CN118496488A - Preparation method of waterborne polyester with antibacterial function - Google Patents
Preparation method of waterborne polyester with antibacterial function Download PDFInfo
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- CN118496488A CN118496488A CN202410980207.3A CN202410980207A CN118496488A CN 118496488 A CN118496488 A CN 118496488A CN 202410980207 A CN202410980207 A CN 202410980207A CN 118496488 A CN118496488 A CN 118496488A
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- 229920000728 polyester Polymers 0.000 title claims abstract description 38
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011973 solid acid Substances 0.000 claims abstract description 25
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001816 cooling Methods 0.000 claims abstract description 19
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010790 dilution Methods 0.000 claims abstract description 15
- 239000012895 dilution Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims abstract description 5
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003113 dilution method Methods 0.000 claims abstract description 5
- 229920000954 Polyglycolide Polymers 0.000 claims description 18
- 239000004633 polyglycolic acid Substances 0.000 claims description 18
- 230000000630 rising effect Effects 0.000 claims description 18
- 150000003512 tertiary amines Chemical class 0.000 claims description 14
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 claims description 8
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 229940043237 diethanolamine Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 claims description 6
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000003973 paint Substances 0.000 abstract description 8
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract description 7
- 239000003242 anti bacterial agent Substances 0.000 abstract description 6
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 229920003180 amino resin Polymers 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000001888 Peptone Substances 0.000 description 1
- 108010080698 Peptones Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000007640 basal medium Substances 0.000 description 1
- 235000015278 beef Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002081 enamines Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000019319 peptone Nutrition 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds 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
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Plant Pathology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a preparation method of water-based polyester with an antibacterial function, which comprises the following steps: s1, under the condition of nitrogen, diethylene glycol and 1, 6-hexanediol are added into a reaction kettle, stirring and heating are carried out to 60-80 ℃, terephthalic acid and a catalyst di-n-butyltin oxide are added, and gradual heating reaction is carried out until the solid acid value is less than 2; S2-S5; s6, introducing nitrogen into the dilution kettle, adding ethylene glycol butyl ether and propylene glycol methyl ether, preheating to 60-80 ℃, stirring for 55-60r/min, transferring the materials of the reaction kettle into the dilution kettle, maintaining the dilution temperature at 80-100 ℃ in the dilution process, cooling to 50-55 ℃ and discharging after the solid content and viscosity are detected to be qualified, and thus obtaining the water-based polyester with an antibacterial function. The beneficial effects of the invention are as follows: compared with the method of adding the antibacterial agent, the method introduces the quaternary ammonium salt polymer into the polyester molecular chain, so that the paint film prepared from the water-based polyester has smooth and high appearance, excellent adhesive force and pencil hardness, and the antibacterial rate can reach 99.99%.
Description
Technical Field
The invention relates to the technical field of waterborne polyesters, in particular to a preparation method of a waterborne polyester with an antibacterial function.
Background
The synthesis of the oily polyester resin generally adopts volatile organic compounds with relatively high toxicity such as dimethylbenzene and the like as solvents, and brings harm to the environment and staff.
The water-based polyester paint is an important environment-friendly water-based paint, has the characteristics of high gloss, strong adhesive force, high fullness, excellent impact resistance and the like, and can be prepared into water-based baking paint with water-soluble amino resin, but the traditional water-based polyester has no antibacterial performance or needs to be added with additional antibacterial agents, so that the application range of polyester materials is limited.
Disclosure of Invention
In order to solve the problems mentioned in the background art, the present invention provides a method for preparing an aqueous polyester having an antibacterial function.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A preparation method of an aqueous polyester with an antibacterial function comprises the following steps:
S1, under the condition of nitrogen, diethylene glycol and 1, 6-hexanediol are added into a reaction kettle, stirring and heating are carried out to 60-80 ℃, terephthalic acid and a catalyst di-n-butyltin oxide are added, and gradual heating reaction is carried out until the solid acid value is less than 2;
S2, adding hexahydrophthalic anhydride into the reaction kettle, and gradually heating to react until the solid acid value is 99-102;
s3, adding trimethylolpropane, tertiary amine modified polyglycolic acid into the reaction kettle, and gradually heating to react until the solid acid value is 18-21;
S4, adding trimellitic anhydride and dipropylene glycol methyl ether into the reaction kettle, and gradually heating to react until the solid acid value is 25.5-27.5;
S5, adding 2-bromoethyl ether into the reaction kettle, gradually heating to 70 ℃, and carrying out heat preservation reaction for 3 hours;
s6, introducing nitrogen into the dilution kettle, adding ethylene glycol butyl ether and propylene glycol methyl ether, preheating to 60-80 ℃, stirring for 55-60r/min, transferring the materials of the reaction kettle into the dilution kettle, maintaining the dilution temperature at 80-100 ℃ in the dilution process, cooling to 50-55 ℃ and discharging after the solid content and viscosity are detected to be qualified, and thus obtaining the water-based polyester with an antibacterial function.
Preferably, the conditions of the gradual temperature increase in the step S1 are: heating to 144-149 deg.c at 0.6-0.9 deg.c/min for 30min, heating to 173-178 deg.c for 40min at 0.4-0.6 deg.c/min, heating to 203-205 deg.c, reacting to solid acid value less than 2, and cooling to 155-159 deg.c.
Preferably, the conditions for gradually increasing the temperature in S2 are as follows: heating to 187-195 deg.c at 0.2-0.3 deg.c/min, maintaining for 20min, heating to 208-210 deg.c, reacting to solid acid value of 99-102, and cooling to 135-140 deg.c.
Preferably, the conditions for gradually increasing the temperature in S3 are as follows: the temperature rising rate is 0.6-0.9 ℃/min, the temperature rising rate is 0.35-0.45 ℃/min after the temperature rising to 150 ℃, the temperature rising rate is 0.2-0.3 ℃/min after the temperature rising to 170 ℃, then the temperature rising to 210-212 ℃, the solid acid value is 18-21 after the reaction, and the temperature is reduced to 100-105 ℃.
Preferably, the conditions for gradually increasing the temperature in S4 are: the temperature rising rate is 0.6-0.8 ℃/min, the temperature rising rate is 0.2-0.3 ℃/min after the temperature rises to 120 ℃, the temperature rising top temperature is 125-135 ℃, the reaction is carried out until the solid acid value is 25.5-27.5, and the temperature is reduced to 50-55 ℃.
Preferably, the conditions for gradually increasing the temperature in S5 are: heating to 70 ℃ at a speed of 0.6-0.8 ℃/min, and reacting for 3h at a temperature of the mixture.
Preferably, the mole ratio of the diethylene glycol, the 1, 6-hexanediol, the terephthalic acid, the hexahydrophthalic anhydride, the trimethylolpropane, the tertiary amine modified polyglycolic acid, the trimellitic anhydride, the dipropylene glycol methyl ether and the 2-bromoethyl ether is as follows: (1-5): (2-6): (1-5): (5-10): (1-3): (0.05-0.2): (0.1-0.5): (1-3): (0.05-0.2).
Preferably, the preparation method of the tertiary amine modified polyglycolic acid comprises the following steps:
Mixing glycollic acid and diethanolamine, adding stannous oxide as catalyst, polymerizing, cooling after reaction to obtain intermediate,
And dispersing the hydroxyethyl methacrylate and the intermediate in a proper amount of DMSO for reaction to obtain the tertiary modified polyglycolic acid.
Preferably, the molar ratio of the glycollic acid to the diethanol amine is (15-25): 1, a step of;
The molar ratio of the hydroxyethyl acrylate to the intermediate is (0.5-2): 1.
Compared with the prior art, the invention has the beneficial effects that:
1. According to the invention, firstly, polymerization is carried out by glycollic acid and diethanolamine, enamine addition is carried out on the glycollic acid and hydroxyethyl methacrylate, tertiary amine modified polyglycolic acid is obtained, and because the tertiary amine modified polyglycolic acid contains unreacted hydroxyl groups, the tertiary amine modified polyglycolic acid is copolymerized with carboxyl groups in a water-based polyester molecular chain, so that the tertiary amine modified polyglycolic acid is introduced into the polyester molecular chain, and finally, quaternization reaction is carried out on the tertiary amine modified polyglycolic acid and 2-bromoethyl ether, so that the water-based polyester with an antibacterial function is obtained.
2. Compared with the method of adding the antibacterial agent, the method introduces the quaternary ammonium salt polymer into the polyester molecular chain, so that the paint film prepared from the water-based polyester has smooth and high appearance, excellent adhesive force and pencil hardness, and the antibacterial rate can reach 99.99%.
Detailed Description
Unless otherwise indicated, the starting materials and reagents used in the present invention are commercially available or may be prepared by known methods.
Preparation example 1
The preparation method of the tertiary amination modified polyglycolic acid comprises the following steps:
760g of glycolic acid and 52.5g of diethanolamine are mixed, heated to 85 ℃, 7.6g of stannous oxide catalyst is added for polymerization reaction, and cooled after the reaction is finished, thus obtaining an intermediate, which has the structure that
；
52G of hydroxyethyl methacrylate and 650g of intermediate are dispersed in a proper amount of DMSO (dimethyl sulfoxide) and reacted for 3 hours at 70 ℃ to obtain tertiary amine modified polyglycolic acid, which has the structure that
。
Preparation example 2
Dispersing 175.5g of tertiary amine modified polyglycolic acid and 15.3g of 2-bromoethyl ether in a proper amount of ethanol, gradually heating up at a heating rate of 0.6-0.8 ℃/min to 70 ℃, and carrying out heat preservation reaction for 3 hours to obtain the quaternary ammonium salt antibacterial agent, wherein the structural formula is as follows
。
Example 1
S1, under the condition of nitrogen, adding 318g of diethylene glycol and 525g of 1, 6-hexanediol into a reaction kettle, stirring and heating to 60-80 ℃, adding 564g of terephthalic acid and 3.76g of di-n-butyltin oxide, gradually heating, heating at a heating rate of 0.6-0.9 ℃/min, heating to 144-149 ℃, preserving heat for 30min after heat preservation, heating to 173-178 ℃ at a heating rate of 0.4-0.6 ℃/min, heating to 203-205 ℃ at a heating rate of 0.2-0.3 ℃/min, reacting until the solid acid value is less than 2, and cooling to 155-159 ℃;
S2, adding 1206g of hexahydrophthalic anhydride into the reaction kettle, gradually heating up, heating up to 187-195 ℃ at a heating rate of 0.2-0.3 ℃/min, preserving heat for 20min, continuously heating up to 208-210 ℃ after the heat preservation is finished, reacting until the solid acid value is 99-102, and cooling down to 135-140 ℃;
S3, adding 200g of trimethylolpropane and 162.5g of tertiary amine modified polyglycolic acid into a reaction kettle, heating gradually, heating at a heating rate of 0.6-0.9 ℃/min, heating to 150 ℃, heating at a heating rate of 0.35-0.45 ℃/min, heating to 170 ℃, heating at a heating rate of 0.2-0.3 ℃/min, heating to 210-212 ℃, reacting to a solid acid value of 18-21, and cooling to 100-105 ℃;
S4, adding 44g of trimellitic anhydride, 240g of dipropylene glycol methyl ether into a reaction kettle, heating gradually, heating at a heating rate of 0.6-0.8 ℃/min, heating to 120 ℃, heating at a heating rate of 0.2-0.3 ℃/min, heating to a top temperature of 125-135 ℃, reacting to a solid acid value of 25.5-27.5, and cooling to 50-55 ℃;
S5, adding 15.3g of 2-bromoethyl ether into the reaction kettle, gradually heating up to 70 ℃ at a heating rate of 0.6-0.8 ℃/min, and preserving heat for reaction for 3 hours;
S6, introducing nitrogen into the dilution kettle, adding 545g of ethylene glycol butyl ether and 236g of propylene glycol methyl ether, preheating to 60-80 ℃, stirring for 55-60r/min, transferring the materials of the reaction kettle into the dilution kettle, maintaining the dilution temperature at 80-100 ℃ in the dilution process, purging a transfer pipeline with nitrogen after the transfer is finished, ensuring no residual resin in the pipeline, sampling and testing after the transfer is finished, cooling to 50-55 ℃ and discharging after the solid content and viscosity are qualified, and thus obtaining the water-based polyester with an antibacterial function.
Example 2
This embodiment differs from embodiment 1 in that:
212g of diethylene glycol, 643.1g of 1, 6-hexanediol are added;
the remainder was identical to example 1.
Example 3
This embodiment differs from embodiment 1 in that:
730.4g of terephthalic acid and 1051g of hexahydrophthalic anhydride were added;
the remainder was identical to example 1.
Comparative example 1 (without addition of Tertiary modified polyglycolic acid, 2-bromoethyl Ether)
S1, under the condition of nitrogen, 318g of diethylene glycol and 525g of 1, 6-hexanediol are added into a reaction kettle, stirring and heating are carried out to 60-80 ℃, 564g of terephthalic acid and 3.76g of di-n-butyltin oxide are added, the temperature is gradually increased, the heating rate is 0.6-0.9 ℃/min, the temperature is increased to 144-149 ℃, the temperature is kept for 30min, the heating rate is 0.4-0.6 ℃/min after the temperature is kept, the temperature is increased to 173-178 ℃ and kept for 40min, the heating rate is 0.2-0.3 ℃/min, the temperature is increased to 203-205 ℃ until the solid acid value is smaller than 2, and the temperature is quickly reduced to 155-159 ℃;
S2, adding 1206g of hexahydrophthalic anhydride into the reaction kettle, gradually heating up, heating up to 187-195 ℃ at a heating rate of 0.2-0.3 ℃/min, preserving heat for 20min, continuously heating up to 208-210 ℃ after the heat preservation is finished, reacting until the solid acid value is 99-102, and rapidly cooling down to 135-140 ℃;
S3, adding 200g of trimethylolpropane into the reaction kettle, heating gradually, heating to the temperature of 150 ℃ at the speed of 0.6-0.9 ℃/min, heating to the temperature of 170 ℃ at the speed of 0.35-0.45 ℃/min, heating to the temperature of 0.2-0.3 ℃/min, heating to the temperature of 210-212 ℃, reacting to the solid acid value of 18-21, and rapidly cooling to the temperature of 100-105 ℃;
S4, adding 44g of trimellitic anhydride, 240g of dipropylene glycol methyl ether into a reaction kettle, heating gradually, heating at a heating rate of 0.6-0.8 ℃/min, heating to 120 ℃, heating at a heating rate of 0.2-0.3 ℃/min, heating to a top temperature of 125-135 ℃, reacting to a solid acid value of 25.5-27.5, and cooling rapidly to 50-55 ℃;
S5, introducing nitrogen into the dilution kettle, adding 545g of ethylene glycol butyl ether and 236g of propylene glycol methyl ether, preheating to 60-80 ℃, stirring for 55-60r/min, transferring the materials of the reaction kettle into the dilution kettle, maintaining the dilution temperature at 80-100 ℃ in the dilution process, purging a transfer pipeline with nitrogen after the transfer is finished, ensuring no residual resin in the pipeline, sampling and testing after the transfer is finished, cooling to 50-55 ℃ and discharging after the solid content and viscosity are qualified, and obtaining the water-based polyester.
Comparative example 2
This comparative example differs from comparative example 1 in that:
S5, purging a transfer pipeline with nitrogen after transfer is finished, ensuring no residual resin in the pipeline, sampling and testing after transfer is finished, cooling to 50-55 ℃ after solid content and viscosity are qualified, adding 170.5g of the quaternary ammonium salt antibacterial agent obtained in preparation example 2, and uniformly stirring and discharging to obtain the water-based antibacterial polyester;
The rest is exactly the same as comparative example 1.
Results and detection
The water-based polyesters obtained in examples 1-3 and comparative examples 1 and 2 are light yellow transparent viscous liquid in appearance, have solid contents of 68-72 and acid values of 16-25 mgKOH/g.
Mixing 45 parts of water and 5 parts of dimethylaminoethanol, adding 50 parts of the aqueous polyester prepared in examples 1-3 and comparative examples 1 and 2 respectively, stirring and mixing uniformly, adding 15 parts of amino resin 325, stirring uniformly again, standing and defoaming, pre-curing at 60-80 ℃ for 5-10 minutes, and finally curing at 120-140 ℃ for 20-30 minutes, mixing 45 parts of water and 5 parts of dimethylaminoethanol according to parts by mass, adding 50 parts of the aqueous polyester prepared in examples 1-3 and comparative examples 1 and 2 respectively, stirring and mixing uniformly, adding 15 parts of amino resin 325, stirring uniformly again, standing and defoaming, pre-curing at 60-80 ℃ for 5-10 minutes, and finally curing at 120-140 ℃ for 20-30 minutes;
Wherein, the appearance of the paint film is visually detected by naked eyes;
The adhesive force is tested according to the hundred-grid method;
pencil hardness was tested according to GB/T6739-2022;
The bacteriostasis test method comprises the following steps: the paint films obtained in examples 1-3 and comparative examples 1 and 2 were cut into test pieces with a radius of 0.5cm, respectively, then E.coli bacterial suspension with a concentration of 10 8 CFU/mL was added to a phosphate buffer solution, the test pieces were added as test groups, the test pieces were not added as blank groups, the test pieces were oscillated at room temperature for 2 hours, 2mL of each test piece was inoculated into beef extract peptone basal medium, the test was repeated 5 times at 37℃for 24 hours, viable count was performed, average value was taken, antibacterial ratio was calculated, antibacterial ratio= (number of colonies of blank group-number of colonies of test group)/number of colonies of blank group was 100%, and the results are shown in Table 1.
TABLE 1
From the data in Table 1, the paint film prepared by the water-based polyester has smooth and high appearance, excellent adhesive force, pencil hardness and antibacterial rate;
As is clear from comparative examples 1,1 and 2, the antibacterial rate of the quaternary ammonium salt alone was only 68.75% when the quaternary ammonium salt antibacterial agent was added to the aqueous polyester, but the antibacterial rate was increased to 99.99% by introducing the quaternary ammonium salt to the molecular chain of the aqueous polyester by chemical reaction.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (9)
1. The preparation method of the water-based polyester with the antibacterial function is characterized by comprising the following steps of:
S1, under the condition of nitrogen, diethylene glycol and 1, 6-hexanediol are added into a reaction kettle, stirring and heating are carried out to 60-80 ℃, terephthalic acid and a catalyst di-n-butyltin oxide are added, and gradual heating reaction is carried out until the solid acid value is less than 2;
S2, adding hexahydrophthalic anhydride into the reaction kettle, and gradually heating to react until the solid acid value is 99-102;
s3, adding trimethylolpropane, tertiary amine modified polyglycolic acid into the reaction kettle, and gradually heating to react until the solid acid value is 18-21;
S4, adding trimellitic anhydride and dipropylene glycol methyl ether into the reaction kettle, and gradually heating to react until the solid acid value is 25.5-27.5;
S5, adding 2-bromoethyl ether into the reaction kettle, gradually heating to 70 ℃, and carrying out heat preservation reaction for 2-4h;
s6, introducing nitrogen into the dilution kettle, adding ethylene glycol butyl ether and propylene glycol methyl ether, preheating to 60-80 ℃, stirring for 55-60r/min, transferring the materials of the reaction kettle into the dilution kettle, maintaining the dilution temperature at 80-100 ℃ in the dilution process, cooling to 50-55 ℃ and discharging after the solid content and viscosity are detected to be qualified, and thus obtaining the water-based polyester with an antibacterial function.
2. The method for preparing the water-based polyester with the antibacterial function according to claim 1, wherein the condition of gradually increasing the temperature in the step S1 is as follows: heating to 144-149 deg.c at 0.6-0.9 deg.c/min for 30min, heating to 173-178 deg.c for 40min at 0.4-0.6 deg.c/min, heating to 203-205 deg.c, reacting to solid acid value less than 2, and cooling to 155-159 deg.c.
3. The method for preparing the water-based polyester with the antibacterial function according to claim 1, wherein the condition of gradually increasing the temperature in the step S2 is as follows: heating to 187-195 deg.c at 0.2-0.3 deg.c/min, maintaining for 20min, heating to 208-210 deg.c, reacting to solid acid value of 99-102, and cooling to 135-140 deg.c.
4. The method for preparing the water-based polyester with the antibacterial function according to claim 1, wherein the condition of gradually increasing the temperature in the step S3 is as follows: the temperature rising rate is 0.6-0.9 ℃/min, the temperature rising rate is 0.35-0.45 ℃/min after the temperature rising to 150 ℃, the temperature rising rate is 0.2-0.3 ℃/min after the temperature rising to 170 ℃, then the temperature rising to 210-212 ℃, the solid acid value is 18-21 after the reaction, and the temperature is reduced to 100-105 ℃.
5. The method for preparing the water-based polyester with the antibacterial function according to claim 1, wherein the condition of gradually increasing the temperature in the step S4 is as follows: the temperature rising rate is 0.6-0.8 ℃/min, the temperature rising rate is 0.2-0.3 ℃/min after the temperature rises to 120 ℃, the temperature rising top temperature is 125-135 ℃, the reaction is carried out until the solid acid value is 25.5-27.5, and the temperature is reduced to 50-55 ℃.
6. The method for preparing the water-based polyester with the antibacterial function according to claim 1, wherein the condition of gradually increasing the temperature in the step S5 is as follows: heating to 70 ℃ at a speed of 0.6-0.8 ℃/min, and reacting for 3h at a temperature of the mixture.
7. The method for preparing the water-based polyester with the antibacterial function according to claim 1, wherein the molar ratio of the diethylene glycol, the 1, 6-hexanediol, the terephthalic acid, the hexahydrophthalic anhydride, the trimethylolpropane, the tertiary amine modified polyglycolic acid, the trimellitic anhydride, the dipropylene glycol methyl ether and the 2-bromoethyl ether is as follows: (1-5): (2-6): (1-5): (5-10): (1-3): (0.05-0.2): (0.1-0.5): (1-3): (0.05-0.2).
8. The method for preparing the aqueous polyester with antibacterial function according to claim 1, wherein the preparation method of the tertiary amine modified polyglycolic acid comprises the following steps:
Mixing glycollic acid and diethanolamine, adding stannous oxide as catalyst, polymerizing, cooling after reaction to obtain intermediate,
And dispersing the hydroxyethyl methacrylate and the intermediate in a proper amount of DMSO for reaction to obtain the tertiary modified polyglycolic acid.
9. The method for preparing the water-based polyester with the antibacterial function according to claim 8, wherein the molar ratio of the glycollic acid to the diethanol amine is (15-25): 1, a step of;
The molar ratio of the hydroxyethyl acrylate to the intermediate is (0.5-2): 1.
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