CN108250347B - Salt-fog-resistant phosphate modified acrylic core-shell emulsion - Google Patents
Salt-fog-resistant phosphate modified acrylic core-shell emulsion Download PDFInfo
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- 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
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
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- 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
- C09D143/00—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 containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/02—Homopolymers or copolymers of monomers containing phosphorus
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- 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
Abstract
The invention relates to a salt-fog-resistant phosphate modified acrylic core-shell emulsion, wherein a shell layer contains long-chain alkyl-acrylate phosphate diester functional groups; the components of the material comprise acrylate soft and hard monomers, acrylic acid, long-chain alkyl-acrylate phosphate diester, a neutralizer, an initiator, an emulsifier and water; the long-chain alkyl-acrylate phosphate ester is prepared from a hydroxyl acrylate monomer and R6‑10OH and phosphorus pentoxide are prepared by reaction; the invention also provides a preparation method of the salt-fog-resistant phosphate modified acrylic core-shell emulsion. The phosphate modified acrylic core-shell emulsion has a glass transition temperature of 30-45 ℃ and a particle size of 60-150 nm; the salt-fog-resistant phosphate modified acrylic core-shell emulsion prepared by the invention has excellent adhesive force, water resistance, acid and alkali resistance, salt fog resistance, flash rust resistance and corrosion resistance, and is widely used for water-based antirust paint, water-based steel structure paint, water-based engineering paint, water-based concrete anticorrosive paint and the like.
Description
Technical Field
The invention relates to a modified acrylic emulsion, in particular to a salt-fog-resistant phosphate modified acrylic core-shell emulsion, belonging to the technical field of aqueous resin synthesis.
Background
In recent years, with the increasing attention of human beings to the problem of environmental pollution and the shortage of global petroleum resources, the application range of solvent-based coatings is greatly limited, and the research and development and production of low-VOC and low-toxicity coatings such as water-based coatings, high-solid coatings, powder wood coatings and radiation curing coatings are rapidly developed. The water-based paint has no pollution, no fire hazard and low production cost due to the adoption of water as a dispersion medium, conforms to green production and has very wide development prospect.
The corrosion of metals causes billions of dollars of economic loss to countries around the world each year, and various technologies have been used to protect metals from corrosion. Among them, corrosion prevention of paint is one of the most effective and most common methods for metal corrosion prevention. At present, with the development of modern industrial technology and the increase of environmental requirements of people, and the stricter emergence of environmental protection regulations, the water-based anticorrosion coating becomes necessary.
Waterborne acrylic resins are typically prepared by free radical polymerization methods, and a wide variety of monomers are available for making such resins, including alkyl esters of acrylic acid, hydroxyalkyl esters, and vinyl monomers such as styrene, among others. The final properties of the acrylic resin can be controlled by selecting an appropriate kind of monomer, and the balance among hardness, impact resistance and flexibility of the resin can be controlled by adjusting the ratio of the soft and hard monomers. The water-based acrylate resin has good flexibility, excellent aging resistance and solvent resistance, has good adhesive force to various base materials due to low shrinkage rate, and is widely applied to building coatings and water-based industrial coatings.
Because the general acrylic ester emulsion is polymerized in the presence of the emulsifier, the emulsifier is easy to migrate to the surface of a coating film due to small molecular weight, thereby influencing the anti-corrosion performance of the emulsion such as adhesion, water resistance, salt fog resistance and the like after film forming.
The phosphate is a common adhesion promoter, is suitable for various substrates such as copper, iron, aluminum, wood, plastic and the like, and particularly has an obvious promoting effect on the adhesion of metal substrates such as copper, iron, aluminum and the like, because the strong polarity of the phosphate group and iron ions in the substrates generate a strong passivating effect, a compact passivating film can be formed, and thus the antirust and anticorrosive functions are achieved.
Chinese patent CN102408513A discloses a preparation method of phosphate modified acrylate emulsion, wherein the phosphate monomer is trichloroethyl phosphate, trichloropropyl phosphate or n-ethyl phosphate, the molecular weight of the polymer in the obtained phosphate modified acrylate emulsion is 2000-3000, the particle size is 0.2-0.6 μm, the initiator is ammonium persulfate, the particle size of the synthesized emulsion is larger, the film forming performance is affected, and the alkyl carbon number of the phosphate monomer is less, and the water resistance and the salt fog resistance are poor.
