阅读说明：本技术 Tpv复合材料及其制备方法 (TPV composite material and preparation method thereof ) 是由 王灿耀 张景中 洪剑城 曾维 于 2020-12-10 设计创作，主要内容包括：本发明涉及一种TPV复合材料及其制备方法,所述TPV复合材料由包括以下重量份的原料制备而成：聚丙烯10～40份,马来酸酐接枝TPV50～80份,无机填料0～20份,抗氧剂0.1～0.5份,耐候剂0.1～0.5份,气味吸附剂0.5～2份；所述聚丙烯、马来酸酐接枝TPV和无机填料的重量份总和为100份。本发明的TPV复合材料常温和高温压变性能好,外观良好。(The invention relates to a TPV composite material and a preparation method thereof, wherein the TPV composite material is prepared from the following raw materials in parts by weight: 10-40 parts of polypropylene, 50-80 parts of maleic anhydride grafted TPV, 0-20 parts of inorganic filler, 0.1-0.5 part of antioxidant, 0.1-0.5 part of weather-resistant agent and 0.5-2 parts of odor adsorbent; the sum of the parts by weight of the polypropylene, the maleic anhydride grafted TPV and the inorganic filler is 100 parts. The TPV composite material has good normal temperature and high temperature deformation performance and good appearance.)

1. The TPV composite material is characterized by being prepared from the following raw materials in parts by weight:

the sum of the parts by weight of the polypropylene, the maleic anhydride grafted TPV and the inorganic filler is 100 parts.

2. The TPV composite material as claimed in claim 1, which is prepared from the following raw materials in parts by weight:

3. the TPV composite material as claimed in claim 2, which is prepared from the following raw materials in parts by weight:

4. the TPV composite material as claimed in any one of claims 1 to 3, wherein the maleic anhydride grafted TPV is formed by grafting TPV material and maleic anhydride.

5. The TPV composite according to claim 4, wherein the maleic anhydride grafted TPV is prepared from the following components in parts by mass: 20-40 parts of polypropylene, 30-50 parts of ethylene propylene diene monomer, 30-50 parts of softener, 0.1-0.5 part of antioxidant, 0.1-1 part of vulcanizing agent, 2-7 parts of maleic anhydride and 0.1-0.4 part of initiator; in the components for preparing the maleic anhydride grafted TPV, the sum of the parts by weight of polypropylene, ethylene propylene diene monomer rubber and softener is 100 parts.

6. The TPV composite of claim 5, wherein the softening agent is at least one of white mineral oil, naphthenic oil, and aromatic oil; the softening agent has a kinematic viscosity at 100 ℃ of more than 25mm²(ii)/s, flash point > 220 ℃; and/or the vulcanizing agent is at least one of di-tert-butyl cumyl peroxide, bis (2, 4-dichlorobenzoyl) peroxide, trimethylolpropane trimethacrylate, 2, 5-dimethyl-2, 5-di-tert-butyl hexane peroxide, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, N-butyl-4, 4-di (tert-butylperoxy) valerate, 4' diphenylmethane bismaleimide, triallyl isocyanurate, triallyl cyanurate, N, -m-phenylene bismaleimide, trimethylolpropane triacrylate, 1, 2-polybutadiene and zinc methacrylate; and/or the initiator is at least one of dicumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate.

7. The TPV composite according to any one of claims 1 to 3, wherein the odor adsorbent is at least one of activated carbon, molecular sieve, zeolite and diatomaceous earth; and/or the inorganic filler is at least one of talcum powder, calcium carbonate and barium sulfate.

8. The TPV composite according to any one of claims 1 to 3, wherein the antioxidant is at least one of tris (2, 4-di-tert-butylbenzene-di-tert-butyl-phenyl) phosphite, pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate.

9. A method of making a TPV composite as claimed in any one of claims 1 to 8 comprising the steps of:

(1) mixing polypropylene, ethylene propylene diene monomer, a softener, an antioxidant and a vulcanizing agent, melting, extruding and granulating to obtain a TPV material;

(2) mixing the TPV material obtained in the step (1) with maleic anhydride and an initiator, and then performing melt extrusion and granulation to obtain maleic anhydride grafted TPV;

(3) and (3) mixing the polypropylene, the maleic anhydride grafted TPV obtained in the step (2), the inorganic filler, the antioxidant, the weather-resistant agent and the odor adsorbent, and then performing melt extrusion and granulation to prepare the TPV composite material.

