Aging-resistant composite material for automobiles and method for preparing the same

Abstract

The application relates to an anti-aging composite material for automobiles and a preparation method thereof, and belongs to the technical field of high polymer composite materials. The composite material comprises the following components: 100 parts of PP master batch, 9-13 parts of POE toughening resin, 28-34 parts of talcum powder, 0.9-1.2 parts of a coupling agent, 1-1.5 parts of a lubricant and 0.25-0.35 parts of an anti-aging auxiliary agent; wherein the anti-aging auxiliary agent has a branched molecular structure and is not prone to migration and segregation, plays a stable antioxidant role, the hindered amine structure at the molecular end has excellent scavenging effect on free radicals generated by light and heat initiation, hinders the aggregation of free radicals in the early aging stage, the thioether structure in the molecular structure has a decomposition effect on peroxides, hinders the chain transfer in the aging process, and in the test, compared with an existing compound antioxidant system, the composite material shows high anti-thermal-oxidative aging capacity and initial mechanical strength and toughness.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of high polymer composite materials, and particularly relates to an anti-aging composite material for automobiles and a preparation method thereof. BACKGROUND

[0002] Polypropylene (PP) is a polymer formed by polyaddition of propylene, and has low density, low price, good chemical resistance, easy molding processing and convenient recycling, so that the composite material taking polypropylene as a matrix has become an indispensable general plastic in the plastic industry. With the development of lightweight automobiles, the use amount of polypropylene material in automobiles is increasing.

[0003] Although polypropylene has many advantages, there is a common thermal-oxidative aging problem in the application of automobile materials, especially the parts in the engine compartment. During the starting process of the automobile, the internal temperature of the engine cover can reach about 90℃, which accelerates the aging of polypropylene, and the macroscopic performance is that the material whitens, hardens and becomes brittle. Under the vibration and bumpy road conditions of the automobile itself, the parts are prone to damage, causing abnormal noise in the engine compartment, and even directly affecting the normal driving of the automobile. To solve the aging problem of polypropylene, the most economical and effective technical means is to add an anti-aging agent to the polypropylene matrix to slow down the thermal-oxidative aging of polypropylene. With the in-depth study of the aging behavior of polypropylene, the types of anti-aging agents are increasing. Among them, the anti-aging effect of the compound system of antioxidant 1010 and antioxidant 168 is the most widely used, but its anti-aging effect is limited, and generally more polypropylene material parts need to be replaced during the service cycle of the automobile. Therefore, the application aims to disclose an anti-aging composite material based on polypropylene. SUMMARY

[0004] In order to solve the technical problems mentioned in the background art, the purpose of the application is to provide an anti-aging composite material for automobiles and a preparation method thereof.

[0005] The purpose of the application can be achieved by the following technical solutions.

[0006] An anti-aging composite material for automobiles comprises, by weight:

[0007] PP master batch 100 parts, POE toughening resin 9-13 parts, talcum powder 28-34 parts, coupling agent 0.9-1.2 parts, lubricant 1-1.5 parts and anti-aging auxiliary agent 0.25-0.35 parts.

[0008] The anti-aging auxiliary agent is prepared by the following method:

[0009] Step A1: uniformly mix triallylamine, beta-mercapto propionic acid, azobisisobutyronitrile and benzene, protect with nitrogen, heat to 55-65℃, apply mechanical stirring at 300-400 rpm, and assist with 280-360 W / m 2Ultraviolet irradiation, constant temperature stirring irradiation reaction 1.2-1.6h, reaction end add a little acetone mixing, reduced pressure rotary evaporation to remove with benzene as the main low boiling point, get intermediate;

[0010] Further, the amount ratio of triallylamine, β-mercaptopropionic acid, azobisisobutyronitrile and benzene is 0.1mol:0.3mol:0.25-0.3g:80-100mL, under the initiation of azobisisobutyronitrile and ultraviolet irradiation, β-mercaptopropionic acid and triallylamine click reaction, the specific reaction process can be expressed as follows:

[0011]

