CN110845652B - Aniline-doped modified polyvinylidene chloride emulsion and preparation method and application thereof - Google Patents
Aniline-doped modified polyvinylidene chloride emulsion and preparation method and application thereof Download PDFInfo
- Publication number
- CN110845652B CN110845652B CN201911234993.8A CN201911234993A CN110845652B CN 110845652 B CN110845652 B CN 110845652B CN 201911234993 A CN201911234993 A CN 201911234993A CN 110845652 B CN110845652 B CN 110845652B
- Authority
- CN
- China
- Prior art keywords
- emulsion
- polyvinylidene chloride
- aniline
- modified
- preparing
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/02—Monomers containing chlorine
- C08F214/04—Monomers containing two carbon atoms
- C08F214/08—Vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/026—Wholly aromatic polyamines
- C08G73/0266—Polyanilines or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C09D127/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides an aniline-doped modified polyvinylidene chloride emulsion which is prepared from the following raw materials: wherein the total mass of the raw materials of the following components is the dry weight of the emulsion; 60-90 parts of vinylidene chloride monomer, 0.1-40 parts of acrylate monomer, 0.1-10 parts of functional monomer acid, 0.1-10 parts of aniline monomer and 0.1-5 parts of emulsifier. The aniline-doped modified polyvinylidene chloride emulsion can be used for preparing water-based metal anticorrosive paint. The invention can successfully disperse polyaniline with poor water solubility in the polyvinylidene chloride resin coating and successfully apply the conductive anticorrosion performance of the polyaniline to the water-based metal anticorrosion coating. Meanwhile, the polyaniline and carboxyl groups carried by the polymer chain segment are bonded to form post-crosslinking in the coating film forming process, so that the strength and the salt spray corrosion resistance of the coating are effectively improved.
Description
Technical Field
The invention belongs to the field of macromolecules, and particularly relates to an aniline-doped modified polyvinylidene chloride emulsion, and a preparation method and application thereof.
Background
Polyaniline is a conductive polymer material and has special electrical and optical properties. As the oxidation-reduction potential of the polyaniline is far higher than that of metal, when the polyaniline acts on a metal surface coating, the polyaniline can passivate the metal surface; in addition, the polyaniline has good application prospect in the field of metal corrosion prevention due to the easily available raw materials, simple synthesis process and good chemical and environmental stability. However, polyaniline has poor film-forming properties due to its rigid molecular segment, and thus it is usually required to be compounded with other film-forming materials such as acrylate resins, and is difficult to disperse in aqueous emulsions due to its poor water solubility, which limits the application of polyaniline in the field of aqueous metal anticorrosive coatings to some extent.
The preparation method of polyaniline mainly comprises chemical oxidative polymerization, electrochemical polymerization and the like. In order to improve the water solubility of polyaniline, the following method is generally employed: introducing substituent on benzene ring or doping with solvent. However, the current research mainly aims at the dielectric property of polyaniline, and there is no report about the application of polyaniline to the field of aqueous metal anticorrosive coatings, nor about the application of polyaniline to polyvinylidene chloride emulsion.
Therefore, the preparation of the aniline-doped modified polyvinylidene chloride emulsion has important significance.
Disclosure of Invention
Therefore, the invention aims to provide an aniline-doped modified polyvinylidene chloride emulsion, a preparation method and application thereof, and a water-based metal anticorrosive paint prepared from the emulsion.
The invention is realized by the following technical scheme:
in a first aspect, the invention provides an aniline-doped modified polyvinylidene chloride emulsion, which is prepared from the following raw materials:
wherein the total mass of the raw materials of the following components is the dry weight of the emulsion;
preferably, the aniline-doped modified polyvinylidene chloride emulsion is prepared from the following raw materials:
wherein the total mass of the raw materials of the following components is the dry weight of the emulsion;
preferably, in the aniline-doped modified polyvinylidene chloride emulsion of the invention,
the acrylate monomer is selected from at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate;
the functional monomer acid is at least one selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid;
the emulsifier is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether and salts thereof, and fatty alcohol ether phosphate and salts thereof.
