CN114437463A - Vulcanized composition, vulcanized rubber composition based on EPDM, vulcanized rubber, and preparation method and application thereof - Google Patents
Vulcanized composition, vulcanized rubber composition based on EPDM, vulcanized rubber, and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Abstract
The invention relates to the field of rubber material production, and discloses a vulcanized composition, a vulcanized rubber composition based on EPDM (ethylene-propylene-diene monomer), a vulcanized rubber and a preparation method and application thereof, wherein the composition contains a main vulcanizing agent A, a main vulcanizing agent B and an auxiliary vulcanizing agent which are mixed and stored or respectively and independently stored, and relative to 1 part by weight of the main vulcanizing agent A, the content of the main vulcanizing agent B is 0.1-2 parts by weight, 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-butyl phenol formaldehyde resin, tert-octyl phenol formaldehyde resin and epoxy resin; the main vulcanizing agent B is at least one of dicumyl peroxide, di-tert-butyl cumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane; the co-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 being 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, 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 market. Because the thermoplastic elastomer has good physical properties and can be processed by thermoplastic processing equipment and technology, the thermoplastic elastomer is widely applied to industries such as household appliances, wires and cables, buildings, automobiles and the like.
The EPDM/PP thermoplastic rubber is prepared by a dynamic vulcanization method, and the tensile flow of the EPDM/PP thermoplastic rubber in the preparation process can better enable all components in the rubber to be uniformly dispersed, so that the EPDM/PP thermoplastic rubber has better performance.
As the range of applications has expanded, EPDM/PP thermoplastic dynamic vulcanizate (TPV) has gradually replaced traditional EPDM/PP thermoplastic elastomers as a "third generation rubber". However, the application range of the current EPDM/PP thermoplastic dynamic vulcanized rubber is limited to a certain extent because the tensile strength is low and the compression set is high.
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, melting and blending the mixture at 180 ℃ through a double-screw extruder, and filling a naphthenic oil softener through a liquid filling port; (2) uniformly mixing the product obtained in the step (1), a tert-octyl phenolic resin vulcanizing agent and stannous chloride in a high-speed mixer, dynamically vulcanizing the mixture at 180 ℃ by a double-screw extruder, and filling a naphthenic oil softening agent; (3) and (3) uniformly mixing the product obtained in the step (2) and black master batch by a high-speed mixer, then carrying out melt extrusion by a double-screw extruder at 180 ℃, and filling a naphthenic oil softener. The usage amount of the vulcanizing agent tert-octyl phenolic resin in the preparation method is up to 7 percent, and the prepared dynamic vulcanization 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 has low elongation at break.
In order to achieve the above object, one aspect of the present invention provides a vulcanized composition comprising a main vulcanizing agent a, a main vulcanizing agent B and a co-vulcanizing agent, which are stored as a mixture of two or more of the main vulcanizing agent a, the main vulcanizing agent B and the co-vulcanizing agent B, respectively, or independently, wherein the main vulcanizing agent B is contained in an amount of 0.1 to 2 parts by weight and the co-vulcanizing agent B is contained in an amount of 0.5 to 4 parts by weight, respectively, based on 1 part by weight of the main vulcanizing agent a;
wherein the main vulcanizing agent A is at least one selected from tert-butyl phenol formaldehyde resin, tert-octyl phenol formaldehyde resin and epoxy resin;
the main vulcanizing agent B is at least one selected from dicumyl peroxide (DCP), di-tert-butyl cumene peroxide (BIBP) and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane (bis 25);
the co-vulcanizing agent is a hydrogen ion transfer crosslinking promoter and/or a free radical transfer crosslinking promoter.
The second aspect of the present invention provides an EPDM-based vulcanized rubber composition containing two or more of ethylene propylene diene monomer, polypropylene, a softener, an antioxidant, an activator, and each component of the vulcanized composition of the first aspect, which are stored in admixture or independently of each other.
In a third aspect, the present invention provides a process for preparing a vulcanized rubber, the process comprising:
(1) carrying out first mixing on an auxiliary vulcanizing agent and a part of ethylene propylene diene monomer to obtain auxiliary vulcanizing agent master batches;
(2) carrying out second mixing on the polypropylene, the antioxidant, the softener, the main vulcanizing agent A, the active agent, the co-vulcanizing agent master batch and the rest of ethylene propylene diene monomer rubber to obtain a rubber compound;
(3) dynamically vulcanizing the mixing gum and a main vulcanizing agent B;
wherein the primary curative A, the primary curative B and the co-curative are correspondingly defined the same as in the vulcanized composition of the first aspect.
In a fourth aspect, the invention provides a vulcanized rubber prepared by the method of the third aspect.
The fifth aspect of the invention provides the use of the vulcanized rubber of the fourth aspect in automobiles, home appliances, electric wires, cables or buildings.
When the vulcanized composition containing the vulcanized rubber is applied to the EPDM/PP dynamic vulcanization technology, the co-vulcanizing agent and two vulcanizing agents with 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 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 vulcanized composition containing a main vulcanizing agent a, a main vulcanizing agent B and a co-vulcanizing agent, which are stored as a mixture of two or more of them or stored independently of each other, wherein the main vulcanizing agent B is contained in an amount of 0.1 to 2 parts by weight and the co-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 selected from tert-butyl phenol formaldehyde resin, tert-octyl phenol formaldehyde resin and epoxy resin; the main vulcanizing agent B is at least one selected from dicumyl peroxide, di-tert-butyl cumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane; the co-vulcanizing agent is a hydrogen ion transfer crosslinking promoter and/or a free radical transfer crosslinking promoter.
In the research process, the inventor of the invention finds 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 A, the auxiliary vulcanizing agent A and the auxiliary vulcanizing agent B can be mutually matched, and the elongation at break 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 the EPDM vulcanized rubber, it is preferable that the primary vulcanizing agent B is contained in an amount of 0.25 to 0.65 parts by weight and the co-vulcanizing agent is contained in an amount of 0.9 to 1.65 parts by weight with respect to 1 part by weight of the primary vulcanizing agent A.
In order to be able to further increase the elongation at break of the EPDM vulcanized rubber, preferably, the hydrogen ion transfer cross-linking promoter is an octene polymer rubber reactant (TOR) and/or Divinylbenzene (DVB). Wherein, TOR is trans-polyoctene rubber, which is a polymer with a double bond agent structure.
In order to be able to further increase the elongation at break of the EPDM vulcanized rubber, preferably, the radical transfer crosslinking accelerator is at least one selected from the group consisting of 1,3, 5-triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), and triallyl trimellitate (DIPB).
In order to be able to further improve the mechanical properties of EPDM vulcanizates, according to a particularly preferred embodiment, the main vulcanization agent a is a tert-octylphenol-formaldehyde resin; the main vulcanizing agent B is di-tert-butyl cumene peroxide; the auxiliary vulcanizing agent is triallyl isocyanurate.
As described above, the second aspect of the present invention provides an EPDM-based vulcanized rubber composition comprising EPDM, PP, a softener, an antioxidant, an activator, and each component of the vulcanized composition described above, wherein the EPDM, the softener, the antioxidant, the activator, and the activator are stored in admixture or independently of each other.
In the second aspect of the present invention, the vulcanized composition is the vulcanized composition described above, and therefore, in the second aspect of the present invention, the information such as the types and contents of the components in the vulcanized composition will not be repeatedly described, and those skilled in the art should not be construed as limiting the present invention.
In order to be able to further increase the elongation at break of the vulcanized rubber, it is preferable that the content of the vulcanized composition is 1.6 to 3.5% by weight, the content of the antioxidant is 0.2 to 0.4% by weight, and the content of the active agent is 0.4 to 0.6% by weight, based on the total weight of the EPDM, the PP and the softener.
In order to further improve the mechanical properties of the vulcanized rubber, the EPDM preferably contains 50 to 70 wt% of ethylene structural units and 4 to 6 wt% of a third monomer; further preferably, the weight average molecular weight of the EPDM is 10-40 ten thousand. The third monomer is at least one selected from the group consisting of 1, 4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene, and is more preferably ENB.
In order to further improve the tensile strength and the elongation at break of the vulcanized rubber, the PP is preferably homo-polypropylene and/or random co-polypropylene, and the polypropylene melt index is 1-20g/10 min.
In order to further improve the mechanical properties of the vulcanized rubber, the comonomer of the random copolymer polypropylene is preferably ethylene.
Preferably, the softening agent is at least one selected from paraffin oil, naphthenic oil and aromatic oil.
Further preferably, in order to further improve the mechanical properties of the vulcanized rubber, the softening agent is paraffin oil. Still more preferably, the paraffin oil is an environmentally friendly paraffin 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-based antioxidant is naphthylamine and derivatives thereof; the p-phenylenediamine antioxidant is p-phenylenediamine and a derivative thereof; the quinoline antioxidant is quinoline and its derivatives, such as 2,2, 4-trimethyl-1, 2-dihydroquinoline; the benzimidazole antioxidant is benzimidazole and its derivatives, such as 2-mercaptobenzimidazole. Further preferably, the antioxidant is pentaerythritol tetrakis [ β - (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 (accelerator M), 2' -dithiodibenzothiazole (accelerator DM) and N-cyclohexyl-2-benzothiazolesulfenamide (accelerator CZ).
In order to obtain a vulcanized rubber having better mechanical properties, it is preferable that the ethylene propylene diene monomer is contained in an amount of 1.8 to 2.4 parts by weight and the softener is contained in an amount of 0.6 to 1.2 parts by weight, relative to 1 part by weight of the polypropylene.
As previously mentioned, a third aspect of the present invention provides a process for preparing a vulcanized rubber, the process comprising:
(1) carrying out first mixing on an auxiliary vulcanizing agent and a part of ethylene propylene diene monomer to obtain auxiliary vulcanizing agent master batches; and
carrying out second mixing on polypropylene, an antioxidant, a softener and the rest part of ethylene propylene diene monomer rubber to obtain rubber and plastic master batches;
(2) dynamically vulcanizing the rubber-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 definitions of the primary vulcanizing agent A, the primary vulcanizing agent B and the co-vulcanizing agent are the same correspondingly in the vulcanized compositions described in the first aspect.
Preferably, the vulcanized composition, the ethylene propylene diene monomer, the polypropylene, the softener, the active agent and the antioxidant are correspondingly defined in the EPDM-based vulcanized rubber composition according to the second aspect. The definition refers to the type, proportion and dosage of each component 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 invention are the same as those of the components in the vulcanized composition provided by the first aspect of the invention; the types, proportions and amounts of the vulcanized composition, EPDM, PP, softener, activator and antioxidant mentioned in the third aspect of the present invention are the same as those of the rubber composition provided in the second aspect of the present invention, and those skilled in the art should not be construed as limiting the present invention.
In order to obtain better mechanical performance, preferably, the operation of step (2) comprises: and after the rubber master batch, the main vulcanizing agent A and the active agent are uniformly mixed, the mixture and the auxiliary vulcanizing agent master batch are dynamically vulcanized. Where mixing can be by stirring.
In order to obtain better mechanical properties, it is preferable that, in step (1), the conditions of the first mixing are at least satisfied: the temperature is 70-110 deg.C, and the time is 3-6 min.
In order to obtain better mechanical properties, it is preferable that in step (1), the conditions of the second mixing at least satisfy: the temperature is 160 ℃ and 200 ℃, and the time is 1-4 min.
In order to further improve the mechanical property of the vulcanized rubber, the weight ratio of the ethylene propylene diene monomer participating in the first mixing to the remaining part of the ethylene propylene diene monomer participating in the second mixing is preferably 1: 20-120.
Further preferably, in order to further improve the tensile strength and elongation at break of the vulcanized rubber and reduce the compression set thereof, the amount by weight ratio of the ethylene propylene diene monomer involved in the first compounding to the remaining portion of the ethylene propylene diene monomer involved in the second compounding is 1: 40-80.
In order to improve the vulcanization efficiency of the EPDM/PP rubber, it is preferable that in step (2), the conditions of the dynamic vulcanization at least satisfy: the temperature is 180 ℃ and 200 ℃, and the time is 1-4 min.
In order to obtain better mechanical properties, it is preferred that the conditions of the dynamic vulcanization at least satisfy: the temperature is 185-195 ℃, the time is 2-3min, and the rotating speed is 200-400 rpm.
As described above, the fourth aspect of the present invention provides a vulcanized rubber obtained by the method according to any one of the third aspect.
