Encapsulated carrier plate, thermoplastic polyester elastomer material and method of manufacture

Abstract

The application discloses a kind of encapsulation carrier plate and thermoplastic polyester elastomer material and preparation method, it is related to polymer material technical field.The thermoplastic polyester elastomer material includes following weight parts raw materials: 25-40 parts modified dimethyl terephthalate, 15-25 parts 1, 4-butanediol, 0.07-0.25 parts titanium acid tetraisopropyl ester, 0.25-0.5 parts antioxidant 168, 12-20 parts polytetrahydrofuran ether glycol, 8-15 parts modified 1, 4-butanediol, 1-3 parts isophorone diisocyanate, 5-10 parts basalt fiber, 2-6 parts flake graphite, 2-5 parts tributyl citrate, 1-4 parts methyl phenyl silicone resin, 2-3 parts polyolefin elastomer, 0.2-0.8 parts ultraviolet absorber UV-1577.The thermoplastic polyester elastomer uses modified dimethyl terephthalate and modified 1, 4-butanediol to improve performance, basalt fiber and flake graphite are treated by silanization to enhance compatibility, stepwise temperature control initiation process optimizes grafting uniformity, by double prepolymer melt blending, mechanical properties and stability are considered, the service life is extended by adding antioxidant and ultraviolet absorber.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, specifically to an adhesive-coated carrier plate and its thermoplastic polyester elastomer material and preparation method. Background Technology

[0002] In the field of polymer materials technology, coated substrates are key components in industries such as electronics and machinery, and must simultaneously meet multiple performance requirements, including mechanical strength, weather resistance, interfacial adhesion, and processing stability. Traditional coated substrates commonly use thermoplastic materials such as ordinary polyesters or polyolefins, which have significant performance shortcomings: insufficient mechanical strength leading to easy breakage, poor resistance to high and low temperatures making them unsuitable for complex environments, poor compatibility with substrates leading to delamination, and long-term use susceptible to performance degradation due to oxidation and UV aging.

[0003] Poor interfacial compatibility of raw materials is a common problem in the preparation of existing thermoplastic polyester elastomers. Unmodified dimethyl terephthalate reacts unevenly with polyols, resulting in irregular polymer molecular chain structures. Ordinary 1,4-butanediol is prone to phase separation with other components during blending, affecting the overall material properties. Furthermore, inorganic fillers such as basalt fiber and flake graphite have poor compatibility with the organic matrix, easily leading to uneven dispersion. This not only fails to effectively enhance material properties but may also become stress concentration points, causing a decline in mechanical properties.

[0004] In traditional manufacturing processes, single-temperature-initiated grafting reactions often result in low and uneven grafting rates. Furthermore, issues such as residual impurities and excessively wide molecular weight distribution during prepolymer synthesis are also prominent. Simultaneously, existing materials suffer from insufficient resistance to oxidation and UV aging, limiting the lifespan of the overmolded substrate. These technical limitations make it difficult for existing materials to meet the high-performance and high-reliability requirements of high-end overmolded substrates. Therefore, developing a thermoplastic polyester elastomer material with balanced performance and stable processing has become an urgent industry need. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides an adhesive-coated carrier plate, its thermoplastic polyester elastomer material, and a preparation method thereof, which solves the problems of poor compatibility, uneven performance, and easy aging of traditional materials.

[0006] To achieve the above objectives, the present invention is implemented through the following technical solution: A thermoplastic polyester elastomer material comprising the following raw materials in parts by weight: 25-40 parts modified dimethyl terephthalate, 15-25 parts 1,4-butanediol, 0.07-0.25 parts tetraisopropyl titanate, 0.25-0.5 parts antioxidant 168, 12-20 parts polytetrahydrofuran ether glycol, 8-15 parts modified 1,4-butanediol, 1-3 parts isophorone diisocyanate, 5-10 parts basalt fiber, 2-6 parts flake graphite, 2-5 parts tributyl citrate, 1-4 parts methylphenyl silicone resin, 2-3 parts polyolefin elastomer, and 0.2-0.8 parts ultraviolet absorber UV-1577.

[0007] Furthermore, the basalt fibers undergo surface silanization treatment. The treatment method is as follows: basalt fibers with an aspect ratio ≥20 are ultrasonically cleaned for 15 minutes with a 1:1 volume ratio of 5% anhydrous ethanol-deionized water mixture, dried at 100℃ for 2 hours, then immersed in a treatment solution of silane coupling agent KH-550 and anhydrous ethanol at a 1:10 volume ratio for 2 hours at room temperature, and finally dried at 120℃ for 3 hours to ensure strong silane bonding. Silanization treatment enhances interfacial compatibility with the organic matrix, improves the mechanical strength and rigidity of the material, and reduces stress concentration.