Preferably, in the aniline-doped modified polyvinylidene chloride emulsion of the invention,
the acrylate monomer is selected from butyl acrylate and/or isooctyl acrylate, and the emulsifier is selected from sodium dodecyl sulfate.
In a second aspect, the present invention provides a method for preparing the above-mentioned aniline-doped modified polyvinylidene chloride emulsion, which comprises the following steps:
(1) dissolving 60-99 wt%, preferably 90 wt% of emulsifier in 20-40 wt%, preferably 30 wt% of water at 0-20 ℃, preferably 10 ℃, then sequentially adding acrylate monomer, functional monomer acid and vinylidene chloride into an emulsifying kettle, and stirring to form pre-emulsion;
(2) dissolving the rest emulsifier with 50-70 weight parts, preferably 53 weight parts of water, adding into a reaction kettle, introducing nitrogen to exhaust air in the reaction kettle, and keeping the reaction temperature at 30-40 ℃ and preferably 35 ℃;
(3) adding 1-10 wt%, preferably 4 wt% of the total amount of the pre-emulsion in the step (1) into a reaction kettle, and adding 10-60 wt%, preferably 40 wt% of the total amount of an initiator to initiate polymerization, wherein the initiator is a redox initiator, and the total amount of the initiator is 0.1-1 wt%, preferably 0.8 wt% of the dry weight of the emulsion calculated by an oxidant; after the polymerization reaction is finished, slowly dropwise adding the residual pre-emulsion and the residual initiator, finishing dropwise adding within 3-8h, preferably 5h, and simultaneously keeping the reaction temperature at 30-40 ℃ and preferably 35 ℃;
(4) after the dropwise addition is finished, heating to 50-60 ℃, preferably 50 ℃, keeping the temperature for 0.5-3h, preferably 2h, cooling to below 30 ℃, preferably 20 ℃, and then adjusting the pH value to 7-9, preferably 9 by using a neutralizing agent;
(5) adding aniline monomer into a reaction kettle, and uniformly mixing;
(6) adding an oxidant aqueous solution into the reaction kettle, uniformly mixing, filtering and discharging.
Preferably, in the preparation method of the aniline-doped modified polyvinylidene chloride emulsion of the invention,
the neutralizing agent is at least one selected from ammonia water, ethanolamine and N, N-dimethylethanolamine.
Preferably, in the preparation method of the aniline-doped modified polyvinylidene chloride emulsion of the invention,
in the step (3), the oxidant is ammonium persulfate, and the reducing agent is sodium bisulfite;
preferably, the weight ratio of the ammonium persulfate to the sodium bisulfite is 1: 1-0.5.
Preferably, in the preparation method of the aniline-doped modified polyvinylidene chloride emulsion of the invention,
in the step (6), the oxidant is ammonium persulfate;
preferably, the amount of said oxidizing agent used in said step (6) is 0.1-1 wt%, preferably 0.5 wt% of the dry weight of the emulsion.
In a third aspect, the invention also provides the use of the aniline-doped modified polyvinylidene chloride emulsion or the aniline-doped modified polyvinylidene chloride emulsion prepared by the preparation method in the preparation of a metal anticorrosive coating.
Preferably, in the above-mentioned use, the use is a use in preparing an aqueous metal anticorrosive coating.
In a fourth aspect, the invention also provides an aqueous metal anticorrosive paint, which is prepared by adopting the aniline-doped modified polyvinylidene chloride emulsion or the aniline-doped modified polyvinylidene chloride emulsion prepared by the preparation method.
Preferably, in the above aqueous metal anticorrosive paint, the aqueous metal anticorrosive paint further comprises the following components: film forming assistant, wetting agent, defoaming agent, titanium dioxide, filler, antirust pigment, pH regulator, dispersant, thickener and flash rust prevention assistant. Other components and amounts of the aqueous metal corrosion protective coating can be selected and adjusted by one skilled in the art using techniques commonly used in the art.
Preferably, in the above aqueous metal anticorrosive coating, the aqueous metal anticorrosive coating is formulated by a conventional method in the art.
