect of (1) organic polymer and organic attapulgite soil, cause the tensile strength of polyurethane leather coating material to increase, elongation at break slightly reduces under the condition that does not influence use properties; (2) nano effect of organic attapulgite soil and small-size effect are greatly improved the heat-resistant stability of material, and water-resistant capacity strengthens; (3) organic attapulgite soil has improved Drawing abillity as the high workability of 1-dimention nano particle in material, makes material surface smooth, and frictional coefficient diminishes, and wear resistance strengthens; (4) inorganic nano-particle makes permeability to water vapour that to a certain degree increase be arranged to the supporting role of macromolecular chain.So be used for leather finish, can significantly improve mechanical strength, heat-resistant stability, the wear-resisting wiping intensity of coating, the water tolerance of coating, sanitation performance etc. there are positive effect.
Embodiment
Provide four embodiment of the present invention below, to specify a kind of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent and preparation method thereof.
Embodiment 1
Earlier with a kind of quaternary ammonium salt-palmityl trimethyl ammonium chloride attapulgite is carried out modification, concrete operation method is as follows: take by weighing the attapulgite of 10.0g, add the sulphuric acid soln 100mL of 1mol/L, at 70 ℃ of following stirring reaction 24h.Filter, being washed with distilled water to does not have SO in the filtrate
4 2-, 100 ℃ of following dry 24h, cooling is pulverized.Take by weighing the acid treatment attapulgite clay of 5.0g then, be made into massfraction and be 10% aqueous dispersions, swelling 1h in the water, the powerful 60min that stirs, ultra-sonic dispersion 30min, add in the reaction vessel, dropping adding mass concentration is 20% palmityl trimethyl ammonium chloride aqueous solution 10g, at 75 ℃ of following stirring reaction 3h of temperature.Postcooling is finished in reaction, filters, and washing to filtrate with the ethanolic soln of distilled water and 50% does not have Cl
-, at 90～120 ℃ of down dry 12～48h, cooling is pulverized.
With 2.5g organic attapulgite clay and distilled water proportionally 0.05: 1, add in the container fully swelling, stir 90min, stirring velocity is 800rpm, is ultra-sonic dispersion 30min under the ultrasonic wave of 50Hz in frequency then, and is standby.
With 25g phenylbenzene-4,4 '-vulcabond and polytetrahydrofuran diol 100g add in the reaction vessel simultaneously, under 80 ℃, and stirring reaction 2h.Add chainextender trishydroxymethyl propionic acid 1.875g and 1,4-butyleneglycol 2.25g carries out chain extending reaction under 80 ℃, and the reaction times is 2h.Adding massfraction is the aqueous solution 500g of 2% triethylamine, under 50 ℃, and dispersed with stirring 2h, stirring velocity is 1500rpm, postcooling is finished in reaction, makes pH and be 4 aqueous polyurethane emulsion.
Will be in water scattered organic attapulgite clay dispersion drips to add in the above-mentioned synthetic aqueous polyurethane emulsion and disperses, and temperature is controlled at 75 ℃, and jitter time is 4h.Postcooling is finished in reaction, and it is 25%～30% that reaction product is concentrated to solid content, leaves standstill to be cooled to 25 ℃ of normal temperature.
Embodiment 2
Earlier with silane coupling agent attapulgite is carried out modification, concrete operation method is as follows: take by weighing the attapulgite of 10.0g, add the hydrochloric acid soln 100mL of 2mol/L, at 60 ℃ of following stirring reaction 24h.Filter, being washed with distilled water to does not have Cl in the filtrate
-, 100 ℃ of following dry 24h, cooling is pulverized.Take by weighing the acid treatment attapulgite clay of 5.0g then, be made into massfraction and be 10% aqueous dispersions, swelling 2h in the water, the powerful 90min that stirs, ultra-sonic dispersion 60min adds in the reaction vessel, adds the 0.3g silane coupling agent, at 60 ℃ of following stirring reaction 2h of temperature.Postcooling is finished in reaction, filters, and washs respectively 3 times with the aqueous isopropanol of distilled water and 80%, and at 105 ℃ times dry 24h, cooling is pulverized.
3.0g organic attapulgite clay mixed with 125g poly-epsilon-caprolactone glycol and Viscotrol C 5.0g add simultaneously in the reaction vessel,, be cooled to normal temperature at 95 ℃ of following dispersed with stirring 4h.Add the 17.5g tolylene diisocyanate, under 65 ℃, stirring reaction 3h.Add chainextender dimethylol propionic acid 2.25 and carry out chain extending reaction under 80 ℃, the reaction times is 1.5h.Adding massfraction is the aqueous solution 500g of 2% trolamine, under 60 ℃, and dispersed with stirring 1.5h, stirring velocity is 1200rpm, and postcooling is finished in reaction, and it is 25%～30% that reaction product is concentrated to solid content, leave standstill and be cooled to 25 ℃ of normal temperature, make pH and be 6 aqueous polyurethane emulsion.
