CN115785575A - High-strength anti-aging ethylene propylene diene monomer/silicone rubber blended rubber and preparation method thereof - Google Patents
High-strength anti-aging ethylene propylene diene monomer/silicone rubber blended rubber and preparation method thereof Download PDFInfo
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- CN115785575A CN115785575A CN202211556742.3A CN202211556742A CN115785575A CN 115785575 A CN115785575 A CN 115785575A CN 202211556742 A CN202211556742 A CN 202211556742A CN 115785575 A CN115785575 A CN 115785575A
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- diene monomer
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- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 118
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 84
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- 239000005060 rubber Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 46
- 230000003712 anti-aging effect Effects 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 238000002156 mixing Methods 0.000 claims abstract description 43
- 125000003396 thiol group Chemical class [H]S* 0.000 claims abstract description 35
- 230000032683 aging Effects 0.000 claims abstract description 27
- 229920002050 silicone resin Polymers 0.000 claims abstract description 23
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- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
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- 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
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-UHFFFAOYSA-N 0.000 description 1
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- OLLFKUHHDPMQFR-UHFFFAOYSA-N dihydroxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](O)(O)C1=CC=CC=C1 OLLFKUHHDPMQFR-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
- -1 ethylene, propylene Chemical group 0.000 description 1
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- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention discloses a high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blend, which takes ethylene propylene diene monomer and silicone rubber as base materials and mercapto MTQ silicone resin as a compatibilizer; the general structural formula of the mercapto 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, z =0.1 to 1; the preparation method of the ethylene propylene diene monomer/silicone rubber blended rubber comprises the steps of mixing ethylene propylene diene monomer, a vulcanizing agent and mercapto MTQ silicone resin serving as a compatibilizer, triggering mercapto double bond click chemical reaction, and blending with the silicone rubber blended rubber; finally, the ethylene propylene diene monomer/silicone rubber blended rubber is obtained through vulcanization treatment. Ternary element disclosed by the inventionThe ethylene propylene rubber/silicon rubber blended rubber has excellent mechanical property and aging resistance.
Description
Technical Field
The invention relates to the technical field of rubber blending, in particular to high-strength anti-aging ethylene propylene diene monomer/silicone rubber blended rubber and a preparation method thereof.
Background
The ethylene propylene diene monomer is prepared by copolymerizing ethylene, propylene and a small amount of third monomers, has good electrical insulation, 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, the silicone rubber has better high-temperature performance and weather resistance. Meanwhile, the silicon rubber has better flexibility, low-temperature performance and good physiological inertia. Therefore, the silicon rubber is widely applied to the fields of aerospace, electric power, medical appliances and the like. But the application range is limited due to poor mechanical property. The ethylene propylene diene monomer and the silicone rubber are blended, so that the heat resistance and aging resistance of a system can be improved, and the defect of poor mechanical property of the silicone rubber can be overcome. However, the difference of the main chain structures of the two rubbers causes the two rubbers to have large viscosity difference and poor compatibility. Therefore, the key to obtaining the blended rubber with excellent performance is to improve the compatibility of the two rubbers.
For example, chinese patent publication No. CN 109867789A discloses a compatilizer for improving blending compatibility of ethylene propylene diene monomer and silicone rubber, which comprises 100 parts of liquid ethylene propylene diene monomer, 30-50 parts of hydrogen-containing silicone oil and 0.5-1 part of catalyst. Firstly, dissolving liquid ethylene propylene diene monomer rubber, then adding hydrogen-containing silicone oil and a catalyst, and grafting the hydrogen-containing silicone oil on the liquid ethylene propylene diene monomer rubber through a hydrosilylation reaction to prepare the compatilizer. However, as can be seen from the performance comparison data of the examples and the comparative examples given in table 1, the method has the advantages of insignificant compatibilization effect, insignificant improvement of the mechanical properties of the blended rubber, and only less than 1MPa improvement of the tensile strength.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a high-strength anti-aging ethylene propylene diene monomer/silicone rubber blend rubber which has excellent mechanical property and anti-aging property.
The specific technical scheme is as follows:
a high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blended rubber takes ethylene propylene diene monomer and silicone rubber as base materials and mercapto MTQ silicone resin as a compatibilizer;
the structural general formula of the mercapto 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, z =0.1 to 1.
The invention discloses an ethylene propylene diene monomer/silicone rubber blended rubber, which takes sulfydryl MTQ silicone resin as a compatibilizer, and can remarkably improve the compatibility of ethylene propylene diene monomer and silicone rubber, thereby obtaining the blended rubber with excellent mechanical property.
x, y and z are calculated by molar ratio, preferably, x =1, y =0.2 to 0.6, z =0.8 to 1.
Tests show that the number of sulfydryl in a single MTQ molecule in the sulfydryl MTQ silicon resin has obvious influence on the compatibilization effect of the ethylene propylene diene monomer and the silicon rubber.
The calculation formula of the number of sulfydryl in a single MTQ molecule is as follows:
in the formula, M n The number average molecular weight of the mercapto MTQ silicone resin.
Preferably, the number of sulfydryl in a single MTQ molecule in the sulfydryl MTQ silicon resin is 1.5-2.5; further preferably 2.1.
The preparation of the compatibilizer adopts the conventional preparation process in the field, and is specifically prepared by hydrolyzing hexamethyldisiloxane, gamma-mercaptopropyltriethoxysilane and tetraethyl orthosilicate in a hydrochloric acid-ethanol-water system. The number of sulfydryl in a single MTQ molecule in the prepared compatibilizer can be regulated and controlled by regulating and controlling the dosage ratio of hexamethyldisiloxane to gamma-mercaptopropyltriethoxysilane and tetraethyl orthosilicate.
The high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blended rubber comprises the following raw materials in parts by weight:
the addition amount of the compatibilizer is 2-8% by taking the mass of the ethylene propylene diene monomer as 100%.
The silicone rubber is selected from methyl vinyl silicone rubber and phenyl silicone rubber;
tests show that the compatibilizer disclosed by the invention has an excellent compatibilization effect on an ethylene propylene diene monomer/silicone rubber system, and the weight ratio of the compatibilizer to an ethylene propylene diene monomer/silicone rubber system is not large. If the total weight of the ethylene propylene diene monomer and the silicone rubber is 100 parts, the weight ratio of the ethylene propylene diene monomer to the silicone rubber can be selected from the following 10.
In the invention, the dosage of the compatibilizer has obvious influence on the mechanical property and the aging resistance of the finally prepared blend rubber. The addition of the compatibilizer is based on the weight part of the ethylene propylene diene monomer, preferably, the addition amount of the compatibilizer is 4-8% by taking the mass of the ethylene propylene diene monomer as 100%; tests show that when the addition amount of the compatibilizer is preferably 4-8%, the mechanical property of the prepared blend rubber is better.
More preferably, the addition amount of the compatibilizer is 6-8%, and tests show that the blend rubber prepared at the moment 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 conventional types in the art, such as organic peroxides, specifically selected from di-tert-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, di (tert-butylperoxyisopropyl) benzene, and the like.
Preferably, the blend disclosed in the present invention may further include additives commonly used in the art, such as reinforcing agents, vulcanization aids, structure control agents, etc., according to practical applications.
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 vulcanizing assistant is selected from zinc oxide, magnesium oxide, stearic acid and the like;
the structure control agent is selected from hydroxyl silicone oil, diphenyl silanediol, hexamethyldisilazane, cyclic trisilazane and the like;
preferably, the high-strength and aging-resistant ethylene propylene diene monomer/silicone rubber blended rubber comprises the following raw materials in parts by weight:
the invention also discloses a preparation method of the high-strength anti-aging ethylene propylene diene monomer/silicone rubber blend, 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 mixed rubber;
(2) Preparation of Silicone rubber mixes
Mixing silicon rubber, a reinforcing agent which can be selectively added and a structure control agent which can be selectively added to obtain silicon rubber compound;
(3) Preparation of ethylene propylene diene monomer/silicone rubber blended rubber
And uniformly mixing the ethylene propylene diene monomer rubber compound, the silicone rubber compound, the reinforcing agent which can be selectively added, the vulcanizing assistant which can be selectively added and the vulcanizing agent to obtain the ethylene propylene diene monomer rubber/silicone rubber compound, and finally, vulcanizing and forming to obtain the ethylene propylene diene monomer rubber/silicone rubber co-compound.
