CN113201094A - Nitrogen-containing functionalized SIBR (substrate oriented brake rubber) integrated rubber with star-shaped coupling structure and preparation method thereof - Google Patents
Nitrogen-containing functionalized SIBR (substrate oriented brake rubber) integrated rubber with star-shaped coupling structure and preparation method thereof Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 76
- 239000005060 rubber Substances 0.000 title claims abstract description 76
- 238000010168 coupling process Methods 0.000 title claims abstract description 45
- 230000008878 coupling Effects 0.000 title claims abstract description 44
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 44
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000758 substrate Substances 0.000 title description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 90
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 88
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000007822 coupling agent Substances 0.000 claims abstract description 42
- -1 alkyl lithium Chemical compound 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229920005683 SIBR Polymers 0.000 claims abstract 16
- ZMYIIHDQURVDRB-UHFFFAOYSA-N 1-phenylethenylbenzene Chemical group C=1C=CC=CC=1C(=C)C1=CC=CC=C1 ZMYIIHDQURVDRB-UHFFFAOYSA-N 0.000 claims abstract 4
- 239000003999 initiator Substances 0.000 claims description 79
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 28
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 26
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 9
- 230000000977 initiatory effect Effects 0.000 claims description 7
- GQWAOUOHRMHSHL-UHFFFAOYSA-N 4-ethenyl-n,n-dimethylaniline Chemical group CN(C)C1=CC=C(C=C)C=C1 GQWAOUOHRMHSHL-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 229920006029 tetra-polymer Polymers 0.000 claims description 5
- 229910007245 Si2Cl6 Inorganic materials 0.000 claims description 4
- 229910003910 SiCl4 Inorganic materials 0.000 claims description 4
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- CBZMQWPBAUBAPO-UHFFFAOYSA-N 4-ethenyl-n,n-diethylaniline Chemical group CCN(CC)C1=CC=C(C=C)C=C1 CBZMQWPBAUBAPO-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- OJHOCVDKOATZFS-UHFFFAOYSA-N n,n-ditert-butyl-4-ethenylaniline Chemical group CC(C)(C)N(C(C)(C)C)C1=CC=C(C=C)C=C1 OJHOCVDKOATZFS-UHFFFAOYSA-N 0.000 claims description 2
- 125000004355 nitrogen functional group Chemical group 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 46
- 239000006229 carbon black Substances 0.000 abstract description 5
- 238000005096 rolling process Methods 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 229920005604 random copolymer Polymers 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 238000006116 polymerization reaction Methods 0.000 description 31
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 238000009826 distribution Methods 0.000 description 19
- 229920001577 copolymer Polymers 0.000 description 17
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 17
- 229920001195 polyisoprene Polymers 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 14
- 229910052786 argon Inorganic materials 0.000 description 14
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 7
- 239000005977 Ethylene Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 2
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- YNXURHRFIMQACJ-UHFFFAOYSA-N lithium;methanidylbenzene Chemical compound [Li+].[CH2-]C1=CC=CC=C1 YNXURHRFIMQACJ-UHFFFAOYSA-N 0.000 description 2
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VLLYOYVKQDKAHN-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene Chemical compound C=CC=C.CC(=C)C=C VLLYOYVKQDKAHN-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920006247 high-performance elastomer Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PCZZEOGNRZGGBK-UHFFFAOYSA-N n,n-dimethyl-4-(1-phenylethyl)aniline Chemical compound C=1C=C(N(C)C)C=CC=1C(C)C1=CC=CC=C1 PCZZEOGNRZGGBK-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000003643 water by type 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/08—Isoprene
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
Abstract
The invention belongs to the technical field of high polymer materials, and provides a nitrogen-containing functionalized SIBR integrated rubber with a star-shaped coupling structure and a preparation method thereof, wherein the nitrogen-containing functionalized SIBR integrated rubber is a multi-arm star-shaped coupling agent coupling quaternary random copolymer of a 1, 1-diphenylethylene functional monomer containing a nitrogen group and styrene, butadiene and isoprene, which are initiated by alkyl lithium and under the action of a polar regulator. According to the invention, a three-arm, four-arm and six-arm coupling mode is adopted, and the relative content of the nitrogen substituted 1, 1-diphenylethylene in a polymer chain can be remarkably improved with high coupling efficiency. The performance of the nitrogenous functionalized SIBR integrated rubber with a star-shaped coupling structure is remarkably improved compared with that of general rubber and rubber with a linear structure, the processability of the integrated rubber is improved, the compatibility of the integrated rubber and carbon black is improved, the rolling resistance and the energy consumption of the rubber are reduced, and the product is a high-end product of the rubber.