According to a particularly preferred embodiment, the preparation process comprises:
(1) mixing a co-vulcanizing agent and EPDM according to a weight ratio of 1: 0.5-1.5, adding the mixture into an internal mixer for first mixing, and then extruding and granulating in a single-screw granulator to obtain the co-vulcanizing agent masterbatch, wherein the first mixing condition at least meets the following requirements: the temperature of the internal mixer is 70-110 ℃, the time is 3-6min, and the rotating speed is 200-400 rpm; the temperature of the single-screw extrusion granulator is 60-90 ℃;
carrying out second mixing on PP, an antioxidant, a softener and the rest EPDM to obtain rubber-plastic master batch; the second mixing condition at least satisfies: the temperature is 160-;
(2) uniformly mixing the rubber-plastic master batch, a main vulcanizing agent and an auxiliary vulcanizing agent A, adding the mixture from a main feeding port at a first section of a double-screw extruder, adding a main vulcanizing agent B from a lateral feeding port at a fourth section of the double-screw extruder, carrying out dynamic vulcanization, and obtaining vulcanized rubber after vulcanization is finished, wherein the dynamic vulcanization condition at least meets the following requirements: the temperature is 180 ℃ and 200 ℃, the time is 1-4min, and the rotating speed is 200 ℃ and 400 rpm.
As previously mentioned, a fifth aspect of the present invention provides the use of the vulcanizate of the fourth aspect in an automobile, appliance, wire, cable, or building.
When the vulcanized composition provided by the invention is applied to vulcanization of EPDM/PP rubber, the mechanical property of the EPDM/PP TPV material is improved due to the mutual cooperation of the main vulcanizing agent and the auxiliary vulcanizing agent with two different action mechanisms, and the ternary dynamic vulcanized thermoplastic elastomer material with excellent processing property is prepared, so that the application range of the EPDM/PP TPV material is greatly widened, and the EPDM/PP TPV composite can be widely applied to industries such as household appliances, wires and cables, buildings, automobiles and the like.
The present invention will be described in detail below by way of examples.
A main vulcanizing agent A: tert-octylphenol formaldehyde resin (hereinafter referred to as primary vulcanizing agent A-1) was purchased from Shanxi chemical research institute; tert-butylphenol formaldehyde resin (hereinafter referred to as primary vulcanizing agent A-2) was purchased from Sancheng bright Biotech Co., Ltd; epoxy resin (hereinafter referred to as primary curing agent A-3) was purchased from Dorbett chemical technology, Inc.;
a main vulcanizing agent B: BIBP (hereinafter referred to as primary vulcanizing agent B-1) was purchased from Shanghai Sendy; DCP (hereinafter referred to as Primary vulcanizing agent B-2) was purchased from Shanghainey corporation; bis 25 (hereinafter referred to as primary curative B-3) was purchased from Shanghai Sendy;
auxiliary vulcanizing agent: TAIC (hereinafter referred to as co-curative-1, free radical transfer crosslinking promoter) was purchased from Shanghai Korea Chemicals, Inc.; TOR (hereinafter referred to as co-curative-2, hydrogen ion transfer crosslinking promoter) available from Aladdin; TAC (hereinafter referred to as co-curative-3, free radical transfer crosslinking promoter) was purchased from Shanghai Farreda Chemicals Co., Ltd; DVB (hereinafter referred to as co-curative-4, hydrogen ion transfer cross-linker) was purchased from Aladdin; DIPB (hereinafter referred to as co-curative-5, free radical transfer pro-crosslinker) was purchased from Shanghai Korea Chemicals, Inc.
EPDM was purchased from mitsui chemical company; wherein the EPDM with a product number of 3092PM (hereinafter referred to as EPDM-1) had an ethylene structural unit content of 65.9 mol%, a third monomer (ENB) content of 4.6 mol%, and a Mooney viscosity of 61(ML125 ℃ C. 1+ 4); EPDM having a product number of 4045 (hereinafter referred to as EPDM-2) had an ethylene structural unit content of 51 mol%, a third monomer (ENB) content of 8 mol%, and a Mooney viscosity of 42(ML125 ℃ C. 1+ 4).
PP is purchased from China petrochemical Yangzi oil chemical Co., Ltd; wherein PP (hereinafter referred to as PP-1) with the product number of F401 is homo-polypropylene, and the melt index is 2.3g/10 min; the melt index of PP (hereinafter referred to as PP-2) having a product number of K9927 was 27g/10 min.
Softening agent: the environment-friendly paraffin oil (hereinafter referred to as softener-1) is purchased from Yongzhen industrial oil products Co., Ltd, the product number is KP6030, and the flash point is 280 ℃; paraffin-based base oil (hereinafter referred to as softener-2) was purchased from Yongzhen Industrial oil Co., Ltd, No. of Sn, product No. 400N, flash point 189 ℃.
Antioxidant: antioxidant 1010 (hereinafter referred to as antioxidant-1) was purchased from basf corporation; antioxidant 168 (hereinafter referred to as antioxidant-2) was purchased from basf corporation.
Active agent(s): stannous chloride (hereinafter referred to as active agent-1) was purchased from alatin corporation; accelerator CZ (hereinafter referred to as activator-2) was purchased from Nanjing Xinyue chemical company.
The twin screw extruder was purchased from cobilong (Nanjing) machinery, Inc. with an instrument model STS35 and parameters set as: phi is 35mm, L/D is 56.
The internal mixer is available from Kunshan Jidlong machinery Co., Ltd, and has an instrument model of M10L and a volume of 10L.
The single-screw granulator is purchased from Kunshan Jiulong mechanical Co., Ltd, has an instrument model of JZD80, and has a yield of 40-60 Kg/h.
Unless otherwise specified, the following represents 10g 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: 200rpm), and then extruding and granulating in a single-screw granulator (temperature: 70 ℃) to prepare co-vulcanizing agent master batch; and
carrying out rubber-plastic blending (rotation speed: 200rpm, temperature: 180 ℃, time: 2min) on PP-1(25 parts by weight), antioxidant 1010(0.3 part by weight), environment-friendly paraffin oil (30 parts by weight) and EPDM-1(43 parts by weight) to obtain rubber-plastic master batch;
(2) uniformly mixing the rubber-plastic master batch, stannous chloride (0.5 weight part), tert-octyl phenol formaldehyde resin (0.5 weight part) and auxiliary vulcanizing agent master batch, adding the mixture from a main feeding port at the first section of a double-screw extruder, adding BIBP (1 weight part) from a side of a feeding port at the fourth section of the double-screw extruder, carrying out dynamic vulcanization (the rotating speed is 400rpm, the temperature is 180 ℃, and the time is 4min), and obtaining vulcanized rubber after the vulcanization is finished.
The remaining examples and comparative examples
The remaining examples were carried out by the same procedure as in example 1 except that the differences are shown in tables 1,2, 3 and 4, unless otherwise specified.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
| Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| EPDM | ||||
| Species of | EPDM-1 | EPDM-1 | EPDM-1 | EPDM-1 |
| Amount per part by weight | 55 | 55 | 55 | 55 |
| PP | ||||
| Species of | PP-1 | PP-1 | PP-1 | PP-1 |
| Amount per part by weight | 25 | 25 | 25 | 25 |
| Softening agent | ||||
| Species of | Softener-1 | Softener-1 | Softener-1 | Softener-1 |
| Amount per part by weight | 20 | 20 | 20 | 20 |
| Principal vulcanizing agent A | ||||
| Species of | Primary vulcanizing agent A-1 | Primary vulcanizing agent A-1 | - | - |
| Amount per part by weight | 0.8 | 0.8 | - | - |
| Principal vulcanizing agent B | ||||
| Species of | Principal vulcanizing agent B-1 | - | Principal vulcanizing agent B-1 | Principal vulcanizing agent B-1 |
| Amount per part by weight | 0.2 | - | 0.2 | 0.2 |
| Auxiliary vulcanizing agent | ||||
| Species of | Co-vulcanizing agent-1 | - | Co-vulcanizing agent-1 | Co-vulcanizing agent-1 |
| Dosage ofPer part by weight | 0.7 | - | 0.7 | 0.7 |
| Antioxidant agent | ||||
| Species of | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 | Antioxidant-1 |
| Amount per part by weight | 0.3 | 0.3 | 0.3 | 0.3 |
| Active agent | ||||
| Species of | Active agent-1 | Active agent-1 | - | Active agent-1 |
| Amount per part by weight | 0.5 | 0.5 | - | 0.5 |
| First mulling | ||||
| Time/min | 5 | 5 | 5 | 5 |
| Temperature/. degree.C | 110 | Same as example 4 | Same as example 4 | Same as example 4 |
| Speed of rotation/rpm | 300 | Same as example 4 | Same as example 4 | Same as example 4 |
| Granulation temperature/. degree.C | 80 | Same as example 4 | Same as example 4 | Same as example 4 |
| Second mulling | ||||
| Time/min | 1 | Same as example 4 | Same as example 4 | Same as example 4 |
| Temperature/. degree.C | 200 | Same as example 4 | Same as example 4 | Same as example 4 |
| Speed of rotation/rpm | 350 | Same as example 4 | Same as example 4 | Same as example 4 |
| Dynamic vulcanization | ||||
| Time/min | 2.5 | 2.5 | 2.5 | 2.5 |
| Temperature/. degree.C | 190 | 190 | 190 | 190 |
| Speed of rotation/rpm | 300 | 300 | 300 | 300 |
Test example
The mechanical properties of the products obtained in all the examples were tested separately and are shown in Table 5. Wherein the tensile strength is tested according to the method in ASTM D412, wherein the tensile rate is set at 500 mm/min; compression set was tested according to ASTM D395B, with test conditions of 70 ℃ X22 h, limiter height 9.4 mm; the elongation at break was tested according to the method in GB/T528-2009; shore A hardness is tested according to the method in GB/T531.1-2008.
TABLE 5
It can be seen from tables 1,2, 4 and 5 that the vulcanized composition of the present invention is not used in comparative examples 1 to 3, but used in examples 1 to 7, and the data of comparative examples 3 to 7 and comparative examples 1 to 3 show that the elongation at break and tensile strength of the vulcanized rubber material are both significantly improved and the compression set is significantly reduced after the vulcanized composition of the present invention is used, which indicates that the main vulcanizing agent a, the main vulcanizing agent B and the co-vulcanizing agent in the protection range of the present invention can be mutually matched by a specific dosage ratio relationship, thereby effectively improving the elongation at break 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 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.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (14)
1. A vulcanized composition comprising a main vulcanizing agent A, a main vulcanizing agent B and a co-vulcanizing agent, wherein the main vulcanizing agent A, the main vulcanizing agent B and the co-vulcanizing agent are stored in admixture or independently of each other, and the content of the main vulcanizing agent B is 0.1 to 2 parts by weight and the content of the co-vulcanizing agent is 0.5 to 4 parts by weight, respectively, based on 1 part by weight of the main vulcanizing agent A;
wherein the main vulcanizing agent A is at least one selected from tert-butyl phenol formaldehyde resin, tert-octyl phenol formaldehyde resin and epoxy resin;
the main vulcanizing agent B is at least one selected from dicumyl peroxide, di-tert-butyl cumyl peroxide and 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane;
the co-vulcanizing agent is a hydrogen ion transfer crosslinking promoter and/or a free radical transfer crosslinking promoter.
2. The vulcanization composition of claim 1, wherein the primary vulcanizing agent B is contained in an amount of 0.25 to 0.65 parts by weight and the co-vulcanizing agent is contained in an amount of 0.9 to 1.65 parts by weight with respect to 1 part by weight of the primary vulcanizing agent a.
3. The vulcanization composition of claim 1 or 2, wherein the hydrogen ion transfer cross-linking promoter is an octene polymer rubber reactant and/or divinylbenzene;
the free radical transfer crosslinking promoter is at least one selected from the group consisting of 1,3, 5-triallyl cyanurate, triallyl isocyanurate and triallyl trimellitate.
4. The vulcanization composition of any one of claims 1-3, wherein the primary curative A is a t-octyl phenol-formaldehyde resin;
the main vulcanizing agent B is di-tert-butyl cumene peroxide;
the auxiliary vulcanizing agent is triallyl isocyanurate.
5. An EPDM-based vulcanized rubber composition comprising at least two of ethylene-propylene-diene monomer, polypropylene, a softener, an antioxidant, an activator, and the respective components of the vulcanized composition according to any one of claims 1 to 4, which are stored in admixture or independently of each other.
6. The EPDM-based vulcanized rubber composition according to claim 5, wherein the vulcanized composition is contained in an amount of 1.6 to 3.5 wt.%, the antioxidant is contained in an amount of 0.2 to 0.4 wt.%, and the active agent is contained in an amount of 0.4 to 0.6 wt.%, based on the total weight of the ethylene-propylene-diene rubber, the polypropylene and the softener.
7. The EPDM-based vulcanized rubber composition according to any one of claims 5 to 6, wherein the ethylene-propylene-diene rubber has an ethylene structural unit content of 50 to 70 wt% and a third monomer content of 4 to 6 wt%;
preferably, the weight average molecular weight of the ethylene propylene diene monomer is 10-40 ten thousand, and the third monomer is at least one of 1, 4-hexadiene, dicyclopentadiene and 5-ethylidene-2-norbornene;
preferably, the polypropylene is homo-polypropylene and/or random co-polypropylene, and the melt index of the polypropylene is 1-20g/10 min;
preferably, the comonomer of the random copolymer polypropylene is ethylene;
preferably, the softening agent is selected from at least one of paraffin oil, naphthenic oil and aromatic oil;
preferably, the antioxidant is selected from at least one of amine antioxidants, quinoline antioxidants and benzimidazole antioxidants;
preferably, the active agent is selected from at least one of stannous chloride, 2-mercaptobenzothiazole, 2' -dithiodibenzothiazole and N-cyclohexyl-2-benzothiazolesulfenamide.
8. The EPDM vulcanized rubber composition as set forth in any one of claims 5 to 7, wherein the ethylene-propylene-diene monomer rubber is contained in an amount of 1.8 to 2.4 parts by weight and the softener is contained in an amount of 0.6 to 1.2 parts by weight, relative to 1 part by weight of the polypropylene.
9. A method of preparing a vulcanizate, the method comprising:
(1) carrying out first mixing on an auxiliary vulcanizing agent and a part of ethylene propylene diene monomer to obtain auxiliary vulcanizing agent master batches; and
carrying out rubber-plastic blending on polypropylene, an antioxidant, a softener and the rest part of the ethylene propylene diene monomer rubber to obtain rubber-plastic master batches;
(2) dynamically vulcanizing the rubber-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 primary curative A, the primary curative B and the co-curative correspond in definition to the corresponding definitions in the vulcanized composition of any one of claims 1 to 4;
preferably, the vulcanized composition, the ethylene propylene diene monomer, the polypropylene, the softener, the active agent, and the antioxidant correspond to the same respective definitions as in the EPDM based vulcanized rubber composition as set forth in any one of claims 5 to 8.
10. The method of claim 9, wherein the operation of step (2) comprises: and after the rubber master batch, the main vulcanizing agent A and the active agent are uniformly mixed, the mixture and the auxiliary vulcanizing agent master batch are dynamically vulcanized.
11. A process according to claim 9 or 10, wherein the ethylene propylene diene monomer rubber involved in the first mixing and the remaining part of the ethylene propylene diene monomer rubber involved in the second mixing are used in a weight ratio of 1: 20-120;
preferably, the weight ratio of the ethylene propylene diene monomer involved in the first mixing to the ethylene propylene diene monomer involved in the second mixing is 1: 40-80.
12. The method according to any one of claims 9 to 11, wherein in step (1), the conditions of the first mixing are at least satisfied: the temperature is 70-110 deg.C, and the time is 3-6 min;
preferably, in step (1), the conditions of the second mixing are at least satisfied: the temperature is 160-;
preferably, in step (2), the conditions of dynamic vulcanization at least satisfy: the temperature is 180 ℃ and 200 ℃, and the time is 1-4 min.
13. A vulcanized rubber produced by the method of any one of claims 9 to 12.
14. Use of the vulcanizate of claim 13 in automobiles, appliances, wires, cables, or buildings.
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| US4808665A (en) * | 1987-10-13 | 1989-02-28 | Monsanto Company | Crosslinked blends |
| JPH0841250A (en) * | 1994-07-28 | 1996-02-13 | Mitsui Toatsu Chem Inc | Thermoplastic elastomer composition having excellent heat resistance and oil resistance, production thereof and laminated material using the composition |
| CN105555858A (en) * | 2013-09-19 | 2016-05-04 | 朗盛艾拉托麦罗斯有限公司 | Molding resin composition including chlorinated vinyl chloride-based resin, and molded article thereof |
| CN110698771A (en) * | 2019-09-27 | 2020-01-17 | 张家港市美特高分子材料有限公司 | TPV micro-foaming material and production process thereof |
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| US4808665A (en) * | 1987-10-13 | 1989-02-28 | Monsanto Company | Crosslinked blends |
| JPH0841250A (en) * | 1994-07-28 | 1996-02-13 | Mitsui Toatsu Chem Inc | Thermoplastic elastomer composition having excellent heat resistance and oil resistance, production thereof and laminated material using the composition |
| CN105555858A (en) * | 2013-09-19 | 2016-05-04 | 朗盛艾拉托麦罗斯有限公司 | Molding resin composition including chlorinated vinyl chloride-based resin, and molded article thereof |
| CN110698771A (en) * | 2019-09-27 | 2020-01-17 | 张家港市美特高分子材料有限公司 | TPV micro-foaming material and production process thereof |
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