WO2022142398A1 - 一种耐磨聚酯树脂及其制备方法 - Google Patents

一种耐磨聚酯树脂及其制备方法 Download PDF

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WO2022142398A1
WO2022142398A1 PCT/CN2021/114197 CN2021114197W WO2022142398A1 WO 2022142398 A1 WO2022142398 A1 WO 2022142398A1 CN 2021114197 W CN2021114197 W CN 2021114197W WO 2022142398 A1 WO2022142398 A1 WO 2022142398A1
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parts
polyester resin
wear
acid
coating
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PCT/CN2021/114197
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English (en)
French (fr)
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王山水
汤方明
钮臧臧
孙晓华
尹立新
吴帆
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江苏恒力化纤股份有限公司
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Publication of WO2022142398A1 publication Critical patent/WO2022142398A1/zh

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    • 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
    • C08G63/68—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
    • 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
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • 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
    • 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
    • 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
    • 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
    • C09D5/033—Powdery paints characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K7/10—Silicon-containing compounds

Definitions

  • the invention belongs to the technical field of polyester resins, and relates to a wear-resistant polyester resin and a preparation method thereof.
  • Powder coating is a kind of solvent-free, pure solid powder coating, which is obtained by physical mixing and hot extrusion of resin, curing agent, filler and pigment and other components. Different from traditional solvent-based coatings, powder coatings do not use chemical solvents, but choose air as the dispersion medium for spraying, which solves the human harm and environmental pollution caused by traditional coatings. At present, powder coatings are widely used in household appliances, auto parts, public facilities, medical equipment, hardware tools and other fields due to their excellent environmental performance, mechanical properties and aging resistance.
  • Polyester powder coatings are one of the most common types of powder coatings. As an important component, polyester resin has a great influence on the performance of powder coatings.
  • the current polyester powder coatings mainly have the problems of poor corrosion and wear resistance. For example, on objects that are prone to rust and rust, we often see lawn lights installed in urban leisure and cultural squares, parks, communities, various parks, schools and other landscaping lawns. Some clubs, private villas, and garden lights in garden courtyards are installed in various types of landscaping bushes and lawns. The environment is humid and the time is not long. Safe and beautiful. At the same time, on frequently used objects that are easy to wear and tear, such as drawer slide guides, desk computer keyboard frame slide guides, etc., due to the lack of high wear-resistant powder coatings on the surface coating, the phenomenon of sliding and flexible sticking is often caused.
  • Adding inorganic fiber powder to polyester resin for reinforcement can not only improve the hardness and wear resistance of the resin, but also improve the crack resistance of the coating, thereby improving its corrosion resistance.
  • the abrasion resistance of the existing polyester resin mainly depends on the chemical cross-linking points of the polyester macromolecules and the inorganic powder to improve, but if the chemical cross-linking points are too many, the strength of the polyester resin will decrease.
  • the present invention provides a wear-resistant polyester resin and a preparation method thereof.
  • a wear-resistant polyester resin in parts by weight, comprising: 25-40 parts of neopentyl glycol; 2-10 parts of ethylene glycol; 2-10 parts of diphenylsilicon glycol; and 2 parts of trimethylolpropane ⁇ 3 parts; 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 stannous oxalate as esterification catalyst; 0.15 part of curing accelerator triphenylethylphosphonium bromide; 2.0-2.6 parts of ferric chloride; 50-150 parts of basalt fiber.
  • the 2,6-pyridinedicarboxylic acid segments of different polyester segments in the wear-resistant polyester resin are coordinated by Fe 3+ , and the coordination structure formed is:
  • the chelate compound formed by Fe(III) and 2,6-pyridinedicarboxylic acid of the present invention acts as a physical cross-linking point, strengthens the intermolecular force, and is a supplement to the chemical cross-linking point of the polyester resin. It has a strengthening effect on the strength of polyester resin, reduces the influence of excessive chemical cross-linking points on strength, and reduces the adhesion of the contact surface caused by the mutual diffusion of the molecular chain sliding of polyester during the friction process. The wear resistance and durability of use are greatly improved.
  • iron, magnesium, calcium and other metal ions in the basalt fiber can also coordinate with 2,6-pyridinedicarboxylic acid, which improves the interfacial bonding force between the basalt fiber and the polyester, and significantly improves the relationship between the polyester resin and the basalt fiber.
  • the compatibility of the interface is beneficial to improve the strength and wear resistance of the polyester powder.
  • the invention solves the problem of agglomeration of the basalt fiber powder when it is mixed with the polyester resin, enables the fiber powder to be uniformly dispersed in the resin, and improves the interface bonding force between the polyester and the basalt fiber, thereby improving the resistance of the polyester resin. Abrasiveness.