[0008] Furthermore, the flake graphite undergoes surface silanization treatment. The treatment method is as follows: 0.5% of the flake graphite mass of silane coupling agent KH-550 is weighed and dissolved in 5 times its mass of anhydrous ethanol to prepare a diluent. The diluent is then added dropwise to the flake graphite under high-speed shearing at 2000 r / min. After the addition is complete, shearing continues for 10 min, followed by vacuum drying at 80℃ and -0.09 MPa for 2 h. Surface modification improves the dispersion uniformity in the matrix, enhances reinforcement and thermal conductivity, and simultaneously improves the dimensional stability of the material.

[0009] Furthermore, the modified dimethyl terephthalate is prepared using the following specific steps: A1. Dimethyl terephthalate and 1,3-propanediol were added to a reaction vessel, followed by tetraisopropyl titanate. The vessel was evacuated to -0.08 MPa and held for 5 minutes. Nitrogen gas was then introduced to 0.1 MPa. This process was repeated three times to completely replace the air. The stirring was started and the speed was stabilized at 200 r / min. The temperature was first raised to 170°C and maintained for 1.5 hours. Then, the temperature was raised to 190°C and the reaction was continued for 2.5 hours. During the reaction, the generated methanol was collected using a condenser. By precisely controlling the vacuum to replace the air and stepwise heating, methanol was fully removed, and the molecular chain was initially grown, laying the foundation for subsequent chain extension reactions. This also improved the reactivity and compatibility of the raw materials. After the reaction was completed, heating was stopped. When the temperature inside the reaction vessel dropped to 80°C, the product was transferred to a separatory funnel and allowed to stand for 30 minutes to allow for complete separation. The upper layer product was the primary modified dimethyl terephthalate. A2. Add the primary modified dimethyl terephthalate to the reaction vessel, add pyromellitic dianhydride and 2-methylimidazole, start stirring, adjust the speed to 150 r / min, raise the temperature to 160℃ and hold for 40 min to complete the initial mixing, then raise the temperature to 180℃ and continue the reaction for 2 h to allow the anhydride group of pyromellitic dianhydride to fully react with the terminal hydroxyl group of the molecular chain, further extending the molecular chain length and introducing a rigid aromatic ring structure, significantly improving the regularity and heat resistance of the molecular chain; during the reaction, the acid value is measured by titration every 30 min. When the acid value drops below 4 mg KOH / g, heating is stopped to ensure the sufficiency of the reaction and avoid interference from residual carboxyl groups in subsequent reactions; when the product cools to 70℃, add a 3% (w / w) ethanol aqueous solution for washing, stir thoroughly for 10 min, let stand for 30 min, remove the supernatant, and obtain the secondary modified dimethyl terephthalate; A3. Mix the secondary modified dimethyl terephthalate, vinyltriethoxysilane, and azobisisobutyronitrile in a beaker, then add the mixture to a reaction vessel. Purge the air with nitrogen, adjust the stirring speed to 250 r / min, and heat to 90℃ for 1.5 h. Then add azobisisobutyronitrile and heat to 110℃ for 3.5 h to uniformly graft siloxane groups onto the molecular chain, which enhances the interfacial bonding force with the inorganic filler and improves the toughness of the material through the flexible segments of the siloxane. After the reaction, place the product in a vacuum drying oven and dry it at 85℃ and -0.095 MPa for 5 h to obtain the desired modified dimethyl terephthalate.

[0010] Furthermore, the ratio of dimethyl terephthalate, 1,3-propanediol, and tetraisopropyl titanate in A1 is 100g:130g:1.2g.

[0011] Furthermore, the ratio of the amount of the one-time modified dimethyl terephthalate, pyromellitic dianhydride, and 2-methylimidazole in A2 is 100g:6g:0.2g.

[0012] Furthermore, the ratio of secondary modified dimethyl terephthalate, vinyltriethoxysilane, and azobisisobutyronitrile in A3 is 100g:9g:0.7g.

[0013] Furthermore, in the preparation process of the modified dimethyl terephthalate, the grafting reaction between the secondary modified dimethyl terephthalate and vinyltriethoxysilane adopts a stepwise temperature-controlled initiation process. By supplementing the initiator in stages, the grafting rate is controlled within the range of 65-75%, avoiding the problem of uneven grafting caused by single-temperature initiation.

