CN118240191A - Preparation method and application of high-fullness polyester resin - Google Patents
Preparation method and application of high-fullness polyester resin Download PDFInfo
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- CN118240191A CN118240191A CN202410535650.XA CN202410535650A CN118240191A CN 118240191 A CN118240191 A CN 118240191A CN 202410535650 A CN202410535650 A CN 202410535650A CN 118240191 A CN118240191 A CN 118240191A
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 45
- 239000004645 polyester resin Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 32
- 239000011248 coating agent Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 17
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- 238000000034 method Methods 0.000 claims description 19
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- 239000001361 adipic acid Substances 0.000 claims description 16
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- 239000000843 powder Substances 0.000 claims description 13
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims description 12
- 230000032050 esterification Effects 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 6
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid group Chemical group C(CCCCCCCCC(=O)O)(=O)O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 6
- 238000005809 transesterification reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 239000000178 monomer Substances 0.000 claims description 4
- QHFSFXIJOPKPMS-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine;4-methylbenzenesulfonic acid Chemical group CN(C)C1=CC=CC=[NH+]1.CC1=CC=C(S([O-])(=O)=O)C=C1 QHFSFXIJOPKPMS-UHFFFAOYSA-N 0.000 claims description 4
- 150000007519 polyprotic acids Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000003623 enhancer Substances 0.000 claims 1
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 16
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- 239000000126 substance Substances 0.000 description 6
- CLBRCZAHAHECKY-UHFFFAOYSA-N [Co].[Pt] Chemical compound [Co].[Pt] CLBRCZAHAHECKY-UHFFFAOYSA-N 0.000 description 5
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 description 4
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- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
- 238000004017 vitrification Methods 0.000 description 2
- UYORHVZNGJVQCF-UHFFFAOYSA-N 3-bromo-4-ethoxy-5-methoxybenzaldehyde Chemical compound CCOC1=C(Br)C=C(C=O)C=C1OC UYORHVZNGJVQCF-UHFFFAOYSA-N 0.000 description 1
- 241001550224 Apha Species 0.000 description 1
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Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention belongs to the technical field of paint, and particularly relates to a preparation method and application of high-fullness polyester resin. The high-fullness polyester resin is further added with additives such as an epoxy curing agent, a filler, a leveling agent, a brightening agent and the like to prepare the coating, and has the characteristics of environmental protection, corrosion resistance, oxidation resistance, moisture resistance, illumination resistance and the like.
Description
Technical Field
The invention belongs to the field of paint, and particularly relates to a preparation method and application of high-fullness polyester resin.
Background
Along with the development of society, the national environmental protection policy goes out, environmental protection requirements are stricter in the coating application industry, the development of the coating meets the requirements of health, low carbon and environmental protection, especially in the industrial field, along with the stricter environmental protection and emission limit policies, the industrial coating has the explosion period of blowout, but the problems of short shelf life, poor paint film fullness and the like caused by easy hydrolysis of the coating also occur, and the reduction degree of VOCs is limited.
Fullness, which is an indicator of the expressivity of a paint coating, is a comprehensive indicator of the effect of the paint film, on the one hand, being evident and, on the other hand, being able to be touched. This is related to the thickness, gloss, refractive index, color, hiding, flatness, smoothness, texture, etc. of the paint film. The fullness of the oily paint is good, but the oily paint contains VOCs and has great influence on human health. When the VOC in the living room reaches a certain concentration, people feel headache, nausea, vomit, hypodynamia and the like in a short time, and when serious, the people can suffer from convulsion and coma, and can hurt the liver, the kidney, the brain and the nervous system of the people, thereby causing serious consequences such as hypomnesis and the like. Oily paint used in home decoration is one of the main sources of indoor VOC. There is a great need for VOC-free coatings for use in home decoration applications. The high-fullness polyester resin powder coating is VOC-free and is a coating harmless to human bodies.
The high-fullness polyester resin powder paint is prepared with high-fullness polyester resin as main filming matter, epoxy resin, leveling agent, assistant, pigment, stuffing, etc. The powder coating is prepared by mixing, melting and other procedures, and is sprayed on a workpiece by static electricity, and after the resin is melted and crosslinked in a certain temperature and time, the resin is solidified into a flat, hard and flexible coating film. The cured coating film is not softened again by the temperature rise. The coating has no solvent and pollution, and 100% film forming, thus saving resources and energy. The coating has the characteristics of high glossiness, good leveling property, plump paint film, light color, yellowing resistance, ultraviolet resistance and the like. In particular to the surface coating of furniture doors and windows, and the like, compared with oily paint, the paint has better glossiness, refractive index, covering property, flatness, smoothness, adhesive force and mechanical strength, and can be suitable for the decoration styles of different crowds.
Among the several basic properties of the resin, the relative molecular mass size of the resin and its distribution are related to the mass ratio of the alkyd to its mass and the synthesis process; t g is mainly related to the flexibility, relative molecular mass, distribution, crystallization and the like of a high molecular chain, influences the storage stability of the powder coating, and generally, the higher the T g is, the better the storage stability of the powder is. T g for high-fullness polyester resins is generally required to be above 50 ℃. The softening point (S p) mainly determines the heat resistance and the cooling easiness of the resin. The melt viscosity (eta) of the resin is mainly related to the magnitude of acting force between molecules and the acid value, so that the leveling property of the powder coating is affected, and generally, the smaller the melt viscosity of the resin is, the better the leveling property of the coating is. To synthesize a polyester resin suitable for powder coating, it is necessary to satisfy the requirements of T g、Sp, eta, etc.
Disclosure of Invention
The invention aims to provide a preparation method of high-fullness polyester resin.
Specifically, the present invention has been achieved by the following technical solutions.
In a first aspect, a method for preparing a high-fullness polyester resin, the raw materials of which comprise: terephthalic Acid (PTA), isophthalic acid (PIA), adipic acid (ADA), trimellitic anhydride (TMA), neopentyl glycol (NPG), ethylene Glycol (EG), methylpropanediol (MDO), 2-methyl-1, 3-propanediol (MPD), diethylene glycol (DEG), and Trimethylolpropane (TMP).
Further, the proportion of the raw materials is that
The polyester resin synthesis method is a vacuum polycondensation depolymerization method. Adding the polyol, the polybasic acid monomer and the esterification catalyst into a synthesis reaction kettle according to the proportion, opening a stirrer, heating to about 240 ℃, reacting until esterification water is distilled off, carrying out vacuum polycondensation, adding an acidolysis agent, reacting until resin is transparent, and discharging to obtain the polymer with a specific acid value: 60+ -3 mgKOH/g of polyester resin.
Further, the esterification catalyst is dimethylaminopyridine p-toluenesulfonic acid, and the addition amount is 1-5% by weight of the total amount.
Further, the acidolysis agent is sebacic acid, and the dosage is 2-8% of the total weight of the raw materials.
In a second aspect, a method for preparing a high-fullness polyester resin, the raw materials of which comprise: adipic acid (ADA), terephthalic acid (PTA), ethylene Glycol (EG), neopentyl glycol (NPG), dimethyl terephthalate, trimethylol propane (TMP), phthalic anhydride, triphenyl phosphite.
Further, the proportion of the raw materials is that
The polyester resin synthesis method adopts transesterification reaction. Adding the formula amount of Ethylene Glycol (EG), neopentyl glycol (NPG), dimethyl terephthalate and zinc acetate catalyst into a reaction kettle, introducing nitrogen, and slowly heating under the condition of stirring and starting to perform transesterification until the theoretical amount of methanol is evaporated; adding trimethylol propane (TMP), terephthalic acid (PTA) and phthalic anhydride in a formula amount, introducing nitrogen after the addition is finished for protection, carrying out esterification reaction under the action of a certain amount of zinc acetate at the temperature of 170-240 ℃ until the reaction rate is more than 90%, adding triphenyl phosphite when the solution in the reaction kettle is clear and has no bubbles, stirring for 3-4min, starting a vacuum pump for polycondensation reaction, keeping the temperature at 240-250 ℃, keeping the vacuum degree to 0.09-0.095MPa for 1 hour, evacuating by nitrogen after the time, cooling to about 170 ℃, heating to about 180-200 ℃ after adipic acid (ADA) is added, carrying out esterification reaction after the reaction is closed for 1.5h, and obtaining pale yellow transparent resin with the viscosity of about 3000 and the acid value of about 60. Thus, a polyester resin having good storage stability, high vitrification, good chemical resistance, excellent leveling property and high acid value is synthesized.
The physical and chemical indexes of the polyester resin obtained by the two preparation methods are as follows:
Acid value: 60+ -3 mgKOH/g
Viscosity: 3000+ -500 mPa.s
Softening point: 115+ -10 DEG C
Tg：60±3℃
Color (platinum cobalt method): 150.+ -.5 APHA
On the other hand, the invention provides the application of the polyester resin, and the prepared high-fullness polyester resin is added with the assistants such as an epoxy curing agent, a filler, a leveling agent, a polishing agent and the like, extruded by an extruder and ground into powder coating by a mill.
Further, the epoxy curing agent is epoxy resin;
Compared with the prior art, the invention has the following beneficial effects:
1. Glass transition temperature and chemical rub resistance are improved: in order to meet the technical requirements, the quaternary ammonium salt curing accelerator is changed into an epoxy curing agent, and particularly the epoxy resin is more stable in storage stability.
2. Control of esterification: the difference (delta T) between the temperatures of different control points of the distillation tower and the set temperature and the speed control parameter frequency (v) of the circulating pump are used as variables, an equation is fitted, and the progress of the esterification reaction is controlled by using a fuzzy control technology. Different fitting equations are adopted according to different temperature differences, so that the constant and controllable loss of alcohol in the reaction process is ensured. V1=c+bΔt+aΔt 2 is applied as a control equation to the production control, and the entire reaction process is smooth.
3. Distribution dispersion control of molecular weight: in order to achieve narrower molecular weight dispersion, ensure that the dispersion is less than 2. Adopt the moderate vacuum degree of vacuum stage and match of reaction temperature, react steadily under the state of semi-vacuum and gradient vacuum, guarantee the peaceful going on of successive reaction. The effectiveness of the gradient vacuum and the combined partial vacuum and full vacuum techniques for molecular weight distribution control was verified by GPC gel chromatography testing.
4. In the case of the unchanged Ethylene Glycol (EG) content, the viscosity of the resin tends to decrease with the increase of the neopentyl glycol (NPG) content; in the absence of neopentyl glycol (NPG), the viscosity of the resin decreases with increasing Ethylene Glycol (EG) content. As the amount fraction of adipic acid (ADA) increases, the viscosity and softening point of the resin tend to decrease significantly within a certain range, and further, the increase in adipic acid (ADA) causes a decrease in T g.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for better illustration of the present invention, but is not to be construed as limiting the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase through regular channels, with no manufacturer noted.
The experimental methods in the following examples are conventional methods unless otherwise specified. The test materials used in the examples described below, unless otherwise specified, are all commercially available products.
Preparation example 1: preparation of high-fullness polyester resin
The raw materials are as follows:
Adding 4g of the polyhydric alcohol, the polybasic acid monomer and an esterification catalyst, namely dimethylaminopyridine p-toluenesulfonic acid, into a synthesis reaction kettle according to a proportion, opening a stirrer, heating to about 240 ℃, reacting until esterification water is distilled off, carrying out vacuum polycondensation, adding 5g of an acidolysis agent, carrying out acid hydrolysis, reacting until the resin is transparent, and discharging to obtain the polyester resin with high fullness.
The index of the high-fullness polyester resin is as follows:
Acid value: 62mgKOH/g
Viscosity: 3300mpa.s
Softening point: 120 DEG C
Tg：62℃
Color (platinum cobalt method): 151APHA.
Preparation example 2: preparation of high-fullness polyester resin
The raw materials are as follows:
adding 5g of the polyol, the polybasic acid monomer and an esterification catalyst, namely dimethylaminopyridine p-toluenesulfonic acid, into a synthesis reaction kettle according to a proportion, opening a stirrer, heating to about 240 ℃, reacting until esterification water is distilled off, carrying out vacuum polycondensation, adding 3g of an acidolysis agent, namely sebacic acid, reacting until the resin is transparent, and discharging to obtain the polyester resin with high fullness.
The index of the high-fullness polyester resin is as follows:
Acid value: 61mgKOH/g
Viscosity: 3100mpa.s
Softening point: 123 DEG C
Tg：63℃
Color (platinum cobalt method): 153APHA.
Preparation example 3: preparation of high-fullness polyester resin
Raw materials:
Adding 5g of Ethylene Glycol (EG), neopentyl glycol (NPG), dimethyl terephthalate and zinc acetate catalyst in the formula amount into a reaction kettle, introducing nitrogen, and slowly heating under the condition of stirring start to perform transesterification until the theoretical amount of methanol is evaporated; adding trimethylol propane (TMP), terephthalic acid (PTA) and phthalic anhydride in a formula amount, introducing nitrogen for protection after the addition, carrying out esterification reaction under the action of zinc acetate at 170-240 ℃ until the reaction rate is more than 90%, adding triphenyl phosphite when the solution in the reaction kettle is clear and has no bubbles, stirring for 3-4min, starting a vacuum pump for polycondensation reaction, keeping the temperature at 240-250 ℃, keeping the vacuum degree to 0.09-0.095MPa for 1 hour, eliminating vacuum by nitrogen after the time, cooling to about 170 ℃, adding adipic acid (ADA), heating to about 180-200 ℃, carrying out esterification reaction after sealing for 1.5h, and obtaining pale yellow transparent resin.
The physical and chemical indexes of the polyester resin obtained by the preparation method are as follows:
Acid value: 59mgKOH/g
Viscosity: 3500mpa.s
Softening point: 118 DEG C
Tg：63℃
Color (platinum cobalt method): 149APHA
Preparation example 4: preparation of high-fullness polyester resin
Raw materials:
Adding 8g of Ethylene Glycol (EG), neopentyl glycol (NPG), dimethyl terephthalate and zinc acetate catalyst in the formula amount into a reaction kettle, introducing nitrogen, and slowly heating under the condition of stirring start to perform transesterification until the theoretical amount of methanol is evaporated; adding trimethylol propane (TMP), terephthalic acid (PTA) and phthalic anhydride in a formula amount, introducing nitrogen for protection after the addition, carrying out esterification reaction at 170-240 ℃ under the action of zinc acetate until the reaction rate is more than 90%, adding triphenyl phosphite when the solution in the reaction kettle is clear and has no bubbles, stirring for 3-4min, starting a vacuum pump for polycondensation reaction, keeping the temperature at 240-250 ℃, keeping the vacuum degree to 0.09-0.095MPa for 1 hour, eliminating vacuum by nitrogen after the time, cooling to about 170 ℃, adding adipic acid (ADA), heating to about 180-200 ℃, carrying out esterification reaction, and sealing for 2 hours to obtain pale yellow transparent resin.
The physical and chemical indexes of the polyester resin obtained by the preparation method are as follows:
Acid value: 61mgKOH/g
Viscosity: 3320mPa.s
Softening point: 123 DEG C
Tg：62℃
Color (platinum cobalt method): 155APHA.
Preparation example 5: preparation of powder coating
The raw materials are as follows:
Mixing the above formula raw materials, extruding with a double screw extruder at 95-125 ℃, tabletting, cooling, pulverizing with a pulverizer, and sieving with a 180-mesh screen to obtain the powder coating. Spraying the surface-pretreated cold-rolled steel plate by adopting an electrostatic spraying method, and baking at 180 ℃ for 12min to cure and form a film. The performance index is shown in Table 1.
TABLE 1 coating Performance index
| Project | Index (I) |
| Gel time | 210s |
| Appearance of the coating film | Plump, flat and no orange peel |
| Hardness of pencil | 2H |
| The adhesive force/grade is less than or equal to | 1 |
| Impact resistance/kg.cm | 50 |
| Cup/mm | ≥8 |
| Gloss (60 degree) | ≥96 |
Preparation example 6: preparation of powder coating
The raw materials are as follows:
Mixing the above formula raw materials, extruding with a double screw extruder at 95-125 ℃, tabletting, cooling, pulverizing with a pulverizer, and sieving with a 180-mesh screen to obtain the powder coating. Spraying the surface-pretreated cold-rolled steel plate by adopting an electrostatic spraying method, and baking at 180 ℃ for 11min to cure the cold-rolled steel plate into a film. The performance index is shown in Table 2.
TABLE 2 coating Performance index
| Project | Index (I) |
| Gel time | 180s |
| Appearance of the coating film | Plump, flat and no orange peel |
| Hardness of pencil | HB |
| The adhesive force/grade is less than or equal to | 1 |
| Impact resistance/kg.cm | 52 |
| Cup/mm | ≥8 |
| Gloss (60 degree) | ≥95 |
As can be seen from the preparation examples 1-4, the polyester resin prepared by the invention has higher Tg temperature and good storage stability; the polyester resin has better softening point (S p) and outstanding heat resistance and cooling easiness; the polyester resin has narrower molecular weight dispersion and more proper viscosity, and ensures the leveling property and the adhesiveness of the coating. In summary, the present invention prepares polyester resins having good storage stability, high vitrification, good chemical resistance, excellent leveling properties, and high acid value.
As can be seen from the preparation examples 5-6, the coating prepared by the invention has shorter gel time, hardness, adhesive force, impact resistance and gloss, is suitable for various coating application scenes such as metal surfaces, furniture surfaces, wall surfaces and the like, and has the characteristics of environmental protection, corrosion resistance, oxidation resistance, moisture resistance, illumination resistance and the like.
It is apparent that the above examples are only illustrative of the present invention and are not limiting of the embodiments of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (8)
1. A preparation method of high-fullness polyester resin is characterized by comprising the following raw materials: the synthetic method of the polyester resin comprises the steps of adding the polyhydric alcohol, the polybasic acid monomer and the esterification catalyst into a synthetic reaction kettle according to the proportion, opening a stirrer, heating to about 240 ℃, reacting until esterification water is distilled out, carrying out vacuum polycondensation, adding an acidolysis agent, reacting until the resin is transparent, and discharging to obtain the polyester resin.
2. The method for preparing high-fullness polyester resin according to claim 1, wherein the raw material ratio is:
3. The process for producing a high-fullness polyester resin according to claim 1, wherein the esterification catalyst is dimethylaminopyridine p-toluenesulfonic acid, and the amount added is 1 to 5% by weight of the total amount.
4. The process for producing a high-fullness polyester resin according to claim 1, wherein the acidolysis agent is sebacic acid in an amount of 2-8% by weight based on the total amount of the raw materials.
5. A preparation method of high-fullness polyester resin is characterized by comprising the following raw materials: adipic acid, terephthalic acid, ethylene glycol, neopentyl glycol, dimethyl terephthalate, trimethylolpropane, phthalic anhydride, triphenyl phosphite; the preparation method adopts transesterification, adds glycol, neopentyl glycol, dimethyl terephthalate and zinc acetate catalyst into a reaction kettle, and simultaneously introduces nitrogen, and slowly heats up under the condition of stirring and starting to carry out transesterification until theoretical amount of methanol is evaporated; adding trimethylolpropane, terephthalic acid and phthalic anhydride, introducing nitrogen for protection after the addition, carrying out esterification reaction at 170-240 ℃ under the action of zinc acetate until the reaction rate is over 90%, adding triphenyl phosphite when the solution in the reaction kettle is clear and has no bubbles, stirring for 3-4min, starting a vacuum pump for polycondensation reaction, keeping the temperature at 240-250 ℃ and the vacuum degree at 0.09-0.095MPa for 1 hour, eliminating vacuum by nitrogen after the time, cooling to about 170 ℃, carrying out esterification reaction after adding adipic acid, heating to about 180-200 ℃, and sealing for 1.5 hours to obtain pale yellow transparent resin.
6. The method for producing a high-fullness polyester resin according to claim 5, wherein the raw material ratio is:
7. Use of the high-fullness polyester resin produced by the process according to any of claims 1-6, wherein the high-fullness polyester resin is used in a coating.
8. The process according to claim 7, wherein the high-fullness polyester resin prepared according to claim 1 to 6 is added with additives such as epoxy curing agent, filler, leveling agent, gloss enhancer, etc., extruded by an extruder and ground into powder coating by a mill.
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