Chinese patent CN101412781A discloses a preparation method of phosphate modified acrylate emulsion, wherein the phosphate monomer is PMA-100 (hydroxyethyl methacrylate phosphate monoester) or PMA-200 (hydroxyethyl methacrylate phosphate diester) of Rodiya, and the prepared acrylic resin is prepared into an aqueous two-component coating which has excellent water resistance and salt fog resistance, but the prepared acrylic resin is not of a core-shell structure, is an aqueous dispersion and needs to be prepared into a two-component system, so that the application cost is increased.
Zhangdong yang (the synthesis and performance research of phosphate modified acrylate emulsion, Chinese paint, 2014, 29 (10); 38-43) reports that methyl methacrylate, styrene, butyl acrylate, acrylic acid and phosphate functional monomers are adopted to synthesize the phosphate modified acrylate emulsion, the phosphate monomer is PMA-100 or PMA-200 of Rodiya, the initiator is ammonium persulfate, and the emulsifier is a single anionic emulsifier.
The prior water-based anticorrosive paint has the problems of short anticorrosive period, easy flash corrosion after coating, emulsion stability, water resistance, antirust property and the like. The development of the salt-fog-resistant phosphate modified acrylic resin is particularly important for improving the corrosion resistance of the water-based paint.
Disclosure of Invention
In order to solve the technical problem, the invention introduces a monomer with alkyl acrylate phosphate diester function on the molecular structure of acrylic resin, the long-chain alkyl on the phosphate group has self-emulsifying function to improve the high-temperature stability of the emulsion, and the hydrophobic property of the long-chain alkyl improves the water resistance of the coating; the phosphate group can generate strong passivation effect with iron in the base material, and a compact passivation film can be formed; due to the dual functions of the phosphate, the adhesive force and compactness between the resin and the base material are enhanced, so that water molecules, chloride ions, sodium ions and the like are effectively isolated from entering between the resin and the base material, the adhesive force and the flash rust resistance are improved in a wet environment, and the water resistance, the salt spray resistance and the rust and corrosion resistance of the resin are improved.
The invention aims to provide a salt-fog-resistant phosphate modified acrylic core-shell emulsion.
The invention introduces the alkyl acrylate phosphate diester functional monomer to the side chain end group of the shell molecular structure of the acrylic copolymer, ensures that phosphate ester groups are more easily enriched on the surface of a base material in the process of resin film forming, and plays the unique functions of passivation and flash rust resistance.
The salt-fog-resistant phosphate modified acrylic acid core-shell emulsion consists of a core layer and a shell layer, wherein the shell layer contains long-chain alkyl-acrylate phosphate diester functional groups, and the molecular structural formula of the shell layer is as follows:
wherein R in the molecular structural formula is C6-10A long chain alkyl group; n is 1 to 3; r2、R3Is H, -CH3And other alkyl-type substituent groups; r4Is butyl ester group, isooctyl ester group, lauryl alcohol ester group, lauryl ester group and octadecyl ester group; m is 18-26; the salt-fog-resistant phosphate modified acrylic core-shell emulsion has a glass transition temperature Tg of 30-45 ℃ and a particle size of 60-150 nm.
The salt-fog-resistant phosphate ester modified acrylate core-shell emulsion comprises the following components in parts by weight: 30.0-50.0 parts of acrylate soft and hard monomer, 1.5-4.0 parts of acrylic acid, 2.0-5.0 parts of long-chain alkyl-acrylate phosphoric acid diester, 1.0-3.0 parts of neutralizer, 0.5-2.0 parts of initiator, 1.5-3.0 parts of emulsifier and 40.0-60.0 parts of deionized water.
Wherein the acrylate hard monomer is one or a combination of methyl acrylate, methyl methacrylate, ethyl methacrylate and ethyl acrylate; the acrylate soft monomer is one or a combination of butyl acrylate, butyl methacrylate, tert-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl methacrylate, lauryl acrylate, stearyl methacrylate and stearyl acrylate; the molar ratio of the acrylate soft monomer to the acrylate hard monomer is 1: 0.1-1.