The technical scheme provided by the invention has the following beneficial effects:
(1) the invention designs and synthesizes an aniline-doped modified polyvinylidene chloride emulsion, which can be used for preparing water-based metal anticorrosive paint with good paint film performance, such as: impact and adhesion, hardness, water resistance, salt spray resistance, storage stability, and the like.
(2) The aniline-doped modified polyvinylidene chloride emulsion is prepared by the following method: firstly, polymerizing polyvinylidene chloride emulsion containing functional monomer acid, then neutralizing the emulsion to be alkalescent by using a neutralizing agent, and then uniformly mixing an aniline monomer and an oxidant with the polyvinylidene chloride emulsion, wherein the system is alkaline, and the aniline polymerization mechanism is cationic radical polymerization after protonation, so that the polymerization condition is not met. In the film forming process of the coating prepared by using the emulsion, a mixed system gradually becomes acidic along with the volatilization of a neutralizing agent, an aniline monomer is polymerized under the action of an oxidant, and meanwhile, in the production process of polyaniline, a polymer chain segment with carboxyl can also be used as a doping agent to react with the polyaniline to form crosslinking. Therefore, the invention can successfully disperse polyaniline with poor water solubility in the polyvinylidene chloride resin coating and successfully apply the conductive anticorrosion performance of the polyaniline to the water-based metal anticorrosion coating. Meanwhile, polyaniline and carboxyl groups carried by polymer chain segments are bonded to form post-crosslinking in the coating film forming process, so that the strength and the salt spray corrosion resistance of the coating are effectively improved.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
In the following examples and comparative examples of the present invention, whether the polymerization reaction was completed was judged by the presence or absence of blue light, that is: the appearance of blue light indicates that the polymerization reaction is complete.
The raw materials used in the following examples and comparative examples are shown in table 1.
TABLE 1 abbreviation, chemical name and manufacturer of each raw material
| Abbreviation of Compound | Chemical name of the Compound | Manufacturer of the product |
| VDC | Vinylidene chloride | Chemical industry of Nantong XiangtaiLimited company |
| BA | Acrylic acid butyl ester | Wanhua Chemical Group Co., Ltd. |
| EHA | Acrylic acid isooctyl ester | Wanhua Chemical Group Co., Ltd. |
| (M)AA | (meth) acrylic acid | Wanhua Chemical Group Co., Ltd. |
| APS | Ammonium persulfate | Jinan Fengle chemical Co Ltd |
| SDS | Sodium dodecyl sulfate | Shanghai Youyang industries Ltd |
| DMEA | N, N-dimethylethanolamine | BASF CHINA Co.,Ltd. |
| MEA | Ethanolamine | BASF CHINA Co.,Ltd. |
Example 1Preparation of aqueous polyvinylidene chloride emulsion 1
The preparation of the aqueous polyvinylidene chloride emulsion 1 in this example comprises the following steps:
(1) 0.9g of SDS was dissolved in 30g of water at 10 ℃ and then 26g of BA, 2g of AA and 70g of VDC were added to the emulsion tank in this order and stirred to form a pre-emulsion.
(2) Dissolving the rest 0.1g of SDS by 53g of deionized water, adding the dissolved SDS into a reaction kettle, introducing nitrogen to exhaust the air in the reaction kettle, and keeping the reaction temperature at 35 ℃.
(3) Taking out 4% (accounting for the total mass of the pre-emulsion) of the pre-emulsion, putting the pre-emulsion into a reaction kettle to serve as seed emulsion of a core, and sequentially adding 40% (accounting for the total mass of the initiator) of initiator aqueous solution: 3.2g of ammonium persulfate aqueous solution with the mass concentration of 10% and 2.4g of sodium bisulfite aqueous solution with the mass concentration of 10%, and after the polymerization reaction is finished for 30min, dropwise adding the rest of pre-emulsion and the rest of initiator aqueous solution (ammonium persulfate aqueous solution with the mass concentration of 10% and sodium bisulfite aqueous solution with the mass concentration of 10%) for 5h in total, and simultaneously keeping the reaction temperature at 35 ℃.
(4) After the dropwise addition, the temperature is raised to 50 ℃, heat preservation is continued for 2 hours, then the temperature is reduced to about 20 ℃, and ammonia water is added to neutralize until the pH value is 9.0.
(5) Adding 2g of aniline monomer into the reaction kettle, and uniformly mixing.
(6) Then 5g of ammonium persulfate aqueous solution with the mass concentration of 10 percent is dripped into the reaction kettle, and the final aqueous polyvinylidene chloride emulsion 1 is obtained after the uniform stirring, filtering and discharging. The solid content was determined to be 50%.
Examples 2 to 18Preparation of aqueous polyvinylidene chloride emulsion 2-18
Aqueous polyvinylidene chloride emulsions 2-18 were prepared in a similar manner to aqueous polyvinylidene chloride emulsion 1 except that the raw materials were used in amounts shown in tables 2-1 and 2-2.
TABLE 2-1 EXAMPLES 1-9 the amounts (unit: g) of the respective raw materials and reaction temperatures of the aqueous polyvinylidene chloride emulsions 1-9
Remarking: APS-1 means: ammonium persulfate as an initiator; APS-2 means: ammonium persulfate as post-addition oxidant
TABLE 2-2 EXAMPLES 10-18 the amounts (unit: g) of the respective raw materials and reaction temperatures of the aqueous polyvinylidene chloride emulsions 10-18
Remarking: APS-1 means: ammonium persulfate as an initiator; APS-2 means: ammonium persulfate as post-addition oxidant
Comparative example
The preparation of the aqueous polyvinylidene chloride emulsion of this comparative example included the following steps:
(1) 0.9g of SDS was dissolved in 30g of water at 10 ℃ and then 28g of BA, 2g of AA and 70g of VDC were added to the emulsion tank in this order and stirred to form a pre-emulsion.
(2) Dissolving the rest 0.1g of SDS by 53g of deionized water, adding the dissolved SDS into a reaction kettle, introducing nitrogen to exhaust the air in the reaction kettle, and keeping the reaction temperature at 35 ℃.
(3) Taking out 4% (accounting for the total mass of the pre-emulsion) of the pre-emulsion, putting the pre-emulsion into a reaction kettle to serve as seed emulsion of a core, and sequentially adding 40% (accounting for the total mass of the initiator) of initiator aqueous solution: 3.2g of ammonium persulfate aqueous solution with the mass concentration of 10% and 2.4g of sodium bisulfite aqueous solution with the mass concentration of 10%, and after the polymerization reaction is finished for 30min, dropwise adding the rest of pre-emulsion and the rest of initiator aqueous solution (ammonium persulfate aqueous solution with the mass concentration of 10% and sodium bisulfite aqueous solution with the mass concentration of 10%) for 5h in total, and simultaneously keeping the reaction temperature at 35 ℃.
(4) After the dropwise addition, the temperature is raised to 50 ℃, heat preservation is continued for 2 hours, then the temperature is reduced to about 20 ℃, and ammonia water is added to neutralize until the pH value is 9.0.
(5) After being stirred evenly, the mixture is filtered and discharged, and the final aqueous polyvinylidene chloride emulsion 1 is obtained. The solid content was determined to be 50%.
Example 19Preparation of water-based metal anticorrosive paint
Aqueous metal anticorrosive paint 1 was prepared from the aqueous polyvinylidene chloride emulsion prepared in example 1 according to the formulation table of aqueous metal anticorrosive paint shown in table 3, as follows.
TABLE 3 water-based metal anticorrosive paint formula table
Note: the raw materials of the non-marked factories can be commonly used in the same type, and Surfynol is the brand name
According to the formulation in Table 3, 9g of water, 1g of BYK-190, 0.1g of Tego 901W, 0.5g of Surfynol 104BC, 2g of diethylene glycol monobutyl ether are initially placed in a dispersion tank and stirred at 500r/min for 10 min. Then adding 10g R-902+, 5g talcum powder, 5g precipitated barium sulfate, 5g aluminium triphosphate and 5g zinc phosphate in sequence, increasing the rotating speed to 800r/min, after uniform dispersion, adding zirconium beads with the volume amount equal to that of pigments and fillers (the pigments and fillers comprise titanium dioxide, talcum powder, precipitated barium sulfate, aluminium triphosphate and zinc phosphate), and grinding the slurry until the fineness is less than or equal to 35 mu m. Reducing the rotating speed, adding 50g of the aqueous polyvinylidene chloride emulsion prepared in the example 1 under stirring at 500r/min, adding a proper amount of ammonia water to adjust the pH value to 8.5, then sequentially adding 5g of dipropylene glycol butyl ether, 0.1g of Tego 1488 and 0.5g of FA-179, adding 0.5g U604 according to the viscosity requirement of the coating, adding 2.8g of water, uniformly stirring, filtering and packaging by using a 100-mesh filter screen to obtain a finished product of the aqueous metal anticorrosive coating.
The aqueous polyvinylidene chloride emulsion prepared in example 1 was replaced with the aqueous polyvinylidene chloride emulsions of examples 2 to 18 and comparative example, respectively, and an aqueous metal anticorrosive paint was prepared according to the above-described method.
Examples of the experimentsPaint film performance evaluation experiment
The aqueous metal anticorrosive coatings prepared from the aqueous polyvinylidene chloride emulsions of examples 1-18 and comparative example were subjected to paint film property evaluation, and the specific experimental results are shown in table 4.
TABLE 4 film Performance index of aqueous Metal anticorrosive coatings prepared from aqueous polyvinylidene chloride emulsions of examples 1-18 and comparative example
Note: in the water resistance, salt water resistance and salt mist resistance tests, the test result is best represented by 5, and the test result is worst represented by 1
As can be seen from Table 4:
(1) the water resistance, salt water resistance and salt spray resistance test results of the aqueous metal anticorrosive coatings prepared by the aqueous polyvinylidene chloride emulsions of comparative example 1 and comparative example show that the salt spray resistance is obviously improved after the polyaniline is introduced;
(2) from the test results of the aqueous metal anticorrosive coatings prepared from the aqueous polyvinylidene chloride emulsions of comparative example 3 and examples 1-2, it can be seen that the salt spray resistance of the coating is slightly reduced with the increase of the VDC content, since the coating is slightly brittle with the increase of the VDC content, resulting in a reduction in the resistance;
(3) the test results of the aqueous metal anticorrosive coatings prepared by the aqueous polyvinylidene chloride emulsions of the comparative example 4 and the example 2 show that when the soft monomer is changed from BA to EHA, the water resistance of the coating is slightly reduced, and the other properties are equivalent;
(4) the test results of the aqueous metal anticorrosive coatings prepared by comparing the aqueous polyvinylidene chloride emulsions of example 5 and example 2 show that when the acid content of the functional monomer is reduced, the salt spray resistance is weakened, and the other properties are equivalent, because the reduction of the acid content affects the polymerization of aniline, and the effect of post-crosslinking is not obvious when the acid content is too small;
(5) as can be seen from the test results of the aqueous metal anticorrosive coatings prepared by comparing the aqueous polyvinylidene chloride emulsions of examples 6-7 and example 2, when the aniline content in the resin is reduced, the salt spray resistance is weakened;
(6) from the test results of the aqueous metal anticorrosive coatings prepared from the aqueous polyvinylidene chloride emulsions of comparative examples 8-12 and example 2, it can be seen that the comprehensive properties are not greatly different when the functional monomer acid is changed from AA to MAA, itaconic acid, maleic acid, crotonic acid and fumaric acid;
(7) from the test results of the aqueous metal anticorrosive coatings prepared from the aqueous polyvinylidene chloride emulsions of comparative example 13 and example 2, it can be seen that when the initiator content is increased, the water resistance of the coating is slightly reduced, but the salt spray resistance is not affected, which may be due to the slightly reduced molecular weight of the polymer caused by the increased initiator, so that the water resistance is slightly deteriorated;
(8) from the test results of the aqueous metal anticorrosive coatings prepared from the aqueous polyvinylidene chloride emulsions of comparative example 14 and example 2, it can be seen that when the content of the oxidizing agent is increased, the overall performance is not greatly different, because the polymerization of aniline is slowly carried out in the process of coating, so that a little change in polymerization conditions has little influence on the polymerization process;
(9) from the results of the tests on the aqueous metal anticorrosive coatings prepared from the aqueous polyvinylidene chloride emulsions of comparative examples 15 to 16 and example 2, it is found that the resistance is slightly deteriorated when the polymerization reaction temperature is increased, because the polymer molecular weight is lowered due to the increase in the polymerization reaction temperature, thereby slightly deteriorating the resistance;
(10) from the test results of the aqueous metal anticorrosive coatings prepared by comparing the aqueous polyvinylidene chloride emulsions of examples 17-18 and example 2, it can be seen that when the neutralizing agent is changed from ammonia water to MEA or DMEA, the overall properties of the coating are not greatly different, and the volatilization speeds of different neutralizing agents are different, so that the polymerization of aniline is affected, but the polymerization of aniline is slowly carried out in the coating process, so that a little change of polymerization conditions has little effect on the polymerization process.