10. The method according to claim 9, wherein the process parameters of the steps (1) and (2) comprise: the temperature of the first zone is 50-175 ℃, the temperature of the second zone to the eighth zone is 150-170 ℃, the temperature of the extrusion opening is 160-180 ℃, and the rotating speed of the screw is 200-500 rpm; the process parameters of the step (3) comprise: the temperature of the first zone is 60-175 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, the temperature of the extrusion opening is 190-220 ℃, and the rotating speed of the screw is 200-500 rpm.

Technical Field

The invention relates to the field of high polymer materials, in particular to a TPV composite material and a preparation method thereof.

Background

In recent years, rapid development of the automobile industry has put increasing demands on interior and exterior materials. Studies have shown that when people touch the interior of an automobile, the soft texture increases their purchase rate, and in addition, the soft feeling simultaneously stimulates the consumer's sense of possession, but the polypropylene materials commonly used for the interior of an automobile have a high hardness and lack a leather-like soft touch. Currently, the soft touch is mainly obtained by adding a large amount of elastomer to the polypropylene component to reduce the hardness. However, in the existing modification system, the melt viscosity of the elastomer is high, and the flowability is poor. The high content of elastomer component seriously reduces the flowability of the polypropylene composition. In addition, some elastomers have poor compatibility with materials such as polypropylene and are difficult to disperse in a matrix. These defects cause problems such as uneven thickness, flow marks, surface pockmarks and the like of the polyolefin composition during extrusion, injection molding, slush molding and the like, and seriously affect the appearance and the performance.

In addition, in recent years, thermoplastic elastomers have been rapidly popularized in the market due to the demands for weight reduction of materials and material processing efficiency, and TPV materials have been widely used in the field of sealing products due to their excellent pressure strain and oil resistance. TPV is made of a lot of materials, and according to the requirements of sealing products on the materials, the TPV material with the largest application amount in the market is the TPV material taking EPDM and PP as main bodies, is mainly applied to automobile sealing strip products, replaces the traditional Ethylene Propylene Diene Monomer (EPDM) dense rubber, and can improve the processing efficiency, reduce the material proportion and reduce VOC. However, compared with ethylene propylene diene monomer dense vulcanized rubber, even compared with imported TPV materials, the domestic TPV materials have small difference in mechanical strength, but the pressure-variable property, especially the high-temperature pressure-variable property of the materials has a larger difference from the products.

Therefore, how to improve the appearance and high-temperature durability of the TPV material is one of the key problems that needs to be solved in the development and application processes of the current TPV material and its products.

Disclosure of Invention

Based on the above, the invention aims to provide the TPV composite material which has good normal-temperature and high-temperature deformation performance and good appearance.

The specific technical scheme is as follows:

the TPV composite material is prepared from the following raw materials in parts by weight:

the sum of the parts by weight of the polypropylene, the maleic anhydride grafted TPV and the inorganic filler is 100 parts.

In some embodiments, the TPV composite is prepared from the following raw materials in parts by weight:

in some embodiments, the TPV composite is prepared from the following raw materials in parts by weight:

in some embodiments, the TPV composite is prepared from the following raw materials in parts by weight:

in some of these embodiments, the maleic anhydride grafted TPV is formed by grafting a TPV material with maleic anhydride.

In some embodiments, the maleic anhydride grafted TPV is prepared from the following components in parts by mass: 20-40 parts of polypropylene, 30-50 parts of ethylene propylene diene monomer, 30-50 parts of softener, 0.1-0.5 part of antioxidant, 0.1-1 part of vulcanizing agent, 2-7 parts of maleic anhydride and 0.1-0.4 part of initiator; in the components for preparing the maleic anhydride grafted TPV, the sum of the parts by weight of polypropylene, ethylene propylene diene monomer rubber and softener is 100 parts.

In some embodiments, the mass ratio of the ethylene propylene diene monomer to the softener is 1: 1-2, further can be 1: 1 to 1.5.

In some of these embodiments, the softening agent is at least one of white mineral oil, naphthenic oil, and aromatic oil. Preferably, the softening agent has a kinematic viscosity at 100 ℃ of > 25mm²S, flash point > 220 ℃.

