CN102286234B - Preparation method of modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ - Google Patents
Preparation method of modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ Download PDFInfo
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Abstract
The invention provides a preparation method of a modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ, comprising the following steps of: treating the single-wall or multi-wall carbon nano tubes with strong acid solution, removing impurities in the carbon nano tubes, and obtaining carboxylated CNTs; reacting the carboxylated CNTs with thionyl chloride and acrylamide in sequence, obtaining CNTs grafted by acrylamide and finally leading the CNTs grafted by acrylamide and acrylate monomer to carry out emulsion polymerization reaction under the action of an emulsifying agent and an initiating agent so as to generate the modified acrylic resin leather coating material of the carbon nano tubes in situ. In the preparation method provided by the invention, the extremely high surface ratio of the carbon nano tubes has excellent enhancing and toughening effects for the composite material, and the extremely high long-diameter ratio is easy for carrying out modification on the acrylic resin leather coating material in the preparation process of the coating material. The preparation method has the advantages that the process is simple, the preparation method is green and environmentally-friendly and the cost is low, and the preparation method is suitable for industrial production. For the coating film with the modified acrylic resin leather coating emulsion of the functionalized carbon nano tubes, the comprehensive performances such as the covering power, the color change resistance, the ageing resistance, the wear resistance, the tensile strength, the hot and cold resistance, the flame resistance and the like are obviously improved, and the quality of a leather product is obviously improved.
Description
Technical field
The invention belongs to the leather chemical industry field, particularly the preparation method of the in-situ modified crylic acid resin coating material for leather of a kind of carbon nanotube.
Background technology
Hide finishes can significantly promote the leather use properties, expands the leather range of application and improve the leather products class by covering with paint, lacquer, colour wash, etc. as leather top layer coating and decorating material.The crylic acid resin hide finishes has a series of advantage, such as good film-forming property, adhesion is strong, production technique is simple and the excellent specific property such as with low cost, is subject to the favor of leather industry, has obtained developing rapidly.Yet common Emulsion acrylic resin films and exists " heat is glutinous, cold short ", the shortcoming such as anti-solvent not, and use is restricted.In order to overcome these shortcomings, need to carry out more deep research and modification to it, to adapt to more Secretary.
In recent years, both at home and abroad the investigator mostly is conceived to adjust kind and the proportioning of monomer and introduces the organic molecule such as organosilicon, organic fluorine or polymkeric substance carries out modification to acrylic resin.But also be difficult to satisfy the required many actual performances of finished leather, can't give leather some specific function.
In the leather middle introducing nanoparticle of filming, and make it to organically combine with membrane-forming agent, can improve the over-all properties of coating, improve the intensity of polymkeric substance, wear-resisting wiping, ageing resistance and weathering resistance, increase the added value of finished leather, being an important directions of hide finishes development, is a focus covering with paint, lacquer, colour wash, etc. the research and development of products field.Carbon nanotube (Carbon nanotubes, CNTs) is as monodimension nanometer material, and is lightweight, and hexagonal structure connects perfect, has that specific surface area is large, physical strength is high, specific conductivity is high, characteristics such as heat conduction and good heat resistance.CNTs is applied to the modification of crylic acid resin finishing agent, and the characteristics of performance CNTs and the enhancing Toughening Properties of nano material can obviously improve the opacifying power of coating, improve tensile strength, elongation at break, the physical and mechanical propertiess such as wear-resisting, flame retardant resistance.To improving the functional of leather, widen the leather range of application, have important application prospect.Application and the research of carbon nanotube in hide finishes yet there are no relevant report.
Summary of the invention
The invention provides the preparation method of the in-situ modified crylic acid resin coating material for leather of a kind of carbon nanotube, when the carbon nanotube emulsion polymerization in situ is acrylic resin modified, can obviously improve the physical and mechanical properties such as wear resistance, tensile strength, elongation at break of resin.