As shown above, the water-based metal anticorrosive paint prepared from the water-based polyvinylidene chloride emulsion has good paint film performance, such as: impact and adhesion, hardness, water resistance, salt spray resistance, storage stability, and the like.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (26)
1. The preparation method of the aniline-doped modified polyvinylidene chloride emulsion is characterized by comprising the following steps of:
(1) dissolving 60-99 wt% of emulsifier in 20-40 parts by weight of water at 0-20 ℃, sequentially adding acrylate monomer, functional monomer acid and vinylidene chloride into an emulsifying kettle, and stirring to form pre-emulsion;
(2) dissolving the rest emulsifier with 50-70 parts by weight of water, adding the water into a reaction kettle, introducing nitrogen to exhaust air in the reaction kettle, and keeping the reaction temperature at 30-40 ℃;
(3) adding 1-10 wt% of the total amount of the pre-emulsion in the step (1) into a reaction kettle, and adding 10-60 wt% of the total amount of an initiator to initiate polymerization, wherein the initiator is a redox initiator, and the total amount of the initiator is 0.1-1 wt% of the dry weight of the emulsion calculated by an oxidant; after the polymerization reaction is finished, slowly dropwise adding the residual pre-emulsion and the residual initiator, finishing dropwise adding within 3-8h, and simultaneously keeping the reaction temperature at 30-40 ℃;
(4) after the dropwise addition is finished, heating to 50-60 ℃, preserving heat for 0.5-3h, cooling to below 30 ℃, and then adjusting the pH value to 7-9 by using a neutralizing agent; the neutralizing agent is at least one of ammonia water, ethanolamine and N, N-dimethylethanolamine;
(5) adding aniline monomer into a reaction kettle, and uniformly mixing;
(6) adding an oxidant aqueous solution into the reaction kettle, uniformly mixing, filtering and discharging;
wherein the total mass of the raw materials of the following components is the dry weight of the emulsion;
2. the method for preparing the emulsion of polyvinylidene chloride doped with aniline and modified according to claim 1, characterized in that the emulsion is prepared by adopting the following raw materials:
wherein the total mass of the raw materials of the following components is the dry weight of the emulsion;
3. the method for preparing the emulsion of polyvinylidene chloride doped with aniline and modified according to claim 2,
the acrylate monomer is selected from at least one of methyl acrylate, ethyl acrylate, butyl acrylate, isooctyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and isooctyl methacrylate;
the functional monomer acid is at least one selected from acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid and maleic acid;
the emulsifier is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, fatty alcohol-polyoxyethylene ether and salts thereof, and fatty alcohol ether phosphate and salts thereof.
4. The method of any one of claims 1-3, wherein the acrylate monomer is selected from butyl acrylate and/or isooctyl acrylate, and the emulsifier is selected from sodium lauryl sulfate.
5. The method for preparing emulsion of polyvinylidene chloride modified by doping aniline according to claim 4, wherein in step (1), 90 wt% of the total amount of emulsifier is dissolved in water.
6. The method for preparing emulsion of polyvinylidene chloride modified by doping aniline according to claim 5, wherein the step (1) is to dissolve the emulsifier in water at 10 ℃.
7. The method for preparing emulsion of polyvinylidene chloride modified by doping aniline according to claim 6, wherein the step (1) is to dissolve the emulsifier in 30 parts by weight of water.
8. The method for preparing an emulsion of polyvinylidene chloride modified by doping aniline according to claim 4, wherein the step (2) is to dissolve the remaining emulsifier with 53 parts by weight of water.
9. The method for preparing emulsion of polyvinylidene chloride modified by doping aniline according to claim 8, wherein the reaction temperature in step (2) is kept at 35 ℃.
10. The method for preparing the emulsion of polyvinylidene chloride doped with aniline and modified in claim 4, wherein in step (3), 4 wt% of the total amount of the pre-emulsion in step (1) is added into the reaction kettle.
11. The method for preparing emulsion of polyvinylidene chloride modified by doping aniline according to claim 10, wherein step (3) is performed by adding 40 wt% of the total amount of initiator.
12. The method for preparing emulsion of polyvinylidene chloride doped with aniline and modified according to claim 11, wherein the total amount of initiator in step (3) is 0.8 wt% of the emulsion dry weight.
13. The method for preparing the emulsion of polyvinylidene chloride doped with aniline and modified in claim 12, wherein the residual pre-emulsion and the residual initiator are dripped off within 5 hours after the polymerization reaction in step (3) is completed.
14. The method for preparing emulsion of polyvinylidene chloride doped with aniline and modified in claim 13, wherein the polymerization reaction in step (3) is completed and the reaction temperature is maintained at 35 ℃.
15. The method for preparing the emulsion of polyvinylidene chloride doped with aniline and modified in claim 4, wherein the temperature is raised to 50 ℃ after the dropwise addition in step (4) is completed.
16. The method for preparing the emulsion of polyvinylidene chloride doped with aniline and modified in claim 15, wherein the temperature is raised and maintained for 2h after the dropwise addition in step (4) is finished.
17. The method for preparing the emulsion of polyvinylidene chloride doped with aniline and modified according to claim 16, wherein the temperature in step (4) is reduced to 20 ℃.
18. The method of claim 17, wherein step (4) is performed by adjusting the pH to 9 with a neutralizing agent.
19. The method for preparing the emulsion of polyvinylidene chloride modified by doping aniline according to any one of claims 1-3 and 5-18,
in the step (3), the oxidant is ammonium persulfate, and the reducing agent is sodium bisulfite.
20. The method for preparing the aniline-doped modified polyvinylidene chloride emulsion according to claim 19, wherein the weight ratio of ammonium persulfate to sodium bisulfite is 1: 1-0.5.
21. The method for preparing emulsion of polyvinylidene chloride modified by doping aniline according to any one of claims 1-3, 5-18 and 20,
in the step (6), the oxidant is ammonium persulfate.
22. The method for preparing emulsion of polyvinylidene chloride doped with aniline and modified in claim 21, wherein the oxidant in step (6) is used in an amount of 0.1-1 wt% based on the dry weight of the emulsion.
23. The method for preparing emulsion of polyvinylidene chloride doped with aniline and modified according to claim 22, wherein the oxidant is used in the amount of 0.5 wt% based on the dry weight of the emulsion in step (6).
24. Use of the aniline-doped modified polyvinylidene chloride emulsion prepared by the preparation method according to any one of claims 1 to 23 for preparing a metal anticorrosive coating.
25. Use according to claim 24, characterized in that it is a use in the preparation of aqueous metal corrosion protection coatings.
26. An aqueous metal anticorrosive paint, which is characterized by being prepared from the aniline-doped modified polyvinylidene chloride emulsion prepared by the preparation method of any one of claims 1 to 23.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911234993.8A CN110845652B (en) | 2019-12-05 | 2019-12-05 | Aniline-doped modified polyvinylidene chloride emulsion and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911234993.8A CN110845652B (en) | 2019-12-05 | 2019-12-05 | Aniline-doped modified polyvinylidene chloride emulsion and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110845652A CN110845652A (en) | 2020-02-28 |
| CN110845652B true CN110845652B (en) | 2022-03-11 |
Family
ID=69608005
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911234993.8A Active CN110845652B (en) | 2019-12-05 | 2019-12-05 | Aniline-doped modified polyvinylidene chloride emulsion and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110845652B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113184979B (en) * | 2021-02-07 | 2022-04-15 | 青海洁神环境科技股份有限公司 | Cation modified PVDC biological rotating disc and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02300267A (en) * | 1989-05-16 | 1990-12-12 | Nippon Steel Corp | Corrosion-resistant coating composition |
| CN104098767A (en) * | 2014-06-11 | 2014-10-15 | 扬州大学 | Preparation method of polyaniline-epoxy graft modified acrylic ester compound |
| CN107759721A (en) * | 2016-08-18 | 2018-03-06 | 摩田化学（昆山）有限公司 | Waterborne metal anti-corrosive paint polyvinylidene chloride acrylate copolymer emulsion and its synthetic method |
| CN110229594A (en) * | 2019-06-26 | 2019-09-13 | 陕西科技大学 | A kind of preparation method of the super-hydrophobic composite anticorrosion coating of terpolymer doped polyaniline |
-
2019
- 2019-12-05 CN CN201911234993.8A patent/CN110845652B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02300267A (en) * | 1989-05-16 | 1990-12-12 | Nippon Steel Corp | Corrosion-resistant coating composition |
| CN104098767A (en) * | 2014-06-11 | 2014-10-15 | 扬州大学 | Preparation method of polyaniline-epoxy graft modified acrylic ester compound |
| CN107759721A (en) * | 2016-08-18 | 2018-03-06 | 摩田化学（昆山）有限公司 | Waterborne metal anti-corrosive paint polyvinylidene chloride acrylate copolymer emulsion and its synthetic method |
| CN110229594A (en) * | 2019-06-26 | 2019-09-13 | 陕西科技大学 | A kind of preparation method of the super-hydrophobic composite anticorrosion coating of terpolymer doped polyaniline |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110845652A (en) | 2020-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE602004009727T2 (en) | Aqueous multi-stage emulsion polymer composition | |
| EP2013297A2 (en) | Method for the application of corrosion-resistant layers to metallic surfaces | |
| CN103387637B (en) | A kind of water-soluble self-crosslinking acrylic resin composition and method of making the same | |
| CA3032277C (en) | Ambient self-crosslinkable latex | |
| CA2303156A1 (en) | Stable waterborne polymer compositions containing poly(alkyleneimines) | |
| CN102219873B (en) | Triallyl isocyanurate modified aqueous hydroxyl acrylic resin and preparation method thereof | |
| CN108129620A (en) | A kind of sulfonic acid type block copolymer aqueous dispersion of RAFT technologies | |
| CN110845652B (en) | Aniline-doped modified polyvinylidene chloride emulsion and preparation method and application thereof | |
| US3845066A (en) | Aqueous based thermosetting acrylamide-acrylic copolymer coating composition | |
| JP4947764B2 (en) | Water-based coating material | |
| CN111909587B (en) | Water-based primer and preparation method and application thereof | |
| CN111116831B (en) | Preparation method of hydroxyl acrylic emulsion | |
| CN110845931B (en) | Polyether amine modified acrylic resin water-based anticorrosive paint and preparation method thereof | |
| EP3652219B1 (en) | Aqueous binder composition | |
| CN111909318B (en) | Alkyl silyl ether modified hydroxy acrylic emulsion, preparation method and application | |
| CN112521786B (en) | Modified polymer environment-friendly coating | |
| JPH07247460A (en) | Aqueous covering composition | |
| CN108276833A (en) | A kind of ternary block polymer aqueous dispersion of RAFT synthesis | |
| JP3643304B2 (en) | Method for producing aqueous resin dispersion | |
| CN112745455B (en) | Oleic acid copolymer dispersion resin and preparation method and application thereof | |
| CN110358400B (en) | Water-based quick-drying coil steel coating based on monodisperse polyacrylic resin and preparation method thereof | |
| KR100501068B1 (en) | cationic electro-deposition paint composition, method of forming the cationic electro-deposition paint composition, pigment-paste composition and electro-deposition paint having the pigment-paste composition | |
| US20040087713A1 (en) | Water-based coating composition | |
| CN108690174B (en) | Preparation process of acrylic polymer emulsion with flash rust resistance function | |
| CN111675779A (en) | High-water-resistance self-crosslinking water-soluble acrylic resin and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |