High-weather-resistance thin-wall polyester elastomer composite material and preparation method thereof

Abstract

The invention discloses a high-weather-resistance thin-wall polyester elastomer composite material and a preparation method thereof, and belongs to the technical field of polymer composite materials. The high-weather-resistance thin-wall polyester elastomer composite material comprises the following raw materials in parts by mass: 80-95 parts of TPEE resin; 5-20 parts of a plasticizer; 1 part of a lubricant; 1-5 parts of an efficient weather-resistant agent; the high-efficiency weather-resistant agent comprises a COFs material serving as a carrier, an antioxidant, an auxiliary antioxidant, a light absorber and a light stabilizer, wherein the high-efficiency weather-resistant agent comprises a COFs material with an adsorption function, an antioxidant and a light stabilizer, the COFs material has high porosity, high specific surface area and a micro-mesoporous structure, and after the antioxidant and the light stabilizer are introduced, adsorption is performed, the addition amount of the antioxidant and the light stabilizer is increased, precipitation of an auxiliary system is effectively prevented, and the weather resistance of the TPEE resin is effectively improved.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer composite materials, and in particular relates to a highly weather-resistant thin-wall polyester elastomer composite material and a preparation method thereof. Background Art

[0002] Polyester elastomer (TPEE) has the characteristics of high strength, high hardness, high modulus and high elongation, as well as good oil resistance, low temperature resistance and wear resistance. It can be used as fiber, plastic, rubber and other aspects, and has a wide range of applications. Although TPEE has many excellent properties in practical applications, its weather resistance is poor, especially thin-walled TPEE resin is exposed to ultraviolet light and high temperature for a long time, and the material is prone to cracking, discoloration and other problems. Usually, in order to improve the weather resistance of TPEE materials, a large amount of black masterbatch, antioxidants, light absorbers, stabilizers, etc. are often added. However, the addition of black masterbatch will affect the color matching of the product, and the color is single, and the addition of a large amount of additives is often accompanied by the problem of additive precipitation, which will bring problems with the appearance of the material and affect the role of the additives in weather resistance. Therefore, it is of great significance to develop a highly weather-resistant thin-walled polyester elastomer composite material. Summary of the invention

[0003] In view of the deficiencies in the prior art, the purpose of the present invention is to provide a highly weather-resistant thin-wall polyester elastomer composite material and a preparation method thereof, thereby solving the problems in the prior art.

[0004] The purpose of the present invention can be achieved through the following technical solutions:

[0005] A polyester elastomer composite material comprises the following raw materials in parts by weight:

[0006]

[0007]

[0008] The high-efficiency weathering agent includes: a COFs material serving as a carrier, an antioxidant, an auxiliary antioxidant, a light absorber and a light stabilizer.

[0009] Furthermore, the mass ratio of the COFs material, antioxidant, auxiliary antioxidant, light absorber and light stabilizer is 2:1:1:1:1.

[0010] Furthermore, the synthesis steps of the COFs material are:

[0011] 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene and n-butanol are mixed evenly, and acetic acid is added; then vacuuming and heating are performed for reaction, and then the mixture is cooled to room temperature and filtered to obtain a COFs product.

[0012] Furthermore, the mass ratio of the 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol and acetic acid is 67:79:3:2:60.

[0013] Furthermore, the antioxidant is a hindered phenol antioxidant, the auxiliary antioxidant is a phosphite antioxidant, the light absorber is a benzotriazole light absorber, and the light stabilizer is a hindered amine light stabilizer.

[0014] Furthermore, the TPEE resin is a polyester-type thermoplastic polyester elastomer.

[0015] Furthermore, the plasticizer is No. 50 white oil.

[0016] Furthermore, the lubricant is at least one of silicone, polyethylene wax, calcium stearate, zinc stearate, and ethylene bisstearamide.

[0017] The above-mentioned method for preparing a polyester elastomer composite material comprises the following steps:

[0018] The TPEE resin, plasticizer, lubricant and high-efficiency weathering agent are mixed and stirred at a speed of 500 r / min for 10 minutes to obtain a mixture; the mixture is put into a parallel twin-screw extruder for melting, extrusion granulation, and thin-wall injection molding to obtain a polyester elastomer composite material;

[0019] The barrel temperature of the parallel twin-screw extruder is 180-240°C, the screw speed is 500r / min, the melt pressure is 1.0MPa, the vacuum degree is -0.06MPa, the barrel temperature of the injection molding machine is 230°C, and the mold temperature is 50°C.

[0020] The above-mentioned polyester elastomer composite material is used in the preparation of automobile interior decoration.

[0021] Beneficial effects of the present invention:

[0022] 1. The highly weather-resistant thin-wall polyester elastomer composite material prepared by the present invention can be recycled and reused, meeting the development needs of green and recycled materials for automobiles.

[0023] 2. The highly weather-resistant thin-wall polyester elastomer composite material prepared by the present invention, wherein the high-efficiency weather-resistant agent is compounded by a COFs material with an adsorption function, an antioxidant, and a light stabilizer. When the antioxidant, light stabilizer and other additives are added to the TPEE resin at the same time as the COFs material, the high-content additives are well dispersed in the TPEE resin under the adsorption effect of the COFs material. At the same time, due to the strong adsorption effect of the COFs material on the additive, the precipitation of the additive can be effectively prevented, thereby improving the weather resistance of the TPEE resin.

[0024] 3. The preparation process of the present invention is simple and can be mass-produced. The injection-molded thin-walled products have high weather resistance.

[0025] 4. The COFs material prepared by the present invention is a porous crystalline polymer material formed by light elements such as carbon, nitrogen, hydrogen, and oxygen being combined together by covalent bonds. The main components include 2,5-dimethylterephthaloylhydrazide and (4-formylbenzene)-1,3,5-triazine, which have a certain polarity. Therefore, the COFs material is endowed with good compatibility with polar TPEE, and according to similar compatibility, it has good dispersion and distribution in TPEE resin. At the same time, the COFs material has a porous structure, low density, high specific surface area, and high porosity, and has a good adsorption effect on weather-resistant additives, plays a certain bridge overlapping role, and can effectively prevent the precipitation of additives, thereby preparing a highly weather-resistant thin-walled polyester elastomer composite material. DETAILED DESCRIPTION

[0026] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solution of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] A highly weather-resistant thin-wall polyester elastomer composite material comprises the following raw materials in parts by weight:

[0028]

[0029] Among them, the thickness of the high weather-resistant thin-wall polyester elastomer composite material is 1.0 mm.

[0030] TPEE resin is a polyester-type thermoplastic polyester elastomer.

[0031] The plasticizer is No. 50 white oil.

[0032] The lubricant is at least one of silicone, polyethylene wax, calcium stearate, zinc stearate, and ethylene bisstearamide.

[0033] The high-efficiency weathering agent includes a COFs material acting as a carrier, an antioxidant, an auxiliary antioxidant, a light absorber and a light stabilizer, with a mass ratio of 2:1:1:1:1.

[0034] The synthesis steps of COFs materials are as follows:

[0035] Weigh 2,5-dimethylterephthaloyl hydrazide and (4-formylphenyl)-1,3,5-triazine in a glass bottle, then add o-dichlorobenzene and n-butanol, mix well, and drop 6 mol / L acetic acid. Then evacuate, react at 120°C for 72 hours, then slowly cool to room temperature, filter and obtain COFs product;

[0036] Among them, the mass ratio of 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol and acetic acid is 67:79:3:2:60.

[0037] The antioxidant is a hindered phenol antioxidant, such as Irganox 565, RIANOX 330;

[0038] The auxiliary antioxidant is a phosphite antioxidant, such as AN 168, PEP-36;

[0039] The light absorber is a benzotriazole light absorber, such as Chiguard 5050, UV-P;

[0040] Light stabilizer is a type of hindered amine light stabilizer, such as LA-52, RIASORB UV-944;

[0041] The following examples are used to specifically illustrate the preparation process of a highly weather-resistant thin-wall polyester elastomer composite material (the parts in Examples 1-5 and Comparative Example 1 are all parts by mass);

[0042] The raw materials used in Examples 1-5 and Comparative Example 1 are as follows:

[0043] TPEE resin is a polyether polyester elastic, brand KYLflex L2520, melt index is 18g / 10min, manufacturer: Jiangsu Keyile New Materials Co., Ltd.

[0044] The plasticizer is No. 50 white oil, brand No. 50 industrial white oil, manufacturer: Hengshui Diyi Petrochemical Co., Ltd.

