1. A rubber composition for a damping material, characterized by comprising the following components stored in admixture or independently:

nitrile butadiene rubber matrix, reinforcing agent, floating bead, vulcanizing agent, accelerator, activator, anti-aging agent, plasticizer A, plasticizer B and tackifying resin,

the plasticizer A is selected from at least one of phthalate compounds; the plasticizer B is carboxyl-terminated butadiene-acrylonitrile rubber;

relative to 100 parts by weight of the nitrile rubber matrix, the reinforcing agent is 15-40 parts by weight, the floating bead is 5-25 parts by weight, the vulcanizing agent is 0.3-3 parts by weight, the accelerator is 1-5 parts by weight, the activator is 2-10 parts by weight, the anti-aging agent is 0.5-3 parts by weight, the plasticizer A is 2-15 parts by weight, the plasticizer B is 2-40 parts by weight, and the tackifying resin is 2-20 parts by weight.

2. The composition according to claim 1, wherein the plasticizer a is contained in an amount of 2 to 12 parts by weight and the plasticizer B is contained in an amount of 2 to 25 parts by weight, relative to 100 parts by weight of the nitrile rubber matrix in the composition.

3. The composition according to claim 1 or 2, wherein the plasticizer a is selected from at least one of dioctyl phthalate, dibutyl phthalate, di (2-ethylhexyl) phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, diisobutyl phthalate, dimethyl phthalate, diethyl phthalate, diisononyl phthalate and diisodecyl phthalate, preferably the plasticizer a is dioctyl phthalate;

preferably, the plasticizer B is carboxyl-terminated liquid nitrile rubber, the number average molecular weight of the carboxyl-terminated liquid nitrile rubber is 3000-4500, the content of acrylonitrile structural units is 10-30 wt%, and the acid value is 25-40 mgKOH/g.

4. The composition according to any one of claims 1 to 3, wherein the nitrile rubber matrix has a content of acrylonitrile structural units of 15 to 35% by weight and a content of 1, 2-butadiene structural units of 5 to 15% by weight;

preferably, ML of said nitrile rubber matrix₍₁₊₄₎The temperature of 100 ℃ is 35-85 ℃.

5. The composition according to any one of claims 1 to 4, wherein the reinforcing agent is carbon black, and the carbon black has a CTAB adsorption specific surface area of 10 to 600m²/g；

Preferably, the floating beads are fly ash hollow spheres with the specific surface area of 300-360cm²G, volume weight of 250-450kg/m³The average grain diameter is 40-200 meshes;

preferably, the vulcanizing agent is selected from at least one of sulfur donors; preferably, the vulcanizing agent is selected from at least one of insoluble sulfur, soluble sulfur and oil-extended sulfur;

preferably, the accelerator is selected from at least one of thiazole accelerators, thiuram accelerators, guanidine accelerators and sulfenamide accelerators; preferably, the accelerator is selected from at least one of diphenylguanidine, tetramethylthiuram disulfide, 2-mercaptobenzothiazole, ethylenethiourea, N-cyclohexyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzothiazolesulfenamide, 2' -dibenzothiazyl disulfide, N-tert-butyl-bis (2-benzothiazole) sulfenimide and N-cyclohexyl-2-benzothiazolesulfenamide; preferably the accelerator is a combination of tetramethylthiuram disulfide and N-cyclohexyl-2-benzothiazolesulfenamide; preferably, the weight ratio of the N-cyclohexyl-2-benzothiazole sulfonamide to the tetramethylthiuram disulfide is 1:1-4, more preferably 1: 1.1-2.5;

preferably, the activator is a mixture of a metal oxide and a fatty acid, preferably the metal oxide is zinc oxide and/or magnesium oxide, preferably the fatty acid is stearic acid;

preferably, the anti-aging agent is selected from at least one of quinoline anti-aging agents, hindered phenol anti-aging agents, amine anti-aging agents and benzimidazole anti-aging agents; preferably, the antioxidant is a combination of N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine and 2, 2' -methylene-bis (4-methyl-6-tert-butylphenol); preferably the weight ratio of N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine to 2, 2' -methylene-bis (4-methyl-6-tert-butylphenol) is from 1:1 to 4, more preferably from 1:1 to 3;

preferably, the tackifying resin is selected from at least one of thermoplastic multi-alkyl phenol-formaldehyde resin, cashew modified phenolic resin, Turkel modified phenolic resin, condensate of tert-butyl phenol and acetylene, thermoplastic non-reactive p-tert-octyl phenolic resin, thermoplastic alkyl phenolic resin and o-cresol novolac epoxy resin.

6. A process for producing a vulcanized rubber, which comprises mixing the components of the composition according to any one of claims 1 to 5, and vulcanizing the final rubber obtained after the mixing, wherein in the composition, the reinforcing agent is used in an amount of 15 to 40 parts by weight, the floating bead is used in an amount of 5 to 25 parts by weight, the vulcanizing agent is used in an amount of 0.3 to 3 parts by weight, the accelerator is used in an amount of 1 to 5 parts by weight, the activator is used in an amount of 2 to 10 parts by weight, the antioxidant is used in an amount of 0.5 to 3 parts by weight, the plasticizer A is used in an amount of 2 to 15 parts by weight, the plasticizer B is used in an amount of 2 to 40 parts by weight, and the tackifier resin is used in an amount of 2 to 20 parts by weight, relative to 100 parts by weight of the nitrile rubber substrate.

7. The method of claim 6, wherein mixing the components of the composition and curing the final mix after mixing comprises:

(1) carrying out first mixing on each component in the component A to obtain a section of master batch, wherein the component A contains a nitrile rubber matrix, a plasticizer B and floating beads;

(2) performing second mixing on the first-stage masterbatch and each component in the component B to obtain second-stage masterbatch, wherein the component B contains a reinforcing agent, an activator, an anti-aging agent, a plasticizer A and tackifying resin;

(3) performing third mixing on the second-stage masterbatch and each component in the component C to obtain a final rubber compound, wherein the component C contains a vulcanizing agent and an accelerator;

(4) vulcanizing the final rubber;

preferably, the plasticizer A is used in an amount of 2 to 12 parts by weight and the plasticizer B is used in an amount of 2 to 25 parts by weight, relative to 100 parts by weight of the nitrile rubber matrix.

8. The method of claim 7, wherein the conditions of the first mixing comprise: the temperature is 70-120 deg.C, and the time is 5-20 min;

preferably, the conditions of the second mixing include: the temperature is 100-150 ℃, and the time is 3-12 min;

preferably, the conditions of the third mixing include: the temperature is not more than 130 ℃, and the time is 5-7 min;

preferably, the conditions of the vulcanization include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 15-35 min.

9. A vulcanized rubber produced by the method of any one of claims 6 to 8.

10. Use of the vulcanizate of claim 9 in a damping material.

Background

With the improvement of science and technology and the improvement of living standard of people, the requirement on comfort is higher and higher, so that the effective treatment of various vibration and noise pollution becomes an important research subject.

The rubber elastomer material is used as a damping material, and is widely applied to vibration reduction and noise reduction in the fields of rail transit, buildings, automobiles, machinery and the like, which becomes the popular research direction of researchers.

The molecular chain segment of the rubber has strong relaxation capacity and generates strong internal friction, but when the rubber elastic body absorbs vibration energy, the mechanical energy is partially converted into heat energy to be dissipated, and the damping effect is achieved. However, the requirement of industry and daily life is difficult to meet only by the damping performance of the material itself, so that the focus of the research on developing a wide temperature range high-damping material is the focus of the present research.

Recently, hybrid bodies formed by small organic molecules and polymers are utilized to obtain high-performance damping materials, and the wide interest of researchers is aroused. For example, CN106543739A discloses a hindered phenol/montmorillonite/nitrile rubber composite damping material for automobiles and a preparation method thereof, the technology utilizes fillers such as montmorillonite and cork fiber to design the damping material, but the technology involves the use of various organic solvents such as xylene and sodium hypophosphite hydroxide, and the process is relatively complex. Meanwhile, the prior art cannot completely solve the problem that damping and mechanical properties are reduced due to outward migration of hindered phenol. Inorganic mineral fillers such as mica powder, pottery clay and calcium carbonate are added into the damping material, so that the modulus and damping factor of the matrix are improved, but negative effects are brought: firstly, the addition amount is large, so that the mechanical strength of the material is greatly reduced; secondly, the density of the inorganic filler is doubled compared with that of the polymer matrix, so that the density of the material is greatly increased.

Therefore, the prior art has not overcome the problems of greatly increased material density and reduced mechanical properties caused by the filler, and there is a need to provide a rubber composition with improved properties to prepare the nitrile rubber damping material with high damping and wide temperature range.

Disclosure of Invention

The invention aims to provide a rubber composition, and vulcanized rubber obtained by the rubber composition has the characteristics of high damping and wide temperature range, and is excellent in mechanical property and forming property and capable of being used as a damping material.

In order to achieve the above object, a first aspect of the present invention provides a rubber composition for a damping material, which comprises the following components stored in admixture or separately:

nitrile butadiene rubber matrix, reinforcing agent, floating bead, vulcanizing agent, accelerator, activator, anti-aging agent, plasticizer A, plasticizer B and tackifying resin,

the plasticizer A is selected from at least one of phthalate compounds; the plasticizer B is carboxyl-terminated butadiene-acrylonitrile rubber;

relative to 100 parts by weight of the nitrile rubber matrix, the reinforcing agent is 15-40 parts by weight, the floating bead is 5-25 parts by weight, the vulcanizing agent is 0.3-3 parts by weight, the accelerator is 1-5 parts by weight, the activator is 2-10 parts by weight, the anti-aging agent is 0.5-3 parts by weight, the plasticizer A is 2-15 parts by weight, the plasticizer B is 2-40 parts by weight, and the tackifying resin is 2-20 parts by weight.

In a second aspect, the present invention provides a method for preparing a vulcanized rubber, which comprises mixing the components of the composition described in the first aspect, and vulcanizing a final rubber obtained after the mixing, wherein, in the composition, the reinforcing agent is used in an amount of 15 to 40 parts by weight, the floating bead is used in an amount of 5 to 25 parts by weight, the vulcanizing agent is used in an amount of 0.3 to 3 parts by weight, the accelerator is used in an amount of 1 to 5 parts by weight, the activator is used in an amount of 2 to 10 parts by weight, the antioxidant is used in an amount of 0.5 to 3 parts by weight, the plasticizer a is used in an amount of 2 to 15 parts by weight, the plasticizer B is used in an amount of 2 to 40 parts by weight, and the tackifying resin is used in an amount of 2 to 20 parts by weight, relative to 100 parts by weight of a nitrile rubber matrix.

A third aspect of the present invention provides a vulcanizate prepared by the method of the second aspect described above.

A fourth aspect of the present invention provides the use of the vulcanized rubber described in the aforementioned third aspect in a damping material.

The components in the rubber composition provided by the invention can be better dispersed in the rubber matrix, so that the further prepared vulcanized rubber has excellent comprehensive properties such as high strength, high damping temperature range, high damping factor and the like.

Drawings

FIG. 1 is a graph of dynamic loss factor versus temperature for vulcanizates from examples 1-5, comparative example 1 and comparative example 2 in a preferred embodiment of the present invention.

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As described above, the first aspect of the present invention provides a rubber composition for damping materials, which contains the following components stored in admixture or separately:

nitrile butadiene rubber matrix, reinforcing agent, floating bead, vulcanizing agent, accelerator, activator, anti-aging agent, plasticizer A, plasticizer B and tackifying resin,

the plasticizer A is selected from at least one of phthalate compounds; the plasticizer B is carboxyl-terminated butadiene-acrylonitrile rubber;

relative to 100 parts by weight of the nitrile rubber matrix, the reinforcing agent is 15-40 parts by weight, the floating bead is 5-25 parts by weight, the vulcanizing agent is 0.3-3 parts by weight, the accelerator is 1-5 parts by weight, the activator is 2-10 parts by weight, the anti-aging agent is 0.5-3 parts by weight, the plasticizer A is 2-15 parts by weight, the plasticizer B is 2-40 parts by weight, and the tackifying resin is 2-20 parts by weight.

According to the present invention, although the plasticizer is used in the above-mentioned amount range to obtain the composition required in the present invention, it is preferable that the plasticizer a is contained in an amount of 2 to 12 parts by weight and the plasticizer B is contained in an amount of 2 to 25 parts by weight with respect to 100 parts by weight of the nitrile rubber matrix in order to obtain a nitrile rubber capable of exhibiting enhanced mechanical properties, damping properties, and excellent processability.

According to a preferred embodiment of the invention, said plasticizer a is selected from at least one of dioctyl phthalate (DOP), dibutyl phthalate (DBP), di (2-ethylhexyl) phthalate, di-n-octyl phthalate, butyl benzyl phthalate, di-sec-octyl phthalate, dicyclohexyl phthalate, diisobutyl phthalate, dimethyl phthalate, diethyl phthalate, diisononyl phthalate and diisodecyl phthalate. Particularly preferably, the plasticizer A is dioctyl phthalate.

Preferably, the plasticizer B is carboxyl-terminated liquid nitrile rubber, the number average molecular weight of the carboxyl-terminated liquid nitrile rubber is 3000-4500, the content of acrylonitrile structural units is 10-30 wt%, and the acid value is 25-40 mgKOH/g.

In the composition of the invention, the inventor finds that the addition of the carboxyl-terminated liquid nitrile rubber serving as the plasticizer B not only can play a role in softening the rubber material, but also can play a role in an interface bonding agent between the floating bead and the nitrile rubber matrix, and is beneficial to improving the mechanical property of the rubber material.

Preferably, in the nitrile rubber matrix, the content of acrylonitrile structural units is 15-35 wt%, and the content of 1, 2-butadiene structural units is 5-15 wt%.

Preferably, the nitrile rubber matrix has an ML (1+4) at 100 ℃ of from 35 to 85.

Preferably, the reinforcing agent is carbon black, and the carbon black has a CTAB adsorption specific surface area of 10 to 600m²(ii)/g; for example, the carbon black may be N330 and/or N550.

Preferably, the floating beads are fly ash hollow spheres with the specific surface area of 300-360cm²G, volume weight of 250-450kg/m³The average grain diameter is 40-200 meshes.

Preferably, the vulcanizing agent is selected from at least one of sulfur donors. In the present invention, the sulfur donor refers to a substance capable of providing sulfur. The sulfur comprises at least one of insoluble sulfur, soluble sulfur and oil-extended sulfur. For example, the vulcanizing agent IS ordinary sulfur S, oil-extended insoluble sulfur IS, or the like.

Preferably, the accelerator is selected from at least one of thiazole accelerators, thiuram accelerators, guanidine accelerators and sulfenamide accelerators; more preferably, the accelerator is at least one selected from the group consisting of diphenylguanidine, tetramethylthiuram disulfide, 2-mercaptobenzothiazole, ethylenethiourea, N-cyclohexyl-2-benzothiazolesulfenamide, N-tert-butyl-2-benzothiazolesulfenamide, 2' -dibenzothiazyl disulfide, N-tert-butyl-bis (2-benzothiazole) sulfenimide and N-cyclohexyl-2-benzothiazolesulfenamide.

According to a preferred embodiment of the present invention, a combination of tetramethylthiuram disulfide (TMTD) and N-cyclohexyl-2-benzothiazolesulfenamide (CZ) is used as the accelerator, further preferably the weight ratio of accelerator CZ and accelerator TMTD is 1:1 to 4, particularly preferably 1: 1.1 to 2.5, the vulcanizates thus prepared have a higher tensile strength.

Preferably, the activator is a mixture of a metal oxide and a fatty acid.

In the present invention, the metal oxide is further preferably zinc oxide and/or magnesium oxide; the fatty acid is further preferably stearic acid.

Preferably, the antioxidant is at least one selected from the group consisting of quinoline antioxidants, hindered phenol antioxidants, amine antioxidants and benzimidazole antioxidants. According to a preferred embodiment of the present invention, a combination of N- (1, 3-dimethylbutyl) -N '-phenyl-p-phenylenediamine (anti-aging agent 4020) and 2, 2' -methylene-bis (4-methyl-6-tert-butylphenol) (anti-aging agent 2246) is used as the anti-aging agent, wherein the weight ratio of the anti-aging agent 4020 to the anti-aging agent 2246 is preferably 1:1 to 4, more preferably 1:1 to 3. The inventors have found that the vulcanized rubber produced using the antioxidant provided in the preferred embodiment has a higher tensile strength.

Preferably, the tackifying resin is selected from at least one of thermoplastic polyalkylphenol-formaldehyde resin, cashew modified phenol-formaldehyde resin, tall modified phenol-formaldehyde resin, condensate of tert-butylphenol and acetylene (e.g., condensate of butylphenol and acetylene, korein), thermoplastic non-reactive p-tert-octylphenol-formaldehyde resin, thermoplastic alkyl phenol-formaldehyde resin, and o-cresol novolac epoxy resin.

The present invention is not particularly limited to the method for preparing a vulcanized rubber using the aforementioned composition, and various methods for preparing a vulcanized rubber generally used in the art can be used, but in order to make the ingredients of the resulting rubber compound more uniform and to obtain better mechanical properties and dynamic mechanical properties after subsequent vulcanization, the present invention provides the method for preparing a vulcanized rubber described in the following second aspect as a preferred embodiment for preparing a vulcanized rubber using the aforementioned composition of the present invention.

As described above, the second aspect of the present invention provides a process for producing a vulcanized rubber, which comprises mixing the components of the composition of the first aspect of the present invention, and vulcanizing the final rubber mixture obtained after the mixing, wherein, in the composition, the reinforcing agent is used in an amount of 15 to 40 parts by weight, the floating bead is used in an amount of 5 to 25 parts by weight, the vulcanizing agent is used in an amount of 0.3 to 3 parts by weight, the accelerator is used in an amount of 1 to 5 parts by weight, the activator is used in an amount of 2 to 10 parts by weight, the antioxidant is used in an amount of 0.5 to 3 parts by weight, the plasticizer A is used in an amount of 2 to 15 parts by weight, the plasticizer B is used in an amount of 2 to 40 parts by weight, and the tackifying resin is used in an amount of 2 to 20 parts by weight, based on 100 parts by weight of the nitrile rubber matrix.

In order to make the composition of the compound more uniform and to obtain better mechanical and dynamic properties after subsequent vulcanization, according to a particularly effective embodiment, the operations of mixing the components of the composition and vulcanizing the final compound obtained after mixing comprise:

(1) carrying out first mixing on each component in the component A to obtain a section of master batch, wherein the component A contains a nitrile rubber matrix, a plasticizer B and floating beads;

(2) performing second mixing on the first-stage masterbatch and each component in the component B to obtain second-stage masterbatch, wherein the component B contains a reinforcing agent, an activator, an anti-aging agent, a plasticizer A and tackifying resin;

(3) performing third mixing on the second-stage masterbatch and each component in the component C to obtain a final rubber compound, wherein the component C contains a vulcanizing agent and an accelerator;

(4) vulcanizing the final rubber.

Further preferably, the plasticizer A is used in an amount of 2 to 12 parts by weight and the plasticizer B is used in an amount of 2 to 25 parts by weight, relative to 100 parts by weight of the nitrile rubber matrix.

The various substances referred to in the second aspect of the invention have the same properties as the corresponding same substances in the first aspect of the invention, and in order to avoid repetition, the properties of the substances in the second aspect of the invention, including the optional nature of the components, etc., are not repeated and the person skilled in the art should not be understood as limiting the second aspect of the invention.

Preferably, the conditions of the first mixing include: the temperature is 70-120 deg.C, and the time is 5-20 min.

Preferably, the conditions of the second mixing include: the temperature is 100-150 ℃ and the time is 3-12 min.

Preferably, the conditions of the third mixing include: the temperature is not more than 130 deg.C, and the time is 5-7 min.

Preferably, the conditions of the vulcanization include: the temperature is 150 ℃ and 170 ℃, the pressure is 10-20MPa, and the time is 15-35 min.

The invention adopts the technical scheme that the component A containing the nitrile rubber matrix, the floating beads and the plasticizer B is firstly mixed to obtain a section of masterbatch, and then the subsequent process steps are carried out, so that the mechanical property and the dynamic mechanical property of the vulcanized rubber obtained by the method are more excellent.

To specifically illustrate the process of the present invention for preparing a vulcanizate, a preferred embodiment is provided below for illustration:

(1) placing a nitrile rubber substrate in an internal mixer, plasticating at the rotation speed of 40-90 rpm, the initial mixing temperature of 70-100 ℃ and the raw rubber plasticating time of 0.3-1 min; then introducing the floating beads and the plasticizer B into the internal mixer for first mixing to obtain a section of master batch;

(2) adding the primary masterbatch and a component B containing a reinforcing agent, an activator, an anti-aging agent, tackifying resin and a plasticizer A into an internal mixer for second mixing, discharging and standing for 3-10 hours to obtain secondary masterbatch;

(3) setting the rotation speed of an internal mixer to be 50-100 rpm, setting the initial mixing temperature to be 25-50 ℃, plasticating the two-stage masterbatch for 0.5-1.5 min, and adding a component C containing an accelerator and a vulcanizing agent to carry out third mixing to obtain final rubber;

(4) and (3) tabletting and cutting the final rubber compound open mill, and then putting the final rubber compound open mill into a flat vulcanizing machine for vulcanization.

In step (3) of the above preferred embodiment, mastication is not essential, but is only required to obtain a better processing effect.

The pressures used in the present invention are gauge pressures unless otherwise specified.

As previously mentioned, a third aspect of the present invention provides a vulcanizate prepared by the method of the second aspect described above.

As mentioned above, a fourth aspect of the present invention provides the use of the vulcanized rubber of the aforementioned third aspect in a damping material.

The present invention will be described in detail below by way of examples, and various commercial products used below are commercially available without specific description.

The chemicals used in the examples and comparative examples are commercially available and are specified below:

nitrile rubber: N240S, acrylonitrile structural unit content of 26% by weight, 1, 2-butadiene structural unit content of 10.0% by weight, Mooney viscosity (ML (1+4)100 ℃)56, JSR Corp, Japan;

nitrile rubber: NBR3345, acrylonitrile structural unit content 33 wt%, 1, 2-butadiene structural unit content 7.1 wt%, Mooney viscosity (ML (1+4)100 ℃)45, Ningbo cis rubber, Inc.;

carbon black: n550, Zideli chemical technology, Inc. of Dongguan;

floating beads: 100 meshes, specific surface area 320cm²G, volume weight 260kg/m³Processing factory for mineral products in bang of lingshou county;

and (3) a plasticizer A: dioctyl phthalate (DOP), dibutyl phthalate (DBP), Shandong Langtai chemical Co., Ltd;

and (3) a plasticizer B: the carboxyl-terminated butadiene-acrylonitrile rubber CTBN1300 multiplied by 18 has the content of acrylonitrile structural units of 21.5 weight percent, the acid value of 39mgKOH/g and the number-average molecular weight of 3400; shenzhen jiadida new materials science and technology, Inc.;

and (3) a plasticizer B: the carboxyl-terminated butadiene-acrylonitrile rubber CTBN1300 multiplied by 31 has the content of acrylonitrile structural units of 10 weight percent, the acid value of 28mgKOH/g and the number-average molecular weight of 3800; shenzhen jiadida new materials science and technology, Inc.;

activating agent: zinc oxide, stearic acid, Weifang Heng Feng chemical Limited;

an anti-aging agent: n- (1, 3-dimethylbutyl) -N' -phenyl-p-phenylenediamine (anti-aging agent 4020), saint-ao chemical science and technology ltd, Jiangsu;

an anti-aging agent: 2, 2' -methylene-bis (4-methyl-6-tert-butylphenol) (anti-aging agent 2246), Nanjing Ningkang chemical Co., Ltd;

vulcanizing agent: sulfur, Heicheng Hechenghuai chemical Limited;

accelerator (b): tetramethylthiuram Disulfide (TMTD) and N-cyclohexyl-2-benzothiazolesulfenamide (Accelerator CZ), Zodiac chemical Limited, Guangzhou;

tackifying resin: condensate Koresin of tert-butylphenol and acetylene, in the form of yellow or brown granules and powder, having a density (20 ℃) of 1.02 to 1.04g/cm³BASF, germany;

tackifying resin: HY-2006 tackifying resin, thermoplastic multi-alkyl phenol-formaldehyde resin, dark brown granular or flaky, softening point of 120-.

The equipment conditions for the vulcanizates prepared in the following examples and comparative examples are shown in Table 1.

The apparatus for testing the vulcanizates prepared in the following examples and comparative examples is shown in Table 2.

The test conditions for the vulcanizates prepared in the following examples and comparative examples are shown in Table 3.

The components in the following examples and comparative examples are used in parts by weight (or parts), and each part by weight represents 10 g.

TABLE 1

Serial number	Device name	Model number	Manufacturer of the product
				1	Internal mixer	BR1600	Farrel America Ltd
2	Open mill	XK-160	QINGDAO XINCHENG YIMING RUBBER MACHINERY Co.,Ltd.
				3	Flat vulcanizing machine	P-50-PCD-3L 400×400\50T	Taiwan rock Hydraulic Industrial Co Ltd

TABLE 2

Serial number	Test items	Model of the test apparatus	Manufacturer of the product
				1	High tensile strengthDegree of rotation	GT-AT-3000	Taiwan high speed railway Co
2	Dynamic viscoelastic property	EPLEXOR500N	Germany GABO Co

TABLE 3

The examples are intended to illustrate the rubber compositions, vulcanizates, and methods of making the same of the present invention.

Example 1

The rubber composition formulation is shown in Table 4.

The preparation process of the vulcanized rubber comprises the following steps:

(1) carrying out first mixing on a rubber matrix, floating beads and a plasticizer B to obtain a section of masterbatch; specifically, the rubber matrix is added into an internal mixer, the set rotating speed is 80rpm, the initial mixing temperature is 90 ℃, and the raw rubber plastication time is 0.5 min; adding the floating beads and the plasticizer B into the internal mixer for mixing at 105 ℃ for 10min to obtain a section of master batch;

(2) carrying out second mixing on the first-stage masterbatch, carbon black, an activating agent, an anti-aging agent, tackifying resin and a plasticizer A to obtain second-stage masterbatch; specifically, adding carbon black, an activating agent, an anti-aging agent, tackifying resin and a plasticizer A into an internal mixer, and carrying out second mixing with the primary masterbatch, wherein the mixing time is 7min, the rubber discharge temperature is 120 ℃, discharging and standing for 4h to obtain secondary masterbatch;

(3) carrying out third mixing on the second-stage masterbatch, an accelerant and a vulcanizing agent to obtain final rubber; specifically, the rotation speed of an internal mixer is set to be 80rpm, the initial mixing temperature is 40 ℃, after the two-stage masterbatch is plasticated for 1min (the same plastication conditions are adopted in other embodiments for plastication, and then the third mixing is carried out), a vulcanizing agent and an accelerator are added for third mixing, the mixing temperature is 105 ℃, the mixing time is 5min, and the final mixed rubber is obtained after discharging;

(4) and (3) tabletting and cutting the final rubber mixing open mill, and then putting the final rubber mixing open mill into a flat plate vulcanizing machine for vulcanizing at the vulcanizing temperature of 160 ℃, the vulcanizing pressure of 15MPa and the vulcanizing time of 25min to obtain a vulcanized rubber sample S1.

Example 8

The formulation of the composition of this example is exactly the same as in example 1.

The preparation process of the vulcanized rubber is as follows:

carrying out first mixing on a rubber matrix, floating beads, carbon black, an activator, an anti-aging agent, tackifying resin, a plasticizer A and a plasticizer B to obtain a section of masterbatch; specifically, the rubber matrix is added into an internal mixer, the set rotating speed is 80rpm, the initial mixing temperature is 90 ℃, and the raw rubber plastication time is 0.5 min; adding floating bead, carbon black, an activator, an anti-aging agent, tackifying resin, a plasticizer A and a plasticizer B into an internal mixer for mixing, wherein the mixing temperature is 120 ℃, the mixing time is 17min, and discharging and standing for 4h to obtain master batch;

carrying out second mixing on the primary rubber, an accelerant and a vulcanizing agent to obtain final rubber; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the primary rubber for 1min, adding a vulcanizing agent and an accelerator to perform third mixing, setting the mixing temperature to be 105 ℃, mixing for 5min, and discharging to obtain final mixed rubber;

and (3) tabletting and cutting the final rubber mixing open mill, and then putting the final rubber mixing open mill into a flat plate vulcanizing machine for vulcanizing at the vulcanizing temperature of 160 ℃, the vulcanizing pressure of 15MPa and the vulcanizing time of 25min to obtain a vulcanized rubber sample, which is recorded as S8.

The remaining examples were carried out using the same procedure as in example 1, except that the rubber composition formulation and the process parameters were different, unless otherwise specified, as shown in Table 4.

Comparative example 1

The rubber composition formulation of this comparative example is shown in Table 4.

The preparation process of the vulcanized rubber adopted in comparative example 1 was:

(1) carrying out first mixing on a rubber matrix, carbon black, an activating agent, an anti-aging agent, tackifying resin and a plasticizer A to obtain a section of masterbatch; specifically, adding a rubber matrix, carbon black, an activating agent, an anti-aging agent, tackifying resin and a plasticizer A into an internal mixer for mixing for 7min at 120 ℃ and discharging and standing for 4h to obtain a section of masterbatch;

(2) carrying out second mixing on the first-stage masterbatch, an accelerant and a vulcanizing agent to obtain a second-stage masterbatch; specifically, setting the rotation speed of an internal mixer to be 80rpm, setting the initial mixing temperature to be 40 ℃, plasticating the primary masterbatch for 1min, adding a vulcanizing agent and an accelerant to perform secondary mixing, wherein the mixing temperature is 105 ℃, the mixing time is 5min, and discharging to obtain secondary masterbatch;

(3) and (3) tabletting and cutting the final rubber mixing open mill, and then putting the final rubber mixing open mill into a flat plate vulcanizing machine for vulcanizing at the vulcanizing temperature of 160 ℃, the vulcanizing pressure of 15MPa and the vulcanizing time of 25min to obtain a vulcanized rubber sample CS 1.

Comparative examples 2 to 3 were conducted in a similar procedure to example 1 except that the rubber composition was formulated differently, as shown in Table 4.

TABLE 4

Table 4 (continuation 1)

Table 4 (continuation 2)

Test example

The products of the examples and the comparative examples are prepared into dumbbell-shaped splines meeting the GB/T528-2009 standard, and a GT-AT-3000 type high-iron material universal tester is adopted to test the tensile property data, and the results are shown in Table 5.

TABLE 5

	Tensile Strength (MPa)	Maximum loss factor corresponding to temperature (. degree. C.)	Temperature range (. degree.C.) with loss factor > 0.5
				Example 1	17.3	-10.4	-20.3～12.5
Example 2	16.1	-10.1	-20.1～13.4
				Example 3	17.5	-10.2	-21.3～11.1
Example 4	15.4	-12.1	-23.3～10.1
				Example 5	16.9	-13.2	-23～10.0
Example 6	14.1	-11.3	-22.1～9.5
				Example 7	14.9	-12.5	-23.4～8.2
Example 8	13.7	-12.3	-22.3～8.7
				Example 9	15.3	-10.9	-21.0～9.4
Example 10	14.0	-12.1	-21.5～8.6
				Example 11	13.8	-12.4	-21.8～9.9
Comparative example 1	13.8	-13.1	-25.8～1.7
				Comparative example 2	14.4	-11.5	-21.5～8.0
Comparative example 3	12.1	-11.9	-22.6～4.8
				Comparative example 4	13.5	-13.9	-25.9～2.6
Comparative example 5	13.0	-14.3	-24.1～1.5
				Comparative example6	13.6	-12.8	-20.3～5.8

Also, illustratively, the dynamic loss factor versus temperature spectra of the vulcanized rubber samples produced by the present invention through examples 1-5, comparative example 1 and comparative example 2 are shown in FIG. 1.

From the above results, it can be seen that the rubber composition of the present invention has better dispersibility of the components in the rubber matrix, so that the further prepared vulcanized rubber has excellent comprehensive properties such as high tensile strength, high damping temperature range and damping factor.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.