The long-chain alkyl-acrylate phosphate diester is prepared by the following reaction formula:
wherein R in the molecular structural formula1Is H, -CH3And other alkyl substituent groups, R is C6-10A long chain alkyl group; n is 1 to 3.
The long-chain alkyl-acrylate phosphate diester comprises the following components in parts by weight: 35.0-45.0 parts of hydroxyl-containing acrylate monomer and R6-1030-40.0 parts of OH, 0.1-0.5 part of hydroquinone and 20-30.0 parts of phosphorus pentoxide.
The hydroxyl-containing acrylate monomer is one or a combination of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate.
Said R6-10OH is C6-10Long chain alkyl monoalcohols.
The preparation process of the long-chain alkyl-acrylate phosphate diester comprises the following steps:
adding a certain amount of hydroxyl-containing acrylate monomer and a certain amount of hydroquinone into a reaction kettle, uniformly stirring, heating to 50 ℃, and adding a certain amount of phosphorus pentoxide and R6-10And adding OH in batches, adding the OH within 1.5h, heating to 82 ℃, keeping the temperature for reaction for 3h, measuring the acid value, cooling after the reaction is qualified, and discharging to obtain the long-chain alkyl-acrylate phosphate diester.
The initiator is azobisisobutyronitrile, and the molecular weight of the azobisisobutyronitrile initiator is uniform and the distribution of the azobisisobutyronitrile initiator is narrower than that of peroxide, so that the emulsion reaches the nanometer level.
The emulsifier is one or a combination of more of COPS-I, CO-436 and OP-10.
The neutralizing agent is at least one of triethylamine, ammonia water and dimethylethanolamine.
The invention also provides a preparation method of the salt-fog-resistant phosphate modified acrylic acid core-shell emulsion, which comprises the following preparation processes:
a) weighing acrylic acid soft and hard monomers, 50-60% of emulsifier and deionized water according to the weight part ratio of the formula, and dispersing at a high speed for 30min at 50 ℃ to prepare pre-emulsion;
b) mixing about 20% of pre-emulsion, a certain amount of long-chain alkyl-acrylate phosphoric acid diester and part of azodiisobutyronitrile, and uniformly stirring to obtain phosphoric acid diester mixed pre-emulsion;
c) adding 10-20% of pre-emulsion, part of azodiisobutyronitrile and the rest of emulsifier into a reaction kettle with a thermometer, a reflux condenser pipe and a stirrer, and heating to 80-84 ℃ for reaction to prepare seed emulsion;
d) when bluing light appears in the reaction, slowly dropwise adding the mixed acrylic acid, the residual pre-emulsion and the residual azodiisobutyronitrile, and finishing dropwise adding within 1.5-2.0 h; and then dropwise adding the phosphate diester mixed pre-emulsion, after dropwise adding is completed within 1.0-1.5 h, heating to 85-90 ℃, carrying out heat preservation reaction for 1h, cooling to below 45 ℃, adjusting the pH value to be 7-8 by using a neutralizing agent, filtering and discharging to obtain the salt mist resistant phosphate modified acrylic core-shell emulsion.
The salt-fog-resistant phosphate modified acrylic acid core-shell emulsion is prepared by a solvent-free method, and meets the requirement of green production. The salt-fog-resistant phosphate modified acrylic core-shell emulsion prepared by the invention has excellent adhesive force, water resistance, acid and alkali resistance, aging resistance, salt fog resistance, flash rust resistance and corrosion resistance, and is widely used for water-based antirust paint, water-based steel structure paint, water-based engineering paint, water-based concrete anticorrosive paint and the like.
Detailed Description
The preparation of the salt spray resistant phosphate modified acrylic core shell emulsion is further described with reference to the following examples.
Example 1
Octyl-hydroxyethyl acrylate phosphoric acid diester A, which has the following preparation process:
adding 35.0 parts of hydroxyethyl acrylate and 0.2 part of hydroquinone into a reaction kettle, uniformly stirring, heating to 50 ℃, adding 28.0 parts of phosphorus pentoxide and 36.8 parts of octanol in batches, adding the phosphorus pentoxide and the octanol in 1.5h, heating to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, cooling after qualification, and discharging to obtain the octyl-hydroxyethyl acrylate phosphate diester A.
