阅读说明：本技术 一种高弹性tpv材料及其制备方法 (High-elasticity TPV material and preparation method thereof ) 是由 陶磊 张文静 于 2019-11-04 设计创作，主要内容包括：本发明公开了一种具有高弹性的TPV材料配方及其制备方法,在EPDM配方中创新性的加入了NR作为改性单元提高材料的弹性,并通过将EPDM橡胶进行预硫化以及调整硫化体系的方式使复合材料中的橡胶相硫化程度一致,其基本组分包括三元乙丙橡胶30-80份、天然橡胶10-40份、聚丙烯20-40份、石蜡油30-100份、填料10-40份、硫化剂1-12份、助硫化剂0.1-3份,运用该发明制备的TPV材料较传统TPV材料具有更好的弹性,力学强度更高,能够显著降低材料压缩永久变形,适合工业化生产。(The invention discloses a TPV material formula with high elasticity and a preparation method thereof, NR is innovatively added in an EPDM formula as a modification unit to improve the elasticity of the material, the rubber phase vulcanization degree in a composite material is consistent by means of pre-vulcanizing EPDM rubber and adjusting a vulcanization system, the basic components of the TPV material formula comprise 30-80 parts of ethylene propylene diene monomer, 10-40 parts of natural rubber, 20-40 parts of polypropylene, 30-100 parts of paraffin oil, 10-40 parts of filler, 1-12 parts of vulcanizing agent and 0.1-3 parts of auxiliary vulcanizing agent.)

1. A high-elasticity TPV material and a preparation method thereof are disclosed, and the formula comprises the following components:

。

2. a high-elasticity TPV material and a preparation method thereof are disclosed, and the preparation method comprises

(1) Mechanically mixing ethylene propylene diene monomer, partial filler and paraffin oil in an internal mixer to obtain EPDM rubber compound, adding a co-vulcanizing agent into the EPDM rubber compound by using an open mill, and pre-vulcanizing the rubber compound added with the co-vulcanizing agent in a high-temperature internal mixer at 160 ℃ for 5 minutes to obtain pre-vulcanized EPDM master batch;

(2) adding materials such as natural rubber, pre-vulcanized EPDM master batch, residual filler, residual paraffin oil, internal and external lubricants and the like into an internal mixer for mixing to obtain binary mixed rubber, and granulating by using a single screw for later use;

(3) respectively adding the binary mixed rubber granules obtained in the step (2), PP, an antioxidant and a vulcanizing agent into a double-screw extruder through different feeding scales, adjusting the rotating speed of a main machine, and dynamically vulcanizing to obtain a TPV vulcanized semi-finished product;

(4) mixing the TPV vulcanization semi-finished product with color master batch, erucamide and other materials, adding the mixture into a hopper of a double-screw extruder, and extruding the mixture to obtain the high-elasticity TPV material.

3. The high-elasticity TPV material and the preparation method thereof are characterized in that the length-diameter ratio of a double-screw extruder is 56: 1-72: 1.

4. The high-elasticity TPV material and the preparation method thereof are characterized in that the main machine rotating speed of a double-screw extruder is 400 rpm-900 rpm.

5. The high-elasticity TPV material is characterized in that a vulcanizing agent in a formula is one or more of DCP, Biediwu and phenolic resin.

6. The high-elasticity TPV material is characterized in that the auxiliary vulcanizing agent in the formula is one or two of sulfur, TMPTMA and TGIA.

7. The high-elasticity TPV material is characterized in that the banburying and rubber discharging temperature of natural rubber is not more than 130 ℃.

8. The high-elasticity TPV material is characterized in that ethylene propylene diene monomer rubber is pre-vulcanized and then co-vulcanized with natural rubber.

Technical Field

The invention belongs to the technical field of production and processing of thermoplastic elastomers, and particularly relates to a high-elasticity TPV material and a preparation method thereof.

Background

With the requirement of people on lightweight materials, the types of materials used by people are changed to a certain extent, from rubber, plastics to elastomers, the properties and the processing technology of the materials can basically cover and meet most of the requirements of the current market, in recent years, the thermoplastic elastomers are rapidly popularized in the market due to the requirements on lightweight materials and the processing efficiency of the materials, and TPV materials are excellent in pressure change and oil resistance, so that the TPV materials are widely applied to the field of sealing products. 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 the ethylene propylene diene monomer dense vulcanized rubber, even compared with the imported TPV material, although the difference in mechanical strength of the domestic TPV material is not large, the pressure-variable property, especially the high-temperature pressure-variable property of the material has a large gap with the above products, so how to develop the low-pressure variable product and how to improve the high-temperature durability of the TPV material are problems to be solved urgently in the field.

The natural rubber is a rubber with high elasticity, compared with ethylene propylene diene monomer, the natural rubber has self-crystallization property, can provide excellent mechanical property of materials, has excellent elasticity, is widely used for preparing damping products and creep-resistant products, has excellent pressure-deformation property of products obtained by using the natural rubber as a main material, and can provide durable usability of the products.

Disclosure of Invention

In order to improve the mechanical property and the pressure-variable property of the current TPV material, the natural rubber is applied to the TPV formula, and from the preparation process of the TPV material, the vulcanization degree and the shear rate of the material in the processing process have a great relationship with the final property of the material, but the vulcanization degree of the natural rubber and the ethylene propylene diene monomer rubber is different at the same vulcanization temperature, and the preparation conditions of the material need to be improved in order to realize the simultaneous vulcanization of the natural rubber and the ethylene propylene diene monomer rubber and complete the crushing at a proper shear rate. And the natural rubber is easy to generate a cracking reaction of rubber molecular chains under the high-temperature vulcanization condition, namely, a vulcanization reversion phenomenon, and oxygen molecules cause oxidative decomposition of the molecular chains due to activity increase at high temperature, so that the organization structure is damaged, and the mechanical property of the material is reduced. Generally, the vulcanization temperature of the natural rubber is not more than 160 ℃, the vulcanization temperature of the ethylene propylene diene monomer is not more than 200 ℃, and the selection and the matching of the vulcanization accelerator have great influence on the co-vulcanization of the natural rubber and the ethylene propylene diene monomer.

The invention prepares NR and EPDM rubber into dynamic co-vulcanization thermoplastic elastomer by preparing the EPDM rubber pre-sulfide, adjusting the preparation process and the equipment process parameters, changing the vulcanization system, avoiding the degradation of NR in the high-temperature vulcanization stage, and simultaneously completing the vulcanization of the NR and the EPDM rubber and the shearing and crushing of the vulcanization phase to form a sea-island structure with micron-sized distribution, and the specific invention process is as follows:

1. a high-elasticity TPV material and a preparation method thereof are disclosed, and the formula comprises the following components:

2. a high-elasticity TPV material and a preparation method thereof are disclosed, and the preparation method comprises

(1) Mechanically mixing ethylene propylene diene monomer, partial filler and paraffin oil in an internal mixer to obtain EPDM rubber compound, adding a co-vulcanizing agent into the EPDM rubber compound by using an open mill, and pre-vulcanizing the rubber compound added with the co-vulcanizing agent in a high-temperature internal mixer at 160 ℃ for 5 minutes to obtain pre-vulcanized EPDM master batch;

(2) adding materials such as natural rubber, pre-vulcanized EPDM master batch, residual filler, residual paraffin oil, internal and external lubricants and the like into an internal mixer for mixing to obtain binary mixed rubber, and granulating by using a single screw for later use;

(3) respectively adding the binary mixed rubber granules obtained in the step (2), PP, an antioxidant and a vulcanizing agent into a double-screw extruder through different feeding scales, adjusting the rotating speed of a main machine, and dynamically vulcanizing to obtain a TPV vulcanized semi-finished product;

(4) mixing the TPV vulcanization semi-finished product with color master batch, erucamide and other materials, adding the mixture into a hopper of a double-screw extruder, and extruding the mixture to obtain the high-elasticity TPV material.

3. The high-elasticity TPV material and the preparation method thereof are characterized in that the length-diameter ratio of a double-screw extruder is 56: 1-72: 1.

4. The high-elasticity TPV material and the preparation method thereof are characterized in that the main machine rotating speed of a double-screw extruder is 400 rpm-900 rpm.

5. The high-elasticity TPV material is characterized in that a vulcanizing agent in a formula is one or more of DCP, Biediwu and phenolic resin.

6. The high-elasticity TPV material is characterized in that the auxiliary vulcanizing agent in the formula is one or two of sulfur, TMPTMA and TGIA.

7. The high-elasticity TPV material is characterized in that the banburying and rubber discharging temperature of natural rubber is not more than 130 ℃.

8. The high-elasticity TPV material is characterized in that ethylene propylene diene monomer rubber is pre-vulcanized and then co-vulcanized with natural rubber.

The TPV material prepared by adopting the vulcanizing agent/auxiliary vulcanizing agent system realizes better co-vulcanization state of NR and EPDM, simultaneously, the performance of a final product can be further improved by using an EPDM rubber pre-vulcanization method, the product performance is superior to that of the TPV material singly using the EPDM, the normal vulcanization time of the EPDM is shortened by carrying out pre-vulcanization treatment on the EPDM, the EPDM can obtain the same vulcanization degree with natural rubber under the low-temperature vulcanization condition, simultaneously, the formation of a two-phase interface crosslinking phase can be promoted, the elasticity of the TPV material obtained by the method is also greatly improved, and the large-scale production is easy.

Detailed Description

The technical solutions of the present invention will be further described in detail with reference to specific embodiments, but the following embodiments are not all examples, and other embodiments that can be made by those skilled in the art without creative efforts based on the specific embodiments of the present invention belong to the protection scope of the present invention.

Comparative example 1

Mechanically mixing 70 parts of ethylene propylene diene monomer and 15 parts of filler in an internal mixer to obtain EPDM rubber compound, then adding 0.3 part of co-vulcanizing agent TGIC into the EPDM rubber compound by using an open mill, and then pre-vulcanizing the rubber compound added with the co-vulcanizing agent in a high-temperature internal mixer at 160 ℃ for 5 minutes to obtain pre-vulcanized EPDM masterbatch; adding the materials such as the pre-vulcanized EPDM master batch, the rest 15 parts of filler, 40 parts of paraffin oil, internal and external lubricants and the like into an internal mixer for mixing to obtain binary mixed rubber, and granulating by using a single screw for later use; a double-screw extruder with the length-diameter ratio of 56: 1 is used, the EPDM mixed rubber granules, 30 parts of PP, 0.2 part of antioxidant and 3 parts of DCP serving as vulcanizing agent are respectively added into the double-screw extruder through different feeding scales, the rotating speed of a main engine is adjusted to 700rpm, the screw combination is 28/28, 28/28, 28/28, 28/28, 40/40, 40/40, 56/56, 56/56, 56/56, 56/28L, 45/5/32, 40/40, 90/5/56, 45/5/28, 45/5/28, 45/5/28, 40/40, 40/40, 45/5/32, 45/5/28L, 45/5/40, 90/5/56 and 40/40, 40/40, 56/56, 45/5/32, 40/40, 40/40, 90/5/40, 45/5/56, 45/5/40, 45/5/40, 40/40, 40/40, 40/40, 56/56, 45/5/28L, 45/5/40, 45/5/40, 45/5/40, 40/40, 40/40, 56/56, 56/28, 56/56, 56/56, 56/56, 28/28, the twin-screw setting temperature is 100 ℃/160 ℃/170 ℃/180 ℃/190 ℃/200 ℃/200 ℃/200 ℃/190 ℃/180 ℃/175 ℃/175 ℃/175 ℃/170 ℃, obtaining a TPV vulcanized semi-finished product after dynamic vulcanization; mixing the TPV vulcanization semi-finished product with color master batch, erucamide and other materials, adding the mixture into a hopper of a double-screw extruder, and extruding the mixture to obtain the high-elasticity TPV material.

Comparative example 2

Mechanically mixing 70 parts of ethylene propylene diene monomer rubber, 30 parts of filler, 40 parts of paraffin oil, an internal lubricant and an external lubricant in an internal mixer, and granulating by using a single screw for later use; using a double-screw extruder with the length-diameter ratio of 56: 1, respectively adding the obtained mixed colloidal particles, 30 parts of PP, 0.2 part of antioxidant, 3 parts of vulcanizing agent DCP and 0.3 part of co-vulcanizing agent TGIC into the double-screw extruder through different feeding scales, adjusting the rotating speed of a main engine to 700rpm, and combining the screws into 28/28, 28/28, 28/28, 28/28, 40/40, 40/40, 56/56, 56/56, 56/56, 56/28L, 45/5/32, 40/40, 90/5/56, 45/5/28, 45/5/28, 45/5/28, 40/40, 40/40, 45/5/32, 45/5/28L, 45/5/40 and 90/5/56, 40/40, 40/40, 56/56, 45/5/32, 40/40, 40/40, 90/5/40, 45/5/56, 45/5/40, 45/5/40, 40/40, 40/40, 40/40, 56/56, 45/5/28L, 45/5/40, 45/5/40, 45/5/40, 40/40, 40/40, 56/56, 56/28, 56/56, 56/56, 56/56, 28/28, the twin-screw is set at 100 ℃/160 ℃/170 ℃/180 ℃/190 ℃/200 ℃/200 ℃/200 ℃/200 ℃/190 ℃/180 ℃/175 ℃/175 ℃/170 ℃, obtaining a TPV vulcanized semi-finished product after dynamic vulcanization; mixing the TPV vulcanization semi-finished product with color master batch, erucamide and other materials, adding the mixture into a hopper of a double-screw extruder, and extruding the mixture to obtain the high-elasticity TPV material.

Comparative example 3

Carrying out mechanical mixing on 60 parts of ethylene propylene diene monomer, 10 parts of natural rubber, 30 parts of filler, 40 parts of paraffin oil, internal and external lubricants and the like in an internal mixer, and carrying out single-screw granulation for later use; using a double-screw extruder with the length-diameter ratio of 56: 1, respectively adding the obtained mixed colloidal particles, 30 parts of PP, 0.2 part of antioxidant, 3 parts of vulcanizing agent DCP and 0.3 part of co-vulcanizing agent TGIC into the double-screw extruder through different feeding scales, adjusting the rotating speed of a main engine to 700rpm, and combining the screws into 28/28, 28/28, 28/28, 28/28, 40/40, 40/40, 56/56, 56/56, 56/56, 56/28L, 45/5/32, 40/40, 90/5/56, 45/5/28, 45/5/28, 45/5/28, 40/40, 40/40, 45/5/32, 45/5/28L, 45/5/40 and 90/5/56, 40/40, 40/40, 56/56, 45/5/32, 40/40, 40/40, 90/5/40, 45/5/56, 45/5/40, 45/5/40, 40/40, 40/40, 40/40, 56/56, 45/5/28L, 45/5/40, 45/5/40, 45/5/40, 40/40, 40/40, 56/56, 56/28, 56/56, 56/56, 56/56, 28/28, the twin-screw is set at 100 ℃/160 ℃/170 ℃/180 ℃/190 ℃/200 ℃/200 ℃/200 ℃/200 ℃/190 ℃/180 ℃/175 ℃/175 ℃/170 ℃, obtaining a TPV vulcanized semi-finished product after dynamic vulcanization; mixing the TPV vulcanization semi-finished product with color master batch, erucamide and other materials, adding the mixture into a hopper of a double-screw extruder, and extruding the mixture to obtain the high-elasticity TPV material.