CN112457474A - Low-temperature cured hydroxyl polyester resin - Google Patents
Low-temperature cured hydroxyl polyester resin Download PDFInfo
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- CN112457474A CN112457474A CN202011079242.6A CN202011079242A CN112457474A CN 112457474 A CN112457474 A CN 112457474A CN 202011079242 A CN202011079242 A CN 202011079242A CN 112457474 A CN112457474 A CN 112457474A
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- Prior art keywords
- curing
- polyester resin
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- low
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- 229920001225 polyester resin Polymers 0.000 title claims abstract description 24
- 239000004645 polyester resin Substances 0.000 title claims abstract description 24
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 23
- 238000001723 curing Methods 0.000 claims abstract description 20
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000012975 dibutyltin dilaurate Substances 0.000 claims abstract description 14
- 238000013035 low temperature curing Methods 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 5
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 5
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 5
- 229920000180 alkyd Polymers 0.000 claims abstract description 4
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 42
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 16
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000011248 coating agent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- BVFSYZFXJYAPQJ-UHFFFAOYSA-N butyl(oxo)tin Chemical compound CCCC[Sn]=O BVFSYZFXJYAPQJ-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003973 paint Substances 0.000 description 3
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000004482 other powder Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- C08G63/66—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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a low-temperature curing hydroxyl polyester resin, wherein a curing agent selects closed polyisocyanate, the curing condition is 160 ℃/15min, and the molecular weight and the branching degree of the resin are adjusted by adjusting the proportion of alkyd and the amount of trifunctional monomer in raw materials; the curing reaction rate is adjusted by adjusting the amount of a curing reaction catalyst dibutyltin dilaurate, so that the hydroxyl polyester resin which has excellent comprehensive performance and can realize low-temperature curing is obtained.
Description
Technical Field
The invention relates to a hydroxy polyester resin, in particular to a low-temperature cured hydroxy polyester resin.
Background
The powder coating has the characteristics of resource saving, energy saving, low pollution and high efficiency, is rapidly increased in proportion in the coating industry, and is widely applied to the fields of household appliances, automobiles, aluminum profiles and the like. The polyurethane powder coating not only has high decoration and excellent physical and mechanical properties, but also has more comprehensive chemical resistance, and is particularly not easy to yellow, and has outstanding weather resistance and light resistance. It has both the advantages of epoxy paint and acrylic paint, and compared with TGIC cured pure polyester powder paint system, it has the great advantages of no toxicity and no harm. With the increasing maturity of the production process of polyurethane powder coating, the proportion of the polyurethane powder coating in the powder coating is larger and larger.
The conventional method for synthesizing the hydroxyl polyester resin comprises the following steps: heating the kettle to about 100 ℃, adding neopentyl glycol, trimethylolpropane, purified terephthalic acid, isophthalic acid and monobutyl tin oxide, heating to 245 ℃ under the protection of nitrogen, maintaining the temperature until the acid value of a reactant is 17-20mgKOH/g, cooling to 230 ℃, performing vacuum operation until the acid value of the reactant is below 5mgKOH/g, cooling the kettle to below 210 ℃, adding dibutyltin dilaurate, and maintaining for 30 minutes to finish the reaction.
The polyurethane powder coating is prepared from hydroxyl polyester resin and closed polyisocyanate as raw materials, and the curing condition is generally 180-200 ℃ for 20 min. With the upgrading of the energy-saving and environment-friendly requirements, the development of low-temperature curing polyurethane powder coating becomes a new trend for the development of polyester resin.
Disclosure of Invention
The invention aims to provide a low-temperature curing hydroxyl polyester resin.
The purpose of the invention is realized by the following technical scheme: the curing agent for curing the hydroxy polyester resin at low temperature is closed polyisocyanate, and the curing condition is 160 ℃/15 min;
the molar ratio of the dihydric alcohol to the alkyd of the dibasic acid is 1.02-1.12: 1;
trimethylolpropane and long-chain aliphatic monomer diethylene glycol are introduced into the dihydric alcohol, the activity and flexibility of the resin are adjusted by adjusting the proportion of the trimethylolpropane and the long-chain aliphatic monomer diethylene glycol, and the trimethylolpropane and the diethylene glycol are respectively in parts by weight: 5-20 parts by weight and 20-40 parts by weight;
the powder coating curing reaction catalyst prepared from the hydroxyl polyester resin is dibutyltin dilaurate, and the curing reaction rate is adjusted by adjusting the using amount of the dibutyltin dilaurate. The weight part of the curing reaction catalyst is 5-20 parts.