In some of these embodiments, the vulcanizing agent is at least one of di-t-butylperoxyisopropyl benzene, bis (2, 4-dichlorobenzoyl) peroxide, trimethylolpropane trimethacrylate, 2, 5-dimethyl-2, 5-di-t-butylperoxyhexane, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, N-butyl-4, 4-di (t-butylperoxy) valerate, 4' diphenylmethane bismaleimide, triallyl isocyanurate, triallyl cyanurate, N, -m-phenylene bismaleimide, trimethylolpropane triacrylate, 1, 2-polybutadiene, and zinc methacrylate.

In some of these embodiments, the initiator is at least one of dicumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.

In some of these embodiments, the odor adsorbent is at least one of activated carbon, molecular sieves, zeolites, and diatomaceous earth.

In some of these embodiments, the odor adsorbent is activated carbon and molecular sieve.

In some of these embodiments, the inorganic filler is at least one of talc, calcium carbonate, and barium sulfate. The mesh of the inorganic filler is 400-3500 meshes.

In some of these embodiments, the antioxidant is at least one of tris (2, 4-di-tert-butylbenzene-di-tert-butyl-phenyl) phosphite, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and dilauryl thiodipropionate.

Another object of the present invention is to provide a method for preparing the above PV composite, comprising the following steps:

(1) mixing polypropylene, ethylene propylene diene monomer, a softener, an antioxidant and a vulcanizing agent, melting, extruding and granulating to obtain a TPV material;

(2) mixing the TPV material obtained in the step (1) with maleic anhydride and an initiator, and then performing melt extrusion and granulation to obtain maleic anhydride grafted TPV;

(3) and (3) mixing the polypropylene, the maleic anhydride grafted TPV obtained in the step (2), the inorganic filler, the antioxidant, the weather-resistant agent and the odor adsorbent, and then performing melt extrusion and granulation to prepare the TPV composite material.

In some embodiments, the process parameters of step (1) and step (2) include: the temperature of the first zone is 50-175 ℃, the temperature of the second zone to the eighth zone is 150-170 ℃, the temperature of the extrusion opening is 160-180 ℃, and the rotation speed of the screw is 200-500 rpm.

In some embodiments, the process parameters of step (3) include: the temperature of the first zone is 60-175 ℃, the temperature of the second zone to the eighth zone is 180-210 ℃, the temperature of the extrusion opening is 190-220 ℃, and the rotating speed of the screw is 200-500 rpm.

Compared with the prior art, the invention has the following beneficial effects:

according to the invention, the TPV soft rubber material is grafted and modified by maleic anhydride and then compounded with other raw materials, so that the compatibility among EPDM, polypropylene resin and inorganic filler can be effectively improved, the EPDM is fully crosslinked to form a network structure, the normal-temperature and high-temperature deformation resistance of the TPV material is effectively enhanced, meanwhile, the EPDM and the inorganic filler are uniformly dispersed in the polypropylene resin, and the appearance defects of uneven thickness resistance, flow marks, surface pits and the like of the product are effectively overcome.

In addition, the TPV composite material with low odor and low VOC is prepared by selecting a proper gas adsorbent, particularly selecting two gas adsorbents of diatomite and a molecular sieve for compounding, can be widely applied to internal and external decorative materials of the automobile industry, such as cup pads, sealing rings, sealing strips, spoilers and the like, and can realize better economic value.

Drawings

Figure 1 is a flow diagram of a process for preparing the TPV composite of example 1.

Detailed Description

Experimental procedures according to the invention, in which no particular conditions are specified in the following examples, are generally carried out under conventional conditions, or under conditions recommended by the manufacturer. The various chemicals used in the examples are commercially available.

Unless defined otherwise, 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 belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

The terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, article, or device that comprises a list of steps is not limited to only those steps or modules listed, but may alternatively include other steps not listed or inherent to such process, method, article, or device.

The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.

The embodiment provides a TPV composite material, which is prepared from the following raw materials in parts by weight:

the sum of the parts by weight of the polypropylene, the maleic anhydride grafted TPV and the inorganic filler is 100 parts.

The TPV composite material is prepared by grafting and modifying the TPV soft rubber material with maleic anhydride and compounding with other raw materials, so that the compatibility among EPDM, polypropylene resin and inorganic filler can be effectively improved, the EPDM is fully crosslinked to form a network structure, the normal-temperature and high-temperature deformation resistance of the TPV material is finally effectively enhanced, the EPDM and the inorganic filler are uniformly dispersed in the polypropylene resin, and the appearance defects of uneven thickness resistance, flow marks, surface pits and the like of a product are effectively overcome. Meanwhile, a proper gas adsorbent is selected to prepare the TPV composite material, and particularly, two gas adsorbents of diatomite and a molecular sieve are selected to be compounded to prepare the TPV composite material with low odor and low VOC.

