CN102504309A - Polyaniline-coated urea-formaldehyde resin nanoparticles and preparation method thereof - Google Patents
Polyaniline-coated urea-formaldehyde resin nanoparticles and preparation method thereof Download PDFInfo
- Publication number
- CN102504309A CN102504309A CN201110392358XA CN201110392358A CN102504309A CN 102504309 A CN102504309 A CN 102504309A CN 201110392358X A CN201110392358X A CN 201110392358XA CN 201110392358 A CN201110392358 A CN 201110392358A CN 102504309 A CN102504309 A CN 102504309A
- Authority
- CN
- China
- Prior art keywords
- polyaniline
- urea
- formaldehyde resin
- resin nano
- preparation
- 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
- 229920001807 Urea-formaldehyde Polymers 0.000 title claims abstract description 64
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 title claims abstract description 64
- 229920000767 polyaniline Polymers 0.000 title claims abstract description 58
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000011248 coating agent Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000006185 dispersion Substances 0.000 claims abstract description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 64
- 238000003756 stirring Methods 0.000 claims description 37
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000376 reactant Substances 0.000 claims description 12
- 206010013786 Dry skin Diseases 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- 150000002978 peroxides Chemical class 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229920001940 conductive polymer Polymers 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000011247 coating layer Substances 0.000 abstract 1
- 230000007797 corrosion Effects 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- 235000019395 ammonium persulphate Nutrition 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- OIRDTQYFTABQOQ-UHTZMRCNSA-N Vidarabine Chemical compound C1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@@H]1O OIRDTQYFTABQOQ-UHTZMRCNSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 210000000617 arm Anatomy 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Abstract
The invention relates to a polyaniline-coated nanoparticle composite material and a preparation method thereof and belongs to the technical fields of metal corrosion resistance and electromagnetic shielding. The method comprises the following steps: firstly preparing urea-formaldehyde resin nanoparticles and then generating a polyaniline coating film on the surfaces of the urea-formaldehyde resin nanoparticles. The polyaniline-coated urea-formaldehyde resin nanoparticles prepared by the preparation method disclosed by the invention have excellent properties of enabling the polyaniline film to be firmly attached on the surface of the resin, being high in conductivity, facilitating the formation of a dispersion system and the like. The polyaniline-coated nanoparticle composite material can be used for materials of conductive coating layers or be used for directly preparing conductive polymer thin film materials.
Description
Technical field:
The present invention relates to a kind of polyaniline encapsulated nanoparticles matrix material and preparation method thereof, belong to anti-corrosion of metal and electromagnetic shielding art neighborhood.
Background technology:
Polyaniline is with its good thermostability; Chemicalstability and electrochemical reversibility, good electromagnetic microwave absorptive character, potential solution and melt-processable; Raw material is easy to get; Simple synthetic method also has unique characteristics such as doping phenomenon, becomes one of the fastest conducting polymer composite of present progress.With it is base mateiral, is developing many new technologies at present, and for example overall plastic anti-corrosion of metal technology, marine antifouling are technological, solar cell, electromangnetic spectrum, antistatic technology, electrochromism, sensor element, electrode materials and stealthy technique etc.But no matter be all to be powder, be difficult to the processing that is shaped, done various trials around the modification of above problem people's p-poly-phenyl amine through the chemical oxidation or the polyaniline of electrochemical oxidation gained.The exploitation water colloidal dispersion system that is wherein at first put forward by Vincent and Armes etc. is to solve the important method that is difficult to the forming process shortcoming.At present, people have developed polyaniline coating inorganic nanoparticles (SiO for example
2, TiO
2, WC etc.) etc. material, polyaniline coats organic nanometer granule materials such as (for example PS, APS etc.).These materials that have polyaniline to coat can solve the processibility of polyaniline to a certain extent, and improve the erosion resistance of body material.
Summary of the invention:
The object of the invention is to provide a kind of polyaniline and coats urea-formaldehyde resin nano particle and preparation method thereof, and the nano particle of preparation has physical properties to stablize, electric conductivity is high, under the situation of sterically hindered dose of existence, be prone to form stable polyaniline nano colloidal dispersion system.
Technical scheme of the present invention is that the urea-formaldehyde resin nano grain surface coats polyaniline, and the thickness of polyaniline layer is 1～2nm, and it is 700nm～1 μ m that the urea-formaldehyde resin nano grain surface coats the polyaniline particle grain size.At first be preparation urea-formaldehyde resin nano particle, generate the polyaniline coating film at the urea-formaldehyde resin nano grain surface then.
Preparation urea-formaldehyde resin nano particle concrete steps comprise as follows:
(1) with 1:1 in molar ratio～2.3 of urea and formaldehyde, urea is dissolved in the formaldehyde at normal temperatures, with the pH value of water-soluble alkali regulator solution; Make its pH value adjust to 7.5～8.5; Solution is heated to 65 ℃～80 ℃, kept 1～3 hour, add the deionized water of 2～3 times of formaldehyde volumes again; Cool to room temperature obtains the performed polymer of urea-formaldehyde resin;
The stirring velocity of (2) performed polymer being pressed 2000r/min～3000r/min stirs, and till whipped state lasts till that this step reaction is accomplished, in the process that stirs, adds the deionized water of 2～3 times of performed polymer volumes; Dripping hydrochloric acid; In 45min～75min, PH is transferred between 2.5～4.5, is warmed to 65 ℃～80 ℃ reactions 1～3 hour again, this step reaction finishes; The product that obtains is regulated PH to 7～7.5 with sodium hydroxide; Filter then, with deionized water wash 3～5 times, centrifugal collection urea-formaldehyde resin nano particle, the dispersion agent that the urea-formaldehyde resin nano particle is added massfraction 1% is dispersed in the aqueous systems to be preserved;
The preparation process that the urea-formaldehyde resin nano grain surface generates the polyaniline coating film comprises as follows:
(3) under the stir speed (S.S.) of 400～1000r/min, be 1～2.5 sour thorough mixing with aniline solution and pH value, be that 10～45% urea-formaldehyde resin nano particle adds in the above-mentioned reactant with the aniline mass percent then; Dispersed with stirring 20～30min; To in one hour, divide with the oxygenant of aniline mol ratio 1:1 then to be added drop-wise to for ten times in the above-mentioned reactant, keep whipped state 8～24 hours, and stop to stir; HCl with 0.2mol/L washes 3 ~ 4 times at last; Use the acetone rinsing 3 ~ 4 times of 0.2mol/L again, after 45 ℃ of dryings, the product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle;
The process that urea-formaldehyde resin nano grain surface of the present invention generates the polyaniline coating film can also be: under the stir speed (S.S.) of 100r/min～300r/min, be 1～2.5 sour thorough mixing with aniline solution and pH value, products therefrom is A; Be that 10%～45% urea-formaldehyde resin nano particle mixes with the oxygenant of aniline mol ratio 1:1 and forms product B with the aniline mass percent; Under the whipped state of 400r/min～1000r/min; In one hour, divide and ten times B is added drop-wise among the A; Reacted 8～24 hours, and, used the acetone rinsing 3 ~ 4 times of 0.2M/L more at last with the HCl of 0.2M/L flushing 3 ~ 4 times; After 45 ℃ of dryings, the product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle;
Water-soluble alkali in the said step (1) is a sodium hydroxide, trolamine, any one in the Pottasium Hydroxide.
Said dispersion agent is any one in commercially available sodium lauryl sulphate, the polyoxyethylene glycol.
The aniline solution mass concentration is in the said step (3): 2% ~ 3.5%.
Described acid is: mineral acid: hydrochloric acid, sulfuric acid, perchloric acid, nitric acid etc.; Organic acid: any one in acetic acid, tosic acid, the alkylsulphonic acid etc.
Said oxygenant is any one in ammonium persulfate, ydrogen peroxide 50, iron trichloride, the permanganic acid.
The pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the said step (3).
Said reagent is CP.