Detailed Description
The invention relates to a low-temperature curing hydroxyl polyester resin,
example 1, the main components thereof are:
terephthalic acid 100 parts by weight
Neopentyl glycol 70 parts by weight
Diethylene glycol 20 parts by weight
Trimethylolpropane 7 parts by weight
10 parts by weight of dibutyltin dilaurate
The preparation process of the low-temperature curing hydroxyl polyester resin in the embodiment is as follows: heating the kettle to about 100 ℃, adding neopentyl glycol, trimethylolpropane, diethylene glycol, purified terephthalic acid and monobutyl tin oxide, heating to 245 ℃ under the protection of nitrogen, maintaining the temperature until the acid value of a reactant is 19-24mgKOH/g, cooling to 230 ℃, performing vacuum operation for 2 hours, wherein the vacancy is less than-0.090 MPa until the acid value of the reactant is less than 5mgKOH/g, reducing the kettle temperature to below 210 ℃, adding dibutyltin dilaurate, and maintaining for 30 minutes to complete the reaction.
The invention relates to a low-temperature curing hydroxyl polyester resin,
example 2, the main components thereof are:
terephthalic acid 100 parts by weight
Neopentyl glycol 75 parts by weight
Diethylene glycol 25 parts by weight
10 parts by weight of trimethylolpropane
10 parts by weight of dibutyltin dilaurate
The preparation process of the low-temperature curing hydroxyl polyester resin in the embodiment is as follows: heating the kettle to about 100 ℃, adding neopentyl glycol, trimethylolpropane, diethylene glycol, purified terephthalic acid and monobutyl tin oxide, heating to 245 ℃ under the protection of nitrogen, maintaining the temperature until the acid value of a reactant is 17-21mgKOH/g, cooling to 230 ℃, performing vacuum operation for 2 hours, wherein the vacancy is less than-0.090 MPa until the acid value of the reactant is less than 5mgKOH/g, reducing the kettle temperature to below 210 ℃, adding dibutyltin dilaurate, and maintaining for 30 minutes to complete the reaction.
The invention relates to a low-temperature curing hydroxyl polyester resin,
example 3, the main components thereof were:
terephthalic acid 90 parts by weight
10 parts by weight of isophthalic acid
Neopentyl glycol 75 parts by weight
Diethylene glycol 35 parts by weight
15 parts by weight of trimethylolpropane
20 parts by weight of dibutyltin dilaurate
The preparation process of the low-temperature curing hydroxyl polyester resin in the embodiment is as follows: heating the kettle to about 100 ℃, adding neopentyl glycol, trimethylolpropane, diethylene glycol, purified terephthalic acid and monobutyl tin oxide, heating to 245 ℃ under the protection of nitrogen, maintaining the temperature until the acid value of a reactant is 15-18mgKOH/g, cooling to 225 ℃, carrying out vacuum operation for 2.5 hours, wherein the vacancy is less than-0.090 MPa, until the acid value of the reactant is less than 5mgKOH/g, reducing the kettle temperature to below 210 ℃, adding dibutyltin dilaurate, and maintaining for 30 minutes to complete the reaction.
The invention relates to a low-temperature curing hydroxyl polyester resin,
example 4, the main components thereof were:
terephthalic acid 90 parts by weight
10 parts by weight of isophthalic acid
Neopentyl glycol 80 parts by weight
Diethylene glycol 35 parts by weight
Trimethylolpropane 20 parts by weight
20 parts by weight of dibutyltin dilaurate
The preparation process of a low temperature curing hydroxy polyester resin in this example is the same as example 3.
The properties of the hydroxy polyester resins prepared in examples 1 to 4 are shown in Table 1 below
TABLE 1
As can be seen from Table 1, the proportion of alkyd in the raw materials is adjusted, the primary acid value can be changed, the molecular weight of the resin is controlled, and the introduction of trimethylolpropane can effectively increase the branching degree of the resin. By adjusting both, a resin of a desired average molecular weight is obtained.
The secondary properties of the powder coatings prepared from the resins prepared in examples 1-4 are shown in Table 2 (curing agent is blocked polyisocyanate, curing conditions are 160 ℃/15 min)
As can be seen from Table 2, the leveling and boiling resistance of the polyurethane powder coating was significantly better than that of other powder coatings. The curing reaction speed can be obviously improved by increasing the dosage of a curing reaction catalyst dibutyltin dilaurate, and the impact resistance of the board surface can be improved. By adjusting the dosage of trimethylolpropane and diethylene glycol, the hydroxyl polyester resin with excellent comprehensive performance and capability of realizing low-temperature curing is obtained.
Claims (1)
1. A low temperature curing hydroxy polyester resin is characterized in that: the curing agent is closed polyisocyanate, the curing condition is 160 ℃/15min,
the molar ratio of the dihydric alcohol to the alkyd of the dibasic acid is 1.02-1.12: 1;
trimethylolpropane and long-chain aliphatic monomer diethylene glycol are introduced into the dihydric alcohol, the activity and flexibility of the resin are adjusted by adjusting the proportion of the trimethylolpropane and the long-chain aliphatic monomer diethylene glycol, and the trimethylolpropane and the diethylene glycol are respectively in parts by weight: 5-20 parts by weight and 20-40 parts by weight;
the powder coating curing reaction catalyst prepared from the hydroxyl polyester resin is dibutyltin dilaurate, the curing reaction rate is adjusted by adjusting the using amount of the dibutyltin dilaurate, and the weight part of the curing reaction catalyst is 5-20 parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011079242.6A CN112457474A (en) | 2020-10-11 | 2020-10-11 | Low-temperature cured hydroxyl polyester resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011079242.6A CN112457474A (en) | 2020-10-11 | 2020-10-11 | Low-temperature cured hydroxyl polyester resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112457474A true CN112457474A (en) | 2021-03-09 |
Family
ID=74833780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011079242.6A Pending CN112457474A (en) | 2020-10-11 | 2020-10-11 | Low-temperature cured hydroxyl polyester resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457474A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387570A (en) * | 2014-10-31 | 2015-03-04 | 安徽神剑新材料股份有限公司 | Method for preparing low-temperature cured polyester resin |
| CN107513339A (en) * | 2017-08-11 | 2017-12-26 | 帝兴树脂(昆山)有限公司 | A kind of high levelling powdery paints semi-crystalline polyester resin of polyisocyanates solidification and preparation method thereof |
| CN108752572A (en) * | 2018-05-22 | 2018-11-06 | 浙江光华科技股份有限公司 | A kind of preparation method of hypocrystalline high-melting-point hydroxyl telechelic polyester resin |
| CN111393980A (en) * | 2020-03-21 | 2020-07-10 | 福建龙泰竹家居股份有限公司 | Powder coating for low-temperature spraying of bamboo products and low-temperature spraying method of bamboo products |
-
2020
- 2020-10-11 CN CN202011079242.6A patent/CN112457474A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387570A (en) * | 2014-10-31 | 2015-03-04 | 安徽神剑新材料股份有限公司 | Method for preparing low-temperature cured polyester resin |
| CN107513339A (en) * | 2017-08-11 | 2017-12-26 | 帝兴树脂(昆山)有限公司 | A kind of high levelling powdery paints semi-crystalline polyester resin of polyisocyanates solidification and preparation method thereof |
| CN108752572A (en) * | 2018-05-22 | 2018-11-06 | 浙江光华科技股份有限公司 | A kind of preparation method of hypocrystalline high-melting-point hydroxyl telechelic polyester resin |
| CN111393980A (en) * | 2020-03-21 | 2020-07-10 | 福建龙泰竹家居股份有限公司 | Powder coating for low-temperature spraying of bamboo products and low-temperature spraying method of bamboo products |
Non-Patent Citations (1)
| Title |
|---|
| 雷文: "低温固化聚酯卷材涂料的研制" * |
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| PB01 | Publication | ||
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| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210309 |
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