[0045] The lubricant is silicone masterbatch, brand MB50-002, manufacturer: Dow Corning, USA;

[0046] The main antioxidant brand is Irganox 565, manufacturer: BASF, Germany;

[0047] Auxiliary antioxidant brand AN 168, manufacturer: Qingdao Deda Special Chemical Group;

[0048] Light absorber brand Chiguard 5050, manufacturer: Chiguard Co., Ltd.;

[0049] Light stabilizer brand LA-52, manufacturer: Aidico (China) Investment Co., Ltd.

[0050] Example 1

[0051] S1, weigh 6.7 mg of 2,5-dimethylterephthaloyl hydrazide and 7.9 mg of (4-formylphenyl)-1,3,5-triazine into a glass bottle, then add 0.3 mg of o-dichlorobenzene and 0.2 mg of n-butanol, mix well, and add 6 mg of 6 mol / L acetic acid dropwise.

[0052] Then, the mixture was vacuumed and reacted at a constant temperature of 120°C for 72 hours, then slowly cooled to room temperature, centrifuged and filtered to obtain the COFs product, which was a light yellow powder. Then, the COFs material, antioxidant Irganox 565, auxiliary antioxidant AN 168, light absorber Chiguard 5050 and light stabilizer LA-52 were physically mixed in a mass ratio of 2:1:1:1:1 to obtain a high-efficiency weathering agent.

[0053] S2, 80 parts of TPEE resin, 20 parts of No. 50 white oil, 1 part of silicone masterbatch and 1 part of weathering agent were mixed, and stirred at a speed of 500 r / min for 10 minutes using a high-speed mixer to obtain a uniformly mixed material.

[0054] S3, putting the uniformly mixed materials into a parallel twin-screw extruder for melting, extrusion and granulation to obtain a TPEE composite material; wherein the barrel temperature of the parallel twin-screw extruder is 180-240°C, the screw speed is 500r / min, the melt pressure is 1.0MPa, and the vacuum degree is -0.06MPa.

[0055] S4, the extruded TPEE composite material is put into an injection molding machine for melting and injection molding of a skin with a thickness of 1 mm to obtain a thin-walled polyester elastomer composite material. The barrel temperature of the injection molding machine is 230°C and the mold temperature is 50°C.

[0056] Example 2

[0057] S1: the same as S1 in Example 1;

[0058] S2, 80 parts of TPEE resin, 20 parts of No. 50 white oil, 1 part of silicone masterbatch and 3 parts of weathering agent were mixed, and stirred at a speed of 500 r / min for 10 minutes using a high-speed mixer to obtain a uniformly mixed material.

[0059] S3, the same as S3 in Example 1;

[0060] S4, the same as S4 in Example 1;

[0061] Example 3

[0062] S1: the same as S1 in Example 1;

[0063] S2, 80 parts of TPEE resin, 20 parts of No. 50 white oil, 1 part of silicone masterbatch and 5 parts of weathering agent were mixed, and stirred at a speed of 500 r / min for 10 minutes using a high-speed mixer to obtain a uniformly mixed material.

[0064] S3, the same as S3 in Example 1;

[0065] S4, the same as S4 in Example 1;

[0066] Example 4

[0067] S1: the same as S1 in Example 1;

[0068] S2, 90 parts of TPEE resin, 10 parts of No. 50 white oil, 1 part of silicone masterbatch and 3 parts of weathering agent were mixed, and stirred at a speed of 500 r / min for 10 minutes using a high-speed mixer to obtain a uniformly mixed material.

[0069] S3, the same as S3 in Example 1;

[0070] S4, the same as S4 in Example 1;

[0071] Example 5

[0072] S1: the same as S1 in Example 1;

[0073] S2, 80 parts of TPEE resin, 5 parts of No. 50 white oil, 1 part of silicone masterbatch and 3 parts of weathering agent were mixed, and stirred at a speed of 500 r / min for 10 minutes using a high-speed mixer to obtain a uniformly mixed material.

[0074] S3, the same as S3 in Example 1;

[0075] S4, the same as S4 in Example 1;

[0076] Comparative Example 1

[0077] S1: the same as S1 in Example 1;

[0078] S2, 80 parts of TPEE resin, 20 parts of No. 50 white oil and 1 part of silicone masterbatch were mixed, and stirred at a speed of 500 r / min for 10 minutes using a high-speed mixer to obtain a uniformly mixed material.

