CN112552805B - Nano modified water-based polyester resin and preparation method thereof - Google Patents

Nano modified water-based polyester resin and preparation method thereof Download PDF

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CN112552805B
CN112552805B CN202011505190.4A CN202011505190A CN112552805B CN 112552805 B CN112552805 B CN 112552805B CN 202011505190 A CN202011505190 A CN 202011505190A CN 112552805 B CN112552805 B CN 112552805B
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polyester resin
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CN112552805A (en
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薛鹏
周海耀
赵蔚菡
王潇
孙涛
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Shanghai Morfant New Material Technology Co ltd
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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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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Abstract

The invention discloses a nano modified water-based polyester resin and a preparation method thereof, wherein the water-based polyester resin comprises the following components in percentage by mass: 50-70% of polymer solution; 2-8% of nano dispersion liquid; 30-40% of deionized water. The invention adopts the method of modifying nano materials to prepare the water-based polyester resin which is uniformly distributed on the interface of water-polymer colloidal particles and can prevent the water-based polyester resin from contacting with water so as to hinder the hydrolysis of ester bonds, thereby having excellent stability and hydrolysis resistance.

Description

Nano modified water-based polyester resin and preparation method thereof
Technical Field
The invention belongs to the field of water-based paint, and particularly relates to nano modified water-based polyester resin and a preparation method thereof.
Background
The water-based polyester resin has excellent mechanical properties and flexibility, and is widely used in the fields of metal baking varnish, leather, woodware, decoration and the like. In general, the synthesis of the water-based polyester resin needs to introduce carboxyl, sulfonic group and other groups, and then amine substances are used for neutralization to form salts. Because ester bonds are easy to hydrolyze under alkaline conditions, the storage time of the existing waterborne polyester resin is less than 3 months, and the stability is poor.
Disclosure of Invention
The invention aims to solve the problems and provide a nano modified water-based polyester resin and a preparation method thereof.
The purpose of the invention is realized by the following steps:
the nano modified water-based polyester resin comprises the following components in percentage by mass:
50-70% of polymer solution;
2-8% of nano dispersion liquid;
30-40% of deionized water;
the sum of the mass percentages of the components is 100 percent;
the polymer solution is prepared from the following components in percentage by mass:
adding 45-65% of organic acid or organic acid anhydride and 10-30% of organic alcohol into a reaction kettle, heating to 130-class temperature of 150 ℃, after the materials are completely dissolved, starting stirring, introducing nitrogen into the reaction kettle, heating to 210-class temperature of 230 ℃ at the speed of 10 ℃/h, continuously removing generated water through a water separator until the acid value reaches 12 +/-0.5 mgKOH/g, then cooling to 120 +/-10 ℃, adding 20-50% of ethylene glycol monobutyl ether, and stirring and dissolving uniformly, wherein the sum of the mass percentage of the components is 100%;
the nano dispersion liquid comprises the following components in parts by weight:
Figure BDA0002844711570000021
the main element precursor is selected from at least one of sodium chloride, calcium chloride, magnesium chloride, titanium tetrachloride, aluminum trichloride, ferrous chloride, copper chloride, beryllium chloride, strontium chloride, barium chloride, boron chloride, germanium chloride, tin chloride, lead chloride, arsenic chloride, strontium chloride, nickel chloride, vanadium chloride and gallium chloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the lipophilic donor is at least one selected from n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid and dodecylsulfonic acid.
The organic acid or organic acid anhydride in the nano modified water-based polyester resin is at least one selected from the group consisting of phthalic anhydride, isophthalic acid, maleic anhydride, adipic acid, sebacic acid, trimellitic anhydride, benzoic acid, abietic acid, soya oleic acid, linoleic acid, dehydrated ricinoleic acid, rape oleic acid, tall oil acid, coconut oleic acid, ricinoleic acid and dimer acid.
