CN102286234A - 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
- Publication number
- CN102286234A CN102286234A CN2011101178421A CN201110117842A CN102286234A CN 102286234 A CN102286234 A CN 102286234A CN 2011101178421 A CN2011101178421 A CN 2011101178421A CN 201110117842 A CN201110117842 A CN 201110117842A CN 102286234 A CN102286234 A CN 102286234A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- acrylamide
- hour
- dissolved
- coating material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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, the preparation method of the in-situ modified crylic acid resin coating material for leather of particularly 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, as good film-forming property, adhesion is strong, production technique is simple and excellent specific property such as with low cost, is subjected to the favor of leather industry, has obtained developing rapidly.Yet common Emulsion acrylic resin films and exists " heat is glutinous, cold short ", shortcoming such as anti-solvent not, and use is restricted.In order to overcome these shortcomings, need carry out more deep research and modification to it, to adapt to the requirement of renewal.
In recent years, both at home and abroad the investigator mostly is conceived to adjust monomeric kind and proportioning and introduces 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 filming, introduces leather nanoparticle, 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 nanotubes, in light weight CNTs) as monodimension nanometer material, hexagonal structure connects perfect carbon nanotube, has that specific surface area is big, 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 toughness reinforcing characteristic of enhancing of nano material can obviously improve the opacifying power of coating, improve tensile strength, elongation at break, 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 prospects.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 and acidic solution with volume ratio be mix at 0.025: 1 after, supersound process is mixed with suspension, leave standstill and soaked 24-48 hour, heat condensing reflux then, it is neutral washing repeatedly at last until PH, and centrifugation obtains carboxylated carbon nanotube, 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 carboxylated carbon nanotube 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 acrylic monomer polyreaction original position under the effect of distilled water, emulsifier sodium lauryl sulfate and initiator ammonium persulfate of band double bond functional group generate the coating material for leather of carbon nano-tube modification crylic acid resin.
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, and carbon nanotube mixes the back and drips the elongation at break that adding can significantly improve resin with monomer.
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, be made into mixed acid solution with mass concentration; Then, is to mix at 0.025: 1 carbon nanotube and mixed acid solution with mass ratio, supersound process forms steady suspension then, soak after 24 hours, heated condensing refluxes 1 hour at 110 ℃, washing centrifugation at last repeatedly is 7 until pH value, to remove the impurity in the carbon nanotube, and make its surface be with active reactive group, obtain carboxylated carbon nanotube;
Step 2: with step 1 obtain carboxylated after carbon nanotube and excessive sulfur oxychloride 60 ℃ of following stirring and refluxing 24 hours, then 85 ℃-90 ℃ distillations 3-4 hour down, vacuum-drying 6-7 hour, obtain the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used organic solvent (as: tetrahydrofuran (THF)) dissolving respectively, 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 drip and dripped off in 1-1.5 hour, then continue reaction after 24 hours, distilled 3-4 hour down at 85 ℃-90 ℃, washing at last, 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 an 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, add ethanol then, then, the carbon nanotube of acrylamide graft is dissolved in distilled water and the emulsifying agent, join behind the ultrasonic 5min and be equipped with in 1/3rd monomeric reactors, 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 intact that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, be cooled to 60 ℃ then, add an amount of ammoniacal liquor neutralization, and regulate pH=6-7, continue to stir 0.5h, be cooled to room temperature and pour out, filter, promptly 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, be made into mixed acid solution with mass concentration; Then, is to mix at 0.025: 1 carbon nanotube and mixed acid solution with mass ratio, supersound process forms steady suspension then, soak after 35 hours, heated condensing refluxes 1 hour at 115 ℃, wash centrifugation at last repeatedly after pH value is 7, to remove the impurity in the carbon nanotube, and make its surface be with active reactive group, obtain carboxylated carbon nanotube;