Description
Technical Field
The invention belongs to the technical field of functional polymer materials, and particularly relates to a nitrogen-containing functionalized SIBR (substrate polymer blend rubber) integrated rubber with a star-shaped coupling structure and a preparation method thereof.
Background
Rubber is an important raw material in the tire industry, the development of high-performance rubber is a necessary trend of industrial development, the automobile industry puts forward requirements on low rolling resistance, high wet skid resistance and good wear resistance on tires, but due to the existence of rubber 'magic triangles', general-purpose rubber such as Styrene Butadiene Rubber (SBR), polybutadiene rubber (BR) and Natural Rubber (NR) can only adopt a method of blending different rubber types to obtain tread rubber with expected performance, can only reach a homogeneous phase on a macroscopic scale, has serious micro phase separation, and seriously limits the comprehensive performance of the rubber. Therefore, the design concept of molecular integration is adopted, the advantages of the general rubber are integrated, and the design of the high-performance integrated rubber SIBR is an important research direction for solving the problem.
The integrated rubber SIBR is a copolymer formed by copolymerizing styrene (S), isoprene (I) and butadiene (B) serving as monomers, is an ideal novel tread rubber, becomes a hotspot for rubber research in recent years, and introduces different types of rubber to the same macromolecular chain in situ by a chemical synthesis method to obtain positive synergistic effect and realize the integration of excellent performances of several types of rubber. The integrated rubber integrates the characteristics of polybutadiene rubber (BR), Styrene Butadiene Rubber (SBR), polyisoprene rubber (SIR) and butadiene-isoprene rubber (IBR), realizes the mixing of chain end levels, different structural units can meet various different performances required by tread rubber, and overcomes the contradiction between the rolling resistance, the wear resistance and the traction performance which is difficult to realize by using general rubber.
Patent CN 112142915 a discloses a method for preparing liquid gum filled type integral rubber by anionic living polymerization. The method realizes low molecular weight liquid integrated rubber and high molecular weight solid integrated rubber with specific structures through active polymerization and introduction of a structure regulator, and plasticizes the solid integrated rubber through the liquid integrated rubber. CN 103772609 a discloses a method for synthesizing integrated rubber SIBR by a reactive extrusion method. At present, the research on the integrated rubber SIBR is mostly limited to the research on a synthesis method of unfunctionalized linear SIBR, CN ensures that the SIBR product has a single grade and a narrow application range, and the linear SIBR has the problems of high Mooney viscosity and difficult processing.
In the molecular structure of rubber, terminal free radicals can not be vulcanized, and side groups capable of freely moving can be formed in vulcanized rubber, which is one of the sources of tire rolling resistance.
The star-structured rubber is synthesized by two main methods, namely, the star-structured rubber is directly obtained by initiating polymerization by using a multifunctional initiator, and the star-structured rubber is obtained by adding a coupling agent for coupling after the polymerization is finished. The method for synthesizing the star-structured rubber by using the multifunctional initiator has the advantages of complex synthesis and difficult control and industrial production due to few initiator types. Although the rubber with a star structure synthesized by a method of subsequently adding a coupling agent cannot obtain the rubber with a complete star structure, the method is simple and convenient to operate and high in realizability, and is a promising synthesis mode of the star rubber. Patent CN 102120798A discloses a method for synthesizing star-shaped solution-polymerized styrene-butadiene rubber by a coupling method, and the obtained solution-polymerized styrene-butadiene rubber has low rolling resistance and good wet skid resistance. At present, the synthesis method of the star-structure integrated rubber is not reported yet, and is a problem to be solved urgently.
Disclosure of Invention
The invention provides a nitrogen-containing functionalized SIBR integrated rubber with a star-shaped coupling structure and a preparation method thereof.
