KR102304589B1 - Reworkable ethylene propylene diene rubber and method for manufacturing the same - Google Patents

Abstract

An embodiment of the present invention, mEPDM (maleated Ethylene Propylene Diene Rubber) and amino-triazole (amino-triazole); including; at least a portion of the aminotriazole is grafted to the mEPDM, providing a modified mEPDM do.

Description

Reusable ethylene propylene rubber and its manufacturing method

The present invention relates to a reusable ethylene propylene rubber and a method for manufacturing the same, and more particularly, to a reusable grafted ethylene propylene rubber modified with amino triazole, and a method for manufacturing the same.

The use of plastic materials or rubber materials is increasing in order to improve the performance of parts for tractors or automobiles. For example, a rubber or plastic material having excellent mechanical properties is widely used as an interior material or exterior material of a tractor or automobile.

Specifically, as an interior or exterior material of a tractor or automobile, conventional maleic anhydride grafted ethylene propylene rubber (maleated Ethylene Propylene Diene Rubber, mEPDM) (hereinafter referred to as "mEPDM") is used became mEPDM is generally crosslinked by sulfur or peroxide, and is molded by an extruder or injection machine under processing temperature to make a product. However, in the manufacturing process of mEPDM, chemical bonding occurs in mEPDM due to heat and mEPDM is hardened, so it is known that the reuse of a product molded by mEPDM is impossible or limited.

The present invention relates to a modified ethylene propylene rubber (modified mEPDM) grafted with maleic anhydride, which can solve the above limitations, and a method for producing the same.

An embodiment of the present invention is to improve maleic anhydride grafted ethylene propylene rubber (mEPDM) to provide a reusable modified mEPDM.

Another embodiment of the present invention is to provide a modified mEPDM capable of having excellent tensile strength and elongation even after high-temperature pressurization.

Another embodiment of the present invention is to provide a mEPDM-modified composition capable of providing the modified mEPDM and a method for preparing mEPDM.

In addition to the aspects of the present invention mentioned above, other features and advantages of the present invention will be described below or will be clearly understood by those of ordinary skill in the art from such description.

According to one aspect of the present invention as described above, in one embodiment of the present invention, mEPDM (maleated Ethylene Propylene Diene Rubber); and amino-triazole; at least a portion of the aminotriazole is grafted onto the mEPDM, providing a modified mEPDM.

The modified mEPDM includes 0.5 to 2.0 parts by weight of the aminotriazole based on 100 parts by weight of the mEPDM.

The aminotriazole is 3,5-diamino-1,2,4-triazole (3,5-diamino-1,2,4-trizole).

The modified mEPDM has a tensile strength of 1.8 to 2.2 MPa and an elongation of 660 to 690% after the first high-temperature pressurization at 230° C. at 15 MPa for 10 minutes.

The modified mEPDM has a tensile strength and an elongation of 90% or more and an elongation of 90% or more after the first high-temperature pressing, respectively, compared to the tensile strength and elongation before the first high-temperature pressing.

The modified mEPDM has a tensile strength of 1.7 to 2.1 MPa and an elongation of 650 to 670% after the first high temperature pressing at 230° C. and a second high temperature pressing at 15 MPa for 10 minutes.

The modified mEPDM has a tensile strength and an elongation of 90% or more and an elongation of 90% or more after the second high-temperature pressing, respectively, compared to the tensile strength and elongation before the first high-temperature pressing.

The mEPDM may include, based on the total weight of the mEPDM, 5 to 10% by weight of ethylidene norbornene; 45 to 70% by weight of ethylene; 20 to 45% by weight of propylene; and 0.1 to 2.0% by weight of maleic anhydride; wherein the maleic anhydride is grafted onto EPDM (Ethylene Propylene Diene Rubber) composed of the ethylidene norbornene, the ethylene, and the propylene.

Another embodiment of the present invention, mEPDM 100 parts by weight; and 0.5 to 2.0 parts by weight of aminotriazole based on 100 parts by weight of the mEPDM.

Another embodiment of the present invention, mEPDM 100 parts by weight; and 0.5 to 2.0 parts by weight of aminotriazole based on 100 parts by weight of the mEPDM; melt-mixing at a temperature of 210° C. or less.

The above general description of the present invention is only for illustrating or explaining the present invention, and does not limit the scope of the present invention.

The modified mEPDM according to an embodiment of the present invention can be reused because it has tensile strength and elongation even after high-temperature pressurization. The modified mEPDM according to an embodiment of the present invention may be used as an interior or exterior material of a tractor or automobile, and may be reused if necessary.

The interior or exterior material of a tractor or automobile manufactured from modified mEPDM according to an embodiment of the present invention has excellent durability, weather resistance and reliability. In addition, the modified mEPDM according to an embodiment of the present invention may be reprocessed and reused.

BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings, which serve to understand the invention and constitute a part of this specification, together with the description, explain the principles of the invention.
1 is a manufacturing process diagram of a modified mEPDM according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail.

It will be apparent to those skilled in the art that various changes and modifications of the present invention are possible without departing from the spirit and scope of the present invention. Accordingly, the present invention includes all modifications and variations falling within the scope of the invention described in the claims and their equivalents.

When 'including', 'having', 'consisting', etc. mentioned in this specification are used, other parts may be added unless the expression 'only' is used. When a component is expressed in the singular, the plural is included unless specifically stated otherwise. In addition, in interpreting the components, it is interpreted as including an error range even if there is no separate explicit description.

In the case of a description of a temporal relationship, for example, if the temporal relationship is described with 'after', 'following', 'next to', 'before', etc., 'immediately' or 'directly' It may include cases that are not continuous unless the expression is used.

To describe various elements, expressions such as 'first', 'second', etc. are used, but these elements are not limited by these terms. These terms are only used to distinguish one component from another.

The term “at least one” should be understood to include all possible combinations from one or more related items.

Each feature of the various embodiments of the present invention may be partially or wholly combined or combined with each other, technically various interlocking and driving are possible, and each of the embodiments may be implemented independently of each other or may be implemented together in a related relationship. may be

One embodiment of the present invention provides a modified mEPDM containing amino triazole (amino triazole).

The modified mEPDM according to an embodiment of the present invention includes maleated ethylene propylene diene rubber (mEPDM) and amino-triazole, and at least a portion of the aminotriazole is grafted to mEPDM.

In one embodiment of the present invention, ethylene propylene rubber (maleated Ethylene Propylene Diene Rubber) grafted with maleic anhydride is referred to as "mEPDM", and by amino-triazole Modified mEPDM is referred to as "modified mEPDM".

Specifically, mEPDM may contain 5 to 10% by weight of ethylidene norbornene, 45 to 70% by weight of ethylene, 20 to 45% by weight of propylene, and 0.1 to 2.0% by weight of maleic anhydride, based on the total weight of mEPDM. can Here, maleic anhydride is grafted to EPDM (Ethylene Propylene Diene Rubber) composed of ethylidene norbornene, ethylene and propylene. At this time, if the content of maleic anhydride is less than 0.1 wt% based on the total weight of the mEPDM, the graft reaction may not occur smoothly, and if it exceeds 2.0 wt%, the elasticity of the mEPDM itself may be reduced.

A commercially available product as mEPDM may be used. For example, Chemtura's Royaltuf 485 or 498 may be used as the mEPDM according to an embodiment of the present invention.

At least a portion of the aminotriazole is grafted onto mEPDM. Aminotriazoles can especially be grafted onto maleic anhydride of mEPDM. Aminotriazole-grafted mEPDM modified mEPDM has excellent tensile strength and elongation even after high-temperature pressurization, and thus has excellent reuse properties.

The modified mEPDM according to an embodiment of the present invention contains 0.5 to 2.0 parts by weight of aminotriazole based on 100 parts by weight of mEPDM. If the content of aminotriazole is less than 0.5 parts by weight based on 100 parts by weight of mEPDM, the graft reaction of aminotriazole is not smooth, so that the reuse characteristics of mEPDM are not sufficiently improved. On the other hand, when the content of aminotriazole exceeds 2.0 parts by weight based on 100 parts by weight of mEPDM, the reactivity between aminotriazole and mEPDM may decrease, and the physical properties of mEPDM may be deteriorated. More specifically, the content of maleic anhydride based on the total weight of mEPDM is about 0.1 to 2.0% by weight. When aminotriazole is added in excess, the reactivity of mEPDM may be reduced.

As the aminotriazole, for example, 3,5-diamino-1,2,4-triazole (3,5-diamino-1,2,4-trizole) can be used. According to an embodiment of the present invention, commercially available aminotriazole may be used. Examples of commercially available aminotriazoles are products from Sigma Aldrich.

In one embodiment of the present invention, when the physical properties of the molded article after the high temperature and pressure treatment are 90% or more compared to the physical properties of the molded article before the high temperature and pressure treatment, it is determined that the molding has reuse characteristics.

More specifically, when the modified mEPDM according to an embodiment of the present invention has physical properties of 90% or more compared to the physical properties before the high temperature and pressure treatment after high temperature and pressure treatment, it is determined that the modified mEPDM has reuse characteristics. To determine the reuse properties, the tensile strength and elongation of the modified mEPDM were measured.

Tensile strength and elongation are measured with a universal testing machine (UTM). The width of the sample used for measurement is 12.7 mm, the distance between grips is 50 mm, and the measurement speed is 50 mm/min.

The modified mEPDM according to an embodiment of the present invention has a tensile strength of 1.9 to 2.3 MPa and an elongation of 670 to 690% at room temperature. Modified mEPDM having tensile strength and elongation in this range can be used as parts for tractors or automobiles, or as interior and exterior materials.

In addition, the modified mEPDM according to an embodiment of the present invention has a tensile strength of 1.8 to 2.2 MPa and an elongation of 660 to 690% after the first high-temperature pressurization at 230° C. at 15 MPa for 10 minutes.

Here, the condition of first pressing the modified mEPDM at 230° C. at 15 MPa at a high temperature for 10 minutes corresponds to the first reuse condition of the modified mEPDM. That is, when the modified mEPDM has a tensile strength of 1.8 to 2.2 MPa and an elongation of 660 to 690% after the first high-temperature pressurization at 230° C. at 15 MPa for 10 minutes, excellent tensile strength and It may have an elongation.

The modified mEPDM according to an embodiment of the present invention has a tensile strength and an elongation of 90% or more and an elongation of 90% or more after the first high-temperature pressing, respectively, compared to the tensile strength and elongation before the first high-temperature pressing. As such, the modified mEPDM according to an embodiment of the present invention may have 90% or more of physical properties before reuse even if it is first reused.

The modified mEPDM according to an embodiment of the present invention has a tensile strength of 1.7 to 2.1 MPa and an elongation of 650 to 670% after the second high temperature pressing at 230° C. for 10 minutes again after the second high temperature pressing.

Here, the condition of secondary high-temperature pressurization of the modified mEPDM at 230° C. at 15 MPa for 10 minutes corresponds to the secondary reuse condition of the modified mEPDM. When the modified mEPDM has a tensile strength of 1.8 to 2.2 MPa and an elongation of 660 to 690% after the modified mEPDM is first hot-pressed at 230° C. at 15 MPa for 10 minutes and then secondly hot-pressed at 230° C. for 10 minutes at 15 MPa, Even if the modified mEPDM is reused a second time, it may have excellent tensile strength and elongation.

The modified mEPDM according to an embodiment of the present invention has a tensile strength and an elongation of 90% or more and an elongation of 90% or more after the second high temperature pressing, respectively, compared to the tensile strength and elongation before the first high temperature pressing. As such, the modified mEPDM according to an embodiment of the present invention may have 90% or more of physical properties compared to before reuse, even if it is secondarily reused.

Another embodiment of the present invention may provide a mEPDM-modified composition comprising 100 parts by weight of mEPDM and 0.5 to 2.0 parts by weight of aminotriazole based on 100 parts by weight of mEPDM. Modified mEPDM can be prepared by rubber molding using the mEPDM-modified composition.

Here, mEPDM may include 5 to 10% by weight of ethylidene norbornene, 45 to 70% by weight of ethylene, 20 to 45% by weight of propylene, and 0.1 to 2.0% by weight of maleic anhydride, based on the total weight of mEPDM. have. In addition, maleic anhydride is grafted onto EPDM composed of ethylidene norbornene, ethylene and propylene.

Another embodiment of the present invention provides a method for preparing a modified mEPDM.

1 is a manufacturing process diagram of a modified mEPDM according to another embodiment of the present invention. Referring to FIG. 1 , the method for preparing the modified mEPDM includes melting and mixing 100 parts by weight of mEPDM and 0.5 to 2.0 parts by weight of aminotriazole based on 100 parts by weight of mEPDM at a temperature of 210° C. or less. The mEPDM modified composition can be prepared by such melt mixing.

The mEPDM-modified composition may be molded under predetermined conditions to prepare a modified mEPDM. Specifically, the modified mEPDM composition is prepared by high-temperature pressurization of the mEPDM-modified composition at 230° C. at 15 MPa for 10 minutes. The modified mEPDM prepared as described above may have, for example, a sheet form. The modified mEPDM prepared by molding can be used after standing at room temperature for about 18 hours.

Hereinafter, the present invention will be described in detail through preparation examples and comparative examples, test examples. However, the following preparation examples, comparative examples and test examples are only for helping the understanding of the present invention, and the scope of the present invention is not limited thereto.

<Preparation Examples 1 to 3>

According to the composition shown in Table 1 below, mEPDM (Royaltuf 498 from Chemtura) and aminotriazole (3,5-diamino-1,2,4-trizole, Sigma Aldrich) were administered to a mixing container, and a temperature of 210° C. The mEPDM-modified composition was prepared by melt-mixing, and the mEPDM-modified composition was pressurized at 230° C. for 10 minutes at 15 MPa to prepare a sheet-form modified mEPDM (Preparation Examples 1 to 3).

<Comparative Example 1>

A sheet form of mEPDM was prepared in the same manner as in Preparation Example 1, except that aminotriazole was not used.

<Test Example>

1) Initial physical property measurement

Tensile strength (MPa) and elongation (%) of the modified mEPDM of Preparation Example 1-3 and mEPDM of Comparative Example 1 prepared as above were measured, respectively.

Specifically, tensile strength and elongation were measured with a universal testing machine (UTM). The width of the sample used for measurement was 12.7 mm, the distance between grips was 50 mm, and the measurement speed was 50 mm/min. The results are shown in Table 1 below.

division Composition (parts by weight) initial physical properties mEPDM aminotriazole Tensile strength (MPa) Elongation (%) Preparation Example 1 100 0.5 1.94 675 Preparation 2 100 One 2.05 688 Preparation 3 100 2 2.17 695 Comparative Example 1 100 - 1.87 630

In Table 1, the initial physical properties show the tensile strength and elongation before the first high-temperature pressurization.

2) Primary reuse characteristic evaluation

The modified mEPDM of Preparation Example 1-3 and the mEPDM of Comparative Example 1 were subjected to a first high-temperature pressurization treatment. Specifically, the modified mEPDM prepared in Preparation Example 1-3 and the mEPDM prepared in Comparative Example 1 were first pressurized at a high temperature of 15 MPa at 230° C. for 10 minutes. The first high temperature pressurization corresponds to the first reuse condition.

Tensile strength (MPa) and elongation (%) were respectively measured for the modified mEPDM of Preparation Example 1-3 and Comparative Example 1 that was first pressurized at high temperature, and the results are shown in Table 2 below.

3) Secondary reuse characteristic evaluation

Secondary high-temperature pressurization was performed on the modified mEPDM of Preparation Example 1-3 and the mEPDM of Comparative Example 1 that was first pressurized at high temperature. Specifically, the modified mEPDM of Preparation Example 1-3 and the mEPDM of Comparative Example 1 that were first pressurized at high temperature were secondarily hot-pressed at 230° C. for 10 minutes at 15 MPa. The secondary high-temperature pressurization corresponds to the secondary reuse condition.

Tensile strength (MPa) and elongation (%) were respectively measured for the modified mEPDM of Preparation Example 1-3 and Comparative Example 1, which were pressurized at secondary high temperature, and the results are shown in Table 2 below.

division 1st high temperature pressurization Secondary high temperature pressurization tensile strength
(MPa) tensile strength
Retention (%) elongation
(%) elongation
Retention (%) tensile strength
(MPa) tensile strength
Retention (%) elongation
(%) elongation
Retention (%) Preparation Example 1 1.86 96 664 98 1.78 92 652 97 Preparation Example 2 1.99 97 680 99 1.92 94 659 96 Preparation 3 2.11 97 688 99 2.03 94 664 96 Comparative Example 1 1.20 64 450 71 0.87 47 320 51

In Table 2, the tensile strength retention and elongation retention ratio represent the ratio of the tensile strength and elongation after the first high-temperature pressurization or the second high-temperature pressurization to the initial tensile strength and initial elongation, respectively. Here, the initial tensile strength and the initial elongation are the tensile strength and the elongation before the first high-temperature pressing, respectively.

Referring to Table 2, the modified mEPDM according to Preparation Example 1-3 has a tensile strength and elongation of 90% or more and an elongation of 90% or more after the first high-temperature pressing, respectively, compared to the tensile strength and elongation of the initial (before the first high-temperature pressing). can be confirmed that As such, the modified mEPDM according to Preparation Example 1-3 may have physical properties of 90% or more before reuse even if it is first reused.

In addition, it can be seen that the modified mEPDM according to Preparation Example 1-3 has a tensile strength of 90% or more and an elongation of 90% or more after the second high temperature pressing, respectively, compared to the tensile strength and elongation of the initial (before the first high temperature pressing). have. In this way, even if the modified mEPDM according to Preparation Example 1-3 is reused for the second time, it has 90% or more of physical properties before reuse, so that it can be reused over the second time.

On the other hand, it can be seen that the mEPDM according to Comparative Example 1 has a tensile strength and an elongation of 65% or less and an elongation of 75% or less after the first high-temperature pressing, respectively, compared to the tensile strength and elongation of the initial stage (before the first high-temperature pressing). In addition, it can be seen that the mEPDM according to Comparative Example 1 has a tensile strength and an elongation of 50% or less and an elongation of 55% or less after the second high temperature pressing, respectively, compared to the tensile strength and elongation of the initial stage (before the first high temperature pressing). As such, the mEPDM according to Comparative Example 1 is not suitable for reuse because its physical properties are rapidly deteriorated upon reuse.

The present invention described above is not limited by the above-described embodiments and the accompanying drawings, and it is a technical field to which the present invention pertains that various substitutions, modifications and changes are possible without departing from the technical matters of the present invention. It will be clear to those of ordinary skill in the art. Therefore, the scope of the present invention is expressed by the following claims, and all changes or modifications derived from the meaning, scope, and equivalent concepts of the claims should be construed as being included in the scope of the present invention.

Claims (10)

maleated Ethylene Propylene Diene Rubber (mEPDM); and
Including; amino-triazole (amino-triazole);
At least a portion of the aminotriazole is grafted to the mEPDM,
Based on 100 parts by weight of the mEPDM, 0.5 to 2.0 parts by weight of the aminotriazole is included,
It has a tensile strength of 1.9 to 2.3 MPa and an elongation of 670 to 690% at room temperature,
After the first high-temperature pressurization to 15 MPa at 230 ° C. for 10 minutes, it has a tensile strength of 1.8 to 2.2 MPa and an elongation of 660 to 690%,
Compared to the tensile strength and elongation before the first high-temperature pressing, the modified mEPDM having a tensile strength of 90% or more and an elongation of 90% or more, respectively, after the first high-temperature pressing. delete According to claim 1,
The aminotriazole is 3,5-diamino-1,2,4-triazole (3,5-diamino-1,2,4-trizole), modified mEPDM. delete delete According to claim 1,
After the first high-temperature pressurization,
A modified mEPDM having a tensile strength of 1.7 to 2.1 MPa and an elongation of 650 to 670% after a second high temperature pressing at 230° C. to 15 MPa for 10 minutes. 7. The method of claim 6,
Compared to the tensile strength and elongation before the first high-temperature pressing, the modified mEPDM having a tensile strength of 90% or more and an elongation of 90% or more, respectively, after the second high-temperature pressing. According to claim 1,
The mEPDM is, based on the total weight of the mEPDM,
5 to 10% by weight of ethylidene norbornene;
45 to 70% by weight of ethylene;
20 to 45% by weight of propylene; and
0.1 to 2.0% by weight of maleic anhydride; contains,
The maleic anhydride is a modified mEPDM that is grafted to EPDM (Ethylene Propylene Diene Rubber) consisting of the ethylidene norbornene, the ethylene and the propylene. 100 parts by weight of mEPDM; and
Containing; 0.5 to 2.0 parts by weight of aminotriazole based on 100 parts by weight of the mEPDM
It has a tensile strength of 1.9 to 2.3 MPa and an elongation of 670 to 690% at room temperature, and a tensile strength of 1.8 to 2.2 MPa and an elongation of 660 to 690% after the first high-temperature pressurization to 15 MPa at 230° C. for 10 minutes, Compared to the tensile strength and elongation before the first high-temperature pressing, the mEPDM-modified composition for manufacturing modified mEPDM having a tensile strength of 90% or more and an elongation of 90% or more, respectively, after the first high-temperature pressing. 100 parts by weight of mEPDM; and 0.5 to 2.0 parts by weight of aminotriazole based on 100 parts by weight of the mEPDM; melt-mixing at a temperature of 210° C. or less,
It has a tensile strength of 1.9 to 2.3 MPa and an elongation of 670 to 690% at room temperature, and a tensile strength of 1.8 to 2.2 MPa and an elongation of 660 to 690% after the first high-temperature pressurization to 15 MPa at 230° C. for 10 minutes, A method of manufacturing a modified mEPDM having a tensile strength and an elongation of 90% or more and an elongation of 90% or more, respectively, after the first high-temperature pressing, compared to the tensile strength and elongation before the first high-temperature pressing.

Images