  • Making the wear-resistant polyester resin into a coating is as follows: in parts by weight, uniformly mix 60 parts of the wear-resistant polyester resin, 18 parts of epoxy resin, 5 parts of titanium dioxide and 5 parts of leveling agent acrylate copolymer,
  • the powder coating is made by melt extrusion, tableting, crushing, crushing and sieving through a twin-screw extruder.
  • the present invention also provides a method for preparing the above-mentioned abrasion-resistant polyester resin, comprising the following steps:
  • Step 1 Synthesize polyester polymer by melting two-step method, mix neopentyl glycol, ethylene glycol, diphenylsilicon diol, trimethylolpropane, terephthalic acid, 2,5-furan in formula dosages.
  • Dicarboxylic acid, isophthalic acid, 2,6-pyridinedicarboxylic acid, esterification catalyst stannous oxalate and ferric chloride were added to the reaction kettle, nitrogen was introduced into the reaction kettle, the temperature was gradually increased and stirred, and the esterification reaction was started at 140°C , when the water starts to flow out, heat up to 200 °C for 1.5-3.5 hours, and then measure the acid value. After the acid value reaches 20 mgKOH/g, add isophthalic acid and trimellitic anhydride.
  • polyester polymer ;
  • Step 2 adding the curing accelerator triphenylethylphosphonium bromide of the formula dosage into the polyester polymer in the molten state in step 1;
  • step 3 the polyester polymer in the molten state in step 2 is coated on the basalt fiber unidirectional cloth to obtain the basalt long fiber reinforced polyester coating, heat treatment, cutting after cooling, and grinding to obtain a wear-resistant polyester resin .
  • Ferric chloride and 2,6-pyridinedicarboxylic acid are in a dissociated state under high temperature melting state. During the cooling process of the melt, coordination will be formed between ferric chloride and 2,6-pyridinedicarboxylic acid. bits have been further improved.
  • the coating thickness is 0.02mm-0.2mm.
  • the size of the fiber-reinforced polyester powder particles obtained by grinding in step 3 is 100-600 mesh.
  • the temperature of the heat treatment in step 3 is 80-100° C., and the time is 50-60 min.
  • the mechanism of the present invention is as follows:
  • the wear of the polymer material is caused by the force generated during the movement process, and there will be a lot of pressure on the contact point during the sliding process, causing the contact surface to produce micro-deformation and micro-convex due to shearing action, and cause a soft surface.
  • frictional heat increases temperature and increases wear.
  • Sliding wear of high molecular polymers mainly includes adhesive wear, abrasive wear and fatigue wear.
  • the main reasons for the adhesion are: (1) the polymer is more easily deformed because of its softness; (2) the molecular chains of the polymer will diffuse to each other during the sliding process, resulting in an increase in the adhesion of the contact surface.
  • Abrasive wear refers to the relative movement of some hard particles or hard rough surfaces on the surface of soft materials during the sliding process, causing deformation or tearing damage. Abrasive wear between the two materials causes damage such as furrows or fractures to the surface of the soft material by the hard material during sliding.
  • FeCl 3 doped polyester resin Fe(III) and pyridine ligands are formed between Fe(III) and one core of Fe(III) contains four five-membered ring pyridine ligands, and the formed chelate has a high stability constant , the coordination structure of the two intermolecular pyridine ligands tends to promote the aggregation of polymer chains and become physical cross-linking points.
  • the chelate compound formed by Fe(III) and 2,6-pyridinedicarboxylic acid of the present invention acts as a physical cross-linking point, strengthens the intermolecular force, and is a supplement to the chemical cross-linking point of the polyester resin. It has a strengthening effect on the strength of polyester resin, reduces the influence of excessive chemical cross-linking points on strength, and reduces the adhesion of the contact surface caused by the mutual diffusion of the molecular chain sliding of polyester during the friction process. The wear resistance and durability of use are greatly improved.
  • the formula of the wear-resistant polyester resin of the invention also contains basalt fiber, and metal ions such as iron, magnesium and calcium in the basalt fiber can coordinate with 2,6-pyridinedicarboxylic acid, which improves the interface between the basalt fiber and the polyester
  • the bonding force can significantly improve the compatibility of the interface between the polyester resin and the basalt fiber, which is beneficial to improve the strength and wear resistance of the polyester powder.
  • Fe(III) is coordinated with 2,6-pyridinedicarboxylic acid to strengthen the intermolecular force, and reduce the adhesion force on the contact surface caused by the mutual diffusion of the molecular chain sliding of the polyester during the friction process.
  • the abrasion resistance and durability of polyester resin are greatly improved.
  • a method for wear-resistant polyester resin the specific steps are as follows:
  • neopentyl glycol 25 parts of neopentyl glycol; 2 parts of ethylene glycol; 2 parts of diphenylsilicon glycol; 2 parts of trimethylolpropane; 15 parts of terephthalic acid; 2,5-furandicarboxylic acid 10 parts; 5 parts of isophthalic acid; 5 parts of 2,6-pyridinedicarboxylic acid; 3 parts of trimellitic anhydride; 0.05 part of stannous oxalate as esterification catalyst; 0.15 part of curing accelerator triphenylethylphosphonium bromide; ferric chloride 2 parts; 50 parts of basalt fiber;
  • step (3) the curing accelerator triphenylethylphosphonium bromide of formula consumption is added in the polyester polymer under molten state in step (2), stirred 10 minutes;
  • the performance index of the prepared wear-resistant polyester resin is: after the wear-resistant polyester resin is made into a coating, the wear resistance test is carried out according to GB/T 23988-2009 and the salt spray resistance test according to GB/T1771-2007 is carried out respectively. , the measured wear resistance is 1.87L/ ⁇ m, and the salt spray test results are: no cracking, no foaming, no whitening, and no peeling for 1000 hours; among them, the wear-resistant polyester resin is made into a coating.
  • a method of wear-resistant polyester resin is basically the same as that of Example 1, except that the preparation of raw materials in step (1) is: by weight: 25 parts of neopentyl glycol; 2 parts of ethylene glycol ; 2 parts of diphenylsilicon glycol; 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; oxalic acid as an esterification catalyst 0.05 part of stannous; 0.15 part of curing accelerator triphenylethylphosphonium bromide; 2.0 part of ferric chloride; 50 parts of basalt fiber.
  • the performance index of a kind of wear-resistant polyester resin prepared is: after the wear-resistant polyester resin is made into a coating according to the same method as in Example 1, the wear resistance test is carried out according to GB/T 23988-2009 and according to GB/T 23988-2009 respectively.
  • /T1771-2007 conducted a salt spray resistance test, the measured abrasion resistance was 3.04L/ ⁇ m, and the salt spray test results were: cracking, foaming, whitening and peeling after 600 hours.
  • Example 1 Compared with Example 1, the abrasion resistance and salt spray test results of Comparative Example 1 are both worse than those of Example 1, because the polyester resin in Example 1 is doped with FeCl 3 , Fe(III) and pyridine
  • the formation between the ligands consists of four five-membered ring pyridine ligands around a core of Fe(III), the chelate formed has a high stability constant, and the coordination structure of the two intermolecular pyridine ligands tends to promote the polymer
  • the aggregation of chains becomes the physical cross-linking point; the chelate formed by Fe(III) and 2,6-pyridinedicarboxylic acid, the chelate acts as the physical cross-linking point, strengthens the intermolecular force, and is the most important factor for polyester resins.
  • a method for wear-resistant polyester resin the specific steps are as follows:
  • step (3) the curing accelerator triphenylethylphosphonium bromide of formula consumption is added in the polyester polymer under molten state in step (2), stirred 14 minutes;
  • the performance index of the prepared wear-resistant polyester resin is: after the wear-resistant polyester resin is made into a coating, the wear resistance test is carried out according to GB/T 23988-2009 and the salt spray resistance test according to GB/T1771-2007 is carried out respectively. , the measured wear resistance is 1.9L/ ⁇ m, and the salt spray test results are: no cracking, no foaming, no whitening, no peeling for 1000 hours; among them, the wear-resistant polyester resin is made into a coating.
  • a method for wear-resistant polyester resin the specific steps are as follows:
  • step (3) the curing accelerator triphenylethylphosphonium bromide of formula consumption is added in the polyester polymer under molten state in step (2), stirs 13 minutes;
  • the performance index of the prepared wear-resistant polyester resin is: after the wear-resistant polyester resin is made into a coating, the wear resistance test is carried out according to GB/T 23988-2009 and the salt spray resistance test according to GB/T1771-2007 is carried out respectively.
  • the measured wear resistance is 1.95L/ ⁇ m
  • the salt spray test results are: no cracking, no foaming, no whitening, no peeling in 1000 hours; among them, the wear-resistant polyester resin is made into a coating specifically: press In parts by weight, 60 parts of wear-resistant polyester resin, 18 parts of epoxy resin, 5 parts of titanium dioxide and 5 parts of leveling agent acrylate copolymer were uniformly mixed, melted and extruded through a twin-screw extruder, pressed into tablets, Crushing, crushing and sieving to make powder coating.