[0012] Step A2: mix the intermediate, thionyl chloride and dimethyl sulfoxide, heat to 50-60℃, apply 120-180rpm mechanical stirring, constant temperature stirring reaction 2-3h, then reduce pressure rotary evaporation to remove excess thionyl chloride, cool to room temperature, add triethylamine mixing, apply 20-28kHz ultrasonic oscillation, slowly add tetramethylpiperidinamine, control the total addition reaction time is 40-50min, reaction end reduce pressure rotary evaporation to remove with dimethyl sulfoxide as the main low boiling point, get anti-aging auxiliary agent;

[0013] Further, the amount ratio of intermediate, tetramethylpiperidinamine, thionyl chloride, triethylamine and dimethyl sulfoxide is 0.1mol:0.3mol:40-50mL:15-22mL:180-240mL, thionyl chloride first reacts with carboxyl in the molecular structure of the intermediate, acyl chloride treatment is carried out on the intermediate, then amide reaction is carried out with the primary amine in tetramethylpiperidinamine, introduce branched hindered amine structure modification, the specific reaction process can be expressed as follows:

[0014]

[0015] Further, the fineness of talc powder is not less than 2000 mesh.

[0016] Further, the coupling agent is silane coupling agent KH-550.

[0017] Further, the lubricant is polypropylene wax.

[0018] A preparation method of an anti-aging composite material for automobile, comprising the following steps:

[0019] Step S1: talc powder is added to a high-speed mixer and preheated to 100℃, high-speed stirring is applied at 1200-1500rpm, the coupling agent is uniformly added and mixed for 20min, and then the remaining raw materials are added and mixed for 2h at 80-120rpm to obtain a batch;

[0020] Step S2: The batch is added into a torque rheometer, and melt blended at 190±5 DEG C under nitrogen protection until the torque is stable, and then the material is discharged, cooled and crushed to obtain the anti-aging composite material for automobiles.

[0021] Advantages of the present application:

[0022] The application discloses a polypropylene-based composite material, which is reinforced and toughened by POE and talcum powder, and has excellent anti-aging performance by compounding a self-prepared anti-aging auxiliary agent. The anti-aging auxiliary agent is obtained by click addition of beta-mercaptopropionic acid and triallylamine to form an intermediate with a branched end carboxyl group, acyl chloride treatment of the intermediate by thionyl chloride, and substitution reaction of the intermediate with tetramethylpiperidylamine to introduce a branched hindered amine structure. The molecular structure of the anti-aging auxiliary agent is three-branched, and a large number of carbon chains are contained in the molecule, so that the anti-aging auxiliary agent has good compatibility with polypropylene. The branched structure makes the anti-aging auxiliary agent not easy to migrate and segregate during solidification, and plays a stable anti-oxidation role. The hindered amine structure at the end of the anti-aging auxiliary agent molecule has excellent scavenging effect on free radicals generated by light and heat, hinders the aggregation of free radicals in the early stage of aging, and the thioether structure in the molecular structure has a decomposition effect on peroxides, hinders the chain transfer in the aging process, and has high anti-thermal-oxidative aging capacity compared with existing compounded antioxidants in tests. In addition, the amide structure in the anti-aging auxiliary agent molecule has an inducing effect on the beta-phase crystallization of polypropylene, so that the polypropylene material has good initial mechanical properties. The polypropylene composite material using the anti-aging auxiliary agent has more excellent strength and toughness. DETAILED DESCRIPTION

[0023] The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the scope of protection of the present application.

[0024] Embodiment 1

[0025] The anti-aging composite material for automobiles is prepared in the embodiment, and the specific implementation process is as follows:

[0026] 1) Preparation of anti-aging auxiliary agent

[0027] 1.1, triallylamine, beta-mercaptopropionic acid, azobisisobutyronitrile and benzene are taken and uniformly mixed, nitrogen is introduced for protection, the temperature is increased to 65 DEG C, 400 rpm mechanical stirring is applied, and 360 W / m 2UV irradiation, constant temperature stirring irradiation reaction 1.2h, in the reaction, the amount ratio of triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene is 0.1mol:0.3mol:0.3g:100mL, after the reaction, 10wt% of the reaction substrate is mixed with acetone, the low boiling point substance mainly composed of benzene is removed by rotary evaporation under reduced pressure, and the intermediate is obtained.

[0028] 1.2, the intermediate, thionyl chloride and dimethyl sulfoxide are mixed and heated to 60℃, and mechanical stirring is applied at 180rpm. The constant temperature stirring reaction is carried out for 2h, then the excess thionyl chloride is removed by rotary evaporation under reduced pressure, the temperature is lowered to room temperature, triethylamine is added and mixed, ultrasonic oscillation is applied at 28kHz, and tetramethylpiperidylamine is slowly added within 20min, and the total reaction time is controlled to be 40min. In the reaction, the amount ratio of the intermediate, tetramethylpiperidylamine, thionyl chloride, triethylamine and dimethyl sulfoxide is 0.1mol:0.3mol:50mL:22mL:240mL. After the reaction, the low boiling point substance mainly composed of dimethyl sulfoxide is removed by rotary evaporation under reduced pressure, and the antioxidant aid is obtained.

[0029] 2) Preparation of composite material

[0030] 2.1, according to the weight ratio, the raw materials are taken:

[0031] PP master batch 100 parts, all of which are EPR30R provided by Dushanzi Petrochemical Company;

[0032] POE toughening resin 9 parts, all of which are type 8015 provided by Dongguan Yinxin Plastic Raw Material Co., Ltd.;

[0033] Talc powder 34 parts, all of which are ultrafine powder with fineness of 2000 mesh and 3000 mesh compounded according to mass ratio of 2:1, provided by Quanzhou Xufeng Powder Raw Material Co., Ltd.;

[0034] Coupling agent 1.2 parts, all of which are silane coupling agent KH-550 provided by Shanghai Kaijin Chemical Co., Ltd.;

[0035] Lubricant 1.3 parts, all of which are polypropylene wax type 1000 provided by Jiangsu Fali Wax Co., Ltd.;

[0036] Antioxidant aid 0.25 parts, prepared in this embodiment.

[0037] 2.2, the talc powder is added to the high-speed mixer and preheated to 100℃, and high-speed stirring is applied at 1500rpm. The coupling agent is uniformly added and mixed for 20min, and then the remaining raw materials are added and mixed at 120rpm for 2h, and the batch material is obtained.

[0038] 2.3, the prepared compound is added into a torque rheometer, and melt blending is carried out under nitrogen protection at 190±5℃ until the torque is stable, and then the material is discharged, cooled and crushed to obtain the anti-aging composite material for automobiles.

[0039] Example 2

[0040] The anti-aging composite material for automobiles is prepared, and the specific implementation process is as follows:

[0041] 1) Preparation of anti-aging auxiliary agent

[0042] 1.1, triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene are uniformly mixed, nitrogen protection is carried out, the temperature is raised to 55℃, 300rpm mechanical stirring is applied, and 280W / m 2 ultraviolet irradiation, constant temperature stirring and irradiation reaction are carried out for 1.6h, in the reaction, the amount ratio of triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene is 0.1mol:0.3mol:0.25g:80mL, 10wt% of the reaction substrate is added after the reaction, and the low boiling point substance mainly composed of benzene is removed by rotary evaporation under reduced pressure to obtain the intermediate.

[0043] 1.2, the intermediate, thionyl chloride and dimethyl sulfoxide are uniformly mixed, the temperature is raised to 50℃, 120rpm mechanical stirring is applied, constant temperature stirring reaction is carried out for 3h, then the excess thionyl chloride is removed by rotary evaporation under reduced pressure, the temperature is lowered to room temperature, triethylamine is added and uniformly mixed, 20kHz ultrasonic oscillation is applied, and tetramethylpiperidamine is slowly added within 30min, the total reaction time is controlled to be 50min, in the reaction, the amount ratio of the intermediate, tetramethylpiperidamine, thionyl chloride, triethylamine and dimethyl sulfoxide is 0.1mol:0.3mol:40mL:15mL:180mL, after the reaction, the low boiling point substance mainly composed of dimethyl sulfoxide is removed by rotary evaporation under reduced pressure to obtain the anti-aging auxiliary agent.

