CN114437463B - Vulcanized composition, EPDM-based vulcanized rubber composition, vulcanized rubber, preparation method and application thereof - Google Patents
Vulcanized composition, EPDM-based vulcanized rubber composition, vulcanized rubber, preparation method and application thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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Abstract
The invention relates to the field of rubber material production, and discloses a vulcanized composition, an EPDM-based vulcanized rubber composition, vulcanized rubber and a preparation method and application thereof, wherein the composition contains more than two main vulcanizing agents A, main vulcanizing agents B and auxiliary vulcanizing agents which are stored in a mixed mode or are stored independently, and the content of the main vulcanizing agents B is 0.1-2 parts by weight and the content of the auxiliary vulcanizing agents is 0.5-4 parts by weight relative to 1 part by weight of the main vulcanizing agents A; wherein the main vulcanizing agent A is at least one of tert-butylphenol formaldehyde resin, tert-octylphenol formaldehyde resin and epoxy resin; the main vulcanizing agent B is at least one of dicumyl peroxide, di-tert-butyl cumene peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane; the auxiliary vulcanizing agent is a hydrogen ion transfer crosslinking promoter and/or a free radical transfer crosslinking promoter. The composition can effectively improve the elongation at break of rubber when used for vulcanizing EPDM/PP rubber.
Description
Technical Field
The invention relates to the field of rubber material production, in particular to a vulcanized composition, an EPDM-based vulcanized rubber composition, vulcanized rubber and a preparation method and application thereof.
Background
Ethylene propylene diene monomer/polypropylene (EPDM/PP) thermoplastic elastomer materials are the earliest class of thermoplastic elastomers to the market. Because of good physical properties, the thermoplastic plastic can be processed by adopting processing equipment and technology of thermoplastic plastics, and the thermoplastic plastic is widely applied to industries of household appliances, wires and cables, buildings, automobiles and the like.
The EPDM/PP thermoplastic rubber is prepared by adopting a dynamic vulcanization method, and the stretching flow in the preparation process can better ensure that all components in the rubber are uniformly dispersed, so that the EPDM/PP thermoplastic rubber has better performance.
With the increasing range of applications, EPDM/PP thermoplastic dynamic vulcanizates (TPV) have gradually replaced traditional EPDM/PP thermoplastic elastomers as "third generation rubber". However, the current EPDM/PP thermoplastic dynamic vulcanizates have somewhat limited application due to their lower tensile strength and higher compression set.
CN101597378A discloses a preparation method of thermoplastic dynamic vulcanized rubber, which comprises the following specific operation steps: (1) Uniformly mixing ethylene propylene diene monomer, polypropylene, talcum powder and antioxidant 1010 in a high-speed mixer, melt blending at 180 ℃ through a double-screw extruder, and filling naphthenic oil softening agent through a liquid filling port; (2) Uniformly mixing the product obtained in the step (1), a tertiary octyl phenolic resin vulcanizing agent and stannous chloride by a high-speed mixer, then dynamically vulcanizing the mixture by a double-screw extruder at 180 ℃, and simultaneously filling a naphthenic oil softening agent; (3) And (3) uniformly mixing the product obtained in the step (2) and the black master batch by a high-speed mixer, and then carrying out melt extrusion by a double-screw extruder at 180 ℃ and simultaneously filling a naphthenic oil softener. The preparation method has the advantages that the consumption of the vulcanizing agent tert-octyl phenolic resin is up to 7%, and the prepared dynamic vulcanized thermoplastic elastomer material has low elongation at break, rough surface and poor processability.
Disclosure of Invention
The invention aims to solve the problem that the TPV material prepared by the existing EPDM/PP dynamic vulcanization technology is low in elongation at break.
