Recyclable reverse vulcanization copolymer vulcanized rubber as well as preparation method and application thereof

Abstract

The invention relates to recoverable reverse vulcanization copolymer vulcanized rubber as well as a preparation method and application thereof, and belongs to the technical field of polymer synthesis. The recoverable reverse vulcanized copolymer vulcanized rubber is prepared from the following raw materials in parts by weight: 100 parts of rubber, 1-10 parts of a reverse vulcanized copolymer, 1-5 parts of zinc oxide, 1-5 parts of stearic acid and 1-5 parts of an accelerant. According to the recoverable reverse vulcanization copolymer vulcanized rubber provided by the invention, the specific reverse vulcanization copolymer is adopted as the vulcanizing agent, a vulcanization network can be endowed with reprocessing performance under the action of the specific accelerant, and the vulcanized rubber can have reprocessing and creep resistance at the same time, so that the application range of the rubber is further expanded; good application prospects are realized.

Description

Technical Field

[0001] The present application relates to the technical field of polymer synthesis, and in particular to a recyclable reverse vulcanized copolymer vulcanized rubber and a preparation method and application thereof. Background Art

[0002] As an important engineering material, rubber is widely used in military and civilian fields such as aerospace, electronics, medical care, weapons and equipment due to its unique properties. With the widespread application and large consumption of rubber products, a large amount of waste rubber is generated. If it cannot be effectively treated and reused, it will not only cause a waste of resources, but also have an impact on the environment. However, the traditional sulfur vulcanization network, as a permanent cross-linked network, does not have the ability to be reprocessed, which seriously affects the recycling of rubber materials and has become one of the important problems to be solved in the rubber industry.

[0003] Although people are currently using a new dynamic cross-linking system in the rubber matrix to replace the traditional vulcanization cross-linking system to achieve the reprocessing of rubber materials. However, to date, the vulcanization network still occupies a dominant position in the rubber industry, and it is difficult to replace the traditional vulcanization network with a new cross-linking network. Therefore, in the rubber industry, how to achieve the recycling of vulcanized rubber is still a very serious problem. Summary of the invention

[0004] In view of this, the present application provides a recyclable inverse vulcanized copolymer vulcanized rubber and its preparation method and application, using a specific inverse vulcanized copolymer as a vulcanizing agent, which can give the vulcanized network reprocessing performance under a specific accelerator, and make the vulcanized rubber have both reprocessing and creep resistance properties, further expanding the application scope of the rubber, having good application prospects, and being able to effectively overcome the defects of the above-mentioned prior art.

[0005] The first aspect of the present application provides a recyclable inverse vulcanized copolymer vulcanized rubber, wherein the inverse vulcanized copolymer vulcanized rubber is prepared from the following raw materials in the following weight ratio:

[0006] 100 parts of rubber, 1-10 parts of inverse vulcanization copolymer, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, and 1-5 parts of accelerator.

[0007] Preferably, the inverse vulcanized copolymer vulcanized rubber is prepared from raw materials in the following weight ratio:

[0008] 100 parts of rubber, 1-10 parts of inverse vulcanization copolymer, 1-5 parts of zinc oxide, 1-3 parts of stearic acid, and 1-3 parts of accelerator.

[0009] Preferably, the inverse vulcanized copolymer vulcanized rubber is prepared from raw materials in the following weight ratio:

[0010] 100 parts of rubber, 2 parts of inverse vulcanized copolymer, 5 parts of zinc oxide, 1 part of stearic acid, and 2 parts of accelerator.

[0011] Preferably, the inverse vulcanized copolymer vulcanized rubber is prepared from raw materials in the following weight ratio:

[0012] 100 parts of rubber, 2 parts of inverse vulcanized copolymer, 5 parts of zinc oxide, 2 parts of stearic acid, and 2 parts of accelerator.

[0013] Preferably, the reverse vulcanization copolymer is at least one of an olefinic reverse vulcanization copolymer, an amine reverse vulcanization copolymer, a lipoic acid reverse vulcanization copolymer, an acrylic reverse vulcanization copolymer, and a fluorine reverse vulcanization copolymer.

[0014] Preferably, the reverse vulcanized copolymer is a butene-3-acid reverse vulcanized copolymer, a thioctic acid reverse vulcanized copolymer, or a thioctic acid derivative reverse vulcanized copolymer.

[0015] Preferably, the rubber is natural rubber or synthetic rubber; and the accelerator is accelerator CZ and / or accelerator DM.

[0016] Preferably, the synthetic rubber is at least one of epoxy rubber, styrene-butadiene rubber and isoprene rubber; and the accelerator is accelerator CZ and accelerator DM.

[0017] The second aspect of the present application also provides a method for preparing the above-mentioned recyclable inverse vulcanized copolymer vulcanized rubber, comprising the following steps:

[0018] S1. Weigh the raw materials of rubber, reverse vulcanization copolymer, zinc oxide, stearic acid and accelerator according to the weight ratio;

[0019] S2. Mix all the raw materials evenly and then vulcanize them to obtain the inverse vulcanized copolymer vulcanized rubber.

[0020] Preferably, in step S1, the preparation process of the reverse vulcanized copolymer is: sulfur is mixed with butene-3-acid, thioctic acid or a thioctic acid derivative, and reacted at 130-160° C. for 2-8 hours to obtain the reverse vulcanized copolymer;

[0021] Wherein, the mass ratio of sulfur to butene-3-acid, thioctic acid or thioctic acid derivative is (0.2-3): 1. Preferably, the mass ratio of sulfur to butene-3-acid, thioctic acid or thioctic acid derivative is (1-3):1.

[0022] Preferably, the preparation process of the butene-3-acid reverse vulcanized copolymer is: sulfur and butene-3-acid are mixed, and reacted at 135° C. for 6 hours to obtain the butene-3-acid reverse vulcanized copolymer.

[0023] Preferably, the preparation process of the thioctic acid reverse vulcanization copolymer is: sulfur, thioctic acid and N-methylimidazole are mixed, and reacted at 150° C. for 6 hours to obtain the thioctic acid reverse vulcanization copolymer.

[0024] Preferably, the preparation process of the lipoic acid derivative copolymer is: sulfur, lipoic acid derivative and N-methylimidazole are mixed, and reacted at 145° C. for 2 hours to obtain the lipoic acid derivative reverse vulcanized copolymer.

[0025] Preferably, in step S2, the vulcanization temperature is 130-160° C., the vulcanization time is 5-18 minutes, and the vulcanization pressure is 10-15 MPa.

[0026] The third aspect of the present application also provides the use of the above-mentioned recyclable inverse vulcanized copolymer vulcanized rubber in the preparation of a formulation or equipment for gaskets and shock-absorbing pads for tires and bridge engineering materials.

[0027] Compared with the prior art, this application has the following beneficial effects:

[0028] The present application provides a recyclable reverse vulcanized copolymer vulcanized rubber and a preparation method and application thereof. By adopting a specific reverse vulcanized copolymer as a vulcanizing agent, the vulcanized network can be given reprocessing performance under a specific accelerator, and the vulcanized rubber can have both reprocessing and creep resistance properties, further expanding the application scope of the rubber and having good application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the present application or the prior art, the drawings required for use in the description of the present application or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0030] Figure 1 Comparison photos before and after hot pressing of Example 1 of the present application;

[0031] Figure 2 These are comparison photos before and after hot pressing of comparative example 1 of this application. DETAILED DESCRIPTION

[0032] In order to make the purpose, technical solutions and advantages of this application clearer, the technical solutions in this application will be clearly and completely described below in conjunction with the drawings in this application. Obviously, the described embodiments are part of the embodiments of this application, not all of them. Based on the embodiments in this application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0033] Unless otherwise specified, the experimental methods used in the examples of this application are all conventional methods.

[0034] In the following examples and comparative examples, unless otherwise specified, all raw materials can be obtained by commercial purchase or conventional methods; and all equipments are known products and were obtained by purchasing commercially available products.

[0035] Example 1: Designing a reprocessing vulcanization network using a butenoic acid inverse vulcanized copolymer

[0036] On an open mill, 2 g of butene-3-acid inverse vulcanized copolymer, 5 g of zinc oxide, 1 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of epoxidized natural rubber (Shanghai McLean Biochemical Technology Co., Ltd.), mixed evenly and then vulcanized at a vulcanization temperature of 160°C, a vulcanization time of 15 minutes, and a vulcanization pressure of 15 MPa to finally obtain an inverse vulcanized copolymer vulcanized rubber (sheet) with a reprocessable vulcanization network.

[0037] Preparation method of butene-3-acid reverse vulcanized copolymer: 14g of sulfur is charged into a three-necked flask, heated to 135°C in an oil bath for 5 minutes at a speed of 900rpm, and then 6g of butene-3-acid is slowly added, and reacted at 135°C for 6 hours to obtain a butene-3-acid reverse vulcanized copolymer.

[0038] According to GB / T 528-2009, the prepared sheet was cut into I-type dumbbell specimens, and the stress-strain curve was obtained using a high-speed rail AI-3000 electronic tensile testing machine, and the tensile strength of the sheet was 13.28MPa. The obtained sheet was cut into pieces and hot-pressed and vulcanized again at a temperature of 160°C, with a vulcanization time of 30 minutes and a vulcanization pressure of 15MPa. The tensile strength of the sheet after reprocessing was 12.72MPa. At the same time, dynamic thermomechanical analysis was used to test the creep resistance of the sheet, and it was found that the inverse vulcanized copolymer vulcanized rubber had both reprocessing performance and certain creep resistance, such as Figure 1 shown.

[0039] The tensile strength is the stress at which the specimen breaks.

[0040] Example 2: Designing and reprocessing vulcanization network using lipoic acid reverse vulcanized copolymer

[0041] On an open mixing mill, 4 g of thioctic acid inverse vulcanized copolymer, 5 g of zinc oxide, 1 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of natural rubber (purchased from Hainan Rubber Golden Oak Company Jinshui Rubber Processing Company), and the mixture was evenly mixed and then vulcanized at a vulcanization temperature of 160°C, a vulcanization time of 15 minutes, and a vulcanization pressure of 15 MPa to finally obtain an inverse vulcanized copolymer vulcanized rubber (sheet) with a reprocessable vulcanization network.

[0042] Preparation method of lipoic acid reverse vulcanized copolymer: 14g sulfur is charged into a three-necked flask, heated to 135°C in an oil bath for 5 minutes at a speed of 900rpm, then 6g lipoic acid and 0.6g N-methylimidazole are slowly added, and reacted at 150°C for 6 hours to obtain lipoic acid reverse vulcanized copolymer.

[0043] The tensile strength of the sheet was tested according to the method described in Example 1, and the tensile strength of the sheet was 20 MPa. The obtained sheet was cut into pieces and hot-pressed and vulcanized again at a temperature of 145°C, the vulcanization time was 30 minutes, and the vulcanization pressure was 15 MPa. The tensile strength of the sheet after reprocessing was 16 MPa. At the same time, the sheet was tested for creep resistance using dynamic thermomechanical analysis, and it was found that the inverse vulcanized copolymer vulcanized rubber had both reprocessing performance and certain creep resistance, and could be recycled.

[0044] Example 3: Design of reprocessed vulcanization network using lipoic acid derivative reverse vulcanized copolymer

[0045] On an open mixing mill, 2g of thioctic acid derivative inverse vulcanized copolymer, 5g of zinc oxide, 1g of stearic acid and 1.5g of accelerator CZ were added to 100g of natural rubber (purchased from Hainan Rubber Golden Oak Company Jinshui Rubber Processing Company), and the mixture was evenly mixed and then vulcanized at a vulcanization temperature of 160°C, a vulcanization time of 15 minutes, and a vulcanization pressure of 15MPa to finally obtain an inverse vulcanized copolymer vulcanized rubber (sheet) with a reprocessable vulcanization network.

[0046] The preparation method of the reverse vulcanized copolymer of thioctic acid derivative is as follows: 14g of sulfur is charged into a three-necked flask, heated to 135°C in an oil bath for 5 minutes at a speed of 900rpm, and then 6g of lipoamide or lipohydrazide and 0.6g of N-methylimidazole are slowly added, and the mixture is reacted at 145°C for 2 hours to obtain the reverse vulcanized copolymer of thioctic acid derivative.

[0047] According to GB / T 528-2009, the prepared sheet was cut into I-type dumbbell specimens, and the stress-strain curve was obtained using the high-speed rail AI-3000 electronic tensile testing machine. The obtained sheet was cut into pieces and hot-pressed and vulcanized again at a temperature of 160°C, the vulcanization time was 30 minutes, and the vulcanization pressure was 15MPa. After reprocessing, the sheet still has a certain tensile strength. At the same time, the sheet was tested for creep resistance using dynamic thermomechanical analysis, and it was found that the inverse vulcanized copolymer vulcanized rubber has both reprocessing performance and certain creep resistance.

[0048] Example 4: Designing a reprocessing vulcanization network using an amine-based inverse vulcanization copolymer

[0049] On an open mixing mill, 2 g of amine inverse vulcanization copolymer, 5 g of zinc oxide, 1 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of natural rubber (purchased from Hainan Rubber Golden Oak Company Jinshui Rubber Processing Company), and the mixture was evenly mixed and then vulcanized at a vulcanization temperature of 160°C, a vulcanization time of 15 minutes, and a vulcanization pressure of 15 MPa to finally obtain an inverse vulcanization copolymer vulcanized rubber (sheet) with a reprocessable vulcanization network.

[0050] Preparation method of amine reverse vulcanization copolymer: 14g sulfur is charged into a three-necked flask, heated to 135°C in an oil bath for 5 minutes at a speed of 900rpm, and then 6g oleylamine is slowly added, reacted at 145°C for 4 hours to obtain an amine reverse vulcanization copolymer.

[0051] According to GB / T 528-2009, the prepared sheet was cut into I-type dumbbell specimens, and the stress-strain curve was obtained using the high-speed rail AI-3000 electronic tensile testing machine. The obtained sheet was cut into pieces and hot-pressed and vulcanized again at a temperature of 160°C, the vulcanization time was 30 minutes, and the vulcanization pressure was 15MPa. After reprocessing, the sheet still has a certain tensile strength. At the same time, the sheet was tested for creep resistance using dynamic thermomechanical analysis, and it was found that the inverse vulcanized copolymer vulcanized rubber has both reprocessing performance and certain creep resistance.

[0052] The tensile strength is the stress at which the specimen breaks.

[0053] Comparative Example 1

[0054] On an open mixing mill, 2 g of sulfur, 5 g of zinc oxide, 1 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of epoxidized natural rubber (Shanghai McLean Biochemical Technology Co., Ltd.), mixed evenly and then vulcanized at a vulcanization temperature of 160°C, a vulcanization time of 15 minutes, and a vulcanization pressure of 15 MPa to finally obtain a vulcanized rubber (sheet).

[0055] The tensile strength of the sheet was tested according to the method described in Example 1, and the tensile strength of the sheet was 14 MPa. The obtained sheet was cut into pieces and hot-pressed and vulcanized again at a temperature of 145°C, the vulcanization time was 30 minutes, and the vulcanization pressure was 15 MPa. The sheet after hot pressing again could not be formed, indicating that traditional sulfur-vulcanized rubber has no reprocessing ability and cannot be recycled. Figure 2 shown.

[0056] Comparative Example 2

[0057] On an open mixing mill, 2 g of sulfur, 5 g of zinc oxide, 1 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of natural rubber (purchased from Hainan Rubber Golden Oak Company Jinshui Rubber Processing Company), and the mixture was evenly mixed and then vulcanized at a vulcanization temperature of 160°C, a vulcanization time of 15 minutes, and a vulcanization pressure of 15 MPa to finally obtain a vulcanized rubber (sheet).

[0058] The tensile strength of the sheet was tested according to the method described in Example 2, and the tensile strength of the sheet was 18 MPa. The obtained sheet was cut into pieces and hot-pressed and vulcanized again at a temperature of 145° C., the vulcanization time was 30 minutes, and the vulcanization pressure was 15 MPa. The sheet after hot pressing again could not be formed, indicating that traditional sulfur-vulcanized rubber does not have the ability to be reprocessed and cannot be recycled.

[0059] Comparative Example 3

[0060] On an open mixing mill, 2 g of sulfur, 5 g of zinc oxide, 1 g of stearic acid and 1.5 g of accelerator CZ were added to 100 g of natural rubber (purchased from Hainan Rubber Golden Oak Company Jinshui Rubber Processing Company), and the mixture was evenly mixed and then vulcanized at a vulcanization temperature of 160°C, a vulcanization time of 15 minutes, and a vulcanization pressure of 15 MPa to finally obtain a vulcanized rubber (sheet).

[0061] The tensile strength and creep resistance of the sheet were tested according to the method described in Example 2. In the experiment, the sheet after hot pressing again could not be formed and had poor creep resistance, indicating that traditional sulfur-vulcanized rubber does not have reprocessing ability and creep resistance.

[0062] In summary, the present application adopts a specific reverse vulcanization copolymer as a vulcanizing agent, and through the vulcanization network design, the vulcanized rubber has reprocessing performance and can be recycled. The vulcanized rubber can also have creep resistance while being reprocessable, further expanding the application scope of rubber and having good application prospects.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit it. Although the present application has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A recyclable inverse vulcanized copolymer vulcanized rubber, characterized in that: The inverse vulcanized copolymer vulcanized rubber is prepared from the following raw materials in weight ratio: 100 parts of rubber, 1-10 parts of inverse vulcanization copolymer, 1-5 parts of zinc oxide, 1-5 parts of stearic acid, and 1-5 parts of accelerator.

2. The recyclable inverse vulcanized copolymer vulcanized rubber according to claim 1, characterized in that: The inverse vulcanized copolymer vulcanized rubber is prepared from the following raw materials in weight ratio: 100 parts of rubber, 2 parts of inverse vulcanized copolymer, 5 parts of zinc oxide, 1 part of stearic acid, and 2 parts of accelerator.

3. The recyclable inverse vulcanized copolymer vulcanized rubber according to claim 1, characterized in that: The reverse vulcanization copolymer is at least one of an olefinic acid reverse vulcanization copolymer, an amine reverse vulcanization copolymer, a lipoic acid reverse vulcanization copolymer, an acrylic acid reverse vulcanization copolymer, and a fluorine reverse vulcanization copolymer.

4. The recyclable inverse vulcanized copolymer vulcanized rubber according to claim 1, characterized in that: The reverse vulcanized copolymer is a butene-3-acid reverse vulcanized copolymer, a thioctic acid reverse vulcanized copolymer, or a thioctic acid derivative reverse vulcanized copolymer.

5. The recyclable inverse vulcanized copolymer vulcanized rubber according to claim 1, characterized in that: The rubber is natural rubber or synthetic rubber; the accelerator is accelerator CZ and / or accelerator DM.

6. The recyclable inverse vulcanized copolymer vulcanized rubber according to claim 5, characterized in that: The synthetic rubber is at least one of epoxy rubber, styrene-butadiene rubber and isoprene rubber; the accelerator is accelerator CZ and accelerator DM.

7. A method for preparing the recyclable inverse vulcanized copolymer vulcanized rubber according to any one of claims 1 to 6, characterized in that: The following steps are involved: S1. Weigh the raw materials of rubber, reverse vulcanization copolymer, zinc oxide, stearic acid and accelerator according to the weight ratio; S2. Mix all the raw materials evenly and then vulcanize them to obtain the inverse vulcanized copolymer vulcanized rubber.

8. The method for preparing the recyclable inverse vulcanized copolymer vulcanized rubber according to claim 7, characterized in that: In step S1, the preparation process of the reverse vulcanized copolymer is: sulfur is mixed with butene-3-acid, thioctic acid or a thioctic acid derivative, and reacted at 130-160° C. for 2-8 hours to obtain the reverse vulcanized copolymer; Wherein, the mass ratio of sulfur to butene-3-acid, thioctic acid or thioctic acid derivative is (0.2-3):

1.

9. The method for preparing the recyclable inverse vulcanized copolymer vulcanized rubber according to claim 7, characterized in that: In step S2, the vulcanization temperature is 130-160°C, the vulcanization time is 5-18 minutes, and the vulcanization pressure is 10-15 MPa.

10. Use of the recyclable inverse vulcanized copolymer vulcanized rubber according to any one of claims 1 to 6 in the preparation of a formulation or equipment for gaskets and shock-absorbing pads used in tires and bridge engineering materials.

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