CN110563936A - Self-flame-retardant antibacterial water-based polyester resin and preparation method thereof - Google Patents
Self-flame-retardant antibacterial water-based polyester resin and preparation method thereof Download PDFInfo
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
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- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
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- 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
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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
- C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
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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
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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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
- C09D5/18—Fireproof paints including high temperature resistant paints
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Abstract
The invention relates to a self-flame-retardant antibacterial water-based polyester resin and a preparation method thereof, wherein the self-flame-retardant antibacterial water-based polyester resin comprises the following components in parts by weight: 6.0-12.0 parts of organic acid anhydride, 3.0-5.0 parts of carboxylic acid Schiff base, 3.0-8.0 parts of polybasic acid, 6.0-20.0 parts of polyhydric alcohol, 1.2-3.5 parts of 2-chloro-5-bromobenzoic acid, 1.5-3.5 parts of dimethylolpropionic acid, 2.0-5.0 parts of dimethylbenzene, 2.0-5.0 parts of neutralizing agent and 45.0-65.0 parts of deionized water; the self-flame-retardant antibacterial water-based polyester resin has the advantages of good coloring performance, low viscosity, high hardness, good fullness, good vividness and the like; when the water-based paint is prepared, a flame retardant and an antibacterial agent are not required to be added, the flame-retardant antibacterial effect is lasting, the efficiency is high, and the water-based paint can be used for internal and external wall paints, water-based industrial paints, water-based wood paints and the like.
Description
Technical Field
The invention relates to a preparation method of modified waterborne polyester resin, in particular to self-flame-retardant antibacterial waterborne polyester resin and a preparation method thereof, belonging to the technical field of synthetic resin.
Background
the polyester resin is a general name of a high molecular compound formed by esterification and polycondensation of dibasic acid or polybasic acid and dihydric alcohol or polyhydric alcohol. The polyester resin has ester groups connected to its chain units, excellent cold resistance, chemical resistance, electric performance, excellent coloring performance, low viscosity, high fullness, high brightness and other advantages, and is one kind of paint resin with excellent performance. Polyester resin is often matched with amino resin to prepare decorative coating, but because the solubility parameters of the polyester resin and the amino resin are greatly different, the polyester varnish has the defects of easy light loss, insufficient transparency and the like in use, and the use range of the polyester resin is limited.
When the polyester resin is synthesized, if some other components are introduced through chemical reaction, the polyester resin can have the performance which is not possessed originally by the polyester resin, the purpose of improving and highlighting certain performance is achieved, the special application performance requirements are met, and epoxy, acrylic acid and organic silicon modified polyester resins are mostly used at present. The most common saturated polyester resin in the coating industry is a polyester resin containing a terminal hydroxyl functional group, and is cured into a film by crosslinking with resins such as isocyanate, amino resin and the like. Different raw materials make different contributions to the resin performance, and the raw materials are selected according to the performance requirement of the resin, and the corresponding raw materials which can help the required performance of the resin are selected, so that the multifunctional polyurethane resin has the advantages of functionality, hardness, flexibility and the like.
along with the development of society and the improvement of living standard of people, self health, living quality and living environment are highly valued by people. In the decoration process, people usually select a coating with an antibacterial effect. Chinese patent CN108192357A discloses an antibacterial unsaturated polyester resin, which belongs to the technical field of resin preparation, and comprises the following raw materials: unsaturated polyester resin, isophthalic anhydride, phthalic anhydride, benzenetriol, hydroquinone, cobalt naphthenate, styrene, methyl ethyl ketone peroxide, phosphate melamine, ethylene glycol, organic silicon, aluminum hydroxide, a carbon nano-tube, N-dimethylaniline, nano-zinc powder, kaolin, calcium sulfate whisker, nano-montmorillonite, nano-titanium dioxide, a silane coupling agent KH-560 and an antibacterial modification auxiliary agent, wherein the antibacterial unsaturated polyester resin is prepared by preparing a base material, preparing a modification material, mixing the base material, the modification material and other materials; chinese patent CN105670238A discloses a bactericidal polyester resin, which comprises the following components in parts by weight: 95 parts of PBT, 5 parts of PET and 0.2-0.4 part of a composite antibacterial agent; chinese patent CN106366600A discloses an antibacterial unsaturated polyester resin for an anchoring agent, which comprises the following raw materials in parts by weight: 0.5-1 part of zinc stearate, 2-4 parts of trioctyl ester, 1.5-2.5 parts of 8-hydroxyquinoline, 1.5-2.5 parts of bis (2, 2, 6, 6-tetramethyl-4-yl) sebacate, 2-4 parts of p-phenylenediamine, 3-7 parts of modified glycerol, 70-90 parts of phthalic anhydride, 20-30 parts of isophthalic acid, 50-70 parts of diethylene glycol, 20-25 parts of methyl methacrylate and 25-45 parts of styrene; the invention achieves the antibacterial effect by adding the antibacterial modification auxiliary agent, has no flame resistance, is difficult to meet the requirement of social multifunctionalization, and has certain limitation.