The inventor of the invention also finds that the compression deformation resisting effect of the TPV composite material is more obvious as the amount of the maleic anhydride grafted TPV is increased.

As a preferred embodiment, the TPV composite material is prepared from the following raw materials in parts by weight:

as a further preferred embodiment, the TPV composite material is prepared from the following raw materials in parts by weight:

the TPV soft rubber material (TPV) refers to Thermoplastic vulcanized rubber (Thermoplastic vulcanizer), and the TPV material prepared by taking EPDM and PP as main bodies is preferable. The invention does not strictly limit the types and preparation processes of other raw materials except EPDM and PP aiming at the TPV material mainly prepared from EPDM and PP.

In some more specific embodiments, the maleic anhydride grafted TPV of the present invention is prepared from components comprising, in parts by mass: 20-40 parts of polypropylene, 30-50 parts of ethylene propylene diene monomer, 30-50 parts of softener, 0.1-0.5 part of antioxidant, 0.1-1 part of vulcanizing agent, 2-7 parts of maleic anhydride and 0.1-0.4 part of initiator; in the components for preparing the maleic anhydride grafted TPV, the sum of the parts by weight of polypropylene, ethylene propylene diene monomer rubber and softener is 100 parts.

In some of these embodiments, the sulfurizing agent is preferably di-t-butylperoxycumene. But not limited thereto, the vulcanizing agent may be at least one of bis (2, 4-dichlorobenzoyl) peroxide, trimethylolpropane trimethacrylate, 2, 5-dimethyl-2, 5-di-tert-butylperoxyhexane, 1-bis (tert-butylperoxy) -3,3, 5-trimethylcyclohexane, N-butyl-4, 4-di (tert-butylperoxy) valerate, 4' diphenylmethane bismaleimide, triallyl isocyanurate, triallyl cyanurate, N, -m-phenylene bismaleimide, trimethylolpropane triacrylate, 1, 2-polybutadiene, and zinc methacrylate.

In some of these embodiments, the initiator is preferably dicumyl peroxide. But not limited thereto, the initiator may also be at least one of dicumyl peroxide, benzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, and dimethyl azobisisobutyrate.

In some of these embodiments, the odor adsorbent is preferably activated carbon and molecular sieves. But not limited thereto, the odor adsorbent may also be at least one of activated carbon, molecular sieve, zeolite, and diatomaceous earth.

In some of these embodiments, the inorganic filler is preferably calcium carbonate. But not limited thereto, the inorganic filler may also be at least one of talc, calcium carbonate and barium sulfate.

The present invention will be described in further detail with reference to specific examples.

The raw materials used in the embodiment of the invention are as follows:

polypropylene: polypropylene BJ356AI, available from northern european chemicals ltd;

talcum powder (B1) available from Dongguan Meirun chemical Co., Ltd, 3000 mesh;

calcium carbonate (B2) available from 500 mesh, Guanyu chemical Co., Ltd, Jiangxi;

antioxidants, tris (2, 4-di-tert-butylbenzene-di-tert-butylphenyl) phosphite (168), pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010), available from Kyoho chemical Co., Ltd;

the weather-resistant agent (bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) nickel (2002)) is purchased from Shanghai city, Wuhan Co-Ltd;

odor adsorbent, diatomaceous earth, available from Qingdao Shengtai silicon industries;

odor adsorbents, molecular sieves, available from jianeng air separation technology ltd, lazhou;

TPV material (TPV-1 # in the following examples) and maleic anhydride grafted TPV (TPV-1 # -g-MAH in the following examples) prepared by self, wherein the polypropylene in the raw material is polypropylene BJ356AI purchased from northern Europe chemical industry Co., Ltd;

the ethylene propylene diene monomer is ethylene propylene diene monomer 4770R which is purchased from Dow chemical company Limited;

softener, white mineral oil AP6020, available from austenitized technical limited, of foshan; the kinematic viscosity at 100 ℃ is 28mm²The flash point was 270 ℃.

Antioxidants, tris (2, 4-di-tert-butylbenzene-di-tert-butylphenyl) phosphite (168), pentaerythrityl tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (1010), available from Kyoho chemical Co., Ltd;

a vulcanizing agent, di-t-butyl cumene peroxide (BIPB), available from Farreda chemical Co., Ltd;

maleic Anhydride (MAH), available from longhui chemical ltd;

initiator, dicumyl peroxide (DCP), available from aksunobel corporation.

The preparation method of TPV-1# -g-MAH (TPV-1 # -g-MAH-a-d, respectively) in the following examples is prepared by the following steps:

(1) uniformly mixing 20-40 parts of polypropylene, 30-50 parts of ethylene propylene diene monomer, 30-50 parts of softener, 0.1-0.5 part of antioxidant and 0.1-1 part of vulcanizing agent, and then performing melt extrusion and granulation in a double-screw extruder to obtain TPV-1 #;

(2) adding 3-7 parts of maleic anhydride and 0.1-0.4 part of initiator into the TPV-1# prepared in the step (1), uniformly mixing, passing through a double-screw extruder, carrying out melt extrusion, and granulating to obtain TPV-1# -g-MAH.

(3) The two steps of process parameters are as follows: the temperature in the first zone was 60 ℃, the temperature in the second to eighth zones was 160 ℃, the temperature of the extrusion port was 170 ℃ and the screw rotation speed was 400 rpm.

The following is a list of TPV-1# -g-MAH-a-d in parts by weight (Table 1):

TABLE 1 preparation of TPV-1# -g-MAH

Example 1

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-a, talcum powder, antioxidant 168, antioxidant 1010, weather resisting agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 60 ℃, the temperature in the second zone to the eighth zone was 190 ℃, the temperature of the extrusion port was 200 ℃ and the screw rotation speed was 500 rpm. The flow chart of the preparation process is shown in figure 1.

Example 2

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-a, talcum powder, antioxidant 168, antioxidant 1010, weather resisting agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 60 ℃, the temperature in the second zone to the eighth zone was 180 ℃, the temperature of the extrusion port was 210 ℃ and the screw speed was 450 rpm.

Example 3

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-b, talcum powder, antioxidant 168, antioxidant 1010, weather-resistant agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 70 ℃, the temperature in the second zone to the eighth zone was 180 ℃, the temperature of the extrusion port was 190 ℃ and the screw rotation speed was 400 rpm.

Example 4

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-b, talcum powder, antioxidant 168, antioxidant 1010, weather-resistant agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 80 ℃, the temperature in the second to eighth zones was 200 ℃, the temperature of the extrusion port was 210 ℃ and the screw speed was 350 rpm.

Example 5

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-c, calcium carbonate, antioxidant 168, antioxidant 1010, weather resisting agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 90 ℃, the temperature in the second zone to the eighth zone was 210 ℃, the temperature of the extrusion port was 220 ℃ and the screw rotation speed was 400 rpm.

Example 6

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-c, calcium carbonate, antioxidant 168, antioxidant 1010, weather resisting agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 90 ℃, the temperature in the second zone to the eighth zone was 190 ℃, the temperature of the extrusion port was 200 ℃ and the screw rotation speed was 300 rpm.

Example 7

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-d, calcium carbonate, antioxidant 168, antioxidant 1010, weather resisting agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 100 ℃, the temperature in the second zone to the eighth zone was 180 ℃, the temperature of the extrusion port was 200 ℃ and the screw rotation speed was 300 rpm.

Example 8

The high-temperature-resistant TPV composite material with good appearance is prepared from the following raw materials:

the preparation method of the good-appearance high-temperature-resistant TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1# -g-MAH-d, calcium carbonate, antioxidant 168, antioxidant 1010, weather resisting agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 60 ℃, the temperature in the second zone to the eighth zone was 190 ℃, the temperature of the extrusion port was 200 ℃ and the screw rotation speed was 400 rpm.

Comparative example 1

The TPV composite material is prepared from the following raw materials:

the preparation method of the TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, the POE-g-MAH C4, the talcum powder, the antioxidant 168, the antioxidant 1010, the weather-resistant agent 2002, the diatomite and the molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 60 ℃, the temperature in the second zone to the eighth zone was 190 ℃, the temperature of the extrusion port was 200 ℃ and the screw rotation speed was 500 rpm.

Comparative example 2

The TPV composite material is prepared from the following raw materials:

the preparation method of the TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, the POE-g-MAH C8, the talcum powder, the antioxidant 168, the antioxidant 1010, the weather-resistant agent 2002, the diatomite and the molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 60 ℃, the temperature in the second zone to the eighth zone was 180 ℃, the temperature of the extrusion port was 210 ℃ and the screw speed was 450 rpm.

Comparative example 3

The TPV composite material is prepared from the following raw materials:

the preparation method of the TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, EPDM-g-MAH, talcum powder, antioxidant 168, antioxidant 1010, weather-resistant agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 70 ℃, the temperature in the second zone to the eighth zone was 180 ℃, the temperature of the extrusion port was 190 ℃ and the screw rotation speed was 400 rpm.

Comparative example 4

The TPV composite material is prepared from the following raw materials:

the preparation method of the TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, the SEBS-g-MAH, the talcum powder, the antioxidant 168, the antioxidant 1010, the weather-resistant agent 2002, the diatomite and the molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 80 ℃, the temperature in the second to eighth zones was 200 ℃, the temperature of the extrusion port was 210 ℃ and the screw speed was 350 rpm.

Comparative example 5

The TPV composite material is prepared from the following raw materials:

the preparation method of the TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1#, calcium carbonate, antioxidant 168, antioxidant 1010, weather-resistant agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 100 ℃, the temperature in the second zone to the eighth zone was 180 ℃, the temperature of the extrusion port was 200 ℃ and the screw rotation speed was 300 rpm.

Comparative example 6

The TPV composite material is prepared from the following raw materials:

the preparation method of the TPV composite material comprises the following steps:

(1) adding the PP BJ356AI, TPV-1#, talcum powder, antioxidant 168, antioxidant 1010, weather-resistant agent 2002, diatomite and molecular sieve into a high-speed stirrer for mixing;

(2) and (2) melting, extruding and granulating the mixed material obtained in the step (1) in a double-screw extruder, wherein the process parameters are as follows: the temperature in the first zone was 60 ℃, the temperature in the second zone to the eighth zone was 190 ℃, the temperature of the extrusion port was 200 ℃ and the screw rotation speed was 500 rpm.

The following is a list of examples and comparative examples (Table 2):

TABLE 2 summary of the composition parts by weight of the raw materials of the examples and comparative examples

Performance testing and results

The TPV composites prepared in the above examples and comparative examples were subjected to the following appearance and performance tests:

(1) injecting the material into a 150mm by 3mm beating plate to observe the appearance;

(2) compression set test: testing according to ISO 815 standard, at 23 deg.C for 22 h;

(3) compression set test: testing according to ISO 815 standard, at 70 deg.C for 22 h;

(4) and (3) odor test: the test was carried out according to BYD-TY-D11F14-10013-A/0 at 80 ℃ for 2 h.

The test results are shown in table 3.

Table 3 test data results of examples and comparative examples

From the settings of the above examples and the results measured in table 3, the following were analyzed:

from examples 1 to 8, it can be seen that: adding the self-made TPV-1# -g-MAH into the material, wherein the sample plate has no appearance defects such as uneven thickness, flow marks, surface pits and the like, and the normal-temperature and high-temperature compression deformation amounts respectively meet the requirements of less than 25% and 40%, so that the grafted MAH has good effects on the appearance and compression deformation resistance of the TPV composite material; and the compression deformation resisting effect in the material is more obvious as the dosage of TPV-1# -g-MAH is increased in a proper range.

As can be seen from the comparison of examples 1 to 8 with comparative examples 5 to 6: the appearance of the sample plate added with the maleic anhydride grafted elastomer has no appearance defects such as uneven thickness, flow marks, surface pockmarks and the like, but when the elastomer has no grafted maleic anhydride, the appearance of the sample plate has defects.

In addition, as can be seen from comparative examples 1 to 4, the compression resistance effect of the material prepared by grafting POE, EPDM and SEBS with MAH is inferior to that of the TPV material vulcanized and crosslinked in examples 1 to 8; in comparative examples 1-5, the normal temperature compression deformation of the material is more than 25%, the high temperature compression deformation is more than 40%, and the requirements that the normal temperature compression deformation and the high temperature compression deformation respectively meet less than 25% and 40% cannot be met. As can be seen from comparative example 6, although the normal temperature compression set of the material satisfies the requirement of less than 25% in Japan, the high temperature compression set thereof cannot satisfy the requirement of less than 40%.

The existing material of the invention reaches 3.5 grade in laboratory production, and can reach the BYD 3.3 grade standard after short-time material drying treatment under the conditions of double vacuum and online material drying in a workshop.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.