Thermoplastic polyester elastomer composite material, preparation method thereof and automobile engine air inlet pipe

Abstract

The invention relates to the technical field of high polymer materials, and particularly discloses a thermoplastic polyester elastomer composite material, a preparation method thereof and an automobile engine intake pipe, the thermoplastic polyester elastomer composite material is prepared from the following components in parts by weight: 100 parts of thermoplastic polyester elastomer resin TPEE, 0.5-1.2 parts of a chain extender and 0.05-0.2 part of a composite catalyst, and 4-10 parts of nano deacidification master batch. According to the invention, by adding the nano deacidification master batch, the chain extender and the composite catalyst and cooperating with staged solid phase polycondensation, the melt index of the obtained material is stabilized at 0.50-0.60 g / 10min (230 DEG C / 2.16 kg), and the extrusion swelling rate is less than or equal to 12%, so that reliable guarantee is provided for stable blow molding of subsequent air pipelines, especially complex air pipelines with 180-degree turning.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a thermoplastic polyester elastomer composite material, its preparation method, and an intake manifold for an automobile engine. Background Technology

[0002] Thermoplastic polyester elastomer (TPEE) is gradually replacing metals in engine intake manifold manufacturing due to its high toughness, oil resistance, and ease of processing. TPEE with a hardness of 55HD has become the mainstream choice due to its combination of flexibility and strength, but the following technical bottlenecks still exist in the processing of complex pipes (especially 180° sharp bends).

[0003] 1. Limitations of traditional thickening processes Defects of chain extender application: Traditional thickening processes use chemical chain extenders such as epoxy and isocyanate to reduce the melt index (MI) from 10g / 10min to 0.5–1.0g / 10min (230℃ / 2.16kg), meeting general blow molding requirements. However, during 180° turn blow molding: the elastic recovery of the melt leads to an extrusion swell rate >20% (ISO 11443), resulting in thinning of the inner wall thickness of the bend and accumulation on the outer side (wall thickness deviation >15%); frequent melt fractures occur under high shear, with a yield rate of less than 60% or even complete blow molding failure.

[0004] Uncontrolled acid degradation: TPEE degrades to produce carboxylic acids during high-temperature processing, catalyzing molecular chain breakage (intrinsic viscosity decreases by ≥30%), increasing the risk of pipeline cracking after long-term use.

[0005] 2. Shortcomings of existing modification schemes Inorganic filler rheology regulation failure: Although conventional addition of talc, calcium carbonate, etc. can inhibit expansion, it leads to material embrittlement (impact strength decreases by 40%) and cannot solve the acid corrosion problem; Dispersion challenges of single-function nanoparticles: When acid removers such as nano-magnesium oxide are added directly, agglomeration occurs during the high-temperature stage of solid-phase polycondensation (particle size increases from 50nm to >500nm); alkaline surface neutralization of titanium-based catalysts reduces the chain extension efficiency of TMA by more than 50%.

[0006] 3. Urgent industry needs The design of automotive intake pipes is becoming increasingly complex (such as turbocharged models requiring 180° sharp bends), requiring materials to simultaneously meet the following requirements: precise rheological control: melt flow index 0.5–0.8 g / 10 min, extrusion swell ≤12%; long-term stability: strength retention ≥90% after aging at 150℃ for 3000 h; process compatibility: compatible with existing blow molding production lines, requiring no equipment modification. Summary of the Invention

[0007] Based on this, the purpose of this invention is to provide a thermoplastic polyester elastomer composite material, its preparation method, and an automotive engine intake pipe. Through catalyst-activated solid-phase polycondensation and chain extension technology, the molecular weight of TPEE and the precise control of its rheological properties are achieved in the presence of a nano-acid remover, making it suitable for high-precision blow-molded parts such as those for 180° turns in automobiles.

[0008] To achieve the above objectives, the present invention adopts the following technical solution: The present invention first provides a thermoplastic polyester elastomer composite material, which is prepared from the following components in parts by weight: 100 parts of thermoplastic polyester elastomer resin TPEE, 0.5-1.2 parts of chain extender, 0.05-0.2 parts of composite catalyst, and 4-10 parts of nano-acid-removing masterbatch.