Example 2
A hexyl-hydroxyethyl methacrylate phosphate diester B is prepared by the following process:
adding 40.0 parts of hydroxyethyl methacrylate and 0.2 part of hydroquinone into a reaction kettle, uniformly stirring, heating to 50 ℃, adding 26.0 parts of phosphorus pentoxide and 33.8 parts of hexyl alcohol in batches within 1.5h, heating to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, cooling after qualification, and discharging to obtain the hexyl-hydroxyethyl methacrylate phosphate diester B.
Example 3
Octyl-hydroxypropyl acrylate phosphoric acid diester C, the preparation process comprises the following steps:
adding 38.0 parts of hydroxypropyl acrylate and 0.2 part of hydroquinone into a reaction kettle, uniformly stirring, heating to 50 ℃, adding 30.0 parts of phosphorus pentoxide and 31.8 parts of octanol in batches, adding the materials within 1.5h, heating to 82 ℃, carrying out heat preservation reaction for 3h, measuring the acid value, cooling after the reaction is qualified, and discharging to obtain the octyl-hydroxypropyl acrylate phosphoric diester C.
Example 4
Salt-fog-resistant phosphate modified acrylic core-shell emulsion A1The preparation process comprises the following steps:
a) weighing 12.0 parts of methyl acrylate, 15.0 parts of methyl methacrylate, 6.0 parts of butyl methacrylate, 8.0 parts of isooctyl methacrylate, 100.3 parts of OP-0 parts and 20.0 parts of deionized water according to the weight part ratio of the formula, and dispersing at a high speed for 30min at 50 ℃ to prepare a pre-emulsion;
b) mixing 12 parts of pre-emulsion, 4.0 parts of diester phosphate A and 0.2 part of azodiisobutyronitrile, and uniformly stirring to obtain diester phosphate mixed pre-emulsion;
c) adding 7.3 parts of pre-emulsion, 30.0 parts of deionized water, 0.2 part of azobisisobutyronitrile and 0.5 part of emulsifier COPS-I into a reaction kettle with a thermometer, a reflux condenser tube and a stirrer, and heating to 80-84 ℃ for reaction to prepare seed emulsion;
d) when bluing light appears in the reaction, slowly dropwise adding a mixed solution of 2.0 parts of acrylic acid, 42.0 parts of pre-emulsion and 0.4 part of azodiisobutyronitrile, and finishing dropwise adding within 1.5-2.0 h; then 16.2 parts of a phosphate diester mixed pre-emulsion is dripped, after dripping is finished within 1.0-1.5 h, the temperature is increased to 85-90 ℃, the reaction is carried out for 1h under the condition of heat preservation, the temperature is reduced to below 45 ℃, 1.4 parts of triethylamine is used for adjusting the pH value to be 7-8, and the filtration and discharge are carried out to obtain the salt mist resistant phosphate modified acrylic core-shell emulsion A1。
Example 5
Salt-fog-resistant phosphate modified acrylic core-shell emulsion B1The preparation process comprises the following steps:
a) weighing 18.0 parts of methyl acrylate, 15.0 parts of methyl methacrylate, 10.0 parts of butyl methacrylate, 100.3 parts of OP-100 and 20.0 parts of deionized water according to the weight part ratio of the formula, and dispersing at a high speed for 30min at 50 ℃ to prepare a pre-emulsion;
b) mixing 12.5 parts of pre-emulsion, 3.0 parts of diester phosphate B and 0.2 part of azobisisobutyronitrile, and uniformly stirring to obtain diester phosphate mixed pre-emulsion;
c) adding 7.5 parts of pre-emulsion, 28.0 parts of deionized water, 0.2 part of azobisisobutyronitrile and 0.5 part of emulsifier COPS-I into a reaction kettle with a thermometer, a reflux condenser tube and a stirrer, and heating to 80-84 ℃ for reaction to prepare seed emulsion;
d) when bluing light appears in the reaction, slowly dropwise adding a mixed solution of 2.5 parts of acrylic acid, 43.3 parts of pre-emulsion and 0.4 part of azodiisobutyronitrile, and finishing dropwise adding within 1.5-2.0 h; then dropwise adding 15.7 parts of a phosphate diester mixed pre-emulsion, after dropwise adding is finished within 1.0-1.5 h, heating to 85-90 ℃, carrying out heat preservation reaction for 1h, cooling to below 45 ℃, adjusting the pH value to 7-8 by using 1.9 parts of triethylamine, filtering and discharging to obtain the salt mist resistant phosphate modified acrylic core-shell emulsion B1。