On the other hand, along with the improvement of living standard of people, flame-retardant architectural coatings and flame-retardant finish coatings are popular with consumers. Chinese patent CN105349016A discloses a novel flame-retardant water-based paint, which is composed of the following raw materials: the composite flame retardant comprises an aqueous polyurethane emulsion, epoxy resin, hydroxyethyl cellulose, aluminum tripolyphosphate, a mixed solvent of absolute ethyl alcohol and N, N-dimethylformamide in a volume ratio of 1:20-1:2, a phosphorus-nitrogen composite flame retardant, dimethyl methyl phosphate, an isocyanate compound and a defoaming agent. The flame retardant property of the flame retardant is provided by the externally added flame retardant, and the externally added flame retardant has the defects of non-uniform dispersion, flame retardant time period, easy migration and pulverization and the like.
The existing coating basically does not have good antibacterial, bactericidal and flame retardant properties, so that the self-flame-retardant antibacterial water-based resin is necessary to be provided.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a self-flame-retardant antibacterial water-based polyester resin.
The invention also aims to provide a preparation method of the self-flame-retardant antibacterial water-based polyester resin, which has the characteristics of simple and convenient process, easy control, stable reaction system and the like.
The invention adds reactive carboxylic acid Schiff base, wherein halogen-containing flame retardant groups and good antibacterial Schiff base groups in the carboxylic acid Schiff base can be subjected to esterification reaction with alcohols to synthesize the flame-retardant antibacterial group-containing polyester water-based resin. The water-based resin can play a role in flame retardance and antibiosis without adding other flame retardants and antibacterial agents, and has durable flame retardance and antibacterial performance because the flame-retardant halogen and antibacterial Schiff base groups are combined with the polyester resin through chemical bonds and are not easy to dissociate.
the self-flame-retardant antibacterial water-based polyester resin prepared by the invention is applied to the coating, and the coating has lasting flame retardance and antibacterial property without adding other flame retardants and antibacterial agents, so that the defects of poor durability, easy elution, easy degradation and the like of physically added antibacterial agents and flame retardants are overcome.
In order to increase the flame retardance of the waterborne polyester resin and adjust the molecular weight of the resin, 2-chloro-5-bromobenzoic acid is added.
In order to solve the technical problems, the invention adopts the following technical scheme: the invention relates to a self-flame-retardant antibacterial water-based polyester resin which comprises the following components in parts by weight: 6.0-12.0 parts of organic acid anhydride, 3.0-5.0 parts of carboxylic acid Schiff base, 3.0-8.0 parts of polybasic acid, 6.0-20.0 parts of polyhydric alcohol, 1.2-3.5 parts of 2-chloro-5-bromobenzoic acid, 1.5-3.5 parts of dimethylolpropionic acid, 2.0-5.0 parts of dimethylbenzene, 2.0-5.0 parts of neutralizing agent and 45.0-65.0 parts of deionized water.
The carboxylic acid Schiff base is prepared by reacting 4-amino-6-chloronicotinic acid with 4-fluorocinnamaldehyde.
The organic acid anhydride is one or a combination of more of phthalic anhydride, acetic anhydride, succinic anhydride, dodecyl succinic anhydride and maleic anhydride.
The polybasic acid is one or a combination of more of terephthalic acid, isophthalic acid, adipic acid, tetradecanedioic acid and sebacic acid.
the polyhydric alcohol is one or a combination of more of propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol and pentaerythritol.
The neutralizing agent is at least one of triethylamine and ammonia water.
The preparation method of the carboxylic acid Schiff base comprises the following steps:
Adding 4-fluorocinnamaldehyde and a proper amount of ethanol into a multifunctional reaction kettle according to the formula ratio (the molar ratio of 4-amino-6-chloronicotinic acid to 4-fluorocinnamaldehyde is 1: 1), heating to 80-84 ℃, and uniformly stirring; and in addition, weighing 4-amino-6-chloronicotinic acid and ethanol according to the formula ratio, adding the mixture into a dropwise adding tank, stirring uniformly, slowly dropwise adding the mixture into a reaction kettle, adding a small amount of glacial acetic acid as a catalyst, continuously performing reflux reaction for 5-6 h, cooling to room temperature, standing overnight, recrystallizing, and performing vacuum drying to obtain the carboxylic acid Schiff base.
the ethanol is mainly used as a solvent and a reflux solvent, and has the functions of dissolving raw materials and keeping the temperature of a reaction system stable.
The invention provides a preparation method of self-flame-retardant antibacterial water-based polyester resin, which comprises the following steps:
a) Sequentially adding polybasic acid, organic acid anhydride, polyalcohol, dimethylolpropionic acid and dimethylbenzene according to the weight part of the formula into a reactor provided with a thermometer, a condenser, a water separator and a stirrer, and introducing N under the condition of low-speed stirring2；
b) Heating to 110-120 ℃ until reflux, keeping the temperature for 0.5h, removing free water, continuously heating to 160-170 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400-500 r/min after the materials are dissolved, then heating to 180 ℃, adding carboxylic acid Schiff base, keeping the temperature for reaction for 1-1.5 h, heating to 210-220 ℃ at the speed of 20 ℃/h, and keeping the temperature for reaction for 2-3 h;
c) Cooling to 180 ℃, adding 2-chloro-5-bromobenzoic acid, carrying out heat preservation reaction for 0.5h, then rapidly heating to 215-225 ℃, carrying out heat preservation reaction for 2.5-3.5 h, then measuring the acid value every 15-30 min, cooling to 160 ℃ when the acid value reaches a theoretical design value, starting a vacuum pump, evaporating to remove a solvent xylene, cooling to 50 ℃, adding a neutralizer, stirring at a high speed to fully neutralize the solvent, adding deionized water with the formula amount, stirring and dispersing uniformly, and filtering to obtain the self-flame-retardant antibacterial waterborne polyester resin.
The self-flame-retardant antibacterial water-based polyester resin prepared by the invention has the following advantages:
1) The self-flame-retardant antibacterial water-based polyester resin has the advantages of good coloring performance, low viscosity, high hardness, good fullness, good vividness and the like.
2) And 2-chloro-5-bromobenzoic acid is added, so that the flame retardant property can be improved, and the molecular weight of the polyester resin can be adjusted.
3) when the water-based paint is prepared, a flame retardant and an antibacterial agent are not required to be added, the flame-retardant antibacterial effect is lasting, the efficiency is high, and the water-based paint can be used for internal and external wall paints, water-based industrial paints, water-based wood paints and the like.
Detailed Description
the present invention will be further described with reference to the following examples. It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
example 1
A self-flame-retardant antibacterial water-based polyester resin is prepared by the following steps:
a) Adding 4.0 parts of terephthalic acid, 8.0 parts of phthalic anhydride, 6.0 parts of neopentyl glycol, 7.0 parts of trimethylolpropane, 2.0 parts of dimethylolpropionic acid and 3.0 parts of dimethylbenzene in a reactor provided with a thermometer, a condenser, a water separator and a stirrer in sequence according to the weight parts of the formula, and introducing N into the reactor under low-speed stirring2；
b) Heating to 115 ℃ until reflux, keeping the temperature for 0.5h, removing free water, continuing to heat to 165 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400r/min after the materials are dissolved, then heating to 180 ℃, adding 4.0 parts of carboxylic acid Schiff base, keeping the temperature for reaction for 1.5h, heating to 215 ℃ at the speed of 20 ℃/h, and keeping the temperature for reaction for 3 h;
c) Cooling to 180 ℃, adding 2.0 parts of 2-chloro-5-bromobenzoic acid, carrying out heat preservation reaction for 0.5h, then rapidly heating to 220 ℃, carrying out heat preservation reaction for 3.0h, then measuring the acid value every 15min, cooling to 160 ℃ when the acid value reaches a theoretical design value, starting a vacuum pump, evaporating off a solvent xylene, cooling to 50 ℃, adding 2.0 parts of triethylamine, stirring at a high speed to fully neutralize the triethylamine, adding 62.0 parts of deionized water according to the formula amount, stirring and dispersing uniformly, and filtering to obtain the self-flame-retardant antibacterial waterborne polyester resin which is marked as sample 1.
Example 2
A self-flame-retardant antibacterial water-based polyester resin is prepared by the following steps:
a) adding 5.0 parts of adipic acid, 8.0 parts of acetic anhydride, 2.0 parts of dodecyl succinic anhydride, 7.0 parts of 1, 4-butanediol, 6.0 parts of trimethylolpropane, 3.0 parts of dimethylolpropionic acid and 4.0 parts of dimethylbenzene in sequence by weight of the formula into a reactor provided with a thermometer, a condenser, a water separator and a stirrer, and introducing N into the reactor under low-speed stirring2；
b) Heating to 120 ℃ until reflux, keeping the temperature for 0.5h, removing free water, continuing to heat to 160 ℃, stirring and keeping the temperature for 1h at the rotating speed of 500r/min after the materials are dissolved, then heating to 180 ℃, adding 4.2 parts of carboxylic acid Schiff base, keeping the temperature for reaction for 1.5h, heating to 220 ℃ at the speed of 20 ℃/h, and keeping the temperature for reaction for 3 h;
c) Cooling to 180 ℃, adding 3.1 parts of 2-chloro-5-bromobenzoic acid, carrying out heat preservation reaction for 0.5h, then rapidly heating to 220 ℃, carrying out heat preservation reaction for 2.5h, then measuring the acid value every 30min, cooling to 160 ℃ when the acid value reaches a theoretical design value, starting a vacuum pump, evaporating off a solvent xylene, cooling to 50 ℃, adding 2.8 parts of ammonia water, stirring at a high speed to fully neutralize the ammonia water, adding 54.9 parts of deionized water according to the formula amount, stirring and dispersing uniformly, and filtering to obtain the self-flame-retardant antibacterial waterborne polyester resin which is marked as sample 2.
Example 3
A self-flame-retardant antibacterial water-based polyester resin is prepared by the following steps:
a) In a reactor equipped with thermometer, condenser, water separator and stirrerThe weight portions are that 6.0 portions of sebacic acid, 6.0 portions of maleic anhydride, 5.0 portions of phthalic anhydride, 5.2 portions of pentaerythritol, 10.0 portions of 1,4 cyclohexanediol, 3.2 portions of dimethylolpropionic acid and 4.6 portions of dimethylbenzene are added in sequence, N is introduced under the condition of low-speed stirring2；
b) Heating to 110 ℃ until reflux, keeping the temperature for 0.5h, removing free water, continuing to heat to 170 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400r/min after the materials are dissolved, then heating to 180 ℃, adding 4.8 parts of carboxylic acid Schiff base, keeping the temperature for reaction for 1.0h, heating to 210 ℃ at the speed of 20 ℃/h, and keeping the temperature for reaction for 3 h;
c) Cooling to 180 ℃, adding 3.2 parts of 2-chloro-5-bromobenzoic acid, carrying out heat preservation reaction for 0.5h, then rapidly heating to 215 ℃, carrying out heat preservation reaction for 3.5h, then measuring the acid value every 30min, cooling to 160 ℃ when the acid value reaches a theoretical design value, starting a vacuum pump, evaporating off a solvent xylene, cooling to 50 ℃, adding 3.5 parts of triethylamine, stirring at a high speed to fully neutralize the triethylamine, adding 48.5 parts of deionized water according to the formula amount, stirring and dispersing uniformly, and filtering to obtain the self-flame-retardant antibacterial waterborne polyester resin, wherein the sample is marked as sample 3.
And (3) testing performance indexes: samples 1, 2 and 3 in the above examples and a conventional waterborne polyester resin 4 were prepared into coatings according to the raw material formulation shown in Table 1, and the corresponding coating samples were respectively designated as coating 1, coating 2, coating 3 and coating 4, and the properties thereof were respectively tested.
Table 1: coating formulation
The prepared coating is subjected to performance index tests according to relevant standards of water resistance (GB/T1733-1993), adhesion (GB/T9286-1998), flexibility (GB/T1731-1993), salt fog resistance (GB/T1771-2007), artificial aging resistance (GB/T14522), pencil hardness (GB/T6739-1996), acid resistance ((10% HCl) GB/T1763-1979), alkali resistance ((10% NaOH) GB/1763-1979) and the like, and the test results are shown in Table 2:
table 2: performance specification of coating
it can be seen from table 2 that the samples of examples 1, 2 and 3 of the present invention have better properties of fullness, hardness, salt spray resistance, artificial aging resistance, alkali resistance, acid resistance, etc. than the conventional aqueous polyester resin.
The prepared paint is tested for the antibacterial performance according to the standard of HG/T3950-2007 antibacterial paint, and the test results are shown in the following table 3:
Table 3: test results of antibacterial properties of the coating
It can be seen from table 3 that the antibacterial performance of the samples of example 1, example 2, and example 3 of the present invention is much better than that of the conventional aqueous polyester resin, and the antibacterial performance is enhanced as the amount of the carboxylic acid schiff base is increased.
The prepared coating is tested for flame retardant property according to GB12441-2005, and the test results are shown in Table 4:
table 4: technical index of flame retardant property of coating
from table 4, it can be seen that the flame retardant performance of the samples of examples 1, 2 and 3 of the present invention is acceptable, while the flame retardant performance of the conventional waterborne polyester resin is unacceptable, and the flame retardant performance of the examples of the present invention is far superior to that of the conventional waterborne polyester resin.
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 (7)
1. A self-flame-retardant antibacterial water-based polyester resin is characterized in that: the self-flame-retardant antibacterial water-based polyester resin comprises the following components in parts by weight: 6.0-12.0 parts of organic acid anhydride, 3.0-5.0 parts of carboxylic acid Schiff base, 3.0-8.0 parts of polybasic acid, 6.0-20.0 parts of polyhydric alcohol, 1.2-3.5 parts of 2-chloro-5-bromobenzoic acid, 1.5-3.5 parts of dimethylolpropionic acid, 2.0-5.0 parts of dimethylbenzene, 2.0-5.0 parts of neutralizing agent and 45.0-65.0 parts of deionized water;
Wherein the carboxylic acid Schiff base is prepared by reacting 4-amino-6-chloronicotinic acid with 4-fluorocinnamaldehyde.
2. The self-flame retardant antibacterial waterborne polyester resin as claimed in claim 1, wherein: the organic acid anhydride is one or a combination of more of phthalic anhydride, acetic anhydride, succinic anhydride, dodecyl succinic anhydride and maleic anhydride.
3. the self-flame retardant antibacterial waterborne polyester resin as claimed in claim 1, wherein: the polybasic acid is one or a combination of more of terephthalic acid, isophthalic acid, adipic acid, tetradecanedioic acid and sebacic acid.
4. the self-flame retardant antibacterial waterborne polyester resin as claimed in claim 1, wherein: the polyhydric alcohol is one or a combination of more of propylene glycol, 1, 4-butanediol, 1, 4-cyclohexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, trimethylolpropane, glycerol and pentaerythritol.
5. The self-flame retardant antibacterial waterborne polyester resin as claimed in claim 1, wherein: the neutralizing agent is at least one of triethylamine and ammonia water.
6. the self-flame retardant antibacterial waterborne polyester resin as claimed in claim 1, wherein: the preparation method of the carboxylic acid Schiff base comprises the following steps:
Adding 4-fluorocinnamaldehyde and a proper amount of ethanol into a multifunctional reaction kettle according to the formula ratio (the molar ratio of 4-amino-6-chloronicotinic acid to 4-fluorocinnamaldehyde is 1: 1), heating to 80-84 ℃, and uniformly stirring; and in addition, weighing 4-amino-6-chloronicotinic acid and ethanol according to the formula ratio, adding the mixture into a dropwise adding tank, stirring uniformly, slowly dropwise adding the mixture into a reaction kettle, adding a small amount of glacial acetic acid as a catalyst, continuously performing reflux reaction for 5-6 h, cooling to room temperature, standing overnight, recrystallizing with ethanol, and performing vacuum drying to obtain the carboxylic acid Schiff base.
7. A method for preparing the self-flame retardant antibacterial waterborne polyester resin as claimed in claim 1, wherein: the preparation steps are as follows:
a) Sequentially adding polybasic acid, organic acid anhydride, polyalcohol, dimethylolpropionic acid and dimethylbenzene according to the weight part of the formula into a reactor provided with a thermometer, a condenser, a water separator and a stirrer, and introducing N under the condition of low-speed stirring2；
b) heating to 110-120 ℃ until reflux, keeping the temperature for 0.5h, removing free water, continuously heating to 160-170 ℃, stirring and keeping the temperature for 1h at the rotating speed of 400-500 r/min after the materials are dissolved, then heating to 180 ℃, adding carboxylic acid Schiff base, keeping the temperature for reaction for 1-1.5 h, heating to 210-220 ℃ at the speed of 20 ℃/h, and keeping the temperature for reaction for 2-3 h;
c) Cooling to 180 ℃, adding 2-chloro-5-bromobenzoic acid, carrying out heat preservation reaction for 0.5h, then rapidly heating to 215-225 ℃, carrying out heat preservation reaction for 2.5-3.5 h, then measuring the acid value every 15-30 min, cooling to 160 ℃ when the acid value reaches a theoretical design value, starting a vacuum pump, evaporating to remove a solvent xylene, cooling to 50 ℃, adding a neutralizer, stirring at a high speed to fully neutralize the solvent, adding deionized water with the formula amount, stirring and dispersing uniformly, and filtering to obtain the self-flame-retardant antibacterial waterborne polyester resin.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540636A (en) * | 2019-09-01 | 2019-12-06 | 合众（佛山）化工有限公司 | rare earth modified waterborne alkyd resin and preparation method thereof |
| CN113801544A (en) * | 2020-06-17 | 2021-12-17 | 陕西名肯新材料有限公司 | A-grade fireproof decorative coating and preparation method thereof |
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| CN102212188A (en) * | 2011-04-22 | 2011-10-12 | 常州市科祥化工有限公司 | Polyester resin for aqueous coil coating and preparation method thereof |
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| CN108084422A (en) * | 2017-12-15 | 2018-05-29 | 合众（佛山）化工有限公司 | A kind of antibacterial aqueous alkyd resin of structural type and preparation method thereof |
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| CN102212188A (en) * | 2011-04-22 | 2011-10-12 | 常州市科祥化工有限公司 | Polyester resin for aqueous coil coating and preparation method thereof |
| CN104448273A (en) * | 2014-12-10 | 2015-03-25 | 泰兴市华盛银洋树脂有限公司 | Indoor physical-matting-type saturated polyester resin as well as preparation method thereof and coating |
| CN107987693A (en) * | 2017-12-15 | 2018-05-04 | 合众（佛山）化工有限公司 | A kind of long-lasting antibacterial water alcohol acid coating |
| CN108084422A (en) * | 2017-12-15 | 2018-05-29 | 合众（佛山）化工有限公司 | A kind of antibacterial aqueous alkyd resin of structural type and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110540636A (en) * | 2019-09-01 | 2019-12-06 | 合众（佛山）化工有限公司 | rare earth modified waterborne alkyd resin and preparation method thereof |
| CN113801544A (en) * | 2020-06-17 | 2021-12-17 | 陕西名肯新材料有限公司 | A-grade fireproof decorative coating and preparation method thereof |
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