[0009] As a further improvement to the above-mentioned solution of the present invention, the nano-acid-removing masterbatch contains 82wt%-84.5wt% carrier resin, 15wt% phosphate-modified nano-magnesium oxide, and 0.5wt%-3wt% dispersant.

[0010] As a further improvement to the above-mentioned solution of the present invention, the preparation method of the nano-acid-removing masterbatch includes the following steps: S11. Dry the carrier resin and nano-magnesium oxide to obtain dried carrier resin and nano-magnesium oxide; S12. Add the phosphate ester surface modifier to anhydrous ethanol, mix to obtain a modifier solution, add the dried nano magnesium oxide to the modifier solution, ultrasonically disperse, centrifuge, and dry to obtain phosphate ester modified nano magnesium oxide; S13. The dried carrier resin, dispersant, and phosphate-modified nano magnesium oxide are premixed in proportion, then added to a twin-screw extruder, melted, extruded, granulated, and dried to obtain nano deacidification masterbatch.

[0011] As a further improvement to the above-mentioned solution of the present invention, in step S11, the particle size of the nano-magnesium oxide is 30-50 nm. And / or, in step S12, the concentration of the modifier solution is 5 wt%, and the thickness of the modification layer in the phosphate-modified nano-magnesium oxide is 2-5 nm.

[0012] As a further improvement to the above-mentioned scheme of the present invention, the carrier resin is PETG resin, and the melt index of the carrier resin at 190°C and 2.16kg load is 15~25g / 10min; the phosphate ester surface modifier is triethyl phosphate; and the dispersant is polyether modified polysiloxane dispersant.

[0013] As a further improvement to the above-mentioned scheme of the present invention, the composite catalyst is composed of tetrabutyl titanate and zirconium n-propoxide in a mass ratio of 2-4:1; and / or, the thermoplastic polyester elastomer resin TPEE has a hardness of 55HD and a melt index of 10g / 10min at 230℃ and 2.16kg load; and / or, the chain extender is trimellitic anhydride chain extender.

[0014] The present invention also proposes a method for preparing the thermoplastic polyester elastomer composite material as described above, which includes the following steps: S21. Thermoplastic polyester elastomer resin TPEE, chain extender, composite catalyst and nano deacidifying masterbatch are premixed in proportion and then added to a twin-screw extruder for granulation to obtain pre-extruded TPEE granules. S22. The pre-extruded TPEE granules are first subjected to dehydration condensation under a protective atmosphere: the reaction is carried out at 130-140℃ for 4-8 hours to achieve dehydration condensation of the TPEE end groups. The temperature of 130-140℃ (preferably 130℃) activates the TPEE end groups (-OH / -COOH condensation), and the reaction time of 4-8 hours (preferably 6 hours) ensures complete dehydration. The flow rate of the protective atmosphere is 10-15 L / min to remove reaction water and inhibit oxidation. The rotation speed of the dehydration condensation is 10-15 rpm to enhance mass transfer and prevent agglomeration. Then, the mixture is subjected to a vacuum degree ≤0.1 kPa and a temperature of 150- The chain extension reaction is carried out at 160℃ for 10-20h to activate the chain extension reaction between the chain extender TMA and the TPEE end group. A temperature of 150-160℃ (preferably 150℃) can activate the ring-opening of TMA anhydride. A reaction time of 10-20h (preferably 15h) can ensure the increase in molecular weight. A vacuum degree of ≤0.1kPa (preferably 0.08kPa) accelerates the diffusion of by-products and promotes the chain extension reaction to proceed in the forward direction. The rotation rate of the chain extension reaction is 5-8rpm, with gentle agitation to protect the nano-dispersion. Finally, a thermoplastic polyester elastomer composite material is obtained.

[0015] As a further improvement to the above-mentioned solution of the present invention, in step S1, the screw length-to-diameter ratio of the twin-screw extruder is ≥40:1, and the high-shear block speed is ≥300rpm; the granulation is carried out at 220-240℃ and die pressure ≤5MPa. And / or, the endpoint determination of the dehydration condensation in step S22 is: the weight loss rate of the material is 0.5wt%-1wt% (detected by an online weighing system); the endpoint determination condition of the chain extension reaction is: the intrinsic viscosity of the material is 1.80-2.10 dL / g (25℃, measured by Ubbelohde viscometer and phenol / tetrachloroethane solution).

[0016] The present invention also proposes an automotive engine intake manifold, which is made of the thermoplastic polyester elastomer composite material as described above by blow molding.

[0017] As a further improvement to the above-mentioned solution of the present invention, the extrusion expansion rate of the automobile engine intake pipe is ≤12%, the wall thickness deviation is ≤5%, and the tensile strength retention rate is ≥90% after aging at 150℃ for 3000h.

[0018] Compared with the prior art, the present invention has the following beneficial effects: 1. Breakthrough improvement in processing performance: By adding nano-acid-removing masterbatch, chain extender, and composite catalyst, and through synergistic staged solid-phase polycondensation, the melt index of the obtained material is stable between 0.50-0.60 g / 10min (230℃ / 2.16kg), and the extrusion swell rate is ≤12%. This provides a reliable guarantee for stable blow molding in subsequent air pipelines, especially complex air pipelines with 180-degree turns. 2. Multiple synergistic effects ensure stable performance improvement: nano-rheological regulation inhibits extrusion swelling; phosphate ester shielding layer protects the activity of catalyst, inhibits extrusion swelling, and ensures resistance to long-term degradation; staged solid-phase polycondensation can regulate molecular weight distribution and ensure resistance to long-term degradation; the addition of chain extenders and composite catalysts reduces the solid-phase reaction temperature and reaction time, greatly improving efficiency.

[0019] 3. Significantly enhanced long-term thermal stability: The phosphate ester shielding layer isolates acid / alkali reactions, and the nano MgO neutralizes the acid generated during degradation in real time, resulting in a thermal aging strength retention rate of ≥90% at 150℃ / 3000h. Detailed Implementation

[0020] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0021] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0022] The specific information of the raw materials used in the following examples and comparative examples is as follows: Thermoplastic polyester elastomer resin TPEE: Shore hardness 55D, self-made; the self-made method is as follows: 45 parts of dimethyl terephthalate, 23 parts of 1,4-butanediol, 35 parts of polyether polyol, 0.1 parts of 4,4'-bis(α,α-dimethylbenzyl)diphenylamine antioxidant, 0.25 parts of tetrabutyl titanate catalyst, 0.2 parts of trimellitic anhydride crosslinking agent, and 0.3 parts of triphenyl phosphite anti-yellowing agent are added to a polymerization reactor. The transesterification reaction is carried out at 190℃, and the polycondensation reaction is carried out at 250℃ and a vacuum degree below 1 mmHg. Finally, a thermoplastic polyester elastomer resin TPEE with a hardness of 55HD and a melt index of 10g / 10min (230℃ / 2.16Kg) is prepared. Composite catalyst: prepared by mixing tetrabutyl titanate and zirconium n-propoxide in a weight ratio of 3:1, freshly prepared and used immediately, sealed and protected from light; Nano-magnesium oxide: Particle size 40±5nm, specific surface area ≥60m² 2 / g; PETG resin: melt index 20g / 10min (190℃ / 2.16kg); Dispersant: Polyether-modified polysiloxane, BYK-2155 from BYK Chemicals; All materials are commercially available, commonly used products.

[0023] The above-mentioned raw materials are only for illustrating the source and composition of the reagents used in the experiments of this invention, so as to fully disclose them, and do not imply that the invention cannot be achieved by using other similar reagents or reagents provided by other suppliers.

[0024] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in this technical field.

[0025] Example 1 This embodiment proposes a thermoplastic polyester elastomer composite material, which is prepared from the following components in parts by weight: 100 parts of thermoplastic polyester elastomer resin TPEE, 0.8 parts of trimellitic anhydride (TMA) chain extender, 0.15 parts of composite catalyst, and 8 parts of nano-acid-removing masterbatch.

[0026] The preparation method of nano-acid deacidification masterbatch in this embodiment includes the following three steps S11-S13: S11. Add triethyl phosphate (TEP) (purity ≥99%) to anhydrous ethanol (analytical grade, water content ≤0.1%, pretreated by molecular sieve dehydration) to obtain a 5wt% TEP ethanol solution; add nano-magnesium oxide (particle size 40±5nm, specific surface area ≥60m²) at a mass-to-volume ratio of 1g:50mL. 2 / g, pre-treatment: vacuum drying at 120℃ for 4h) added to the prepared TEP ethanol solution, ultrasonic dispersion: ultrasonic dispersion at 60℃ for 1h, power of 300W, frequency of 40kHz, temperature control ≤65℃ to prevent agglomeration; centrifugation: centrifugation at 8000rpm for 10min, vacuum drying: vacuum drying at 50℃ for 12h to obtain triethyl phosphate modified nano magnesium oxide powder; S12. By weight, 15 parts of triethyl phosphate modified nano magnesium oxide powder, 83 parts of PETG resin (melt index of 20 g / 10 min at 190℃ / 2.16 kg, pre-treated by drying at 80℃ for 6 h) and 2 parts of dispersant BYK-2155 are dry-mixed and stirred at high speed at 2000 rpm for 15 min to obtain a premix (moisture content ≤0.03%). S13. The premixed material is melted, extruded, and granulated using a co-rotating twin-screw extruder (L / D=44:1, screw diameter 40mm), and dried: vacuum dried at 60℃ for 6 hours (moisture content ≤0.02%); sieving: particles with a diameter of 2-3mm are collected using a vibrating screen (sieving rate ≥95%), which is the nano-acid-removing masterbatch. The process parameters of the co-rotating twin-screw extruder are shown in Table 1. Table 1. Process parameters of co-rotating twin-screw extruder 1

[0027] Co-rotating twin-screw extruder: Screw speed: 300 rpm, torque ≤75%; Feed rate: 15 kg / h, ensuring melt residence time ≤90 s; Pelletizing method: water ring hot cutting (water temperature 40℃, cutter speed 800 rpm).

[0028] The preparation method of the thermoplastic polyester elastomer composite material in this embodiment includes the following four steps S21-S24: S21. Raw material pretreatment: Thermoplastic polyester elastomer resin TPEE is vacuum dried at 100℃ for 4 hours to reduce its moisture content to ≤50ppm; TMA chain extender is dried in a forced-air environment at 60℃ for 2 hours to reduce its moisture content to ≤0.1%. S22. Add thermoplastic polyester elastomer resin TPEE, TMA chain extender, and nano deacidifying masterbatch to a high-speed mixer according to the proportion. First, mix at a low speed of 500 rpm for 5 minutes. Then, add the composite catalyst and mix at a high speed of 1500 rpm for 3 minutes. The mixing temperature is controlled at ≤40℃ to obtain the mixture. S23. The mixture is melted, extruded, and pelletized using a co-rotating twin-screw extruder (L / D=44:1, screw diameter 50mm): water cooling (25℃) → air knife dewatering → pelletizer (600rpm, particle size 2-3mm); drying: 80℃ hot air circulating drying for 30min (moisture content ≤100ppm); sealed packaging: nitrogen-filled aluminum foil bags for storage (oxygen content ≤0.1%), yielding pre-extruded TPEE pellets (melt index 8.2g / 10min). The equipment configuration of the co-rotating twin-screw extruder is shown in Table 2, and its process parameters are shown in Table 3.

[0029] Table 2 Equipment Configuration of Co-rotating Twin-Screw Extruder II

[0030] Table 3 Process parameters of co-rotating twin-screw extruder II

[0031] S24. Two-stage solid-state polycondensation: (1) Loading and pretreatment: The pre-extruded TPEE granules are loaded into the rotary reactor at a rate of 60%-70% of the reactor volume (to avoid dead corners of accumulation). The N2 is replaced 3 times to ensure that the O2 content in the rotary reactor is ≤100ppm. Then, the reactor is preheated to 100℃ for 1h by low-speed rotation (5rpm) to eliminate thermal stress. (2) Nitrogen dehydration condensation (first stage): The reaction was carried out at 130℃ for 7 hours, with the N2 flow rate controlled at 10-15 L / min. The weight loss rate was detected by an online weighing system. The reaction was stopped when the weight loss rate reached 0.9 wt%. The reaction equation for the first stage is: TPEE-OH+HOOC-TPEE→TPEE-OCO-TPEE+H2O; (3) Vacuum chain extension reaction (second stage): The reaction was carried out at a vacuum of 0.06 kPa and 150 °C for 14 h, with a rotation speed of 5-8 rpm; the intrinsic viscosity was measured by Ubbelohde viscometer, and the reaction was stopped when the intrinsic viscosity reached 1.90 dL / g; the reaction equation for the second stage is: TPEE-OH+TMA→TPEE-OCO-C6H3(COOH)2+H2O TPEE-OCO-C6H3(COOH)2+HO-TPEE→TPEE-OCO-C6H3(COO-TPEE)2+H2O; (4) Cooling and post-treatment Programmed cooling: 150℃ under vacuum → 100℃ (rate 2℃ / min) → N2 replacement followed by cooling to 40℃; Anti-oxidation material handling: The rotary kettle is filled with high-purity N2 (O2≤50ppm), and then sealed and transferred to the drying room; Screening and packaging: Vibrating screen removes fine powder (≤1mm particles), aluminum foil bags are filled with nitrogen and sealed (residual moisture ≤50ppm), finally obtaining the desired thermoplastic polyester elastomer composite material.

[0032] Example 2 The difference between this embodiment and Embodiment 1 is that: The thermoplastic polyester elastomer composite material of this embodiment is prepared from the following components in parts by weight: 100 parts of thermoplastic polyester elastomer resin TPEE, 1.2 parts of TMA chain extender, 0.2 parts of composite catalyst, and 10 parts of nano-acid-removing masterbatch. In step S24 of the preparation method of thermoplastic polyester elastomer composite material in this embodiment, the vacuum gradient setting of the second stage is: 0.5kPa (0-2h) → 0.2kPa (2-5h) → 0.05kPa (>5h). When the intrinsic viscosity reaches 2.10dL / g in the second stage, the reaction is stopped.

[0033] Example 3 The difference between this embodiment and Embodiment 1 is that: The thermoplastic polyester elastomer composite material of this embodiment is prepared from the following components in parts by weight: 100 parts of thermoplastic polyester elastomer resin TPEE, 0.5 parts of TMA chain extender, 0.05 parts of composite catalyst, and 4 parts of nano-acid-removing masterbatch. In step S24 of the preparation method of the thermoplastic polyester elastomer composite material in this embodiment: the first stage is reacted at 130°C for 5 hours, with a weight loss rate of 0.7 wt%; the reaction time of the second stage is extended to 18 hours.

[0034] Comparative Example 1 The difference between this comparative example and Example 1 is that: The nano-acid-removing masterbatch used in this comparative example is unmodified nano-MgO (40nm). Step S24 in this comparative example employs a single-stage solid-state polycondensation: (1) Loading and pretreatment: The pre-extruded TPEE granules are loaded into the rotary reactor at a rate of 60%-70% of the reactor volume (to avoid dead corners of accumulation). The N2 is replaced 3 times to ensure that the O2 content in the rotary reactor is ≤100ppm. Then, the reactor is preheated to 100℃ for 1h by low-speed rotation (5rpm) to eliminate thermal stress. (2) Single-stage solid-state polycondensation (i.e., only the first stage of nitrogen dehydration condensation stage is passed, without the second stage of vacuum chain extension reaction): the reaction is carried out in a vacuum of 0.1 kPa and 130℃ for 24 h, the N2 flow rate is controlled at 10-15 L / min, the weight loss rate is detected by an online weighing system, and the reaction is stopped when the weight loss rate reaches 0.9 wt%. (3) Cooling and post-treatment Programmed cooling: 130℃ under vacuum → 100℃ (rate 2℃ / min) → after N2 replacement, the temperature drops to 40℃; Anti-oxidation material handling: The rotary kettle is filled with high-purity N2 (O2≤50ppm) and then sealed and transferred to the drying room.

[0035] Comparative Example 2 The difference between this comparative example and Example 1 is that the amount of nano-acid-removing masterbatch used in this comparative example is 3 parts.

[0036] Comparative Example 3 The difference between this comparative example and Example 1 is that the amount of nano-acid-removing masterbatch used in this comparative example is 12 parts.