[0014] Furthermore, the modified 1,4-butanediol is prepared using the following specific steps: B1. Add 1,4-butanediol and glycidyl ether to a reaction vessel, add potassium hydroxide powder, stir at 200 r / min, heat to 65℃, maintain this temperature, monitor the residual amount of glycidyl ether by high performance liquid chromatography every 30 min, stop the reaction when the residual amount is ≤0.8%, to ensure that the epoxy group is fully opened to introduce hydroxyl groups and increase the active sites of the molecular chain; after cooling to 35℃, add deionized water, stir for 30 min, let stand for 40 min to separate the aqueous phase, dry the organic phase with anhydrous calcium chloride for 4 h, filter to obtain primary modified 1,4-butanediol; effectively remove electrolyte impurities generated in the reaction, avoid interference with catalytic activity in subsequent reactions, and improve the purity and stability of the primary modified product; B2. Add the primary modified 1,4-butanediol to the reactor, along with methacrylic acid, p-toluenesulfonic acid, and phenothiazine. Install a water separator and a reflux condenser. Stir at 200 r / min, heat the system to 85℃ and maintain the temperature for 5 hours to promote the forward esterification reaction and introduce unsaturated double bonds and ester groups into the molecular chain. After the reaction, cool to 45℃ and neutralize with 6% sodium bicarbonate solution to pH=7.5. Allow to stand and separate the aqueous phase to remove residual acid catalyst and salts, avoiding the damage of acidic substances to the aging resistance of the material. Wash the organic phase three times with deionized water, and then distill at 85℃ for 1.5 hours to further remove trace amounts of water and unreacted monomers, obtaining the secondary modified 1,4-butanediol. B3. The secondary modified 1,4-butanediol was mixed with dimethyl diallyl ammonium chloride isopropanol and added to a reflux reactor. The stirring speed was 150 r / min, and the system was heated to 82℃ and kept under reflux for 7 hours. This allowed the quaternary ammonium salt groups to be grafted onto the molecular chain via double bond polymerization, introducing polar cationic groups. These groups can enhance the hydrogen bonding with the polar matrix, significantly improving the antistatic properties and compatibility with other components of the material. After the reaction was completed, heating was stopped, and the reaction solution was transferred to a rotary evaporator. The solvent was recovered by distillation under a vacuum of -0.08 MPa and 90℃. The remaining product was transferred to a vacuum drying oven and dried at 85℃ and -0.095 MPa for 6 hours, with the material turned over every 2 hours. After drying, the material was pulverized through a 200-mesh sieve to obtain modified 1,4-butanediol.

[0015] Furthermore, the ratio of 1,4-butanediol, glycidyl ether, potassium hydroxide, deionized water, and anhydrous calcium chloride in B1 is 100g:90g:6.5g:60g:10g.

[0016] Furthermore, the ratio of the amount of the one-time modified 1,4-butanediol, methacrylic acid, p-toluenesulfonic acid and phenothiazine in B2 is 100g:130g:1.5g:0.15g.

[0017] Furthermore, the ratio of the amount of the secondary modified 1,4-butanediol, dimethyl diallyl ammonium chloride, and isopropanol in B3 is 100g:11g:380mL.

[0018] A method for preparing a thermoplastic polyester elastomer material specifically includes the following steps: S1. Modified dimethyl terephthalate and 1,4-butanediol are added to a reaction vessel, along with tetraisopropyl titanate and antioxidant 168. Under nitrogen protection, the temperature is raised to 225-245℃ for esterification reaction for 2.5-3.5 hours. Then, the temperature is raised to 265-285℃ and polycondensation reaction is carried out under a vacuum of 0.5-1.2 kPa for 1.5-2.5 hours to obtain dihydroxyl-terminated polyester prepolymer A. S2. Polytetrahydrofuran ether diol and modified 1,4-butanediol are added to another reactor, along with tetraisopropyl titanate and antioxidant 168. Under nitrogen protection, the temperature is raised to 165-185℃ for prepolymerization reaction for 1.5-2.5 hours. Then, the temperature is raised to 205-225℃ and the reaction is continued for 2.5-3.5 hours under a vacuum of 0.4-0.8 kPa to obtain dihydroxyl-terminated polyether prepolymer B. S3. Add prepolymer A and prepolymer B to a twin-screw extruder, along with isophorone diisocyanate, basalt fiber, flake graphite, tributyl citrate, methylphenyl silicone resin, polyolefin elastomer, and UV absorber UV-1577. Set the extruder temperature to segmented control: feeding section 185-195℃, screw front section 190-200℃, screw middle section 200-210℃, screw rear section 210-220℃, and die temperature 215-225℃. Perform melt blending extrusion and granulation to obtain thermoplastic polyester elastomer material.

[0019] A rubber-coated carrier plate includes a receiving base and a receiving portion. The receiving portion is formed by a recess in the top surface of the receiving base, and the elastomeric soft rubber portion is fixed in the receiving portion by injection molding, for receiving electronic products.