Step 2: with step 1 obtain carboxylated after carbon nanotube and excessive sulfur oxychloride 65 ℃ of following stirring and refluxing 30 hours, then 85 ℃-90 ℃ distillations 4-5 hour down, vacuum-drying 7-8 hour, obtain the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used organic solvent (as: tetrahydrofuran (THF)) dissolving respectively, 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 drip and dripped off in 1-1.5 hour, then continue reaction after 24 hours, distilled 4-5 hour down at 85 ℃-90 ℃, washing at last, 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, add ethanol then, then, the carbon nanotube of acrylamide graft is dissolved in distilled water and the emulsifying agent, join behind the ultrasonic 5min and be equipped with in 1/3rd monomeric reactors, 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 intact that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, be cooled to 60 ℃ then, add an amount of ammoniacal liquor neutralization, and regulate pH=6-7, continue to stir 0.5h, be cooled to room temperature and pour out, filter, promptly 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, be made into mixed acid solution with mass concentration; Then, is to mix at 0.025: 1 carbon nanotube and mixed acid solution with mass ratio, supersound process forms steady suspension then, soak after 48 hours, heated condensing refluxes 1 hour at 120 ℃, wash centrifugation at last repeatedly after pH value is 7, to remove the impurity in the carbon nanotube, and make its surface be with active reactive group, obtain carboxylated carbon nanotube;
Step 2: with step 1 obtain carboxylated after carbon nanotube and excessive sulfur oxychloride 70 ℃ of following stirring and refluxing 36 hours, then 85 ℃-90 ℃ distillations 5-6 hour down, vacuum-drying 8 hours obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used organic solvent (as: tetrahydrofuran (THF)) dissolving respectively, 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 drip and dripped off in 1-1.5 hour, then continue reaction after 24 hours, distilled 5-6 hour down at 85 ℃-90 ℃, washing at last, 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 an 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, add ethanol then, then, the carbon nanotube of acrylamide graft is dissolved in distilled water and the emulsifying agent, join behind the ultrasonic 5min and be equipped with in 1/3rd monomeric reactors, 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 intact that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, be cooled to 60 ℃ then, add an amount of ammoniacal liquor neutralization, and regulate pH=6-7, continue to stir 0.5h, be cooled to room temperature and pour out, filter, promptly 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, be made into mixed acid solution with mass concentration; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, ultrasonic its formation steady suspension that makes; Soaked 24 hours, then, at 110 ℃ of heating condensing refluxes 1 hour, washing and centrifugation are 6 until pH value repeatedly more again, removing the impurity in the carbon nanotube, and make its surface be with active reactive group, obtain carboxylated carbon nanotube;
Step 2: carboxylated carbon nanotube that step 1 is obtained and excessive sulfur oxychloride be 60 ℃ of-70 ℃ of following stirring and refluxing 24 hours, then 85 ℃-90 ℃ distillations 3-4 hour down, vacuum-drying 6-7 hour, obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used organic solvent (as: tetrahydrofuran (THF)) dissolving respectively, carbon nanotube and excessive acrylamide are joined respectively in there-necked flask and the constant pressure funnel, dripped off in 1-1.5 hour 60-65 ℃ of slow the dropping, then continue reaction after 24 hours, 85 ℃-90 ℃ down distillations 3-4 hour, washing at last, centrifugation, vacuum-drying obtain 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 an 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, add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the ethanol then, 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 intact that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, be cooled to 60 ℃ then, add an amount of ammoniacal liquor neutralization, and adjusting pH=6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, promptly 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, be made into mixed acid solution with mass concentration; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, ultrasonic its formation steady suspension that makes; Soaked 40 hours, then, at 115 ℃ of heating condensing refluxes 1 hour, washing and centrifugation are 6 until pH value repeatedly more again, removing the impurity in the carbon nanotube, and make its surface be with active reactive group, obtain carboxylated carbon nanotube;
Step 2: carboxylated carbon nanotube that step 1 is obtained and excessive sulfur oxychloride be 60 ℃ of-70 ℃ of following stirring and refluxing 32 hours, then 85 ℃-90 ℃ distillations 5-6 hour down, vacuum-drying 7-8 hour, obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used organic solvent (as: tetrahydrofuran (THF)) dissolving respectively, carbon nanotube and excessive acrylamide are joined respectively in there-necked flask and the constant pressure funnel, dripped off in 1-1.5 hour 60-65 ℃ of slow the dropping, then continue reaction after 24 hours, 85 ℃-90 ℃ down distillations 4-5 hour, washing at last, centrifugation, vacuum-drying obtain 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 an 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, add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the ethanol then, 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 intact that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, be cooled to 60 ℃ then, add an amount of ammoniacal liquor neutralization, and adjusting pH=6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, promptly 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, be made into mixed acid solution with mass concentration; Then, the carbon nanotube of getting 0.025 times of relative nitration mixture quality joins in the mixed acid solution, ultrasonic its formation steady suspension that makes; Soaked 48 hours, then, at 120 ℃ of heating condensing refluxes 1 hour, washing and centrifugation are 6 until pH value repeatedly more again, removing the impurity in the carbon nanotube, and make its surface be with active reactive group, obtain carboxylated carbon nanotube;
Step 2: carboxylated carbon nanotube that step 1 is obtained and excessive sulfur oxychloride be 60 ℃ of-70 ℃ of following stirring and refluxing 36 hours, then 85 ℃-90 ℃ distillations 5-6 hour down, vacuum-drying 7-8 hour, obtains the carbon nanotube of chloride; Then, after the carbon nanotube of acrylamide and chloride used organic solvent (as: tetrahydrofuran (THF)) dissolving respectively, carbon nanotube and excessive acrylamide are joined respectively in there-necked flask and the constant pressure funnel, dripped off in 1-1.5 hour 60-65 ℃ of slow the dropping, then continue reaction after 24 hours, 85 ℃-90 ℃ down distillations 5-6 hour, washing at last, centrifugation, vacuum-drying obtain 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 an 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, add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the ethanol then, 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 intact that initiator should be slightly later to monomer dropping, after all dropwising, at 80 ℃ of left and right sides constant temperature 1h, be cooled to 60 ℃ then, add an amount of ammoniacal liquor neutralization, and adjusting pH=6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, promptly make carbon nano-tube modification water-borne acrylic resin emulsion.
In washing repeatedly and the centrifugation described in the step 1 of the foregoing description, be meant at first washing, centrifugation is then got rid of clear liquid solid retained thing, then, adding water in solids again washes, then, clear liquid solid retained thing is removed in centrifugation again, carry out so repeatedly, reach the requirement of regulation until PH.
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 and acidic solution with volume ratio be mix at 0.025: 1 after, supersound process is mixed with suspension, leave standstill and soaked 24-48 hour, heat condensing reflux then, it is neutral washing repeatedly at last until PH, and centrifugation obtains carboxylated carbon nanotube, 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:, obtain the modified carbon nano-tube of acrylamide graft with above-mentioned carboxylated carbon nanotube priority and excessive sulfur oxychloride, acrylamide reaction;
Step 3: the modified carbon nano-tube of the acrylamide graft that step 2 is obtained and the acrylic monomer that has double bond functional group polyreaction original position under the effect of distilled water, emulsifier sodium lauryl sulfate and initiator ammonium persulfate generate the coating material for leather of carbon nano-tube modification crylic acid resin.
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: earlier with acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, an amount of/3rd of getting then joins in the reactor, then in reactor, add dehydrated alcohol, the carbon nanotube that will be dissolved in the acrylamide graft in distilled water and the emulsifying agent then joins after supersound process in the previous reaction device, with the rotating speed is 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 promptly get carbon nano-tube modification water-borne acrylic resin emulsion.
5. the preparation method of carbon nano-tube modification crylic acid resin coating material for leather as claimed in claim 3, it is characterized in that: in step 3, the concrete steps of described polyreaction are: earlier with acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate and acrylamide stir, an amount of/3rd of getting then joins in the reactor, add the emulsifier sodium lauryl sulfate that is dissolved in distilled water and the dehydrated alcohol then, 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, carbon nanotube and remaining 2/3rds monomers with acrylamide graft are added drop-wise in the reactor with dropping funnel behind ultrasonic 5min then, after 2/3rds monomers begin to drip, drip remaining 3/4ths initiators, wherein, it is intact 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 promptly get carbon nano-tube modification water-borne acrylic resin emulsion.
6. 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: earlier with carboxylated carbon nanotube and excessive sulfur oxychloride stirring and refluxing, distillation, vacuum-drying then, obtain the carbon nanotube of chloride, the excessive propene acid amides that will be dissolved in then 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: according to mass ratio be 0.025: 1 with carbon nanotube with after acidic solution mixes, handled in ultrasonic 10-20 minute and be mixed with suspension, leave standstill and soaked 24-48 hour, heated condensing refluxes 1-2 hour at 110 ℃-120 ℃ then, wash repeatedly at last and separate and be neutrality until PH, obtain carboxylated carbon nanotube, 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 carboxylated carbon nanotube and excessive sulfur oxychloride 60 ℃-70 ℃ following stirring and refluxing 24-36 hour, then 85 ℃-90 ℃ distillations 3-6 hour down, 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, 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 then, slowly drip and dripped off in 1-1.5 hour, continue reaction 24 hours then, again 85 ℃-90 ℃ down distillations 3-6 hour, washing at last, centrifugation, vacuum-drying obtain the modified carbon nano-tube of acrylamide graft;
Step 3: according to mass ratio is 1: (2-6): (3-6): (0.3-0.6): (3-6) get acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate, acrylamide and dehydrated alcohol; With the ammonium persulphate is initiator, and 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 distilled water and the alcoholic acid mixed solution, then, the dissolved sodium lauryl sulphate 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, be added dropwise to modified carbon nano-tube and remaining 2/3rds basic monomers and remaining 3/4ths initiators of acrylamide graft then simultaneously, 1h drips off, after dropwising, at 80 ℃ of constant temperature 1h, be cooled to 60 ℃ then, adjusting pH is 6-7, continue to stir 0.5h, being cooled to room temperature pours out, filter, promptly 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 intact 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 the mode that pH=6-7 adopts dropping ammonia.
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: according to mass ratio be 0.025: 1 with carbon nanotube with after acidic solution mixes, handled in ultrasonic 10-20 minute and be mixed with suspension, leave standstill and soaked 24-48 hour, heated condensing refluxes 1-2 hour at 110 ℃-120 ℃ then, wash repeatedly at last and separate and be neutrality until PH, obtain carboxylated carbon nanotube, 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 carboxylated carbon nanotube and excessive sulfur oxychloride 60 ℃-70 ℃ following stirring and refluxing 24-36 hour, then 85 ℃-90 ℃ distillations 3-6 hour down, 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, 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 then, slowly drip and dripped off in 1-1.5 hour, continue reaction 24 hours then, again 85 ℃-90 ℃ down distillations 3-6 hour, washing at last, centrifugation, vacuum-drying obtain the modified carbon nano-tube of acrylamide graft;
Step 3: according to mass ratio is 1: (2-6): (3-6): (0.3-0.6): (3-6) get acrylic monomer vinylformic acid, methyl methacrylate, butyl acrylate, acrylamide and dehydrated alcohol; With the ammonium persulphate is initiator, and 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, add ethanol then, 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, drip remaining 2/3rds monomers and remaining 3/4ths initiators then simultaneously, 1h drips off, it is intact that wherein initiator is later than residue 2/3rds monomer dropping, after dropwising, at 80 ℃ of constant temperature 1h, be cooled to 60 ℃ then, adjusting pH is 6-7, continues to stir 0.5h, is cooled to room temperature and pours out, filter, promptly get the in-situ modified crylic acid resin coating material for leather of carbon nanotube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110117842 CN102286234B (en) | 2011-05-09 | 2011-05-09 | Preparation method of modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110117842 CN102286234B (en) | 2011-05-09 | 2011-05-09 | Preparation method of modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102286234A true CN102286234A (en) | 2011-12-21 |
| CN102286234B CN102286234B (en) | 2013-03-20 |
Family
ID=45332999
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110117842 Expired - Fee Related CN102286234B (en) | 2011-05-09 | 2011-05-09 | Preparation method of modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102286234B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160178A (en) * | 2013-04-12 | 2013-06-19 | 段宝荣 | Preparation method of carbon nanometer-tube modified acrylic resin light-resistant paint |
| CN104119760A (en) * | 2014-06-27 | 2014-10-29 | 苏州市盛百威包装设备有限公司 | Carbon nanotube coating for packing machine and preparation method thereof |
| CN104194547A (en) * | 2014-08-10 | 2014-12-10 | 朱蕾 | Preparation method for improving flame retardance of water-based paint and adhesive by virtue of carbon nanotubes |
| CN109608780A (en) * | 2018-12-31 | 2019-04-12 | 王爱绿 | A kind of flame-retardant expanded insulating board for building and preparation method thereof |
| CN112708316A (en) * | 2020-12-29 | 2021-04-27 | 广州集泰化工股份有限公司 | Water-based indoor intumescent fire-retardant coating for steel structure and preparation method thereof |
| CN113201262A (en) * | 2021-04-20 | 2021-08-03 | 南昌荣腾实业有限公司 | Amorphous nano anti-abrasion and anti-corrosion ceramic coating |
| CN113428893A (en) * | 2021-07-14 | 2021-09-24 | 陕西科技大学 | Carboxylation modified nano titanium dioxide ultraviolet screening agent and preparation method thereof |
| CN114106652A (en) * | 2022-01-10 | 2022-03-01 | 刘新霞 | Environment-friendly latex paint and preparation method thereof |
| CN117364500A (en) * | 2023-10-10 | 2024-01-09 | 东莞市粤雄纺织品有限公司 | Anhydrous dyeing preparation process of color-changing yarn and yarn prepared by same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
| WO2004001107A2 (en) * | 2002-06-19 | 2003-12-31 | The Board Of Regents Of The University Of Oklahoma | Carbon nanotube-filled composites |
| CN101104512A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Method for preparing macromolecule modified carbon nano-tube and application thereof |
-
2011
- 2011-05-09 CN CN 201110117842 patent/CN102286234B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1410455A (en) * | 2002-03-14 | 2003-04-16 | 四川大学 | Preparation method of polymer/carbon nano pipe composite emulsion and its in situ emulsion polymerization |
| WO2004001107A2 (en) * | 2002-06-19 | 2003-12-31 | The Board Of Regents Of The University Of Oklahoma | Carbon nanotube-filled composites |
| CN101104512A (en) * | 2006-07-14 | 2008-01-16 | 同济大学 | Method for preparing macromolecule modified carbon nano-tube and application thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103160178A (en) * | 2013-04-12 | 2013-06-19 | 段宝荣 | Preparation method of carbon nanometer-tube modified acrylic resin light-resistant paint |
| CN104119760A (en) * | 2014-06-27 | 2014-10-29 | 苏州市盛百威包装设备有限公司 | Carbon nanotube coating for packing machine and preparation method thereof |
| 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 |
| CN104194547A (en) * | 2014-08-10 | 2014-12-10 | 朱蕾 | Preparation method for improving flame retardance of water-based paint and adhesive by virtue of carbon nanotubes |
| CN109608780A (en) * | 2018-12-31 | 2019-04-12 | 王爱绿 | A kind of flame-retardant expanded insulating board for building and preparation method thereof |
| CN112708316A (en) * | 2020-12-29 | 2021-04-27 | 广州集泰化工股份有限公司 | Water-based indoor intumescent fire-retardant coating for steel structure and preparation method thereof |
| CN113201262A (en) * | 2021-04-20 | 2021-08-03 | 南昌荣腾实业有限公司 | Amorphous nano anti-abrasion and anti-corrosion ceramic coating |
| CN113428893A (en) * | 2021-07-14 | 2021-09-24 | 陕西科技大学 | Carboxylation modified nano titanium dioxide ultraviolet screening agent and preparation method thereof |
| CN114106652A (en) * | 2022-01-10 | 2022-03-01 | 刘新霞 | Environment-friendly latex paint and preparation method thereof |
| CN117364500A (en) * | 2023-10-10 | 2024-01-09 | 东莞市粤雄纺织品有限公司 | Anhydrous dyeing preparation process of color-changing yarn and yarn prepared by same |
| CN117364500B (en) * | 2023-10-10 | 2024-04-16 | 东莞市粤雄纺织品有限公司 | Anhydrous dyeing preparation process of color-changing yarn and yarn prepared by same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102286234B (en) | 2013-03-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102286234B (en) | Preparation method of modified acrylic resin leather coating material of carbon nano tubes (CNTs) in situ | |
| CN102040714B (en) | Preparation method of polymer-grafted graphene | |
| CN100591735C (en) | Method of preparing organic/inorganic hybridization reactivity semi-interpenetrating network structure emulsion | |
| CN103992421B (en) | The preparation method of Pickering acrylate polymer emulsions | |
| CN102206395B (en) | Preparation method and application of nano-montmorillonite/polyacrylate composite material | |
| CN102304204A (en) | Fluorine-containing bi-functional microspheres and application thereof | |
| CN102604006A (en) | Preparation method for acidic silica sol in-situ modified acrylate emulsion | |
| CN105131332B (en) | A kind of method of surface grafting polymerization thing modified carbon fiber | |
| CN101514090B (en) | Ornamental model external thermal insulation rendering mortar composition | |
| CN103254365B (en) | Method for preparing ASA (Acrylonitrile-Styrene-Acrylate) copolymer latex by using water-solubility redox initiator at low temperature | |
| US20200216619A1 (en) | End-group functionalized comb structure polycarboxylic acid and method for preparing the same | |
| CN106674442A (en) | Water-based fluorosilicone acrylic resin and preparation method thereof | |
| CN102140217B (en) | Preparation method and use of polyacrylate/silica solution composite material | |
| CN101275051A (en) | Acroid resin coating agent and preparation thereof | |
| CN103303909B (en) | Method for preparing hydrophilic graphene with pH sensitivity | |
| CN104831364B (en) | A kind of modified method in calcium sulfate crystal whiskers surface | |
| CN103980431A (en) | Amphoteric polycarboxylic-acid water reducer and synthesis thereof | |
| CN105732439A (en) | Multi-sulfonic-acid-group acidic functionalized ionic liquid and preparation method thereof | |
| CN104292391A (en) | Melting production method for unsaturated anhydride grafted chlorinated polyethylene | |
| CN102887977B (en) | Production method of styrene modified carboxylic butadiene-acrylonitrite latex | |
| CN102489215A (en) | Amphoteric reaction-type surfactant and preparation method thereof | |
| DE3390062T1 (en) | Process for the preparation of amidoalkanesulfonic acids and derivatives thereof | |
| WO2010066193A1 (en) | Method for preparing polyvinyl alcohol and polyvinyl acetate latex by use of the bottom residue from vinyl acetate production process | |
| CN101805275A (en) | Method for synthesizing sodium methyl allylsulfonate | |
| CN107129561B (en) | The preparation method of the stable fluoropolymer emulsion of nano-micelle containing Ag |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130320 Termination date: 20210509 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |