CN121574466A - A low-odor thermoplastic vulcanizate for automotive skin, its preparation method and application - Google Patents
A low-odor thermoplastic vulcanizate for automotive skin, its preparation method and applicationInfo
- Publication number
- CN121574466A CN121574466A CN202511990693.8A CN202511990693A CN121574466A CN 121574466 A CN121574466 A CN 121574466A CN 202511990693 A CN202511990693 A CN 202511990693A CN 121574466 A CN121574466 A CN 121574466A
- Authority
- CN
- China
- Prior art keywords
- odor
- parts
- low
- ethylene
- tert
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
本发明公开了一种低气味汽车蒙皮用热塑性硫化橡胶及其制备方法与应用。原料包含乙烯‑丙烯‑二烯烃共聚物橡胶50~80份、聚丙烯20~50份、相容剂5~15份、复配交联剂0.5~2.5份、气味吸附剂0.5~2.0份、抗氧剂0.5~1.0份。制备包括：密炼共混、第一双螺杆挤出机动态硫化、第二双螺杆挤出机吸附与深度脱挥、100℃真空烘烤。本发明利用交联剂与助交联剂的协同效应，在保证交联效率的同时抑制了聚丙烯的降解，并通过多级脱挥工艺彻底移除了低沸点的反应副产物（叔丁醇），解决了传统TPV材料气味大、易雾化的问题。所得材料气味等级≤3.0级，雾化值<0.5mg，适用于高端汽车内饰表皮。This invention discloses a low-odor thermoplastic vulcanizate rubber for automotive skin, its preparation method, and its application. The raw materials include 50-80 parts of ethylene-propylene-diolefin copolymer rubber, 20-50 parts of polypropylene, 5-15 parts of compatibilizer, 0.5-2.5 parts of compound crosslinking agent, 0.5-2.0 parts of odor adsorbent, and 0.5-1.0 parts of antioxidant. The preparation process includes: internal mixing, dynamic vulcanization using a first twin-screw extruder, adsorption and deep devolatilization using a second twin-screw extruder, and vacuum baking at 100℃. This invention utilizes the synergistic effect of the crosslinking agent and co-crosslinking agent to inhibit polypropylene degradation while ensuring crosslinking efficiency. Furthermore, a multi-stage devolatilization process thoroughly removes low-boiling-point reaction byproducts (tert-butanol), solving the problems of strong odor and easy fogging in traditional TPV materials. The resulting material has an odor level ≤3.0 and a fogging value <0.5mg, making it suitable for high-end automotive interior skin.
Description
Technical Field
The invention relates to the technical field of polymer material science and automotive interior materials, in particular to a thermoplastic vulcanized rubber for low-odor automotive skins, and a preparation method and application thereof.
Background
In the modern automobile manufacturing industry, with increasing consumer demands for cabin health and comfort, the quality of air in a vehicle has become one of the core indexes for evaluating the quality of automobiles. The automobile skin is used as a surface covering material of interior trim parts such as instrument panels, door panels, center consoles and the like, has the characteristics of large surface area and direct exposure to illumination and high-temperature environments, and is one of main potential sources of volatile organic compounds and peculiar smell in the automobile. Thermoplastic vulcanizates, particularly dynamic vulcanizates based on polypropylene and ethylene-propylene-diene copolymer rubber, have gradually replaced the traditional polyvinyl chloride and expensive polyurethane as the preferred materials for weight reduction and environmental protection of automotive interiors due to the high elasticity of the vulcanizates and the easy processability, low density and recyclability of the thermoplastics.
However, existing commercial TPV materials still face significant challenges in meeting the stringent low odor, low fogging standards of high end host factories. The technical bottleneck mainly comes from the inherent chemical composition and preparation process defects of the material:
First, the problem of pungent odor caused by the crosslinking system. The most well established process for the industrial preparation of TPVs is dynamic vulcanization, i.e. chemical crosslinking of the rubber phase during melt blending of plastics. The traditional process generally adopts dicumyl peroxide as an initiator. While the DCP is decomposed at high temperature to initiate the crosslinking reaction, unavoidable beta-homolytic side reaction can occur to generate acetophenone. Acetophenone has a very typical and unpleasant "bitter almond" or intense sweet taste. More troublesome is that its boiling point is as high as 202 ℃ and much higher than the conventional post-treatment temperature of TPV, which is extremely difficult to remove thoroughly by conventional extrusion vacuum devolatilization. This means that the acetophenone produced by the reaction remains almost permanently in the product, resulting in conventional TPV with odor ratings typically only up to 4.0, which is difficult to meet for high end applications.