[0020] This invention provides an adhesive-coated carrier plate, its thermoplastic polyester elastomer material, and a preparation method thereof, which have the following beneficial effects: 1. Through a three-step modification of dimethyl terephthalate (DMT): transesterification with 1,3-propanediol, chain extension reaction of pyromellitic dianhydride, and graft modification with vinyltriethoxysilane, multifunctional groups are introduced, forming complementary molecular segments with 1,4-butanediol modified by glycidyl ether ring-opening and methacrylate esterification. Under the crosslinking effect of isophorone diisocyanate, these two components, together with the flexible segments of polytetrahydrofuran ether diol, construct a multi-level network structure of "rigid skeleton-flexible connection," enhancing the tensile strength, impact toughness, and fatigue resistance of the material at the molecular level, thus solving the problem of the limited mechanical properties of traditional polyester materials.

[0021] 2. After treatment with the silane coupling agent KH-550, the surface hydroxyl groups of basalt fibers form chemical bonds with the active groups of the modified raw materials; flake graphite undergoes silanization treatment to achieve surface organic modification. Both are uniformly dispersed in the organic matrix to construct a continuous reinforcing skeleton. Methylphenyl silicone resin fills the gaps in the skeleton to improve interfacial wettability, while polyolefin elastomer enhances interfacial forces through chain segment entanglement, forming a gradient structure of "inorganic reinforcing phase - organic transition phase - continuous matrix phase". This not only provides rigid support for the inorganic filler but also alleviates stress concentration through the interfacial transition layer, achieving a synergistic improvement in the rigidity and toughness of the material.

[0022] 3. Polyester prepolymer A undergoes high-temperature esterification and high-vacuum polycondensation to precisely control its molecular weight distribution, while polyether prepolymer B's chain segment regularity is regulated through a gradient-temperature prepolymerization reaction. Both prepolymers retain the heat resistance of polyester and the elasticity of polyether, respectively. During twin-screw extrusion, segmented temperature control from the feed section to the die enables melt blending, allowing the molecular chains of the two prepolymers to fully entangle and form an interpenetrating network structure. This effectively avoids the performance imbalance between heat resistance and elasticity inherent in single prepolymer materials, ensuring stable mechanical properties and dimensional stability across a wide temperature range.

[0023] 4. Antioxidant 168 inhibits oxidative degradation of molecular chains by capturing free radicals, while UV absorber UV-1577 blocks UV-induced aging reactions through energy conversion, forming a synergistic anti-aging defense. Tributyl citrate improves processing fluidity while reducing thermal damage to molecular chains during high-temperature processing. Silanized inorganic fillers delay environmental corrosion through physical barrier action. The combination of multiple protective mechanisms with the structural stability of the modified substrate provides comprehensive protection from internal material structure to external environmental resistance, significantly extending the service life of the coated substrate under complex working conditions. Attached Figure Description

[0024] Figure 1 This is a schematic diagram of the adhesive-coated carrier plate structure of the present invention.

[0025] In the diagram: 1. Support base, 2. Elastic soft rubber part, 3. Receiving part. Detailed Implementation

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0027] Example 1: Preparation of thermoplastic polyester elastomer material. The specific preparation steps are as follows: S1. 25 parts of modified dimethyl terephthalate and 15 parts of 1,4-butanediol were added to a reaction vessel, along with 0.05 parts of tetraisopropyl titanate and 0.2 parts of antioxidant 168. Under nitrogen protection, the temperature was raised to 225°C for esterification reaction for 2.5 hours. Then, the temperature was raised to 265°C and polycondensation reaction was carried out under a vacuum of 0.5 kPa for 1.5 hours to obtain dihydroxyl-terminated polyester prepolymer A. S2. Add 12 parts of polytetrahydrofuran ether diol and 8 parts of modified 1,4-butanediol to another reactor, along with 0.02 parts of tetraisopropyl titanate and 0.05 parts of antioxidant 168. Under nitrogen protection, heat to 165°C for prepolymerization reaction for 1.5 hours, then heat to 205°C and continue the reaction under a vacuum of 0.4 kPa for 2.5 hours to obtain dihydroxyl-terminated polyether prepolymer B. S3. Add 40 parts of prepolymer A and 40 parts of prepolymer B to a twin-screw extruder, along with 1 part of isophorone diisocyanate, 5 parts of basalt fiber, 2 parts of flake graphite, 2 parts of tributyl citrate, 1 part of methylphenyl silicone resin, 2 parts of polyolefin elastomer, and 0.2 parts of UV absorber UV-1577. Set the extruder temperature to segmented control: feeding section 185℃, screw front section 190℃, screw middle section 200℃, screw rear section 210℃, and die temperature 215℃. Perform melt blending extrusion and granulation to obtain thermoplastic polyester elastomer material.

[0028] Example 2: Preparation of thermoplastic polyester elastomer material. The specific preparation steps are as follows: S1. 40 parts of modified dimethyl terephthalate and 25 parts of 1,4-butanediol were added to a reaction vessel, along with 0.2 parts of tetraisopropyl titanate and 0.4 parts of antioxidant 168. Under nitrogen protection, the mixture was heated to 245°C for esterification reaction for 3.5 hours. Then, the mixture was heated to 285°C and polycondensation reaction was carried out under a vacuum of 1.2 kPa for 2.5 hours to obtain dihydroxyl-terminated polyester prepolymer A. S2. Add 20 parts of polytetrahydrofuran ether diol and 15 parts of modified 1,4-butanediol to another reactor, along with 0.05 parts of tetraisopropyl titanate and 0.1 parts of antioxidant 168. Under nitrogen protection, heat to 185°C for prepolymerization reaction for 2.5 hours, then heat to 225°C and continue the reaction under a vacuum of 0.8 kPa for 3.5 hours to obtain dihydroxyl-terminated polyether prepolymer B. S3. Add 60 parts of prepolymer A and 60 parts of prepolymer B to a twin-screw extruder, along with 3 parts of isophorone diisocyanate, 10 parts of basalt fiber, 6 parts of flake graphite, 5 parts of tributyl citrate, 4 parts of methylphenyl silicone resin, 3 parts of polyolefin elastomer, and 0.8 parts of UV absorber UV-1577. Set the extruder temperature to segmented control: feeding section 195℃, screw front section 200℃, screw middle section 210℃, screw rear section 220℃, and die temperature 225℃. Perform melt blending extrusion and granulation to obtain a thermoplastic polyester elastomer material.

[0029] Example 3: Preparation of thermoplastic polyester elastomer material. The specific preparation steps are as follows: S1. 32 parts of modified dimethyl terephthalate and 18 parts of 1,4-butanediol were added to a reaction vessel, along with 0.1 parts of tetraisopropyl titanate and 0.3 parts of antioxidant 168. Under nitrogen protection, the temperature was raised to 235°C for esterification reaction for 3 hours. Then, the temperature was raised to 275°C and polycondensation reaction was carried out under a vacuum of 0.8 kPa for 2 hours to obtain dihydroxyl-terminated polyester prepolymer A. S2. Add 16 parts of polytetrahydrofuran ether diol and 11 parts of modified 1,4-butanediol to another reactor, along with 0.03 parts of tetraisopropyl titanate and 0.07 parts of antioxidant 168. Under nitrogen protection, heat to 175°C for prepolymerization reaction for 2 hours, then heat to 215°C and continue the reaction for 3 hours under a vacuum of 0.6 kPa to obtain dihydroxyl-terminated polyether prepolymer B. S3. Add 50 parts of prepolymer A and 50 parts of prepolymer B to a twin-screw extruder, along with 2 parts of isophorone diisocyanate, 7 parts of basalt fiber, 4 parts of flake graphite, 3 parts of tributyl citrate, 2 parts of methylphenyl silicone resin, 2 parts of polyolefin elastomer, and 0.5 parts of UV absorber UV-1577. Set the extruder temperature to segmented control: feeding section 190℃, screw front section 195℃, screw middle section 205℃, screw rear section 215℃, and die temperature 220℃. Perform melt blending extrusion and granulation to obtain a thermoplastic polyester elastomer material.

[0030] Example 4: Preparation of modified dimethyl terephthalate. The specific preparation steps are as follows: A1. Add 100g of dimethyl terephthalate and 130g of 1,3-propanediol to a reaction vessel, then add 1.2g of tetraisopropyl titanate. Evacuate to -0.08MPa and maintain for 5 minutes. Then introduce nitrogen gas to 0.1MPa. Repeat this operation 3 times to completely replace the air. Start stirring and stabilize the speed at 200r / min. First, raise the temperature to 170℃ and keep it at that temperature for 1.5h. Then, continue to raise the temperature to 190℃ and continue to react for 2.5h. Collect the generated methanol through a condenser during the reaction. After the reaction is completed, stop heating. When the temperature inside the reaction vessel drops to 80℃, transfer the product to a separatory funnel and let it stand for 30 minutes to allow it to fully separate into layers. The upper layer product is the primary modified dimethyl terephthalate. A2. Take 100g of primary modified dimethyl terephthalate and add it to the reaction vessel. Add 6g of pyromellitic dianhydride and 0.2g of 2-methylimidazole. Start stirring and adjust the speed to 150r / min. Heat to 160℃ and keep it at that temperature for 40min to complete the initial mixing. Then heat to 180℃ and continue the reaction for 2h. During the reaction, the acid value is measured by titration every 30min. When the acid value drops to below 4mgKOH / g, stop heating. When the product cools to 70℃, add 100mL of 3% ethanol aqueous solution for washing. Stir thoroughly for 10min and let stand for 30min. Remove the supernatant. After completion, secondary modified dimethyl terephthalate is obtained. A3. Take 100g of secondary modified dimethyl terephthalate, 9g of vinyltriethoxysilane and 0.4g of azobisisobutyronitrile and mix them evenly in a beaker. Then add the mixture to the reaction vessel, purge the air with nitrogen, adjust the stirring speed to 250r / min, raise the temperature to 90℃ and react for 1.5h. Then add 0.3g of azobisisobutyronitrile and raise the temperature to 110℃ and react for 3.5h. After the reaction is completed, put the product into a vacuum drying oven and dry it at 85℃ and -0.095MPa for 5h. This is the desired modified dimethyl terephthalate.

[0031] Example 5: Preparation of modified 1,4-butanediol. The specific preparation steps are as follows: B1. Take 100g of 1,4-butanediol and 90g of glycidyl ether and add them to the reaction vessel. Add 6.5g of potassium hydroxide powder, stir at 200r / min, heat to 65℃, and maintain the temperature for reaction. Monitor the residual amount of glycidyl ether by high performance liquid chromatography every 30min. Stop the reaction when the residual amount is ≤0.8%. After cooling to 35℃, add 60g of deionized water, stir for 30min, and let stand for 40min to remove the aqueous phase. Dry the organic phase with 10g of anhydrous calcium chloride for 4h. After filtration, obtain the first-modified 1,4-butanediol. B2. Take 100g of primary modified 1,4-butanediol and add it to the reaction vessel. Add 130g of methacrylic acid, 1.5g of p-toluenesulfonic acid and 0.15g of phenothiazine. Install a water separator and a reflux condenser. Stir at 200r / min. Heat the system to 85℃ and maintain the temperature for 5h. After the reaction, cool to 45℃ and neutralize with 6% sodium bicarbonate solution to pH=7.5. Let it stand to separate the aqueous phase. Wash the organic phase three times with deionized water. Then distill at 85℃ for 1.5h to obtain secondary modified 1,4-butanediol. B3. Take 100g of secondary modified 1,4-butanediol, mix it with 11g of dimethyl diallyl ammonium chloride and 380mL of isopropanol, and add it to a reflux reactor. Stir at 150r / min and heat the system to 82℃. Maintain the reflux state for 7h. After the reaction is completed, stop heating and transfer the reaction solution to a rotary evaporator. Distill and recover the solvent under vacuum of -0.08MPa and 90℃. Transfer the remaining product to a vacuum drying oven and dry it at 85℃ and -0.095MPa for 6h. Turn the material over every 2h during the drying process. After drying, pulverize it through a 200-mesh sieve to obtain modified 1,4-butanediol.

[0032] Example 6: A coated carrier plate includes a receiving base 1 and a receiving part 3. The receiving part 3 is formed by the indentation of the top surface of the receiving base 1. The elastic soft rubber part 2 is fixed in the receiving part by injection molding and is used to support electronic products.

[0033] Comparative Example 1: A thermoplastic polyester elastomer material was prepared. The specific preparation steps are as follows: The remaining steps remain unchanged, except that the modified dimethyl terephthalate in Example 3 is replaced with untreated dimethyl terephthalate to prepare a thermoplastic polyester elastomer material.

[0034] Comparative Example 2: A thermoplastic polyester elastomer material was prepared. The specific preparation steps are as follows: The remaining steps remain unchanged, except that the modified 1,4-butanediol in Example 3 is replaced with untreated 1,4-butanediol to prepare a thermoplastic polyester elastomer material.

[0035] Performance testing Tensile strength (50 mm / min, 23℃, MPa) GB / T 1040.3-2006 32.5 35.8 38.2 22.3 25.6 Elongation at break (%) GB / T 1040.3-2006 380 405 420 250 280 Shore hardness (D) GB / T 2411-2008 58 60 62 45 48 Heat distortion temperature (120℃ / h, 0.45MPa, ℃) GB / T 1634.2-2019 165 168 172 135 142 <![CDATA[ Izod impact strength (kJ / m 2 ). ]]> GB / T 1043.1-2008 28.5 30.6 32.8 18.2 20.5 Weather resistance (tensile strength retention rate after 1000h of UV aging, %) GB / T 16422.3-2022 85 87 88 62 65 Abrasion resistance (abrasion loss, mg / 1000 rpm) GB / T 9867-2008 12.5 11.2 10.8 25.3 22.6 After 1000 hours of UV aging, the tensile strength retention rate was 88%, and the abrasion loss was 10.8 mg / 1000 rpm. In contrast, the control group using unmodified raw materials showed a significant decrease in tensile strength, heat distortion temperature, weather resistance, and abrasion resistance. The tensile strength was only 22.3-25.6 MPa, the heat distortion temperature was 135-142℃, the weather resistance retention rate was 62-65%, and the abrasion loss reached 22.6-25.3 mg / 1000 rpm.

[0036] The above description is merely an example and illustration of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A thermoplastic polyester elastomer material, characterized in that: It contains the following raw materials in parts by weight: 25-40 parts modified dimethyl terephthalate, 15-25 parts 1,4-butanediol, 0.07-0.25 parts tetraisopropyl titanate, 0.25-0.5 parts antioxidant 168, 12-20 parts polytetrahydrofuran ether glycol, 8-15 parts modified 1,4-butanediol, 1-3 parts isophorone diisocyanate, 5-10 parts basalt fiber, 2-6 parts flake graphite, 2-5 parts tributyl citrate, 1-4 parts methylphenyl silicone resin, 2-3 parts polyolefin elastomer, and 0.2-0.8 parts ultraviolet absorber UV-1577; The modified dimethyl terephthalate is prepared using the following specific steps: A1. Dimethyl terephthalate and 1,3-propanediol were added to a reaction vessel, followed by tetraisopropyl titanate. The vessel was evacuated to -0.08 MPa and held for 5 minutes. Nitrogen gas was then introduced to 0.1 MPa. This process was repeated three times to completely replace the air. The stirring was started and the speed was stabilized at 200 r / min. The temperature was first raised to 170°C and maintained for 1.5 hours. Then, the temperature was raised to 190°C and the reaction was continued for 2.5 hours. During the reaction, the methanol generated was collected using a condenser. After the reaction was completed, the heating was stopped. When the temperature inside the reaction vessel dropped to 80°C, the product was transferred to a separatory funnel and allowed to stand for 30 minutes to allow for complete separation. The upper layer product was the primary modified dimethyl terephthalate. A2. Add the primary modified dimethyl terephthalate to the reaction vessel, add pyromellitic dianhydride and 2-methylimidazole, start stirring, adjust the speed to 150 r / min, raise the temperature to 160℃ and keep it at 40 min to complete the initial mixing, then raise the temperature to 180℃ and continue the reaction for 2 h. During the reaction, the acid value is measured by titration every 30 min. When the acid value drops to below 4 mg KOH / g, stop heating. When the product cools to 70℃, add a 3% (w / w) ethanol aqueous solution for washing, stir thoroughly for 10 min, let stand for 30 min, remove the supernatant, and the secondary modified dimethyl terephthalate is obtained. A3. Mix the secondary modified dimethyl terephthalate, vinyltriethoxysilane and azobisisobutyronitrile in a beaker and then add them to the reaction vessel. Purge the air with nitrogen, adjust the stirring speed to 250 r / min, raise the temperature to 90℃ and react for 1.5 h. Then add azobisisobutyronitrile and raise the temperature to 110℃ and react for 3.5 h. After the reaction is completed, put the product into a vacuum drying oven and dry it at 85℃ and -0.095 MPa for 5 h to obtain the desired modified dimethyl terephthalate. The modified 1,4-butanediol is prepared using the following specific steps: B1. Add 1,4-butanediol and glycidyl ether to a reaction vessel, add potassium hydroxide powder, stir at 200 r / min, heat to 65℃, maintain the temperature and react. Monitor the residual amount of glycidyl ether by high performance liquid chromatography every 30 min. Stop the reaction when the residual amount is ≤0.8%. After cooling to 35℃, add deionized water, stir for 30 min, let stand for 40 min to separate the aqueous phase, dry the organic phase with anhydrous calcium chloride for 4 h, filter to obtain primary modified 1,4-butanediol; B2. Add the primary modified 1,4-butanediol to the reactor, along with methacrylic acid, p-toluenesulfonic acid, and phenothiazine. Install a water separator and a reflux condenser. Stir at 200 r / min. Heat the system to 85℃ and maintain the temperature for 5 h. After the reaction, cool to 45℃ and neutralize with 6% sodium bicarbonate solution to pH 7.

5. Allow to stand and separate the aqueous phase. Wash the organic phase three times with deionized water, and then distill at 85℃ for 1.5 h to obtain the secondary modified 1,4-butanediol. B3. The modified 1,4-butanediol was mixed with dimethyl diallyl ammonium chloride and isopropanol and then added to a reflux reactor. The stirring speed was 150 r / min, and the system was heated to 82℃ and kept under reflux for 7 h. After the reaction was completed, the heating was stopped, and the reaction solution was transferred to a rotary evaporator. The solvent was recovered by distillation under a vacuum of -0.08 MPa and 90℃. The remaining product was transferred to a vacuum drying oven and dried at 85℃ and -0.095 MPa for 6 h, with the material turned over every 2 h. After drying, the material was pulverized and passed through a 200-mesh sieve to obtain the modified 1,4-butanediol.

2. The thermoplastic polyester elastomer material according to claim 1, characterized in that: The basalt fiber undergoes surface silanization treatment. The treatment method is as follows: basalt fibers with an aspect ratio ≥20 are ultrasonically cleaned for 15 minutes with a 5% anhydrous ethanol-deionized water mixture with a volume ratio of 1:1, dried at 100℃ for 2 hours, then immersed in a treatment solution of silane coupling agent KH-550 and anhydrous ethanol with a volume ratio of 1:10 at room temperature for 2 hours, and finally dried at 120℃ for 3 hours to ensure strong silane bonding.

3. The thermoplastic polyester elastomer material according to claim 1, characterized in that: The flake graphite was subjected to surface silanization treatment. The treatment method was as follows: 0.5% of the flake graphite mass of silane coupling agent KH-550 was weighed and dissolved in 5 times the mass of anhydrous ethanol to prepare a diluent. The diluent was added dropwise to the flake graphite under high-speed shearing at 2000 r / min. After the addition was complete, shearing was continued for 10 min, and then the graphite was dried under vacuum at 80℃ and -0.09 MPa for 2 h.

4. The thermoplastic polyester elastomer material according to claim 1, characterized in that: The ratio of dimethyl terephthalate, 1,3-propanediol, and tetraisopropyl titanate in A1 is 100g:130g:1.2g. The ratio of the amount of the modified dimethyl terephthalate, pyromellitic dianhydride, and 2-methylimidazole in A2 is 100g:6g:0.2g. The ratio of secondary modified dimethyl terephthalate, vinyltriethoxysilane, and azobisisobutyronitrile in A3 is 100g:9g:0.7g.

5. The thermoplastic polyester elastomer material according to claim 1, characterized in that: In the preparation of the modified dimethyl terephthalate, the grafting reaction between the secondary modified dimethyl terephthalate and vinyltriethoxysilane adopts a stepwise temperature-controlled initiation process. By supplementing the initiator in stages, the grafting rate is controlled within the range of 65-75%, avoiding the problem of uneven grafting caused by single-temperature initiation.

6. The thermoplastic polyester elastomer material according to claim 1, characterized in that: The ratio of 1,4-butanediol, glycidyl ether, potassium hydroxide, deionized water, and anhydrous calcium chloride in B1 is 100g:90g:6.5g:60g:10g. The ratio of the amount of 1,4-butanediol, methacrylic acid, p-toluenesulfonic acid and phenothiazine in B2 is 100g:130g:1.5g:0.15g; The ratio of the amount of the secondary modified 1,4-butanediol, dimethyl diallyl ammonium chloride, and isopropanol in B3 is 100g:11g:380mL.

7. A method for preparing a thermoplastic polyester elastomer material, characterized in that: Specifically, it includes the following steps: S1. Modified dimethyl terephthalate and 1,4-butanediol are added to a reaction vessel, along with tetraisopropyl titanate and antioxidant 168. Under nitrogen protection, the temperature is raised to 225-245℃ for esterification reaction for 2.5-3.5 hours. Then, the temperature is raised to 265-285℃ and polycondensation reaction is carried out under a vacuum of 0.5-1.2 kPa for 1.5-2.5 hours to obtain dihydroxyl-terminated polyester prepolymer A. S2. Polytetrahydrofuran ether diol and modified 1,4-butanediol are added to another reactor, along with tetraisopropyl titanate and antioxidant 168. Under nitrogen protection, the temperature is raised to 165-185℃ for prepolymerization reaction for 1.5-2.5 hours. Then, the temperature is raised to 205-225℃ and the reaction is continued for 2.5-3.5 hours under a vacuum of 0.4-0.8 kPa to obtain dihydroxyl-terminated polyether prepolymer B. S3. Add prepolymer A and prepolymer B to a twin-screw extruder, along with isophorone diisocyanate, basalt fiber, flake graphite, tributyl citrate, methylphenyl silicone resin, polyolefin elastomer, and UV absorber UV-1577. Set the extruder temperature to segmented control: feeding section 185-195℃, screw front section 190-200℃, screw middle section 200-210℃, screw rear section 210-220℃, and die temperature 215-225℃. Perform melt blending extrusion and granulation to obtain thermoplastic polyester elastomer material.

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