CN114874394B - Ethylene propylene diene monomer rubber and preparation method and application thereof - Google Patents
Ethylene propylene diene monomer rubber and preparation method and application thereof Download PDFInfo
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 40
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 40
- 239000000178 monomer Substances 0.000 claims abstract description 28
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000005977 Ethylene Substances 0.000 claims abstract description 14
- 229920001971 elastomer Polymers 0.000 claims abstract description 13
- 239000005060 rubber Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 11
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- -1 ethylene, propylene Chemical group 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 150000003682 vanadium compounds Chemical class 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 13
- 230000004913 activation Effects 0.000 claims description 12
- 230000003712 anti-aging effect Effects 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009826 distribution Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 150000004820 halides Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- SJMLNDPIJZBEKY-UHFFFAOYSA-N ethyl 2,2,2-trichloroacetate Chemical group CCOC(=O)C(Cl)(Cl)Cl SJMLNDPIJZBEKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000004566 building material Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 abstract description 30
- 238000005516 engineering process Methods 0.000 abstract description 6
- 238000010060 peroxide vulcanization Methods 0.000 abstract description 4
- 238000010059 sulfur vulcanization Methods 0.000 abstract description 4
- 229920000181 Ethylene propylene rubber Polymers 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 229920003051 synthetic elastomer Polymers 0.000 abstract description 2
- 239000005061 synthetic rubber Substances 0.000 abstract description 2
- 239000004636 vulcanized rubber Substances 0.000 abstract description 2
- 238000004132 cross linking Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000001993 dienes Chemical class 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000004513 sizing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- 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
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
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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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The application relates to the field of synthetic rubber, and discloses ethylene propylene diene monomer rubber and a preparation method and application thereof. The ethylene propylene diene monomer takes liquid polybutadiene as a third monomer, the number average molecular weight of the liquid polybutadiene is 200-5000, and the content of 1, 2-structures is more than 80% by weight based on the total weight of the liquid polybutadiene; based on the total weight of the ethylene propylene diene monomer, the content of the ethylene structural unit is 50-80 wt% and the content of the third monomer structural unit is 0.5-10 wt%. In the ethylene propylene diene monomer, the liquid polybutadiene is used as a third monomer, and the prepared ethylene propylene rubber can be applicable to peroxide and sulfur vulcanization, has better fluidity in the initial stage of vulcanization, ensures the performance of vulcanized rubber, can be applicable to continuous vulcanization processing technology, can be used for preparing industrial rubber products such as automobile parts, waterproof coiled materials, wires and cables and the like, and is particularly applicable to preparing thermoplastic elastomer materials through dynamic vulcanization.
Description
Technical Field
The application relates to the field of synthetic rubber, in particular to ethylene propylene diene monomer rubber and a preparation method and application thereof.
Background
Ethylene propylene rubber is an ethylene-propylene copolymer, a small amount of non-conjugated diene is introduced for convenient vulcanization, and the ethylene propylene rubber is generally used as thermosetting rubber or an EPDM/PP dynamic vulcanized thermoplastic elastomer TPV material and is widely used in industries of household appliances, wires and cables, buildings, automobiles and the like. Currently ethylene propylene diene monomer rubber typically uses ethylidene norbornene ENB as the third monomer. The ENB has high reactivity, and the generated copolymer has high vulcanization speed, and is the third monomer which is most widely used in industry.
Because ENB is expensive, and can greatly reduce polymerization activity, has strong stink-stimulating toxicity, is difficult to remove, and is unfavorable for environmental protection. For this reason CN101709105a discloses ethylene propylene diene monomer with a liquid oligomer of diolefin as the third monomer and a process for its preparation. The mol fraction of the combined propylene units in the ethylene propylene diene monomer is 20-45%, the third monomer is a diolefin liquid oligomer, the mol fraction of the combined units of the third monomer in the ethylene propylene diene monomer is 0.5-15%, and the total number of the combined units of ethylene, propylene and the third monomer is 100%; the third monomer diene liquid oligomer is liquid polybutadiene with a1, 2-structure content of 20-80% or liquid polyisoprene with a1, 4-structure of more than 90% and has different double bond structures and different double bond contents. The side chain contains more double bonds, so that the sulfur-containing modified polyurethane has good vulcanization performance, can be vulcanized by sulfur, and has good processability; the polymer has a molecular weight distribution index of 2 to 10; can be used for manufacturing industrial rubber products of automobile parts, waterproof materials, telecommunication cables and the like.