[0079] S3, the same as S3 in Example 1;

[0080] S4, the same as S4 in Example 1;

[0081] The addition amount (parts by mass) of each component in Examples 1-5 and Comparative Examples is shown in Table 1;

[0082] Table 1 不 Effect of weathering agent with the same content on the weathering properties of TPEE

[0083]

[0084]

[0085] The highly weather-resistant thin-wall polyester elastomer composite materials prepared in Examples 1 to 5 and Comparative Example 1 were subjected to light aging and thermal oxidation aging tests. The light aging test was based on the accelerated aging test of Geely Automobile Interior for 650 hours, and the specific standard was SAEJ1885:2005. The thermal oxidation aging was based on the accelerated aging test at 120°C for 500 hours. The samples before and after treatment were tested for tensile strength, elongation at break, and visual observation of product appearance according to ISO standards, and color difference tests were performed on a colorimeter. The test results are shown in Table 2.

[0086] Table 2 Effect of different contents of weathering agent on the weathering performance of TPEE

[0087]

[0088]

[0089] From the test results of comparative example 1, it can be seen that the tensile strength and elongation at break of the formula without high-efficiency weathering agent significantly decreased after light aging treatment for 650 or heat aging treatment, and after light aging treatment, there were obvious cracks on the surface of the material, indicating that the TPEE material has poor weather resistance. The test results of Examples 1 to 5 show that the addition of high-efficiency weathering agent can significantly improve the weather resistance of TPEE composite materials and has little effect on the mechanical properties of the products.

[0090] In the description of this specification, the description with reference to the terms "one embodiment", "example", "specific example", etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representation of the above terms does not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner.

[0091] The above shows and describes 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, and the above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the scope of the present invention to be protected.

Claims

1. A polyester elastomer composite material, characterized in that: Including the following raw materials by weight: The high-efficiency weathering agent includes: a COFs material serving as a carrier, an antioxidant, an auxiliary antioxidant, a light absorber and a light stabilizer.

2. A polyester elastomer composite material according to claim 1, characterized in that: The mass ratio of the COFs material, antioxidant, auxiliary antioxidant, light absorber and light stabilizer is 2:1:1:1:

1.

3. A polyester elastomer composite material according to claim 1 or 2, characterized in that: The synthesis steps of the COFs material are: 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene and n-butanol are mixed evenly, and acetic acid is added; then vacuuming and heating are performed for reaction, and then the mixture is cooled to room temperature and filtered to obtain a COFs product.

4. A polyester elastomer composite material according to claim 3, characterized in that: The mass ratio of the 2,5-dimethylterephthaloyl hydrazide, (4-formylphenyl)-1,3,5-triazine, o-dichlorobenzene, n-butanol and acetic acid is 67:79:3:2:

60.

5. A polyester elastomer composite material according to claim 1 or 2, characterized in that: The antioxidant is a hindered phenol antioxidant, the auxiliary antioxidant is a phosphite antioxidant, the light absorber is a benzotriazole light absorber, and the light stabilizer is a hindered amine light stabilizer.

6. The polyester elastomer composite material according to claim 1, characterized in that: The TPEE resin is a polyester-type thermoplastic polyester elastomer.

7. The polyester elastomer composite material according to claim 1, characterized in that: The plasticizer is No. 50 white oil.

8. The polyester elastomer composite material according to claim 1, characterized in that: The lubricant is at least one of silicone, polyethylene wax, calcium stearate, zinc stearate, and ethylene bisstearamide.

9. The method for preparing a polyester elastomer composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: The TPEE resin, plasticizer, lubricant and high-efficiency weathering agent are mixed and stirred at a speed of 500 r / min for 10 minutes to obtain a mixture; the mixture is put into a parallel twin-screw extruder for melting, extrusion granulation, and thin-wall injection molding to obtain a polyester elastomer composite material; The barrel temperature of the parallel twin-screw extruder is 180-240°C, the screw speed is 500r / min, the melt pressure is 1.0MPa, the vacuum degree is -0.06MPa, the barrel temperature of the molding machine is 230°C, and the mold temperature is 50°C.

10. Use of the polyester elastomer composite material according to any one of claims 1 to 8 in the preparation of automobile interior decoration.

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