Advantage of the present invention and positively effect:
The urea-formaldehyde resin nano particle that polyaniline coats has improved the workability of polyaniline, can make the dispersion system of nano particle, the preparation that conveniently prepares coating; The urea-formaldehyde resin nano particle that also can p-poly-phenyl amine coats carries out mechanical compaction and is shaped, and the sample that is prepared into has higher mechanical properties and electric conductivity.
Embodiment:
Embodiment 1:
(1) with the 1:1 in molar ratio of urea and formaldehyde, urea is dissolved in the formaldehyde at normal temperatures, with the pH value of sodium hydrate regulator solution; Make its pH value adjust to 7.5; Solution is heated to 70 ℃, kept 1 hour, add the deionized water of 2 times of formaldehyde volumes again; Cool to room temperature obtains the performed polymer of urea-formaldehyde resin;
The stirring velocity of (2) performed polymer being pressed 2000r/min stirs, and till whipped state lasts till that this step reaction is accomplished, in the process that stirs, adds the deionized water of 2 times of performed polymer volumes; Dripping hydrochloric acid; In 45min, PH is transferred to 2.5, is warmed to 65 ℃ of reactions 2 hours again, this step reaction finishes; The product that obtains is regulated PH to 7 with sodium hydroxide; Filter then, with deionized water wash 4 times, centrifugal collection urea-formaldehyde resin nano particle, the sodium lauryl sulphate that the urea-formaldehyde resin nano particle is added massfraction 1% is dispersed in the aqueous systems preserves;
(3) under the stir speed (S.S.) of 800r/min, be that 2% aniline solution and pH value are 2.5 hydrochloric acid thorough mixing with concentration, be that 10% urea-formaldehyde resin nano particle adds in the above-mentioned reactant with the aniline mass percent then; Dispersed with stirring 20min will divide with the ammonium persulphate of aniline mol ratio 1:1 to be added drop-wise to for ten times in the above-mentioned reactant then in one hour, keep whipped state 8 hours; Stop to stir, the HCl with 0.2mol/L washes 4 times at last, uses the acetone rinsing 3 times of 0.2mol/L again; After 45 ℃ of dryings; The product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle, records the gained particle, and particle diameter is mainly between 700nm～1 μ m; Film thickness is 1nm, electric conductivity: 0.24S/cm.The pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the step (3).
Embodiment 2:
(1) with the 1:2 in molar ratio of urea and formaldehyde, urea is dissolved in the formaldehyde at normal temperatures, with the pH value of trolamine regulator solution; Make its pH value adjust to 8; Solution is heated to 65 ℃, kept 2 hours, add the deionized water of 2.5 times of formaldehyde volumes again; Cool to room temperature obtains the performed polymer of urea-formaldehyde resin;
The stirring velocity of (2) performed polymer being pressed 2400r/min stirs, and till whipped state lasts till that this step reaction is accomplished, in the process that stirs, adds the deionized water of 2.5 times of performed polymer volumes; Dripping hydrochloric acid; In 50min, PH is transferred to 3, is warmed to 70 ℃ of reactions 1 hour again, this step reaction finishes; The product that obtains is regulated PH to 7.2 with sodium hydroxide; Filter then, with deionized water wash 3 times, centrifugal collection urea-formaldehyde resin nano particle, the polyoxyethylene glycol that the urea-formaldehyde resin nano particle is added massfraction 1% is dispersed in the aqueous systems to be preserved;
(3) under the stir speed (S.S.) of 400r/min, be that 3% aniline solution and pH value are 1 sulfuric acid thorough mixing with concentration, be that 30% urea-formaldehyde resin nano particle adds in the above-mentioned reactant with the aniline mass percent then; Dispersed with stirring 25min will divide with the ydrogen peroxide 50 of aniline mol ratio 1:1 to be added drop-wise to for ten times in the above-mentioned reactant then in one hour, keep whipped state 20 hours; Stop to stir, the HCl with 0.2mol/L washes 3 times at last, uses the acetone rinsing 4 times of 0.2mol/L again; After 45 ℃ of dryings; The product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle, records the gained particle, and particle diameter is mainly between 1 μ m～1.5 μ m; Film thickness is 2nm, electric conductivity: 1.3 * 10
-2S/cm.The pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the step (3).