For achieving the above object, the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube of the present invention may further comprise the steps:
Step 1: with the carbon nanotube of single wall or many walls with after acidic solution mixes as 0.025: 1 take volume ratio, supersound process is mixed with suspension, leave standstill and soaked 24-48 hour, then heating-condensing refluxes, washing is until PH is neutral repeatedly at last, and centrifugation obtains carbon nanotube functionalized with carboxylic acid group, wherein, described acidic solution refers to that the vitriol oil and concentrated nitric acid are (1-3) according to volume ratio: 1 nitration mixture that forms;
Step 2: above-mentioned carbon nanotube functionalized with carboxylic acid group is successively reacted with excess chlorination sulfoxide, acrylamide, obtain the modified carbon nano-tube of acrylamide graft;
Step 3: the modified carbon nano-tube of the acrylamide graft that step 2 is obtained and coating material for leather with acrylic monomer acrylic resin modified class of polyreaction original position Formed nanotube under the effect of distilled water, emulsifier sodium lauryl sulfate and initiator ammonium persulfate of double bond functional group.
Compared with prior art, the preparation method of carbon nano-tube modification crylic acid resin coating material for leather of the present invention has the following advantages at least: when the carbon nanotube emulsion polymerization in situ is acrylic resin modified, can obviously improve the physical and mechanical properties such as wear resistance, tensile strength, elongation at break of resin.Wherein, the whole carbon nanotubes of disposable adding can significantly improve the tensile strength of resin, drip after carbon nanotube mixes with monomer to add the elongation at break that can significantly improve resin.
Embodiment
Embodiment one:
Step 1: the purifying of carbon nanotube and modification: at first, be that 95% sulfuric acid and mass concentration are that 68% nitric acid is to mix at 1: 1 by volume with mass concentration, be made into mixed acid solution; Then, carbon nanotube was mixed as 0.025: 1 take mass ratio with mixed acid solution, then supersound process forms stable suspension, soak after 24 hours, refluxed 1 hour at 110 ℃ of heating-condensings, repeatedly wash centrifugation at last until pH value is 7, to remove the impurity in the carbon nanotube, and make active reactive group on its surface band, obtain carbon nanotube functionalized with carboxylic acid group;
Step 2: with step 1 obtain carboxylated after carbon nanotube and excessive sulfur oxychloride 60 ℃ of lower stirring and refluxing 24 hours, then 85 ℃-90 ℃ lower distillations 3-4 hour, vacuum-drying 6-7 hour, obtain the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used respectively organic solvent (as: tetrahydrofuran (THF)) dissolving, acrylamide is joined constant pressure funnel, the carbon nanotube of chloride joins in the there-necked flask, then in 60-65 ℃ of carbon nanotube that excessive acrylamide is joined chloride, slowly dripping 1-1.5 hour drips off, then continue reaction after 24 hours, 85 ℃-90 ℃ lower distillations 3-4 hour, at last washing, centrifugation, vacuum-drying obtain the modified carbon nano-tube of acrylamide graft;
Step 3: take monomer and solubility promoter dehydrated alcohol in emulsion synthesizing propylene acid resin, amount to 100 parts, used monomer vinylformic acid: methyl methacrylate: butyl acrylate: acrylamide: the mass ratio of dehydrated alcohol is 1: (2-6): (3-6): (0.3-0.6): (3-6), the ammonium persulphate that takes by weighing monomer and dehydrated alcohol total mass 0.3% is initiator, the sodium lauryl sulphate that takes by weighing monomer total mass 2% is as the emulsifying agent of reaction, takes by weighing the carbon nanotube of the acrylamide graft that the step 2 of monomer total mass 0.01% obtains;
Step 4: with basic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide etc. stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, then add ethanol, then, the carbon nanotube of acrylamide graft is dissolved in distilled water and the emulsifying agent, join behind the ultrasonic 5min in the reactor that 1/3rd monomers are housed, heated and stirred, mixing speed is set to 300r/min, when temperature is increased to 70 ℃, add 1/4th initiators that are dissolved in the distilled water, simultaneously, drip remaining 2/3rds amount monomer and remaining 3/4ths initiator solutions with constant pressure funnel, about 1h drips off, wherein, it is complete that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, then be cooled to 60 ℃, add an amount of ammonia neutralization, and regulate pH=6-7, continue to stir 0.5h, be cooled to room temperature and pour out, filter, namely get carbon nano-tube modification water-borne acrylic resin emulsion.
Embodiment two:
Step 1: the purifying of carbon nanotube and modification: at first, be that 95% sulfuric acid and mass concentration are that 68% nitric acid is to mix at 2: 1 by volume with mass concentration, be made into mixed acid solution; Then, carbon nanotube was mixed as 0.025: 1 take mass ratio with mixed acid solution, then supersound process forms stable suspension, soak after 35 hours, refluxed 1 hour at 115 ℃ of heating-condensings, repeatedly wash centrifugation at last until after pH value is 7, to remove the impurity in the carbon nanotube, and make active reactive group on its surface band, obtain carbon nanotube functionalized with carboxylic acid group;
Step 2: with step 1 obtain carboxylated after carbon nanotube and excessive sulfur oxychloride 65 ℃ of lower stirring and refluxing 30 hours, then 85 ℃-90 ℃ lower distillations 4-5 hour, vacuum-drying 7-8 hour, obtain the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used respectively organic solvent (as: tetrahydrofuran (THF)) dissolving, acrylamide is joined constant pressure funnel, the carbon nanotube of chloride joins in the there-necked flask, then in 60-65 ℃ of carbon nanotube that excessive acrylamide is joined chloride, slowly dripping 1-1.5 hour drips off, then continue reaction after 24 hours, 85 ℃-90 ℃ lower distillations 4-5 hour, at last washing, centrifugation, vacuum-drying obtain the modified carbon nano-tube of acrylamide graft;
Step 3: take monomer and solubility promoter dehydrated alcohol in emulsion synthesizing propylene acid resin, amount to 100 parts, used monomer vinylformic acid: methyl methacrylate: butyl acrylate: acrylamide: the mass ratio of dehydrated alcohol is 1: (4-6): (4-6): (0.4-0.6): (4-6), take by weighing the initiator of monomer and dehydrated alcohol total mass 0.4%, the sodium lauryl sulphate that takes by weighing monomer total mass 3% is as the emulsifying agent of reaction, takes by weighing the carbon nanotube of the acrylamide graft that the step 2 of monomer total mass 0.02% obtains;
Step 4: with basic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide etc. stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, then add ethanol, then, the carbon nanotube of acrylamide graft is dissolved in distilled water and the emulsifying agent, join behind the ultrasonic 5min in the reactor that 1/3rd monomers are housed, heated and stirred, mixing speed is set to 400r/min, when temperature is increased to 75 ℃, add 1/4th initiators that are dissolved in the distilled water, simultaneously, drip remaining 2/3rds amount monomer and remaining 3/4ths initiator solutions with constant pressure funnel, about 1h drips off, wherein, it is complete that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, then be cooled to 60 ℃, add an amount of ammonia neutralization, and regulate pH=6-7, continue to stir 0.5h, be cooled to room temperature and pour out, filter, namely get carbon nano-tube modification water-borne acrylic resin emulsion.
Embodiment three:
Step 1: the purifying of carbon nanotube and modification: at first, be that 95% sulfuric acid and mass concentration are that 68% nitric acid is to mix at 3: 1 by volume with mass concentration, be made into mixed acid solution; Then, carbon nanotube was mixed as 0.025: 1 take mass ratio with mixed acid solution, then supersound process forms stable suspension, soak after 48 hours, refluxed 1 hour at 120 ℃ of heating-condensings, repeatedly wash centrifugation at last until after pH value is 7, to remove the impurity in the carbon nanotube, and make active reactive group on its surface band, obtain carbon nanotube functionalized with carboxylic acid group;
Step 2: with step 1 obtain carboxylated after carbon nanotube and excessive sulfur oxychloride 70 ℃ of lower stirring and refluxing 36 hours, then 85 ℃-90 ℃ lower distillations 5-6 hour, vacuum-drying 8 hours obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used respectively organic solvent (as: tetrahydrofuran (THF)) dissolving, acrylamide is joined constant pressure funnel, the carbon nanotube of chloride joins in the there-necked flask, then in 60-65 ℃ of carbon nanotube that excessive acrylamide is joined chloride, slowly dripping 1-1.5 hour drips off, then continue reaction after 24 hours, 85 ℃-90 ℃ lower distillations 5-6 hour, at last washing, centrifugation, vacuum-drying obtain the modified carbon nano-tube of acrylamide graft;
Step 3: take monomer and solubility promoter dehydrated alcohol in emulsion synthesizing propylene acid resin, amount to 100 parts, used monomer vinylformic acid: methyl methacrylate: butyl acrylate: acrylamide: the mass ratio of dehydrated alcohol is 1: (5-6): (5-6): (0.4-0.6): (4-6), the ammonium persulphate that takes by weighing monomer and dehydrated alcohol total mass 0.5% is initiator, the sodium lauryl sulphate that takes by weighing monomer total mass 4% is as the emulsifying agent of reaction, takes by weighing the carbon nanotube of the acrylamide graft that the step 2 of monomer total mass 0.04% obtains;
Step 4: with basic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide etc. stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, then add ethanol, then, the carbon nanotube of acrylamide graft is dissolved in distilled water and the emulsifying agent, join behind the ultrasonic 5min in the reactor that 1/3rd monomers are housed, heated and stirred, mixing speed is set to 500r/min, when temperature is increased to 70-80 ℃, add 1/4th initiators that are dissolved in the distilled water, simultaneously, drip remaining 2/3rds amount monomer and remaining 3/4ths initiator solutions with constant pressure funnel, about 1h drips off, wherein, it is complete that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, then be cooled to 60 ℃, add an amount of ammonia neutralization, and regulate pH=6-7, continue to stir 0.5h, be cooled to room temperature and pour out, filter, namely make carbon nano-tube modification water-borne acrylic resin emulsion.
Embodiment four:
Step 1: the purifying of carbon nanotube and modification: at first, be that 96% sulfuric acid and mass concentration are that 67% nitric acid is to mix at 1: 1 by volume with mass concentration, be made into mixed acid solution; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, the ultrasonic stable suspension of its formation that makes; Soaked 24 hours again, and then, refluxed 1 hour at 110 ℃ of heating-condensings, washing and centrifugation removing the impurity in the carbon nanotube, and make active reactive group on its surface band until pH value is 6 repeatedly again, obtain carbon nanotube functionalized with carboxylic acid group;
Step 2: the carbon nanotube functionalized with carboxylic acid group that step 1 is obtained and excessive sulfur oxychloride be 60 ℃ of-70 ℃ of lower stirring and refluxing 24 hours, then 85 ℃-90 ℃ lower distillations 3-4 hour, vacuum-drying 6-7 hour, obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used respectively organic solvent (as: tetrahydrofuran (THF)) dissolving, carbon nanotube and excessive acrylamide are joined respectively in there-necked flask and the constant pressure funnel, slowly dripping 1-1.5 hour at 60-65 ℃ drips off, then continue reaction after 24 hours, 85 ℃-90 ℃ lower distillations 3-4 hour, at last washing, centrifugation, vacuum-drying obtained the modified carbon nano-tube of acrylamide graft;
Step 3: take in the monomer of emulsion synthesizing propylene acid resin and solubility promoter dehydrated alcohol and amount to 100 parts, used monomer vinylformic acid: methyl methacrylate: butyl acrylate: acrylamide: the mass ratio of dehydrated alcohol is 1: (2-6): (3-6): (0.3-0.6): (3-6); The ammonium persulphate that takes by weighing monomer and dehydrated alcohol total mass 0.3% is initiator, and the sodium lauryl sulphate that takes by weighing monomer total mass 2% is as the emulsifying agent of reaction, takes by weighing the carbon nanotube of the acrylamide graft that the step 2 of monomer total mass 0.01% obtains;
Step 4: with basic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, then add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the ethanol, heated and stirred, mixing speed is set to 300-500r/min, when being increased to 70-80 ℃, temperature adds 1/4th initiators that are dissolved in the distilled water, to be added drop-wise in the reactor with constant pressure funnel behind the carbon nanotube of acrylamide graft and the ultrasonic 5min of remaining 2/3rds basic monomers, after beginning to drip monomer, slowly and equably drip remaining 3/4ths initiators with constant pressure funnel, about 1h drips off, it is complete that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, then be cooled to 60 ℃, add an amount of ammonia neutralization, and adjusting pH=6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, namely make carbon nano-tube modification water-borne acrylic resin emulsion.
Embodiment five
Step 1: the purifying of carbon nanotube and modification: at first, be that 96% sulfuric acid and mass concentration are that 68% nitric acid is to mix at 2: 1 by volume with mass concentration, be made into mixed acid solution; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, the ultrasonic stable suspension of its formation that makes; Soaked 40 hours again, and then, refluxed 1 hour at 115 ℃ of heating-condensings, washing and centrifugation removing the impurity in the carbon nanotube, and make active reactive group on its surface band until pH value is 6 repeatedly again, obtain carbon nanotube functionalized with carboxylic acid group;
Step 2: the carbon nanotube functionalized with carboxylic acid group that step 1 is obtained and excessive sulfur oxychloride be 60 ℃ of-70 ℃ of lower stirring and refluxing 32 hours, then 85 ℃-90 ℃ lower distillations 5-6 hour, vacuum-drying 7-8 hour, obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used respectively organic solvent (as: tetrahydrofuran (THF)) dissolving, carbon nanotube and excessive acrylamide are joined respectively in there-necked flask and the constant pressure funnel, slowly dripping 1-1.5 hour at 60-65 ℃ drips off, then continue reaction after 24 hours, 85 ℃-90 ℃ lower distillations 4-5 hour, at last washing, centrifugation, vacuum-drying obtained the modified carbon nano-tube of acrylamide graft;
Step 3: take in the monomer of emulsion synthesizing propylene acid resin and solubility promoter dehydrated alcohol and amount to 100 parts, used monomer vinylformic acid: methyl methacrylate: butyl acrylate: acrylamide: the mass ratio of dehydrated alcohol is 1: (3-6): (4-6): (0.4-0.6): (5-6); The ammonium persulphate that takes by weighing monomer and dehydrated alcohol total mass 0.4% is initiator, and the sodium lauryl sulphate that takes by weighing monomer total mass 3% is as the emulsifying agent of reaction, takes by weighing the carbon nanotube of the acrylamide graft that the step 2 of monomer total mass 0.03% obtains;
Step 4: with basic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, then add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the ethanol, heated and stirred, mixing speed is set to 350r/min, when being increased to 70-80 ℃, temperature adds 1/4th initiators that are dissolved in the distilled water, to be added drop-wise in the reactor with constant pressure funnel behind the carbon nanotube of acrylamide graft and the ultrasonic 5min of remaining 2/3rds basic monomers, behind the beginning monomer, slowly and equably drip remaining 3/4ths initiators with constant pressure funnel, about 1h drips off, it is complete that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, then be cooled to 60 ℃, add an amount of ammonia neutralization, and adjusting pH=6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, namely make carbon nano-tube modification water-borne acrylic resin emulsion.
Embodiment six
Step 1: the purifying of carbon nanotube and modification: at first, be that 96% sulfuric acid and mass concentration are that 68% nitric acid is to mix at 3: 1 by volume with mass concentration, be made into mixed acid solution; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, the ultrasonic stable suspension of its formation that makes; Soaked 48 hours again, and then, refluxed 1 hour at 120 ℃ of heating-condensings, washing and centrifugation removing the impurity in the carbon nanotube, and make active reactive group on its surface band until pH value is 6 repeatedly again, obtain carbon nanotube functionalized with carboxylic acid group;
Step 2: the carbon nanotube functionalized with carboxylic acid group that step 1 is obtained and excessive sulfur oxychloride be 60 ℃ of-70 ℃ of lower stirring and refluxing 36 hours, then 85 ℃-90 ℃ lower distillations 5-6 hour, vacuum-drying 7-8 hour, obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used respectively organic solvent (as: tetrahydrofuran (THF)) dissolving, carbon nanotube and excessive acrylamide are joined respectively in there-necked flask and the constant pressure funnel, slowly dripping 1-1.5 hour at 60-65 ℃ drips off, then continue reaction after 24 hours, 85 ℃-90 ℃ lower distillations 5-6 hour, at last washing, centrifugation, vacuum-drying obtained the modified carbon nano-tube of acrylamide graft;
Step 3: take in the monomer of emulsion synthesizing propylene acid resin and solubility promoter dehydrated alcohol and amount to 100 parts, used monomer vinylformic acid: methyl methacrylate: butyl acrylate: acrylamide: the mass ratio of dehydrated alcohol is 1: (5-6): (4-6): (0.5-0.6): (4-6); The ammonium persulphate that takes by weighing monomer and dehydrated alcohol total mass 0.5% is initiator, and the sodium lauryl sulphate that takes by weighing monomer total mass 4% is as the emulsifying agent of reaction, takes by weighing the carbon nanotube of the acrylamide graft that the step 2 of monomer total mass 0.04% obtains;
Step 4: with basic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, then add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the ethanol, heated and stirred, mixing speed is set to 500r/min, when being increased to 70-80 ℃, temperature adds 1/4th initiators that are dissolved in the distilled water, to be added drop-wise in the reactor with constant pressure funnel behind the carbon nanotube of acrylamide graft and the ultrasonic 5min of remaining 2/3rds basic monomers, after beginning to drip monomer, slowly and equably drip remaining 3/4ths initiators with constant pressure funnel, about 1h drips off, it is complete that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, then be cooled to 60 ℃, add an amount of ammonia neutralization, and adjusting pH=6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, namely make carbon nano-tube modification water-borne acrylic resin emulsion.
In repeatedly washing and the centrifugation described in the step 1 of above-described embodiment, refer at first wash, then centrifugation is got rid of clear liquid and is kept solids, then, adding water in solids washes again, then, again centrifugation is removed clear liquid and is kept solids, so repeatedly carry out, until PH reaches the requirement of regulation.
The above only is one embodiment of the present invention, it or not whole or unique embodiment, the conversion of any equivalence that those of ordinary skills take technical solution of the present invention by reading specification sheets of the present invention is claim of the present invention and contains.
Claims (10)
1. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube, its feature may further comprise the steps:
Step 1: with the carbon nanotube of single wall or many walls with after acidic solution mixes take mass ratio as 0.025:1, supersound process is mixed with suspension, leave standstill and soaked 24-48 hour, then heating-condensing refluxes, washing is until pH is neutral repeatedly at last, and centrifugation obtains carbon nanotube functionalized with carboxylic acid group, wherein, described acidic solution refers to that the vitriol oil and concentrated nitric acid are (1-3) according to volume ratio: 1 nitration mixture that forms;
Step 2: with above-mentioned carbon nanotube functionalized with carboxylic acid group successively with excessive sulfur oxychloride, acrylamide reaction, obtain the modified carbon nano-tube of acrylamide graft;
Step 3: the modified carbon nano-tube of the acrylamide graft that step 2 is obtained and coating material for leather with acrylic monomer acrylic resin modified class of polyreaction original position Formed nanotube under the effect of distilled water, emulsifier sodium lauryl sulfate and initiator ammonium persulfate of double bond functional group.
2. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube as claimed in claim 1, it is characterized in that: in step 3, described double bond functional group's acrylic monomer is the mixture that is dissolved in vinylformic acid in the dehydrated alcohol, methyl methacrylate, butyl acrylate, acrylamide, wherein, vinylformic acid: methyl methacrylate: butyl acrylate: acrylamide: the mass ratio of dehydrated alcohol is 1:(2-6): (3-6): (0.3-0.6): (3-6).
3. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube as claimed in claim 2, it is characterized in that: in step 3, the consumption of described emulsifier sodium lauryl sulfate is the 2-4% of acrylic monomer total mass, and the consumption of described initiator ammonium persulfate is the 0.3-0.5% of acrylic monomer and dehydrated alcohol total mass; The consumption of acrylic amide modified carbon nanotube is the 0.01-0.04% of crylic acid resin monomer total mass, the consumption of distilled water is for making acrylic monomer, dehydrated alcohol, emulsifying agent, initiator, distilled water, and the solid content of the system that forms of acrylic amide modified carbon nanotube is 20-30%.
4. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube as claimed in claim 3, it is characterized in that: in step 3, the concrete steps of described polyreaction are: first with acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, then 1/3rd the amount of getting joins in the reactor, then in reactor, add dehydrated alcohol, the carbon nanotube that then will be dissolved in the acrylamide graft in distilled water and the emulsifying agent joins after supersound process in the previous reaction device, take rotating speed as the 300-500r/min heated and stirred, when temperature is increased to 70-80 ℃, in above-mentioned reactor, add 1/4th initiators that are dissolved in the distilled water, simultaneously, drip remaining three/diacrylate class monomer and remaining 3/4ths initiator solutions with constant pressure funnel, wherein, initiator is slightly later to acrylic monomer and drips, after all dripping, be cooled to 60 ℃ after 1 hour at 80 ℃ of constant temperature, adjusting pH is 6-7, after stirring is cooled to room temperature, filters and namely get carbon nano-tube modification water-borne acrylic resin emulsion.
5. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube as claimed in claim 3, it is characterized in that: in step 3, the concrete steps of described polyreaction are: first with acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, then 1/3rd the amount of getting joins in the reactor, then add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the dehydrated alcohol, rotating speed heated and stirred with 300-500r/min, when being increased to 70 ~ 80 ℃, temperature adds 1/4th initiators that are dissolved in the distilled water, then carbon nanotube and remaining 2/3rds monomers with acrylamide graft are added drop-wise in the reactor with dropping funnel behind ultrasonic 5min, after 2/3rds monomers begin to drip, drip remaining 3/4ths initiators, wherein, it is complete that initiator should be slightly later to monomer dropping, after all dripping, be cooled to 60 ℃ after 1 hour at 80 ℃ of constant temperature, regulating pH is 6 ~ 7, after stirring is cooled to room temperature, filters and namely get carbon nano-tube modification water-borne acrylic resin emulsion.
6. such as the preparation method of claim 4 or the in-situ modified crylic acid resin coating material for leather of 5 described carbon nanotubes, it is characterized in that: described step 2 is specially: first with carbon nanotube functionalized with carboxylic acid group and excessive sulfur oxychloride stirring and refluxing, then distillation, vacuum-drying, obtain the carbon nanotube of chloride, the excessive propene acid amides that then will be dissolved in the tetrahydrofuran (THF) slowly is added drop-wise in the carbon nanotube that is dissolved in the chloride in the tetrahydrofuran (THF), and reaction generates the modified carbon nano-tube of acrylamide graft.
7. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube is characterized in that: may further comprise the steps:
Step 1: be 0.025:1 with carbon nanotube with after acidic solution mixes according to mass ratio, processed in ultrasonic 10-20 minute and be mixed with suspension, leave standstill and soaked 24-48 hour, then 110 ℃ of-120 ℃ of heating-condensing backflows 1-2 hour, repeatedly wash at last and separate until pH for neutral, obtain carbon nanotube functionalized with carboxylic acid group, described acidic solution refers to that the vitriol oil and concentrated nitric acid are (1-3) according to volume ratio: 1 nitration mixture that forms;
Step 2: with above-mentioned carbon nanotube functionalized with carboxylic acid group and excessive sulfur oxychloride 60 ℃-70 ℃ lower stirring and refluxing 24-36 hour, then 85 ℃-90 ℃ lower distillations 3-6 hour, obtained the carbon nanotube of chloride in vacuum-drying 6-8 hour; Then, the carbon nanotube of acrylamide and chloride is dissolved with organic solvent tetrahydrofuran respectively, then be added drop-wise in the carbon nanotube that is dissolved in the chloride in the organic solvent the 60-65 ℃ of excessive propene amide solution that will be dissolved in the organic solvent, slowly dripping 1-1.5 hour drips off, then continue reaction 24 hours, again 85 ℃-90 ℃ lower distillations 3-6 hour, at last washing, centrifugation, vacuum-drying obtain the modified carbon nano-tube of acrylamide graft;
Step 3: be 1:(2-6 according to mass ratio): (3-6): (0.3-0.6): (3-6) get acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate, acrylamide and dehydrated alcohol; Take ammonium persulphate as initiator, its consumption is the 0.3-0.5% of acrylic monomer and dehydrated alcohol total mass; With the emulsifying agent of sodium lauryl sulphate as reaction, consumption is the 2-4% of acrylic monomer total mass, get the modified carbon nano-tube of the acrylamide graft that step 2 obtains, consumption is the 0.01-0.04% of acrylic monomer total mass, get distilled water, consumption is that to make the solid content of the system that acrylic monomer, dehydrated alcohol, emulsifying agent, initiator, distilled water and acrylic amide modified carbon nanotube form be 20 ~ 30%;
Step 4: with the acrylic monomer of step 3 preparation: vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, meanwhile, emulsifier sodium lauryl sulfate is dissolved in the mixed solution of distilled water and ethanol, then, the sodium lauryl sulphate of dissolving is joined in the above-mentioned reactor that 1/3rd basic monomers are housed, be to heat under the condition of 300-500r/min at mixing speed, when temperature rises to 70-80 ℃, pour the initiator that is dissolved in 1/4th in the distilled water into, then be added dropwise to simultaneously modified carbon nano-tube and remaining 2/3rds basic monomers and remaining 3/4ths initiators of acrylamide graft, 1h drips off, after dropwising, at 80 ℃ of constant temperature 1h, then be cooled to 60 ℃, adjusting pH is 6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, namely make the in-situ modified crylic acid resin coating material for leather of carbon nanotube.
8. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube as claimed in claim 7 is characterized in that: in described step 4, it is complete that described initiator is slightly later to residue 2/3rds monomer droppings.
9. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube as claimed in claim 7 is characterized in that: in described step 4, regulate pH=6-7 and adopt the mode that drips ammoniacal liquor.
10. the preparation method of the in-situ modified crylic acid resin coating material for leather of carbon nanotube is characterized in that: may further comprise the steps:
Step 1: be 0.025:1 with carbon nanotube with after acidic solution mixes according to mass ratio, processed in ultrasonic 10-20 minute and be mixed with suspension, leave standstill and soaked 24-48 hour, then 110 ℃ of-120 ℃ of heating-condensing backflows 1-2 hour, repeatedly wash at last and separate until pH for neutral, obtain carbon nanotube functionalized with carboxylic acid group, described acidic solution refers to that the vitriol oil and concentrated nitric acid are (1-3) according to volume ratio: 1 nitration mixture that forms;
Step 2: with above-mentioned carbon nanotube functionalized with carboxylic acid group and excessive sulfur oxychloride 60 ℃-70 ℃ lower stirring and refluxing 24-36 hour, then 85 ℃-90 ℃ lower distillations 3-6 hour, obtained the carbon nanotube of chloride in vacuum-drying 6-8 hour; Then, the carbon nanotube of acrylamide and chloride is dissolved with organic solvent tetrahydrofuran respectively, then be added drop-wise in the carbon nanotube that is dissolved in the chloride in the organic solvent at the 60-65 ℃ of excessive propene acid amides that will be dissolved in the organic solvent, slowly dripping 1-1.5 hour drips off, then continue reaction 24 hours, again 85 ℃-90 ℃ lower distillations 3-6 hour, at last washing, centrifugation, vacuum-drying obtain the modified carbon nano-tube of acrylamide graft;
Step 3: be 1:(2-6 according to mass ratio): (3-6): (0.3-0.6): (3-6) get acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate, acrylamide and dehydrated alcohol; Take ammonium persulphate as initiator, its consumption is the 0.3-0.5% of acrylic monomer and dehydrated alcohol total mass; With the emulsifying agent of sodium lauryl sulphate as reaction, consumption is the 2-4% of acrylic monomer total mass, get the modified carbon nano-tube of the acrylamide graft that step 2 obtains, consumption is the 0.01-0.04% of acrylic monomer total mass, get distilled water, consumption is for making acrylic monomer, dehydrated alcohol, emulsifying agent, initiator, distilled water, and the solid content of the system that forms of acrylic amide modified carbon nanotube is 20 ~ 30%;
Step 4: with acrylic monomer: vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, an amount of/3rd of getting joins agitator is housed, reflux condensing tube, in the reactor of thermometer, then add ethanol, then, the modified carbon nano-tube of acrylamide graft is dissolved in distilled water and the emulsifying agent, join in the reactor that 1/3rd basic monomers are housed behind the ultrasonic 5min, heated and stirred, mixing speed is 300-500r/min, when temperature rises to 70-80 ℃, pour 1/4th initiators that are dissolved in the distilled water into, then drip simultaneously remaining 2/3rds monomers and remaining 3/4ths initiators, 1h drips off, it is complete that wherein initiator is later than residue 2/3rds monomer dropping, after dropwising, at 80 ℃ of constant temperature 1h, then be cooled to 60 ℃, adjusting pH is 6-7, continues to stir 0.5h, is cooled to room temperature and pours out, filter, namely get the in-situ modified crylic acid resin coating material for leather of carbon nanotube.
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| CN104119760B (en) * | 2014-06-27 | 2016-07-13 | 太原科技大学 | A kind of carbon nano-tube coating for packer and preparation method thereof |
| CN104194547B (en) * | 2014-08-10 | 2016-05-11 | 朱蕾 | A kind of CNT improves the preparation method of water paint and adhesive anti-flammability |
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