However, the crosslinking degree of the ethylene propylene diene monomer rubber in the prior art is rapidly improved at the initial stage of vulcanization, so that the flowability of the rubber material in the vulcanization process is poor, and the prepared product has vulcanization defects or cannot be suitable for a continuous vulcanization processing technology.
Disclosure of Invention
Based on the prior art, in order to solve the problems of the third monomer for producing the ethylene propylene diene monomer in practical application in technical economy, the limitation of the existing third monomer is broken through, the liquid polybutadiene with high 1, 2-structure content is used as the third monomer, and the prepared ethylene propylene diene monomer can be vulcanized by sulfur and peroxide, has better fluidity in the initial vulcanization stage, ensures the performance of vulcanized rubber, and can be suitable for continuous vulcanization processing technology.
In order to achieve the above object, according to a first aspect of the present application, there is provided an ethylene propylene diene monomer, wherein the ethylene propylene diene monomer uses liquid polybutadiene as a third monomer, the number average molecular weight of the liquid polybutadiene is 200-5000, and the content of 1,2 structures is more than 80wt% based on the total weight of the liquid polybutadiene;
based on the total weight of the ethylene propylene diene monomer, the content of the ethylene structural unit is 50-85 wt% and the content of the third monomer structural unit is 0.5-10 wt%.
The second aspect of the application provides a method for preparing ethylene propylene diene monomer, which is characterized by comprising the following steps: introducing mixed gas containing ethylene, propylene and hydrogen in the presence of inert atmosphere and a solvent, sequentially adding an activation accelerator, liquid polybutadiene, an aluminum alkyl compound and a vanadium compound, and carrying out polymerization reaction to obtain the ethylene propylene diene monomer;
the number average molecular weight of the liquid polybutadiene is 200-5000, and the content of 1,2 structures is more than 80wt% based on the total weight of the liquid polybutadiene.
The third aspect of the application provides ethylene propylene diene monomer rubber prepared by the method.
The fourth aspect of the application provides an application of the ethylene propylene diene monomer in preparing rubber products and thermoplastic elastomer composite materials.
Through the technical scheme, the ethylene propylene diene monomer rubber provided by the application and the preparation method and application thereof have the following beneficial effects:
the application adopts liquid 1, 2-polybutadiene as the third monomer, can effectively copolymerize with ethylene and propylene, and has higher polymerization activity and high conversion rate of the comonomer. Compared with the traditional ethylene propylene diene monomer, the side chain contains more double bonds, so that the sulfur vulcanization is easy, and the peroxide vulcanization is facilitated. Particularly, the ethylene propylene diene monomer provided by the application has low crosslinking rate in the initial vulcanization stage, so that the ethylene propylene diene monomer has good processability in the initial vulcanization stage, and can be suitable for continuous vulcanization processing technologies such as a double-screw extruder and the like.
Further, the ethylene propylene diene monomer rubber provided by the application can be used for preparing industrial rubber products such as automobile parts, waterproof coiled materials, wires and cables, and the like, and is particularly suitable for being applied to preparing thermoplastic elastomer materials through dynamic vulcanization, including but not limited to industries such as household appliances, wires and cables, buildings, automobiles, and the like.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The application provides ethylene propylene diene monomer, which is characterized in that the ethylene propylene diene monomer takes liquid polybutadiene as a third monomer, the number average molecular weight of the liquid polybutadiene is 200-5000, and the content of 1, 2-structures is more than 80wt% based on the total weight of the liquid polybutadiene;
based on the total weight of the ethylene propylene diene monomer, the content of the ethylene structural unit is 50-85 wt% and the content of the third monomer structural unit is 0.5-10 wt%.
In the application, the ethylene propylene diene monomer contains a third monomer structural unit which is liquid polybutadiene. Compared with the traditional ethylene propylene diene monomer, the side chain contains more double bonds, so that the sulfur vulcanization is easy, and the peroxide vulcanization is facilitated.
Further, the ethylene propylene diene monomer provided by the application has low crosslinking rate in the initial vulcanization stage, so that the ethylene propylene diene monomer has good processability in the initial vulcanization stage, and the ethylene propylene diene monomer can be suitable for continuous vulcanization processing technologies such as a double-screw extruder and the like.
Further, when the number average molecular weight of the liquid polybutadiene is 500 to 5000 and the content of 1, 2-structures is 81 to 95% by weight based on the total weight of the liquid polybutadiene, the initial crosslinking rate of the obtained ethylene propylene diene monomer rubber at the initial stage of vulcanization is further reduced, so that the processability of the rubber during vulcanization is further improved.
According to the application, the content of ethylene structural units is 55-80 wt% and the content of the third monomer structural units is 1-8 wt%, based on the total weight of the ethylene propylene diene monomer.
According to the application, the number average molecular weight of the ethylene propylene diene monomer is 7-40 ten thousand, preferably 10-30 ten thousand; the molecular weight distribution of the ethylene propylene diene monomer is 2-4, preferably 2-3.
The second aspect of the application provides a method for preparing ethylene propylene diene monomer, which is characterized by comprising the following steps: introducing mixed gas containing ethylene, propylene and hydrogen in the presence of inert atmosphere and a solvent, sequentially adding an activation accelerator, liquid polybutadiene, an aluminum alkyl compound and a vanadium compound, and carrying out polymerization reaction to obtain the ethylene propylene diene monomer;
the number average molecular weight of the liquid polybutadiene is 200-5000, and the content of 1, 2-structure is more than 80wt% based on the total weight of the liquid polybutadiene.
The application adopts liquid polybutadiene as a third monomer, can effectively copolymerize with ethylene and propylene, has higher polymerization activity and high conversion rate of the comonomer. Compared with the traditional ethylene propylene diene monomer, the side chain contains more double bonds, so that the sulfur vulcanization is easy, and the peroxide vulcanization is facilitated. Particularly, the ethylene propylene diene monomer provided by the application has the characteristic of low initial vulcanization speed, so that the ethylene propylene diene monomer has good processability in the initial vulcanization stage, and can be suitable for continuous vulcanization processing technologies such as a double-screw extruder and the like.
Further, the number average molecular weight of the liquid polybutadiene is 500-5000, and the content of 1, 2-structure is 81-95 wt% based on the total weight of the liquid polybutadiene.
According to the application, in the mixed gas, the mol ratio of ethylene to propylene is 1:10-3:4, a step of; the molar content of the hydrogen is 0.2 to 2mol% based on the total amount of the substances of the mixed gas.
Further, in the mixed gas, the molar ratio of ethylene to propylene is 1:10-3:4, a step of; the molar content of the hydrogen is 0.3 to 1.8mol% based on the total amount of the substances of the mixed gas.
According to the application, the molar ratio of the alkyl aluminum compound to the vanadium compound is between 1 and 50:1, the molar ratio of the activation accelerator to the vanadium compound is 10-40:1. in the application, when the dosage of the alkyl aluminum compound, the activation accelerator and the vanadium compound meets the above range, the effect of higher polymerization activity can be obtained, and the prepared ethylene propylene diene monomer has the characteristic of narrower molecular weight distribution.
Further, when the molar ratio of the alkyl aluminum compound to the vanadium compound is 5 to 30:1, a step of; when the molar ratio of the activation accelerator to the vanadium compound is 15-30:1, the ethylene propylene diene monomer prepared by the method has more excellent comprehensive performance.
According to the present application, the activation accelerator is at least one selected from the group consisting of halides, sulfonyl chloride compounds and oxygen-containing nitrogen-containing compounds, preferably ethyl trichloroacetate.
According to the application, the alkyl aluminum compound is selected from AlR 3 、AlR 2 X、Al 2 R 3 X 3 And AlRX 2 Wherein R is C 1 -C 8 X is halogen.
According to the present application, the vanadium compound is selected from a +4 valent metal vanadium compound and/or a +5 valent metal vanadium compound, preferably at least one of a halide, an oxyhalide, an organic acid salt, and an organic acid ester.
In the present application, the solvent is a saturated alkane of C5-C10, preferably hexane.
According to the application, the polymerization conditions include: the polymerization pressure is 0.1MPa to 1MPa; the polymerization temperature is-30 ℃ to 50 ℃; the polymerization time is 5-30min. In the application, the polymerization reaction of ethylene, propylene and the third monomer is carried out under the polymerization reaction condition, so that the catalyst system can have higher catalytic activity, the third monomer can be copolymerized with the ethylene and the propylene, the conversion rate of the comonomer is higher, and the ethylene propylene diene monomer with liquid polybutadiene as the third monomer is prepared.
Further, the polymerization conditions include: the polymerization pressure is 0.3MPa to 0.8MPa; the polymerization temperature is-20 ℃ to 30 ℃; the polymerization time is 10-20min.
According to the application, the preparation method of the ethylene propylene diene monomer rubber further comprises the step of adding a terminator and/or an anti-aging agent after the polymerization reaction.
According to the application, the terminator is selected from water and/or an alcohol, preferably ethanol.
According to the application, the terminators are used in amounts of 0.1 to 2ml/L, preferably 0.5 to 1.5ml/L.
According to the application, the anti-ageing agent is selected from phenolic and/or amine anti-ageing agents.
In the present application, the antioxidant is at least one selected from the group consisting of an antioxidant 1520, an antioxidant 1010 and an antioxidant 168 combined type, an antioxidant 1076 and an antioxidant 168 combined type, an antioxidant 264 and an antioxidant 1076.
According to the application, the anti-ageing agent is used in an amount of 0.005 to 2% by weight, preferably 0.01 to 1% by weight.
In one specific embodiment of the application, the ethylene propylene diene monomer is prepared according to the following steps:
repeatedly replacing the stainless steel reactor with nitrogen for three times, adding quantitative solvent according to design, introducing mixed gas of ethylene, propylene and hydrogen, stirring, sequentially and quantitatively adding an activation accelerator, liquid polybutadiene, an aluminum alkyl compound and a vanadium compound, controlling the polymerization pressure between 0.1 and 1MPa, reacting for 5 to 30min at the temperature of between minus 30 and 50 ℃, adding a terminator and an anti-aging agent after polymerization, and condensing and drying in a conventional mode.
The third aspect of the application provides ethylene propylene diene monomer produced by the above process.
The fourth aspect of the application provides the use of the ethylene propylene diene monomer rubber described above in the preparation of rubber articles and thermoplastic elastomer composites.
Preferably, the ethylene propylene diene monomer is applied to at least one of automobile parts, building materials, wires and cables and household appliances.
The present application will be described in detail by examples.
The microstructure of the ethylene propylene diene monomer rubber adopts a Bruker AVANCE400 superconducting nuclear magnetic resonance spectrometer of Bruker company in the United states 1 H-NMR) determination, the solvent was deuterated chloroform CDCl 3 ；
The number average molecular weight and molecular weight distribution of the ethylene propylene diene monomer are measured by a high temperature Gel Permeation Chromatograph (GPC), trichlorobenzene is a mobile phase, and the temperature is 135 ℃;
the glass transition temperature of the ethylene propylene diene monomer is measured by using a type MDSC2910 Differential Scanning Calorimeter (DSC) of the company TA of America;
the other raw materials used in the examples and comparative examples are all commercially available.
Examples 1 to 6
In a 2 liter stainless steel stirring kettle, under the protection of high-purity nitrogen, introducing mixed gas with the molar ratio of ethylene to propylene of 1 to reach 0.6 MPa: 5, hydrogen content 0.5mol%, stirring, adding 1000ml of hexane, 1mmol of ethyl trichloroacetate, 2mmol of aluminum sesquioxide Al 2 (C 2 H 5 ) 3 Cl 3 A quantity of liquid polybutadiene A (number average molecular weight 3000,1,2-content of structure 85% by weight), 0.1mmol of VOCl 3 The reaction was carried out at 10℃for 15min. After the polymerization was completed, 1ml of ethanol as a terminator and 1ml of age resistor 1076 (10 wt% hexane solution) were added, followed by coagulation and drying in a conventional manner to obtainEthylene propylene diene rubbers EPDM-A1 to EPDM-A6 were subjected to GPC, NMR, DSC test, and the results are shown in Table 1.
Example 7
EPDM was prepared as in preparation example 1, except that: the content of 1,2 structures in the liquid polybutadiene was 90% by weight. EPDM-A7 was prepared.
Comparative example 1
EPDM was prepared as in preparation example 1, except that: the content of 1, 2-structures in the liquid polybutadiene was 60% by weight. EPDM-D1 was prepared.
Comparative example 2
EPDM was prepared as in preparation example 1, except that: the content of 1,2 structures in the liquid polybutadiene was 80% by weight. EPDM-D2 was prepared.
Comparative example 3
The third monomer is EPDM, brand 3092PM for ENB.
TABLE 1 EPDM performance parameters from examples 1-7 and comparative examples 1-3
Examples 8 to 12
EPDM was prepared according to the method of example 1, except that EPDM-A8, EPDM-A9, EPDM-A10, EPDM-A11, EPDM-A12 were prepared under different polymerization conditions, and the performance parameters of EPDM are shown in Table 2.
TABLE 2
Test case
(1) Preparation of the rubber compound:
100 parts by weight of EPDM prepared in examples 1 to 12 and comparative examples 1 to 3, 0.3 part by weight of peroxide F40-P, and 2 parts by weight of zinc oxide were added to an open mill, and kneaded at 50.+ -. 5 ℃ for 20 minutes to obtain rubber compounds H1 to H12 and rubber compounds DH1 to DH3, respectively.
(2) And (3) testing by a vulcanizing instrument:
the test examples are used to demonstrate the vulcanization properties of EPDM-A1-EPDM-A12 and of the comparative EPDM-D1-EPDM-D3.
Minimum torques for the rubber mixtures H1 to H12 and DH1 to DH3, respectively, were determined according to the GB/T16584-1996 standard (S min ) Maximum torque (S) max ) Tests were performed on Ts1 and Tc90, and the test conditions included: the temperature was 200℃and the test time was 10 minutes. The results obtained are shown in Table 3. Wherein, ts1 represents the time when the torque of the sizing material reaches (minimum torque+1), and the vulcanizing of the sizing material is just started at the moment and can be indirectly regarded as the time when the vulcanizing of the sizing material is just started; t90 represents the time for the compound to reach 90% cure. Calculated, a torque difference Δs=s is obtained max -S min 。
TABLE 3 Table 3
| Project | H1 | H2 | H3 | H4 | H5 | H6 | H7 | H8 | H9 |
| S min /N·m | 1.38 | 1.36 | 1.32 | 1.31 | 1.28 | 1.27 | 1.23 | 1.3 | 1.3 |
| △S/N·m | 8.96 | 9.04 | 9.02 | 9.05 | 9.09 | 9.18 | 9.57 | 8.98 | 9.05 |
| Ts1/min | 0.59 | 0.61 | 0.61 | 0.63 | 0.63 | 0.65 | 0.77 | 0.59 | 0.63 |
| t90/min | 3.61 | 3.60 | 3.61 | 3.62 | 3.61 | 3.62 | 3.73 | 3.60 | 3.62 |
Table 3 (subsequent)
As can be seen from Table 3, the EPDM prepared in examples 1-12 had a lower minimum torque and a higher Ts1 than the EPDM prepared in comparative examples 1-3; at the same time, the EPDM prepared in examples 1-12 gave a much higher torque difference than the EPDM prepared in comparative examples 1-3. From this, it was revealed that the EPDM prepared in examples 1 to 12 of the present application hardly underwent crosslinking at the initial stage of vulcanization during vulcanization, and that the torque significantly increased with the increase in the vulcanization time, indicating that the crosslinking bond formed rapidly in EPDM and the degree of crosslinking increased. The EPDM provided by the application is not easy to be burnt in the early stage of crosslinking, has excellent processability in the vulcanization processing process due to lower crosslinking degree, is suitable for continuous vulcanization processes such as a double-screw extruder and the like, and has obviously increased crosslinking rate in the later stage of crosslinking, so that the comprehensive performance of the crosslinked EPDM can be obviously improved.
The preferred embodiments of the present application have been described in detail above, but the present application is not limited thereto. Within the scope of the technical idea of the application, a number of simple variants of the technical solution of the application are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the application, all falling within the scope of protection of the application.
Claims (20)
1. The ethylene propylene diene monomer is characterized in that the ethylene propylene diene monomer takes liquid polybutadiene as a third monomer, the number average molecular weight of the liquid polybutadiene is 200-5000, and the content of 1, 2-structures is more than or equal to 81wt% based on the total weight of the liquid polybutadiene;
based on the total weight of the ethylene propylene diene monomer, the content of the ethylene structural unit is 50-85 wt% and the content of the third monomer structural unit is 0.5-10 wt%.
2. Ethylene propylene diene monomer according to claim 1, wherein the liquid polybutadiene has a number average molecular weight of 500 to 5000 and a content of 1, 2-structure of 81 to 95% by weight, based on the total weight of the liquid polybutadiene.
3. Ethylene propylene diene monomer according to claim 1, wherein the content of ethylene structural units is from 55 to 80% by weight and the content of third monomer structural units is from 1 to 8% by weight, based on the total weight of the ethylene propylene diene monomer.
4. Ethylene propylene diene monomer according to any one of claims 1 to 3, wherein the ethylene propylene diene monomer has a number average molecular weight of 7 to 40 ten thousand; the molecular weight distribution of the ethylene propylene diene monomer is 2-4.
5. The ethylene propylene diene monomer rubber according to claim 4, wherein the number average molecular weight of the ethylene propylene diene monomer rubber is 10-30 ten thousand; the molecular weight distribution of the ethylene propylene diene monomer is 2-3.
6. A process for preparing ethylene propylene diene monomer according to any one of claims 1 to 5, characterized in that it comprises the steps of: introducing mixed gas containing ethylene, propylene and hydrogen in the presence of inert atmosphere and a solvent, sequentially adding an activation accelerator, liquid polybutadiene, an aluminum alkyl compound and a vanadium compound, and carrying out polymerization reaction to obtain the ethylene propylene diene monomer;
the number average molecular weight of the liquid polybutadiene is 200-5000, and the content of 1, 2-structure is more than or equal to 81wt% based on the total weight of the liquid polybutadiene.
7. The process according to claim 6, wherein the liquid polybutadiene has a number average molecular weight of 500 to 5000 and a content of 1, 2-structure of 81 to 95% by weight, based on the total weight of the liquid polybutadiene.
8. The method according to claim 6, wherein the molar ratio of ethylene to propylene in the mixed gas is 1:10-3:4, a step of; the molar content of the hydrogen is 0.2 to 2mol% based on the total amount of the substances of the mixed gas.
9. The method of claim 8, wherein the molar ratio of ethylene to propylene in the mixed gas is 1:9-5:7, preparing a base material; the molar content of the hydrogen is 0.3 to 1.8mol% based on the total amount of the substances of the mixed gas.
10. The method of any of claims 6-9, wherein the molar ratio of the alkyl aluminum compound to the vanadium compound is from 1 to 50:1, a step of; the molar ratio of the activation accelerator to the vanadium compound is 10-40:1.
11. the method of claim 10, wherein the molar ratio of the alkyl aluminum compound to the vanadium compound is from 5 to 30:1, a step of; the molar ratio of the activation promoter to the vanadium compound is 15-30:1.
12. The method according to any one of claims 6 to 9, wherein the activation promoter is selected from at least one of a halide, a sulfonyl chloride compound and an oxygen-containing nitrogen-containing compound;
and/or the alkyl aluminum compound is selected from AlR 3 、AlR 2 X、Al 2 R 3 X 3 And AlRX 2 Wherein R is C 1 -C 8 X is halogen;
and/or the vanadium compound is selected from a +4 valent metal vanadium compound and/or a +5 valent metal vanadium compound.
13. The method of claim 12, wherein the activation promoter is ethyl trichloroacetate;
and/or the metal vanadium compound is selected from at least one of halides, oxyhalides, organic acid salts, and organic acid esters.
14. The method of any of claims 6-9, wherein the polymerization conditions include: the polymerization pressure is 0.1MPa to 1MPa; the polymerization temperature is-30 ℃ to 50 ℃; the polymerization time is 5-30min.
15. The method of claim 14, wherein the polymerization conditions comprise: the polymerization pressure is 0.3MPa to 0.8MPa; the polymerization temperature is-20 ℃ to 30 ℃; the polymerization time is 10-20min.
16. The method according to any one of claims 6 to 9, wherein the ethylene propylene diene monomer preparation method further comprises adding a terminator and/or an anti-aging agent after the polymerization reaction.
17. The method of claim 16, wherein the terminator is selected from water and/or alcohol;
and/or the dosage of the terminator is 0.1-2 ml/L;
and/or the anti-aging agent is selected from phenolic anti-aging agents and/or amine anti-aging agents;
and/or the usage amount of the anti-aging agent is 0.005-2wt%.
18. The method of claim 16, wherein the terminator is ethanol;
and/or the dosage of the terminator is 0.5-1.5ml/L;
and/or the usage amount of the anti-aging agent is 0.01-1wt%.
19. Use of the ethylene propylene diene monomer rubber according to any one of claims 1 to 5 for the preparation of rubber articles and thermoplastic elastomer composites.
20. The use according to claim 19, wherein the ethylene propylene diene monomer is used in at least one of automotive parts, building materials, electric wires and cables and household appliances.
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