CN110922571A - Modified bio-based polyester resin and preparation method thereof - Google Patents
Modified bio-based polyester resin and preparation method thereof Download PDFInfo
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- CN110922571A CN110922571A CN201911201041.6A CN201911201041A CN110922571A CN 110922571 A CN110922571 A CN 110922571A CN 201911201041 A CN201911201041 A CN 201911201041A CN 110922571 A CN110922571 A CN 110922571A
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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
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
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- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
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Abstract
A modified bio-based polyester resin and a preparation method thereof are disclosed, which comprises the following raw materials: a polyol; an aromatic polybasic acid; ethylene glycol monobutyl ether; dimethylethanolamine; a branching agent; an acidolysis agent; an esterification catalyst; e-12 epoxy resin; a curing accelerator; an antioxidant; deionized water. The modified bio-based polyester resin synthesized by the invention has the advantages of average elongation at break up to 200%, average impact strength up to 470J/m, obvious advantages in high-temperature baking resistance experiments, storage stability, simple resin synthesis process, low resin cost and the like, and fully expands the application field of powder coating.
Description
Technical Field
The invention relates to the technical field of polyester resin, in particular to modified bio-based polyester resin and a preparation method thereof.
Background
After the twenty-first century, human beings are troubled by energy and environmental problems, and in order to realize sustainable, green and environment-friendly development of macromolecules and related fine chemical industries, bio-based raw materials capable of replacing the existing petroleum are searched globally, so that the dependence on the petroleum is reduced, the national energy safety is improved, and the pollution of the petroleum industry to the environment is reduced.
Researches show that the bio-based polymer aromatic ring monomer 2, 5-furandicarboxylic acid (FDCA) with a 'rigid' planar structure can be polymerized with monomers such as diol, diamine and the like to prepare a novel synthetic material of bio-based polyester resin with excellent performance. Moreover, the 2, 5-furandicarboxylic acid (FDCA) has stable structure and wide source, and can be prepared from biomass such as straw, fruit shell, grass and wood. The structure of 2, 5-furandicarboxylic acid (FDCA) is similar to that of terephthalic acid (PTA), and the two sides of the FDCA have a carboxyl group respectively, so that the FDCA can replace a Part of Terephthalic Acid (PTA).
Based on the above, the technical scheme provides a modified bio-based polyester resin added with 2, 5-furandicarboxylic acid (FDCA).
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a modified bio-based polyester resin and a preparation method thereof.
The technical scheme adopted by the invention for solving the technical problems is as follows:
a modified bio-based polyester resin comprises the following raw materials in parts by mass: 15-25 parts of polyol; 5-60 parts of aromatic polybasic acid; 8-25 parts of ethylene glycol monobutyl ether; 10-20 parts of dimethylethanolamine; 6 parts to 12 parts of a branching agent; 5-35 parts of acidolysis agent; 0.03 to 0.5 portion of esterification catalyst; 10-35 parts of E-12 epoxy resin; 0-1 part of curing accelerator; 0.03 to 1 portion of antioxidant; 60-100 parts of deionized water.
A preparation method of modified bio-based polyester resin comprises the following steps:
step (1): adding 5-60 parts of aromatic polybasic acid, 6-12 parts of branching agent, 0.03-0.5 part of esterification catalyst, 15-25 parts of polyol and 5-35 parts of acidolysis agent into a reaction kettle according to the formula amount; introducing nitrogen for protection, heating for melting, heating to 140 deg.C for melting most of solid substances, and stirring; heating to 180 ℃ and keeping the temperature for 0.5 h; heating to 230 ℃ and 255 ℃, and preserving the temperature for 2-3h to perform esterification polycondensation reaction.
Step (2): sampling and measuring the acid value, adding 8-25 parts of ethylene glycol monobutyl ether, and rapidly cooling to below 100 ℃; adding 10-20 parts of dimethylethanolamine, cooling to 70 ℃, and keeping the temperature for 0.2-0.3 h.
And (3): adding 60-100 parts of deionized water, heating to 190 ℃ again, adding 10-35 parts of E-12 epoxy resin, maintaining for 0.5-3h, adding 0-1 part of curing accelerator and 0.03-1 part of antioxidant, maintaining for 15-30min, stirring, discharging, filtering and packaging to obtain the modified bio-based polyester resin.
The invention also has the following additional technical features:
the technical scheme of the invention is further specifically optimized as follows: the polyol is 15-25 parts of neopentyl glycol; the branching agent is 6 to 12 parts of trimethylolpropane; the aromatic polybasic acid is 5 to 15 parts of 2, 5-furandicarboxylic acid and/or 5 to 30 parts of terephthalic acid and/or 6 to 15 parts of hexahydrophthalic acid; the acidolysis agent is 15-25 parts of isophthalic acid and/or 5-10 parts of adipic acid; the esterification catalyst is titanium dioxide of titanium catalyst 0.03-0.5 parts.
The technical scheme of the invention is further specifically optimized as follows: the raw materials and the parts by mass are as follows: 15 parts of polyol; 5 parts of aromatic polybasic acid; 8 parts of ethylene glycol monobutyl ether; 10 parts of dimethylethanolamine; 6 parts of a branching agent; 5 parts of acidolysis agent; esterification catalyst 0.03; 10 parts of E-12 epoxy resin; 0 part of curing accelerator; 0.03 part of antioxidant; 60 parts of deionized water.
The technical scheme of the invention is further specifically optimized as follows: the raw materials and the parts by mass are as follows: 25 parts of polyol; 60 parts of aromatic polybasic acid; 25 parts of ethylene glycol monobutyl ether; 20 parts of dimethylethanolamine; 12 parts of a branching agent; 35 parts of acidolysis agent; 0.5 part of esterification catalyst; 35 parts of E-12 epoxy resin; 1 part of a curing accelerator; 1 part of an antioxidant; 100 parts of deionized water.
The technical scheme of the invention is further specifically optimized as follows: the raw materials and the parts by mass are as follows: 20 parts of polyol; 30 parts of aromatic polybasic acid; 15 parts of ethylene glycol monobutyl ether; 15 parts of dimethylethanolamine; 9 parts of a branching agent; 20 parts of acidolysis agent; 0.25 part of esterification catalyst; 22 parts of E-12 epoxy resin; 0.5 part of curing accelerator; 0.5 part of antioxidant; 80 parts of deionized water.
The technical scheme of the invention is further specifically optimized as follows: the preparation method of the 2, 5-furandicarboxylic acid comprises the following steps: uniformly mixing 5-hydroxymethylfurfural, a bromine catalyst, a noble metal catalyst, an oxidation catalyst and an alkaline solution, and reacting the 5-hydroxymethylfurfural and the oxidation catalyst with each other in the presence of an oxygen source at the reaction temperature of 40-80 ℃ for 10-30 hours; after the catalytic conversion, the pH of the reaction solution is adjusted to be less than 3 by concentrated acid, the water generated by the reaction is removed by a dehydrating agent, and 2, 5-furandicarboxylic acid is obtained by precipitation.
The technical scheme of the invention is further specifically optimized as follows: the noble metal catalyst is Pt/C, Au/C, Pd/C, Pt/C/CuO-Ag2O、Au/C/CuO-Ag2O or Pd/C/CuO-Ag2O; the mass ratio of the noble metal catalyst to the 5-hydroxymethylfurfural is 0.1:1-0.3: 1; the alkaline solution is a lithium hydroxide solution, a sodium hydroxide solution or a potassium hydroxide solution; the concentrated acid is concentrated sulfuric acid, and the waste liquid after reaction is treated by adding Ca (OH)2Precipitated and removed as calcium sulfate.
Compared with the prior art, the invention has the advantages that:
advantage (1): the modified bio-based polyester resin synthesized by the invention has the advantages of average elongation at break up to 200%, average impact strength up to 470J/m, obvious advantages in high-temperature baking resistance experiments, storage stability, simple resin synthesis process, low resin cost and the like, and fully expands the application field of powder coating.
Advantage (2): the preparation method of the 2, 5-furandicarboxylic acid is simple, the reaction mixture of saccharides in the ionic liquid is used as a raw material, the noble metal is used as a catalyst, and the high-purity 2, 5-furandicarboxylic acid can be obtained with high yield by modulating the activity of the catalyst, selecting a proper alkaline solvent, and performing a proper reaction time and a post-treatment process; the raw materials can be directly from carbohydrate compounds which can be derived from wood fibers such as agricultural straws, wood and the like, and the production cost can be obviously reduced. Meanwhile, the catalyst and the reaction system of the method are convenient to separate and can be reused for more than 10 times, and the 2, 5-furandicarboxylic acid with the yield of 93 percent and the purity can still be obtained.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a method for preparing a modified bio-based polyester resin according to the present invention.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings, in order that the present disclosure may be more fully understood and fully conveyed to those skilled in the art. While the exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the invention is not limited to the embodiments set forth herein.
A modified bio-based polyester resin comprises the following raw materials in parts by mass: 15-25 parts of polyol; 5-60 parts of aromatic polybasic acid; 8-25 parts of ethylene glycol monobutyl ether; 10-20 parts of dimethylethanolamine; 6 parts to 12 parts of a branching agent; 5-35 parts of acidolysis agent; 0.03 to 0.5 portion of esterification catalyst; 10-35 parts of E-12 epoxy resin; 0-1 part of curing accelerator; 0.03 to 1 portion of antioxidant; 60-100 parts of deionized water.
Specifically, the polyol is 15-25 parts of neopentyl glycol; the branching agent is 6 to 12 parts of trimethylolpropane; the aromatic polybasic acid is 5 to 15 parts of 2, 5-furandicarboxylic acid and/or 5 to 30 parts of terephthalic acid and/or 6 to 15 parts of hexahydrophthalic acid; the acidolysis agent is 15-25 parts of isophthalic acid and/or 5-10 parts of adipic acid; the esterification catalyst is titanium dioxide of titanium catalyst 0.03-0.5 parts.
A preparation method of modified bio-based polyester resin comprises the following steps:
step (1): adding 5-60 parts of aromatic polybasic acid, 6-12 parts of branching agent, 0.03-0.5 part of esterification catalyst, 15-25 parts of polyol and 5-35 parts of acidolysis agent into a reaction kettle according to the formula amount; introducing nitrogen for protection, heating for melting, heating to 140 deg.C for melting most of solid substances, and stirring; heating to 180 ℃ and keeping the temperature for 0.5 h; heating to 230 ℃ and 255 ℃, and preserving the temperature for 2-3h to perform esterification polycondensation reaction.
Step (2): sampling and measuring the acid value, adding 8-25 parts of ethylene glycol monobutyl ether, and rapidly cooling to below 100 ℃; adding 10-20 parts of dimethylethanolamine, cooling to 70 ℃, and keeping the temperature for 0.2-0.3 h.
And (3): adding 60-100 parts of deionized water, heating to 190 ℃ again, adding 10-35 parts of E-12 epoxy resin, maintaining for 0.5-3h, adding 0-1 part of curing accelerator and 0.03-1 part of antioxidant, maintaining for 15-30min, stirring, discharging, filtering and packaging to obtain the modified bio-based polyester resin.
Example 1
The preparation method of the 2, 5-furandicarboxylic acid comprises the following steps: uniformly mixing 5-hydroxymethylfurfural, a bromine catalyst, a noble metal catalyst, an oxidation catalyst and an alkaline solution, and reacting the 5-hydroxymethylfurfural and the oxidation catalyst with each other in the presence of an oxygen source at the reaction temperature of 40 ℃ for 10 hours; after the catalytic conversion, the pH of the reaction solution is adjusted to be less than 3 by concentrated acid, the water generated by the reaction is removed by a dehydrating agent, and 2, 5-furandicarboxylic acid is obtained by precipitation.
Specifically, the noble metal catalyst is CuO-Ag2O; the mass ratio of the noble metal catalyst to the 5-hydroxymethylfurfural is 0.1: 1; the alkaline solution is sodium hydroxide solution; the concentrated acid is concentrated sulfuric acid, and the waste liquid after reaction is treated by adding Ca (OH)2Precipitated and removed as calcium sulfate.
Example 2
The preparation method of the 2, 5-furandicarboxylic acid comprises the following steps: uniformly mixing 5-hydroxymethylfurfural, a bromine catalyst, a noble metal catalyst, an oxidation catalyst and an alkaline solution, and reacting the 5-hydroxymethylfurfural and the oxidation catalyst with each other in the presence of an oxygen source at the reaction temperature of 80 ℃ for 30 hours; after the catalytic conversion, the pH of the reaction solution is adjusted to be less than 3 by concentrated acid, the water generated by the reaction is removed by a dehydrating agent, and 2, 5-furandicarboxylic acid is obtained by precipitation.
Specifically, the noble metal catalyst is Pd/C/CuO-Ag2O; the mass ratio of the noble metal catalyst to the 5-hydroxymethylfurfural is 0.3: 1; the alkaline solution is a lithium hydroxide solution; the concentrated acid is concentrated sulfuric acid, and the waste liquid after reaction is treated by adding Ca (OH)2Precipitated and removed as calcium sulfate.
Example 3
The modified bio-based polyester resin comprises the following raw materials in parts by mass: 15 parts of polyol; 5 parts of 2, 5-furandicarboxylic acid prepared in example 1; 8 parts of ethylene glycol monobutyl ether; 10 parts of dimethylethanolamine; 6 parts of a branching agent; 5 parts of acidolysis agent; esterification catalyst 0.03; 10 parts of E-12 epoxy resin; 0 part of curing accelerator; 0.03 part of antioxidant; 60 parts of deionized water.
A preparation method of modified bio-based polyester resin comprises the following steps:
step (1): in a reaction kettle, 5 parts of 2, 5-furan dicarboxylic acid prepared in example 1, 6 parts of branching agent, 0.03 part of esterification catalyst, 15 parts of polyol and 5 parts of acidolysis agent are added according to the formula amount; introducing nitrogen for protection, heating for melting, heating to 140 deg.C for melting most of solid substances, and stirring; heating to 180 ℃ and keeping the temperature for 0.5 h; heating to 230 ℃ and 255 ℃, and preserving the temperature for 2-3h to perform esterification polycondensation reaction.
Step (2): sampling and measuring the acid value, adding 8 parts of ethylene glycol monobutyl ether, and rapidly cooling to below 100 ℃; adding 10 parts of dimethylethanolamine, cooling to 70 ℃, and keeping the temperature for 0.2-0.3 h.
And (3): adding 60 parts of deionized water, heating to the temperature of 150-190 ℃, adding 10 parts of E-12 epoxy resin, maintaining for 0.5-3h, adding 0.03 part of antioxidant, maintaining for 15-30min, stirring, discharging, filtering and packaging to obtain the modified bio-based polyester resin.
Example 4
The modified bio-based polyester resin comprises the following raw materials in parts by mass: 25 parts of polyol; 15 parts of 2, 5-furandicarboxylic acid, 30 parts of terephthalic acid, 15 parts of hexahydrophthalic acid prepared in example 2; 25 parts of ethylene glycol monobutyl ether; 20 parts of dimethylethanolamine; 12 parts of a branching agent; 35 parts of acidolysis agent; 0.5 part of esterification catalyst; 35 parts of E-12 epoxy resin; 1 part of a curing accelerator; 1 part of an antioxidant; 100 parts of deionized water.
A preparation method of modified bio-based polyester resin comprises the following steps:
step (1): 15 parts of 2, 5-furan dicarboxylic acid prepared in example 2, 30 parts of terephthalic acid, 15 parts of hexahydrophthalic acid, 12 parts of branching agent, 0.5 part of esterification catalyst, 25 parts of polyol and 35 parts of acidolysis agent are added into a reaction kettle according to the formula amount; introducing nitrogen for protection, heating for melting, heating to 140 deg.C for melting most of solid substances, and stirring; heating to 180 ℃ and keeping the temperature for 0.5 h; heating to 230 ℃ and 255 ℃, and preserving the temperature for 2-3h to perform esterification polycondensation reaction.
Step (2): sampling and measuring the acid value, adding 25 parts of ethylene glycol monobutyl ether, and rapidly cooling to below 100 ℃; adding 20 parts of dimethylethanolamine, cooling to 70 ℃, and keeping the temperature for 0.2-0.3 h.
And (3): adding 100 parts of deionized water, heating to the temperature of 150-190 ℃, adding 35 parts of E-12 epoxy resin, maintaining for 0.5-3h, adding 1 part of curing accelerator and 1 part of antioxidant, maintaining for 15-30min, stirring, discharging, filtering and packaging to obtain the modified bio-based polyester resin.
Example 5
The modified bio-based polyester resin comprises the following raw materials in parts by mass: 20 parts of polyol; 5 parts of 2, 5-furandicarboxylic acid prepared in example 2, 15 parts of terephthalic acid, 10 parts of hexahydrophthalic acid; 15 parts of ethylene glycol monobutyl ether; 15 parts of dimethylethanolamine; 9 parts of a branching agent; 20 parts of acidolysis agent; 0.25 part of esterification catalyst; 22 parts of E-12 epoxy resin; 0.5 part of curing accelerator; 0.5 part of antioxidant; 80 parts of deionized water.
A preparation method of modified bio-based polyester resin comprises the following steps:
step (1): adding 5 parts of 2, 5-furandicarboxylic acid, 15 parts of terephthalic acid and 10 parts of hexahydrophthalic acid which are prepared in example 2 into a reaction kettle according to the formula amount; 9 parts of branching agent, 0.25 part of esterification catalyst, 20 parts of polyol and 20 parts of acidolysis agent; introducing nitrogen for protection, heating for melting, heating to 140 deg.C for melting most of solid substances, and stirring; heating to 180 ℃ and keeping the temperature for 0.5 h; heating to 230 ℃ and 255 ℃, and preserving the temperature for 2-3h to perform esterification polycondensation reaction.
Step (2): sampling and measuring the acid value, adding 15 parts of ethylene glycol monobutyl ether, and rapidly cooling to below 100 ℃; adding 15 parts of dimethylethanolamine, cooling to 70 ℃, and keeping the temperature for 0.2-0.3 h.
And (3): adding 80 parts of deionized water, heating to the temperature of 150-190 ℃, adding 22 parts of E-12 epoxy resin, maintaining for 0.5-3h, adding 0.5 part of curing accelerator and 0.5 part of antioxidant, maintaining for 15-30min, stirring, discharging, filtering and packaging to obtain the modified bio-based polyester resin.
The method for calculating the elongation at break comprises the steps of deforming the original length L and the cross-sectional area A under the action of axial tension N to obtain the length at break L ', then introducing (1) and (2) into Hokking to obtain the elongation at break △ L' -L, the strain is epsilon △ L/L, and the normal stress delta is P/A on the cross-sectional area, wherein P/A is E △ L/L, △ L is PL/EA, E is the elastic modulus of the material, and the elongation at break is △ L/L100%
The impact strength was calculated by using a special inclined plate impact tester and testing under specific conditions.
Through relevant detection, the modified bio-based polyester resin synthesized according to the embodiment 3-the embodiment 5 of the technical scheme has the average elongation at break up to 186% and the average impact strength up to 430J/m.
| Elongation at break% | Impact strength J/m | Performance of performance | |
| Example 3 | 180 | 430 | Is excellent in |
| Example 4 | 195 | 440 | Is excellent in |
| Example 5 | 183 | 420 | Is excellent in |
| Mean value of | 186 | 430 | Is excellent in |
Although the embodiments have been described, once the basic inventive concept is obtained, other variations and modifications of these embodiments can be made by those skilled in the art, so that the above embodiments are only examples of the present invention, and not intended to limit the scope of the present invention, and all equivalent structures or equivalent processes using the contents of the present specification and drawings, or any other related technical fields, which are directly or indirectly applied thereto, are included in the scope of the present invention.
Claims (8)
1. The modified bio-based polyester resin is characterized by comprising the following raw materials in parts by mass: 15-25 parts of polyol; 5-60 parts of aromatic polybasic acid; 8-25 parts of ethylene glycol monobutyl ether; 10-20 parts of dimethylethanolamine; 6 parts to 12 parts of a branching agent; 5-35 parts of acidolysis agent; 0.03 to 0.5 portion of esterification catalyst; 10-35 parts of E-12 epoxy resin; 0-1 part of curing accelerator; 0.03 to 1 portion of antioxidant; 60-100 parts of deionized water.
2. The modified bio-based polyester resin of claim 1, wherein: the polyol is 15-25 parts of neopentyl glycol; the branching agent is 6 to 12 parts of trimethylolpropane; the aromatic polybasic acid is 5 to 15 parts of 2, 5-furandicarboxylic acid and/or 5 to 30 parts of terephthalic acid and/or 6 to 15 parts of hexahydrophthalic acid; the acidolysis agent is 15-25 parts of isophthalic acid and/or 5-10 parts of adipic acid; the esterification catalyst is titanium dioxide of titanium catalyst 0.03-0.5 parts.
3. The modified bio-based polyester resin according to claim 1 or 2, wherein: the raw materials and the parts by mass are as follows: 15 parts of polyol; 5 parts of aromatic polybasic acid; 8 parts of ethylene glycol monobutyl ether; 10 parts of dimethylethanolamine; 6 parts of a branching agent; 5 parts of acidolysis agent; esterification catalyst 0.03; 10 parts of E-12 epoxy resin; 0 part of curing accelerator; 0.03 part of antioxidant; 60 parts of deionized water.
4. The modified bio-based polyester resin according to claim 1 or 2, wherein: the raw materials and the parts by mass are as follows: 25 parts of polyol; 60 parts of aromatic polybasic acid; 25 parts of ethylene glycol monobutyl ether; 20 parts of dimethylethanolamine; 12 parts of a branching agent; 35 parts of acidolysis agent; 0.5 part of esterification catalyst; 35 parts of E-12 epoxy resin; 1 part of a curing accelerator; 1 part of an antioxidant; 100 parts of deionized water.
5. The modified bio-based polyester resin according to claim 1 or 2, wherein: the raw materials and the parts by mass are as follows: 20 parts of polyol; 30 parts of aromatic polybasic acid; 15 parts of ethylene glycol monobutyl ether; 15 parts of dimethylethanolamine; 9 parts of a branching agent; 20 parts of acidolysis agent; 0.25 part of esterification catalyst; 22 parts of E-12 epoxy resin; 0.5 part of curing accelerator; 0.5 part of antioxidant; 80 parts of deionized water.
6. The modified bio-based polyester resin of claim 2, wherein: the preparation method of the 2, 5-furandicarboxylic acid comprises the following steps: uniformly mixing 5-hydroxymethylfurfural, a bromine catalyst, a noble metal catalyst, an oxidation catalyst and an alkaline solution, and reacting the 5-hydroxymethylfurfural and the oxidation catalyst with each other in the presence of an oxygen source at the reaction temperature of 40-80 ℃ for 10-30 hours; after the catalytic conversion, the pH of the reaction solution is adjusted to be less than 3 by concentrated acid, the water generated by the reaction is removed by a dehydrating agent, and 2, 5-furandicarboxylic acid is obtained by precipitation.
7. The modified bio-based polyester resin of claim 6, wherein: the noble metal catalyst is Pt/C, Au/C, Pd/C, Pt/C/CuO-Ag2O、Au/C/CuO-Ag2O or Pd/C/CuO-Ag2O; the mass ratio of the noble metal catalyst to the 5-hydroxymethylfurfural is 0.1:1-0.3: 1; the alkaline solution is a lithium hydroxide solution, a sodium hydroxide solution or a potassium hydroxide solution; the concentrated acid is concentrated sulfuric acid, and the waste liquid after reaction is treated by adding Ca (OH)2Precipitated and removed as calcium sulfate.
8. The preparation method of the modified bio-based polyester resin is characterized by comprising the following steps:
step (1): adding 5-60 parts of aromatic polybasic acid, 6-12 parts of branching agent, 0.03-0.5 part of esterification catalyst, 15-25 parts of polyol and 5-35 parts of acidolysis agent into a reaction kettle according to the formula amount; introducing nitrogen for protection, heating for melting, heating to 140 deg.C for melting most of solid substances, and stirring; heating to 180 ℃ and keeping the temperature for 0.5 h; heating to 230 ℃ and 255 ℃, and preserving the temperature for 2-3h to perform esterification polycondensation reaction;
step (2): sampling and measuring the acid value, adding 8-25 parts of ethylene glycol monobutyl ether, and rapidly cooling to below 100 ℃; adding 10-20 parts of dimethylethanolamine, cooling to 70 ℃, and keeping the temperature for 0.2-0.3 h;
and (3): adding 60-100 parts of deionized water, heating to 190 ℃ again, adding 10-35 parts of E-12 epoxy resin, maintaining for 0.5-3h, adding 0-1 part of curing accelerator and 0.03-1 part of antioxidant, maintaining for 15-30min, stirring, discharging, filtering and packaging to obtain the modified bio-based polyester resin.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891719A (en) * | 2010-07-15 | 2010-11-24 | 华南理工大学 | Method for synthesizing 2,5-furandicarboxylic acid |
| CN106893087A (en) * | 2017-04-20 | 2017-06-27 | 滁州市全丰物资有限公司 | A kind of aqueous polyester resin and preparation method thereof |
| CN107163234A (en) * | 2017-05-31 | 2017-09-15 | 广东猛特新材料有限公司 | A kind of powdery paints bio-based polyester resin and preparation method thereof |
| CN108084416A (en) * | 2017-12-22 | 2018-05-29 | 安徽神剑新材料股份有限公司 | A kind of saturated polyester resin and preparation method thereof |
-
2019
- 2019-11-29 CN CN201911201041.6A patent/CN110922571A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891719A (en) * | 2010-07-15 | 2010-11-24 | 华南理工大学 | Method for synthesizing 2,5-furandicarboxylic acid |
| CN106893087A (en) * | 2017-04-20 | 2017-06-27 | 滁州市全丰物资有限公司 | A kind of aqueous polyester resin and preparation method thereof |
| CN107163234A (en) * | 2017-05-31 | 2017-09-15 | 广东猛特新材料有限公司 | A kind of powdery paints bio-based polyester resin and preparation method thereof |
| CN108084416A (en) * | 2017-12-22 | 2018-05-29 | 安徽神剑新材料股份有限公司 | A kind of saturated polyester resin and preparation method thereof |
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