Secondly, the problem of degradation odor of the polypropylene matrix. In the peroxide-initiated dynamic vulcanization process, free radicals not only initiate EPDM crosslinking, but also attack tertiary carbon and hydrogen atoms on the PP backbone, resulting in β -scission degradation of PP. This degradation not only reduces the mechanical properties of the material, but also generates a series of low molecular weight aldehydes, ketones, acids, which are important causes of the material to develop sour or burnt odors.
In addition, the residue removal efficiency in the process is low. Traditional TPV production is typically accomplished using a "one-step" twin screw extrusion process, i.e., all mixing, shearing, reacting, and devolatilizing are accomplished in one extruder. Because the reaction section and the devolatilization section are short in distance and the melt viscosity is high, volatile small molecules wrapped in the rubber particles or deep layers are difficult to diffuse to the surface of the melt in a short time and are pumped away by vacuum. Although there have been attempts to introduce adsorbents or masking agents, these methods often address the symptoms but not the root cause, and adsorbents tend to deactivate or saturate at high temperatures and high shear.
In view of these challenges, developing a novel TPV technology that can not only maintain excellent physical and mechanical properties, but also thoroughly eliminate odor sources from both chemical reaction sources and physical preparation processes has become a critical challenge in the current industry.
Disclosure of Invention
The invention aims to provide a thermoplastic vulcanized rubber for a low-odor automobile skin, and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The thermoplastic vulcanized rubber for the low-odor automobile skin comprises the following raw materials in parts by weight:
50-80 parts of ethylene-propylene-diene copolymer rubber (EPDM),
20-50 Parts of polypropylene resin (PP),
5-15 Parts of a compatilizer,
0.5 To 2.5 parts of compound cross-linking agent,
0.5-2.0 Parts of odor adsorbent,
0.5-1.0 Parts of antioxidant.
In the scheme, EPDM, PP and a compound crosslinking agent are used as core reaction components. EPDM as a dispersed phase imparts excellent elasticity and soft touch to the material, and PP as a continuous phase provides a heat resistant backbone and process flowability to the material. The compound cross-linking agent is the key for realizing the dynamic vulcanization process and controlling the odor grade of the material.
According to a further technical scheme, the ethylene-propylene-diene copolymer rubber is semi-crystalline ethylene propylene diene monomer rubber, the ethylene content of the ethylene-propylene diene monomer rubber is 65% -75%, the ethylidene norbornene content of a third monomer is 4.0% -5.5%, and the Mooney viscosity of the ethylene-propylene-diene monomer rubber under the condition of ML (1+4) 125 ℃ is 20-25 MU.
According to a further technical scheme, the polypropylene resin is high-fluidity impact-resistant copolymerized polypropylene, the density of the polypropylene resin is 0.90-0.91 g/cm 3, the melt mass flow rate of the polypropylene resin under the conditions of 230 ℃ per 2.16kg is 15-35 g/10min, and the flexural modulus of the polypropylene resin is 900-1300 MPa. The high flowability PP is advantageous in forming a continuous phase during dynamic vulcanization, encapsulating the crosslinked rubber particles.
The compatilizer is one or a mixture of two of styrene-ethylene-butylene-styrene block copolymer and ethylene-octene copolymer, and can be used as an interface modifier to reduce the interfacial tension of rubber and plastic two phases, improve the compatibility and ensure that the rubber particles are finer in size and more uniform in distribution.
According to a further technical scheme, the compound cross-linking agent consists of a main cross-linking agent and an auxiliary cross-linking agent in a mass ratio of 2:1-4:1, wherein the main cross-linking agent is bis (tert-butyl isopropyl peroxide) benzene (BIBP) with purity more than or equal to 96%, and the auxiliary cross-linking agent is trimethylolpropane trimethacrylate (TMPTMA). The thermal decomposition products of BIBP mainly include t-butanol and diisopropylbenzene, and do not produce acetophenone with bitter almond taste. Tertiary butanol has a boiling point of about 82 ℃, which makes it easy to gasify and remove in a subsequent extrusion vacuum devolatilization and 100 ℃ vacuum baking process. Meanwhile, the adopted trifunctional auxiliary crosslinking agent TMPTMA has the dual functions of 1, synergistic crosslinking, namely three high-activity methacrylate double bonds in TMPTMA molecules can rapidly react with free radicals generated by peroxide decomposition and branch on EPDM molecular chains, so that a compact crosslinking network is promoted to be formed, and the crosslinking efficiency is improved. 2. And (3) inhibiting degradation, wherein TMPTMA is used as a high-efficiency free radical capturing agent, and the reaction rate of TMPTMA and free radicals is obviously higher than the beta-chain scission degradation rate of polypropylene. By preferential combination with free radicals, the polypropylene molecular chain can be competitively protected, thereby remarkably reducing the small molecular odor substances generated by polypropylene degradation.
According to a further technical scheme, the odor adsorbent is one or a mixture of a plurality of modified zeolite molecular sieves, mesoporous silica and zinc ricinoleate master batch, and the pore size distribution of the odor adsorbent is between 0.5nm and 2.0 nm.
According to a further technical scheme, the antioxidant is selected from one or a mixture of more of pentaerythritol tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010), tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168) and n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076). Preferably a mixture of tris [2, 4-di-tert-butylphenyl ] phosphite (antioxidant 168) and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010).
Further, the invention also discloses a preparation method of the thermoplastic vulcanized rubber for the low-odor automobile skin, which comprises the following steps:
Firstly, adding ethylene-propylene-diene copolymer rubber, polypropylene resin, a compatilizer and an antioxidant in an internal mixer according to a formula proportion, and mixing for 5-10 minutes at 160-190 ℃ at a rotating speed of 40-80 rpm to form a blending melt;
Feeding the blending melt into a first double-screw extruder, injecting a compound cross-linking agent, carrying out dynamic vulcanization reaction under the strong shearing conditions of 180-220 ℃ and 300-500 rpm, removing volatile matters through a first vacuum exhaust port, and extruding and granulating to obtain intermediate particles;
step three, after mixing the intermediate particles with the odor adsorbent, feeding the mixture into a second double-screw extruder, performing melt dispersion and adsorption treatment at 170-200 ℃, performing deep devolatilization through a second vacuum exhaust port, and performing extrusion granulation;
And fourthly, placing the particles obtained in the third step in a vacuum oven, and baking for 1-2 hours at 90-110 ℃ under vacuum conditions to obtain the low-odor thermoplastic vulcanized rubber finished product for the automobile skin.
According to a further technical scheme, in the second step, the temperature of the first double-screw extruder is set to 140-160 ℃, the temperature of the compression melting section is 170-190 ℃, the temperature of the reaction vulcanization section is 190-210 ℃, the temperature of the vacuum devolatilization section is 180-200 ℃, the temperature of the machine head is 170-190 ℃, and the rotating speed of the main screw is 300-600 rpm.
According to the further technical scheme, a vacuum devolatilization system is started in the extrusion process in the second step and the third step, the vacuum degree is controlled to be-0.08 to-0.1 MPa, and the synergistic crosslinking reaction is carried out in the second step:
Firstly, a main crosslinking agent bis (tert-butyl isopropyl peroxide) benzene is decomposed under the heating condition to generate tert-butyl alcohol and active free radicals;
Subsequently, the auxiliary crosslinking agent trimethylolpropane trimethacrylate preferentially captures the free radical and is connected to the molecular chain of the ethylene-propylene-diene copolymer rubber through a grafting reaction;
Finally, under the action of shearing force field, the ethylene-propylene-diene copolymer rubber phase is crosslinked and phase inversion is realized, and the by-product tert-butanol is removed in the subsequent vacuum heat treatment process.
In the fourth step, the boiling point of tert-butanol as a decomposition product of BIBP is 82 ℃ and the baking temperature is set to 100 ℃, so that the residual tert-butanol is in an overheated state by utilizing a thermodynamic principle, and the residual tert-butanol is completely steamed out of the particles by matching with negative pressure provided by high vacuum, thereby realizing the low odor requirement.
Furthermore, the invention also discloses application of the thermoplastic vulcanized rubber for the low-odor automobile skin, and the thermoplastic vulcanized rubber for the low-odor automobile skin is used for preparing an automobile interior trim product comprising an automobile instrument panel skin, a door panel protection surface and a central channel cover plate through injection molding, extrusion or calendaring processes, and the product is free from oil mist precipitation under high-temperature illumination at 80-120 ℃.
As used herein, the terms "comprising," "including," "having," and the like are intended to be open-ended terms, meaning including, but not limited to.
The words used herein are words of description which, unless otherwise specifically noted, generally have the ordinary meaning of each word used in this field, in this disclosure, and in the specific context. Certain terms used to describe the present disclosure are discussed below, or elsewhere in this specification, to provide additional guidance to those skilled in the art in connection with the description herein.
The working principle and the advantages of the invention are as follows:
The invention provides a thermoplastic vulcanized rubber for a low-odor automobile skin, a preparation method and application thereof, and the odor problem of a TPV material is systematically solved through the synergistic effect of a chemical formula and a physical process.
In the chemical aspect, the main cross-linking agent BIBP is adopted to replace the traditional DCP, the thermal decomposition products of the main cross-linking agent BIBP are mainly tertiary butanol (with the boiling point of about 82 ℃) and diisopropylbenzene, and the generation of acetophenone with bitter almond taste (with the boiling point of 202 ℃) is stopped from the reaction source. Meanwhile, a trifunctional auxiliary cross-linking agent TMPTMA is introduced, and a plurality of high-activity double bonds of the TMPTMA are used for capturing free radicals preferentially and grafting the free radicals on an EPDM molecular chain, so that the cross-linking efficiency is improved, more importantly, the beta-chain breakage attack of the free radicals on a PP main chain is effectively inhibited through a competition reaction, and therefore acid odor type micromolecular odor substances generated by PP degradation are greatly reduced.
In the physical process level, the invention designs a unique process of two-step extrusion and vacuum baking. The first extrusion is mainly used for realizing dynamic vulcanization reaction, and the second extrusion is specially used for introducing the adsorbent and providing a new melt surface for performing secondary efficient devolatilization, so that the early failure of the adsorbent in a high-temperature high-shear reaction section is avoided. Finally, through a 100 ℃ vacuum baking step, the volatile substances remained in the deep layer are thoroughly driven off and removed by utilizing the thermodynamic condition that the boiling point (82 ℃) of tertiary butanol is lower than the baking temperature and combining vacuum negative pressure.
The invention ensures that the odor grade of the obtained TPV material stably reaches less than or equal to 3.0 grade while maintaining excellent mechanical property through the deep coupling of chemical and physical measures, and the atomization value is lower than 0.5mg, thereby comprehensively meeting the severity standard of high-end automobile interior trim.
Detailed Description
The following detailed description will clearly illustrate the present invention, and it will be apparent to those skilled in the art from this disclosure that various changes and modifications can be made in the technology taught herein without departing from the spirit and scope of the present invention.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present disclosure. Singular forms such as "a," "an," "the," and "the" are intended to include the plural forms as well, as used herein.
The raw materials used in the scheme have the following specifications:
EPDM, arrheniaceae 2470C, 69% ethylene, 4.5% ENB, and Mooney viscosity 22MU.
PP, medium petrochemical M2600R, melt index (MFR) 25g/10min, flexural modulus 1100MPa.
Compatibilizing agent SEBS, U.S. Korotten (Kraton) G1651.
The main crosslinking agent is BIBP, bis (tert-butyl isopropyl peroxide) benzene with the purity of 96 percent.
Auxiliary cross-linking agent TMPTMA, trimethylol propane trimethacrylate.
Odor adsorbent, modified zeolite molecular sieve master batch.
Irganox1010 and Irgafos168 are compounded according to a ratio of 1:1.
The contrast cross-linking agent is DCP, dicumyl peroxide.
Examples 1 to 4 thermoplastic vulcanizates for low odor automobile skins, the raw material formulations are shown in Table 1.
Table 1 example 1 composition of the formula (parts by weight) for 4
The preparation process comprises the following steps:
Step one, dividing the EPDM2470C rubber block into irregular small blocks of 3-5 kg by a hydraulic rubber cutter. The EPDM pellets, polypropylene, SEBS and antioxidant were fed into a 35L mesh internal mixer, the initial temperature was set at 140 ℃, and the rotor speed was 60rpm. Mixing for 8 minutes under the action of shearing heat, and raising the temperature of the materials to about 180 ℃ to form a macroscopically uniform blend, and then granulating through a single-screw extruder.
And step two, feeding the particles obtained in the step one into a first homodromous double-screw extruder through a weightless feeder. After the extruder melting section, a pre-mixed liquid cross-linking agent (BIBP is dissolved in TMPTMA) is injected, and intermediate particles are obtained through dynamic vulcanization reaction. The temperature of each section of the extruder is set to be 140-160 ℃ in the feeding section, 170-190 ℃ in the compression melting section, 190-210 ℃ in the reaction vulcanization section, 180-200 ℃ in the vacuum devolatilization section and 170-190 ℃ in the machine head, the rotating speed of a screw of a main machine is 400rpm, and the vacuum degree of-0.09 MPa is maintained in the vacuum devolatilization section.
And thirdly, uniformly mixing the intermediate particles with the odor adsorbent, and feeding the mixture into a second double-screw extruder through a feeder. The temperature of the whole extrusion line is controlled at about 180 ℃ to prevent the secondary degradation of materials, and the vacuum degree is kept at-0.095 MPa. The dispersion of the adsorbent and the updating of the surface of the melt are utilized to further remove residual peculiar smell substances, and secondary granulation particles are obtained after granulation.
And fourthly, placing the particles obtained in the third step into a vacuum oven for baking. The baking temperature was set at 100℃for 2 hours and the vacuum was-0.09 MPa. This step uses conditions where the bake temperature is above the boiling point (about 82 ℃) of t-butanol, the decomposition product of BIBP, and is forced to remove it under negative pressure. Cooling and packaging after baking to obtain the low-odor TPV finished product.
To verify the technical effect of the present invention, 3 comparative examples were set up, and the formulations are shown in table 2.
Comparative example 1 uses a conventional DCP system and does not assist the crosslinking agent, the preparation method is the same as example 3, the influence of the type of the crosslinking agent is verified, comparative example 2 uses the formulation of example 3 but simplifies the process, only internal mixing and one-time extrusion are used, the influence of the preparation method is verified, comparative example 3 uses BIBP and does not assist the crosslinking agent, the preparation method is the same as example 3, and the synergistic effect of TMPTMA is verified.
Table 2 comparative example formulation and process variation
Performance testing and results analysis:
the TPV particles prepared in examples and comparative examples were injection molded into standard test pieces and tested as follows:
Hardness according to GB/T531.1, average value of 5 points
Tensile Strength and elongation at break measured according to GB/T528, tensile speed 500mm/min
Odor grade VDA270C3 standard, 3L dry bottle method, 80 ℃ heating for 2 hours, by 3 professional sniffers (grade 1 odorless to grade 6 intolerable).
Atomization value DIN75201-B weight method, mg.
TABLE 3 Performance test results
Analysis of results:
The hardness of example 1 is 90A, the tensile strength reaches 19.5MPa, the material is suitable for being used as a high-hardness supporting material, the hardness of example 2 is reduced to 60A, the touch is soft, the tensile strength is still kept at 14.5MPa, and the material is suitable for soft touch skins. In the protection range of the formula, the odor grade of the product is stable at 3.0 level, and the atomization value is lower than 0.5mg, which indicates that the BIBP/TMPTMA+double-order extrusion+vacuum baking technology route has general applicability and effectiveness in the coverage range of the whole claims.
Comparative example 1 uses a conventional crosslinker DCP, which has an odor grade as high as 4.5 and a slightly higher atomization value, and proves that the use of BIBP instead of DCP is a key chemical basis for improving odor from the source.
Comparative example 2, which used the low odor cross-linker BIBP, but did not undergo a second extrusion and 100 ℃ vacuum bake, had an odor rating of 4.0, indicating that the tbutanol was not completely removed from the BIBP decomposition product. Example 1 the successful removal of t-butanol by a 100 ℃ vacuum bake verifies the necessity of this particular process step.
Comparative example 3 used the BIBP and full set process, but without the addition of the co-crosslinking agent TMPTMA. Example 3, which had a significantly lower tensile strength than the equivalent, had an odor rating of 4.0. The result proves that TMPTMA plays a key role in capturing free radicals in the system, and can inhibit beta-chain scission degradation of peroxide on a polypropylene matrix, so that small molecular odor caused by degradation is reduced, and simultaneously, the crosslinking efficiency and the mechanical property are improved.
In conclusion, the comprehensive optimization of the TPV material in odor, atomization and mechanical properties is realized through the cooperation of the specific formula combination and the multistage processing technology, and the severe application requirements of the automobile skin are completely met.
The above embodiments are provided to illustrate the technical concept and features of the present invention and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (10)
1. The thermoplastic vulcanized rubber for the low-odor automobile skin is characterized by comprising the following raw materials in parts by weight:
50-80 parts of ethylene-propylene-diene copolymer rubber,
20-50 Parts of polypropylene resin,
5-15 Parts of a compatilizer,
0.5 To 2.5 parts of compound cross-linking agent,
0.5-2.0 Parts of odor adsorbent,
0.5-1.0 Parts of antioxidant.
2. The thermoplastic vulcanizate of claim 1, wherein the ethylene-propylene-diene copolymer rubber is a semi-crystalline ethylene propylene diene monomer having an ethylene content of 65% to 75%, a ethylidene norbornene content of 4.0% to 5.5%, and a Mooney viscosity of 20 to 25MU at ML (1+4) 125 ℃.
3. The thermoplastic vulcanizate of claim 1, wherein the polypropylene resin is a high-flowability impact-resistant copolymer polypropylene having a density of 0.90 to 0.91g/cm 3, a melt mass flow rate of 15 to 35g/10min at 230 ℃ per 2.16kg, and a flexural modulus of 900 to 1300MPa.
4. A thermoplastic vulcanizate for low odor automotive skins according to claim 1, wherein the compatibilizing agent is selected from one or a mixture of two of styrene-ethylene-butene-styrene block copolymers, ethylene-octene copolymers.
5. The low-odor thermoplastic vulcanized rubber for automobile skins, which is characterized in that the compound cross-linking agent consists of a main cross-linking agent and an auxiliary cross-linking agent in a mass ratio of 2:1-4:1, wherein the main cross-linking agent is bis (tert-butyl isopropyl peroxide) benzene, the purity of the main cross-linking agent is more than or equal to 96%, and the auxiliary cross-linking agent is trimethylolpropane trimethacrylate.
6. The thermoplastic vulcanizate for low odor automobile skin of claim 1, wherein the odor adsorbent is selected from one or more of modified zeolite molecular sieve, mesoporous silica, and zinc ricinoleate master batch, and has a pore size distribution of 0.5nm to 2.0 nm.
7. A thermoplastic vulcanizate for low odor automotive skins according to claim 1, wherein the antioxidant is selected from one or a mixture of more of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite, n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
8. A method for preparing the thermoplastic vulcanized rubber for the low-odor automobile skin, which is characterized by comprising the following steps of:
Firstly, adding ethylene-propylene-diene copolymer rubber, polypropylene resin, a compatilizer and an antioxidant in an internal mixer according to a formula proportion, and mixing for 5-10 minutes at 160-190 ℃ at a rotating speed of 40-80 rpm to form a blending melt;
Feeding the blending melt into a first double-screw extruder, injecting a compound cross-linking agent, carrying out dynamic vulcanization reaction under the strong shearing conditions of 180-220 ℃ and 300-500 rpm, removing volatile matters through a first vacuum exhaust port, and extruding and granulating to obtain intermediate particles;
step three, after mixing the intermediate particles with the odor adsorbent, feeding the mixture into a second double-screw extruder, performing melt dispersion and adsorption treatment at 170-200 ℃, performing deep devolatilization through a second vacuum exhaust port, and performing extrusion granulation;
And fourthly, placing the particles obtained in the third step in a vacuum oven, and baking for 1-2 hours at 90-110 ℃ under vacuum conditions to obtain the low-odor thermoplastic vulcanized rubber finished product for the automobile skin.
9. The preparation method of the thermoplastic vulcanized rubber for the low-odor automobile skin, which is disclosed in claim 8, is characterized in that a vacuum devolatilization system is required to be started in the extrusion process in the second step and the third step, the vacuum degree is controlled to be-0.08 to-0.1 MPa, and the cooperative crosslinking reaction is carried out in the second step:
Firstly, a main crosslinking agent bis (tert-butyl isopropyl peroxide) benzene is decomposed under the heating condition to generate tert-butyl alcohol and active free radicals;
Subsequently, the auxiliary crosslinking agent trimethylolpropane trimethacrylate preferentially captures the free radical and is connected to the molecular chain of the ethylene-propylene-diene copolymer rubber through a grafting reaction;
Finally, under the action of shearing force field, the ethylene-propylene-diene copolymer rubber phase is crosslinked and phase inversion is realized, and the by-product tert-butanol is removed in the subsequent vacuum heat treatment process.
10. The application of the thermoplastic vulcanized rubber for the low-odor automobile skin is characterized in that the thermoplastic vulcanized rubber for the low-odor automobile skin is implemented by any one of claims 1-7 and is used for preparing an automobile interior trim product comprising an automobile instrument panel skin, a door panel facing and a central passage cover plate through injection molding, extrusion or calendaring processes, and the product is free from oil mist precipitation under high-temperature illumination at 80-120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202511990693.8A CN121574466A (en) | 2025-12-26 | 2025-12-26 | A low-odor thermoplastic vulcanizate for automotive skin, its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202511990693.8A CN121574466A (en) | 2025-12-26 | 2025-12-26 | A low-odor thermoplastic vulcanizate for automotive skin, its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN121574466A true CN121574466A (en) | 2026-02-27 |
Family
ID=98840480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202511990693.8A Pending CN121574466A (en) | 2025-12-26 | 2025-12-26 | A low-odor thermoplastic vulcanizate for automotive skin, its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN121574466A (en) |
-
2025
- 2025-12-26 CN CN202511990693.8A patent/CN121574466A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0252648B2 (en) | ||
| WO2007001601A1 (en) | Dynamic vulcanization process for preparing thermoplastic elastomers | |
| EP1279684A1 (en) | Polypropylene copolymers and method of preparing polypropylene copolymers | |
| JP7499006B2 (en) | Elastomer composition, water-crosslinkable elastomer composition, and method for producing same | |
| JP2658222B2 (en) | Thermoplastic elastomer composition and method for producing the same | |
| EP0336780B1 (en) | Thermoplastic resin or elastomer composition having excellent paint adhesion and laminate comprising layer of said thermoplastic elastomer and polyurethane layer | |
| JP2006526694A (en) | Co-reagent for preparing thermoplastic elastomer blends of rubber and polyolefin | |
| WO2007001600A1 (en) | Process for preparing thermoplastic elastomers by dynamic vulcanization | |
| CN118085457A (en) | A low-odor thermoplastic elastomer and its preparation method and application | |
| WO2008008129A1 (en) | Method for improving extrusion surface smoothness in thermoplastic vulcanizates | |
| JPH0349927B2 (en) | ||
| JP3418013B2 (en) | Thermoplastic olefin based elastomer composition and method for producing the same | |
| JP4625150B2 (en) | Flame-retardant thermoplastic elastomer resin composition and method for producing the same | |
| JPH0556780B2 (en) | ||
| KR940003261B1 (en) | Process for preparing thermoplastic elastomer composition and thermoplastic elastomer composition | |
| CN1164667C (en) | Polypropylene resin composition and injection molded product thereof | |
| CN121574466A (en) | A low-odor thermoplastic vulcanizate for automotive skin, its preparation method and application | |
| CN1869119A (en) | Preparation method of partly cross-linked dystectic strength polypropylene | |
| JP3731459B2 (en) | Process for producing olefinic thermoplastic elastomer composition | |
| JP5076255B2 (en) | Method for producing thermoplastic elastomer composition for extrusion molding | |
| JP4758588B2 (en) | Cross-linked olefin rubber composition | |
| JP2000072933A (en) | Olefin elastomer composition | |
| JP2000103909A (en) | Production of elastomer composition | |
| JP2798303B2 (en) | Method for producing thermoplastic elastomer composition and thermoplastic elastomer composition | |
| JPWO2001064783A1 (en) | Olefin-based rubber composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |