An ultra-high flowability polyester elastomer material, a method for preparing the same, and a method for using the same

Abstract

The application discloses a kind of superhigh fluidity polyester elastomer material and its preparation method and application method, raw material is by weight parts, including: 100 parts polyester elastomer matrix;10-50 parts semi-hydrogenated SBS;5-30 parts plasticizer;2-20 parts compatibilizer;2-15 parts crosslinking agent;1-10 parts hydrolysis agent;0.5-5 parts anti-oxidation anti-ultraviolet aid.The superhigh fluidity polyester dynamic vulcanization elastomer material of the application is prepared by vulcanization crosslinking process and dynamic hydrolysis process, compared with traditional polyester elastomer process, vulcanization crosslinking makes polyester elastomer have higher thermal stability and light aging resistance, dynamic hydrolysis process is that the molecular weight of polyester elastomer is controllable reduction, fluidity improves, more suitable for thin-walled large-area molding products, for example instrument panel skin, door panel skin and other various skin products instead of PVC, polyurethane, leather, etc.;It can be used for coating ABS, PC, PC / ABS and other hard skeleton, and can be used alone for coating polyurethane foaming product.

Description

Technical Field

[0001] This invention relates to the field of polymer modification technology, and in particular to an ultra-high flowability polyester elastomer material and its preparation and application methods. Background Technology

[0002] Currently, automotive interior materials are mainly divided into two categories based on their tactile feel: one is hard materials, represented by engineering plastics, metals, and natural wood panels; the other is soft materials, represented by genuine leather, PVC, and thermoplastic elastomers. Hard materials, due to their less pleasant tactile feel, are mostly used in automotive interior products that are not in direct human contact, while soft materials are increasingly used in automotive interior products that come into direct contact with the human body.

[0003] Among automotive soft-touch interior products, genuine leather has the highest cost, complex processes, low utilization rate, and long production cycle, and is mainly used in high-end cars with higher costs. PVC products are the most widely used and have excellent overall performance, but they also have disadvantages such as high energy consumption, complex processes, and low efficiency in slush molding. Thermoplastic elastomers are gradually gaining attention. They can be injection molded, which is efficient, energy-saving, and has a high yield. However, thermoplastic elastomers have disadvantages such as difficult molding, poor light and heat aging performance, and difficulty in bonding polyurethane foaming agents. Thermoplastic polyester elastomers (TPC) are block copolymers containing polyester hard segments and polyether soft segments. The polyester portion crystallizes to form crystalline microdomains that act as physical crosslinking points, while the polyether soft segments and uncrystallized polyester form an amorphous phase, giving TPC elasticity and processability. TPC has excellent low-temperature resistance, abrasion resistance, and chemical solvent resistance, and it exhibits good elasticity at low temperatures. Summary of the Invention

[0004] The main objective of this invention is to provide an ultra-high flowability polyester elastomer material and its preparation and application methods. It overcomes the shortcomings of the prior art by improving the polyester material formulation and production process, thereby enhancing the processability and temperature and weather resistance of the polyester material, effectively preventing aging, cracking, and yellowing of the product, and making it suitable for large-area, thin-walled automotive interior and exterior products.

[0005] To achieve the above objectives, the technical solution adopted in this invention is as follows: an ultra-high flowability polyester elastomer material, the raw materials of which, by weight, include 100 parts of polyester elastomer matrix; 10-50 parts of semi-hydrogenated SBS; 5-30 parts of plasticizer; 2-20 parts of compatibilizer; 2-15 parts of crosslinking agent; 1-10 parts of hydrolysate; and 0.5-5 parts of antioxidant and UV resistant additives.

[0006] According to an embodiment of the present invention, the raw materials include, by weight, 100 parts of polyester elastomer matrix; 20 parts of semi-hydrogenated SBS; 15 parts of plasticizer; 10 parts of compatibilizer; 5 parts of crosslinking agent; 4 parts of hydrolysate and 5 parts of antioxidant and UV-resistant additives.

[0007] According to one embodiment of the present invention, the polyester elastomer is selected from one or more of TPC-EE, TPC-ES, and TPC-ET.

[0008] According to one embodiment of the present invention, the compatibilizer is a styrene-grafted polyester elastomer.

[0009] According to one embodiment of the present invention, the raw materials for preparing the styrene-grafted polyester elastomer include 100 parts of polyester elastomer, 2-15 parts of styrene (ST) monomer, 0.25-1 parts of dicumyl peroxide (DCP), 0.01-0.03 parts of antioxidant (1076) and antioxidant (9228), and 0.01-0.1 parts of TiCl4 catalyst.

[0010] According to one embodiment of the present invention, the plasticizer is an ultra-high viscosity paraffin oil, wherein the kinematic viscosity of the paraffin oil at 40°C is not less than 80 mmHg. 2 / s, flash point not less than 270℃, CP value greater than 65%.

[0011] According to one embodiment of the present invention, the semi-hydrogenated SBS has a styrene to butadiene ratio of 0.2-0.7 and an unsaturation degree of 2-6%.

[0012] According to one embodiment of the present invention, the crosslinking agent is selected from one or more of 1,2-polybutadiene (1,2-PBR), dicumyl peroxide (DCP), triallyl isocyanurate (TAIC), benzoyl peroxide (BPO), 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane (BPMC), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DBPMH), 1,3-bis(tert-butylperoxyisopropyl)benzene (BIPB), triallyl cyanurate (TAC), trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTAMA), ethylene glycol diacrylate (EGDA), ethylene glycol dimethacrylate (EGDMA), zinc dimethacrylate (ZDMA), N,N′-p-phenylbismaleimide (PDM or HVA-2), and zinc diacrylate (ZDA).

[0013] According to one embodiment of the present invention, the hydrolysing agent is selected from one or more of water, 1-20% aqueous solution of sodium bicarbonate, 0.1-5% aqueous solution of sodium hydroxide, 0.1-5% aqueous solution of potassium hydroxide, 1-20% aqueous solution of sodium carbonate, dicumyl peroxide (DCP), benzoyl peroxide (BPO), 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane (DBPMH), and 1,3-bis(tert-butylperoxyisopropyl)benzene (BIPB).

[0014] According to one embodiment of the present invention, the antioxidant and UV stabilizer are selected from one or more of 1010, 1076, 1330, 1024, 168, 626, DLTDP, UV531, UV326, UV328, UV329, UV234, UV770, UV944, and UV622.

[0015] A method for preparing an ultra-high flowability polyester elastomer material, comprising the following steps:

[0016] S100 mixes the appropriate weight parts of polyester elastomer matrix, semi-hydrogenated SBS, plasticizer, compatibilizer, antioxidant and UV stabilizer evenly using a high-speed mixer or coloring machine.

[0017] S200 uses a peristaltic pump to inject the corresponding weight of crosslinking agent through the pre-reserved injection holes in the 3rd to 5th sections of the screw, which is called pump A;

[0018] S300 uses a peristaltic pump to inject the corresponding weight of hydrolysate through the pre-reserved injection hole in section 7-8 of the screw, which is called pump B.

[0019] According to an embodiment of the present invention, the preparation method of the ultra-high flowability polyester elastomer material further includes the following steps: S400 Adjusting the feeding speed of the twin-screw extruder's loss-in-weight weigher and the rotation speeds of pumps A and B to achieve a corresponding material ratio, wherein the twin-screw rotation speed is 200-650 r / min, the twin-screw temperature is 180-250℃, and when the screws reach a specific rotation speed, the loss-in-weight weigher is activated first, followed by pump A after 1 minute, and pump B after 2 minutes. The ultra-high flowability polyester elastomer material is obtained by underwater pelletizing.

[0020] According to one embodiment of the present invention, the coloring machine temperature in step S100 is 20-80°C and the mixing speed is 10-500 r / min; the crosslinking agent temperature in step S200 is 20-50°C and the A pump speed is 5-50 r / min; and the hydrolysant temperature in step S300 is 10-50°C and the B pump speed is 5-50 r / min.

[0021] According to an embodiment of the present invention, the polyester elastomer in step S100 is selected from one or more of TPC-EE, TPC-ES, and TPC-ET; the plasticizer is ultra-high viscosity paraffin oil, and the kinematic viscosity of the paraffin oil at 40°C is not less than 80 mmHg. 2 / s, flash point not less than 270℃, CP value greater than 65%; the semi-hydrogenated SBS has a styrene to butadiene ratio of 0.2-0.7 and an unsaturation degree of 2-6%; the compatibilizer is styrene-grafted polyester elastomer.

[0022] According to one embodiment of the present invention, the crosslinking agent content in step S200 is 5 parts by weight, and the hydrolysant content in step S300 is 4 parts by weight.

[0023] According to an embodiment of the present invention, the styrene-grafted polyester elastomer includes the following steps:

[0024] S510 produces masterbatch A by granulating polyester elastomer matrix, antioxidant, and catalyst in corresponding weight parts through twin-screw extrusion at a speed of 200-550 r / min and a temperature of 185-220℃.

[0025] S520 involves dissolving styrene monomer and crosslinking agent in appropriate weight proportions at 20–50°C to prepare vulcanized liquid B, wherein the stirring speed is 10–50 r / min;

[0026] The S530 grafting reaction involves grafting and crosslinking masterbatch A and vulcanizing liquid B in a twin-screw extruder to produce a compatibilizer. The rotation speed in the twin-screw extruder is 300–600 r / min, and the reaction temperature is 180–215 °C. The product is then processed into styrene-grafted polyester elastomer granules by underwater pelletizing.

[0027] A method for applying the ultra-high flow polyester elastomer material as described in claim 1 includes the following steps: adding the prepared polyester elastomer material particles into an injection molding machine, injecting the molten elastomer material into a simulated leather mold, removing it after cooling, placing it together with PP or other rigid skeletons into a foaming mold, injecting a foaming agent at a temperature of 50-80°C, stabilizing for 2-5 minutes, and opening the mold to remove the product after cooling.

[0028] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0029] (1) The ultra-high flow polyester dynamic vulcanized elastomer material of the present invention is prepared by vulcanization crosslinking process and dynamic hydrolysis process. Compared with the traditional polyester elastomer process, vulcanization crosslinking makes the polyester elastomer have higher thermal stability and light aging resistance. The dynamic hydrolysis process makes the molecular weight of the polyester elastomer controllable and reduces, and improves the flowability, making it more suitable for thin-walled large-area molded products, such as dashboard skin, door panel skin and other skin products that replace PVC, polyurethane, genuine leather and other skins.

[0030] (2) The compatibilizer manufacturing process of the present invention adopts twin-screw dynamic grafting technology, and adds a crosslinking agent that can be grafted to vulcanize the grafting. This type of compatibilizer can not only increase the strength of polyester elastomer, but also make semi-hydrogenated SBS and polyester elastomer melt together better, increase the interfacial bonding force, and make the final product have higher mechanical properties.

[0031] (3) The paraffin oil used is ultra-high viscosity paraffin oil. Due to its high kinematic viscosity and flash point, it has fewer volatile substances, less heat loss at high temperatures, improved product production stability, and is suitable for the strict odor and VOC requirements of automotive interior products.

[0032] (4) The present invention uses polyester elastomer as the base material. This material is a polar material and has good compatibility with automotive polyurethane foaming agents, as well as PC, ABS, etc. It can be used to coat rigid skeletons such as ABS, PC, and PC / ABS, or it can be used alone to coat polyurethane foam products.

[0033] (5) This invention employs a special twin-screw extruder with a high length-to-diameter ratio, small screw clearance, and specially structured water injection holes on the screw body. It uses a one-step process to allow the material to undergo sulfidation cross-linking in the screw before dynamic hydrolysis. The finished material has both high mechanical properties and temperature and weather resistance, as well as excellent processing performance, which can meet the production and processing requirements of ultra-thin-walled products. Detailed Implementation

[0034] The following description is intended to disclose the invention and enable those skilled in the art to implement it. The preferred embodiments described below are merely examples, and other obvious variations will occur to those skilled in the art.

[0035] As used herein, the terms “prepared from” and “comprising” are synonymous. The terms “comprising,” “including,” “having,” “containing,” or any other variations thereof, as used herein, are intended to cover non-exclusive inclusion. For example, a composition, step, method, article, or apparatus that includes the listed elements is not necessarily limited to those elements, but may include other elements not expressly listed or elements inherent to such composition, step, method, article, or apparatus.

[0036] When a quantity, concentration, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper and lower preferred values, this should be understood as specifically disclosing all ranges formed by any pair of any upper or preferred value with any lower or preferred value, regardless of whether the range is disclosed individually. For example, when the range “1 to 5” is disclosed, the described range should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1-2”, “1-2 and 4-5”, “1-3 and 5”, etc. When numerical ranges are described herein, unless otherwise stated, the range is intended to include its endpoints and all integers and fractions within that range.

[0037] "Polymer" refers to a polymeric compound prepared by polymerizing the same or different types of monomers. The general term "polymer" includes the terms "homopolymer," "copolymer," "terpolymer," and "copolymer."

[0038] Example 1

[0039] An ultra-high flow polyester elastomer material is prepared by dynamic crosslinking and dynamic hydrolysis processes. The raw materials of the polyester elastomer material are, by weight, 100 parts polyester elastomer matrix; 20 parts semi-hydrogenated SBS; 15 parts plasticizer; 10 parts compatibilizer; 5 parts crosslinking agent; 4 parts hydrolyzing agent; and 5 parts antioxidant and UV resistant additives.

[0040] The polyester elastomer is TPC-ET, the plasticizer is ultra-high viscosity paraffin oil with a kinematic viscosity of not less than 80 mm² / s at 40°C, a flash point of not less than 270°C, and a straight-chain hydrocarbon (CP) content of more than 65%. The styrene-butadiene mass ratio in the semi-hydrogenated SBS is 1:4, and the degree of unsaturation is 4.5%. The crosslinking agent is a mixture of dicumyl peroxide (DCP) and triallyl isocyanurate (TAIC) in a ratio of 1:1.2. The hydrolysate is a mixture of 1.5% sodium bicarbonate aqueous solution and 1,3-bis(tert-butylperoxyisopropyl)benzene in a ratio of 1:1. The antioxidant and UV stabilizer is a mixture of 1010, UV329, and UV770 in a ratio of 1:2:1.5.

[0041] The method for preparing the styrene-grafted polyester elastomer includes the following steps:

[0042] (1.a) The polyester elastomer matrix, antioxidant and catalyst of corresponding weight parts are granulated by twin screw extrusion to prepare masterbatch A, with a rotation speed of 200 to 550 r / min and a temperature of 185 to 220 °C.

[0043] (1.b) Stir and dissolve the appropriate weight parts of styrene monomer and crosslinking agent at 20-50°C to prepare vulcanized liquid B, wherein the stirring speed is 10-50 r / min;

[0044] (1.c) Grafting reaction: Masterbatch A and vulcanizing liquid B are grafted and crosslinked in a twin-screw extruder to form a compatibilizer. The rotation speed in the twin-screw extruder is 300-600 r / min, and the reaction temperature is 180-215℃. The styrene-grafted polyester elastomer particles are then produced by underwater pelletizing.

[0045] 1. The preparation of the styrene-grafted polyester elastomer includes 100 parts of polyester elastomer matrix (TPC-ET), 8 parts of styrene (ST) monomer, 0.5 parts of dicumyl peroxide (DCP), 0.2 parts of antioxidant (1076) and antioxidant (9228), and 0.1 parts of TiCl4 catalyst. The polyester elastomer matrix is ​​characterized by a melt index greater than 40 g / 10 min at 220℃*2.16 kg, a weight-average molecular weight of 15,000-20,000, and a polybutylene terephthalate (PBT) content greater than 60% in the molecular chain. Due to its higher melt index and smaller molecular weight, it has greater reactivity and is more likely to undergo grafting reaction with styrene monomer.

[0046] A method for preparing an ultra-high flow polyester elastomer material includes the following steps:

[0047] (1) Mix the appropriate weight parts of polyester elastomer matrix, semi-hydrogenated SBS, plasticizer, compatibilizer, antioxidant and UV stabilizer evenly through a high-speed mixer or coloring machine at a speed of 10-500 r / min and a temperature of 20-80℃.

[0048] (2) The corresponding weight parts of crosslinking agent are injected into the screw through the pre-reserved injection hole in the 3rd to 5th section of the screw at 20 to 50°C using a peristaltic pump. This is called pump A. The speed of the peristaltic pump is 5 to 50 r / min.

[0049] (3) The corresponding weight of hydrolysate is injected into the screw through the pre-reserved injection hole in the 7th-8th section of the screw at 10-50℃ using a peristaltic pump. This pump is called pump B. The speed of the peristaltic pump is 5-50 r / min.

[0050] (4) The appropriate material ratio is achieved by adjusting the feeding speed of the loss-in-weight weigher and the rotation speeds of pumps A and B in the twin-screw extruder. The twin-screw speed is 450-650 r / min, and the twin-screw temperature is 180-250℃. When the screws reach a specific speed, the loss-in-weight weigher is activated first, followed by pump A after 1 minute, and pump B after 2 minutes. The ultra-high flowability special-purpose polyester dynamic vulcanized elastomer material is obtained through underwater pelletizing.

[0051] In step (1), the coloring machine temperature is 25°C and the mixing speed is 100 rpm. In step (2), the crosslinking agent temperature is 20°C, the A pump speed is 17 rpm and the weight content is 5 parts. In step (3), the hydrolysant temperature is 35°C, the B pump speed is 25 r / min and the weight content is 4 parts.

[0052] A method for applying the ultra-high flow polyester elastomer material as described in claim 1, characterized by comprising the following steps: adding the obtained polyester elastomer material particles into an injection molding machine, injecting the molten elastomer material into a simulated leather mold, removing it after cooling, placing it together with PP or other rigid skeletons into a foaming mold, injecting a foaming agent at a temperature of 50-80°C, stabilizing for 2-5 minutes, and removing the product after cooling and opening the mold.

[0053] Examples 2-5

[0054] The preparation and application methods of Examples 2-12 are the same as those of Example 1, but the formula ratios are adjusted as shown in Table 1.

[0055] Table 1 Formulation ratios for Examples 2-12

[0056]

[0057]

[0058] Comparative Example 1

[0059] The raw materials of an ultra-high flow polyester elastomer material are, by weight, 100 parts polyester elastomer matrix; 10 parts plasticizer; 20 parts semi-hydrogenated SBS; 15 parts plasticizer; 5 parts crosslinking agent; and 5 parts antioxidant and UV resistant additives.

[0060] The polyester elastomer is TPC-ET, the plasticizer is ultra-high viscosity paraffin oil with a kinematic viscosity of not less than 80 mm² / s at 40°C, a flash point of not less than 270°C, and a linear hydrocarbon (CP) content of more than 65%. The styrene-butadiene mass ratio in the semi-hydrogenated SBS is 1:4, and the degree of unsaturation is 4.5%. The crosslinking agent is a mixture of dicumyl peroxide (DCP) and triallyl isocyanurate (TAIC) in a ratio of 1:1.2. The antioxidant and UV stabilizer is a mixture of 1010, UV329, and UV770 in a ratio of 1:2:1.5.

[0061] The method for preparing the styrene-grafted polyester elastomer includes the following steps:

[0062] (1.a) The polyester elastomer matrix, antioxidant and catalyst of corresponding weight parts are granulated by twin screw extrusion to prepare masterbatch A, with a rotation speed of 200 to 550 r / min and a temperature of 185 to 220 °C.

[0063] (1.b) Stir and dissolve the appropriate weight parts of styrene monomer and crosslinking agent at 20-50°C to prepare vulcanized liquid B, wherein the stirring speed is 10-50 r / min;

[0064] (1.c) Grafting reaction: Masterbatch A and vulcanizing liquid B are grafted and crosslinked in a twin-screw extruder to form a compatibilizer. The rotation speed in the twin-screw extruder is 300-600 r / min, and the reaction temperature is 180-215℃. The styrene-grafted polyester elastomer particles are then produced by underwater pelletizing.

[0065] 2. The preparation of the styrene-grafted polyester elastomer includes 100 parts of polyester elastomer matrix (TPC-ET), 8 parts of styrene (ST) monomer, 0.5 parts of dicumyl peroxide (DCP), 0.2 parts of antioxidant (1076) and antioxidant (9228), and 0.1 parts of TiCl4 catalyst. The polyester elastomer matrix is ​​characterized by a melt index greater than 40 g / 10 min at 220℃*2.16 kg, a weight-average molecular weight of 15,000-20,000, and a polybutylene terephthalate (PBT) content greater than 60% in the molecular chain. Due to its higher melt index and smaller molecular weight, it has greater reactivity and is more likely to undergo grafting reaction with styrene monomer.

[0066] A method for preparing an ultra-high flow polyester elastomer material includes the following steps:

[0067] (1) Mix the appropriate weight parts of polyester elastomer matrix, semi-hydrogenated SBS, plasticizer, compatibilizer, antioxidant and UV stabilizer evenly through a high-speed mixer or coloring machine at a speed of 10-500 r / min and a temperature of 20-80℃.

[0068] (2) The corresponding weight parts of crosslinking agent are injected into the screw through the pre-reserved injection hole in the 3rd to 5th section of the screw at 20 to 50°C using a peristaltic pump. This is called pump A. The speed of the peristaltic pump is 5 to 50 r / min.

[0069] (3) The appropriate material ratio is achieved by adjusting the feed rate of the loss-in-weight weigher and the speed of pump A in the twin-screw extruder. The twin-screw speed is 200-650 r / min, and the twin-screw temperature is 180-250℃. When the screw reaches a specific speed, the loss-in-weight weigher is started first, and pump A is started 1 minute later. After underwater pelleting, the ultra-high flowability special-purpose polyester dynamic vulcanized elastomer material is obtained.

[0070] In step (1), the coloring machine temperature is 25°C and the mixing speed is 100 rpm. In step (2), the crosslinking agent temperature is 20°C, the A pump speed is 17 rpm, and the weight content is 5 parts.

[0071] A method for applying the special polyester elastomer material as described in claim 1, characterized by comprising the following steps: adding the obtained polyester elastomer material particles into an injection molding machine, injecting the molten elastomer material into a simulated leather mold, removing it after cooling, placing it together with PP or other rigid skeletons into a foaming mold, injecting a foaming agent at a temperature of 50-80°C, stabilizing for 2-5 minutes, and removing the product after cooling and opening the mold.

[0072] Comparative Example 2

[0073] The raw materials of an ultra-high flow polyester elastomer material are, by weight: 100 parts polyester elastomer matrix; 4 parts hydrolyzing agent; and 5 parts antioxidant and UV resistant additives.

[0074] Wherein, the polyester elastomer is TPC-ET, the hydrolysant is a mixture of 1.5% sodium bicarbonate aqueous solution and 1,3-bis(tert-butylperoxyisopropyl)benzene in a ratio of 1:1, and the antioxidant and UV stabilizer is a mixture of 1010, UV329 and UV770 in a ratio of 1:2:1.5.

[0075] A method for preparing an ultra-high flow polyester elastomer material includes the following steps:

[0076] (1) Mix the appropriate weight parts of polyester elastomer matrix and antioxidant and UV stabilizer evenly through a high-speed mixer or coloring machine at a speed of 10-500 r / min and a temperature of 20-80℃.

[0077] (2) The corresponding weight of hydrolysate is injected into the screw through the pre-reserved injection hole in the 7th-8th section of the screw at 10-50℃ using a peristaltic pump. This pump is called pump B. The speed of the peristaltic pump is 5-50 r / min.

[0078] (3) The appropriate material ratio is achieved by adjusting the feed rate of the loss-in-weight weigher and the speed of pump B in the twin-screw extruder. The twin-screw speed is 200-650 r / min, and the twin-screw temperature is 180-250℃. When the screw reaches a specific speed, the loss-in-weight weigher is started first, and pump B is started 2 minutes later. After underwater pelleting, the ultra-high flowability special-purpose polyester dynamic vulcanized elastomer material is obtained.

[0079] In step (1), the coloring machine temperature is 25°C and the mixing speed is 100 rpm. In step (2), the hydrolysant temperature is 35°C, the B pump speed is 25 r / min, and the weight content is 4 parts.

[0080] A method for applying the ultra-high flow polyester elastomer material as described in claim 1, characterized by comprising the following steps: adding the obtained polyester elastomer material particles into an injection molding machine, injecting the molten elastomer material into a simulated leather mold, removing it after cooling, placing it together with PP or other rigid skeletons into a foaming mold at a temperature of 50-80°C, injecting a foaming agent, stabilizing for 2-5 minutes, and then opening the mold to remove the product.

[0081] Comparative Example 3

[0082] The preparation and application methods of Comparative Example 3 are the same as those of Example 1, except that the raw material content of the ultra-high flow polyester elastomer material is different, and the amount of compatibilizer is 0 parts.

[0083] Comparative Example 4

[0084] The preparation and application methods of Comparative Example 4 are the same as those of Example 1, except that the raw material content of the ultra-high flow polyester elastomer material is different. Specifically, the semi-hydrogenated SBS is 0 parts, the plasticizer is 0 parts, and the crosslinking agent is 0 parts.

[0085] Comparative Example 5

[0086] The preparation and application methods of Comparative Example 5 are the same as those of Example 1, except that the raw material content of the ultra-high flow polyester elastomer material is different, wherein the antioxidant and UV resistant additives are 0 parts.

[0087] Comparative Example 6

[0088] The preparation and application methods of Comparative Example 6 are the same as those of Example 1, except that the raw material content of the ultra-high flow polyester elastomer material is different, wherein the plasticizer is 0 parts.

[0089] Performance testing:

[0090] Tensile breaking strength was tested according to ISO 37 standard, using type 2 specimens at a tensile speed of 500 mm / min. Tear strength was tested according to ISO 34-1 standard, using right-angle tear specimens at a tensile speed of 500 mm / min. Hardness was tested according to ISO 868 standard, with a reading time of 15 seconds. Cross scratch testing was tested according to PV 3952 standard, with a weight of 10 N and a scraper head of 1 mm. Light aging was tested according to PV 1303 standard, with 5 and 10 cycles. Heat aging was tested according to ISO 188 standard, with a temperature of 120℃ and times of 252 and 504 hours, including changes in hardness, tensile strength, and elongation at break. Melt flow index was tested according to ISO 1133-1 standard, with a test condition of 220℃ and a weight of 2.16 kg. Adhesion testing used dyne values, with higher dyne values ​​indicating better adhesion. Four samples were tested, and the average value was taken. The performance test results of Examples 1-12 are shown in Table 2.

[0091] Table 2 Performance test results of Examples 1-12

[0092]

[0093]

[0094] The performance test results of Comparative Examples 1 to 6 are shown in Table 3.

[0095] Table 3 Performance test results of Comparative Examples 1-6

[0096]

[0097] The performance comparisons of Examples 1-4 and Comparative Examples 4 and 6 show that the present invention increases the scratch resistance, light resistance, and temperature resistance of the material by adding semi-hydrogenated SBS and plasticizer. However, adding too much will affect the dyne value of the treated material, thus affecting the adhesive and foaming agent effect. The performance comparisons of Examples 1, 5, and 6 and Comparative Example 3 show that the addition of compatibilizer improves the mechanical properties and scratch resistance of the material. However, as the amount of compatibilizer continues to increase, the improvement effect becomes less significant. The performance comparisons of Examples 1, 7, and 8 and Comparative Example 2 show that the addition of crosslinking agent significantly improves... The material exhibits good scratch resistance, light resistance, and temperature resistance. However, the increased crosslinking agent significantly affects the material's flowability, increasing the difficulty of molding. A comparison of the performance of Examples 1, 9, 10, and Comparative Example 1 shows that the hydrolysant can significantly increase the material's flowability and improve its processing characteristics. However, excessive addition of the hydrolysant leads to a significant decrease in the material's mechanical properties and temperature resistance. A comparison of the performance of Examples 1, 11, 12, and Comparative Example 5 shows that antioxidants and UV stabilizers improve the material's temperature and light resistance; however, excessive amounts do not significantly improve the effect and increase the risk of material exudation. Under dynamic vulcanization and dynamic hydrolysis processes, the synergistic effect of raw materials and processes enhances the system's mechanical properties, temperature and weather resistance, and significantly improves scratch resistance and the performance of the adhesive foaming agent. The prepared elastomer material exhibits excellent thin-wall molding properties.

[0098] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention. The scope of protection claimed by the appended claims and their equivalents is defined.

Claims

1. A high-flowability polyester elastomer material, characterized in that: The raw materials, by weight, include: 100 parts polyester elastomer matrix; 10-50 parts semi-hydrogenated SBS; 5-30 parts plasticizer; 2-20 parts compatibilizer; 2-15 parts crosslinking agent; 1-10 parts hydrolysate; 0.5-5 parts antioxidant and UV resistant additives; wherein the plasticizer is ultra-high viscosity paraffin oil, and the kinematic viscosity of the paraffin oil at 40°C is not less than 80 mmHg. 2 / s, flash point not less than 270℃, CP value greater than 65%; the hydrolysant is selected from one or more of water, sodium bicarbonate 1-20% aqueous solution, sodium hydroxide 0.1-5% aqueous solution, potassium hydroxide 0.1-5% aqueous solution, and sodium carbonate 1-20% aqueous solution; the compatibilizer is styrene-grafted polyester elastomer, the preparation of which includes: 100 parts of raw material polyester elastomer, 2-15 parts of styrene monomer, 0.25-1 parts of dicumyl peroxide DCP, 0.01-0.03 parts of antioxidant 1076 and 0.01-0.03 parts of antioxidant 9228, and 0.01-0.1 parts of TiCl4 catalyst.

2. The ultra-high flowability polyester elastomer material according to claim 1, characterized in that: The polyester elastomer is selected from one or more of TPC-EE, TPC-ES, and TPC-ET.

3. The ultra-high flowability polyester elastomer material according to claim 1, characterized in that: The semi-hydrogenated SBS has a styrene to butadiene ratio of 0.2-0.7 and an unsaturation degree of 2-6%.

4. The ultra-high flowability polyester elastomer material according to claim 1, characterized in that: The crosslinking agent is selected from one or more of 1,2-polybutadiene, dicumyl peroxide, triallyl isocyanurate, benzoyl peroxide, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 1,3-bis(tert-butylperoxyisopropyl)benzene, triallyl cyanurate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, zinc dimethacrylate, N,N′-p-phenylbismaleimide, and zinc diacrylate.

5. The ultra-high flowability polyester elastomer material according to claim 1, characterized in that: The antioxidant and UV-resistant additives are selected from one or more of 1010, 1076, 1330, 1024, 168, 626, DLTDP, UV531, UV326, UV328, UV329, UV234, UV770, UV944, and UV622.

6. A high-flowability polyester elastomer material according to any one of claims 1-5, characterized in that: Its raw materials, by weight, include: 100 parts polyester elastomer matrix; 20 parts semi-hydrogenated SBS; 15 parts plasticizer; 10 parts compatibilizer; 5 parts crosslinking agent; 4 parts hydrolysate and 5 parts antioxidant and UV resistant additives.

7. The method for preparing the ultra-high flowability polyester elastomer material according to any one of claims 1-5, characterized in that: It includes the following steps: S100: Mix the appropriate weight parts of polyester elastomer matrix, semi-hydrogenated SBS, plasticizer, compatibilizer, antioxidant and UV stabilizer evenly using a high-speed mixer or coloring machine. S200. The corresponding weight parts of crosslinking agent are injected through the pre-reserved injection holes in the 3rd to 5th sections of the screw using a peristaltic pump, which is called pump A. S300. The corresponding weight of hydrolysate is injected into the screw through the pre-reserved injection hole in section 7-8 using a peristaltic pump, which is called pump B.

8. The method for preparing the ultra-high flowability polyester elastomer material according to claim 7, characterized in that: The process also includes step S400, which involves adjusting the feed rate of the twin-screw extruder's loss-in-weight weigher and the rotation speeds of pumps A and B to achieve the appropriate material ratio. The twin-screw speed is 200-650 r / min, and the twin-screw temperature is 180-250℃. When the screws reach a specific speed, the loss-in-weight weigher is activated first, followed by pump A after 1 minute, and pump B after 2 minutes. The ultra-high flow polyester elastomer material is obtained through underwater pelletizing.

9. The method for preparing the ultra-high flowability polyester elastomer material according to claim 7, characterized in that: In step S100, the coloring machine temperature is 20~80℃ and the mixing speed is 10~500r / min. In step S200, the crosslinking agent temperature is 20~50℃ and the A pump speed is 5~50r / min. In step S300, the hydrolysate temperature is 10~50℃ and the B pump speed is 5~50r / min.

10. The method for preparing the ultra-high flowability polyester elastomer material according to claim 7, characterized in that: The polyester elastomer in step S100 is selected from one or more of TPC-EE, TPC-ES, and TPC-ET; the plasticizer is ultra-high viscosity paraffin oil, and the kinematic viscosity of the paraffin oil at 40°C is not less than 80 mmHg. 2 / s, flash point not less than 270℃, CP value greater than 65%; the semi-hydrogenated SBS has a styrene to butadiene ratio of 0.2-0.7 and an unsaturation degree of 2-6%.

11. The method for preparing the ultra-high flowability polyester elastomer material according to claim 7, characterized in that: The crosslinking agent content in step S200 is 5 parts by weight, and the hydrolysant content in step S300 is 4 parts by weight.

12. The method for preparing the ultra-high flowability polyester elastomer material according to claim 7, characterized in that: The preparation steps of the styrene-grafted polyester elastomer include: S510 produces masterbatch A by granulating polyester elastomer matrix, antioxidant, and catalyst in corresponding weight parts through twin-screw extrusion at a speed of 200~550 r / min and a temperature of 185~220℃. S520 involves dissolving styrene monomer and crosslinking agent in appropriate weight proportions at 20~50℃ to prepare vulcanized liquid B, wherein the stirring speed is 10~50 r / min; The S530 grafting reaction involves grafting and crosslinking masterbatch A and vulcanizing liquid B in a twin-screw extruder to produce a compatibilizer. The rotation speed in the twin-screw extruder is 300~600 r / min, and the reaction temperature is 180~215℃. The product is then processed into styrene-grafted polyester elastomer particles by underwater pelletizing.

13. A method for applying the ultra-high flow polyester elastomer material as described in any one of claims 1-5, characterized in that, The process includes the following steps: adding the obtained polyester elastomer material particles into an injection molding machine, injecting the molten elastomer material into a simulated leather mold, removing it after cooling, and placing it together with PP or other rigid skeletons into a foaming mold at a temperature of 50~80℃, injecting foaming agent, stabilizing for 2~5 minutes, and opening the mold to remove the product after cooling.

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