CN115785575B - High-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber and preparation method thereof - Google Patents
High-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 50
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 4
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- -1 ethylene, propylene Chemical group 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
- CCNDOQHYOIISTA-UHFFFAOYSA-N 1,2-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1C(C)(C)OOC(C)(C)C CCNDOQHYOIISTA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 description 1
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- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical group C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 description 1
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
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- 239000004636 vulcanized rubber Substances 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend, which takes ethylene propylene diene monomer and silicone rubber as base materials and sulfydryl MTQ silicone resin as a compatibilizer; the structural general formula of the sulfhydryl MTQ silicone resin is as follows: (Me) 3 SiO 1/2 ) x (SHCH 2 CH 2 SiO 3/2 ) y (SiO 4/2 ) z (I); wherein x=0.1 to 1, y=0.2 to 0.8, and z=0.1 to 1; the preparation method of the ethylene propylene diene monomer/silicone rubber blend comprises the steps of firstly mixing ethylene propylene diene monomer, a vulcanizing agent and mercapto MTQ silicone resin serving as a compatibilizer, and then blending the mixture with silicone rubber blend after initiating a mercapto double bond click chemical reaction; finally, the ethylene propylene diene monomer/silicone rubber blend is obtained through vulcanization treatment. The ethylene propylene diene monomer/silicone rubber blend disclosed by the invention has excellent mechanical properties and ageing resistance.
Description
Technical Field
The invention relates to the technical field of rubber blending, in particular to high-strength aging-resistant ethylene propylene diene monomer rubber/silicone rubber blending rubber and a preparation method thereof.
Background
Ethylene propylene diene monomer is prepared by copolymerizing ethylene, propylene and a small amount of a third monomer, has good electrical insulation property, impact elasticity and the like, and is widely applied to the fields of wires and cables, automobile elements, high-temperature conveying belts and the like. Compared with ethylene propylene diene monomer rubber, the silicone rubber has better high-temperature performance and weather resistance. Meanwhile, the silicone rubber has better flexibility, low-temperature performance and good physiological inertia. Therefore, the silicone rubber is widely applied to the fields of aerospace, electric power, medical appliances and the like. But the application range is limited due to the poor mechanical properties. The ethylene propylene diene monomer rubber and the silicone rubber are blended, so that the heat resistance and ageing resistance of the system can be improved, and the defect of poor mechanical property of the silicone rubber can be overcome. However, the difference of the two rubber main chain structures leads to large viscosity difference and poor compatibility. Therefore, improving the compatibility of the two rubbers is critical to obtaining a blend with excellent properties.
The Chinese patent document with the application publication number of CN 109867789A discloses a compatilizer for improving the blending compatibility of ethylene propylene diene monomer rubber and silicone rubber, which comprises 100 parts of liquid ethylene propylene diene monomer rubber, 30-50 parts of hydrogen-containing silicone oil and 0.5-1 part of catalyst. Firstly, dissolving liquid ethylene propylene diene monomer, then adding hydrogen-containing silicone oil and a catalyst, and grafting the hydrogen-containing silicone oil on the liquid ethylene propylene diene monomer through hydrosilylation reaction to prepare the compatilizer. However, according to the performance comparison data of the examples and the comparative examples given in table 1, the compatibilization effect of the method is not obvious, the mechanical property of the blend is not obviously improved, and the tensile strength is only improved by less than 1MPa at most.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber which has excellent mechanical properties and aging resistance.
The specific technical scheme is as follows:
a high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend is prepared from ethylene propylene diene monomer and silicone rubber as base materials and mercapto MTQ silicone resin as a compatibilizer;
the structural general formula of the sulfhydryl MTQ silicone resin is shown as the following formula (I):
(Me 3 SiO 1/2 ) x (SHCH 2 CH 2 SiO 3/2 ) y (SiO 4/2 ) z (Ⅰ)；
wherein x=0.1 to 1, y=0.2 to 0.8, and z=0.1 to 1.
The invention discloses an ethylene propylene diene monomer/silicone rubber blend, which takes sulfhydryl MTQ silicone resin as a compatibilizer, and can obviously improve the compatibility of the ethylene propylene diene monomer and the silicone rubber, thereby obtaining the blend with excellent mechanical properties.
Preferably, x=1, y=0.2 to 0.6, and z=0.8 to 1, calculated as molar ratios.