Example 6
Salt-fog-resistant phosphate modified acrylic core-shell emulsion C1The preparation process comprises the following steps:
a) weighing 28.0 parts of methyl methacrylate, 10.0 parts of lauryl acrylate, 5.0 parts of butyl methacrylate, 100.3 parts of OP-100 and 20.0 parts of deionized water according to the weight part ratio of the formula, and dispersing at a high speed for 30min at 50 ℃ to prepare a pre-emulsion;
b) mixing 12.5 parts of pre-emulsion, 2.5 parts of phosphoric acid diester C and 0.2 part of azodiisobutyronitrile, and uniformly stirring to obtain phosphoric acid diester mixed pre-emulsion;
c) adding 7.0 parts of pre-emulsion, 29.0 parts of deionized water, 0.2 part of azobisisobutyronitrile and 0.5 part of emulsifier COPS-I into a reaction kettle with a thermometer, a reflux condenser tube and a stirrer, and heating to 80-84 ℃ for reaction to prepare seed emulsion;
d) when bluing light appears in the reaction, slowly dropwise adding a mixed solution of 2.0 parts of acrylic acid, 43.8 parts of pre-emulsion and 0.4 part of azodiisobutyronitrile, and finishing dropwise adding within 1.5-2.0 h; then dropwise adding 15.2 parts of a phosphate diester mixed pre-emulsion, after dropwise adding is finished within 1.0-1.5 h, heating to 85-90 ℃, carrying out heat preservation reaction for 1h, cooling to below 45 ℃, adjusting the pH value to 7-8 by using 1.9 parts of dimethylethanolamine, filtering and discharging to obtain the salt mist resistant phosphate modified acrylic core-shell emulsion C1。
The example emulsions of the invention were compared to the comparative example PMA-200 phosphate modified acrylic emulsion D according to the relevant standards, and the properties of the emulsions are shown in Table 1.
Glass transition temperature: the measurement was carried out by differential scanning calorimetry DSC.
Particle size and particle size distribution: a sample of about 100g of the emulsion was taken and tested with a particle size distribution instrument.
And (3) water resistance of the coating: the water absorption of the coating film is used for representing the water resistance of the coating film, and the higher the water absorption is, the poorer the water resistance is; adding the film-forming assistant into the emulsion, uniformly stirring, coating on a polytetrafluoroethylene plate, drying at room temperature for 7 days, stripping off a coating film, and weighing W1Completely immersing the coating film into deionized water, taking out after 24h, sucking the water on the surface by using filter paper, and weighing the weight W2When the water absorption of the coating film is (W)2－W1)/W1×100％。
Flash rust resistance: and (3) coating the emulsion on the treated tinplate, drying at room temperature, and visually observing whether flash rust exists in the coating drying process.
Table 1: comparison of emulsion coating film Performance between examples of the present invention and comparative examples
As seen from Table 1, the examples of the present invention are superior to the comparative examples in water resistance and high temperature resistance, because the self-emulsifying function of the long chain alkyl group on the phosphate group improves the high temperature stability of the emulsion, and the hydrophobic property of the long chain alkyl group improves the water resistance of the coating film.
Example emulsion A of the invention1、B1、C1The aqueous anticorrosive paint A and a comparative example (PMA-200 phosphate modified acrylic emulsion D) are respectively prepared according to the following formula2、B2、C2And comparative example D1。
The formula of the water-based anticorrosive paint comprises the following components: 30-50% of emulsion, 10-18% of filler (talcum powder and mica powder), 10-20% of iron oxide red, 20-30% of composite zinc phosphate, 0.5-1.5% of dispersing agent, 1.0-5.0% of film-forming assistant, 1.0-4.0% of other assistant and the balance of deionized water.
According to the relevant standards, the performance of the water-based anticorrosive paint is compared and detected, and the technical indexes of the performance are shown in table 2.
