CN112940230A - Alkyd resin and preparation method thereof - Google Patents
Alkyd resin and preparation method thereof Download PDFInfo
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- CN112940230A CN112940230A CN202110148667.6A CN202110148667A CN112940230A CN 112940230 A CN112940230 A CN 112940230A CN 202110148667 A CN202110148667 A CN 202110148667A CN 112940230 A CN112940230 A CN 112940230A
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- acid
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- alkyd resin
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- 229920000180 alkyd Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000007599 discharging Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 31
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 23
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 239000003930 superacid Substances 0.000 claims description 15
- 239000001361 adipic acid Substances 0.000 claims description 12
- 235000011037 adipic acid Nutrition 0.000 claims description 12
- 229920005862 polyol Polymers 0.000 claims description 10
- 150000003077 polyols Chemical class 0.000 claims description 10
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 2
- 229930195725 Mannitol Natural products 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000000594 mannitol Substances 0.000 claims description 2
- 235000010355 mannitol Nutrition 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000600 sorbitol Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 5
- 150000005846 sugar alcohols Polymers 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 238000005070 sampling Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- 229920005906 polyester polyol Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- -1 alkali metal alkoxides Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 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
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil 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
- C08G63/02—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
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- 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
- C08G63/826—Metals not provided for in groups C08G63/83 - C08G63/86
-
- 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
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 discloses a preparation method of alkyd resin and the alkyd resin. The preparation method comprises the specific steps of taking raw materials of polyhydric alcohol and polybasic acid, heating and mixing, adding a catalyst, continuously heating, discharging water, continuously reacting in a vacuum state, and cooling to obtain the product with good water resistance, oil resistance and adhesion capability. The method has the advantages of low reaction temperature, low energy consumption, simple method and easy realization of industrial production.
Description
Technical Field
The invention relates to the field of chemistry, in particular to a preparation method of alkyd resin and the alkyd resin.
Background
The alkyd resin is used in paint in relatively great amount and is prepared with vegetable oil or unsaturated fatty acid, polyfunctional alcohol, polybasic acid and other material and through condensation and esterification. Alkyd resin is a synthetic resin, has a wide use amount in China, and becomes an indispensable resin in synthetic resins. The synthetic raw materials are wide in source, low in cost, relatively mature in synthetic technology, good in comprehensive performance of a resin paint film, capable of being dissolved in various solvents and convenient to construct, so that the resin paint film is widely applied to many fields of automobile manufacturing, refrigerator manufacturing, transportation, civil construction, shoes, synthetic leather, textiles, electromechanics, petrochemical industry, mining machinery, aviation, medical treatment, agriculture and the like.
The alkyd resin has various types, can obtain different performances of paint films by adopting various modification methods, meets different market requirements, and can be almost used in all types of coatings. With the increasing requirements of all industries on alkyd resins, the improvement of the preparation method of alkyd resins becomes a hot spot in the field of current coatings.
The alkyd resin is synthesized by mainly using polybasic acid and polyalcohol as raw materials and performing catalytic esterification polymerization. The catalysts which are commonly used at present are alkali metals or alkali metal alkoxides such as sodium ethoxide and sodium methoxide, organotin compounds such as dibutyltin dilaurate and bis (tributyltin) oxide, titanates such as tetrabutyl titanate and isopropyl titanate, etc. However, the above catalysts have certain disadvantages, such as that alkali metals or alkali metal alkoxides are easy to cause more side reactions due to strong basicity, and organotin compounds are potential carcinogens for human beings and have poor activity; titanates have good catalytic activity, but such catalysts are sensitive to moisture and are not stable in air. These deficiencies all limit their industrial applicability.
Therefore, the invention of preparing multipurpose alkyd resin by using a high-efficiency and low-pollution catalyst system is important. Since the 40 th of the 20 th century, solid super acid catalysts which can replace liquid acids are continuously sought, and the solid super acids are more popular research objects. The solid acid overcomes the defects of liquid acid, has the characteristics of easy separation from a liquid phase reaction system, no corrosion to equipment, simple post-treatment, little environmental pollution, high selectivity and the like, can be used in a higher temperature range, and enlarges the application range of acid catalytic reaction which can be possibly carried out thermodynamically.
Disclosure of Invention
The invention aims to provide a preparation method of alkyd resin, which is simple, greatly reduces polycondensation time, is easy to implement industrial process, and has excellent performance.
The preparation method of the alkyd resin provided by the invention comprises the following operation steps:
heating and mixing polyol and polybasic acid, adding a catalyst, continuously heating, discharging water, continuously reacting in a vacuum state, and cooling to obtain the catalyst;
the reaction sequence is shown as follows:
further, heating and mixing raw material polyol and polybasic acid under the protection of inert gas, adding a catalyst, continuously heating, discharging water when the temperature reaches 120-155 ℃, continuously reacting under the condition that the vacuum degree is 70-110 KPa when the acid value of a reactant reaches 10-20 KOH/g, finishing the reaction when the acid value reaches 1-5 mgKOH/g, and cooling to 50-90 ℃ to obtain the catalyst.
Further, heating and mixing raw material polyol and polybasic acid under the protection of inert gas, adding a catalyst, continuously heating, discharging water when the temperature reaches 145 +/-5 ℃, continuously reacting under the condition that the vacuum degree is 85-90 when the acid value of a reactant reaches 15mgKOH/g, finishing the reaction when the acid value reaches 2.0mgKOH/g, and cooling to 60-80 ℃ to obtain the catalyst;
further, heating raw materials of polyol and polyacid under the protection of inert gas, mixing after melting the materials, adding a catalyst, continuing to heat, discharging water when the temperature reaches 145 +/-5 ℃, continuing to react under the condition that the vacuum degree is 85-90 when the acid value of a reactant reaches 15mgKOH/g, finishing the reaction when the acid value reaches 2.0mgKOH/g, and cooling to 60-80 ℃ to obtain the water-saving catalyst, wherein the water is discharged when the temperature reaches 145 +/-5 ℃;
controlling the water outlet rate and the top temperature of the reaction kettle within the range of 100 +/-2 ℃, sampling and measuring the acid value;
in the present invention, the catalyst comprises S2O8 2-/SnO2Solid super acid, SO4 2-/ZrO2-Al2O3Solid super acid, SO4 2-/ZrO2-Al2O3-V2O5One or more of solid super acid and phosphotungstic acid, and further comprises mesoporous S2O8 2-/SnO2Solid super strong acid, mesoporous SO4 2-/ZrO2-Al2O3Mixing one or more of solid super acid and phosphotungstic acid; further preferred is S2O8 2-/SnO2Solid super acid, phosphotungstic acid.
Said S2O8 2-/SnO2Solid super acid, SO4 2-/ZrO2-Al2O3Solid super acid, SO4 2-/ZrO2-Al2O3-V2O5The catalyst of solid super acid, phosphotungstic acid, etc. can be prepared by the method in the prior art.
In the invention, the polybasic acid comprises one or more of succinic acid, adipic acid, sebacic acid and terephthalic acid, and is preferably adipic acid;
in the invention, the polyhydric alcohol comprises one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, 1, 4-propylene glycol, sorbitol and mannitol, and further comprises 1, 4-butanediol, ethylene glycol and diethylene glycol, preferably 1, 4-butanediol and ethylene glycol;
in a specific embodiment of the present invention, the mass ratio of the polyol to the polyacid is 6: (3-5);
in one embodiment of the invention is 6:4
In the specific implementation mode of the invention, the dosage of the catalyst is 0.01-0.5 wt% of the raw materials,
and in one embodiment of the invention is 0.1 wt%.
In the invention, the mixing mass ratio of the 1, 4-butanediol and the ethylene glycol is 5: 3-1: 1, and in a specific embodiment of the invention, the mass ratio is 5: 3.
In the invention, the mass ratio of the oxalic acid to the 1, 4-butanediol is 6: 2.5.
The alkyd resin prepared by the method has low reaction temperature of only 145 +/-5 ℃, low energy consumption and simple method, and is easy for industrial chemical production.
The invention also provides the alkyd resin prepared by the preparation method.
The invention has the beneficial effects that:
(1) the reaction temperature is low, the reaction temperature of the catalyst used by the alkyd resin is obviously lower than that of other similar reactions, so that the method reflects more excellent reaction conditions and is convenient for industrial production with low energy consumption, and simultaneously greatly shortens the reaction time, and is also beneficial to low-energy-consumption and low-cost application type reactions in industrial production, thereby indicating that the catalyst has higher catalytic activity.
(2) The solid super acid is easy to separate, and the post-treatment process is simplified.
(3) The molecular weight proportion and the number of functional groups of the raw material species and components can be changed, different additives can be added, the formula can be adjusted, and products with wider application can be prepared.
(4) The method is simple, greatly reduces the energy consumption cost of the production of the alkyd resin product, and is easy for industrial production.
Detailed Description
Example 1:
weighing 60g of adipic acid, 25g of 1, 4-butanediol and 15g of ethylene glycol, adding the adipic acid, the 25g of 1, the 4-butanediol and the 15g of ethylene glycol into a four-neck flask provided with a thermometer, an oil-water separator and a stirrer, introducing nitrogen for protection for about 10min, slowly heating, starting the stirrer after the material flow is melted, adding 0.1g of phosphotungstic acid catalyst, gradually heating, starting water discharging when the temperature reaches about 145 ℃, controlling the water discharging rate and the top temperature to be within the range of (100 +/-2) DEG C, simultaneously increasing the stirring rate, sampling and measuring the acid value, starting vacuumizing when the acid value of a sample is lower than 15mgKOH/g, reacting under the vacuum degree of 85-90 KPa, and finishing the reaction when the acid value is lower than 2.. Cooling to 60-80 ℃, and discharging to obtain the polyester polyol. The hydroxyl value is 55-57 mgKOH/g, and the relative molecular mass is about 2000.
Example 2:
60g of adipic acid, 25g of 1, 4-butanediol and 15g of ethylene glycol are weighed into a flask equipped with a thermometer, a water-oil separator and stirredCharging nitrogen into a four-neck flask of the device for protection for about 10min, slowly heating, starting a stirrer after the material flow is molten, and adding 0.1g of mesoporous S2O8 2-/SnO2And (3) gradually heating the solid super acidic catalyst, starting water discharging when the temperature reaches about 150 ℃, controlling the water discharging rate and the top temperature to be within the range of (100 +/-2) DEG C, simultaneously increasing the stirring rate, sampling to measure the acid value, starting vacuumizing when the acid value of the sample is lower than 15mgKOH/g, reacting under the vacuum degree of 85-90 KPa, and finishing the reaction when the acid value is lower than 2.0 mgKOH/g. Cooling to 60-80 ℃, and discharging to obtain the polyester polyol. The hydroxyl value is 51-54 mgKOH/g, and the relative molecular mass is about 2500.
Example 3:
weighing 60g of adipic acid, 25g of 1, 4-butanediol and 15g of ethylene glycol, adding the materials into a four-neck flask provided with a thermometer, an oil-water separator and a stirrer, introducing nitrogen for protection for about 10min, slowly heating, starting the stirrer after the material flow is molten, and adding 0.1g of mesoporous SO4 2-/ZrO2-Al2O3And (3) gradually heating the solid super acidic catalyst, starting water discharging when the temperature reaches about 150 ℃, controlling the water discharging rate and the top temperature to be within the range of (100 +/-2) DEG C, simultaneously increasing the stirring rate, sampling to measure the acid value, starting vacuumizing when the acid value of the sample is lower than 15mgKOH/g, reacting under the vacuum degree of 85-90 KPa, and finishing the reaction when the acid value is lower than 2.0 mgKOH/g. Cooling to 60-80 ℃, and discharging to obtain the polyester polyol. The hydroxyl value is 51-54 mgKOH/g, and the relative molecular mass is about 2300.
Example 4:
weighing 60g of adipic acid and 30g of ethylene glycol, adding the adipic acid and the ethylene glycol into a four-neck flask provided with a thermometer, an oil-water separator and a stirrer, introducing nitrogen for protection for about 10min, slowly heating, starting the stirrer after material flow is molten, adding 0.1g of phosphotungstic acid catalyst, gradually heating, starting water discharging when the temperature reaches about 145 ℃, controlling the water discharging rate and the top temperature within the range of (100 +/-2) DEG C, simultaneously increasing the stirring rate, sampling and measuring the acid value, starting vacuumizing when the acid value of a sample is lower than 15mgKOH/g, reacting under the vacuum degree of 85-90 KPa, and finishing the reaction when the acid value is lower than 2.0 mgKOH/g. Cooling to 60-80 ℃, and discharging to obtain the polyester polyol. The hydroxyl value is 53-55 mgKOH/g, and the relative molecular mass is about 1900.
Example 5:
weighing 60g of adipic acid and 50g of diethylene glycol, adding the adipic acid and the 50g of diethylene glycol into a four-neck flask provided with a thermometer, an oil-water separator and a stirrer, introducing nitrogen for protection for about 10min, slowly heating, starting the stirrer after material flow is molten, adding 0.1g of phosphotungstic acid catalyst, gradually heating, starting water outlet when the temperature reaches about 145 ℃, controlling the water outlet rate and the top temperature within the range of (100 +/-2) DEG C, simultaneously increasing the stirring rate, sampling and measuring the acid value, starting vacuumizing when the acid value of a sample is lower than 15mgKOH/g, reacting under the vacuum degree of 85-90 KPa, and finishing the reaction when the acid value is lower than 2.0 mgKOH/g. Cooling to 60-80 ℃, and discharging to obtain the polyester polyol. The hydroxyl value is 53-55 mgKOH/g, and the relative molecular mass is about 2200.
Example 6:
TABLE 1 alkyd resin test data prepared in different examples
Attached: the various test methods in the table are referred to in the specification citation of GBT25251-2010 alkyd paint.
From the test data in the table, it can be seen that all technical indexes of the alkyd resin obtained in the experiment all reach the national standard, and the test results are combined to determine that the alkyd resin in the experimental scheme has excellent characteristics of better drying speed, better water resistance and oil resistance, obviously shortened surface drying and actual drying time (CN201510797258, surface drying: 1 hour, actual drying: 12 hours) and the like compared with common alkyd resin at normal temperature. From the foregoing examples, it can be seen that the molecular weights of the alkyd resins obtained by us can reach the requirements (the molecular weight is generally 2000-8000), and the catalysts used have good selectivitySolids (less used), lower reaction temperature (CN201610999828, T)max＝250℃；CN201510797258,Tmax240 ℃), simple operation, easy separation and suitability for industrial production.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications made by the equivalent structures or equivalent processes in the present specification, or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. The preparation method of the alkyd resin is characterized by heating and mixing raw materials including polyol and polybasic acid, adding a catalyst, continuously heating, discharging water when the temperature reaches 120-155 ℃, continuously reacting in a vacuum degree of 70-110 KPa when the acid value of a reactant reaches 10-20 KOH/g, finishing the reaction when the acid value reaches 1-5 mgKOH/g, and cooling to 50-90 ℃ to obtain the alkyd resin.
2. The preparation method according to claim 1, wherein the raw material polyol and the polybasic acid are heated and mixed under the protection of inert gas, the catalyst is added, heating is continued, water is discharged when the temperature reaches 145 ± 5 ℃, the reaction is continued under the condition that the vacuum degree is 85-90 KPa when the acid value of the reactant reaches 15mgKOH/g, the reaction is ended when the acid value reaches 2.0mgKOH/g, and the reaction is cooled to 60-80 ℃ to obtain the product.
3. The method of claim 1 or 2, wherein the catalyst comprises S2O8 2-/SnO2Solid super acid, SO4 2-/ZrO2-Al2O3Solid super acid, SO4 2-/ZrO2-Al2O3-V2O5One or more of solid super acid and phosphotungstic acid, and further comprises mesoporous S2O8 2-/SnO2Solid super strong acid, mesoporous SO4 2-/ZrO2-Al2O3One or more of solid super acid and phosphotungstic acid.
4. The method of claim 1, wherein the polybasic acid comprises one or more of succinic acid, adipic acid, sebacic acid, and terephthalic acid, preferably adipic acid.
5. The method of claim 1, wherein the polyol comprises one or more of ethylene glycol, propylene glycol, glycerol, diethylene glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, 1, 4-propanediol, sorbitol, and mannitol, and further comprises 1, 4-butanediol, ethylene glycol, and diethylene glycol.
6. The method of claim 5, wherein the polyol is a mixture of 1, 4-butanediol and ethylene glycol.
7. The preparation method according to claim 1, wherein the mixing mass ratio of the 1, 4-butanediol to the ethylene glycol is (2-5): (1-3), preferably 5: 3.
8. The method according to claim 1, wherein the mass ratio of the polyol to the polyacid is 6: (3-5).
9. The preparation method according to claim 1, wherein the catalyst is used in an amount of 0.01 to 0.5 wt% based on the raw material.
10. An alkyd resin prepared by the method of any one of claims 1 to 9.
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| JP2006016427A (en) * | 2004-06-30 | 2006-01-19 | Mitsubishi Chemicals Corp | Method for producing polyester |
| CN101254468A (en) * | 2008-03-20 | 2008-09-03 | 山西大学 | Nano load phosphotungstic acid catalyst and method of preparing the same |
| CN101616953A (en) * | 2007-03-27 | 2009-12-30 | Dic株式会社 | The polyester manufacturing is with solid acid catalyst, its manufacture method and use the manufacture method of its polyester |
| CN102617836A (en) * | 2012-03-15 | 2012-08-01 | 肇庆市森德利化工实业有限公司 | High polymer ester calcium and synthesis method thereof |
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| JP2006016427A (en) * | 2004-06-30 | 2006-01-19 | Mitsubishi Chemicals Corp | Method for producing polyester |
| CN101616953A (en) * | 2007-03-27 | 2009-12-30 | Dic株式会社 | The polyester manufacturing is with solid acid catalyst, its manufacture method and use the manufacture method of its polyester |
| CN101254468A (en) * | 2008-03-20 | 2008-09-03 | 山西大学 | Nano load phosphotungstic acid catalyst and method of preparing the same |
| CN102617836A (en) * | 2012-03-15 | 2012-08-01 | 肇庆市森德利化工实业有限公司 | High polymer ester calcium and synthesis method thereof |
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Application publication date: 20210611 |