CN115028928B - High-performance ethylene propylene diene monomer rubber/silicone rubber combined rubber and preparation method thereof - Google Patents
High-performance ethylene propylene diene monomer rubber/silicone rubber combined rubber and preparation method thereof Download PDFInfo
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- CN115028928B CN115028928B CN202210660557.2A CN202210660557A CN115028928B CN 115028928 B CN115028928 B CN 115028928B CN 202210660557 A CN202210660557 A CN 202210660557A CN 115028928 B CN115028928 B CN 115028928B
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- rubber
- propylene diene
- diene monomer
- ethylene propylene
- silicone rubber
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 103
- 229920002379 silicone rubber Polymers 0.000 title claims abstract description 101
- 239000004945 silicone rubber Substances 0.000 title claims abstract description 81
- 229920001971 elastomer Polymers 0.000 title claims abstract description 55
- 239000005060 rubber Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title description 19
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000005977 Ethylene Substances 0.000 claims abstract description 48
- 229920001897 terpolymer Polymers 0.000 claims abstract description 45
- 239000002994 raw material Substances 0.000 claims abstract description 9
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 58
- -1 polysiloxane Polymers 0.000 claims description 46
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 28
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 20
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000004073 vulcanization Methods 0.000 claims description 11
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 9
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 7
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 6
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 claims description 6
- YGHUUVGIRWMJGE-UHFFFAOYSA-N chlorodimethylsilane Chemical compound C[SiH](C)Cl YGHUUVGIRWMJGE-UHFFFAOYSA-N 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 238000012653 anionic ring-opening polymerization Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000000977 initiatory effect Effects 0.000 claims description 4
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 239000012968 metallocene catalyst Substances 0.000 claims description 3
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- 150000001450 anions Chemical group 0.000 claims description 2
- OECBVSKJRQNLTD-UHFFFAOYSA-N bicyclo[2.2.1]hepta-2,4(7),5-triene Chemical compound C=1C2C=CC=1C=C2 OECBVSKJRQNLTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002981 blocking agent Substances 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 claims description 2
- IYPLTVKTLDQUGG-UHFFFAOYSA-N dodeca-1,11-diene Chemical compound C=CCCCCCCCCC=C IYPLTVKTLDQUGG-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- HIHIPCDUFKZOSL-UHFFFAOYSA-N ethenyl(methyl)silicon Chemical group C[Si]C=C HIHIPCDUFKZOSL-UHFFFAOYSA-N 0.000 claims description 2
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 23
- WXOFQPMQHAHBKI-UHFFFAOYSA-N 4-ethylbicyclo[2.2.1]hept-2-ene Chemical compound C1CC2C=CC1(CC)C2 WXOFQPMQHAHBKI-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000005979 thermal decomposition reaction Methods 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 238000007599 discharging Methods 0.000 description 7
- 239000005543 nano-size silicon particle Substances 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 description 5
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 5
- 229960003493 octyltriethoxysilane Drugs 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000012065 filter cake Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- SDRZFSPCVYEJTP-UHFFFAOYSA-N 1-ethenylcyclohexene Chemical compound C=CC1=CCCCC1 SDRZFSPCVYEJTP-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- ZKWZOHZHYKMHQZ-UHFFFAOYSA-N chloro-dimethyl-oct-1-enylsilane Chemical compound CCCCCCC=C[Si](C)(C)Cl ZKWZOHZHYKMHQZ-UHFFFAOYSA-N 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- SJMLNDPIJZBEKY-UHFFFAOYSA-N ethyl 2,2,2-trichloroacetate Chemical compound CCOC(=O)C(Cl)(Cl)Cl SJMLNDPIJZBEKY-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-performance ethylene propylene diene monomer rubber/silicone rubber combined rubber, which comprises the following raw materials in parts by weight: 10 to 90 parts of ethylene propylene diene monomer rubber, 10 to 90 parts of silicon rubber and 0.5 to 5.0 parts of compatilizer; the compatilizer is selected from ethylene/cyclodiene/siloxane terpolymer, and has a structural general formula shown in the specification, wherein x is selected from natural numbers of 10-200, y is selected from natural numbers of 500-2000, z is selected from natural numbers of 1-100, and n is selected from natural numbers of 1-12; r is R 1 Selected from hexyl, octyl, decyl, dodecyl,One or more of the following; r is R 2 Selected from the group consisting of One or more of the following. The high-performance ethylene propylene diene monomer/silicone rubber combined rubber disclosed by the invention takes ethylene/cyclodiene/siloxane terpolymer as a compatilizer, so that the compatibility of the ethylene propylene diene monomer and the silicone rubber is effectively improved, and the mechanical strength and the thermal stability of the ethylene propylene diene monomer/silicone rubber combined rubber are obviously enhanced.
Description
Technical Field
The invention relates to the technical field of rubber blending, in particular to high-performance ethylene propylene diene monomer rubber/silicone rubber combined rubber and a preparation method thereof.
Background
Ethylene propylene diene monomer is mainly prepared by copolymerizing ethylene, propylene and diene serving as a third monomer through a Ziegler-Natta catalyst or a metallocene catalyst, has wide raw material sources, has good ageing resistance, oxidation resistance and mechanical properties, and is widely applied to the fields of wires and cables, automobile elements, conveyor belts and the like, but the heat resistance of the ethylene propylene diene monomer is poor, and the mechanical strength of the material is obviously reduced at high temperature. In contrast, silicone rubber has excellent high and low temperature resistance, the material performance changes little with temperature, and meanwhile, the weather resistance, dielectric property and biocompatibility of the silicone rubber are better than those of most rubbers, but the mechanical property of the silicone rubber is poorer, the price is higher, and the application of the silicone rubber is limited.
Therefore, if the ethylene propylene diene monomer rubber and the silicone rubber are blended to prepare the rubber, the excellent mechanical property of the ethylene propylene diene monomer rubber and the excellent heat resistance of the silicone rubber can be combined simultaneously to prepare the composite material with excellent comprehensive performance. The difficulty in preparing the high-performance ethylene propylene diene monomer/silicone rubber combined rubber is that the composition of the molecular chains of the ethylene propylene diene monomer and the molecular chains of the silicone rubber are large in difference, the main chain of the ethylene propylene diene monomer consists of C-C saturated single bonds, the main chain of the silicone rubber consists of Si-O bonds which are alternately arranged, and the compatibility of the two is poor. In addition, the viscosity and vulcanization speed of the ethylene propylene diene monomer rubber and the silicone rubber are not matched, so that better dispersion of the ethylene propylene diene monomer rubber and the silicone rubber is more difficult to realize.
The addition of the compatilizer during blending can reduce interfacial tension between different components and enhance interaction, thereby improving the intersolubility of the components and the final performance of the combined glue. In the Chinese patent document with the publication number of CN109867789A, the liquid ethylene propylene diene monomer rubber containing a siloxane chain segment is prepared by hydrosilylation between hydrogen-containing silicone oil and liquid ethylene propylene diene monomer rubber, and can be used as a compatilizer for ethylene propylene diene monomer rubber/silicone rubber combined rubber, but Si-H bonds on the hydrogen-containing silicone oil are on a silicone oil main chain, and can be crosslinked with the liquid ethylene propylene diene monomer rubber by hydrosilylation, the compatilizer has an undefined structure, the compatibilizing effect is not obvious, and the tensile strength and the elongation at break of the combined rubber are only increased by 8.4 percent and 11.5 percent to the maximum, so that the improvement of mechanical property is limited. In the research of Polymer Engineering and Science,2018,719-728, vinyltrimethoxysilane was grafted onto ethylene-vinyl acetate copolymer, which was then used as a compatibilizer for ethylene propylene diene monomer/silicone rubber. After the compatibilization, the mechanical property and the heat resistance of the adhesive are improved, but the addition amount of the compatilizer is 10 parts when the optimal effect is achieved, and the dosage is larger.
Therefore, the key to preparing high performance ethylene propylene diene monomer rubber/silicone rubber combination is to develop a suitable compatibilizer.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses a high-performance ethylene propylene diene monomer/silicone rubber combined rubber, which uses an ethylene/cyclodiene monomer/silicone terpolymer as a compatilizer, so that the compatibility of the ethylene propylene diene monomer and the silicone rubber is effectively improved, and the mechanical strength and the thermal stability of the ethylene propylene diene monomer/silicone rubber combined rubber are obviously enhanced.
The specific technical scheme is as follows:
the high-performance ethylene propylene diene monomer rubber/silicone rubber combined rubber comprises the following raw materials in parts by weight:
the compatilizer is selected from ethylene/cyclodiene/siloxane terpolymer, and has the following structural general formula:
wherein x is a natural number of 10 to 200, y is a natural number of 500 to 2000, z is a natural number of 1 to 100, and n is a natural number of 1 to 12;
R 1 selected from hexyl, octyl, decyl, dodecyl, One or more of the following; r is R 2 Selected from-> One or more of the following.
The invention discloses an ethylene/cyclodiene/polysiloxane terpolymer with special structure as a compatilizer for preparing ethylene propylene diene monomer/silicone rubber and rubber, and the compatilizer simultaneously contains a polyolefin main chain and a polysiloxane branched chain, so that the interfacial tension between ethylene propylene diene monomer and silicone rubber can be effectively reduced, and the action strength is enhanced; in addition, the compatilizer also contains C=C bond which can be used as a reactive group, and the compatilizer and ethylene propylene diene monomer rubber or silicon rubber are chemically bonded through vulcanization reaction in the subsequent vulcanization step, so that a better compatibilizing effect is realized.
In the formula of the ethylene propylene diene monomer/silicone rubber combined rubber, ethylene propylene diene monomer and silicone rubber are used as base materials, the total mass parts of the ethylene propylene diene monomer and the silicone rubber are 100 parts, and other raw materials except the base materials are calculated in an externally added mode.
Preferably, in the structural general formula of the compatilizer, R 1 Selected from the group consisting ofR 2 Selected from the group consisting ofFurther preferably, R 2 Selected from->It has been found by experiments that R in the structural general formula of the compatilizer 1 And R is R 2 The type of the ethylene propylene diene monomer rubber/silicone rubber combined rubber prepared finally is preferable, and the ethylene propylene diene monomer rubber/silicone rubber combined rubber has higher mechanical strength and thermal stability.
Preferably, in the structural general formula of the compatilizer, x is selected from natural numbers of 15-100, y is selected from natural numbers of 500-2000, z is selected from natural numbers of 1-50, and n is selected from natural numbers of 1-3.
It has been found by experiment that the ethylene/cyclodiene/siloxane terpolymer has silicon-oxygen unitsWhen the mass ratio of the ethylene/cyclodiene/siloxane terpolymer compatilizer is equal to the content of the silicon rubber in the base material of the ethylene propylene diene/silicon rubber combined rubber formula, the ethylene/cyclodiene/siloxane terpolymer compatilizer has better compatibilizing performance on the ethylene propylene diene/silicon rubber combined rubber.
When the content of the silicone rubber in the base material of the ethylene propylene diene monomer/silicone rubber combined rubber formula is A%, the mass ratio of the silicone chain segments in the ethylene/cyclodiene monomer/silicone rubber terpolymer is preferably within the range of A+/-10 percent, and at the moment, the ethylene/cyclodiene monomer/silicone rubber combined rubber compatibilizing agent has better compatibilizing performance on the ethylene propylene diene monomer/silicone rubber combined rubber.
Such as: when the content of the silicon rubber in the base material of the ethylene propylene diene monomer/silicon rubber combined rubber formula is 40 percent and the mass ratio of the silicon-oxygen chain segments in the added ethylene/cyclodiene/siloxane terpolymer is 30-50 percent, the compatibilization performance of the ethylene propylene diene monomer/silicon rubber combined rubber is better.
In the invention, the following components are added:
the ethylene propylene diene monomer has a vinyl content of 50-70 wt% and a third monomer content of 0.5-9.5 wt%.
The silicon rubber is methyl vinyl silicon rubber, and the vinyl content is 0.2-0.8 mol%; preferably 0.2 to 0.5mol percent, too high results in too high a curing speed of the combined glue and too high a crosslinking density, which affects the product performance.
The vulcanizing agent is selected from 2, 5-dimethyl-2, 5-bis hexane and/or dicumyl peroxide;
the vulcanization aid is one or more selected from zinc oxide, stearic acid and silicone oil.
The raw material composition also comprises a filler selected from nano silicon dioxide and/or carbon black.
The invention also discloses a preparation method of the high-performance ethylene propylene diene monomer rubber/silicone rubber combined rubber, which comprises the following steps:
(1) Performing hydrosilylation reaction on dimethyl monochlorosilane and diene under a platinum catalyst to prepare olefin functional dimethyl chlorosilane;
the diene is selected from one or more of 1, 5-hexadiene, 1, 7-octadiene, 1, 9-decadiene, 1, 11-dodecadiene, 5-vinyl-2-norbornene, 2, 5-norbornene diene and 4-vinyl-1-cyclohexene;
(2) N-butyllithium initiates hexamethylcyclotrisiloxane to carry out anion ring-opening polymerization, and the alkene functional dimethyl chlorosilane prepared in the step (1) is used as a blocking agent to synthesize alkene functional polysiloxane;
(3) Initiating ethylene and cyclodiolefin and olefin functional polysiloxane prepared in the step (2) to carry out coordination copolymerization by using a Ziegler-Natta catalyst or a metallocene catalyst, and obtaining an ethylene/cyclodiolefin/polysiloxane terpolymer after post-treatment;
the cyclodiolefin is selected from one or more of ethylidene norbornene, 5-vinyl-2-norbornene, cyclopentadiene and 4-ethylene-1-cyclohexene;
(4) Mixing all the raw materials except the vulcanizing agent uniformly, then mixing for a period of time, adding the vulcanizing agent, and after mixing uniformly, performing hot press molding and vulcanization to obtain the ethylene propylene diene monomer rubber/silicone rubber composite rubber.
In step (1):
the molar ratio of dimethyl monochlorosilane to diolefin is 1:2 to 10; preferably 1:2 to 5;
the temperature of the hydrosilylation reaction is 0-100 ℃; based on the comprehensive consideration of the reaction rate and the reduction of energy consumption, the temperature is preferably 20-60 ℃ and the time is 12-48 h.
In the step (2):
the molar ratio of n-butyllithium to hexamethylcyclotrisiloxane is 1:1 to 12; preferably 1:1 to 5.
The temperature of the anionic ring-opening polymerization is-20 to 50 ℃; preferably at a temperature of 0 to 30 ℃ for a time of 1 to 4 hours.
The addition amount of the alkene functional dimethyl chlorosilane is 1.05 to 1.10 times of the molar amount of the n-butyl lithium.
In the step (3):
the molar ratio of cyclic diolefins to olefin functional polysiloxanes is 1:1 to 10; considering the polymerization activity in combination with the content of the polysiloxane segment, it is preferably 1:3 to 7.
After ethylene is introduced, the pressure in the system is kept at 0.1-1.0 MPa.
The temperature of the coordination copolymerization is 0-70 ℃, preferably 10-30 ℃ and the time is 5-30 min.
The post-treatment comprises washing and drying.
In the step (4):
the temperature of the mixing is 70-130 ℃; preferably 90-110 ℃, the temperature is too low, the viscosity of the ethylene propylene diene monomer is too high, and effective dispersion and blending of the components are difficult to realize; too high a temperature can easily lead to premature decomposition of the vulcanizing agent to pre-crosslink.
The temperature of the hot press molding and the vulcanization is 150-180 ℃.
If a filler is added in step (4), it is preferably: uniformly blending ethylene propylene diene monomer rubber and a half of filler, then uniformly adding the mixture into silicon rubber and the rest of filler in batches, adding a compatilizer and a vulcanization aid, firstly mixing for a period of time, then adding a vulcanizing agent, continuously mixing for a period of time, discharging, placing the discharged rubber at room temperature for 24 hours, and finally carrying out hot press molding and vulcanization on a flat vulcanizing machine to obtain the high-performance ethylene propylene diene monomer rubber/silicon rubber.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a high-performance ethylene propylene diene monomer/silicone rubber combined rubber, which can obviously improve the mechanical property and the thermal stability of the ethylene propylene diene monomer/silicone rubber combined rubber by adding a small amount of ethylene/cyclodiene monomer/polysiloxane terpolymer and has better improvement effect on ethylene propylene diene monomer with different brands. The mass fraction of the polysiloxane chain segment in the ternary polymerization is adjusted, so that the ternary ethylene propylene rubber/silicone rubber hybrid rubber can be suitable for the fields of high-temperature-resistant conveying belts, damping materials, engine insulating layers and the like.
Drawings
FIGS. 1 to 4 are nuclear magnetic resonance hydrogen spectra of ethylene/cyclodiene/polysiloxane terpolymers prepared in examples 1 to 4, respectively;
FIG. 5 is a graph showing strain-stress curves of ethylene propylene diene monomer rubber/silicone rubber combined rubber prepared in example 1 and comparative example 1, respectively;
FIG. 6 is a graph showing the thermal decomposition of ethylene propylene diene monomer rubber/silicone rubber and rubber blend prepared in example 1 and comparative example 1, respectively, under nitrogen atmosphere;
fig. 7 is an SEM image of fracture surfaces of the ethylene propylene diene monomer rubber/silicone rubber combined rubber prepared in example 1 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.
Ethylene propylene diene monomer and silicone rubber are commercially available, ethylene propylene diene monomer (KEP-2320): 57.5% by weight of vinyl groups and 4.7% by weight of a third monomer; ethylene propylene diene monomer (KEP-430H): 57.0wt% vinyl and 1.6wt% third monomer; ethylene propylene diene monomer (3745P): vinyl content 70.0wt% and third monomer content 0.5wt%; vinyl silicone rubber: vinyl content 0.22mol%.
Example 1
(1) 12.0g of 5-vinyl-2-norbornene (0.1 mol) and Karstedt's catalyst (Pt: 1.2. Mu. Mol) were added to a 100mL flask at 25℃under nitrogen, followed by dropwise addition of 3.78g of dimethylmonochlorosilane (0.04 mol); after 24h of reaction, unreacted 5-vinyl-2-norbornene was removed by rotary evaporation (95 ℃ C., 5 KPa) to give pale yellow ethylnorbornenyl dimethylchlorosilane.
(2) 4.27g (0.019 mol) of hexamethylcyclotrisiloxane was charged into a round-bottomed flask, the vacuum-nitrogen-charging operation was repeated three times, the flask was replaced with a nitrogen atmosphere, the temperature was maintained at 10 ℃, then 5mL of tetrahydrofuran and 8mL of n-butyllithium/hexane solution (2.4M) were respectively added to initiate anionic ring opening polymerization, and after 2 hours of reaction, 4.24g (0.02 mol) of ethylnorbornenyl dimethylsilane was added to terminate the reaction to obtain ethylnorbornenyl polysiloxane.
(3) A250 mL glass reactor was evacuated for 10min and then charged with ethylene to maintain a system pressure of 0.1MPa. After repeating the operation for 6 cycles, the temperature was set at 30℃and anhydrous toluene and Et were added, respectively 2 AlCl (2 mmol), ethyl trichloroacetate (0.15 mmol), ethylidene norbornene (1.125 mmol) and ethylnorbornene-based polysiloxane prepared in step (2) (2.4 g,5.25 mmol) were stirred for 5min and then injected with 1. Mu. Mol VCl 3 (THF) 3 Initiating reaction, and continuously charging ethylene gas in the process to keep the pressure of the system at 0.1MPa. After a period of reaction, the mixture is poured into acid ethanol for precipitation, the filter cake is washed three times by using absolute ethanol, and the filter cake is dried in vacuum for 24 hours at 40 ℃.
(4) 60 parts by mass of EPDM (brand: KEP-2320) was chopped and then added to an internal mixer together with 15 parts by mass of nano silica, and kneaded at 110℃for 5 minutes.
(5) Continuously adding 40 parts by mass of silicon rubber, 15 parts by mass of nano silicon dioxide, 3 parts by mass of ZnO and 2 parts by mass of ethylene/cyclodiene/polysiloxane terpolymer, mixing for 10min, adding 1.5 parts by mass of 2, 5-dimethyl-2, 5-bishexane, continuously mixing for 5min, and discharging.
(6) After 24 hours of standing, the rubber compound was hot-pressed and vulcanized at 180℃and then subjected to mechanical and thermal decomposition tests.
The terpolymer prepared in the embodiment is an ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymer, and the structural formula is shown as follows:
x, y and z are 96, 1417 and 28, respectively, the silicone segments in the copolymerThe ratio of (C) was 31.0wt%.
Example 2
(1) 22.0g of 1, 7-octadiene (0.2 mol) and Karstedt's catalyst (Pt: 1.2. Mu. Mol) were added to a 100mL flask at 35℃under nitrogen, followed by dropwise addition of 3.78g of dimethylmonochlorosilane (0.04 mol); after 24h of reaction, unreacted 1, 7-octadiene was removed by rotary evaporation (85 ℃,5 KPa) to give pale yellow octenyl dimethylchlorosilane.
(2) 4.27g of hexamethylcyclotrisiloxane was added to a round-bottom flask, the vacuum-nitrogen-charging operation was repeated three times, the flask was replaced with a nitrogen atmosphere, the temperature was kept at 10 ℃, then 5mL of tetrahydrofuran and 8mL of n-butyllithium/hexane solution (2.4M) were added to initiate anionic ring-opening polymerization, and after 2 hours of reaction, 4.15g of octenyl dimethylchlorosilane was added to terminate the end, thus obtaining octenyl polysiloxane.
(3) A250 mL glass reactor was evacuated for 10min and then charged with ethylene to maintain a system pressure of 0.1MPa. After repeating the operation for 6 cycles, the temperature was set at 30℃and anhydrous toluene and Et were added, respectively 2 AlCl (2 mmol), ethyl trichloroacetate (0.15 mmol), ethylidene norbornene (1.125 mmol) and octenyl polysiloxane prepared in step (2) (2.35 g), stirring for 5min and injecting 1. Mu. Mol VCl 3 (THF) 3 Initiating reaction, and continuously charging ethylene gas in the process to keep the pressure of the system at 0.1MPa. After a period of reaction, the mixture is poured into acid ethanol for precipitation, the filter cake is washed three times by using absolute ethanol, and the filter cake is dried in vacuum for 24 hours at 40 ℃.
Steps (4) to (6) are the same as in example 1.
The terpolymer prepared in the embodiment is an ethylene/ethylidene norbornene/octenyl polysiloxane terpolymer, and the structural formula is shown as follows:
x, y and z are 18, 1835 and 42, respectively, the silicone segment content of the copolymer being 8.2wt%
Example 3
The preparation process was essentially the same as in example 1, except that ethylidene norbornene in step (3) was replaced with equimolar cyclopentadiene, and the compatibilizing agent added in the subsequent step (5) was the terpolymer prepared in step (3) of this example.
The terpolymer prepared in the embodiment is an ethylene/cyclopentadiene/ethylnorbornene-based polysiloxane terpolymer, and the structural formula of the terpolymer is shown as follows:
x, y and z are 70, 949 and 1, respectively, with a silicone segment content of 32.4wt% in the copolymer.
Example 4
The preparation process was essentially the same as in example 1, except that ethylidene norbornene in step (3) was replaced with equimolar vinylcyclohexene, and the compatibilizing agent added in the subsequent step (5) was the terpolymer prepared in this example (3).
The terpolymer prepared in the embodiment is an ethylene/vinyl cyclohexene/ethylnorbornene-based polysiloxane terpolymer, and the structural formula of the terpolymer is shown as follows:
x, y and z are 52, 730 and 1, respectively, with a silicone segment content of 32.1wt% in the copolymer.
Example 5
The preparation process was substantially the same as in example 1 except that the addition amount of ethylnorbornene-based polysiloxane in the step (3) was replaced by 1.37g (3 mmol).
The terpolymer prepared in the embodiment is an ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymer, and the structural formula is shown as follows:
x, y and z are 22, 659 and 12, respectively, with a silicone segment content of 20.9wt% in the copolymer.
Example 6
The preparation process was substantially the same as in example 1 except that the addition amount of hexamethylcyclotrisiloxane in step (2) was replaced with 12.81g (0.058 mol) and the ethylnorbornene-based polysiloxane added in the subsequent step (3) was 2.71g (3.0 mmol).
The terpolymer prepared in the embodiment is an ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymer, and the structural formula is shown as follows:
x, y and z are 20, 883 and 16, respectively, with a silicone segment content of 29.9wt% in the copolymer.
Example 7
The preparation process was substantially the same as in example 1 except that the ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymer was added in an amount of 1 part by mass in the step (5).
Example 8
The preparation process was substantially the same as in example 1 except that the ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymer was added in an amount of 3 parts by mass in the step (5).
Example 9
The preparation process was substantially the same as in example 1 except that the ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymer was added in an amount of 4 parts by mass in the step (5).
Example 10
The preparation process is essentially the same as in example 1, except that the EPDM in step (4) is replaced by an equal mass of EPDM under the trademark KEP-430H.
Example 11
The preparation process is essentially the same as in example 1, except that the EPDM in step (4) is replaced by an equal mass of EPDM with a designation 3745P.
Comparative example 1
The procedure for the preparation of the ethylene propylene diene monomer/silicone rubber blend is the same as in example 1, except that no compatibilizing agent is added, as follows:
(1) 60 parts by mass of EPDM (brand: KEP-2320) was chopped and then added to an internal mixer together with 15 parts by mass of nano silica, and kneaded at 110℃for 5 minutes.
(2) Continuously adding 40 parts by mass of silicon rubber, 15 parts by mass of nano silicon dioxide and 3 parts by mass of ZnO, mixing for 10min, adding 1.5 parts by mass of 2, 5-dimethyl-2, 5-bishexane, continuously mixing for 5min, and discharging.
(3) After 24 hours of standing, the rubber compound was hot-pressed and vulcanized at 180℃and then subjected to mechanical and thermal decomposition tests.
Comparative example 2
The preparation procedure of the ethylene propylene diene monomer/silicone rubber blend is the same as in example 1, except that the compatibilizing agent added is replaced by maleic anhydride grafted polyethylene of equal mass, specifically as follows:
(1) 60 parts by mass of EPDM (brand: KEP-2320) was chopped and then added to an internal mixer together with 15 parts by mass of nano silica, and kneaded at 110℃for 5 minutes.
(2) Continuously adding 40 parts by mass of silicon rubber, 15 parts by mass of nano silicon dioxide, 3 parts by mass of ZnO and 2 parts by mass of maleic anhydride grafted polyethylene, mixing for 10min, adding 1.5 parts by mass of 2, 5-dimethyl-2, 5-bishexane, continuously mixing for 5min, and discharging.
(3) After 24 hours of standing, the rubber compound was hot-pressed and vulcanized at 180℃and then subjected to mechanical and thermal decomposition tests.
Comparative example 3
The procedure for the preparation of the ethylene propylene diene monomer/silicone rubber blend is the same as in example 1, except that the compatibilizing agent added is replaced by an equal mass of octyltriethoxysilane, as follows:
(1) 60 parts by mass of EPDM (brand: KEP-2320) was chopped and then added to an internal mixer together with 15 parts by mass of nano silica, and kneaded at 110℃for 5 minutes.
(2) 40 parts by mass of silicon rubber, 15 parts by mass of nano silicon dioxide, 3 parts by mass of ZnO and 2 parts by mass of octyl triethoxysilane are continuously added, after mixing for 10min, 1.5 parts by mass of 2, 5-dimethyl-2, 5-bishexane is added, and after mixing for 5min, discharging is performed.
(3) After 24 hours of standing, the rubber compound was hot-pressed and vulcanized at 180℃and then subjected to mechanical and thermal decomposition tests.
Comparative example 4
The procedure for the preparation of the ethylene propylene diene monomer/silicone rubber blend was the same as in example 9, except that no compatibilizing agent was added, as follows:
(1) 60 parts by mass of EPDM (brand: KEP-430H) was chopped and then charged into an internal mixer together with 15 parts by mass of nano silica, and kneaded at 110℃for 5 minutes.
(2) Continuously adding 40 parts by mass of silicon rubber, 15 parts by mass of nano silicon dioxide and 3 parts by mass of ZnO, mixing for 10min, adding 1.5 parts by mass of 2, 5-dimethyl-2, 5-bishexane, continuously mixing for 5min, and discharging.
(3) After 24 hours of standing, the rubber compound was hot-pressed and vulcanized at 180℃and then subjected to mechanical and thermal decomposition tests.
Comparative example 5
The procedure for the preparation of the ethylene propylene diene monomer/silicone rubber blend was the same as in example 10, except that no compatibilizing agent was added, as follows:
(1) 60 parts by mass of EPDM (trade name: 3745P) was chopped, and then charged into an internal mixer together with 15 parts by mass of nano silica, and kneaded at 110℃for 5 minutes.
(2) Continuously adding 40 parts by mass of silicon rubber, 15 parts by mass of nano silicon dioxide and 3 parts by mass of ZnO, mixing for 10min, adding 1.5 parts by mass of 2, 5-dimethyl-2, 5-bishexane, continuously mixing for 5min, and discharging.
(3) After 24 hours of standing, the rubber compound was hot-pressed and vulcanized at 180℃and then subjected to mechanical and thermal decomposition tests.
Ethylene propylene diene monomer rubber/silicone rubber combination prepared in each example and comparative example was tested for elongation at 20mm/min using a Zwick/Roell Z020 universal tester, and the results are summarized in table 1:
TABLE 1
The ethylene propylene diene monomer KEP-2320 and the silicone rubber are directly blended to prepare the combined rubber in comparative example 1, no compatilizer is added, the mechanical strength is poor, the tensile strength and the elongation at break are only 8.3MPa and 580% respectively, and the ethylene/cyclodiene/polysiloxane copolymers with different compositions are added in examples 1-6 as compatilizers, so that the tensile strength and the elongation at break are both greatly improved. Comparative examples 1 and 2 show that the terpolymer prepared by copolymerizing ethylnorbornyl polysiloxane has better effect of modifying and compatibilizing ethylene propylene diene monomer/silicone rubber and rubber, and the reason is probably due to the fact that the ethylnorbornyl polysiloxane has higher insertion capability during copolymerization, so that higher polysiloxane content in the terpolymer can be realized, and the interfacial tension of the ethylene propylene diene monomer and the silicone rubber is better reduced. Comparative examples 1 and 5 show that when the prepared terpolymers are ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymers, there is a difference in the effect of compatibilizing the ethylene propylene diene monomer/silicone rubber blends, which is probably due to the difference in the mass fraction of polysiloxane segments in the copolymers; experiments show that when the mass fraction of the polysiloxane chain segment in the copolymer is closer to that of the silicone rubber in the rubber, the modification effect is better; in addition, the mass fraction of polysiloxane segments of the terpolymers of examples 1, 3 and 4 is close, but the modification is better when the cyclic diene is ethylidene norbornene, probably because the third monomer in the ethylene-propylene-diene monomer is also usually ethylidene norbornene, and the ethylidene norbornene units in the ethylene/ethylidene norbornene/ethylnorbornenyl polysiloxane terpolymer are better able to co-vulcanize with the ethylene-propylene-diene monomer, thereby achieving a stronger compatibilizing effect by chemical bonding.
Examples 1 and 7 to 9 compare the effect of the ethylene/ethylidene norbornene/ethylnorbornene based polysiloxane terpolymer content on the mechanical properties of ethylene propylene diene monomer/silicone rubber and rubber, and when the addition amount is 2 parts, the tensile strength and elongation at break of the rubber reach 11.5MPa and 878%, respectively, which are improved by 38.5% and 51.3% compared with the non-compatibilized comparative example 1, and the optimal compatibilization effect is achieved. The comparative examples 2 and 3, to which 2 parts of maleic anhydride grafted polyethylene and octyltriethoxysilane, respectively, are added, they are widely used as compatibilizers for ethylene propylene diene monomer rubber and silicone rubber, but the tensile strength improvement of the ethylene propylene diene monomer rubber/silicone rubber combined rubber in comparative examples 2 and 3 is not obvious, demonstrating that the compatibilizing effect of maleic anhydride grafted polyethylene and octyltriethoxysilane is far inferior to that of ethylene/ethylidene norbornene/ethylnorbornene based polysiloxane copolymer.
In examples 10 and 11, the ethylene propylene diene monomer KEP-2320 in example 1 was replaced by KEP-430H and 3745P, respectively, to investigate the compatibilizing effect of the ethylene/cyclodiene/polysiloxane copolymer of the present invention when blending different grades of ethylene propylene diene monomer and silicone rubber. Compared with comparative example 4 and comparative example 5, the ethylene propylene diene monomer/silicone rubber blend prepared by using the ethylene/cyclodiene/polysiloxane copolymer disclosed by the invention as a compatilizer has greatly improved tensile strength and elongation at break. Proved to have universality on the preparation of ethylene propylene diene monomer/silicone rubber combined rubber with excellent mechanical properties for ethylene propylene diene monomer/cyclodiene/polysiloxane copolymers with different brands.
Thermal decomposition tests were performed on a part of the ethylene propylene diene monomer rubber/silicone rubber and rubber prepared in examples and comparative examples under nitrogen atmosphere, using TAQ 500, at a heating rate of 10 ℃/min, and after the sample was warmed from room temperature to 100 ℃ for 5 minutes, the temperature was kept constant and then was continued to be raised to 800 ℃, and the results are summarized in table 2:
TABLE 2
The mass in comparative example 1 was reduced by 1% and 5% at the corresponding temperature (T 1 And T 5 ) Only 337.6 and 410.0 ℃, the ethylene propylene diene monomer rubber/silicone rubber combined rubber prepared by the comparative example has poor heat stability, and the excellent heat stability of the silicone rubber cannot be fully exerted. T of the combined glue is improved after the ethylene/cyclodiene/polysiloxane copolymer is added 1 And T 5 In particular, in example 1, when 2 parts of an ethylene/ethylidene norbornene polysiloxane terpolymer are added, T 5 The temperature is increased by 46.2 ℃, and the thermal stability is obviously improved. Comparative example 2 and comparative example 3 were added maleic anhydride grafted polyethylene and octyltriethoxysilane, although T 1 And T 5 But the improvement is far inferior to that of ethylene/cyclodiene/polysiloxane copolymer.
It can also be seen from the SEM images of the fracture surfaces of the ethylene propylene diene monomer/silicone rubber separately prepared in example 1 and comparative example 1 that in example 1 after the ethylene/cyclodiene monomer/silicone copolymer was added, the phase interface between the ethylene propylene diene monomer and the silicone rubber became difficult to observe, and a two-phase continuous structure was shown to have good dispersibility.
In summary, ethylene/cyclo-diene/polysiloxane copolymer ethylene propylene diene/silicone rubber combined rubber added in the blending process has excellent mechanical property and thermal stability, and particularly ethylene/ethylidene norbornene/ethylnorbornene-based polysiloxane terpolymer is selected, and when the addition amount is 2 parts, the combined rubber performance is optimal, and the material can be used for high temperature resistant transmission belts, damping materials, oil resistant automobile elements and the like and has a very high application prospect.
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 high-performance ethylene propylene diene monomer/silicone rubber combined rubber is characterized by comprising the following raw materials in parts by weight:
the compatilizer is selected from ethylene/cyclodiene/siloxane terpolymer, and has the following structural general formula:
wherein x is a natural number of 10 to 200, y is a natural number of 500 to 2000, z is a natural number of 1 to 100, and n is a natural number of 1 to 12;
R 1 selected from the group consisting ofR 2 Selected from->
When the content of the silicone rubber in the base material of the ethylene propylene diene monomer rubber/silicone rubber blend formula is A%, the mass ratio of the silicone chain segments in the ethylene/cyclodiene/silicone terpolymer is A+/-10%.
2. The high performance ethylene propylene diene monomer/silicone rubber combination of claim 1, wherein:
the ethylene propylene diene monomer comprises 50-70wt% of vinyl and 0.5-9.5wt% of third monomer;
the silicon rubber is methyl vinyl silicon rubber, and the vinyl content is 0.2-0.8 mol%;
the vulcanizing agent is selected from 2, 5-dimethyl-2, 5-bis hexane and/or dicumyl peroxide;
the vulcanization aid is one or more selected from zinc oxide, stearic acid and silicone oil.
3. The high performance ethylene propylene diene monomer/silicone rubber combination of claim 1, further comprising a filler in the raw material composition;
the filler is selected from nano silica and/or carbon black.
4. A method for preparing the high-performance ethylene propylene diene monomer/silicone rubber hybrid rubber according to any one of claims 1 to 3, comprising:
(1) Performing hydrosilylation reaction on dimethyl monochlorosilane and diene under a platinum catalyst to prepare olefin functional dimethyl chlorosilane;
the diene is selected from one or more of 1, 5-hexadiene, 1, 7-octadiene, 1, 9-decadiene, 1, 11-dodecadiene, 5-vinyl-2-norbornene, 2, 5-norbornene diene and 4-vinyl-1-cyclohexene;
(2) N-butyllithium initiates hexamethylcyclotrisiloxane to carry out anion ring-opening polymerization, and the alkene functional dimethyl chlorosilane prepared in the step (1) is used as a blocking agent to synthesize alkene functional polysiloxane;
(3) Initiating ethylene and cyclodiolefin and olefin functional polysiloxane prepared in the step (2) to carry out coordination copolymerization by using a Ziegler-Natta catalyst or a metallocene catalyst, and obtaining an ethylene/cyclodiolefin/polysiloxane terpolymer after post-treatment;
the cyclodiolefin is selected from one or more of ethylidene norbornene, 5-vinyl-2-norbornene, cyclopentadiene and 4-ethylene-1-cyclohexene;
(4) Mixing all the raw materials except the vulcanizing agent uniformly, then mixing for a period of time, adding the vulcanizing agent, and after mixing uniformly, performing hot press molding and vulcanization to obtain the ethylene propylene diene monomer rubber/silicone rubber composite rubber.
5. The method for preparing the high-performance ethylene propylene diene monomer/silicone rubber blend according to claim 4, wherein in the step (1):
the molar ratio of dimethyl monochlorosilane to diolefin is 1:2 to 10;
the temperature of the hydrosilylation reaction is 0-100 ℃.
6. The method for preparing the high-performance ethylene propylene diene monomer/silicone rubber blend according to claim 4, wherein in the step (2):
the molar ratio of n-butyllithium to hexamethylcyclotrisiloxane is 1:1 to 12;
the temperature of the anionic ring-opening polymerization is-20 to 50 ℃;
the addition amount of the alkene functional dimethyl chlorosilane is 1.05 to 1.10 times of the molar amount of the n-butyl lithium.
7. The method for preparing the high-performance ethylene propylene diene monomer/silicone rubber blend according to claim 4, wherein in the step (3):
the molar ratio of cyclic diolefins to olefin functional polysiloxanes is 1:1 to 10;
after ethylene is introduced, the pressure in the system is kept at 0.1-1.0 MPa;
the temperature of coordination copolymerization is 0-70 ℃;
the post-treatment comprises washing and drying.
8. The method for preparing the high-performance ethylene propylene diene monomer/silicone rubber blend according to claim 4, wherein in the step (4):
the temperature of the mixing is 70-130 ℃;
the temperature of the hot press molding and the vulcanization is 150-180 ℃.
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| CN112225852A (en) * | 2020-09-28 | 2021-01-15 | 浙江大学 | Polysiloxane functionalized ethylene-norbornene copolymer and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104672463A (en) * | 2015-01-21 | 2015-06-03 | 浙江大学 | Polyalkysiloxane-polyolefin segmented copolymer as well as preparation method and application 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 |
| CN109867789A (en) * | 2017-12-04 | 2019-06-11 | 北京化工大学 | A kind of compatilizer and preparation method thereof improving ethylene propylene diene rubber and silicon rubber comixing compatibility |
| CN111363102A (en) * | 2020-03-18 | 2020-07-03 | 浙江大学 | Ethylene- α olefin-polyfluorosiloxane ternary graft copolymer and preparation method thereof |
| CN112225852A (en) * | 2020-09-28 | 2021-01-15 | 浙江大学 | Polysiloxane functionalized ethylene-norbornene copolymer and preparation method thereof |
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