In order to achieve the above object, according to one aspect of the present invention, there is provided a vulcanization composition comprising a main vulcanizing agent a, a main vulcanizing agent B and an auxiliary vulcanizing agent, wherein the main vulcanizing agent a, the main vulcanizing agent B and the auxiliary vulcanizing agent are stored in a mixed manner or are stored independently of each other, the main vulcanizing agent B is contained in an amount of 0.1 to 2 parts by weight, and the auxiliary vulcanizing agent is contained in an amount of 0.5 to 4 parts by weight, based on 1 part by weight of the main vulcanizing agent a;
wherein the main vulcanizing agent A is at least one of tert-butylphenol formaldehyde resin, tert-octylphenol formaldehyde resin and epoxy resin;
the main vulcanizing agent B is at least one selected from dicumyl peroxide (DCP), di-tert-butylperoxyisopropyl benzene (BIBP) and 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane (bis 25);
the auxiliary vulcanizing agent is a hydrogen ion transfer crosslinking promoting agent and/or a free radical transfer crosslinking promoting agent.
In a second aspect, the invention provides an EPDM-based vulcanized rubber composition, which contains two or more of ethylene propylene diene monomer, polypropylene, a softener, an antioxidant, an active agent, and the components of the vulcanized composition of the first aspect, stored in a mixed manner or stored independently of each other.
In a third aspect, the present invention provides a process for producing a vulcanized rubber, comprising:
(1) Carrying out first mixing on the auxiliary vulcanizing agent and a part of ethylene propylene diene monomer rubber to obtain auxiliary vulcanizing agent master batches;
(2) Performing secondary mixing on polypropylene, an antioxidant, a softener, a main vulcanizing agent A, an active agent, a vulcanizing aid master batch and the rest ethylene propylene diene monomer to obtain a mixed rubber;
(3) Dynamically vulcanizing the mixed rubber and the main vulcanizing agent B;
wherein the definition of the main curative A, the main curative B and the auxiliary curative are correspondingly the same as the corresponding definitions in the vulcanized composition according to the first aspect.
According to a fourth aspect of the present invention, there is provided a vulcanized rubber prepared by the method of the third aspect.
In a fifth aspect, the present invention provides a use of the vulcanized rubber according to the fourth aspect in automobiles, household appliances, wires, cables or buildings.
When the vulcanization composition provided by the invention is applied to the EPDM/PP dynamic vulcanization technology, the auxiliary vulcanizing agent and the vulcanizing agents with two different action mechanisms are matched with each other, so that the elongation at break of the EPDM/PP thermoplastic dynamic vulcanized rubber can be effectively improved.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a vulcanization composition comprising a main vulcanizing agent a, a main vulcanizing agent B and an auxiliary vulcanizing agent, wherein the main vulcanizing agent a, the main vulcanizing agent B and the auxiliary vulcanizing agent are stored in a mixed state or each independently, the main vulcanizing agent B is contained in an amount of 0.1 to 2 parts by weight, and the auxiliary vulcanizing agent is contained in an amount of 0.5 to 4 parts by weight, relative to 1 part by weight of the main vulcanizing agent a;
wherein the main vulcanizing agent A is at least one of tert-butylphenol formaldehyde resin, tert-octylphenol formaldehyde resin and epoxy resin; the main vulcanizing agent B is at least one selected from dicumyl peroxide, di-tert-butyl cumene peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane; the auxiliary vulcanizing agent is a hydrogen ion transfer crosslinking promoting agent and/or a free radical transfer crosslinking promoting agent.
The inventor of the present invention found in the research process that when the combination of the main vulcanizing agent A, the main vulcanizing agent B and the auxiliary vulcanizing agent is applied to the dynamic vulcanization process of the EPDM rubber, the main vulcanizing agent, the auxiliary vulcanizing agent A and the auxiliary vulcanizing agent B can be mutually matched, so that the breaking elongation of the EPDM rubber is effectively improved.
In order to be able to further improve the mechanical properties such as compression set and tensile strength of EPDM vulcanized rubber, it is preferable that the content of the main vulcanizing agent B is 0.25 to 0.65 parts by weight and the content of the auxiliary vulcanizing agent is 0.9 to 1.65 parts by weight with respect to 1 part by weight of the main vulcanizing agent a.
In order to be able to further increase the elongation at break of EPDM vulcanized rubber, preferably the hydrogen ion transfer promoting cross-linking agent is an octene polymer rubber reactant (TOR) and/or Divinylbenzene (DVB). Wherein TOR is trans-polyoctene rubber, and is a polymer with a double-bond agent structure.
In order to be able to further improve the elongation at break of the EPDM vulcanized rubber, it is preferable that the radical transfer-promoting crosslinking agent is selected from at least one of triallyl 1,3, 5-isocyanurate (TAC), triallyl isocyanurate (TAIC), and triallyl trimellitate (DIPB).
In order to be able to further improve the mechanical properties of EPDM vulcanized rubber, according to a particularly preferred embodiment, the main vulcanizing agent a is a tertiary octyl phenol formaldehyde resin; the main vulcanizing agent B is di-tert-butyl isopropyl benzene peroxide; the co-vulcanizing agent is triallyl isocyanurate.
As previously described, the second aspect of the present invention provides an EPDM-based vulcanized rubber composition comprising EPDM, PP, softener, antioxidant, active agent and components of the vulcanized composition described herein either stored in a mixture of two or more or each independently.
In the second aspect of the present invention, the vulcanized composition is the vulcanized composition described in the foregoing, and therefore, in the second aspect of the present invention, information such as the kind and content of components in the vulcanized composition will not be repeated, and those skilled in the art should not understand the limitation of the present invention.
In order to be able to further increase the elongation at break of the vulcanized rubber, it is preferable that the vulcanized composition is contained in an amount of 1.6 to 3.5% by weight, the antioxidant is contained in an amount of 0.2 to 0.4% by weight, and the active agent is contained in an amount of 0.4 to 0.6% by weight, based on the total weight of the EPDM, the PP and the softener.
In order to be able to further improve the mechanical properties of the vulcanized rubber, it is preferable that the content of ethylene structural units in the EPDM is 50 to 70 wt% and the content of the third monomer is 4 to 6 wt%; further preferably, the EPDM has a weight average molecular weight of 10 to 40 tens of thousands. The third monomer is at least one selected from 1, 4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene, and more preferably ENB.
In order to be able to further increase the tensile strength and elongation at break of the vulcanized rubber, it is preferred that the PP is homo-and/or random co-polypropylene, the polypropylene melt index being 1-20g/10min.
In order to be able to further improve the mechanical properties of the vulcanizate, it is preferred that the comonomer of the random copolymer polypropylene is ethylene.
Preferably, the softener is selected from at least one of paraffinic oil, naphthenic oil and aromatic oil.
Further preferably, the softener is paraffin oil in order to further improve the mechanical properties of the vulcanized rubber. Still more preferably, the paraffinic oil is an environmental protection paraffinic oil.
Preferably, the antioxidant is at least one selected from amine antioxidants, quinoline antioxidants and benzimidazole antioxidants. Specifically, the amine antioxidant is a naphthylamine antioxidant and/or a p-phenylenediamine antioxidant. More specifically, the naphthylamine antioxidant is naphthylamine and its derivatives; the p-phenylenediamine antioxidant is p-phenylenediamine and derivatives thereof; the quinoline antioxidant is quinoline and derivatives thereof, such as 2, 4-trimethyl-1, 2-dihydroquinoline; the benzimidazole antioxidant is benzimidazole and its derivatives, such as 2-mercaptobenzimidazole. Further preferably, the antioxidant is pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1010).
Preferably, the active agent is selected from at least one of stannous chloride, 2-mercaptobenzothiazole (promoter M), 2' -dithiodibenzothiazyl (promoter DM) and N-cyclohexyl-2-benzothiazole sulfenamide (promoter CZ).
In order to be able to obtain a vulcanized rubber with better mechanical properties, it is preferable that the ethylene propylene diene monomer content is 1.8 to 2.4 parts by weight and the softener content is 0.6 to 1.2 parts by weight with respect to 1 part by weight of the polypropylene.
As previously described, a third aspect of the present invention provides a process for producing a vulcanized rubber, the process comprising:
(1) Carrying out first mixing on the auxiliary vulcanizing agent and a part of ethylene propylene diene monomer rubber to obtain auxiliary vulcanizing agent master batches; and
carrying out second mixing on polypropylene, an antioxidant, a softener and the rest ethylene propylene diene monomer rubber to obtain rubber and plastic master batches;
(2) Dynamically vulcanizing the rubber and plastic master batch, the main vulcanizing agent A, the active agent, the auxiliary vulcanizing agent master batch and the main vulcanizing agent B;
wherein, the definition of the main vulcanizing agent A, the main vulcanizing agent B and the auxiliary vulcanizing agent are the same in the corresponding definition in the vulcanizing composition according to the technical schemes of the first aspect.
Preferably, the vulcanized composition, the ethylene propylene diene monomer, the polypropylene, the softener, the active agent and the antioxidant are correspondingly the same as the corresponding definitions in the EPDM-based vulcanized rubber composition according to the respective technical solutions of the second aspect. The definition refers to the types, proportions and amounts of the components in the composition. That is, the types and proportions of the main vulcanizing agent a, the main vulcanizing agent B, and the auxiliary vulcanizing agent mentioned in the third aspect of the present invention are the same as those of the respective components in the vulcanized composition provided in the first aspect of the present invention; the types, proportions and amounts of the vulcanized composition, EPDM, PP, softener, active agent and antioxidant mentioned in the third aspect of the present invention are also the same correspondingly as those of the rubber composition provided in the second aspect of the present invention, and those skilled in the art should not understand the limitation of the present invention.
In order to obtain better mechanical properties, preferably, the operation of step (2) comprises: and uniformly mixing the rubber master batch, the main vulcanizing agent A and the active agent, and then carrying out dynamic vulcanization together with the auxiliary vulcanizing agent master batch. Where the mixing may be by stirring.
In order to obtain better mechanical properties, preferably, in step (1), the conditions of the first mixing at least satisfy: the temperature is 70-110deg.C, and the time is 3-6min.
In order to obtain better mechanical properties, preferably, in step (1), the conditions of the second mixing at least satisfy: the temperature is 160-200deg.C, and the time is 1-4min.
In order to further improve the mechanical properties of the vulcanized rubber, preferably, the weight ratio of the ethylene propylene diene monomer rubber participating in the first mixing to the rest ethylene propylene diene monomer rubber participating in the second mixing is 1:20-120.
Further preferably, in order to further improve the tensile strength and the elongation at break of the vulcanized rubber and reduce the compression set thereof, the weight ratio of the ethylene propylene diene monomer rubber used in the first mixing to the ethylene propylene diene monomer rubber used in the second mixing is 1:40-80.
In order to increase the vulcanization efficiency of EPDM/PP rubber, preferably, in step (2), the conditions of the dynamic vulcanization at least satisfy: the temperature is 180-200deg.C, and the time is 1-4min.
In order to obtain better mechanical properties, preferably, the conditions of the dynamic vulcanization at least satisfy: the temperature is 185-195 ℃, the time is 2-3min, and the rotating speed is 200-400rpm.
As described above, the fourth aspect of the present invention provides a vulcanized rubber produced by the method according to any one of the third aspects.
According to a particularly preferred embodiment, the preparation method comprises:
(1) The auxiliary vulcanizing agent and EPDM are mixed according to the weight ratio of 1: adding 0.5-1.5 into an internal mixer for first mixing, and then extruding and granulating in a single-screw granulator to obtain a vulcanization aid master batch, wherein the first mixing conditions at least meet the following conditions: the temperature of the internal mixer is 70-110 ℃, the time is 3-6min, and the rotating speed is 200-400rpm; the temperature of the single screw extrusion granulator is 60-90 ℃;
secondly mixing PP, an antioxidant, a softener and the rest of EPDM to obtain rubber-plastic master batches; the second mixing condition at least satisfies: the temperature is 160-200 ℃, the time is 1-4min, and the rotating speed is 150-350rpm;
(2) Uniformly mixing rubber and plastic master batch, main vulcanizing agent and auxiliary vulcanizing agent A, adding the main vulcanizing agent B into a first section of a main feeding port of a double-screw extruder, adding the main vulcanizing agent B into a fourth section of a side feeding port of the double-screw extruder, and carrying out dynamic vulcanization to obtain vulcanized rubber after vulcanization, wherein the dynamic vulcanization conditions at least meet the following conditions: the temperature is 180-200deg.C, the time is 1-4min, and the rotation speed is 200-400rpm.
As previously mentioned, the fifth aspect of the present invention provides the use of the vulcanized rubber of the fourth aspect in automobiles, household appliances, wires, cables or buildings.
When the vulcanization composition provided by the invention is applied to EPDM/PP rubber vulcanization, as the main vulcanizing agent and the auxiliary vulcanizing agent with two different action mechanisms are matched with each other, the mechanical property of the EPDM/PP TPV material is improved, and the ternary dynamic vulcanization thermoplastic elastomer material with excellent processability is prepared, so that the application range of the EPDM/PP TPV material is greatly widened, and the vulcanization composition can be widely applied to industries such as household appliances, wires and cables, buildings, automobiles and the like.
The invention will be described in detail below by way of examples.
Main vulcanizing agent a: tertiary octyl phenol formaldehyde resin (hereinafter referred to as primary curative a-1) is purchased from the shanxi chemical institute; tertiary butyl phenol formaldehyde resin (hereinafter referred to as primary vulcanizing agent a-2) is purchased from sandisk bright biotechnology limited; epoxy resin (hereinafter referred to as main vulcanizing agent A-3) was purchased from Chenopodie chemical technology Co., ltd;
main vulcanizing agent B: BIBP (hereinafter referred to as primary curative B-1) is purchased from Shanghai Sendi corporation; DCP (hereinafter referred to as main vulcanizing agent B-2) is available from Shanghai Sendi corporation; bis 25 (hereinafter referred to as main vulcanizing agent B-3) is purchased from shanghai sendai company;
auxiliary vulcanizing agent: TAIC (hereinafter co-vulcanizing agent-1, free radical transfer crosslinking promoter) is available from Shanghai Fang Rui to chemical Co., ltd; TOR (hereinafter referred to as co-sulfiding agent-2, hydrogen ion transfer promoting cross-linking agent) was purchased from ala Ding Gongsi; TAC (hereinafter called co-vulcanizing agent-3, a radical transfer crosslinking promoter) was purchased from Shanghai Fang Rui to chemical Co., ltd; DVB (hereinafter called co-sulfiding agent-4, hydrogen ion transfer promoting cross-linker) was purchased from Aba Ding Gongsi; DIPB (hereinafter called co-vulcanizing agent-5, free radical transfer crosslinking promoter) was purchased from shanghai Fang Rui to chemical limited.
EPDM was purchased from mitsunobu chemical company; wherein the content of ethylene structural unit in EPDM (hereinafter referred to as EPDM-1) having a product number of 3092PM is 65.9 mol%, the content of the third monomer (ENB) is 4.6 mol%, and the Mooney viscosity is 61 (ML 125 ℃ C. 1+4); the EPDM (hereinafter referred to as EPDM-2) having a product number of 4045 had a content of ethylene structural units of 51 mol%, a content of the third monomer (ENB) of 8 mol% and a Mooney viscosity of 42 (ML 125 ℃ C. 1+4).
PP is purchased from chinese petrochemical, yang, petrochemical limited; wherein, PP with the product number of F401 (hereinafter referred to as PP-1) is homo-polypropylene, and the melt index is 2.3g/10min; the PP (hereinafter referred to as PP-2) having a product number of K9927 had a melt index of 27g/10min.
Softening agent: environment-friendly paraffin oil (hereinafter referred to as softener-1) is purchased from Yongzhen industrial oil products Co., ltd in Wuxi city, the product number is KP6030, and the flash point is 280 ℃; the paraffin-based base oil (hereinafter referred to as softener-2) was purchased from Yongzhen industrial oil Co., ltd. In Wuxi city under the product number 400N and flash point 189 ℃.
Antioxidant: antioxidant 1010 (hereinafter referred to as antioxidant-1) is purchased from basf corporation; antioxidant 168 (hereinafter referred to as antioxidant-2) is available from basf corporation.
Active agent: stannous chloride (hereinafter active agent-1) was purchased from ala Ding Gongsi; promoter CZ (hereinafter referred to as active agent-2) was purchased from the chemical company of the german chemical industry of the south kyo.
The twin-screw extruder was purchased from Corbegron (Nanj) mechanical Co., ltd, the instrument model was STS35, and the parameters were set as follows: phi=35 mm, l/d=56.
The internal mixer was purchased from Kunshan Jiulong mechanical Co., ltd, instrument model M10L, volume 10L.
The single screw granulator is purchased from Kunshan Delong mechanical Co., ltd, the instrument model is JZD80, and the yield is 40-60Kg/h.
Unless otherwise specified, 10g is expressed per part by weight.
Example 1
(1) Adding 2 parts by weight of TAIC and 2 parts by weight of EPDM-1 into an internal mixer for first mixing (temperature: 100 ℃, time: 3min, rotating speed: 200 rpm), and then extruding and granulating in a single-screw granulator (temperature: 70 ℃) to prepare a vulcanization aid master batch; and
rubber-plastic blending (rotation speed: 200rpm, temperature: 180 ℃ C., time: 2 min) is performed on PP-1 (25 parts by weight), antioxidant 1010 (0.3 parts by weight), environment-friendly paraffin oil (30 parts by weight) and EPDM-1 (43 parts by weight), so as to obtain rubber-plastic master batch;
(2) Rubber and plastic master batches, stannous chloride (0.5 part by weight), tert-octyl phenol formaldehyde resin (0.5 part by weight) and auxiliary vulcanizing agent master batches are uniformly mixed, the mixture is added from a first section main feeding port of a double-screw extruder, BIBP (1 part by weight) is added from a fourth section side feeding port of the double-screw extruder, dynamic vulcanization is carried out (the rotating speed is 400rpm, the temperature is 180 ℃ and the time is 4 min), and vulcanized rubber is obtained after vulcanization is finished.
Remaining examples and comparative examples
The remaining examples were carried out using the same process flow as example 1, except for the differences set forth in tables 1,2, 3 and 4, unless otherwise specified.
TABLE 1
TABLE 2
TABLE 3 Table 3
TABLE 4 Table 4
| Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| EPDM | ||||
| Species of type | EPDM-1 | EPDM-1 | EPDM-1 | EPDM-1 |
| Amount/weight part | 55 | 55 | 55 | 55 |
| PP | ||||
| Species of type | PP-1 | PP-1 | PP-1 | PP-1 |
| Amount/weight part | 25 | 25 | 25 | 25 |
| Softening agent | ||||
| Species of type | Softener-1 | Softener-1 | Softener-1 | Softener-1 |
| Amount/weight part | 20 | 20 | 20 | 20 |
| Main vulcanizing agent A | ||||
| Species of type | Main vulcanizing agent A-1 | Main vulcanizing agent A-1 | - | - |
| Amount/weight part | 0.8 | 0.8 | - | - |
| Main vulcanizing agent B | ||||
| Species of type | Main vulcanizing agent B-1 | - | Main vulcanizing agent B-1 | Main vulcanizing agent B-1 |
| Amount/weight part | 0.2 | - | 0.2 | 0.2 |
| Vulcanization aid | ||||
| Species of type | Auxiliary vulcanizing agent-1 | - | Auxiliary vulcanizing agent-1 | Auxiliary vulcanizing agent-1 |
| Amount/weight part | 0.7 | - | 0.7 | 0.7 |
| Antioxidant agent | ||||
| Species of type | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 |
| Amount/weight part | 0.3 | 0.3 | 0.3 | 0.3 |
| Active agent | ||||
| Species of type | Active agent-1 | Active agent-1 | - | Active agent-1 |
| Amount/weight part | 0.5 | 0.5 | - | 0.5 |
| First mixing | ||||
| Time/min | 5 | 5 | 5 | 5 |
| Temperature/. Degree.C | 110 | Same as in example 4 | Same as in example 4 | Same as in example 4 |
| Rotational speed/rpm | 300 | Same as in example 4 | Same as in example 4 | Same as in example 4 |
| Granulating temperature/DEGC | 80 | Same as in example 4 | Same as in example 4 | Same as in example 4 |
| Second mixing | ||||
| Time/min | 1 | Same as in example 4 | Same as in example 4 | Same as in example 4 |
| Temperature/. Degree.C | 200 | Same as in example 4 | Same as in example 4 | Same as in example 4 |
| Rotational speed/rpm | 350 | Same as in example 4 | Same as in example 4 | Same as in example 4 |
| Dynamic vulcanization | ||||
| Time/min | 2.5 | 2.5 | 2.5 | 2.5 |
| Temperature/. Degree.C | 190 | 190 | 190 | 190 |
| Rotational speed/rpm | 300 | 300 | 300 | 300 |
Test case
The mechanical properties of the products obtained in all examples are respectively tested and are listed in Table 5. Wherein the tensile strength is tested according to the method in ASTM D412, wherein the tensile rate is set at 500mm/min; compression set was tested according to the method in ASTM D395B, wherein the test conditions were 70 ℃ x 22h, restrictor height 9.4mm; elongation at break was tested according to the method in GB/T528-2009; shore A hardness was measured according to the method in GB/T531.1-2008.
TABLE 5
As can be seen from the combination of tables 1,2, 4 and 5, the vulcanizing compositions of the present invention are not used in comparative examples 1 to 3, but the vulcanizing compositions provided by the present invention are used in examples 1 to 7, and the data of comparative examples 3 to 7 show that the breaking elongation and tensile strength of the vulcanized rubber material are significantly improved and the compression set is significantly reduced after the vulcanizing compositions provided by the present invention are used, so that the main vulcanizing agent A, the main vulcanizing agent B and the auxiliary vulcanizing agent in the protection range of the present invention are matched with each other through the specific dosage proportion relationship, thereby effectively improving the breaking elongation and tensile strength of the EPDM rubber and also effectively reducing the compression set of the EPDM rubber.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.
Claims (19)
1. An EPDM-based vulcanized rubber composition is characterized by comprising more than two ethylene propylene diene monomer rubbers which are stored in a mixed mode or are stored independently, polypropylene, a softener, an antioxidant, an active agent and each component in the vulcanized composition;
the content of the vulcanized composition is 1.6-3.5 wt%, the content of the antioxidant is 0.2-0.4 wt% and the content of the active agent is 0.4-0.6 wt% based on the total weight of the ethylene propylene diene monomer, the polypropylene and the softener;
the active agent is at least one selected from stannous chloride, 2-mercaptobenzothiazole, 2' -dithiodibenzothiazyl and N-cyclohexyl-2-benzothiazole sulfenamide;
the vulcanizing composition consists of a main vulcanizing agent A, a main vulcanizing agent B and an auxiliary vulcanizing agent, wherein the content of the main vulcanizing agent B is 0.1-2 parts by weight relative to 1 part by weight of the main vulcanizing agent A, and the content of the auxiliary vulcanizing agent is 0.5-4 parts by weight;
wherein the main vulcanizing agent A is at least one of tert-butylphenol formaldehyde resin, tert-octylphenol formaldehyde resin and epoxy resin;
the main vulcanizing agent B is at least one selected from dicumyl peroxide, di-tert-butyl cumene peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane;
the vulcanization accelerator is a free radical transfer crosslinking accelerator, and the free radical transfer crosslinking accelerator is at least one selected from the group consisting of triallyl 1,3, 5-isocyanurate, triallyl isocyanurate and triallyl trimellitate.
2. EPDM-based vulcanized rubber composition according to claim 1, wherein the content of the main vulcanizing agent B is 0.25-0.65 parts by weight and the content of the auxiliary vulcanizing agent is 0.9-1.65 parts by weight, relative to 1 part by weight of the main vulcanizing agent a.
3. EPDM-based vulcanized rubber composition according to claim 1, wherein the primary vulcanizing agent a is a tertiary octyl phenol formaldehyde resin;
the main vulcanizing agent B is di-tert-butyl isopropyl benzene peroxide;
the co-vulcanizing agent is triallyl isocyanurate.
4. An EPDM-based vulcanized rubber composition as claimed in any one of claims 1 to 3, wherein the ethylene structural unit content in the ethylene propylene diene monomer is 50 to 70 wt% and the content of the third monomer is 4 to 6 wt%.
5. The EPDM-based vulcanized rubber composition of claim 4, wherein the weight average molecular weight of the ethylene propylene diene monomer is from 10 to 40 tens of thousands, and the third monomer is at least one selected from the group consisting of 1, 4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene.
6. EPDM-based vulcanized rubber composition according to claim 5, wherein the polypropylene is homo-and/or random co-polypropylene, the polypropylene having a melt index of 1-20g/10min.
7. EPDM-based vulcanized rubber composition according to claim 6, wherein the comonomer of the random copolymer polypropylene is ethylene.
8. The EPDM-based vulcanized rubber composition of claim 7, wherein the softener is selected from at least one of paraffinic, naphthenic and aromatic oils.
9. The EPDM-based vulcanized rubber composition of claim 8, wherein the antioxidant is selected from at least one of an amine antioxidant, a quinoline antioxidant, and a benzimidazole antioxidant.
10. An EPDM-based vulcanized rubber composition as claimed in any one of claims 1-3, wherein the ethylene propylene diene monomer is present in an amount of 1.8-2.4 parts by weight and the softener is present in an amount of 0.6-1.2 parts by weight relative to 1 part by weight of the polypropylene.
11. A process for producing a vulcanized rubber using the vulcanized rubber composition as defined in any one of claims 1 to 10, characterized in that the process comprises:
(1) Carrying out first mixing on the auxiliary vulcanizing agent and a part of ethylene propylene diene monomer rubber to obtain auxiliary vulcanizing agent master batches; and
carrying out rubber-plastic blending on polypropylene, an antioxidant, a softener and the rest ethylene propylene diene monomer rubber to obtain rubber-plastic master batches;
(2) And dynamically vulcanizing the rubber and plastic master batch, the main vulcanizing agent A, the active agent, the auxiliary vulcanizing agent master batch and the main vulcanizing agent B.
12. The method of claim 11, wherein the operation of step (2) comprises: and uniformly mixing the rubber master batch, the main vulcanizing agent A and the active agent, and then carrying out dynamic vulcanization together with the auxiliary vulcanizing agent master batch.
13. The method of claim 11, wherein the ethylene propylene diene monomer rubber involved in the first mixing and the remainder ethylene propylene diene monomer rubber involved in the second mixing are used in a weight ratio of 1:20-120.
14. The method of claim 13, wherein the ethylene propylene diene monomer rubber involved in the first mixing and the remainder ethylene propylene diene monomer rubber involved in the second mixing are used in a weight ratio of 1:40-80.
15. A method according to any one of claims 11 to 14, wherein in step (1) the conditions of the first mixing are at least: the temperature is 70-110deg.C, and the time is 3-6min.
16. The method of claim 15, wherein in step (1), the conditions of the second mixing satisfy at least: the temperature is 160-200deg.C, and the time is 1-4min.
17. The method of claim 16, wherein in step (2), the conditions of the dynamic vulcanization at least satisfy: the temperature is 180-200deg.C, and the time is 1-4min.
18. A vulcanized rubber prepared by the method of any one of claims 11-17.
19. Use of the vulcanizate of claim 18 in automobiles, household appliances, wires, cables, or buildings.
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