  • a method for wear-resistant polyester resin the specific steps are as follows:
  • neopentyl glycol 34 parts of neopentyl glycol; 9 parts of ethylene glycol; 5 parts of diphenylsilicon glycol; 2 parts of trimethylolpropane; 19 parts of terephthalic acid; 2,5-furandicarboxylic acid 22 parts; 11 parts of isophthalic acid; 8 parts of 2,6-pyridinedicarboxylic acid; 4 parts of trimellitic anhydride; 0.05 part of stannous oxalate as esterification catalyst; 0.15 part of curing accelerator triphenylethylphosphonium bromide; ferric chloride 2.6 parts; 90 parts of basalt fiber;
  • step (3) the curing accelerator triphenylethylphosphonium bromide of formula consumption is added in the polyester polymer under molten state in step (2), stirred 12 minutes;
  • the performance index of the prepared wear-resistant polyester resin is: after the wear-resistant polyester resin is made into a coating, the wear resistance test is carried out according to GB/T 23988-2009 and the salt spray resistance test according to GB/T1771-2007 is carried out respectively. , the measured wear resistance is 2L/ ⁇ m, and the salt spray test results are: no cracking, no blistering, no whitening, no peeling in 1000 hours; among them, the wear-resistant polyester resin is made into a coating specifically: by weight In terms of parts, 60 parts of wear-resistant polyester resin, 18 parts of epoxy resin, 5 parts of titanium dioxide and 5 parts of leveling agent acrylate copolymer are uniformly mixed, melt extruded, tableted and crushed through a twin-screw extruder. , crushed and sieved to make powder coating.
  • a method for wear-resistant polyester resin the specific steps are as follows:
  • step (3) the curing accelerator triphenylethylphosphonium bromide of formula consumption is added in the polyester polymer under molten state in step (2), stirred 11 minutes;
  • the performance index of the prepared wear-resistant polyester resin is: after the wear-resistant polyester resin is made into a coating, the wear resistance test is carried out according to GB/T 23988-2009 and the salt spray resistance test according to GB/T1771-2007 is carried out respectively. , the measured wear resistance is 2.05L/ ⁇ m, and the salt spray test results are: no cracking, no foaming, no whitening, and no peeling for 1000 hours; among them, the wear-resistant polyester resin is made into a coating.
  • a method for wear-resistant polyester resin the specific steps are as follows:
  • neopentyl glycol 38 parts of neopentyl glycol; 7 parts of ethylene glycol; 5 parts of diphenylsilicon glycol; 3 parts of trimethylolpropane; 18 parts of terephthalic acid; 2,5-furandicarboxylic acid 20 parts; 14 parts of isophthalic acid; 9 parts of 2,6-pyridine dicarboxylic acid; 4 parts of trimellitic anhydride; 0.05 part of stannous oxalate as esterification catalyst; 0.15 part of curing accelerator triphenylethylphosphonium bromide; ferric chloride 2.5 parts; 60 parts of basalt fiber;
  • step (3) the curing accelerator triphenylethylphosphonium bromide of formula consumption is added in the polyester polymer under molten state in step (2), stirred 10 minutes;
  • the performance index of the prepared wear-resistant polyester resin is: after the wear-resistant polyester resin is made into a coating, the wear resistance test is carried out according to GB/T 23988-2009 and the salt spray resistance test according to GB/T1771-2007 is carried out respectively.
  • the measured wear resistance is 2.1L/ ⁇ m
  • the salt spray test results are: no cracking, no foaming, no whitening, and no peeling for 1000 hours; among them, the wear-resistant polyester resin is made into a coating specifically: press In parts by weight, 60 parts of wear-resistant polyester resin, 18 parts of epoxy resin, 5 parts of titanium dioxide and 5 parts of leveling agent acrylate copolymer were uniformly mixed, melted and extruded through a twin-screw extruder, pressed into tablets, Crushing, crushing and sieving to make powder coating.
  • a method for wear-resistant polyester resin the specific steps are as follows:
  • neopentyl glycol 40 parts of neopentyl glycol; 10 parts of ethylene glycol; 10 parts of diphenylsilicon glycol; 3 parts of trimethylolpropane; 20 parts of terephthalic acid; 2,5-furandicarboxylic acid 30 parts; 15 parts of isophthalic acid; 10 parts of 2,6-pyridinedicarboxylic acid; 5 parts of trimellitic anhydride; 0.05 part of stannous oxalate as esterification catalyst; 2.6 parts; 150 parts of basalt fiber;
  • step (3) the curing accelerator triphenylethylphosphonium bromide of formula consumption is added in the polyester polymer under molten state in step (2), stirs 15 minutes;
  • the performance index of the prepared wear-resistant polyester resin is: after the wear-resistant polyester resin is made into a coating, the wear resistance test is carried out according to GB/T 23988-2009 and the salt spray resistance test according to GB/T1771-2007 is carried out respectively. , the measured wear resistance is 2.13L/ ⁇ m, and the salt spray test results are: no cracking, no foaming, no whitening, and no peeling for 1000 hours; among them, the wear-resistant polyester resin is made into a coating.

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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Abstract

本发明涉及一种耐磨聚酯树脂及其制备方法，制备方法为：采用熔融两步法合成聚酯聚合物，原料为新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸；2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、偏苯三酸酐、催化剂、固化促进剂、氯化铁、玄武岩纤维；将熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得玄武岩长纤维增强聚酯涂布，热处理，冷却后切断，研磨，得到纤维增强聚酯粉末颗粒，即耐磨聚酯树脂；耐磨聚酯树脂中不同聚酯链段的2,6-吡啶二甲酸链段之间经Fe3+配位提高聚酯粉体的强度和耐磨性；将耐磨聚酯树脂制成涂料，进行耐磨性试验和耐盐雾试验，测得的耐磨性为1.87～2.13L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离。

Description

一种耐磨聚酯树脂及其制备方法 技术领域
本发明属于聚酯树脂技术领域，涉及一种耐磨聚酯树脂及其制备方法。
背景技术
粉末涂料是一种不含溶剂，纯固体粉末状的涂料，是由树脂，固化剂、填料及颜料等组分，经物理混合和热挤出后，得到的粉末状涂料。与传统溶剂型涂料不同，粉末涂料没有采用化学溶剂，而是选择空气作为喷涂分散介质，解决了传统涂料带来的人体危害和环境污染。目前，粉末涂料以其优异的环保性能、力学性能和耐老化性能，广泛应用于家用电器、汽车部件、公共设施、医疗器械、五金工具等领域。
聚酯类粉末涂料是最为常见的粉末涂料类型之一，聚酯树脂作为重要的组分对粉末涂料的性能有着很大的影响。目前的聚酯类粉末涂料主要存在着腐蚀和耐磨性差的问题。比如在户外雨淋日晒，容易锈浊腐损的物件上，我们经常看到安装于城市休闲文化广场、公园、小区、各类园区、学校等各类园林绿化的草坪中的草坪灯，在一些会所、私家别墅、园林庭院中的庭院灯由于安装在各类园林绿化的灌木丛中以及草坪中，环境潮湿，时间不长，灯杆却失去光泽锈渍斑驳，严重影响了城市绿地景观的安全与美丽。同时，在频繁来回使用容易磨损的物件上，比如抽屉滑导，办公桌电脑键盘架滑导等，由于表面涂层缺乏高耐磨性能粉末涂料，经常造成滑动灵活卡死现现象。
在聚酯树脂中加入无机纤维粉末进行增强，不仅可以提高树脂的硬度和耐磨性，而且还能够改善涂层的抗裂性，进而提高其抗腐蚀能力。
现有聚酯树脂的耐磨性主要依赖聚酯大分子的化学交联点以及无机粉末来提高，但化学交联点过多，聚酯树脂的强度会下降。
因此，如何进一步提高聚酯树脂的强度和耐磨性具有十分重要的意义。
发明内容
为了解决现有技术中耐磨性的问题，本发明提供一种耐磨聚酯树脂及其制备方法。
为达到上述目的，本发明采用的方案如下：
一种耐磨聚酯树脂，按重量份数计，包括：新戊二醇25～40份；乙二醇2～10份；二苯基硅二醇2～10份；三羟甲基丙烷2～3份；对苯二甲酸15～20份；2,5-呋喃二甲酸10～30份；间 苯二甲酸5～15份；2,6-吡啶二甲酸5～10份；偏苯三酸酐3～5份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.0～2.6份；玄武岩纤维50～150份。
耐磨聚酯树脂中不同聚酯链段的2,6-吡啶二甲酸链段之间经Fe 3+配位，形成的配位结构为：
Figure PCTCN2021114197-appb-000001
本发明Fe(Ⅲ)与2,6-吡啶二甲酸所形成的螯合物，螯合物作为物理交联点，强化分子间的作用力，是对聚酯树脂化学交联点的补充，同时对聚酯树脂的强度有增强作用，减少了化学交联点过多对强度的影响，降低了聚酯在摩擦过程中分子链滑动所发生的相互扩散而导致接触表面的粘着力，聚酯树脂的耐磨性和使用耐久性大大提高。
同时，玄武岩纤维中的铁、镁、钙等金属离子也可与2,6-吡啶二甲酸配位，提高了玄武岩纤维与聚酯之间的界面结合力，显著提高聚酯树脂与玄武岩纤维之间界面的相容性，有利于提高聚酯粉体的强度和耐磨性。
本发明解决了玄武岩纤维粉末在与聚酯树脂混合时的团聚问题，使纤维粉末能够均匀地分散在树脂当中，并且改善了聚酯与玄武岩纤维的界面结合力，从而提高了聚酯树脂的耐磨性。
作为优选的技术方案：
如上所述的一种耐磨聚酯树脂，耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为1.87～2.13L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；
将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。
本发明还提供制备如上所述的一种耐磨聚酯树脂的方法，包括以下步骤：
步骤一，采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，热升温至200℃保温反应1.5～3.5h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，得到熔融状态下的聚酯聚合物；
步骤二，将配方用量的固化促进剂三苯基乙基溴化磷加入步骤一中熔融状态下的聚酯聚合物中；
步骤三，将步骤二中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得玄武岩长纤维增强聚酯涂布，热处理，冷却后切断，研磨，得到耐磨聚酯树脂。
氯化铁与2,6-吡啶二甲酸在高温融融状态下处于一种解离状态，熔体冷却的过程中氯化铁与2,6-吡啶二甲酸之间会形成配位，热处理时配位得到进一步完善。
如上所述的方法，步骤三中涂布厚度为0.02mm～0.2mm。
如上所述的方法，步骤三中研磨制得的纤维增强聚酯粉末颗粒的尺寸为100～600目。
如上所述的方法，步骤三中热处理的温度为80～100℃，时间为50～60min。
本发明的机理如下：
聚合物材料的磨损是由运动过程产生的作用力导致的，在滑动过程中接触点上会有很大的压力，使接触表面因为剪切作用而产生微变形和微凸体，并造成软表面的塑性变形、磨粒磨损的宏观变形以及粘弹性材料的弹性滞后变形。除此之外，摩擦热造成温度升高使磨损加剧。高分子聚合物的滑动磨损主要包括粘着磨损、磨粒磨损以及疲劳磨损。产生粘着的主要原因有：(1)聚合物因为质软所以更容易变形；(2)聚合物的分子链在滑动过程中会发生相互扩散，导致接触表面的粘着力增大。磨粒磨损是指在滑动过程中一些硬颗粒或硬粗糙面在软材料表面发生相对运动造成形变或撕裂损伤的行为。两种材料之间的磨粒磨损，在滑动时硬质材料对软质材料表面造成了犁沟或断裂等损伤。
金属-配体配位相互作用增强了大分子链段的分子相互作用，阻碍了聚合物链的运动。在FeCl 3掺杂的聚酯树脂中，Fe(Ⅲ)与吡啶配体之间形成以Fe(Ⅲ)的一个核心周围含有四个五元环吡啶配体，所形成的螯合物稳定常数高，两个分子间吡啶配体的配位结构趋于促进聚合物链的聚集，成为物理交联点。
本发明Fe(Ⅲ)与2,6-吡啶二甲酸所形成的螯合物，螯合物作为物理交联点，强化分子间 的作用力，是对聚酯树脂化学交联点的补充，同时对聚酯树脂的强度有增强作用，减少了化学交联点过多对强度的影响，降低了聚酯在摩擦过程中分子链滑动所发生的相互扩散而导致接触表面的粘着力，聚酯树脂的耐磨性和使用耐久性大大提高。
本发明耐磨聚酯树脂的配方中还含有玄武岩纤维，玄武岩纤维中的铁、镁、钙等金属离子可与2,6-吡啶二甲酸配位，提高了玄武岩纤维与聚酯之间的界面结合力，显著提高聚酯树脂与玄武岩纤维之间界面的相容性，有利于提高聚酯粉体的强度和耐磨性。
有益效果
本发明通过Fe(Ⅲ)与2,6-吡啶二甲酸进行配位，强化分子间的作用力，降低了聚酯在摩擦过程中分子链滑动所发生的相互扩散而导致接触表面的粘着力，聚酯树脂的耐磨性和使用耐久性大大提高。
具体实施方式
下面结合具体实施方式，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
一种耐磨聚酯树脂的方法，具体步骤如下：
(1)原料的准备；
按重量份数计：新戊二醇25份；乙二醇2份；二苯基硅二醇2份；三羟甲基丙烷2份；对苯二甲酸15份；2,5-呋喃二甲酸10份；间苯二甲酸5份；2,6-吡啶二甲酸5份；偏苯三酸酐3份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2份；玄武岩纤维50份；
(2)采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，以1℃/min，热升温至200℃保温反应1.5h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，真空度为100Pa，得到熔融状态下的聚酯聚合物；
(3)将配方用量的固化促进剂三苯基乙基溴化磷加入步骤(2)中熔融状态下的聚酯聚合物中，搅拌10分钟；
(4)将步骤(3)中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得厚度为0.02mm的玄武岩长纤维增强聚酯涂布，然后进行热处理，热处理的温度为80℃，时间为60min；接着冷却后切断，研磨，得到尺寸为100目的纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为1.87L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；其中，将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。
对比例1
一种耐磨聚酯树脂的方法，基本同实施例1，不同之处仅在于，步骤(1)中原料的准备为：按重量份数计：新戊二醇25份；乙二醇2份；二苯基硅二醇2份；三羟甲基丙烷2份；对苯二甲酸15份；2,5-呋喃二甲酸10份；间苯二甲酸10份；偏苯三酸酐3份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.0份；玄武岩纤维50份。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂按照与实施例1相同的方法制成涂料后，分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为3.04L/μm，盐雾试验结果为：600小时开裂、起泡、变白、剥离。
与实施例1相比，对比例1的耐磨性和盐雾试验结果均比实施例1差，这是因为实施例1中的聚酯树脂中掺杂了FeCl 3，Fe(Ⅲ)与吡啶配体之间形成以Fe(Ⅲ)的一个核心周围含有四个五元环吡啶配体，所形成的螯合物稳定常数高，两个分子间吡啶配体的配位结构趋于促进聚合物链的聚集，成为物理交联点；Fe(Ⅲ)与2,6-吡啶二甲酸所形成的螯合物，螯合物作为物理交联点，强化分子间的作用力，是对聚酯树脂化学交联点的补充，同时对聚酯树脂的强度有增强作用，减少了化学交联点过多对强度的影响，降低了聚酯在摩擦过程中分子链滑动所发生的相互扩散而导致接触表面的粘着力，聚酯树脂的耐磨性和使用耐久性提高。
实施例2
一种耐磨聚酯树脂的方法，具体步骤如下：
(1)原料的准备；
按重量份数计：新戊二醇28份；乙二醇4份；二苯基硅二醇3份；三羟甲基丙烷2份；对苯二甲酸15份；2,5-呋喃二甲酸14份；间苯二甲酸12份；2,6-吡啶二甲酸9份；偏苯三酸酐5份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.2份；玄武岩纤维130份；
(2)采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，以1℃/min，热升温至200℃保温反应2h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，真空度为90Pa，得到熔融状态下的聚酯聚合物；
(3)将配方用量的固化促进剂三苯基乙基溴化磷加入步骤(2)中熔融状态下的聚酯聚合物中，搅拌14分钟；
(4)将步骤(3)中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得厚度为0.04mm的玄武岩长纤维增强聚酯涂布，然后进行热处理，热处理的温度为85℃，时间为59min；接着冷却后切断，研磨，得到尺寸为300目的纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为1.9L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；其中，将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。
实施例3
一种耐磨聚酯树脂的方法，具体步骤如下：
(1)原料的准备；
按重量份数计：新戊二醇32份；乙二醇6份；二苯基硅二醇7份；三羟甲基丙烷3份；对苯二甲酸16份；2,5-呋喃二甲酸25份；间苯二甲酸9份；2,6-吡啶二甲酸7份；偏苯三酸酐3份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.2份；玄武岩纤维70份；
(2)采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、 三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，以1℃/min，热升温至200℃保温反应2.5h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，真空度为50Pa，得到熔融状态下的聚酯聚合物；
(3)将配方用量的固化促进剂三苯基乙基溴化磷加入步骤(2)中熔融状态下的聚酯聚合物中，搅拌13分钟；
(4)将步骤(3)中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得厚度为0.06mm的玄武岩长纤维增强聚酯涂布，然后进行热处理，热处理的温度为87℃，时间为54min；接着冷却后切断，研磨，得到尺寸为200目的纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为1.95L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；其中，将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。
实施例4
一种耐磨聚酯树脂的方法，具体步骤如下：
(1)原料的准备；
按重量份数计：新戊二醇34份；乙二醇9份；二苯基硅二醇5份；三羟甲基丙烷2份；对苯二甲酸19份；2,5-呋喃二甲酸22份；间苯二甲酸11份；2,6-吡啶二甲酸8份；偏苯三酸酐4份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.6份；玄武岩纤维90份；
(2)采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，以1℃/min，热升温至200℃保温反应2.5h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，真空度为30Pa，得到熔融状态下的聚酯聚合物；
(3)将配方用量的固化促进剂三苯基乙基溴化磷加入步骤(2)中熔融状态下的聚酯聚合物中，搅拌12分钟；
(4)将步骤(3)中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得厚度为0.08mm的玄武岩长纤维增强聚酯涂布，然后进行热处理，热处理的温度为92℃，时间为56min；接着冷却后切断，研磨，得到尺寸为400目的纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为2L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；其中，将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。
实施例5
一种耐磨聚酯树脂的方法，具体步骤如下：
(1)原料的准备；
按重量份数计：新戊二醇36份；乙二醇8份；二苯基硅二醇6份；三羟甲基丙烷3份；对苯二甲酸18份；2,5-呋喃二甲酸25份；间苯二甲酸7份；2,6-吡啶二甲酸6份；偏苯三酸酐4份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.4份；玄武岩纤维110份；
(2)采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，以1℃/min，热升温至200℃保温反应3h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，真空度为15Pa，得到熔融状态下的聚酯聚合物；
(3)将配方用量的固化促进剂三苯基乙基溴化磷加入步骤(2)中熔融状态下的聚酯聚合物中，搅拌11分钟；
(4)将步骤(3)中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得厚度为0.1mm的玄武岩长纤维增强聚酯涂布，然后进行热处理，热处理的温度为96℃，时间为58min；接着冷却后切断，研磨，得到尺寸为300目的纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为2.05L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；其中，将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。
实施例6
一种耐磨聚酯树脂的方法，具体步骤如下：
(1)原料的准备；
按重量份数计：新戊二醇38份；乙二醇7份；二苯基硅二醇5份；三羟甲基丙烷3份；对苯二甲酸18份；2,5-呋喃二甲酸20份；间苯二甲酸14份；2,6-吡啶二甲酸9份；偏苯三酸酐4份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.5份；玄武岩纤维60份；
(2)采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，以1℃/min，热升温至200℃保温反应3h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，真空度为20Pa，得到熔融状态下的聚酯聚合物；
(3)将配方用量的固化促进剂三苯基乙基溴化磷加入步骤(2)中熔融状态下的聚酯聚合物中，搅拌10分钟；
(4)将步骤(3)中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得厚度为0.15mm的玄武岩长纤维增强聚酯涂布，然后进行热处理，热处理的温度为98℃，时间为54min；接着冷却后切断，研磨，得到尺寸为500目的纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为2.1L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；其中，将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉 末涂料。
实施例7
一种耐磨聚酯树脂的方法，具体步骤如下：
(1)原料的准备；
按重量份数计：新戊二醇40份；乙二醇10份；二苯基硅二醇10份；三羟甲基丙烷3份；对苯二甲酸20份；2,5-呋喃二甲酸30份；间苯二甲酸15份；2,6-吡啶二甲酸10份；偏苯三酸酐5份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.6份；玄武岩纤维150份；
(2)采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，以1℃/min，热升温至200℃保温反应3.5h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，真空度为19Pa，得到熔融状态下的聚酯聚合物；
(3)将配方用量的固化促进剂三苯基乙基溴化磷加入步骤(2)中熔融状态下的聚酯聚合物中，搅拌15分钟；
(4)将步骤(3)中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得厚度为0.2mm的玄武岩长纤维增强聚酯涂布，然后进行热处理，热处理的温度为100℃，时间为50min；接着冷却后切断，研磨，得到尺寸为600目的纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
制得的一种耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为2.13L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；其中，将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。

Claims (6)

  1. 一种耐磨聚酯树脂，其特征在于，按重量份数计，包括：新戊二醇25～40份；乙二醇2～10份；二苯基硅二醇2～10份；三羟甲基丙烷2～3份；对苯二甲酸15～20份；2,5-呋喃二甲酸10～30份；间苯二甲酸5～15份；2,6-吡啶二甲酸5～10份；偏苯三酸酐3～5份；酯化催化剂草酸亚锡0.05份；固化促进剂三苯基乙基溴化磷0.15份；氯化铁2.0～2.6份；玄武岩纤维50～150份。
  2. 根据权利要求1所述的一种耐磨聚酯树脂，其特征在于，耐磨聚酯树脂的性能指标为：将耐磨聚酯树脂制成涂料后分别按照GB/T 23988-2009进行耐磨性试验和按照GB/T1771-2007进行耐盐雾试验，测得的耐磨性为1.87～2.13 L/μm，盐雾试验结果为：1000小时无开裂、无起泡、无变白、无剥离；
    将耐磨聚酯树脂制成涂料具体为：按重量份数计，将耐磨聚酯树脂60份、环氧树脂18份、钛白粉5份和流平剂丙烯酸酯共聚物5份均匀混合，通过双螺杆挤出机熔融挤出、压片、破碎、粉碎过筛制成粉末涂料。
  3. 制备如权利要求1或2所述的一种耐磨聚酯树脂的方法，其特征在于包括以下步骤：
    步骤一，采用熔融两步法合成聚酯聚合物，将配方用量的新戊二醇、乙二醇、二苯基硅二醇、三羟甲基丙烷、对苯二甲酸、2,5-呋喃二甲酸、间苯二甲酸、2,6-吡啶二甲酸、酯化催化剂草酸亚锡和氯化铁加入反应釜，向反应釜中通入氮气，逐步升温并搅拌，在140℃开始酯化反应，待开始出水，热升温至200℃保温反应1.5～3.5h后测酸值，酸值达到20mgKOH/g后，加入间苯二甲酸和偏苯三酸酐，酯化结束后开始抽真空缩聚，得到熔融状态下的聚酯聚合物；
    步骤二，将配方用量的固化促进剂三苯基乙基溴化磷加入步骤一中熔融状态下的聚酯聚合物中；
    步骤三，将步骤二中熔融状态下的聚酯聚合物涂覆在玄武岩纤维单向布上，制得玄武岩长纤维增强聚酯涂布，热处理，冷却后切断，研磨，得到纤维增强聚酯粉末颗粒，即耐磨聚酯树脂。
  4. 根据权利要求3所述的方法，其特征在于，步骤三中涂布厚度为0.02mm～0.2mm。
  5. 根据权利要求3所述的方法，其特征在于，步骤三中研磨制得的纤维增强聚酯粉末颗粒的尺寸为100～600目。
  6. 根据权利要求3所述的方法，其特征在于，步骤三中热处理的温度为80～100℃，时间为50～60min。
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