Embodiment 3
Earlier with titanate coupling agent attapulgite is carried out modification, concrete operation method is as follows: take by weighing the attapulgite of 10.0g, add the hydrochloric acid soln 50mL of 6mol/L, at 40 ℃ of following stirring reaction 36h.Filter, being washed with distilled water to does not have Cl in the filtrate
-, 100 ℃ of following dry 24h, cooling is pulverized.Take by weighing the acid treatment attapulgite clay of 5.0g then, be made into massfraction and be 10% aqueous dispersions, swelling 1h in the water, the powerful 120min that stirs, ultra-sonic dispersion 90min adds in the reaction vessel, add the 0.5g titanate coupling agent, at 70 ℃ of following stirring reaction 4h of temperature.Postcooling is finished in reaction, filters, and washs respectively 3 times with the aqueous isopropanol of distilled water and 75%, and at 100 ℃ times dry 48h, cooling is pulverized.
5.0g organic attapulgite clay mixed with 125g poly-epsilon-caprolactone glycol add simultaneously in the reaction vessel,, be cooled to normal temperature at 120 ℃ of following dispersed with stirring 3h.Add 25g phenylbenzene-4,4 '-vulcabond, under 80 ℃, stirring reaction 2.5h.Add chainextender dimethylol propionic acid 2.25 and Viscotrol C 5.0g and carry out chain extending reaction under 80 ℃, the reaction times is 2h.Adding massfraction is the aqueous solution 500g of 2% trolamine, under 50 ℃, and dispersed with stirring 2.5h, stirring velocity is 1500rpm, and postcooling is finished in reaction, and it is 25%～30% that reaction product is concentrated to solid content, leave standstill and be cooled to 25 ℃ of normal temperature, make pH and be 6 aqueous polyurethane emulsion.
Embodiment 4
Earlier with octadecyl dihydroxy ethyl ammonio methacrylate attapulgite is carried out modification, concrete operation method is as follows: take by weighing the attapulgite of 10.0g, add the salpeter solution 50mL of 2mol/L, at 40 ℃ of following stirring reaction 36h.Filter, being washed with distilled water to does not have NO in the filtrate
3 -, 100 ℃ of following dry 24h, cooling is pulverized.Take by weighing the acid treatment attapulgite clay of 5.0g then, be made into massfraction and be 10% aqueous dispersions, swelling 1h in the water, the powerful 120min that stirs, ultra-sonic dispersion 90min, add in the reaction vessel, adding massfraction is 10% octadecyl dihydroxy ethyl ammonio methacrylate 10g, at 75 ℃ of following stirring reaction 2h of temperature.Postcooling is finished in reaction, filters, and washs respectively 3 times with the aqueous isopropanol of distilled water and 75%, and at 100 ℃ times dry 48h, cooling is pulverized.
With 5.0g organic attapulgite clay and the poly-carbonic acid-1 of 100g, 6-adipate diol and Viscotrol C 5.0g mix and add simultaneously in the reaction vessel, at 100 ℃ of following dispersed with stirring 6h, are cooled to normal temperature.Add the 22.23g isophorone diisocyanate, under 95 ℃, stirring reaction 3h.Add chainextender dimethylol propionic acid 2.25 and carry out chain extending reaction under 80 ℃, the reaction times is 3h.Adding massfraction is the aqueous solution 500g of 2.5% trolamine, under 60 ℃, and dispersed with stirring 2h, stirring velocity is 1200rpm, and postcooling is finished in reaction, and it is 25%～30% that reaction product is concentrated to solid content, leave standstill and be cooled to 25 ℃ of normal temperature, make pH and be 7 aqueous polyurethane emulsion.
Claims (9)
1. an organic attapulgite soil-water-borne polyurethane nano composite leather coating agent is characterized in that by the emulsion blending of aqueous polyurethane emulsion and organic attapulgite soil aqueous dispersions or the method preparation of in-situ polymerization.
2. organic attapulgite soil-water-borne polyurethane nano composite leather coating agent according to claim 1 is characterized in that the emulsion blending preparation method of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent is as follows:
1) with a certain amount of organic attapulgite soil and distilled water according to mass ratio (0.005～0.2): 1, add abundant swelling in the container, low whipping speed is under the condition of 100～2000rpm, stir 30～150min, be ultra-sonic dispersion 30～120min in the ultrasonic wave of 40～100Hz in frequency then, make organic attapulgite soil aqueous dispersions, standby;
2) mol ratio with isocyanate group and hydroxyl is (1.05～2): 1 polyisocyanates and polymer polyatomic alcohol add in the reaction vessel simultaneously, under 40～150 ℃, and stirring reaction 2～5h;
3) in above-mentioned reaction vessel, add be (0.05～1) with the mol ratio of reactive group and polymer polyatomic alcohol hydroxyl: 1 chainextender, under 25～90 ℃, stir chain extending reaction 1～4h;
4) in reaction vessel, add the aqueous solution of a certain amount of neutralizing agent behind the chain extending reaction, in temperature is that 25～60 ℃ and stirring velocity are that neutralization disperses 1～3h under the condition of 500～2000rpm, obtain aqueous polyurethane emulsion, and to make aqueous polyurethane emulsion pH value be 4～9;
5) according to the dry weight of organic attapulgite soil and urethane than (0.005～0.1): add the native aqueous dispersions of scattered organic attapulgite in 1 hydrotropisms's polyaminoester emulsion,, obtain reaction product at 60～90 ℃ of following dispersed with stirring 2～6h;
6) reaction product being concentrated to solid content is 25%～30%, leaves standstill to be cooled to below 40 ℃.