[0044] 2) Preparation of composite material

[0045] 2.1, the raw materials are weighed and taken according to the weight ratio:

[0046] PP master batch 100 parts, POE toughening resin 11 parts, talc 28 parts, coupling agent 0.9 parts, lubricant 1 part and the anti-aging auxiliary agent prepared in this example 0.35 parts;

[0047] 2.2, the talc is added into a high-speed mixer and preheated to 100℃, 1200rpm high-speed stirring is applied, the coupling agent is added at a uniform speed and mixed for 20min, and then the remaining raw materials are added and mixed at 80rpm for 2h to obtain the compound;

[0048] 2.3, the prepared compound is added into a torque rheometer, and melt blending is carried out under nitrogen protection at 190±5℃ until the torque is stable, and then the material is discharged, cooled and crushed to obtain the anti-aging composite material for automobiles.

[0049] Example 3

[0050] This example prepares an anti-aging composite material for automobiles, and the specific implementation process is as follows:

[0051] 1) Preparation of anti-aging auxiliary

[0052] 1.1, take triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene, mix uniformly, protect with nitrogen, heat to 60℃, apply 360 rpm mechanical stirring, assist with 320 W / m 2 ultraviolet irradiation, constant temperature stirring irradiation reaction for 1.5h, in the reaction, the amount ratio of triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene is 0.1 mol:0.3 mol:0.28 g:90 mL, after the reaction, add 10 wt% of the reaction substrate to the mixture, remove the low boiling point substance mainly with benzene by rotary evaporation under reduced pressure, and obtain the intermediate.

[0053] 1.2, take the intermediate, thionyl chloride and dimethyl sulfoxide, mix uniformly, heat to 55℃, apply 180 rpm mechanical stirring, constant temperature stirring reaction for 2.5h, then remove the excess thionyl chloride by rotary evaporation under reduced pressure, cool to room temperature, mix uniformly with triethylamine, apply 28 kHz ultrasonic oscillation, slowly add tetramethylpiperidinamine within 30 min, control the total reaction time to be 45 min, in the reaction, the amount ratio of intermediate, tetramethylpiperidinamine, thionyl chloride, triethylamine and dimethyl sulfoxide is 0.1 mol:0.3 mol:45 mL:18 mL:200 mL, after the reaction, remove the low boiling point substance mainly with dimethyl sulfoxide by rotary evaporation under reduced pressure, and obtain the anti-aging auxiliary.

[0054] 2) Preparation of composite material

[0055] 2.1, according to the weight ratio, take the raw materials:

[0056] PP master batch 100 parts, POE toughening resin 13 parts, talc 32 parts, coupling agent 1.1 parts, lubricant 1.2 parts and anti-aging auxiliary prepared in this example 0.3 parts;

[0057] 2.2, add talc to the high-speed mixer and preheat to 100℃, apply 1500 rpm high-speed stirring, uniformly add coupling agent and mix for 20 min, then add the remaining raw materials and mix for 2h at 80 rpm, and obtain the compound;

[0058] 2.3, add the compound to the torque rheometer, melt blend under nitrogen protection at 190±5℃ until the torque is stable, discharge and cool, crush, and obtain the anti-aging composite material for automobiles.

[0059] Example 4

[0060] The embodiment prepares the anti-aging composite material for automobile, and the specific implementation process is as follows.

[0061] 1) Preparation of anti-aging auxiliary agent

[0062] 1.1, the triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene are mixed, nitrogen is introduced, the temperature is increased to 62℃, 400rpm mechanical stirring is applied, and 320W / m 2 ultraviolet irradiation, constant temperature stirring irradiation reaction is carried out for 1.5h, in the reaction, the amount ratio of triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene is 0.1mol: 0.3mol: 0.28g: 100mL, 10wt% of the reaction substrate is added, acetone is mixed, low boiling point substances mainly containing benzene are removed by rotary evaporation under reduced pressure, and the intermediate is obtained.

[0063] 1.2, the intermediate, thionyl chloride and dimethyl sulfoxide are mixed, the temperature is increased to 58℃, 180rpm mechanical stirring is applied, constant temperature stirring reaction is carried out for 2.2h, then the excess thionyl chloride is removed by rotary evaporation under reduced pressure, the temperature is decreased to room temperature, triethylamine is added and mixed, 28kHz ultrasonic oscillation is applied, tetramethylpiperidinamine is slowly added within 30min, the total reaction time is controlled to be 50min, in the reaction, the amount ratio of intermediate, tetramethylpiperidinamine, thionyl chloride, triethylamine and dimethyl sulfoxide is 0.1mol: 0.3mol: 50mL: 20mL: 220mL, after the reaction, low boiling point substances mainly containing dimethyl sulfoxide are removed by rotary evaporation under reduced pressure, and the anti-aging auxiliary agent is obtained.

[0064] 2) Preparation of composite material

[0065] 2.1, according to the weight ratio, the raw materials are taken:

[0066] PP master batch 100 parts, POE toughening resin 12 parts, talc 30 parts, coupling agent 1 part, lubricant 1.5 parts and the anti-aging auxiliary agent prepared in the embodiment 0.28 parts;

[0067] 2.2, the talc is added to the high-speed mixer and preheated to 100℃, 1200rpm high-speed stirring is applied, the coupling agent is uniformly added and mixed for 20min, and then the remaining raw materials are added and mixed for 2h at 120rpm, so as to obtain the mixture;

[0068] 2.3, the mixture is added to the torque rheometer, melt blending is carried out under nitrogen protection at 190±5℃ until the torque is stable, the material is discharged and cooled, and then crushed, so as to obtain the anti-aging composite material for automobile.

[0069] Comparative example

[0070] The specific implementation process of the comparative example is the same as that of Example 3. Commercial antioxidants 1010 and 168 are used in a mass ratio of 1:1. The amount of the compounded antioxidant is 0.4 parts.

[0071] The above prepared composite material is extruded, wherein the barrel temperature of the extruder is set as follows: zone 1, 180°C; zone 2, 200°C; zone 3, 200°C; zone 4, 190°C; the die temperature is 200°C; the injection and holding pressure is 5 MPa; the pre-plasticizing pressure is 6 MPa; the injection and holding time is 20 s; and the sample is prepared;

[0072] The above prepared sample is taken and the relevant performance tests are carried out according to the following standards:

[0073] Tensile properties: according to GB / T 1040.2-2022 standard, using 1A type sample, test rate: 50 mm / min, gauge length: 75 mm;

[0074] Bending properties: according to GB / T 9341-2008 standard, test rate: 2 mm / min;

[0075] Impact properties: according to GB / T 1843-2008 standard, test temperature is 23°C, and the sample is tested after being static at the corresponding temperature for 4 h;

[0076] The test data of the virgin composite material are shown in Table 1:

[0077] Table 1

[0078]

[0079] From the data in Table 1, it can be seen that the composite material prepared in the example has good comprehensive mechanical properties, and the elongation at break and impact strength are significantly better than those of the comparative example, showing good toughness.

[0080] In order to verify the aging resistance of the above prepared composite material, the sample is subjected to artificial accelerated aging test according to DIN75220 standard. The specific test parameters are set as follows: a total of 15 dry heat climate cycles and 10 wet heat climate cycles are tested, wherein the single cycle test process of dry heat climate is 8 h of daytime dry heat climate and 3.5 h of nighttime dry heat climate, and the single cycle test process of wet heat climate is 5 h of nighttime wet heat climate, 12 h of daytime wet heat climate and 6 h of nighttime wet heat climate. The daytime dry heat and wet heat climate cycle test conditions are shown in Table 2:

[0081] Table 2

[0082] Climate parameter Unit Dry heat climate Humid heat climate Black panel temperature ℃ 110±5 110±5 Test chamber temperature ℃ 42±2 42±2 Relative humidity ％ 25±5 65±5 Irradiance [W / m 2 ]]> 1000±100 1000±100

[0083] The nighttime dry heat and wet heat climate cycle test conditions are shown in Table 3:

[0084] Table 3

[0085] Climate parameter Unit Dry heat climate Humid heat climate Test chamber temperature ℃ 10±3 0±3 Relative humidity ％ 55±5 Condensation allowed

[0086] According to the test standard, the related performance test of the test after artificial accelerated aging is carried out again, and the change rate is calculated. The specific calculation method is: change rate = (original detection data - detection data after aging) x 100%, and the specific test data is shown in Table 4:

[0087] Table 4

[0088]

[0089] From the data in Table 4, it can be seen that the mechanical properties of the composite materials prepared in the examples and the comparative examples all decrease after aging, and the decrease amplitude of the comparative examples is much higher than that of the examples, which indicates that the composite material prepared in the examples has more excellent aging resistance performance compared with the comparative examples.

[0090] In the description of the specification, the description of the reference terms "one embodiment", "example", "specific example" and the like means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are contained in at least one embodiment or example of the present application. In the present specification, the illustrative description 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 is only an example and description of the present application, and those skilled in the art can make various modifications or supplements or use similar ways to replace the described specific embodiments, as long as they do not deviate from the invention or exceed the scope defined by the present claims, which shall belong to the protection scope of the present application.

Claims

1. An anti-aging composite material for automobiles, characterized by comprising a resin composition containing a polyamide resin, a reinforcing fiber, and a silane coupling agent. According to parts by weight, comprising: PP master batch 100 parts, POE toughening resin 9-13 parts, talc 28-34 parts, coupling agent 0.9-1.2 parts, lubricant 1-1.5 parts and anti-aging aid 0.25-0.35 parts; The anti-aging aid is prepared by the following method: Step A1: Mix triallylamine, β-mercaptopropionic acid, azobisisobutyronitrile and benzene, protect with nitrogen, heat to 55-65°C, apply 300-400 rpm mechanical stirring, and supplement with 280-360 W / m 2 UV irradiation, constant temperature stirring, irradiate for 1.2-1.6 h, add a small amount of acetone after the reaction is completed, remove the low boiling point substance mainly benzene by rotary evaporation under reduced pressure, and obtain the intermediate; Step A2: mix the intermediate, thionyl chloride and dimethyl sulfoxide, heat to 50-60℃, apply 120-180rpm mechanical stirring, constant temperature stirring reaction for 2-3h, then remove excess thionyl chloride under reduced pressure, cool to room temperature, add triethylamine and mix well, apply 20-28kHz ultrasonic oscillation, slowly add tetramethylpiperidinamine, control the total addition reaction time for 40-50min, after the reaction is completed, remove the low boiling point substances mainly with dimethyl sulfoxide under reduced pressure, and obtain the anti-aging aid.

2. The weatherable composite material for an automobile according to claim 1, wherein The amount ratio of triallylamine, β-mercapto propionic acid, azobisisobutyronitrile and benzene is 0.1mol:0.3mol:0.25-0.3g:80-100mL.

3. The weatherable composite material for an automobile according to claim 2, wherein The amount ratio of intermediate, tetramethylpiperidinamine, thionyl chloride, triethylamine and dimethyl sulfoxide is 0.1mol:0.3mol:40-50mL:15-22mL:180-240mL.

4. The weatherable composite material for an automobile according to claim 1, wherein The fineness of talc is not less than 2000 mesh.

5. The weatherable composite material for an automobile according to claim 1, wherein The coupling agent is silane coupling agent KH-550.

6. The weatherable composite material for an automobile according to claim 1, wherein The lubricant is polypropylene wax.

7. The method of claim 1, wherein the anti-aging composite material is prepared by mixing the anti-aging material with the base material in a ratio of 1: 1 to 1:

10. The method comprises the following steps: Step S1: add talc to a high-speed mixer and preheat to 100℃, stir at high speed and add coupling agent at a uniform speed for 20min, then add the remaining raw materials and stir at low speed for 2h to obtain a batch; Step S2: add the batch to a torque rheometer, melt blend under nitrogen protection at 190±5℃ until the torque is stable, discharge and cool, and crush to obtain an anti-aging composite material for automobiles.

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