Embodiment 3:
(1) with the 1:2.3 in molar ratio of urea and formaldehyde, urea is dissolved in the formaldehyde at normal temperatures, with the pH value of trolamine regulator solution; Make its pH value adjust to 8.5; Solution is heated to 80 ℃, kept 3 hours, add the deionized water of 3 times of formaldehyde volumes again; Cool to room temperature obtains the performed polymer of urea-formaldehyde resin;
The stirring velocity of (2) performed polymer being pressed 3000r/min stirs, and till whipped state lasts till that this step reaction is accomplished, in the process that stirs, adds the deionized water of 3 times of performed polymer volumes; Dripping hydrochloric acid; In 75min, PH is transferred to 4.5, is warmed to 80 ℃ of reactions 3 hours again, this step reaction finishes; The product that obtains is regulated PH to 7.5 with sodium hydroxide; Filter then, with deionized water wash 5 times, centrifugal collection urea-formaldehyde resin nano particle, the polyoxyethylene glycol that the urea-formaldehyde resin nano particle is added massfraction 1% is dispersed in the aqueous systems to be preserved;
(3) under the stir speed (S.S.) of 1000r/min, be that 3.5% aniline solution and pH value are 1 sulfuric acid thorough mixing with concentration, be that 45% urea-formaldehyde resin nano particle adds in the above-mentioned reactant with the aniline mass percent then; Dispersed with stirring 30min will divide with the ydrogen peroxide 50 of aniline mol ratio 1:1 to be added drop-wise to for ten times in the above-mentioned reactant then in one hour, keep whipped state 24 hours; Stop to stir, the HCl with 0.2mol/L washes 3 times at last, uses the acetone rinsing 4 times of 0.2mol/L again; After 45 ℃ of dryings; The product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle, records the gained particle, and particle diameter is mainly between 1.5 μ m～700 μ m; Film thickness is 1.2nm, electric conductivity: 1.2 * 10
-2S/cm.The pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the step (3).
Embodiment 4:
Identical with step (2) with embodiment 1 step (1), wherein water-soluble alkali adopts Pottasium Hydroxide, and perchloric acid is adopted in acid; Oxygenant adopts iron trichloride; Step (3) is as follows: under the stir speed (S.S.) of 100r/min, be 1 sour thorough mixing with aniline solution and pH value, products therefrom is A; Be that 10% urea-formaldehyde resin nano particle mixes with the oxygenant of aniline mol ratio 1:1 and forms product B with the aniline mass percent; Under the whipped state of 800r/min, in one hour, divide ten times B to be added drop-wise among the A, reacted 8 hours; At last with the HCl of 0.2M/L flushing 3 times, use the acetone rinsing 4 times of 0.2M/L again, after 45 ℃ of dryings; The product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle, records the gained particle, and particle diameter is mainly between 700nm～1 μ m; Film thickness is 1nm, electric conductivity: 0.23S/cm.The pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the step (3).
Embodiment 5:
Identical with step (2) with embodiment 2 steps (1), wherein nitric acid is adopted in acid, and oxygenant adopts permanganic acid, step (3) as follows: under the stir speed (S.S.) of 200r/min, be 2 sour thorough mixing with aniline solution and pH value, products therefrom is A; Be that 30% urea-formaldehyde resin nano particle mixes with the oxygenant of aniline mol ratio 1:1 and forms product B with the aniline mass percent; Under the whipped state of 400r/min, in one hour, divide ten times B to be added drop-wise among the A, reacted 20 hours; At last with the HCl of 0.2M/L flushing 4 times, use the acetone rinsing 3 times of 0.2M/L again, after 45 ℃ of dryings; The product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle, records the gained particle, and particle diameter is mainly between 1000nm～1 μ m; Film thickness is 1nm, electric conductivity: 0.13S/cm.The pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the step (3).
Embodiment 6:
Identical with step (2) with embodiment 3 steps (1), wherein acetic acid is adopted in acid, step (3) as follows: under the stir speed (S.S.) of 300r/min, be 2.5 sour thorough mixing with aniline solution and pH value, products therefrom is A; Be that 45% urea-formaldehyde resin nano particle mixes with the oxygenant of aniline mol ratio 1:1 and forms product B with the aniline mass percent; Under the whipped state of 1000r/min, in one hour, divide ten times B to be added drop-wise among the A, reacted 24 hours; At last with the HCl of 0.2M/L flushing 4 times, use the acetone rinsing 3 times of 0.2M/L again, after 45 ℃ of dryings; The product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle, records the gained particle, and particle diameter is mainly between 1000nm～1 μ m; Film thickness is 1nm, electric conductivity: 0.22S/cm.The pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the step (3).
Embodiment 7:
Identical with embodiment 4 said steps, wherein tosic acid is adopted in acid, finally obtain product be polyaniline and coat the urea-formaldehyde resin nano particle, record the gained particle, mainly between 800nm～1 μ m, film thickness is 2nm to particle diameter, electric conductivity: 1.4 * 10
-2S/cm.
Embodiment 8:
Identical with embodiment 5 said steps, wherein acid is adopted alkylsulphonic acid, finally obtain product be polyaniline and coat the urea-formaldehyde resin nano particle; Record the gained particle; Mainly between 800nm～1 μ m, film thickness is 1.5nm to particle diameter, electric conductivity: 1.6 * 10
-2S/cm.
Claims (9)
1. polyaniline encapsulated nanoparticles matrix material is characterized in that: the urea-formaldehyde resin nano grain surface coats polyaniline, and the thickness of polyaniline layer is 1～2nm.
2. according to claims 1 described polyaniline encapsulated nanoparticles matrix material, it is characterized in that: it is 700nm～1 μ m that the urea-formaldehyde resin nano grain surface coats the polyaniline particle grain size.
3. the preparation method of a polyaniline encapsulated nanoparticles matrix material is characterized in that: concrete preparation process comprises as follows:
(1) with 1:1 in molar ratio～2.3 of urea and formaldehyde, urea is dissolved in the formaldehyde at normal temperatures, with the pH value of water-soluble alkali regulator solution; Make its pH value adjust to 7.5～8.5; Solution is heated to 65 ℃～80 ℃, kept 1～3 hour, add the deionized water of 2 times of formaldehyde volumes again; Cool to room temperature obtains the performed polymer of urea-formaldehyde resin;
The stirring velocity of (2) performed polymer being pressed 2000r/min～3000r/min stirs; Till whipped state lasts till that this step reaction is accomplished, in the process that stirs, add the deionized water of 2～3 times of performed polymer volumes, dripping hydrochloric acid; In 45min～75min, PH is transferred between 2.5～4.5; Be warmed to 65 ℃～80 ℃ reactions 1～3 hour again, then the product that obtains regulated PH to 7～7.5 with sodium hydroxide, filter then, with deionized water wash 3～5 times; Centrifugal collection urea-formaldehyde resin nano particle adds the urea-formaldehyde resin nano particle in the aqueous systems of the dispersion agent contain massfraction 1% and preserves;
The urea-formaldehyde resin nano grain surface generates the preparation process of polyaniline coating film and passes through as follows:
(3) under the stir speed (S.S.) of 400r/min～1000r/min, be 1～2.5 sour thorough mixing with aniline solution and pH value, will be with the aniline mass percent then: 10%～45% urea-formaldehyde resin nano particle adds in the above-mentioned reactant; Dispersed with stirring 20min～30min; To become the oxygenant of amount 1:1 mol ratio in one hour, to divide with aniline and be added drop-wise to for ten times in the above-mentioned reactant, keep whipped state 8～24 hours, and stop to stir; HCl with 0.2M/L washes 3 ~ 4 times at last; Use the acetone rinsing 3 ~ 4 times of 0.2M/L again, 45 ℃ of dryings in the moisture eliminator, the product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle;
The urea-formaldehyde resin nano grain surface generates the preparation process of polyaniline coating film and can also pass through as follows:
(3) under the stir speed (S.S.) of 400～1000r/min, be 1～2.5 sour thorough mixing with aniline solution and pH value, be that 10～45% urea-formaldehyde resin nano particle adds in the above-mentioned reactant with the aniline mass percent then; Dispersed with stirring 20～30min; To in one hour, divide with the oxygenant of aniline mol ratio 1:1 then to be added drop-wise to for ten times in the above-mentioned reactant, keep whipped state 8～24 hours, and stop to stir; HCl with 0.2mol/L washes 3 ~ 4 times at last; Use the acetone rinsing 3 ~ 4 times of 0.2mol/L again, after 45 ℃ of dryings, the product that obtains is polyaniline and coats the urea-formaldehyde resin nano particle.
4. according to the preparation method of claims 2 described polyaniline encapsulated nanoparticles matrix materials, it is characterized in that: the water-soluble alkali in the said step (1) is a sodium hydroxide, trolamine, any one in the Pottasium Hydroxide.
5. according to the preparation method of claims 2 described polyaniline encapsulated nanoparticles matrix materials, it is characterized in that: the dispersion agent in the said step (2) is any one in sodium lauryl sulphate, the polyoxyethylene glycol.
6. according to the preparation method of claims 2 described polyaniline encapsulated nanoparticles matrix materials, it is characterized in that: the aniline solution mass concentration is in the said step (3): 2% ~ 3.5%.
7. according to the preparation method of claims 2 described polyaniline encapsulated nanoparticles matrix materials, it is characterized in that described acid is: any one in hydrochloric acid, sulfuric acid, perchloric acid, nitric acid, acetic acid, tosic acid or the alkylsulphonic acid.
8. according to the preparation method of claims 2 described polyaniline encapsulated nanoparticles matrix materials, it is characterized in that: said oxygenant is any one in ammonium persulfate, ydrogen peroxide 50, iron trichloride or the permanganic acid.
9. according to the preparation method of claims 2 described polyaniline encapsulated nanoparticles matrix materials, it is characterized in that: the pH value of urea-formaldehyde resin nano grain surface generation polyaniline coating film whole process remains 0.5～2.5 in the said step (3).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110392358.XA CN102504309B (en) | 2011-12-01 | 2011-12-01 | Polyaniline-coated urea-formaldehyde resin nanoparticles and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110392358.XA CN102504309B (en) | 2011-12-01 | 2011-12-01 | Polyaniline-coated urea-formaldehyde resin nanoparticles and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102504309A true CN102504309A (en) | 2012-06-20 |
| CN102504309B CN102504309B (en) | 2015-01-28 |
Family
ID=46216447
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110392358.XA Expired - Fee Related CN102504309B (en) | 2011-12-01 | 2011-12-01 | Polyaniline-coated urea-formaldehyde resin nanoparticles and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504309B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110374529A (en) * | 2019-06-25 | 2019-10-25 | 四川广阳环保科技有限公司 | A kind of recovery and treatment method of well drilling detritus and products thereof and application |
| CN113382621A (en) * | 2021-05-18 | 2021-09-10 | 浙江工业大学 | Preparation method of high-conductivity MXene/silver nanowire composite electromagnetic shielding film |
| CN115504843A (en) * | 2022-09-19 | 2022-12-23 | 西安近代化学研究所 | Coating method of ammonium perchlorate triethylene diamine perchlorate complex salt |
| CN117126573A (en) * | 2023-10-25 | 2023-11-28 | 江苏新福乐威涂料有限公司 | Anti-fouling wear-resistant nano fluorocarbon coating and preparation method thereof |
-
2011
- 2011-12-01 CN CN201110392358.XA patent/CN102504309B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| H. J. CHOI¤, Y. H. LEE, C. A. KIM: "Microencapsulated polyaniline particles for electrorheological materials", 《JOURNAL OF MATERIALS SCIENCE LETTERS》 * |
| K. S. KIM，J. Y. LEE，B. J. PARK: "Synthesis and characteristics of microcapsules containing electrophoretic particle suspensions", 《COLLOID POLYM SCI》 * |
| Y.H.LEE，C.A.KIM，W.H.JANG: "Synthesis and electrorheological characteristics of microencapsulated polyaniline particles with melamine formaldehyde resins", 《POLYMER》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110374529A (en) * | 2019-06-25 | 2019-10-25 | 四川广阳环保科技有限公司 | A kind of recovery and treatment method of well drilling detritus and products thereof and application |