Experiments show that the number of mercapto groups in a single MTQ molecule in the mercapto MTQ silicone resin has a remarkable influence on the compatibilization effect of ethylene propylene diene monomer rubber and silicone rubber.
The calculation formula of the number of sulfhydryl groups in a single MTQ molecule is as follows:
wherein M is n Is the number average molecular weight of the mercapto MTQ silicone resin.
Preferably, the number of mercapto groups in a single MTQ molecule in the mercapto MTQ silicone resin is 1.5-2.5; further preferably 2.1.
The compatibilizer is prepared by adopting a conventional preparation process in the field, and is prepared by hydrolyzing hexamethyldisiloxane, gamma-mercaptopropyl triethoxysilane and tetraethyl orthosilicate in a hydrochloric acid-ethanol-water system. The quantity of mercapto groups in a single MTQ molecule in the prepared compatibilizer can be regulated and controlled by regulating and controlling the dosage ratio of hexamethyldisiloxane, gamma-mercaptopropyl triethoxysilane and tetraethyl orthosilicate.
The invention discloses a high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend, which comprises the following raw materials in parts by weight:
the mass of the ethylene propylene diene monomer is 100 percent, and the addition amount of the compatibilizer is 2 to 8 percent.
The silicone rubber is selected from methyl vinyl silicone rubber and phenyl silicone rubber;
experiments show that the compatibilizer disclosed by the invention has excellent compatibilizer effect on ethylene propylene diene monomer rubber/silicone rubber systems, and has little weight ratio relationship with the ethylene propylene diene monomer rubber/silicone rubber systems. For example, the weight ratio of the ethylene propylene diene monomer to the silicone rubber can be selected from 10:90, 20:80, 30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 90:10 and the like based on 100 parts of the total weight of the ethylene propylene diene monomer and the silicone rubber.
In the invention, the dosage of the compatibilizer has obvious influence on the mechanical property and ageing resistance of the finally prepared blend adhesive. The compatibilizer is added based on the weight part of ethylene propylene diene monomer, preferably, the mass of the ethylene propylene diene monomer is 100 percent, and the addition amount of the compatibilizer is 4-8 percent; experiments show that when the addition amount of the compatibilizer is preferably 4-8%, the mechanical properties of the prepared blend are better.
Further preferably, the addition amount of the compatibilizer is 6-8%, and experiments show that the prepared blend has more excellent ageing resistance.
Preferably, the addition amount of the compatibilizer is 6%, and the mechanical property and the ageing resistance of the prepared blend are optimal.
In the present invention, the vulcanizing agent is selected from the conventional types in the art, such as organic peroxides, specifically selected from di-t-butyl peroxide, dicumyl peroxide, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane, di (t-butylperoxyisopropyl) benzene, and the like.
Preferably, the blending adhesive disclosed in the invention can be added with common auxiliary agents in the field, such as reinforcing agents, vulcanization auxiliary agents, structure control agents and the like according to actual application conditions.
The reinforcing agent is selected from the common types in the field, such as white carbon black, montmorillonite, kaolin, calcium carbonate and the like;
the vulcanization aid is selected from zinc oxide, magnesium oxide, stearic acid and the like;
the structure control agent is selected from hydroxyl silicone oil, diphenyl silicon glycol, hexamethyldisilazane, cyclic trisilane and the like;
preferably, the high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend comprises the following raw materials in parts by weight:
the invention also discloses a preparation method of the high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber, which comprises the following steps:
(1) Preparation of ethylene-propylene-diene monomer rubber compound
Uniformly mixing ethylene propylene diene monomer, compatibilizer and vulcanizing agent, heating to 140-160 ℃ and continuously mixing for a period of time to obtain ethylene propylene diene monomer;
(2) Preparation of a Silicone rubber Compound
Mixing silicone rubber, a reinforcing agent which can be selectively added and a structure control agent which can be selectively added to obtain silicone rubber compound;
(3) Preparation of ethylene propylene diene monomer/silicone rubber blend
And uniformly mixing the ethylene propylene diene monomer rubber compound, the silicone rubber compound, the optional reinforcing agent, the optional vulcanization auxiliary agent and the optional vulcanizing agent to obtain an ethylene propylene diene monomer rubber/silicone rubber compound, and finally, vulcanizing and forming to obtain the ethylene propylene diene monomer rubber/silicone rubber blend.
The ethylene propylene rubber/silicone rubber compound prepared by the invention can be mixed by a rolling method, and the plastic is cut into particles after being sheet-shaped, or can be plasticated by a base, and the particles are cut into particles after being extruded out of strips.
The invention discloses a compatibilization method of ethylene propylene diene monomer/silicone rubber blend with easily available raw materials and good compatibilization effect, wherein the addition time of a compatibilizer is also critical, and experiments show that the mercapto MTQ silicone resin needs to be uniformly mixed with ethylene propylene diene monomer and a vulcanizing agent to cause a mercapto double bond click chemical reaction and then is blended with silicone rubber blend. The method can effectively enhance the interfacial compatibility of the ethylene propylene diene monomer rubber and the silicone rubber, has good compatibilization effect, and can lead to the reduction of the mechanical property of the prepared blend rubber if the ethylene propylene diene monomer rubber, the silicone rubber and the compatibilizer are mixed at one time or the silicone rubber and the compatibilizer are mixed first and then the ethylene propylene diene monomer rubber is added for mixing.
In the preparation process, the addition amount of each raw material is added according to the weight parts of the raw materials, wherein the vulcanizing agent is added twice, when the ethylene-propylene-diene monomer mixture is prepared, about 4-14% of the total weight of the vulcanizing agent is added, and when the blend is prepared, the rest vulcanizing agent is added; the reinforcing agent is added in two times, 40-60% of the total weight is added when preparing the silicone rubber compound, and the rest reinforcing agent is added when preparing the blend.
Preferably, in the step (1), the temperature is raised to 140-160 ℃ and the mixing is continued for 3-9 min; more preferably, the temperature is raised to 145 to 155℃and kneading is continued for 6 minutes. Experiments show that the process parameters have obvious influence on the mechanical properties of the finally prepared blend, and the blend prepared in the further preferable range has better mechanical properties. More preferably, the temperature is raised to 150℃and kneading is continued for 6 minutes.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses an ethylene propylene diene monomer/silicone rubber blend rubber, which takes special sulfydryl MTQ silicone resin as a compatibilizer, and the compatibilizer has excellent compatibilizer effect on an ethylene propylene diene monomer/silicone rubber system and is little influenced by the weight ratio of the ethylene propylene diene monomer/silicone rubber system; experiments show that the compatibilization effect of the compatibilizer is mainly influenced by three aspects, namely the number of mercapto groups in a single MTQ molecule in the compatibilizer, the addition amount of the compatibilizer, the addition time of the compatibilizer and the mixing condition of the compatibilizer and ethylene propylene diene monomer, and the blend rubber with excellent mechanical property and ageing resistance can be prepared under the condition that all three are suitable.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of mercaptoMTQ silicone resin prepared in example 1: (a) A nuclear magnetic resonance hydrogen spectrogram, (b) a nuclear magnetic resonance silicon spectrogram;
FIG. 2 is a stress-strain graph of the ethylene propylene diene monomer/silicone rubber blends prepared in example 5 and comparative example 1, respectively;
FIG. 3 is a TEM image of the ethylene propylene diene monomer/silicone rubber blends prepared in example 5 and comparative example 1, respectively;
FIG. 4 is a graph showing the tensile strength of the ethylene propylene diene monomer/silicone rubber blends prepared in examples 2, 4 to 6 and comparative example 1, respectively, before and after aging;
FIG. 5 is a graph showing elongation at break before and after aging of the ethylene propylene diene monomer/silicone rubber blends prepared in examples 2, 4 to 6 and comparative example 1, respectively.
Detailed Description
The present invention will be further described in detail with reference to specific examples, for the purpose of further illustrating the objects, technical solutions and advantages of the present invention, but the scope of the present invention is not limited thereto.
The ethylene propylene diene monomer rubber and the silicone rubber adopted in the invention are all sold in the market:
ethylene propylene diene monomer (4725 p): vinyl content 70wt%, third monomer content 4.9wt%;
vinyl silicone rubber (110-3): vinyl content 0.22mol%.
Example 1
(1) Preparation of mercapto MTQ silicone resin
To a three-necked flask equipped with a condenser and magnetic stirring, 5.0g of deionized water, 5.0g of absolute ethanol, 2.8g of concentrated hydrochloric acid (36 wt%) and 13.7g of hexamethyldisiloxane were added, and after reacting at 70℃for 30 minutes, a mixed solution of 14.4g of tetraethyl orthosilicate and 23.84g of gamma-mercaptopropyl triethoxysilane was added at a rate of 1 mL/min. Cooling to room temperature after the reaction is continued for 2 hours, adding toluene for extraction, washing saturated sodium bicarbonate solution and deionized water to be neutral, and distilling under reduced pressure to remove toluene to obtain the sulfhydryl MTQ silicon resin, wherein x=1, y=0.47, z=0.64 and M n =900. The number of thiol groups in a single MTQ molecule was 2.2.
(2) Preparation of ethylene-propylene-diene monomer rubber compound
Firstly, 70 parts of ethylene propylene diene monomer and 1.4 parts of mercapto MTQ silicone resin are added into a Hash torque rheometer, mixed for 10min at 80 ℃ and the rotating speed is 50rpm, then 0.14 part of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane is added, after mixing uniformly, the temperature is raised to 150 ℃ and mixing is continued for 3min, and then the ethylene propylene diene monomer is discharged, thus obtaining the ethylene propylene diene monomer.
(3) Preparation of a Silicone rubber Compound
Firstly, adding 30 parts of silicone rubber into a Hash torque rheometer, then adding 15 parts of fumed silica, mixing for 10min at 100 ℃ and rotating at 100rpm, then adding 5 parts of hydroxyl silicone oil, continuing mixing for 5min, and discharging to obtain silicone rubber compound.
(4) Preparation of ethylene propylene diene monomer rubber/silicone rubber compound
Adding all the ethylene propylene diene monomer rubber compound prepared in the step (2) and all the silicone rubber compound prepared in the step (3) into a Hark torque rheometer, mixing for 5min at 80 ℃, adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, adding 1.2 parts of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicone rubber compound.
(5) Preparation of the Mixed glue
And (3) vulcanizing and forming the ethylene propylene diene monomer rubber/silicone rubber compound which is parked for one day at room temperature on a flat vulcanizing machine at 180 ℃ to finally obtain a blended rubber sample.
Example 2
The preparation process is basically the same as that of example 1, except that 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane is added in the step (2), and after uniform mixing, the temperature is raised to 150 ℃ and the mixing is continued for 6min for discharging, so as to obtain the ethylene-propylene-diene monomer mixture.
Example 3
The preparation process is basically the same as that of example 1, except that 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane is added in the step (2), and after uniform mixing, the temperature is raised to 150 ℃ and the mixing is continued for 9min for discharging, so as to obtain the ethylene-propylene-diene monomer mixture.
Example 4
The preparation process was substantially the same as in example 1, except that 2.8 parts of mercaptoMTQ silicone resin was added in step (2).
Example 5
The preparation process was substantially the same as in example 1, except that 4.2 parts of mercaptomtq silicone resin was added in step (2).
Example 6
The preparation process was substantially the same as in example 1, except that 5.6 parts of mercaptoMTQ silicone resin was added in step (2).
Example 7
The preparation process is basically the same as that of example 5, except that 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane is added in the step (2), and after uniform mixing, the temperature is raised to 140 ℃ and the mixture is continuously mixed for 6 minutes for discharging, so as to obtain the ethylene-propylene-diene monomer mixture.
Example 8
The preparation process is basically the same as that of example 5, except that 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane is added in the step (2), and after uniform mixing, the temperature is raised to 160 ℃ and the mixing is continued for 6min for discharging, so as to obtain the ethylene-propylene-diene monomer mixture.
Example 9
(1) Preparation of mercapto MTQ silicone resin was the same as in example 1;
(2) Preparation of a Silicone rubber Compound
Firstly, adding 30 parts of silicon rubber into a Hash torque rheometer, then adding 15 parts of fumed silica, mixing for 10min at 100 ℃ and rotating at 100rpm, then adding hydroxyl silicone oil, continuing mixing for 5min, and discharging to obtain the silicon rubber compound.
(3) Preparation of ethylene propylene diene monomer rubber/silicone rubber compound
Adding 70 parts of ethylene propylene diene monomer rubber and all the silicone rubber compound prepared in the step (2) into a Hark torque rheometer, mixing for 5min at 80 ℃ and 50rpm, adding 4.2 parts of sulfhydryl MTQ silicone resin, 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, and finally adding 1.2 parts of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicone rubber compound.
(4) Preparation of the Mixed glue
And (3) vulcanizing and forming the ethylene propylene diene monomer rubber/silicone rubber compound which is parked for one day at room temperature on a flat vulcanizing machine at 180 ℃ to finally obtain a blended rubber sample.
Example 10
(1) Preparation of mercapto MTQ silicone resin was the same as in example 1;
(2) Preparation of a Silicone rubber Compound
Firstly, 30 parts of silicone rubber is added into a Hash torque rheometer, then 15 parts of fumed silica is added, mixing is carried out at 100 ℃ for 10min, the rotating speed is 100rpm, then 1.8 parts of sulfhydryl MTQ silicone resin and hydroxyl silicone oil are added, mixing is continued for 5min, then 0.06 part of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane is added, mixing is carried out at 150 ℃ for 6min, and then the silicone rubber compound is obtained.
(3) Preparation of ethylene propylene diene monomer rubber/silicone rubber compound
And (3) adding 70 parts of ethylene propylene diene monomer rubber compound and all the silicone rubber compound prepared in the step (2) into a Hark torque rheometer, mixing for 5min at 80 ℃ and 50rpm, adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, and finally adding 1.2 parts of 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane, mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicone rubber compound.
(4) Preparation of the Mixed glue
And (3) vulcanizing and forming the ethylene propylene diene monomer rubber/silicone rubber compound which is parked for one day at room temperature on a flat vulcanizing machine at 180 ℃ to finally obtain a blended rubber sample.
Example 11
(1) Preparation of mercapto MTQ silicone resin
To a three-necked flask equipped with a condenser and magnetic stirring, 5.0g of deionized water, 5.0g of absolute ethanol, 2.8g of concentrated hydrochloric acid (36 wt%) and 8.7g of hexamethyldisiloxane were added, and after reacting at 70℃for 30 minutes, a mixed solution of 14.4g of tetraethyl orthosilicate and 15.4g of gamma-mercaptopropyl triethoxysilane was added at a rate of 1 mL/min. Cooling to room temperature after the reaction is continued for 2 hours, adding toluene for extraction, washing saturated sodium bicarbonate solution and deionized water to be neutral, and distilling under reduced pressure to remove toluene to obtain the sulfhydryl MTQ silicon resin, wherein x=1, y=0.52, z=0.92 and M n =1040. The number of thiol groups in a single MTQ molecule was 2.5.
Steps (2) to (4) are exactly the same as in example 5.
Example 12
(1) Preparation of mercapto MTQ silicone resin
Into a three-necked flask equipped with a condenser and magnetic stirring, 5.0g of deionized water, 5.0g of absolute ethanol, 2.8g of concentrated hydrochloric acid (36 wt%) and 6.1g of hexamethyldisiloxane were charged, and after reaction at 70℃for 30 minutes, 14.4g of tetraethyl orthosilicate and 6.0g of gamma-mercaptopropyl triethoxyThe silane mixed solution was added to the three-necked flask at a rate of 1 mL/min. Cooling to room temperature after the reaction is continued for 2 hours, adding toluene for extraction, washing saturated sodium bicarbonate solution and deionized water to be neutral, and distilling under reduced pressure to remove toluene to obtain the sulfhydryl MTQ silicon resin, wherein x=1, y=0.27, z=0.89 and M n =1050. The number of thiol groups in a single MTQ molecule was 1.6.
Steps (2) to (4) are exactly the same as in example 5.
Comparative example 1
(1) Preparation of ethylene-propylene-diene monomer rubber compound
Firstly, 70 parts of ethylene propylene diene monomer is added into a Hark torque rheometer, the rotating speed is 50rpm, then 0.14 part of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane is added, after uniform mixing, the temperature is raised to 150 ℃ and mixing is continued for 3 minutes, and then the ethylene propylene diene monomer is discharged, thus obtaining ethylene propylene diene monomer.
(2) Preparation of a Silicone rubber Compound
Firstly, adding 30 parts of silicone rubber into a Hash torque rheometer, then adding 15 parts of fumed silica, mixing for 10min at 100 ℃ and rotating at 100rpm, then adding 5 parts of hydroxyl silicone oil, continuing mixing for 5min, and discharging to obtain silicone rubber compound.
(3) Preparation of ethylene propylene diene monomer rubber/silicone rubber compound
Adding all the ethylene propylene diene monomer rubber compound prepared in the step (1) and all the silicone rubber compound prepared in the step (2) into a Hark torque rheometer, mixing for 5min at 80 ℃, adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, adding 1.2 parts of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicone rubber compound.
(4) Preparation of the Mixed glue
And (3) vulcanizing and forming the ethylene propylene diene monomer rubber/silicone rubber compound which is parked for one day at room temperature on a flat vulcanizing machine at 180 ℃ to finally obtain a blended rubber sample.
Comparative example 2
(1) Preparation of ethylene-propylene-diene monomer rubber compound
Firstly, 70 parts of ethylene propylene diene monomer and 1.2 parts of trimethylolpropane tri (3-mercaptopropionic acid) ester (the number converted into mercapto groups is equal to that of the mercapto groups in the example 5, the structural formula is shown below) are added into a Hark torque rheometer, the mixing is carried out for 10 minutes at 80 ℃, the rotating speed is 50rpm, then 0.14 part of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane is added, the mixing is carried out uniformly, the temperature is raised to 150 ℃, the mixing is continued for 3 minutes, and then the ethylene propylene diene monomer is obtained.
(2) Preparation of a Silicone rubber Compound
Firstly, adding 30 parts of silicone rubber into a Hash torque rheometer, then adding 15 parts of fumed silica, mixing for 10min at 100 ℃ and rotating at 100rpm, then adding 5 parts of hydroxyl silicone oil, continuing mixing for 5min, and discharging to obtain silicone rubber compound.
(3) Preparation of ethylene propylene diene monomer rubber/silicone rubber compound
Adding all the ethylene propylene diene monomer rubber compound prepared in the step (1) and all the silicone rubber compound prepared in the step (2) into a Hark torque rheometer, mixing for 5min at 80 ℃, adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, adding 1.2 parts of 2, 5-dimethyl-2, 5-di (tert-butyl peroxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicone rubber compound.
(4) Preparation of the Mixed glue
And (3) vulcanizing and forming the ethylene propylene diene monomer rubber/silicone rubber compound which is parked for one day at room temperature on a flat vulcanizing machine at 180 ℃ to finally obtain a blended rubber sample.
Ethylene propylene diene monomer/silicone rubber blends prepared in each example and comparative example were tensile tested at a tensile rate of 50mm/min using a Zwick/Roell Z020 universal tester, and the results are summarized in table 1:
TABLE 1
In the table 1, the comparative example 1 is a combined rubber prepared by directly blending ethylene propylene diene monomer 4725P and silicone rubber, no compatilizer is added, the mechanical strength is poor, the tensile strength and the elongation at break are only 9.1MPa and 424%, and the mercapto MTQ silicone resin is added as the compatilizer in the examples 1-6, so that the tensile strength and the elongation at break are both greatly improved. As can be seen from comparative examples 1 to 3, when 1.4 parts of mercapto MTQ silicone resin is added in the step (2), the ethylene propylene diene monomer/silicone rubber blend finally obtained by blending at 150 ℃ for 6min has the best mechanical properties, and the analysis reasons are probably that 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane can cause ethylene propylene diene monomer crosslinking during banburying at 150 ℃ and the excessive banburying time can cause excessive ethylene propylene diene monomer crosslinking to be difficult to mix uniformly with silicone rubber. Comparative examples 5, 7 and 8 show that the ethylene propylene diene monomer/silicone rubber blend obtained by blending at 150 ℃ has the best mechanical properties when the click chemistry reaction is carried out for 6min in the step (2). As can be seen from comparative examples 1 and 4 to 6, the mechanical properties of the ethylene propylene diene monomer/silicone rubber blends prepared by adding 4.2 parts of mercapto MTQ silicone resin during the blending process are best, the tensile strength and elongation at break are 18.2MPa and 705%, respectively, and the tensile strength and elongation at break are improved by 100% and 66% respectively compared with comparative example 1 without the addition of the compatilizer. As can be seen from comparative examples 5, 9, 10, the timing of the addition of the mercaptoMTQ silicone resin is important and requires a mercapto-click reaction with the EPDM prior to blending with the silicone rubber. As can be seen from comparative examples 5, 11, 12 and comparative example 2, the proper number of mercapto groups on a single molecule can exert a better compatibility effect.
TEM images of the ethylene propylene diene monomer/silicone rubber blend chips prepared respectively from example 5 and comparative example 1 also showed that in example 5 after addition of the mercapto MTQ silicone resin, the phase separation size between the ethylene propylene diene monomer and the silicone rubber became significantly smaller, indicating an increase in the compatibility of the ethylene propylene diene monomer and the silicone rubber.
To further evaluate the aging properties, the vulcanized rubber samples prepared in examples 2, 4 to 6 and comparative example 1 were put into a forced air oven for aging at 150℃for 2 days and 3 days, respectively, and the mechanical properties of the aged samples were tested as described above, and the results are summarized in Table 2. To more intuitively express the above changes, the tensile strength comparisons before and after aging are shown in fig. 4, and the elongation at break comparisons before and after aging are shown in fig. 5.
TABLE 2
The results in comparative Table 2 show that the tensile strength and elongation at break of the blend after aging with the mercapto MTQ silicone resin are both better than those of comparative example 1, wherein the tensile strength after aging for 3d in example 5 is 17.4MPa, the elongation at break is 561%, and the aging resistance is excellent.
The above examples are intended to aid in understanding the method and key points of the invention. The description is not to be taken as limiting the invention.
Claims (8)
1. The preparation method of the high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber is characterized by comprising the following steps of:
(1) Preparation of ethylene-propylene-diene monomer rubber compound
Uniformly mixing ethylene propylene diene monomer, a compatibilizer and a vulcanizing agent, and then heating to 140-160 ℃ to continuously mix for a period of time to obtain ethylene propylene diene monomer;
the sulfhydryl MTQ silicone resin is used as a compatibilizer, and the structural general formula of the sulfhydryl MTQ silicone resin is shown as the following formula (I):
（Me 3 SiO 1/2 ） x （SHCH 2 CH 2 SiO 3/2 ） y （SiO 4/2 ） z （Ⅰ）；
wherein x, y and z are calculated according to a molar ratio, x=0.1-1, y=0.2-0.8 and z=0.1-1;
the number of mercapto groups in a single MTQ molecule in the mercapto MTQ silicone resin is 1.5-2.5;
(2) Preparation of a Silicone rubber Compound
Mixing silicone rubber, a reinforcing agent which can be selectively added and a structure control agent which can be selectively added to obtain silicone rubber compound;
(3) Preparation of ethylene propylene diene monomer/silicone rubber blend
Uniformly mixing the ethylene propylene diene monomer rubber compound, the silicone rubber compound, the optional reinforcing agent, the optional vulcanization auxiliary agent and the optional vulcanizing agent to obtain an ethylene propylene diene monomer rubber/silicone rubber compound, and finally preparing the ethylene propylene diene monomer rubber/silicone rubber blend through vulcanization molding;
the adhesive comprises the following raw materials in parts by weight:
10-90 parts of ethylene propylene diene monomer rubber;
10-90 parts of silicon rubber;
0.2-7.2 parts of compatibilizer;
0.8-2.0 parts of vulcanizing agent;
the mass of the ethylene propylene diene monomer is 100%, and the addition amount of the compatibilizer is 2-8%.
2. The preparation method of the high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber according to claim 1, wherein x, y and z are calculated according to a molar ratio, x=1, y=0.2-0.6 and z=0.8-1.
3. The method for preparing the high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blend according to claim 1, wherein the number of mercapto groups in a single MTQ molecule in the mercapto MTQ silicone resin is 2.1.
4. The preparation method of the high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber according to claim 1, wherein the addition amount of the compatibilizer is 4-8% based on 100% of the mass of the ethylene propylene diene monomer.
5. The preparation method of the high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber according to claim 1, wherein the addition amount of the compatibilizer is 6-8% based on 100% of the mass of the ethylene propylene diene monomer.
6. The preparation method of the high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber as claimed in claim 1, which is characterized by comprising the following raw materials in parts by weight:
10-90 parts of ethylene propylene diene monomer rubber;
10-90 parts of silicon rubber;
0.2-7.2 parts of compatibilizer;
0.8-2.0 parts of vulcanizing agent;
20-50 parts of a reinforcing agent;
1-5 parts of a vulcanization aid;
1-10 parts of a structure control agent.
7. The preparation method of the high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend rubber is characterized in that in the step (1), the temperature is raised to 140-160 ℃ and the mixing is continued for 3-9 min.
8. The preparation method of the high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blend according to claim 1, which is characterized in that the temperature is raised to 145-155 ℃ and the mixing is continued for 6min.
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