The organic alcohol in the nano modified water-based polyester resin is at least one selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, 1, 4-butanediol and diethylene glycol.
The pH value of the nano dispersion liquid in the nano modified water-based polyester resin is 2-5, and/or the solid content is 15% -25%, and/or the viscosity value is controlled to be 10-25s when the nano modified water-based polyester resin is coated in a 4-cup mode at the temperature of 25 ℃.
The particle size of the nano material in the nano dispersion liquid in the nano modified water-based polyester resin is 15nm-200 nm.
The preparation method of the nano dispersion liquid in the nano modified water-based polyester resin comprises the following steps:
(1) hydrolysis:
sequentially adding 20-30 parts of deionized water, an alkali neutralizing agent and 4-7 parts of lower alcohol into a reaction kettle, and starting stirring; adding the rest deionized water and the rest lower alcohol into a head tank, stirring at the speed of 300-; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding is completed, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
and (3) carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization.
The invention also provides a preparation method of the nano modified waterborne polyester resin, which comprises the following steps:
(1) adding the polymer solution into an emulsifying kettle, and starting stirring;
(2) and (3) dropwise adding the nano dispersion liquid into the polymer solution, and then dropwise adding deionized water until a continuous water phase is formed, so as to obtain the nano modified waterborne polyester resin.
The invention adopts the method of modifying the nano material to prepare the water-based polyester resin which is uniformly distributed on the interface of the water-polymer colloidal particles, can prevent the water-based polyester resin from contacting with water so as to prevent the hydrolysis of ester bonds, and has excellent stability and hydrolysis resistance.
Detailed Description
The present invention will be further described with reference to the following examples.
The nano modified water-based polyester resin comprises the following components in percentage by mass:
50-70% of polymer solution;
2-8% of nano dispersion liquid;
30-40% of deionized water;
the sum of the mass percentages of the components is 100 percent;
wherein,
the polymer solution comprises the following components in percentage by mass: 20-30% of ethylene glycol monobutyl ether, 35-65% of organic acid or organic acid anhydride and 10-30% of organic alcohol, wherein the sum of the mass percentages of the components is 100%;
the organic acid or organic acid anhydride is at least one selected from phthalic anhydride, isophthalic acid, maleic anhydride, adipic acid, sebacic acid, trimellitic anhydride, benzoic acid, abietic acid, soya oil acid, linoleic acid, dehydrated ricinoleic acid, rape oil acid, tall oil acid, coconut oil acid, ricinoleic acid and dimer acid;
the organic alcohol is at least one selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, 1, 4-butanediol and diethylene glycol;
the polymer solution was prepared by the following process:
adding 45-65% of organic acid or organic acid anhydride and 10-30% of organic alcohol into a reaction kettle, heating to 130-class temperature of 150 ℃, after the materials are completely dissolved, starting stirring, introducing nitrogen into the reaction kettle, heating to 210-class temperature of 230 ℃ at the speed of 10 ℃/h, continuously removing generated water through a water separator until the acid value reaches 12 +/-0.5 mgKOH/g, then cooling to 120 +/-10 ℃, adding 20-50% of ethylene glycol monobutyl ether, and stirring and dissolving uniformly, wherein the sum of the mass percentage of the components is 100%.
The nano dispersion liquid comprises the following components in parts by weight:
Figure BDA0002844711570000041
the main element precursor is selected from at least one of sodium chloride, calcium chloride, magnesium chloride, titanium tetrachloride, aluminum trichloride, ferrous chloride, copper chloride, beryllium chloride, strontium chloride, barium chloride, boron chloride, germanium chloride, tin chloride, lead chloride, arsenic chloride, strontium chloride, nickel chloride, vanadium chloride and gallium chloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the lipophilic donor is at least one selected from n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid, and dodecylsulfonic acid.
The pH value of the nano dispersion liquid is 2-5, and/or the solid content is 15% -25%, and/or the viscosity value is controlled to be 10-25s when the nano dispersion liquid is coated in a 4-cup mode under the condition of 25 ℃, and the particle size of the nano material in the nano dispersion liquid is 15nm-200 nm.
The preparation method of the nano dispersion liquid in the nano modified waterborne polyester resin comprises the following steps:
(1) hydrolysis:
sequentially adding 20-30 parts of deionized water, an alkali neutralizing agent and 4-7 parts of lower alcohol into a reaction kettle, and starting stirring; adding the rest deionized water and the rest lower alcohol into a head tank, stirring at the speed of 300-; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding is completed, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
and (3) carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization.
The preparation method of the nano modified waterborne polyester resin comprises the following steps:
(1) adding the polymer solution into an emulsifying kettle, and starting stirring;
(2) and (3) dropwise adding the nano dispersion liquid into the polymer solution, and then dropwise adding deionized water until a continuous water phase is formed.
Example 1:
the polymer solution comprises the following components in percentage by mass:
Figure BDA0002844711570000051
the polymerization process comprises the following steps: adding phthalic anhydride, linoleic acid and pentaerythritol into a reaction kettle, and heating to 140 ℃ until the materials are completely dissolved. Introducing nitrogen into the reaction kettle, heating to 220 ℃ at the speed of 10 ℃/h, and continuously removing water through a water separator. The acid value was sampled and measured until the acid value was less than 12 mgKOH/g. Then cooling to 120 ℃, adding ethylene glycol butyl ether and stirring to dissolve the mixture evenly.
The nano dispersion liquid comprises the following components in parts by weight:
Figure BDA0002844711570000052
Figure BDA0002844711570000061
adding 26 parts of deionized water and 2 parts of ethanol into a head tank, then slowly adding 28 parts of titanium tetrachloride, 1.2 parts of sodium dihydrogen phosphate and 4.8 parts of dodecyl trimethoxy silane in sequence, and uniformly stirring for later use. 30 parts of deionized water, 5 parts of ethanol and 3 parts of ammonia water are added into a reaction kettle and stirred at the speed of 500 r/min. And dropwise adding the solution in the head tank, finishing dropwise adding for 3 hours, and reacting for 2 hours after dropwise adding. Then the temperature is increased to 90 ℃, the reaction is carried out for 3 hours, and then the temperature is reduced to the room temperature.
Centrifuging the reaction solution for 45min at 4000r/min by using a centrifuge, then performing suction filtration under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solids to obtain clear liquid, namely the nano dispersion liquid of the embodiment 1. The dispersion had a solids content of 20%, a pH of 3.2, an average particle size of 35nm and a viscosity of 12s at 25 ℃ over-4 cups.
And transferring 55 parts of the polymer solution into a dispersion kettle, slowly dripping 6 parts of the nano dispersion liquid, and then dripping 39 parts of deionized water until a water continuous phase is formed to obtain the nano modified waterborne polyester resin of the embodiment.
Example 2:
preparation of polymer solution:
Figure BDA0002844711570000062
the polymerization process comprises the following steps: adding isophthalic acid, trimethylolpropane and tall oil acid into a reaction kettle, and heating to 140 ℃ until the materials are completely dissolved. Introducing nitrogen into the reaction kettle, heating to 220 ℃ at the speed of 10 ℃/h, and continuously removing water through a water separator. The acid value was sampled and measured until the acid value was less than 12 mgKOH/g. Then cooling to 120 ℃, adding ethylene glycol butyl ether and stirring to dissolve the mixture evenly.
The nano dispersion liquid comprises the following components in parts by weight:
Figure BDA0002844711570000063
Figure BDA0002844711570000071
