CN112724387A - Wear-resistant polyester resin and preparation method thereof - Google Patents
Wear-resistant polyester resin and preparation method thereof Download PDFInfo
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- CN112724387A CN112724387A CN202011607865.6A CN202011607865A CN112724387A CN 112724387 A CN112724387 A CN 112724387A CN 202011607865 A CN202011607865 A CN 202011607865A CN 112724387 A CN112724387 A CN 112724387A
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- 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
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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- 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
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- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- 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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
- C09D167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
- C09D5/033—Powdery paints characterised by the additives
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
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Abstract
The invention relates to a wear-resistant polyester resin and a preparation method thereof, wherein the preparation method comprises the following steps: synthesizing a polyester polymer by adopting a melting two-step method, wherein the raw materials comprise neopentyl glycol, ethylene glycol, diphenyl silanediol, trimethylolpropane and terephthalic acid; 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, trimellitic anhydride, a catalyst, a curing accelerator, ferric chloride and basalt fiber; coating a polyester polymer in a molten state on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating, carrying out heat treatment, cooling, cutting, and grinding to obtain fiber reinforced polyester powder particles, namely wear-resistant polyester resin; fe is arranged between 2, 6-pyridine dicarboxylic acid chain segments of different polyester chain segments in the wear-resistant polyester resin3+The coordination improves the strength and the wear resistance of the polyester powder; preparing the wear-resistant polyester resin into a coating, and performing a wear resistance test and a salt spray resistance test to obtain a product with the wear resistance of 1.87-2.13L/mum and the salt spray test result: no cracking, no foaming, no whitening and no peeling after 1000 hours.
Description
Technical Field
The invention belongs to the technical field of polyester resin, and relates to wear-resistant polyester resin and a preparation method thereof.
Background
The powder paint is a pure solid powder paint without solvent, and is prepared by physically mixing and hot extruding the components of resin, curing agent, filler and pigment. Different from the traditional solvent-based paint, the powder paint does not adopt a chemical solvent, but selects air as a spraying dispersion medium, and solves the problems of human harm and environmental pollution caused by the traditional paint. At present, the powder coating is widely applied to the fields of household appliances, automobile parts, public facilities, medical instruments, hardware tools and the like due to excellent environmental protection performance, mechanical property and aging resistance.
Polyester-based powder coatings are one of the most common types of powder coatings, and polyester resins as an important component have a great influence on the performance of the powder coatings. The current polyester powder coatings mainly have the problems of corrosion and poor wear resistance. For example, on the objects which are exposed to rain and sunshine and are easily rusted and rotten, people often see lawn lamps arranged in various landscaping lawns such as urban leisure culture squares, parks, districts, various parks, schools and the like, and because the lawn lamps in certain places, private villas and garden yards are arranged in various landscaping shrub clusters and lawns, the environment is moist, the time is short, the lamp posts lose luster, rust stains and mottle, and the safety and beauty of the urban green land landscape are seriously influenced. Meanwhile, on articles which are frequently used back and forth and are easy to wear, such as drawer sliding guides, desk computer keyboard sliding guides and the like, due to the fact that the surface coating is lack of high-wear-resistance powder coating, the phenomenon of flexible sliding and blocking is often caused.
The polyester resin is added with the inorganic fiber powder for reinforcement, so that the hardness and the wear resistance of the resin can be improved, the crack resistance of a coating can be improved, and the corrosion resistance of the coating can be improved.
The wear resistance of the existing polyester resin is mainly improved by depending on chemical crosslinking points of polyester macromolecules and inorganic powder, but the strength of the polyester resin is reduced due to excessive chemical crosslinking points.
Therefore, how to further improve the strength and the wear resistance of the polyester resin has very important significance.
Disclosure of Invention
In order to solve the problem of wear resistance in the prior art, the invention provides a wear-resistant polyester resin and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following scheme:
the wear-resistant polyester resin comprises the following components in parts by weight: 25-40 parts of neopentyl glycol; 2-10 parts of ethylene glycol; 2-10 parts of diphenyl silanediol; 2-3 parts of trimethylolpropane; 15-20 parts of terephthalic acid; 10-30 parts of 2, 5-furandicarboxylic acid; 5-15 parts of isophthalic acid; 5-10 parts of 2, 6-pyridinedicarboxylic acid; 3-5 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.0-2.6 parts of ferric chloride; 50-150 parts of basalt fibers.
Fe is arranged between 2, 6-pyridine dicarboxylic acid chain segments of different polyester chain segments in the wear-resistant polyester resin3+Coordination, the coordination structure formed is:
the chelate formed by Fe (III) and 2, 6-pyridinedicarboxylic acid is used as a physical crosslinking point to strengthen intermolecular force, supplements the chemical crosslinking point of polyester resin, has an enhancement effect on the strength of the polyester resin, reduces the influence of excessive chemical crosslinking points on the strength, reduces the adhesive force of the contact surface caused by the interdiffusion of molecular chain sliding in the friction process of the polyester, and greatly improves the wear resistance and the use durability of the polyester resin.
Meanwhile, metal ions such as iron, magnesium, calcium and the like in the basalt fiber can also be coordinated with the 2, 6-pyridinedicarboxylic acid, so that the interface bonding force between the basalt fiber and the polyester is improved, the compatibility of the interface between the polyester resin and the basalt fiber is obviously improved, and the strength and the wear resistance of the polyester powder are favorably improved.
The invention solves the problem of agglomeration of basalt fiber powder when the basalt fiber powder is mixed with polyester resin, enables the fiber powder to be uniformly dispersed in the resin, and improves the interface bonding force of the polyester and the basalt fiber, thereby improving the wear resistance of the polyester resin.
As a preferred technical scheme:
the wear-resistant polyester resin has the following performance indexes: after the wear-resistant polyester resin is prepared into the coating, a wear resistance test is respectively carried out according to GB/T23988-: no cracking, no foaming, no whitening and no peeling after 1000 hours;
the preparation of the wear-resistant polyester resin into the coating specifically comprises the following steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
The invention also provides a method for preparing the wear-resistant polyester resin, which comprises the following steps:
step one, synthesizing a polyester polymer by adopting a two-step melting method, adding neopentyl glycol, ethylene glycol, diphenyl silicon glycol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after starting water outlet, heating to 200 ℃ and carrying out heat preservation reaction for 1.5-3.5 h, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and starting vacuum-pumping polycondensation after esterification to obtain the polyester polymer in a molten state;
step two, adding a curing accelerator triphenyl ethyl phosphorus bromide with the dosage of the formula into the polyester polymer in the molten state in the step one;
and step three, coating the polyester polymer in the molten state in the step two on basalt fiber unidirectional cloth to prepare basalt long fiber reinforced polyester coating, performing heat treatment, cooling, cutting, and grinding to obtain the wear-resistant polyester resin.
The ferric chloride and the 2, 6-pyridinedicarboxylic acid are in a dissociation state under a high-temperature melting state, the ferric chloride and the 2, 6-pyridinedicarboxylic acid can form coordination in the process of cooling the melt, and the coordination is further improved during heat treatment.
The method comprises the step three, wherein the coating thickness is 0.02 mm-0.2 mm.
According to the method, the size of the fiber reinforced polyester powder particles prepared by grinding in the third step is 100-600 meshes.
The method comprises the steps of heating at 80-100 ℃ for 50-60 min.
The mechanism of the invention is as follows:
the wear of the polymer material is caused by the forces generated during the movement, which during sliding can generate high pressures on the contact points, which cause micro-deformations and micro-protrusions of the contact surfaces due to shearing, and cause plastic deformations of the soft surfaces, macro-deformations due to wear of the abrasive particles and elastic hysteresis deformations of the viscoelastic material. In addition, friction heat causes an increase in temperature which exacerbates wear. The sliding wear of the high molecular polymer mainly includes adhesive wear, abrasive wear, and fatigue wear. The main reasons for the occurrence of sticking are: (1) polymers are more easily deformed because they are soft; (2) the molecular chains of the polymer interdiffuse during sliding, resulting in an increase in the adhesion of the contacting surfaces. Abrasive wear refers to the action of deformation or tear damage caused by the relative motion of some hard particles or hard rough surfaces on the surface of a soft material during sliding. Abrasive grains between the two materials are abraded, and the hard material causes damage such as furrowing or fracture to the surface of the soft material during sliding.
The metal-ligand coordination interaction enhances the molecular interaction of the macromolecular chain segment, impeding the movement of the polymer chain. In FeCl3In the doped polyester resin, four five-membered ring pyridine ligands are contained around one core of Fe (III) formed between the Fe (III) and the pyridine ligands, the stability constant of the formed chelate is high, and the coordination structure of the two intermolecular pyridine ligands tends to promote the aggregation of polymer chains and become physical crosslinking points.
The chelate formed by Fe (III) and 2, 6-pyridinedicarboxylic acid is used as a physical crosslinking point to strengthen intermolecular force, supplements the chemical crosslinking point of polyester resin, has an enhancement effect on the strength of the polyester resin, reduces the influence of excessive chemical crosslinking points on the strength, reduces the adhesive force of the contact surface caused by the interdiffusion of molecular chain sliding in the friction process of the polyester, and greatly improves the wear resistance and the use durability of the polyester resin.
The formula of the wear-resistant polyester resin also contains basalt fibers, metal ions such as iron, magnesium, calcium and the like in the basalt fibers can be coordinated with the 2, 6-pyridinedicarboxylic acid, the interface bonding force between the basalt fibers and the polyester is improved, the interface compatibility between the polyester resin and the basalt fibers is obviously improved, and the strength and the wear resistance of polyester powder are favorably improved.
Advantageous effects
According to the invention, Fe (III) and 2, 6-pyridinedicarboxylic acid are coordinated to strengthen intermolecular acting force, so that the adhesive force of the contact surface caused by interdiffusion of molecular chain sliding in the friction process of polyester is reduced, and the wear resistance and the service durability of the polyester resin are greatly improved.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A method for preparing wear-resistant polyester resin comprises the following specific steps:
(1) preparing raw materials;
the weight portion is as follows: 25 parts of neopentyl glycol; 2 parts of ethylene glycol; 2 parts of diphenyl silanediol; 2 parts of trimethylolpropane; 15 parts of terephthalic acid; 10 parts of 2, 5-furandicarboxylic acid; 5 parts of isophthalic acid; 5 parts of 2, 6-pyridinedicarboxylic acid; 3 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2 parts of ferric chloride; 50 parts of basalt fibers;
(2) synthesizing a polyester polymer by adopting a melting two-step method, adding neopentyl glycol, ethylene glycol, diphenylsilanediol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after heating to 200 ℃ at 1 ℃/min and keeping the temperature for reaction for 1.5h after water begins to be discharged, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and starting vacuum-pumping polycondensation after the esterification is finished, wherein the vacuum degree is 100Pa, so as to obtain the polyester polymer in a molten state;
(3) adding the curing accelerator triphenylethyl phosphorus bromide with the formula dosage into the polyester polymer in the molten state in the step (2), and stirring for 10 minutes;
(4) coating the polyester polymer in the molten state in the step (3) on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating with the thickness of 0.02mm, and then carrying out heat treatment at the temperature of 80 ℃ for 60 min; then cutting and grinding after cooling to obtain fiber reinforced polyester powder particles with the size of 100 meshes, namely the wear-resistant polyester resin.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating, a wear resistance test is respectively carried out according to GB/T23988-2009 and a salt spray resistance test is carried out according to GB/T1771-2007, the measured wear resistance is 1.87L/mum, and the salt spray test result is as follows: no cracking, no foaming, no whitening and no peeling after 1000 hours; the wear-resistant polyester resin is prepared into the paint, which comprises the following specific steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
Comparative example 1
A process for preparing an abrasion resistant polyester resin, substantially as described in example 1, except that in step (1) the raw materials are prepared by: the weight portion is as follows: 25 parts of neopentyl glycol; 2 parts of ethylene glycol; 2 parts of diphenyl silanediol; 2 parts of trimethylolpropane; 15 parts of terephthalic acid; 10 parts of 2, 5-furandicarboxylic acid; 10 parts of isophthalic acid; 3 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.0 parts of ferric chloride; 50 parts of basalt fiber.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating according to the same method as the example 1, the wear resistance test is carried out according to GB/T23988-: cracking, foaming, whitening and peeling in 600 hours.
The abrasion resistance and the salt spray test result of comparative example 1 are inferior to those of example 1, compared to example 1, because the polyester resin of example 1 is doped with FeCl3，Fe(Ⅲ) Four five-membered ring pyridine ligands are contained around a core formed by Fe (III) between the pyridine ligands, the stability constant of the formed chelate is high, and the coordination structure of the two intermolecular pyridine ligands tends to promote the aggregation of polymer chains and becomes a physical crosslinking point; the chelate formed by Fe (III) and 2, 6-pyridinedicarboxylic acid is used as a physical crosslinking point to strengthen intermolecular force, supplements the chemical crosslinking point of the polyester resin, has a reinforcing effect on the strength of the polyester resin, reduces the influence of excessive chemical crosslinking points on the strength, reduces the adhesive force of the contact surface caused by interdiffusion of molecular chain sliding in the friction process of the polyester, and improves the wear resistance and the use durability of the polyester resin.
Example 2
A method for preparing wear-resistant polyester resin comprises the following specific steps:
(1) preparing raw materials;
the weight portion is as follows: 28 parts of neopentyl glycol; 4 parts of ethylene glycol; 3 parts of diphenyl silanediol; 2 parts of trimethylolpropane; 15 parts of terephthalic acid; 14 parts of 2, 5-furandicarboxylic acid; 12 parts of isophthalic acid; 9 parts of 2, 6-pyridinedicarboxylic acid; 5 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.2 parts of ferric chloride; 130 parts of basalt fibers;
(2) synthesizing a polyester polymer by adopting a melting two-step method, adding neopentyl glycol, ethylene glycol, diphenylsilanediol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after heating to 200 ℃ at 1 ℃/min and carrying out heat preservation reaction for 2 hours after water begins to be discharged, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and carrying out vacuum polycondensation after the esterification is finished, wherein the vacuum degree is 90Pa to obtain the polyester polymer in a molten state;
(3) adding the curing accelerator triphenylethyl phosphorus bromide with the formula dosage into the polyester polymer in the molten state in the step (2), and stirring for 14 minutes;
(4) coating the polyester polymer in the molten state in the step (3) on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating with the thickness of 0.04mm, and then carrying out heat treatment at the temperature of 85 ℃ for 59 min; then cutting after cooling and grinding to obtain the fiber reinforced polyester powder particles with the size of 300 meshes, namely the wear-resistant polyester resin.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating, a wear resistance test is respectively carried out according to GB/T23988-2009 and a salt spray resistance test is carried out according to GB/T1771-2007, the measured wear resistance is 1.9L/mum, and the salt spray test result is as follows: no cracking, no foaming, no whitening and no peeling after 1000 hours; the wear-resistant polyester resin is prepared into the paint, which comprises the following specific steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
Example 3
A method for preparing wear-resistant polyester resin comprises the following specific steps:
(1) preparing raw materials;
the weight portion is as follows: 32 parts of neopentyl glycol; 6 parts of ethylene glycol; 7 parts of diphenyl silanediol; 3 parts of trimethylolpropane; 16 parts of terephthalic acid; 25 parts of 2, 5-furandicarboxylic acid; 9 parts of isophthalic acid; 7 parts of 2, 6-pyridinedicarboxylic acid; 3 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.2 parts of ferric chloride; 70 parts of basalt fibers;
(2) synthesizing a polyester polymer by adopting a melting two-step method, adding neopentyl glycol, ethylene glycol, diphenylsilanediol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after heating to 200 ℃ at 1 ℃/min and carrying out heat preservation reaction for 2.5h after water begins to be discharged, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and carrying out vacuum polycondensation after the esterification is finished, wherein the vacuum degree is 50Pa to obtain the polyester polymer in a molten state;
(3) adding the curing accelerator triphenylethyl phosphorus bromide with the formula dosage into the polyester polymer in the molten state in the step (2), and stirring for 13 minutes;
(4) coating the polyester polymer in the molten state in the step (3) on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating with the thickness of 0.06mm, and then carrying out heat treatment at 87 ℃ for 54 min; then cutting after cooling and grinding to obtain the fiber reinforced polyester powder particles with the size of 200 meshes, namely the wear-resistant polyester resin.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating, a wear resistance test is respectively carried out according to GB/T23988-2009 and a salt spray resistance test is carried out according to GB/T1771-2007, the measured wear resistance is 1.95L/mum, and the salt spray test result is as follows: no cracking, no foaming, no whitening and no peeling after 1000 hours; the wear-resistant polyester resin is prepared into the paint, which comprises the following specific steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
Example 4
A method for preparing wear-resistant polyester resin comprises the following specific steps:
(1) preparing raw materials;
the weight portion is as follows: 34 parts of neopentyl glycol; 9 parts of ethylene glycol; 5 parts of diphenyl silanediol; 2 parts of trimethylolpropane; 19 parts of terephthalic acid; 22 parts of 2, 5-furandicarboxylic acid; 11 parts of isophthalic acid; 8 parts of 2, 6-pyridinedicarboxylic acid; 4 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.6 parts of ferric chloride; 90 parts of basalt fibers;
(2) synthesizing a polyester polymer by adopting a two-step melting method, adding neopentyl glycol, ethylene glycol, diphenylsilanediol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after heating to 200 ℃ at 1 ℃/min and carrying out heat preservation reaction for 2.5h after water begins to be discharged, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and carrying out vacuum polycondensation after the esterification is finished, wherein the vacuum degree is 30Pa to obtain the polyester polymer in a molten state;
(3) adding the curing accelerator triphenylethyl phosphorus bromide with the formula dosage into the polyester polymer in the molten state in the step (2), and stirring for 12 minutes;
(4) coating the polyester polymer in the molten state in the step (3) on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating with the thickness of 0.08mm, and then carrying out heat treatment at the temperature of 92 ℃ for 56 min; then cutting and grinding after cooling to obtain the fiber reinforced polyester powder particles with the size of 400 meshes, namely the wear-resistant polyester resin.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating, a wear resistance test is respectively carried out according to GB/T23988-2009 and a salt spray resistance test is carried out according to GB/T1771-2007, the measured wear resistance is 2L/mum, and the salt spray test result is as follows: no cracking, no foaming, no whitening and no peeling after 1000 hours; the wear-resistant polyester resin is prepared into the paint, which comprises the following specific steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
Example 5
A method for preparing wear-resistant polyester resin comprises the following specific steps:
(1) preparing raw materials;
the weight portion is as follows: neopentyl glycol 36 parts; 8 parts of ethylene glycol; 6 parts of diphenyl silanediol; 3 parts of trimethylolpropane; 18 parts of terephthalic acid; 25 parts of 2, 5-furandicarboxylic acid; 7 parts of isophthalic acid; 6 parts of 2, 6-pyridinedicarboxylic acid; 4 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.4 parts of ferric chloride; 110 parts of basalt fibers;
(2) synthesizing a polyester polymer by adopting a melting two-step method, adding neopentyl glycol, ethylene glycol, diphenylsilanediol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after heating to 200 ℃ at 1 ℃/min and carrying out heat preservation reaction for 3 hours after water begins to be discharged, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and carrying out vacuum polycondensation after the esterification is finished, wherein the vacuum degree is 15Pa to obtain the polyester polymer in a molten state;
(3) adding the curing accelerator triphenylethyl phosphorus bromide with the formula dosage into the polyester polymer in the molten state in the step (2), and stirring for 11 minutes;
(4) coating the polyester polymer in the molten state in the step (3) on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating with the thickness of 0.1mm, and then carrying out heat treatment at 96 ℃ for 58 min; then cutting after cooling and grinding to obtain the fiber reinforced polyester powder particles with the size of 300 meshes, namely the wear-resistant polyester resin.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating, a wear resistance test is respectively carried out according to GB/T23988-2009 and a salt spray resistance test is carried out according to GB/T1771-2007, the measured wear resistance is 2.05L/mum, and the salt spray test result is as follows: no cracking, no foaming, no whitening and no peeling after 1000 hours; the wear-resistant polyester resin is prepared into the paint, which comprises the following specific steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
Example 6
A method for preparing wear-resistant polyester resin comprises the following specific steps:
(1) preparing raw materials;
the weight portion is as follows: 38 parts of neopentyl glycol; 7 parts of ethylene glycol; 5 parts of diphenyl silanediol; 3 parts of trimethylolpropane; 18 parts of terephthalic acid; 20 parts of 2, 5-furandicarboxylic acid; 14 parts of isophthalic acid; 9 parts of 2, 6-pyridinedicarboxylic acid; 4 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.5 parts of ferric chloride; 60 parts of basalt fibers;
(2) synthesizing a polyester polymer by adopting a melting two-step method, adding neopentyl glycol, ethylene glycol, diphenylsilanediol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after heating to 200 ℃ at 1 ℃/min and carrying out heat preservation reaction for 3 hours after water begins to be discharged, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and carrying out vacuum polycondensation after the esterification is finished, wherein the vacuum degree is 20Pa to obtain the polyester polymer in a molten state;
(3) adding the curing accelerator triphenylethyl phosphorus bromide with the formula dosage into the polyester polymer in the molten state in the step (2), and stirring for 10 minutes;
(4) coating the polyester polymer in the molten state in the step (3) on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating with the thickness of 0.15mm, and then carrying out heat treatment at the temperature of 98 ℃ for 54 min; then, the mixture was cooled, cut and ground to obtain 500-mesh fiber-reinforced polyester powder particles, i.e., abrasion-resistant polyester resin.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating, a wear resistance test is respectively carried out according to GB/T23988-2009 and a salt spray resistance test is carried out according to GB/T1771-2007, the measured wear resistance is 2.1L/mum, and the salt spray test result is as follows: no cracking, no foaming, no whitening and no peeling after 1000 hours; the wear-resistant polyester resin is prepared into the paint, which comprises the following specific steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
Example 7
A method for preparing wear-resistant polyester resin comprises the following specific steps:
(1) preparing raw materials;
the weight portion is as follows: 40 parts of neopentyl glycol; 10 parts of ethylene glycol; 10 parts of diphenyl silanediol; 3 parts of trimethylolpropane; 20 parts of terephthalic acid; 30 parts of 2, 5-furandicarboxylic acid; 15 parts of isophthalic acid; 10 parts of 2, 6-pyridinedicarboxylic acid; 5 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.6 parts of ferric chloride; 150 parts of basalt fibers;
(2) synthesizing a polyester polymer by adopting a two-step melting method, adding neopentyl glycol, ethylene glycol, diphenylsilanediol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after heating to 200 ℃ at 1 ℃/min and carrying out heat preservation reaction for 3.5h after water begins to be discharged, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and carrying out vacuum polycondensation after the esterification is finished, wherein the vacuum degree is 19Pa to obtain the polyester polymer in a molten state;
(3) adding the curing accelerator triphenylethyl phosphorus bromide with the formula dosage into the polyester polymer in the molten state in the step (2), and stirring for 15 minutes;
(4) coating the polyester polymer in the molten state in the step (3) on basalt fiber unidirectional cloth to prepare a basalt long fiber reinforced polyester coating with the thickness of 0.2mm, and then carrying out heat treatment at the temperature of 100 ℃ for 50 min; then, the mixture was cooled, cut and ground to obtain 600 mesh fiber-reinforced polyester powder particles, i.e., abrasion-resistant polyester resin.
The performance indexes of the prepared wear-resistant polyester resin are as follows: after the wear-resistant polyester resin is prepared into a coating, a wear resistance test is respectively carried out according to GB/T23988-2009 and a salt spray resistance test is carried out according to GB/T1771-2007, the measured wear resistance is 2.13L/mum, and the salt spray test result is as follows: no cracking, no foaming, no whitening and no peeling after 1000 hours; the wear-resistant polyester resin is prepared into the paint, which comprises the following specific steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
Claims (6)
1. The wear-resistant polyester resin is characterized by comprising the following components in parts by weight: 25-40 parts of neopentyl glycol; 2-10 parts of ethylene glycol; 2-10 parts of diphenyl silanediol; 2-3 parts of trimethylolpropane; 15-20 parts of terephthalic acid; 10-30 parts of 2, 5-furandicarboxylic acid; 5-15 parts of isophthalic acid; 5-10 parts of 2, 6-pyridinedicarboxylic acid; 3-5 parts of trimellitic anhydride; 0.05 part of esterification catalyst stannous oxalate; 0.15 part of curing accelerator triphenyl ethyl phosphonium bromide; 2.0-2.6 parts of ferric chloride; 50-150 parts of basalt fibers.
2. The abrasion-resistant polyester resin according to claim 1, wherein the performance index of the abrasion-resistant polyester resin is as follows: after the wear-resistant polyester resin is prepared into the coating, a wear resistance test is respectively carried out according to GB/T23988-: no cracking, no foaming, no whitening and no peeling after 1000 hours;
the preparation of the wear-resistant polyester resin into the coating specifically comprises the following steps: according to the weight portion, 60 portions of wear-resistant polyester resin, 18 portions of epoxy resin, 5 portions of titanium dioxide and 5 portions of leveling agent acrylate copolymer are uniformly mixed, and the mixture is subjected to melt extrusion, tabletting, crushing and sieving by a double-screw extruder to prepare the powder coating.
3. A process for preparing an abrasion resistant polyester resin as claimed in claim 1 or 2, comprising the steps of:
step one, synthesizing a polyester polymer by adopting a two-step melting method, adding neopentyl glycol, ethylene glycol, diphenyl silicon glycol, trimethylolpropane, terephthalic acid, 2, 5-furandicarboxylic acid, isophthalic acid, 2, 6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride which are used according to the formula and used in the formula into a reaction kettle, introducing nitrogen into the reaction kettle, gradually heating and stirring, starting esterification reaction at 140 ℃, measuring an acid value after starting water outlet, heating to 200 ℃ and carrying out heat preservation reaction for 1.5-3.5 h, adding isophthalic acid and trimellitic anhydride after the acid value reaches 20mgKOH/g, and starting vacuum-pumping polycondensation after esterification to obtain the polyester polymer in a molten state;
step two, adding a curing accelerator triphenyl ethyl phosphorus bromide with the dosage of the formula into the polyester polymer in the molten state in the step one;
and step three, coating the polyester polymer in the molten state in the step two on basalt fiber unidirectional cloth to prepare basalt long fiber reinforced polyester coating, performing heat treatment, cooling, cutting, and grinding to obtain fiber reinforced polyester powder particles, namely the wear-resistant polyester resin.
4. The method of claim 3, wherein the coating thickness in step three is 0.02mm to 0.2 mm.
5. The method of claim 3, wherein the size of the fiber reinforced polyester powder particles obtained by the grinding in the third step is 100 to 600 mesh.
6. The method according to claim 3, wherein the temperature of the heat treatment in the third step is 80-100 ℃ for 50-60 min.
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| CN202011607865.6A CN112724387A (en) | 2020-12-29 | 2020-12-29 | Wear-resistant polyester resin and preparation method thereof |
| PCT/CN2021/114197 WO2022142398A1 (en) | 2020-12-29 | 2021-08-24 | Anti-abrasion polyester resin and preparation method therefor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022142398A1 (en) * | 2020-12-29 | 2022-07-07 | 江苏恒力化纤股份有限公司 | Anti-abrasion polyester resin and preparation method therefor |
| JP2023553509A (en) * | 2020-12-29 | 2023-12-21 | 江蘇恒力化繊股▲ふん▼有限公司 | High strength/thermally stable polyester industrial yarn and its manufacturing method |
| JP2023553510A (en) * | 2020-12-29 | 2023-12-21 | 江蘇恒力化繊股▲ふん▼有限公司 | Flame-retardant polyester fiber for clothing and its manufacturing method |
| JP2023553508A (en) * | 2020-12-29 | 2023-12-21 | 江蘇恒力化繊股▲ふん▼有限公司 | High strength/low elongation polyester industrial yarn and its manufacturing method |
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| CN115518569B (en) * | 2022-09-23 | 2023-08-15 | 安徽桑瑞斯环保新材料有限公司 | Preparation device and method of insulating high-heat-conductivity coating |
| CN115518578B (en) * | 2022-09-23 | 2023-05-30 | 安徽桑瑞斯环保新材料有限公司 | Preparation device and method of high-temperature-resistant insulating high-heat-conductivity coating |
| CN115340668B (en) * | 2022-09-23 | 2024-03-26 | 黄山嘉恒科技有限公司 | Wear-resistant and high-temperature-resistant polyester resin for powder coating and preparation method thereof |
| CN115594831B (en) * | 2022-10-31 | 2023-08-01 | 广东四方威凯高新技术有限公司 | Polyester resin for finishing paint, preparation method thereof and finishing paint |
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| CN110903745A (en) * | 2019-11-12 | 2020-03-24 | 浙江光华科技股份有限公司 | Anti-corrosion wear-resistant polyester resin and preparation method thereof |
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| CN110964416B (en) * | 2019-12-24 | 2021-07-13 | 浙江光华科技股份有限公司 | Weather-resistant wear-resistant polyester resin, powder coating and preparation method thereof |
| CN112779809B (en) * | 2020-12-29 | 2022-08-19 | 江苏恒力化纤股份有限公司 | Papermaking forming net and preparation method thereof |
| CN112724387A (en) * | 2020-12-29 | 2021-04-30 | 江苏恒力化纤股份有限公司 | Wear-resistant polyester resin and preparation method thereof |
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| CN110903745A (en) * | 2019-11-12 | 2020-03-24 | 浙江光华科技股份有限公司 | Anti-corrosion wear-resistant polyester resin and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022142398A1 (en) * | 2020-12-29 | 2022-07-07 | 江苏恒力化纤股份有限公司 | Anti-abrasion polyester resin and preparation method therefor |
| JP2023553509A (en) * | 2020-12-29 | 2023-12-21 | 江蘇恒力化繊股▲ふん▼有限公司 | High strength/thermally stable polyester industrial yarn and its manufacturing method |
| JP2023553510A (en) * | 2020-12-29 | 2023-12-21 | 江蘇恒力化繊股▲ふん▼有限公司 | Flame-retardant polyester fiber for clothing and its manufacturing method |
| JP2023553508A (en) * | 2020-12-29 | 2023-12-21 | 江蘇恒力化繊股▲ふん▼有限公司 | High strength/low elongation polyester industrial yarn and its manufacturing method |
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