3. organic attapulgite soil-water-borne polyurethane nano composite leather coating agent according to claim 1 is characterized in that the preparation method of in-situ polymerization of organic attapulgite soil-water-borne polyurethane nano composite leather coating agent is as follows:
1) organic attapulgite soil is (0.001～0.1) with polymer polyatomic alcohol according to mass ratio: 1 joins in the reactor, and 70～150 ℃ of following dispersed with stirring 3～6h are cooled to below 40 ℃;
2) mol ratio according to the hydroxyl of isocyanate group and polymer polyatomic alcohol is (1.05～2): 1 adds polyisocyanates in reactor, under 40～150 ℃, and stirring reaction 2～5h;
3) according to chainextender be (0.05～1) with the mol ratio of reactive group and polyvalent alcohol hydroxyl: 1 adds chainextender in reactor, stir chain extending reaction 1～4h under 25～90 ℃;
4) add the aqueous solution of neutralizing agent in reactor, low whipping speed is that 500～2000rpm and temperature are that neutralization disperses 1～3h under 25～60 ℃ the condition, and making the pH value is 4～9, obtains reaction product;
5) reaction product being concentrated to solid content is 25%～30%, leaves standstill to be cooled to below 40 ℃.
4. organic attapulgite soil-water-borne polyurethane nano composite leather coating agent according to claim 1 is characterized in that the preparation method of described organic attapulgite soil is as follows:
1) taking by weighing a certain amount of attapulgite, is (5～20) according to the mass ratio of acid solution and attapulgite: 1 adds acid solution, at 25～90 ℃ of following stirring reaction 12～48h, acid attapulgite solution;
2) filter acid attapulgite solution, washing leaching cake does not have acid ion to filtrate, in 90～120 ℃ of down dry 12～48h, pulverizes after the cooling afterwards, makes the acid treatment attapulgite;
3) get a certain amount of acid treatment attapulgite and add in the reaction vessel, behind swelling 1～2h, stir 30～150min, ultra-sonic dispersion 30～90min in the water;
4) in above-mentioned reactor, add modifier solution and carry out organically-modified reaction, the mass ratio of properties-correcting agent and acid treatment attapulgite is (0.01～0.8): 1, in temperature is under 50～90 ℃, stirring reaction 2～6h, cooling is afterwards filtered, washing, at 90～120 ℃ of down dry 12～48h, cooling is pulverized, and gets organic attapulgite soil.
5. according to claim 2 or 3 described organic attapulgite soil-water-borne polyurethane nano composite leather coating agents, it is characterized in that described polymer polyatomic alcohol is polyester polyol, polyether glycol, polybutadiene diol, Resins, epoxy or Viscotrol C, molecular weight is 200～8000.
6. according to claim 2 or 3 described organic attapulgite soil-water-borne polyurethane nano composite leather coating agents, it is characterized in that described chainextender is that short chain small molecules polyvalent alcohol, polyamine, hydramine, alcohol amide, thionamic acid, polyhydroxy-acid, polyprotonic acid, multi-anhydride, amino or hydroxy-end capped organopolysiloxane or molecular weight are one or several in 200～600 the polyhydric alcohol polymer.
7. according to claim 2 or 3 described organic attapulgite soil-water-borne polyurethane nano composite leather coating agents, it is characterized in that described neutralizing agent is inorganic neutralizing agent or organic neutralizer, wherein inorganic neutralizing agent is one or several in ammoniacal liquor, sodium hydroxide, the potassium hydroxide; Organic neutralizer is one or several in triethylamine, tripropyl amine, diethanolamine, trolamine, the dimethylethanolamine.
8. organic attapulgite soil-water-borne polyurethane nano composite leather coating agent according to claim 4 is characterized in that described acid is H
2SO
4, HCl, HNO
3And H
3PO
4In one or several, the concentration of acid solution is 0.5～6mol/L.
9. organic attapulgite soil-water-borne polyurethane nano composite leather coating agent according to claim 4 is characterized in that described properties-correcting agent is one or several in quadrol, amino dodecane, stearylamine, palmityl trimethyl ammonium chloride, octadecyl trimethylammonium bromide, double hexadecyl dimethyl brometo de amonio, hexadecyl benzyl dimethly ammonium chloride, octadecyl dihydroxy ethyl ammonio methacrylate, silane coupling agent, titanate coupling agent, aluminate coupling agent, aluminium titanium composite coupler, polyisocyanates, the amino acid.
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