adding 25 parts of deionized water and 3 parts of isopropanol into a head tank, then slowly adding 22 parts of titanium tetrachloride, 10 parts of aluminum chloride, 2.5 parts of sodium dihydrogen phosphate and 7 parts of dodecyl trimethoxy silane in sequence, and uniformly stirring for later use. 20 parts of deionized water, 6 parts of isopropanol and 4.5 parts of N, N-dimethylethanolamine are added into a reaction kettle, and stirring is started. And dropwise adding the solution in the head tank, finishing dropwise adding for 2.5 hours, and reacting for 3 hours after dropwise adding. Then the temperature is increased to 80 ℃, the reaction is carried out for 4 hours, and then the temperature is reduced to the room temperature. The reaction solution was centrifuged by a centrifuge, and then filtered to remove the solid, to obtain a clear solution, i.e., the nanodispersion of example 2, having a solid content of 23%, a pH of 3, an average particle diameter of 60nm, and a viscosity of 13s in 4 cups at 25 ℃.
And transferring 52 parts of the polymer solution into a dispersion kettle, slowly dropwise adding 5.5 parts of the nano dispersion liquid, and then dropwise adding 42.5 parts of deionized water until a water continuous phase is formed, thereby obtaining the nano modified waterborne polyester resin of the embodiment.
Example 3:
preparation of polymer solution:
Figure BDA0002844711570000072
the polymerization process comprises the following steps: adding trimethylolpropane, diethylene glycol, isophthalic acid, phthalic anhydride and benzoic acid into a reaction kettle, and heating to 140 ℃ until the materials are completely dissolved. Introducing nitrogen into the reaction kettle, heating to 220 ℃ at the speed of 10 ℃/h, and continuously removing water through a water separator. The acid value was sampled and measured until the acid value was less than 12 mgKOH/g. Then cooling to 120 ℃, adding ethylene glycol butyl ether and stirring to dissolve the mixture evenly.
The nano dispersion liquid comprises the following components in parts by weight:
Figure BDA0002844711570000081
adding 24.3 parts of deionized water and 4 parts of propanol into a head tank, then slowly adding 20 parts of titanium tetrachloride, 11 parts of strontium chloride, 2.2 parts of tripotassium phosphate and 6 parts of dodecyl trimethoxy silane in sequence, and uniformly stirring for later use. 25 parts of deionized water, 4 parts of propanol and 3.5 parts of monoethanolamine are added to the reaction kettle and stirred at a speed of 800 r/min. And dropwise adding the solution in the head tank, finishing dropwise adding for 3.5 hours, and reacting for 4 hours after dropwise adding. Then the temperature is increased to 95 ℃, the reaction is carried out for 5 hours, and then the temperature is reduced to the room temperature.
The reaction solution was centrifuged at 4500r/min for 45min, and then vacuum filtered at-0.4 MPa to-0.9 MPa, and the solid was filtered off to obtain the clear solution, i.e., the nanodispersion of example 3. The nano dispersion has a solid content of 21.7%, a pH of 2.9, an average particle diameter of 49nm, and a viscosity of 17s at 25 ℃ after coating in 4 cups.
And (3) transferring 57 parts of the polymer solution into a dispersion kettle, slowly dropwise adding 3.2 parts of the nano dispersion liquid, and then dropwise adding 39.8 parts of deionized water until a water continuous phase is formed, thereby obtaining the nano modified waterborne polyester resin of the embodiment.
Examples 1-3 and comparative examples the results of the storage test are shown in table 1:
table 1 examples 1-3 and comparative examples storability test results
Example 1 Example 2 Example 3 Comparative example
Acid value of solid, before storage 10mgKOH/g 8mgKOH/g 7mgKOH/g 45mgKOH/g
Solid acid value, 70 ℃/14d 12mgKOH/g 11mgKOH/g 11mgKOH/g 91mgKOH/g
Comparative example CM-0075 waterborne alkyd resin
It can be seen that although the acid values of the examples of the present invention are different from those of the comparative examples, the acid values of the examples are hardly changed after the same storage conditions, while the acid values of the examples are increased by more than 1-fold, indicating that most of the ester bonds are hydrolyzed to form acids and alcohols.
The invention adopts the method of modifying the nano material to prepare the water-based polyester resin which is uniformly distributed on the interface of the water-polymer colloidal particles, can prevent the water-based polyester resin from contacting with water so as to prevent the hydrolysis of ester bonds, and has excellent stability and hydrolysis resistance.
The above embodiments are provided only for illustrating the present invention and not for limiting the present invention, and those skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, and therefore all equivalent technical solutions should also fall within the scope of the present invention, and should be defined by the claims.

Claims (3)

1. The nano modified waterborne polyester resin is characterized by comprising the following components in percentage by mass:
50-70% of polymer solution;
2-8% of nano dispersion liquid;
30-40% of deionized water;
the sum of the mass percentages of the components is 100 percent;
the polymer solution is prepared from the following components in percentage by mass:
adding 45-65% of organic acid or organic acid anhydride and 10-30% of organic alcohol into a reaction kettle, heating to 130-plus-150 ℃, after the materials are completely dissolved, starting stirring, introducing nitrogen into the reaction kettle, heating to 210-plus-230 ℃ at the speed of 10 ℃/h, continuously removing generated water through a water separator until the acid value reaches 12 +/-0.5 mgKOH/g, then cooling to 120 +/-10 ℃, adding 20-50% of ethylene glycol monobutyl ether, stirring and dissolving uniformly, wherein the sum of the mass percentages of the components is 100%;
the organic acid or the organic acid anhydride is selected from at least one of phthalic anhydride, isophthalic acid, maleic anhydride, adipic acid, sebacic acid, trimellitic anhydride, benzoic acid, abietic acid, soyaoleic acid, linoleic acid, dehydrated ricinoleic acid, erucic acid, tall oil acid, coconut oil acid, ricinoleic acid and dimer acid;
the organic alcohol is at least one selected from ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol, 1, 4-butanediol and diethylene glycol;
the nano dispersion liquid comprises the following components in parts by weight:
25-35 parts of a main element precursor;
1-4 parts of a doping element precursor;
3-8 parts of a lipophilic donor;
1-5 parts of an alkali neutralizing agent;
5-10 parts of lower alcohol;
50-85 parts of deionized water;
the main element precursor is selected from titanium tetrachloride, titanium tetrachloride and aluminum trichloride, or titanium tetrachloride and strontium chloride;
the doping element precursor is selected from at least one of sodium dihydrogen phosphate, tripotassium phosphate, potassium nitrate, sodium sulfate and potassium sulfate;
the oleophylic donor is selected from at least one of n-hexyltrichlorosilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrichlorosilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, dodecyltrichlorosilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, dodecylcarboxylic acid, hexadecylcarboxylic acid and dodecylsulfonic acid;
the preparation method of the nano dispersion liquid comprises the following steps:
(1) hydrolysis:
sequentially putting 20-30 parts of the deionized water, the alkali neutralizing agent and 4-7 parts of the lower alcohol into a reaction kettle, and starting stirring; adding the rest deionized water and the rest lower alcohol into a head tank, stirring at the speed of 300-800r/min, sequentially and slowly adding the main element precursor, the doped element precursor and the lipophilic donor, and stirring to form a uniform solution; dropwise adding the solution in the elevated tank into the reaction kettle at a constant speed for 2-5h, continuously reacting for 1-5h after dropwise adding, heating to 80-120 ℃, reacting for 2-8h, and cooling to room temperature;
(2) centrifugal separation:
introducing the liquid in the reactor into a centrifuge for centrifugal separation at the speed of 3000-5000r/min for 30-60 min;
(3) and (3) suction filtration:
carrying out suction filtration on the liquid after centrifugal separation under the vacuum pressure of-0.4 Mpa to-0.9 Mpa, and filtering out solid matters to obtain clear liquid, namely the nano dispersion liquid for emulsion polymerization;
the preparation method of the nano modified water-based polyester resin comprises the following steps:
(1) adding the polymer solution into an emulsifying kettle, and starting stirring;
(2) and (3) dropwise adding the nano dispersion liquid into the polymer solution, and then dropwise adding deionized water until a continuous water phase is formed, so as to obtain the nano modified waterborne polyester resin.
2. The nano-modified waterborne polyester resin of claim 1, wherein the nano-dispersion has a pH of 2 to 5, and/or a solid content of 15% to 25%, and/or a viscosity value controlled at 25 ℃ for 10 to 25s in-4 cups.
3. The nano-modified waterborne polyester resin of claim 1, wherein the nano-material in the nano-dispersion has a particle size of 15nm to 200 nm.
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Denomination of invention: A nano modified waterborne polyester resin and its preparation method

Granted publication date: 20220909

Pledgee: Shanghai Rural Commercial Bank Co.,Ltd. Jinshan sub branch

Pledgor: SHANGHAI MORFANT NEW MATERIAL TECHNOLOGY Co.,Ltd.

Registration number: Y2024310000172