[0037] Comparative Example 4 The difference between this comparative example and Example 1 is that: Step S24 in this comparative example employs a single-stage solid-state polycondensation: (1) Loading and pretreatment: The pre-extruded TPEE granules are loaded into the rotary reactor at a rate of 60%-70% of the reactor volume (to avoid dead corners of accumulation). The N2 is replaced 3 times to ensure that the O2 content in the rotary reactor is ≤100ppm. Then, the reactor is preheated to 100℃ for 1h by low-speed rotation (5rpm) to eliminate thermal stress. (2) Single-stage solid-state polycondensation (i.e., directly entering the second stage of solid-state polycondensation, i.e., vacuum chain extension reaction): react in a vacuum of 0.06 kPa and 150 °C for 21 h, and measure the intrinsic viscosity by Ubbelohde viscometer. When the intrinsic viscosity is ≥1.60 dL / g, the reaction is stopped. (3) Cooling and post-treatment Programmed cooling: 150℃ under vacuum → 100℃ (rate 2℃ / min) → N2 replacement followed by cooling to 40℃; Anti-oxidation material handling: The rotary kettle is filled with high-purity N2 (O2≤50ppm) and then sealed and transferred to the drying room.

[0038] Comparative Example 5 The difference between this comparative example and Example 1 is that no composite catalyst was used in this comparative example.

[0039] The amounts of each component used in Examples 1-3 and Comparative Examples 1-5 are shown in Table 4.

[0040] Table 4. Amounts (parts by weight) of each component in Examples 1-3 and Comparative Examples 1-5

[0041] Test case The composite materials obtained in Examples 1-3 and Comparative Examples 1-5 were subjected to the following performance tests: melt flow index (230℃ / 2.16kg); extrusion swell (180° bend): according to ISO 11443; strength retention after aging at 150℃ for 3000h: according to ISO 527; the test results are shown in Table 5.

[0042] Table 5 Performance Test Results

[0043] According to the results in Table 1: Examples 1-3, through the use of phosphate-modified nano-MgO combined with a staged solid-phase chain extension process, solved three major defects of TPEE thickening technology: First, it solved the catalyst deactivation problem, achieving a stable and controllable melt index of 0.50-0.60 g / 10min; second, the addition of nano-acid-removing masterbatch solved rheological stability and extrusion swell, achieving an extrusion swell of 9.5%-12%, fully meeting the requirements for blow molding of complex pipelines in automobiles with 180° turns; third, the relatively low-temperature chain extension increased molecular weight, and the phosphate ester shielding layer isolated acid / alkali reactions, while the nano-MgO neutralized the acid generated by degradation in real time, resulting in a heat aging strength retention rate of ≥90% at 150℃ / 3000h, meeting the long-term high-temperature resistance requirements of engine intake pipes.

[0044] Compared with Example 1, Comparative Example 1 used unmodified nano-magnesium oxide and adopted single-stage solid-phase polycondensation. The composite catalyst was deactivated, and insufficient chain extension led to uncontrollable melt index. At the same time, nano-agglomeration caused rheological runaway, resulting in an extrusion expansion rate of 23%. Acid degradation was not neutralized, and the strength retention rate was greatly reduced.

[0045] Compared with Example 1, Comparative Example 2 used a small amount of nano-acid-removing masterbatch, resulting in insufficient acid neutralization and a decrease in residual carboxyl groups, with the melt index reaching 0.72 g / min. At the same time, due to insufficient nano-dosage, rheological regulation failed, and the extrusion expansion rate reached 15.8%. Acid corrosion was not completely suppressed, reducing the strength retention rate.

[0046] Compared with Example 1, Comparative Example 3 used more nano-acid-removing masterbatch. Excessive nanoparticles hindered molecular chain movement and reduced the melt index. At the same time, due to excessive rheological control, the melt elasticity was insufficient, which reduced the extrusion expansion rate. Furthermore, the nano-agglomerates caused brittleness and reduced the strength retention rate.

[0047] Compared with Example 1, Comparative Example 4 directly adopted single-stage solid-state polycondensation without staged solid-state polycondensation, which led to competition between dehydration and chain extension, catalyst deactivation, and uncontrollable melt index. Furthermore, the nano-acid-removing masterbatch irreversibly agglomerated under vacuum at 150°C. The single-stage reaction caused the molecular weight distribution to deteriorate, resulting in extrusion expansion. At the same time, the uncontrolled acid degradation reduced the strength retention rate.

[0048] Compared with Example 1, Comparative Example 5 did not use a composite catalyst. The melt index of Comparative Example 5 reached 1.10 g / min, which may be because the TMA chain extender was not activated, resulting in a low chain extension reaction rate. The extrusion swell rate of Comparative Example 5 was 20.8%, which may be because the relatively low molecular weight melt has strong elastic recovery. The strength retention rate of Comparative Example 5 was only 72%, which is because it relied solely on nano-acid removal, resulting in the failure to inhibit molecular chain breakage.

[0049] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0050] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A thermoplastic polyester elastomer composite material, characterized in that, It is prepared from the following components in parts by weight: 100 parts of thermoplastic polyester elastomer resin TPEE, 0.5-1.2 parts of chain extender, 0.05-0.2 parts of composite catalyst, and 4-10 parts of nano-acid-removing masterbatch.

2. The thermoplastic polyester elastomer composite material according to claim 1, characterized in that, The nano-acid-removing masterbatch contains 82wt%-84.5wt% carrier resin, 15wt% phosphate-modified nano-magnesium oxide, and 0.5wt%-3wt% dispersant.

3. The thermoplastic polyester elastomer composite material according to claim 1, characterized in that, The preparation method of the nano-acid-removing masterbatch includes the following steps: S11. Dry the carrier resin and nano-magnesium oxide to obtain dried carrier resin and nano-magnesium oxide; S12. Add the phosphate ester surface modifier to anhydrous ethanol, mix to obtain a modifier solution, add the dried nano magnesium oxide to the modifier solution, ultrasonically disperse, centrifuge, and dry to obtain phosphate ester modified nano magnesium oxide; S13. The dried carrier resin, dispersant, and phosphate-modified nano magnesium oxide are premixed in proportion, then added to a twin-screw extruder, melted, extruded, granulated, and dried to obtain nano deacidification masterbatch.

4. The thermoplastic polyester elastomer composite material according to claim 3, characterized in that, In step S11, the particle size of the nano-magnesium oxide is 30-50 nm; And / or, in step S12, the concentration of the modifier solution is 5 wt%, and the thickness of the modification layer in the phosphate-modified nano-magnesium oxide is 2-5 nm.

5. The thermoplastic polyester elastomer composite material according to claim 2, characterized in that, The carrier resin is PETG resin, and the melt index of the carrier resin at 190℃ and 2.16kg load is 15-25g / 10min; the phosphate ester surface modifier is triethyl phosphate; and the dispersant is polyether-modified polysiloxane dispersant.

6. The thermoplastic polyester elastomer composite material according to claim 1, characterized in that, The composite catalyst is composed of tetrabutyl titanate and zirconium n-propoxide in a mass ratio of 2-4:1; and / or, the thermoplastic polyester elastomer resin TPEE has a hardness of 55HD and a melt index of 10g / 10min at 230℃ and 2.16kg load; and / or, the chain extender is trimellitic anhydride chain extender.

7. A method for preparing a thermoplastic polyester elastomer composite material as described in any one of claims 1-6, characterized in that, It includes the following steps: S21. Thermoplastic polyester elastomer resin TPEE, chain extender, composite catalyst and nano deacidifying masterbatch are premixed in proportion and then added to a twin-screw extruder for granulation to obtain pre-extruded TPEE granules. S22. The pre-extruded TPEE granules are first dehydrated and condensed under a protective atmosphere: the reaction is carried out at 130-140℃ for 4-8 hours; then the chain extension reaction is carried out under vacuum degree ≤0.1kPa and 150-160℃ for 10-20 hours to obtain a thermoplastic polyester elastomer composite material.

8. The method for preparing the thermoplastic polyester elastomer composite material according to claim 7, characterized in that, In step S1, the twin-screw extruder has a screw length-to-diameter ratio ≥40:1 and a high-shear block speed ≥300 rpm; the granulation is carried out at 220-240℃ and a die pressure ≤5MPa. And / or, in step S22, the weight loss rate of the material after dehydration and condensation is 0.5wt%-1wt%, and the intrinsic viscosity of the material after chain extension reaction is 1.80-2.10 dL / g.

9. An intake manifold for an automobile engine, characterized in that, It is made by blow molding of a thermoplastic polyester elastomer composite material as described in any one of claims 1-6.

10. The automobile engine intake manifold according to claim 9, characterized in that, The extrusion swell rate of the automobile engine intake pipe is ≤12%, the wall thickness deviation is ≤5%, and the tensile strength retention rate is ≥90% after aging at 150℃ for 3000h.

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