| CN113382621A (en) * | 2021-05-18 | 2021-09-10 | 浙江工业大学 | Preparation method of high-conductivity MXene/silver nanowire composite electromagnetic shielding film |
| CN115504843A (en) * | 2022-09-19 | 2022-12-23 | 西安近代化学研究所 | Coating method of ammonium perchlorate triethylene diamine perchlorate complex salt |
| CN117126573A (en) * | 2023-10-25 | 2023-11-28 | 江苏新福乐威涂料有限公司 | Anti-fouling wear-resistant nano fluorocarbon coating and preparation method thereof |
| CN117126573B (en) * | 2023-10-25 | 2023-12-26 | 江苏新福乐威涂料有限公司 | Anti-fouling wear-resistant nano fluorocarbon coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102504309B (en) | 2015-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101654243B (en) | Preparation method of functional nano-graphene | |
| CN102160998A (en) | Preparation method of graphene-silver nano particle composite material | |
| CN101633779A (en) | Conductive polyaniline composite electrode material and preparation method thereof | |
| CN100549097C (en) | The preparation method of polyaniline/attapulgite nano-electric conducting composite material | |
| CN100588680C (en) | Method for preparing morphology-controlled polyphenylethene/polyaniline conductive polymeric composite microspheres | |
| CN102504309B (en) | Polyaniline-coated urea-formaldehyde resin nanoparticles and preparation method thereof | |
| CN102701192B (en) | Method for preparing monolayer MoS2 and graphene compounded nano material | |
| CN103971941B (en) | Graphene/polyaniline/oxidation tin composite material applied to ultracapacitor and preparation method thereof | |
| CN105199134A (en) | Polyaniline-modified graphene conductive composite film and preparation method thereof | |
| CN103242512B (en) | Method for preparing composite nanoparticles of Au/poly(3,4-dioxyethyl) thiophene core shell structure | |
| CN106410139A (en) | Silicon/carbon nitride/carbon nanocomposite material for lithium battery with high stability | |
| CN106810675A (en) | A kind of graphene composite conductive material and preparation method | |
| CN105576133A (en) | Sprayable photovoltaic material of perovskite structure and preparation method thereof | |
| CN102558586A (en) | Preparation method of polyethylene-vinyl acetate composite film | |
| CN111961411A (en) | Preparation of super-hydrophobic coating with excellent self-repairing and anti-corrosion properties | |
| CN103920537A (en) | Method for preparing magnetic polyaniline noble metal nanometer catalyst | |
| Gao et al. | Interfacial polymerization for controllable fabrication of nanostructured conducting polymers and their composites | |
| CN103303909B (en) | Method for preparing hydrophilic graphene with pH sensitivity | |
| CN102964716B (en) | Preparation method of high electric conduction and magnetic conduction graphene doping modified polyvinyl chloride | |
| CN105331054A (en) | Composite conductive film | |
| CN100575420C (en) | The mixture of poly m-phenylene diamine and nanometer silver and in-situ reduction preparation method thereof | |
| CN103232597B (en) | 2-mercaptobenzimidazole/polyaniline anticorrosion matrix material and preparation method thereof | |
| CN104475141B (en) | Nitrogen-doped graphene/silicon carbide microsphere nanometer composite material as well as preparation method and application thereof | |
| CN105253920A (en) | Preparation method of ferriferrous oxide@nitrogen doped carbon compound | |
| CN116144200A (en) | Preparation of super-hydrophobic coating with excellent self-repairing and anti-corrosion properties |
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: 20150128 Termination date: 20201201 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |