CN112552493A - Low-cost synthesis method of 130-grade polyester resin - Google Patents
Low-cost synthesis method of 130-grade polyester resin Download PDFInfo
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- CN112552493A CN112552493A CN202011420435.3A CN202011420435A CN112552493A CN 112552493 A CN112552493 A CN 112552493A CN 202011420435 A CN202011420435 A CN 202011420435A CN 112552493 A CN112552493 A CN 112552493A
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- polyester resin
- viscosity
- grade polyester
- synthesis method
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 27
- 239000004645 polyester resin Substances 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 29
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002253 acid Substances 0.000 claims abstract description 16
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 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 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000004246 zinc acetate Substances 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 5
- 238000005070 sampling Methods 0.000 claims abstract description 5
- 239000007787 solid Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000004321 preservation Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims 1
- 229930003836 cresol Natural products 0.000 claims 1
- 239000012790 adhesive layer Substances 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 11
- 239000002994 raw material Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003973 paint Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 2
- 150000007519 polyprotic acids Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000013008 thixotropic agent Substances 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/123—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/127—Acids containing aromatic rings
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention provides a low-cost synthesis method of 130-grade polyester resin, which comprises the following steps: 1) adding glycol, glycerol, n-butyl titanate solution and zinc acetate into a reaction kettle, mixing and heating; 2) adding purified terephthalic acid; 3) continuously heating until water is discharged; 4) cooling and preserving heat for a period of time; 5) after the heat preservation is finished, sampling to measure the acid value and the viscosity, vacuumizing, discharging alcohol, reducing the acid value and improving the viscosity; 6) and after the acid value and the viscosity of the resin are detected to be qualified, cooling, adding m-cresol, stirring, and detecting the solid content of the resin. Compared with the prior art, the invention replaces expensive mosaic with cheap ethylene glycol and glycerol, effectively reduces the production cost, and the prepared 130-grade polyester resin has small viscosity, easy wetting, good manufacturability, large hardness, good transparency and high brightness of a cured adhesive layer, can be pressurized and quickly cured at room temperature, and has good heat resistance and excellent electrical property.
Description
Technical Field
The invention relates to a low-cost synthesis method of 130-grade polyester resin, belonging to the technical field of material chemistry.
Background
The polyester resin is the abbreviation of unsaturated polyester adhesive, and mainly comprises unsaturated polyester resin, an initiator, an accelerator, a filler, a thixotropic agent and the like. If linear structure polyester resin containing-CH-double bond in main chain is adopted, the linear structure polyester resin is mixed with alkene monomer, such as styrene, acrylic ester, vinyl acetate and the like, and then the mixture is polymerized into insoluble and infusible products under the action of initiator and accelerator, and the product is mainly used for producing coil coating; if the polyol and the polybasic acid with the straight chain structure are adopted, the synthesized polyester resin has a linear structure and very good flexibility, and is mainly used in the coating industry.
When the polybasic acid of benzene ring is reacted with the polyalcohol to synthesize the polyester resin, the resin containing benzene ring structure is obtained, the rigidity characteristic of the benzene ring endows the resin with hardness, and the stable structure characteristic of the benzene ring endows the resin with chemical resistance. The raw materials for synthesizing the saturated polyester resin mainly comprise dihydric alcohol, dibasic acid and trihydric alcohol, and also comprise monohydric alcohol or monobasic acid, wherein the most commonly used alcohol is neopentyl glycol, and the water resistance of the esterified product of the neopentyl glycol is greatly superior to that of ethylene glycol and propylene glycol; the trihydric alcohol mainly adopts trimethylolpropane, trimethylolethane and the like.
Tris (2-hydroxyethyl) isocyanurate is commonly called as mosaic, is mainly used for preparing polyester heat-resistant insulating paint, can also be used for the aspects of coatings, medicines, insecticides, organic synthetic intermediates and the like, and is an important raw material. If a grade polyester resin with higher heat-resistant grade is produced, a large amount of the mosaic needs to be used, but the purchase cost of the mosaic is higher, so that the product cost is increased, and the burden is larger for medium-sized and small-sized enterprises.
Disclosure of Invention
The invention aims to overcome the defects of high raw material cost and high consumption of the existing polyester resin synthesis technology, and provides a low-cost synthesis method of 130-grade polyester resin, which is characterized in that on the basis of the existing 130-grade polyester resin synthesis technology, relatively expensive mosaic is replaced by relatively cheap ethylene glycol and glycerol, and the 130-grade polyester resin which is low in cost and meets the internal control standard is synthesized.
The technical solution of the invention is as follows: a low-cost synthesis method of 130-grade polyester resin specifically comprises the following steps:
1) adding ethylene glycol, glycerol, n-butyl titanate solution and zinc acetate into a reaction kettle at normal temperature, mixing, and heating to 110-120 ℃;
2) adding purified terephthalic acid when the temperature of the kettle reaches 110 ℃;
3) heating the reaction kettle to 230 ℃ at the heating rate of 10 ℃/h, and discharging water when the temperature of the reaction kettle reaches about 180 ℃;
4) after the temperature of the kettle reaches 230 ℃, cooling to 225 ℃ and preserving heat for 3 h;
5) after the heat preservation is finished, sampling and measuring the acid value and the viscosity, and vacuumizing at the temperature of 205-215 ℃ according to the situation to discharge alcohol, reduce the acid value and improve the viscosity, so that the acid value is less than 2mg KOH/g, and the viscosity range is 900-1200mPa & s;
6) and after the acid value and the viscosity of the resin are detected to be qualified, cooling the temperature of the reaction kettle to 180 ℃, adding m-cresol at the temperature, stirring for 2 hours, and detecting the solid content of the resin.
The mass ratio of the raw materials in the reaction system is as follows:
glycerol: 10 to 15 percent;
ethylene glycol: 15% -20%;
purified terephthalic acid: 38% -43%;
zinc acetate: 0.02 percent;
butyl orthotitanate solution: 0.1% -0.2%;
m-cresol: 20 to 30 percent.
Compared with the prior art, the invention has the advantages that:
1) compared with the prior art, 228 kg of ethylene glycol and 610 kg of glycerol can be used for replacing each 1 ton of the mosaic; according to the market price estimation of the current raw materials, when 1t of the polyester resin produced by the mosaic is consumed, 8200RMB can be relatively saved by adopting the method provided by the invention;
2) the 130-grade polyester resin prepared by the invention has the advantages of small viscosity, easy wetting, good manufacturability, large hardness of a cured adhesive layer, good transparency, high brightness, capability of being pressurized and rapidly cured at room temperature, good heat resistance and excellent electrical property.
Detailed Description
The technical scheme of the invention is further illustrated by the following examples. The technical solutions, reaction conditions and related parameters given in the examples are all illustrative and are intended to be used for explaining the present invention, and should not be construed as limiting the present invention.
1) Adding 636g of ethylene glycol, 502.8g of glycerol, 10g of n-butyl titanate solution and 0.5g of zinc acetate into a reaction kettle at normal temperature, mixing, and heating to 110-120 ℃;
2) adding 1580g of purified terephthalic acid when the temperature of the kettle reaches 110 ℃;
3) heating the reaction kettle to 230 ℃ at the heating rate of 10 ℃/h, and discharging water when the temperature of the reaction kettle reaches about 180 ℃;
4) after the temperature of the kettle reaches 230 ℃, cooling to 225 ℃ and preserving heat for 3 h;
5) after the heat preservation is finished, sampling and measuring the acid value and the viscosity, and vacuumizing at the temperature of 205-215 ℃ according to the situation, discharging alcohol to reduce the acid value and improve the viscosity, so that the acid value is less than 2mg KOH/g, and the viscosity range is 900-1200mPa & s;
6) after the resin is qualified, cooling the temperature of the reaction kettle to 180 ℃, adding 1300g of m-cresol at the temperature, stirring for two hours to obtain a solution of polyester resin, and detecting the solid content of the resin;
7) adding m-cresol, xylene and S-100 into the solution obtained in the step 6), cooling to below 90 ℃, and stirring for 1 h;
8) adding tetrabutyl titanate and m-cresol (mass ratio is 1:1) into the solution obtained in the step 7), cooling to below 70 ℃, and stirring for 2 hours;
9) adding m-cresol, xylene and 2402 resin solution into the solution obtained in the step 8), and stirring for 1h at 70 ℃;
10) sampling and analyzing the finished paint obtained after the paint mixing in the steps 7) -9), and detecting indexes such as viscosity, solid content and the like, wherein the indexes are shown in the following table:
the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (7)
1. A low-cost synthesis method of 130-grade polyester resin is characterized by comprising the following steps:
1) adding ethylene glycol, glycerol, n-butyl titanate solution and zinc acetate into a reaction kettle at normal temperature, mixing, and heating to 110-120 ℃;
2) adding purified terephthalic acid when the temperature of the kettle reaches 110 ℃;
3) heating the reaction kettle to 230 ℃ at the heating rate of 10 ℃/h, and discharging water when the temperature of the reaction kettle reaches 180 ℃;
4) after the temperature of the kettle reaches 230 ℃, cooling to 225 ℃ and preserving heat for 3 h;
5) after the heat preservation is finished, sampling and measuring the acid value and the viscosity, and vacuumizing at the temperature of 205-215 ℃ according to the situation to discharge alcohol, reduce the acid value and improve the viscosity, so that the acid value is less than 2mg KOH/g, and the viscosity range is 900-1200mPa & s;
6) and after the acid value and the viscosity of the resin are detected to be qualified, cooling the temperature of the reaction kettle to 180 ℃, adding m-cresol at the temperature, stirring for 2 hours, and detecting the solid content of the resin.
2. The low-cost synthesis method of 130-grade polyester resin according to claim 1, wherein the mass fraction of ethylene glycol in step 1) is 15% -20%.
3. The low-cost synthesis method of 130-grade polyester resin according to claim 1, wherein the mass fraction of glycerol in step 1) is 10-15%.
4. The low-cost synthesis method of 130-grade polyester resin according to claim 1, wherein the mass fraction of the n-butyl titanate solution in the step 1) is 0.1-0.2%.
5. The low-cost synthesis method of 130-grade polyester resin according to claim 1, wherein the mass fraction of zinc acetate in step 1) is 0.02%.
6. The low-cost synthesis method of 130-grade polyester resin according to claim 1, wherein the mass fraction of the purified terephthalic acid in the step 2) is 38% -43%.
7. The method for synthesizing 130-grade polyester resin according to claim 1, wherein the mass fraction of the cresol in step 6) is 20-30%.
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CN202011420435.3A CN112552493A (en) | 2020-12-08 | 2020-12-08 | Low-cost synthesis method of 130-grade polyester resin |
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CN202011420435.3A CN112552493A (en) | 2020-12-08 | 2020-12-08 | Low-cost synthesis method of 130-grade polyester resin |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1111668A (en) * | 1995-04-06 | 1995-11-15 | 中国石化扬州石油化工公司 | Novel process for producing polyester wire enamel by normal pressure esterification of terephthalic acid |
CN101343353A (en) * | 2008-08-12 | 2009-01-14 | 无锡市虎皇漆业有限公司 | Polyester resin special for winding steel paint base and preparation thereof |
CN110041511A (en) * | 2019-04-11 | 2019-07-23 | 江苏睿浦树脂科技有限公司 | A kind of powder coating polyester resin and preparation method thereof of energy storage-stable |
-
2020
- 2020-12-08 CN CN202011420435.3A patent/CN112552493A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1111668A (en) * | 1995-04-06 | 1995-11-15 | 中国石化扬州石油化工公司 | Novel process for producing polyester wire enamel by normal pressure esterification of terephthalic acid |
CN101343353A (en) * | 2008-08-12 | 2009-01-14 | 无锡市虎皇漆业有限公司 | Polyester resin special for winding steel paint base and preparation thereof |
CN110041511A (en) * | 2019-04-11 | 2019-07-23 | 江苏睿浦树脂科技有限公司 | A kind of powder coating polyester resin and preparation method thereof of energy storage-stable |
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Application publication date: 20210326 |