The ethylene propylene rubber/silicon rubber compound prepared by the invention can be mixed by a rolling method, and is cut into particles after plastic sheets are extruded, or is ground into particles after plastic sheets are extruded.
The invention discloses a method for increasing the volume of ethylene propylene diene monomer/silicon rubber mixed rubber with easily-obtained raw materials and good volume-increasing effect, wherein the adding time of a volume-increasing agent is more critical, and tests show that the sulfydryl MTQ silicon resin needs to be uniformly mixed with ethylene propylene diene monomer and a vulcanizing agent to initiate sulfydryl double bond click chemical reaction and then be mixed with silicon rubber mixed rubber. The addition method can effectively enhance the interface compatibility of the ethylene propylene diene monomer/silicone rubber, has good compatibilization effect, and can cause the reduction of the mechanical property of the prepared blended rubber if the ethylene propylene diene monomer, the silicone rubber and the compatibilizer are mixed at one time or the silicone rubber and the compatibilizer are mixed firstly and then the ethylene propylene diene monomer is added for mixing.
In the preparation process, the raw materials are added according to the weight parts of the raw materials, wherein the vulcanizing agent is added twice, 4-14% of the total weight of the vulcanizing agent is added when ethylene propylene diene monomer is prepared, and the rest vulcanizing agent is added when the blending rubber is prepared; the reinforcing agent is added in two times, 40-60% of the total weight is added when the silicon rubber compound is prepared, and the rest reinforcing agent is added when the co-mixed rubber is prepared.
Preferably, in the step (1), the temperature is increased to 140-160 ℃, and the mixture is continuously mixed for 3-9 min; more preferably, the temperature is raised to 145 to 155 ℃ and the mixture is kneaded for 6min. Tests show that the process parameters have a remarkable influence on the mechanical properties of the finally prepared blend glue, and the blend glue prepared in the further preferable range has better mechanical properties. More preferably, the temperature is raised to 150 ℃ and the kneading is continued for 6min.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses an ethylene propylene diene monomer/silicone rubber blend, which takes special mercapto MTQ silicone resin as a compatibilizer, and the compatibilizer has excellent compatibilization effect on an ethylene propylene diene monomer/silicone rubber system and is slightly influenced by the weight ratio of the ethylene propylene diene monomer to the silicone rubber; tests show that the compatibilization effect of the compatibilizer is mainly influenced by three aspects, namely the number of sulfydryl in a single MTQ molecule in the compatibilizer, the addition amount of the compatibilizer, the adding 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 aging resistance can be prepared under the appropriate conditions.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a mercapto MTQ silicone resin prepared in example 1: (a) A nuclear magnetic resonance hydrogen spectrum, (b) a nuclear magnetic resonance silicon spectrum;
FIG. 2 is a stress-strain curve of the EPDM/Silicone rubber blends prepared in example 5 and comparative example 1, respectively;
FIG. 3 is a TEM image of EPDM/silicone rubber blends prepared in example 5 and comparative example 1, respectively;
FIG. 4 is a graph showing tensile strengths of ethylene propylene diene monomer/silicone rubber blends prepared in examples 2 and 4 to 6 and comparative example 1 before and after aging, respectively;
FIG. 5 is a graph showing elongation at break before and after aging of the EPDM/Silicone rubber blends prepared in examples 2 and 4 to 6 and comparative example 1, respectively.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific examples, which should not be construed as limiting the scope of the present invention.
The ethylene propylene diene monomer and the silicon rubber adopted in the invention are commercially available:
ethylene propylene diene monomer (4725 p): vinyl content 70wt%, third monomer content 4.9wt%;
vinyl silicone rubber (110-3): the vinyl content was 0.22mol%.
Example 1
(1) Preparation of mercapto MTQ silicone resin
Into a three-necked flask equipped with a condenser and magnetic stirring was charged 5.0g of deionized water, 5.0g of anhydrous ethanol, 2.8g of concentrated hydrochloric acid (36 wt%), 13.7g of hexamethyldisiloxane, and after 30 minutes of reaction at 70 ℃, a mixed solution of 14.4g of tetraethyl orthosilicate and 23.84g of gamma-mercaptopropyltriethoxysilane was added at a rate of 1mL/minA neck flask. After the reaction is continued for 2 hours, the temperature is reduced to room temperature, toluene is added for extraction, a saturated sodium bicarbonate solution and deionized water are washed to be neutral, and the toluene is removed by reduced pressure distillation to obtain the mercapto MTQ silicon resin, wherein x =1, y =0.47, z =0.64 n =900. The number of mercapto 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 Haake torque rheometer and 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, the mixture is uniformly mixed and heated to 150 ℃ to be continuously mixed for 3min, and then the mixture is discharged, so that the ethylene propylene diene monomer mixed rubber is obtained.
(3) Preparation of Silicone rubber mixes
Firstly, adding 30 parts of silicon rubber into a Haake torque rheometer, then adding 15 parts of fumed silica, mixing at 100 ℃ for 10min, rotating at 100rpm, then adding 5 parts of hydroxy silicone oil, continuously mixing for 5min, and then discharging to obtain the silicon rubber compound.
(4) Preparation of ethylene propylene diene monomer/silicone rubber compound
And (3) adding the whole ethylene propylene diene monomer rubber compound prepared in the step (2) and the whole silicon rubber compound prepared in the step (3) into a Haake torque rheometer, mixing for 5min at 80 ℃ and at the rotating speed of 50rpm, then adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, finally adding 1.2 parts of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicon rubber compound.
(5) Preparation of blend rubber
And vulcanizing and molding the ethylene propylene diene monomer/silicone rubber compound after standing for one day at room temperature on a flat vulcanizing instrument at 180 ℃ to finally obtain a co-mixed rubber sample.
Example 2
The preparation process is basically the same as that of the embodiment 1, and the difference is only that 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane is added in the step (2), the mixture is uniformly mixed, and then the temperature is increased to 150 ℃, the mixture is continuously mixed for 6min, and the ethylene propylene diene rubber compound is obtained.
Example 3
The preparation process is basically the same as that of the embodiment 1, and the difference is only that 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane is added in the step (2), the mixture is uniformly mixed, and then the temperature is increased to 150 ℃, the mixture is continuously mixed for 9min, and the ethylene propylene diene rubber compound is obtained.
Example 4
The preparation process was substantially the same as in example 1 except that 2.8 parts of mercapto MTQ 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 mercapto MTQ 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 mercapto MTQ silicone resin was added in step (2).
Example 7
The preparation process is basically the same as that of the embodiment 5, and the difference is only that 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane is added in the step (2), the mixture is uniformly mixed, and then the temperature is increased to 140 ℃, the mixture is continuously mixed for 6min, and the ethylene propylene diene rubber compound is obtained.
Example 8
The preparation process is basically the same as that of the example 5, and the difference is that 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane is added in the step (2), the mixture is uniformly mixed, and then the temperature is increased to 160 ℃, the mixture is continuously mixed for 6min, and the ethylene propylene diene rubber compound is obtained.
Example 9
(1) The preparation of mercapto MTQ silicone was the same as in example 1;
(2) Preparation of Silicone rubber mixes
Firstly, adding 30 parts of silicon rubber into a Haake torque rheometer, then adding 15 parts of fumed silica, mixing at 100 ℃ for 10min, rotating at 100rpm, then adding hydroxyl silicone oil, continuously mixing for 5min, and then discharging to obtain the silicon rubber compound.
(3) Preparation of ethylene propylene diene monomer/silicone rubber compound
And (3) adding 70 parts of ethylene propylene diene monomer and the whole silicon rubber compound prepared in the step (2) into a Hack torque rheometer to mix for 5min at the temperature of 80 ℃, rotating at the speed of 50rpm, then adding 4.2 parts of mercapto MTQ silicon resin, 3 parts of zinc oxide and 15 parts of white carbon black to mix for 15min, finally adding 1.2 parts of 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane to continue mixing for 5min, and discharging to obtain the ethylene propylene diene monomer/silicon rubber compound.
(4) Preparation of blend rubber
And vulcanizing and molding the ethylene propylene diene monomer/silicone rubber compound after standing for one day at room temperature on a flat vulcanizing instrument at 180 ℃ to finally obtain a co-mixed rubber sample.
Example 10
(1) The preparation of mercapto MTQ silicone was the same as in example 1;
(2) Preparation of Silicone rubber mixes
Firstly, 30 parts of silicon rubber is added into a Haake torque rheometer, 15 parts of fumed silica is added, the mixture is mixed for 10min at 100 ℃ and the rotating speed is 100rpm, then 1.8 parts of mercapto MTQ silicon resin and hydroxyl silicone oil are added, and after the mixture is continuously mixed for 5min, 0.06 part of 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane is added, and the mixture is mixed for 6min at 150 ℃ and then discharged, so that silicon rubber compound is obtained.
(3) Preparation of ethylene propylene diene monomer/silicone rubber compound
And (3) adding 70 parts of ethylene propylene diene monomer rubber compound and the whole silicon rubber compound prepared in the step (2) into a Haake torque rheometer, mixing for 5min at the temperature of 80 ℃, rotating at the speed of 50rpm, then adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, finally adding 1.2 parts of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer/silicon rubber compound.
(4) Preparation of blend rubber
And vulcanizing and molding the ethylene propylene diene monomer/silicone rubber compound standing for one day at room temperature on a flat vulcanizing instrument at 180 ℃ to finally obtain a co-mixed rubber sample.
Example 11
(1) Preparation of mercapto MTQ silicone resin
5.0g of deionized water, 5.0g of absolute ethanol, 2.8g of concentrated hydrochloric acid (36 wt%), 8.7g of hexamethyldisiloxane were placed in a three-necked flask equipped with a condenser and magnetic stirring, and after 30 minutes reaction at 70 ℃, 14.4g of tetraethylorthosilicate was addedA mixed solution of the ester and 15.4g of gamma-mercaptopropyltriethoxysilane was added to the three-necked flask at a rate of 1 mL/min. The reaction is continued for 2 hours, then the temperature is reduced to room temperature, toluene is added for extraction, saturated sodium bicarbonate solution and deionized water are washed to be neutral, the toluene is removed by reduced pressure distillation, and the mercapto MTQ silicon resin is obtained, wherein x =1, y =0.52, z =0.92 n =1040. The number of mercapto groups in a single MTQ molecule was 2.5.
Steps (2) to (4) were 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 anhydrous ethanol, 2.8g of concentrated hydrochloric acid (36 wt%), 6.1g of hexamethyldisiloxane were charged, and after 30 minutes of reaction at 70 ℃, a mixed solution of 14.4g of tetraethyl orthosilicate and 6.0g of γ -mercaptopropyltriethoxysilane was charged into the three-necked flask at a rate of 1 mL/min. The reaction is continued for 2 hours, then the temperature is reduced to room temperature, toluene is added for extraction, saturated sodium bicarbonate solution and deionized water are washed to be neutral, the toluene is removed by reduced pressure distillation, and the mercapto MTQ silicon resin is obtained, wherein x =1, y =0.27, z =0.89 n =1050. The number of mercapto groups in a single MTQ molecule was 1.6.
Steps (2) to (4) were 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 rubber is added into a Haake torque rheometer, the rotating speed is 50rpm, then 0.14 part of 2,5-dimethyl-2,5-di (tert-butyl peroxy) hexane is added, the temperature is raised to 150 ℃ after uniform mixing, mixing is continued for 3min, and discharging is carried out, thus obtaining the ethylene propylene diene monomer rubber compound.
(2) Preparation of Silicone rubber mixes
Firstly, adding 30 parts of silicon rubber into a Haake torque rheometer, then adding 15 parts of fumed silica, mixing at 100 ℃ for 10min, rotating at 100rpm, then adding 5 parts of hydroxy silicone oil, continuously mixing for 5min, and then discharging to obtain the silicon rubber compound.
(3) Preparation of ethylene propylene diene monomer/silicone rubber compound
And (2) adding the whole ethylene propylene diene monomer rubber compound prepared in the step (1) and the whole silicon rubber compound prepared in the step (2) into a Haake torque rheometer, mixing for 5min at 80 ℃ and at the rotating speed of 50rpm, then adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, finally adding 1.2 parts of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicon rubber compound.
(4) Preparation of blend rubber
And vulcanizing and molding the ethylene propylene diene monomer/silicone rubber compound after standing for one day at room temperature on a flat vulcanizing instrument at 180 ℃ to finally obtain a co-mixed 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-mercaptopropionate) (the number of the mercapto groups converted is equivalent to that in example 5, the structural formula is shown in the specification) are added into a Haake torque rheometer, the mixture is mixed for 10min at 80 ℃ and the rotating speed is 50rpm, then 0.14 part of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane is added, the mixture is uniformly mixed and heated to 150 ℃ to be continuously mixed for 3min, and then the mixture is discharged, so that the ethylene propylene diene monomer mixed rubber is obtained.
(2) Preparation of Silicone rubber mixes
Firstly, 30 parts of silicon rubber is added into a Haake torque rheometer, 15 parts of fumed silica is added, the mixture is mixed for 10min at 100 ℃ and the rotating speed is 100rpm, 5 parts of hydroxyl silicone oil is added, and the mixture is continuously mixed for 5min and then discharged, so that the silicon rubber compound is obtained.
(3) Preparation of ethylene propylene diene monomer/silicone rubber compound
And (2) adding the whole ethylene propylene diene monomer rubber compound prepared in the step (1) and the whole silicon rubber compound prepared in the step (2) into a Haake torque rheometer, mixing for 5min at 80 ℃ and at the rotating speed of 50rpm, then adding 3 parts of zinc oxide and 15 parts of white carbon black, mixing for 15min, finally adding 1.2 parts of 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, continuously mixing for 5min, and discharging to obtain the ethylene propylene diene monomer rubber/silicon rubber compound.
(4) Preparation of blend rubber
And vulcanizing and molding the ethylene propylene diene monomer/silicone rubber compound after standing for one day at room temperature on a flat vulcanizing instrument at 180 ℃ to finally obtain a co-mixed rubber sample.
The EPDM/Silicone rubber blends prepared in each of the examples and comparative examples were tensile tested using a Zwick/Roell Z020 universal materials tester at a tensile rate of 50mm/min and the results are summarized in Table 1:
TABLE 1
In the above table 1, the comparative example 1 is a blend rubber prepared by directly blending ethylene propylene diene monomer 4725P and silicone rubber, no compatibilizer is added, the mechanical strength is poor, the tensile strength and the elongation at break are only 9.1MPa and 424% respectively, and the tensile strength and the elongation at break are both improved strongly by adding the mercapto MTQ silicone resin as the compatibilizer in the examples 1 to 6. Comparative examples 1 to 3 show that when 1.4 parts of mercapto MTQ silicone resin is added in 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 reason may be that 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane can initiate crosslinking of ethylene propylene diene monomer during banburying at 150 ℃, and excessively long banburying time can cause excessive crosslinking of ethylene propylene diene monomer so that the ethylene propylene diene monomer is difficult to be uniformly mixed with silicone rubber. Comparing examples 5, 7 and 8, it can be found that the ethylene propylene diene monomer/silicone rubber blended rubber obtained by blending at 150 ℃ has the best mechanical property when the click chemistry reaction is carried out for 6min in the step (2). It can be seen from comparison of examples 1 and 4-6 that the ethylene propylene diene monomer/silicone rubber blend prepared by adding 4.2 parts of mercapto MTQ silicone during blending has the best mechanical properties, the tensile strength and elongation at break are respectively 18.2MPa and 705%, and the tensile strength and elongation at break are respectively 100% and 66% higher than those of comparative example 1 without adding a compatibilizer. Comparing examples 5, 9, 10, it can be seen that the timing of the addition of the mercapto MTQ silicone is important and requires the mercapto click reaction with EPDM prior to blending with the silicone rubber. It can be seen from comparison of examples 5, 11, 12 and comparative example 2 that a suitable amount of thiol groups on a single molecule gives good compatibility.
It can also be observed from the TEM images of the ethylene propylene diene monomer/silicone rubber blend sections prepared in example 5 and comparative example 1, respectively, that the size of phase separation between the ethylene propylene diene monomer and the silicone rubber becomes significantly smaller in example 5 after the mercapto MTQ silicone resin is added, indicating that the compatibility between the ethylene propylene diene monomer and the silicone rubber is increased.
To further evaluate the aging properties, samples of the vulcanizates prepared in examples 2, 4 to 6 and comparative example 1, respectively, were aged in a forced air oven 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 change, the tensile strength comparison before and after aging is shown in fig. 4, and the elongation at break comparison before and after aging is shown in fig. 5.
TABLE 2
The results in the comparison table 2 show that the tensile strength and elongation at break of the blend rubber after aging after adding the mercapto MTQ silicone resin are better than those of the blend rubber in the comparison example 1, wherein the tensile strength is 17.4MPa and the elongation at break is 561% after aging for 3d in the example 5, and the blend rubber has excellent aging resistance.
The above examples are intended to aid in the understanding of the method and key points of the invention. This summary should not be construed to limit the present invention.
Claims (10)
1. The high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blended rubber is characterized in that ethylene propylene diene monomer and silicone rubber are used as base materials, and mercapto MTQ silicone resin is used as a compatibilizer;
the structural general formula of the mercapto 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, z =0.1 to 1.
2. The high strength aging resistant EPDM/silicone rubber blend of claim 1, wherein:
x＝1，y＝0.2～0.6，z＝0.8～1；
the number of sulfydryl in a single MTQ molecule in the sulfydryl MTQ silicon resin is 1.5-2.5.
3. The high-strength aging-resistant EPDM/silicone rubber blend according to claim 2, wherein the number of mercapto groups in a single MTQ molecule in the mercapto MTQ silicone resin is 2.1.
4. The high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend according to any one of claims 1 to 3, characterized by comprising the following raw materials in parts by weight:
10-90 parts of ethylene propylene diene monomer;
10-90 parts of silicon rubber;
0.2 to 7.2 portions of compatibilizer;
0.8-2.0 parts of vulcanizing agent;
the addition amount of the compatibilizer is 2-8% by taking the mass of the ethylene propylene diene monomer as 100%.
5. The high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend as claimed in claim 4, wherein the compatibilizer is added in an amount of 4 to 8% based on 100% by mass of the ethylene propylene diene monomer.
6. The high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blend as claimed in claim 5, wherein the compatibilizer is added in an amount of 6 to 8% based on 100% by mass of the ethylene propylene diene monomer.
7. The high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blended rubber according to claim 4, comprising the following raw materials in parts by weight:
8. a method for preparing the high-strength aging-resistant ethylene propylene diene monomer/silicone rubber blended rubber according to any one of claims 1 to 7, which is characterized by comprising 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 mixed rubber;
(2) Preparation of Silicone rubber mixes
Mixing silicon rubber, a reinforcing agent which can be selectively added and a structure control agent which can be selectively added to obtain a silicon rubber compound;
(3) Preparation of ethylene propylene diene monomer/silicone rubber blended rubber
And uniformly mixing the ethylene propylene diene monomer rubber compound, the silicone rubber compound, the reinforcing agent which can be selectively added, the vulcanizing assistant which can be selectively added, and the vulcanizing agent to obtain the ethylene propylene diene monomer rubber/silicone rubber compound, and finally, vulcanizing and forming to obtain the ethylene propylene diene monomer rubber/silicone rubber blended rubber.
9. The preparation method of the high-strength aging-resistant EPDM/silicone rubber blended rubber according to claim 8, wherein in the step (1), the temperature is raised to 140-160 ℃ and the blending is continued for 3-9 min.
10. The preparation method of the high-strength aging-resistant EPDM/silicone rubber blended rubber according to claim 9, wherein the temperature is raised to 145-155 ℃ and the blending is continued for 6min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116987347A (en) * | 2023-07-31 | 2023-11-03 | 特变电工山东鲁能泰山电缆有限公司 | Cable insulation material for offshore wind power generation, preparation method of cable insulation material and cable for offshore wind power generation |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236234A (en) * | 1988-07-27 | 1990-02-06 | Shin Etsu Chem Co Ltd | Silicone resin composition and production thereof |
| CN105482200A (en) * | 2015-12-20 | 2016-04-13 | 成都硅宝科技股份有限公司 | High abrasion-resistant low rolling resistance tread rubber material containing silicone rubber and preparation method thereof |
| CN106046379A (en) * | 2016-06-25 | 2016-10-26 | 北京化工大学 | Hydrophobic sulfydryl-modified silicone rubber and preparation method thereof |
| CN106496566A (en) * | 2016-11-02 | 2017-03-15 | 山东大学 | A kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto alkene reaction and preparation method and application |
| CN110183665A (en) * | 2019-05-28 | 2019-08-30 | 安庆北化大科技园有限公司 | A kind of preparation method and applications of the resin of MTQ containing sulfydryl |
| CN115028928A (en) * | 2022-06-13 | 2022-09-09 | 浙江大学 | High-performance ethylene propylene diene monomer/silicone rubber blend and preparation method thereof |
-
2022
- 2022-12-06 CN CN202211556742.3A patent/CN115785575B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0236234A (en) * | 1988-07-27 | 1990-02-06 | Shin Etsu Chem Co Ltd | Silicone resin composition and production thereof |
| CN105482200A (en) * | 2015-12-20 | 2016-04-13 | 成都硅宝科技股份有限公司 | High abrasion-resistant low rolling resistance tread rubber material containing silicone rubber and preparation method thereof |
| CN106046379A (en) * | 2016-06-25 | 2016-10-26 | 北京化工大学 | Hydrophobic sulfydryl-modified silicone rubber and preparation method thereof |
| CN106496566A (en) * | 2016-11-02 | 2017-03-15 | 山东大学 | A kind of silicon rubber/unsaturated carbon chains rubber compatilizer based on mercapto alkene reaction and preparation method and application |
| CN110183665A (en) * | 2019-05-28 | 2019-08-30 | 安庆北化大科技园有限公司 | A kind of preparation method and applications of the resin of MTQ containing sulfydryl |
| CN115028928A (en) * | 2022-06-13 | 2022-09-09 | 浙江大学 | High-performance ethylene propylene diene monomer/silicone rubber blend and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨淑丽: "大辞海 化工轻工纺织卷", 中国石化出版社, pages: 199 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116987347A (en) * | 2023-07-31 | 2023-11-03 | 特变电工山东鲁能泰山电缆有限公司 | Cable insulation material for offshore wind power generation, preparation method of cable insulation material and cable for offshore wind power generation |
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