Ultralow-temperature epoxy curing polyester resin and preparation method thereof
Technical Field
The invention relates to the field of coating chemistry, in particular to an ultralow-temperature epoxy curing polyester resin and a preparation method thereof.
Background
Powder coating as a solid coating also presents problems compared to conventional coatings: 1. the baking and curing temperature is higher, so that a user needs to invest huge cost of baking finish equipment and energy when spraying and baking; 2. higher baking temperatures also limit the field of application of powder coatings. For example, at such high baking temperatures, heat sensitive substrates such as Medium Density Fiberboard (MDF), wood, plastic, etc. cannot be coated and baked; 3. powder coatings are relatively viscous and difficult to achieve a thickness of 40 μm, resulting in coatings that are less effective overall than liquid coatings. Therefore, it is very important to develop a powder coating material that can be cured at a low temperature, from the viewpoints of saving energy and reducing cost, and from the viewpoints of improving efficiency and expanding the range of applications of the powder coating material.
In order to lower the curing temperature of the powder coating, the speed of the curing reaction needs to be increased; this is generally achieved by the following two aspects: on the one hand, the reaction speed is improved by improving the reaction rate constant and the concentration of carboxyl and epoxy groups. On the other hand, the reaction activation energy of the resin and the curing agent in the powder coating is reduced.
The market is improved, and the patent CN104497289B mainly increases the type and the amount of the trihydric alcohol with high branching degree in the polyhydric alcohol, increases the amount of the high-activity polybasic acid isophthalic acid, and uses the high-activity pyromellitic dianhydride to realize the low-temperature curing at 140-160 ℃. Patent CN101735432B reports that the defects of the synthetic polyester of US5262510 and US 56765, such as too low glass transition temperature, large viscosity, easy oxidation due to the addition of unsaturated monomer, etc., are improved, and the mixed powder with proper glass transition temperature, softening point, viscosity and storage stability is synthesized, and the polyester resin is cured at low temperature of 160 ℃; although the low-temperature curing is realized, the impact performance and the surface leveling grade of the prepared cured powder are not high, the market needs an ultralow-temperature cured powder which can realize the low-temperature curing, has excellent impact resistance and high surface leveling grade, and the invention solves the problems.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an ultralow temperature epoxy curing polyester resin and a preparation method thereof, wherein the polyester resin can realize low temperature curing, and the ultralow temperature curing powder prepared from the polyester resin also has the advantages of excellent impact resistance and high surface leveling grade.
In order to achieve the above object, the present invention adopts the following technical solutions:
the ultra-low temperature epoxy curing polyester resin comprises the following components in parts by weight: 1-5 parts of core monomer dipentaerythritol, 0.08-0.12 part of catalyst, 30-55 parts of polybasic acid, 30-42 parts of polyalcohol, 10-25 parts of blocking acid and 1-5 parts of curing accelerator.
The ultralow-temperature epoxy curing polyester resin comprises the following catalysts: monobutyl tin oxide, stannous oxalate and titanium catalyst.
In the ultra-low temperature epoxy curing polyester resin, the polybasic acid comprises: terephthalic acid, isophthalic acid, adipic acid, 1, 4 cyclohexanedicarboxylic acid.
In the ultra-low temperature epoxy curing polyester resin, the polyol comprises: neopentyl glycol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, propylene glycol, 1, 4-cyclohexanedimethanol, trimethylolpropane.
In the ultra-low temperature epoxy curing polyester resin, the blocking acid comprises: trimellitic anhydride, pyromellitic dianhydride.
The curing accelerator for the ultralow-temperature epoxy curing polyester resin comprises: ammonium salts, phosphonium salts, imidazoles and derivatives thereof.
A preparation method of ultralow temperature epoxy curing polyester resin comprises the following steps:
step one, preparing materials according to a formula; the formula comprises the following components in parts by mass: 1-5 parts of core monomer dipentaerythritol, 0.08-0.12 part of catalyst, 30-42 parts of polyol, 30-55 parts of polybasic acid, 10-25 parts of blocked acid and 1-5 parts of curing accelerator; 1-50% of polybasic acid is used as first-batch polybasic acid, and the rest is used as second-batch polybasic acid; the molar ratio of the polyhydric alcohol to the polybasic acid is 1.02-1.5: 1.
secondly, in a reaction kettle provided with a heating device, a stirrer and a condenser, firstly adding a nuclear monomer dipentaerythritol and a catalyst, heating and melting to 100 ℃, firstly adding a first batch of polybasic acid, then slowly heating to 200 ℃, and preserving heat for 2-3 hours; adding polyalcohol and polybasic acid of the second batch, slowly heating to 240 deg.C, and keeping the temperature until the acid value is 10-20 mgKOH/g;
step three, vacuumizing until the acid value is 2-10 mgKOH/g;
cooling to 220 ℃, adding a blocking acid, and keeping the temperature at 210 ℃ until the acid value is 70-85 mgKOH/g;
and step five, cooling to 180 ℃ and 200 ℃, adding a curing accelerator, maintaining for 30-60 minutes, and discharging to obtain the ultralow-temperature epoxy curing polyester resin.
In the preparation method of the ultralow temperature epoxy curing polyester resin,
step one, preparing materials according to a formula; the formula comprises the following components in parts by mass: 1 part of core monomer dipentaerythritol, 0.08 part of catalyst monobutyl tin oxide, and a first batch of polybasic acid: 5 parts of terephthalic acid, a second batch of polybasic acid: 4 parts of adipic acid and 42 parts of terephthalic acid, polyol: neopentyl glycol 30 parts and 1, 6-hexanediol 3 parts, blocking acid: 15 parts of trimellitic anhydride, and a curing accelerator: 2.5 parts of 2-methylimidazole;
secondly, in a reaction kettle provided with a heating device, a stirrer and a condenser, firstly adding a nuclear monomer dipentaerythritol and a catalyst, heating and melting to 100 ℃, firstly adding a first batch of polybasic acid, then slowly heating to 200 ℃, and preserving heat for 2-3 hours; adding polyalcohol and second batch of polybasic acid, slowly heating to 240 deg.C, and keeping the temperature until the acid value is 10-20 mgKOH/g;
step three, vacuumizing until the acid value is 2-10 mgKOH/g;
cooling to 220 ℃, adding a blocking acid, and keeping the temperature at 210 ℃ until the acid value is 70-85 mgKOH/g;
and step five, cooling to 180 ℃ and 200 ℃, adding a curing accelerator, maintaining for 30-60 minutes, and discharging to obtain the ultralow-temperature epoxy curing polyester resin.
And step three, vacuumizing until the acid value is 2-10mgKOH/g and the vacuum degree is less than-0.095M Pa.
The invention has the advantages that:
the core monomer of the invention is dipentaerythritol, and the dipentaerythritol has more hydroxyl groups compared with pentaerythritol and trimethylolpropane, so that the core monomer has more branching degrees and active end groups, and can perform better in curing speed and leveling property;
the product obtained by adopting the formula has a hyperbranched structure and lower viscosity, is beneficial to melt flow solidification, realizes low-temperature solidification, and has excellent impact performance and high leveling grade;
according to the preparation method, alcohol with six functional groups is introduced as a core monomer, a part of polybasic acid is added, and the rest of polybasic acid and the polybasic acid are added, so that the product obtained by the method has a certain hyperbranched structure, and is good in impact resistance and high in leveling grade.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The ultra-low temperature epoxy curing polyester resin comprises the following components in parts by weight: 1-5 parts of core monomer dipentaerythritol, 0.08-0.12 part of catalyst, 30-55 parts of polybasic acid, 30-42 parts of polyalcohol, 10-25 parts of blocking acid and 1-5 parts of curing accelerator. The core monomer of the invention is dipentaerythritol, and the dipentaerythritol has more hydroxyl groups compared with pentaerythritol and trimethylolpropane, so that the core monomer has more branching degrees and active end groups, and can perform better in curing speed and leveling property.
As an example, the catalyst comprises: monobutyl tin oxide, stannous oxalate and titanium catalyst. The polybasic acid includes: terephthalic acid, isophthalic acid, adipic acid, 1, 4 cyclohexanedicarboxylic acid. The polyhydric alcohol includes: neopentyl glycol, 1, 6-hexanediol, ethylene glycol, diethylene glycol, propylene glycol, 1, 4-cyclohexanedimethanol, trimethylolpropane. The blocking acid comprises: trimellitic anhydride, pyromellitic dianhydride. The curing accelerator includes: ammonium salts, phosphonium salts, imidazoles and derivatives thereof. It should be noted that: these are not exhaustive and any compound that can be applied to ultra-low temperature epoxy-cured polyester resins and perform this function is within the scope of the present invention.
A preparation method of ultralow temperature epoxy curing polyester resin comprises the following steps:
step one, preparing materials according to a formula; the formula comprises the following components in parts by mass: 1-5 parts of core monomer dipentaerythritol, 0.08-0.12 part of catalyst, 30-42 parts of polyol, 30-55 parts of polybasic acid, 10-25 parts of blocked acid and 1-5 parts of curing accelerator; 1-50% of polybasic acid is used as first-batch polybasic acid, and the rest is used as second-batch polybasic acid; the molar ratio of the polyhydric alcohol to the polybasic acid is 1.02-1.5: 1;
secondly, in a reaction kettle provided with a heating device, a stirrer and a condenser, firstly adding a nuclear monomer dipentaerythritol and a catalyst, heating and melting to 100 ℃, firstly adding a first batch of polybasic acid, then slowly heating to 200 ℃, and preserving heat for 2-3 hours; adding polyalcohol and second batch of polybasic acid, slowly heating to 240 deg.C, and keeping the temperature until the acid value is 10-20 mgKOH/g;
step three, vacuumizing (the vacuum degree is less than-0.095M Pa) until the acid value is 2-10 mgKOH/g;
cooling to 220 ℃, adding a blocking acid, and keeping the temperature at 210 ℃ until the acid value is 70-80 mgKOH/g;
and step five, cooling to 180 ℃ and 200 ℃, adding a curing accelerator, maintaining for 30-60 minutes, and discharging to obtain the ultralow-temperature epoxy curing polyester resin.
Samples 1-5 were prepared according to the preparation method described above by the formulations of examples 1-5; comparative example 1 the formulation and process substantially corresponds to example 3 except that the polyacid is added in a second batch at a time to provide comparative sample 1. Comparative example 2 is comparative sample 2 obtained from a formulation and process commonly used in the market.
Preparing the obtained samples 1-5 and the comparative samples 1 and 2 into ultralow-temperature curing powder according to the following formula, detecting the ultralow-temperature curing powder, detecting the mechanical property and leveling, wherein the curing condition is 130 ℃/20 min;
the synthesized polyester resin is matched with epoxy resin to prepare ultralow temperature curing powder, and the formula is as follows: polyester resin: 325g, epoxy 663: 325 g; leveling agent: 10 g: titanium dioxide: 320g, benzoin: 10 g.
Impact properties: measured according to the national standard GB1732/1993, wherein + indicates passing, -indicates not passing;
gel time: measured according to national standard GB 1699/1997;
surface leveling grade: the sprayed sample plate is compared with the PCI standard sample plate, the leveling grade is determined, the numerical value is higher, and the surface leveling effect is better.
And (3) detection results:
from the above experiments and results, it can be seen that the product obtained by using the formulation of the present invention has a generally longer gel time, the gel time obtained by comparing the formulation of sample 2 is the shortest, and the impact resistance and leveling level are the worst, and the product obtained by introducing the core monomer dipentaerythritol and adding the polyacid in batches has better impact resistance and leveling property.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the present invention in any way, and all technical solutions obtained by using equivalent alternatives or equivalent variations fall within the scope of the present invention.