Table 2: technical performance index of water-based anticorrosive paint
As seen from Table 2, the water-based anticorrosive paint prepared from the emulsion of the invention has better water resistance, salt spray resistance and wet adhesion than the comparative examples, which is based on the dual functions (passivation effect and high water resistance) of the phospholipid modified acrylic resin of the invention, enhances the adhesion and compactness between a coating film and a base material, effectively isolates water molecules, chloride ions, sodium ions and the like from entering between the resin and the base material, and improves the adhesion and flash rust resistance under a wet environment, thereby improving the water resistance, the salt spray resistance and the rust and corrosion resistance.
Although the present invention has been described in detail and with reference to exemplary embodiments thereof, it will be apparent to one skilled in the art that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (4)
1. A preparation method of a salt-fog-resistant phosphate ester modified acrylic acid core-shell emulsion is characterized by comprising the following steps:
a) weighing acrylic acid soft and hard monomers, 50-60% of emulsifier and deionized water according to the weight part ratio of the formula, and dispersing at a high speed for 30min at 50 ℃ to prepare pre-emulsion;
b) mixing 20% of pre-emulsion, a certain amount of long-chain alkyl-acrylate phosphoric acid diester and part of azodiisobutyronitrile, and uniformly stirring to obtain phosphoric acid diester mixed pre-emulsion;
c) adding 10-20% of pre-emulsion, part of azodiisobutyronitrile and the rest of emulsifier into a reaction kettle with a thermometer, a reflux condenser pipe and a stirrer, and heating to 80-84 ℃ for reaction to obtain seed emulsion;
d) when bluing light appears in the reaction, slowly dropwise adding the mixed acrylic acid, the residual pre-emulsion and the residual azobisisobutyronitrile, and finishing dropwise adding within 1.5-2.0 h; then dropwise adding a phosphate diester mixed pre-emulsion, after dropwise adding is completed within 1.0-1.5 h, heating to 85-90 ℃, carrying out heat preservation reaction for 1h, cooling to below 45 ℃, adjusting the pH value to be 7-8 by using a neutralizing agent, filtering and discharging to obtain the salt mist resistant phosphate modified acrylic core-shell emulsion;
the composition of the raw materials in parts by weight is as follows:
30.0-50.0 parts of acrylate soft and hard monomer
1.5-4.0 parts of acrylic acid
2.0-5.0 parts of long-chain alkyl-acrylate phosphate diester
1.0-3.0 parts of neutralizer
0.5-2.0 parts of azobisisobutyronitrile
1.5-3.0 parts of emulsifier
40.0-60.0 parts of deionized water;
the long-chain alkyl-acrylate phosphoric acid diester comprises the following components in parts by weight: 35.0-45.0 parts of hydroxyl-containing acrylate monomer and R6-1030-40.0 parts of OH, 0.1-0.5 part of hydroquinone and 20-30.0 parts of phosphorus pentoxide; the preparation method comprises the following steps: adding a certain amount of hydroxyl-containing acrylate monomer and a certain amount of hydroquinone into a reaction kettle, uniformly stirring, heating to 50 ℃, and adding a certain amount of phosphorus pentoxide and R6-10Adding OH in batches, heating to 82 ℃ after adding OH within 1.5h, keeping the temperature for reaction for 3h, measuring the acid value, cooling after the acid value is qualified, and discharging to obtain the long-chain alkyl-acrylate phosphate diester; wherein, the hydroxyl-containing acrylate monomer is one or a combination of more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate; the R is6-10OH is C6-10A long chain alkyl monol;
the salt spray resistant phosphate modified acrylic acid core-shell emulsion comprises a core layer and a shell layer, wherein the shell layer contains long-chain alkyl-acrylate phosphate diester functional groups, the glass transition temperature Tg of the emulsion is 30-45 ℃, and the particle size is 60-150 nm.
2. The preparation method according to claim 1, wherein the acrylate hard monomer is one or a combination of methyl acrylate, methyl methacrylate, ethyl methacrylate and ethyl acrylate; the acrylate soft monomer is one or a combination of butyl acrylate, tert-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, isooctyl methacrylate, lauryl acrylate, stearyl methacrylate and stearyl acrylate; the molar ratio of the acrylate soft monomer to the acrylate hard monomer is 1: 0.1-1.
3. The preparation method of claim 1, wherein the emulsifier is one or more of COPS-I, CO-436 and OP-10.
4. The preparation method according to claim 1, wherein the neutralizing agent is one or more of triethylamine, ammonia water and dimethylethanolamine.
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