The technical scheme of the invention is as follows:
the nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure is a tetrapolymer prepared by copolymerizing a nitrogen-containing functional group 1, 1-diphenylethylene functional monomer with styrene, butadiene and isoprene by adopting alkyl lithium initiation and multi-arm star-shaped coupling agent coupling; the number average molecular weight of the nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure is 9 multiplied by 104-50×104g/mol；
The coupling agent is SiCl3CH3、SiCl4、SnCl3CH3、SnCl4、Si2Cl6Is selected from the group consisting of monofunctional alkyllithium, which is a mixture of one or more of the initiators disclosed in the prior art for the anionic polymerization of butadiene and styrene, including but not limited to n-butyllithium and sec-butyllithium.
Based on the mass of the quadripolymer as 100 percent, the mass of styrene accounts for 10 to 30 percent, the mass of isoprene accounts for 20 to 60 percent, and the mass of butadiene accounts for 20 to 60 percent;
the initiating end or chain of the quadripolymer at least contains 1 nitrogen-containing functional group 1, 1-diphenylethylene functional monomer, and the number of arms of the quadripolymer is between 3.0 and 6.0.
Further, the nitrogen-containing functional group 1, 1-diphenylethylene functional monomer includes 1,1 ' -bis [4- (N, N-dimethylamino) phenyl ] ethylene, 1,1 ' -bis [4- (N, N-diethylamino) phenyl ] ethylene, 1,1 ' -bis [4- (N, N-di-tert-butylamino) phenyl ] ethylene, 1- [4- (N, N-dimethylamino) phenyl ] -1 ' -phenylethene, 1- [4- (N, N-diethylamino) phenyl ] -1 ' -phenylethene, 1- [4- (N, N-di-tert-butylamino) phenyl ] -1 ' -phenylethene, 1- [4- (N, N-methyltrimethylsilylamino) phenyl ] -1 ' -phenylethene, 1- [4- (N, N-ethyltrimethylsilylamino) phenyl ] -1 ' -phenylethene, 1- [4- (N, N-tert-butyltrimethylsilylamino) phenyl ] -1 ' -phenylethene, one or more amino functionalized monomers of 1- [4- (N, N-bistrimethylsilylamino) phenyl ] -1 ' -phenylethene; preferably at least one of 1,1 '-bis [4- (N, N-dimethylamino) phenyl ] ethylene and 1- [4- (N, N-dimethylamino) phenyl ] -1' -phenylethene.
Further, the mass of the quadripolymer is 100%, the mass of the styrene accounts for 15% -25%, the mass of the isoprene accounts for 25% -50%, and the mass of the butadiene accounts for 25% -50%.
Further, the initiation end and the chain of the quadripolymer contain 1 diphenyl ethylene functional monomer, and the arm number of the quadripolymer is between 4.0 and 5.0.
In a second aspect, the invention provides a preparation method of a nitrogen-containing functionalized SIBR integral rubber with a star-shaped coupling structure, which comprises the following steps:
s1, according to the mass ratio of the nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure, according to the ratio of the nitrogen-containing functional group 1, 1-diphenylethylene functional monomer to the initiator being 1-500: 1, weighing a nitrogen-containing functional group 1, 1-diphenylethylene functional monomer in a container, adding an organic solvent, an alkyl lithium initiator and a polarity regulator according to the designed mass concentration of 5-20% of the SIBR integrated rubber, and reacting for 1-3 h; wherein the molar ratio of the polarity modifier to the amount of the alkyllithium initiator is 1: 1-100;
s2, adding 15-25% of styrene, 25-50% of isoprene and 25-50% of butadiene according to 100% of the total mass of the added monomers, and reacting for 12-24h at the temperature of 20-90 ℃;
s3, adding a coupling agent into a container, and reacting at 20-90 ℃ for 12-24 h; the ratio of the initiator to the coupling agent is 1: 3-6;
and S4, adding isopropanol to terminate the reaction, settling in ethanol, and drying to obtain the nitrogen-containing functionalized SIBR integrated rubber with a star-shaped coupling structure.
Further, the ratio of the nitrogen-containing functional group 1, 1-diphenylethylene functional monomer to the initiator is 1: 1, the functional group of the prepared nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure is positioned at the chain end.
Further, the ratio of the nitrogen-containing functional group 1, 1-diphenylethylene functional monomer to the initiator is 1: 1-500 hours later, the functional group of the prepared nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure is positioned in a chain.
Further, the alkyllithium initiator is selected from monofunctional alkyllithium. Wherein the monofunctional alkyl lithium initiator is one or a mixture of several initiators disclosed in the prior art and applicable to butadiene and styrene anionic polymerization, and is generally selected from the following: one or more monofunctional lithium initiators in RLi, wherein R is C2-20 alkyl, alkyl or aryl, preferably ethyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, or benzyl lithium.
Further, the organic solvents are selected from one or a mixture of several of nonpolar aromatic hydrocarbons and nonpolar aliphatic hydrocarbons. Are generally selected from: benzene, toluene, ethylbenzene, xylene, pentane, hexane, heptane, octane, cyclohexane, mixed aromatic hydrocarbons (e.g., mixed xylene), mixed aliphatic hydrocarbons (e.g., raffinate oil), preferably benzene, toluene, n-hexane, cyclohexane.
Further, the polarity modifier is added in order to control the randomness of the butadiene block 1,2 structure, isoprene block 3,4 structure, and integral rubber, and to control the polymer activity and distribution in the polymer chain of the diphenylethylene derivative. The polarity regulator is selected from one or more of oxygen-containing, sulfur-containing and phosphorus-containing polar compounds and metal alkoxide compounds, such as: (1) an oxygenate, typically selected from: diethyl ether, tetrahydrofuran, R1OCH2CH2OR2 (wherein R1 and R2 are alkyl groups having 1-6 carbon atoms, which may be the same OR different, and preferably R1 and R2 are different, such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether), and R1OCH2CH2OCH2CH2OR2 (wherein R1 and R2 are alkyl groups having 1 to 6 carbon atoms, which may be the same OR different, and preferably R1 and R2 are different, such as diethylene glycol dimethyl ether and diethylene glycol dibutyl ether), and crown ether; (2) a compound, typically selected from: triethylamine, Tetramethylethylenediamine (TMEDA), dipiperidine ethane (DPE); (3) a phosphorus-containing compound, generally selected from: hexamethylphosphoric triamide (N-methyl-N-ethyl-N-methyl-phosphoric triamide)HMPA); (4) metal alkoxide compounds, generally selected from ROM, wherein: r is an alkyl group having 1 to 6 carbon atoms, O is an oxygen atom, M is metallic sodium or potassium, and is preferably selected from: potassium tert-butoxide, potassium tert-pentoxide.
Further, the coupling agent is SiCl3CH3、SiCl4、SnCl3CH3、SnCl4,Si2Cl6At least one of (1).
The invention has the beneficial effects that:
the invention prepares the SIBR integrated rubber by using alkyl lithium to initiate a functional monomer of diphenylethylene containing a nitrogen functional group, copolymerizing styrene, butadiene and isoprene under the action of a polarity regulator and coupling by using a coupling agent. According to the invention, through topological design of rubber molecules and introduction of polar functional groups, the compatibility of a rubber matrix and fillers such as carbon black or white carbon black can be increased, the performance of rubber is improved, the dispersibility of the carbon black in the rubber matrix is improved, and the reinforcing effect of the carbon black is improved.
Detailed Description
In order that the above objects, features and advantages of the present invention may be more clearly understood, a solution of the present invention will be further described below. It should be noted that the embodiments of the present invention and features of the embodiments may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those described herein; it is to be understood that the embodiments described in this specification are only some embodiments of the invention, and not all embodiments.
Preferred embodiments of the present invention will be described in detail with reference to the following examples. It is to be understood that the following examples are given for illustrative purposes only and are not intended to limit the scope of the present invention. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the spirit and scope of this invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. Examples the following examples are presented to analyze the copolymer compositional sequence distribution and microstructure using a nuclear magnetic resonance spectrometer and to analyze the molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the copolymer using a gel permeation chromatograph. The NMR spectrum test was performed by Bruker Avance 400M, Switzerland, the molecular weight and molecular weight distribution were measured by a volume exclusion chromatograph, model 2414 differential refractometer, model 1515 HPLC pump, manufactured by Waters, USA.
Example 1
Under the protection of argon, 100ml of benzene and 900ml of cyclohexane as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, sec-butyl lithium as an initiator is added according to the designed molecular weight of 100kg/mol, and 1- [4- (N, N-dimethylamino) phenyl ] ethyl benzene is added according to the proportion of 1.0 of a functionalized diphenylethylene monomer/initiator]-1' -phenylethene (DPE-NMe)2) Reacting for 1 h; adding Tetramethylethylenediamine (TMEDA), styrene 20g, isoprene 40g and butadiene 40g according to the ratio of regulator/initiator of 1.0, reacting at 20 ℃ for 24h, and adding coupling agent SiCH according to the ratio of initiator/coupling agent of 3.03Cl3After 24 hours of reaction at 30 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.6 percent, the mass percent of the isoprene content is 39.6 percent, and the mass percent of the butadiene content is 37.2 percent; the number average molecular weight is 291.3kg/mol, the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 76.2%, the 1, 2-polybutadiene content was 62.0%, the number of polymer arms was 2.91, and the coupling efficiency was 83.0%.
Example 2
Under the protection of argon, adding 100ml of benzene and 900ml of n-hexane serving as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, adding n-butyllithium serving as an initiator according to the designed molecular weight of 100kg/mol,adding 1, 1' -bis [4- (N, N-dimethylamino) phenyl according to the ratio of the functionalized diphenylethylene monomer to the initiator of 50.0]Ethylene DPE- (NMe)2)2Reacting for 2 hours; tetrahydrofuran (THF), 10g of styrene, 50g of isoprene and 40g of butadiene are added according to the ratio of the regulator/the initiator of 100.0, the mixture reacts for 12 hours at 40 ℃, and a coupling agent SiCl is added according to the ratio of the initiator/the coupling agent of 4.04After reaction at 40 ℃ for 12h, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 10.2 percent, the mass percent of the isoprene content is 50.8 percent, and the mass percent of the butadiene content is 39.0 percent; the number average molecular weight is 432.2kg/mol, the molecular weight distribution is 1.19; the 3.4-polyisoprene content was 56.2%, the 1, 2-polybutadiene content was 52.0%, the number of polymer arms was 4.32, and the coupling efficiency was 79.0%.
Example 3
Under the protection of argon, 100ml of benzene and 900ml of pentane solvent are sequentially added into a 2L polymerization reactor which is vacuumized and supplied with gas for three times, 30kg/mol of ethyl lithium initiator is added according to the designed molecular weight, and 1, 1' -bis [4- (N, N-di-tert-butylamino) phenyl ] is added according to the proportion of 10.0 of the functionalized diphenylethylene monomer/initiator]Ethylene DPE- (NtButyl)2)2Reacting for 3 hours; diethylene glycol dimethyl ether, 10g of styrene, 40g of isoprene and 50g of butadiene are added according to the ratio of the regulator/the initiator of 100.0, the mixture reacts for 12 hours at the temperature of 90 ℃, and a coupling agent SnCH is added according to the ratio of the initiator/the coupling agent of 3.53Cl3After reacting at 90 ℃ for 18h, degassed isopropanol is added to terminate the polymerization, the reaction solution is precipitated in excess absolute ethanol, and the resulting polymer is dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 10.5 percent, the mass percent of the isoprene content is 39.1 percent, and the mass percent of the butadiene content is 50.4 percent; the number average molecular weight is 90.4kg/mol, and the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 46.3%, and the 1, 2-polybutadiene content was 42.0% polymer arm number 3.01 and coupling efficiency 86.0%.
Example 4
Under the protection of argon, adding 100ml of benzene and 900ml of heptane as solvents into a 2L polymerization reactor which is vacuumized and supplied with gas for three times, adding isopropyl lithium as an initiator according to the designed molecular weight of 125kg/mol, and adding 1, 1' -bis [4- (N, N-diethylamino) phenyl ] according to the ratio of the functionalized diphenylethylene monomer to the initiator of 1.0]Ethylene DPE- (NEt)2)2Reacting for 1 h; adding diethyl ether, 30g of styrene, 50g of isoprene and 20g of butadiene according to the ratio of the regulator/the initiator of 50.0, reacting for 18h at 20 ℃, and adding a coupling agent SnCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 20 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 29.6 percent, the mass percent of the isoprene content is 49.3 percent, and the mass percent of the butadiene content is 21.1 percent; the number average molecular weight is 499.1kg/mol, and the molecular weight distribution is 1.13; the content of 3.4-polyisoprene was 36.2%, the content of 1, 2-polybutadiene was 33.3%, the number of polymer arms was 4.99, and the coupling efficiency was 73.6%.
Example 5
Under the protection of argon, adding 100ml of toluene and 900ml of octane into a 2L polymerization reactor which is vacuumized and supplied with gas for three times, adding benzyl lithium as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (N, N-methyl trimethylsilyl amido) phenyl ] according to the proportion of 1.0 of a functionalized diphenylethylene monomer/initiator]-1' -Phenylethylene DPE-NMe/SiMe3Reacting for 2 hours; adding crown ether, 10g of styrene, 60g of isoprene and 30g of butadiene according to the ratio of the regulator/the initiator of 50.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100% of the polymer, the total amount ofThe mass percent of the combined styrene content in the polymer is 11.3%, the mass percent of the isoprene content is 59.7%, and the mass percent of the butadiene content is 29.0%; the number average molecular weight is 410.4kg/mol, and the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 36.7%, the 1, 2-polybutadiene content was 37.5%, the number of polymer arms was 4.10, and the coupling efficiency was 73.0%.
Example 6
Under the protection of argon, 100ml of solvent mixed xylene and 900ml of raffinate oil are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, the initiator N-butyllithium is added according to the designed molecular weight of 100kg/mol, and 1- [4- (N, N-ethyltrimethylsilylamino) phenyl ] is added according to the proportion of the functionalized diphenylethylene monomer/the initiator of 1.0]-1' -phenylethylene DPE-NEt/SiMe3Reacting for 2 hours; adding potassium tert-butoxide, 10g of styrene, 30g of isoprene and 60g of butadiene according to the ratio of the regulator to the initiator of 10.0, reacting at 50 ℃ for 18h, and adding SiCl as a coupling agent according to the ratio of the initiator to the coupling agent of 4.04After 24 hours of reaction at 50 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100% of the polymer, the mass percent of the combined styrene content in the copolymer is 11.1%, the mass percent of the isoprene content is 31.2%, and the mass percent of the butadiene content is 57.7%; the number average molecular weight is 387.2kg/mol, and the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 41.9%, the 1, 2-polybutadiene content was 43.0%, the number of polymer arms was 3.87, and the coupling efficiency was 82.1%.
Example 7
Under the protection of argon, adding 100ml of xylene and 900ml of cyclohexane serving as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, adding N-butyllithium serving as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (N, N-tert-butyltrimethylsilylamino) phenyl ] according to the proportion of a functionalized diphenylethylene monomer/initiator of 1.0]-1' -phenylethene DPE-NtButyl/SiMe3Reacting for 2 hours; according to the ratio of 10.0 of regulator/initiator, 30g of tert-pentoxy potassium, 30g of styrene, 20g of isoprene,50g of butadiene, reacting for 18h at 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator to the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 29.9 percent, the mass percent of the isoprene content is 20.6 percent, and the mass percent of the butadiene content is 49.5 percent; the number average molecular weight is 390.1kg/mol, the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 36.2%, the 1, 2-polybutadiene content was 32.0%, the number of polymer arms was 3.90, and the coupling efficiency was 83.0%.
Example 8
Under the protection of argon, 100ml of ethylbenzene and 900ml of normal hexane serving as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, N-butyllithium serving as an initiator is added according to the designed molecular weight of 100kg/mol, and 1- [4- (N, N-ditrimethylsilyl amino) phenyl ] ethyl is added according to the proportion of 25.0 of a functionalized diphenylethylene monomer/initiator]-1' -Phenylethylene DPE- (SiMe)3)2Reacting for 2 hours; adding hexamethylphosphoric triamide, 30g of styrene, 50g of isoprene and 20g of butadiene according to the proportion of 1.0 of a regulator/an initiator, reacting for 18h at 30 ℃, and adding a coupling agent SiCl according to the proportion of 4.0 of the initiator/the coupling agent4After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 28.8 percent, the mass percent of the isoprene content is 51.1 percent, and the mass percent of the butadiene content is 21.1 percent; the number average molecular weight is 388.8kg/mol, and the molecular weight distribution is 1.19; the 3.4-polyisoprene content was 26.2%, the 1, 2-polybutadiene content was 32.4%, the number of polymer arms was 3.89, and the coupling efficiency was 81.9%.
Example 9
Under the protection of argon, 100ml of benzene and 900ml of n-hexane, which are solvents, are sequentially added into a 2L polymerization reactor which is vacuumized and supplied with gas for three timesDesigning the molecular weight to be 100kg/mol, adding initiator N-butyllithium, and adding 1, 1' -bis [4- (N, N-dimethylamino) phenyl group according to the ratio of the functionalized diphenylethylene monomer to the initiator of 1.0]Ethylene DPE- (NMe)2)2Reacting for 2 hours; adding triethylamine, 10g of styrene, 60g of isoprene and 30g of butadiene according to the ratio of the regulator/the initiator of 1.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 11.1 percent, the mass percent of the isoprene content is 52.0 percent, and the mass percent of the butadiene content is 36.9 percent; the number average molecular weight is 390.9kg/mol, and the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 76.2%, the 1, 2-polybutadiene content was 62.0%, the number of polymer arms was 3.90, and the coupling efficiency was 82.2%.
Example 10
Under the protection of argon, adding 100ml of benzene and 900ml of N-hexane serving as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times in sequence, adding N-butyllithium serving as an initiator according to the designed molecular weight of 100kg/mol, and adding 1- [4- (N, N-ditrimethylsilyl amino) phenyl ] according to the proportion of a functionalized diphenylethylene monomer/initiator of 1.0]-1' -Phenylethylene DPE- (SiMe)3)2Reacting for 2 hours; adding ethylene glycol dimethyl ether, 10g of styrene, 30g of isoprene and 60g of butadiene according to the ratio of a regulator/an initiator of 1.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 10.0 percent, the mass percent of the isoprene content is 29.6 percent, and the mass percent of the butadiene content is 60 percent; the number average molecular weight is 396.6kg/mol, and the molecular weight distribution is 1.14; 3.4-Polyisoprene content 363%, 1, 2-polybutadiene content 32.7%, polymer arm number 3.96, coupling efficiency 83.0%.
Example 11
Under the protection of argon, adding 100ml of benzene and 900ml of N-hexane serving as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times in sequence, adding N-butyllithium serving as an initiator according to the designed molecular weight of 100kg/mol, and adding 1, 1' -bis [4- (N, N-dimethylamino) phenyl ] phenyl according to the ratio of functionalized diphenylethylene monomer/initiator of 1.0]Ethylene DPE- (NMe)2)2Reacting for 2 hours; adding ethylene glycol diethyl ether, 20g of styrene, 40g of isoprene and 40g of butadiene according to the ratio of a regulator/an initiator of 1.0, reacting for 18h at the temperature of 30 ℃, and adding a coupling agent SnCl according to the ratio of the initiator/the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.6 percent, the mass percent of the isoprene content is 41.6 percent, and the mass percent of the butadiene content is 38.8 percent; the number average molecular weight is 370.6kg/mol, the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 26.2%, the content of 1, 2-polybutadiene was 22.4%, the number of polymer arms was 3.70, and the coupling efficiency was 88.0%.
Example 12
Under the protection of argon, adding 100ml of benzene and 900ml of N-hexane serving as solvents into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times in sequence, adding N-butyllithium serving as an initiator according to the designed molecular weight of 100kg/mol, and adding 1, 1' -bis [4- (N, N-dimethylamino) phenyl ] phenyl according to the ratio of functionalized diphenylethylene monomer/initiator of 50.0]Ethylene DPE- (NMe)2)2Reacting for 2 hours; diethylene glycol dibutyl ether, styrene 20g, isoprene 20g and butadiene 60g are added according to the proportion of 1.0 of regulator/initiator, the mixture reacts for 18h at the temperature of 30 ℃, and coupling agent SnCl is added according to the proportion of 4.0 of initiator/coupling agent4Reacting at 40 deg.C for 24 hr, adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive anhydrous ethanol, and drying the obtained polymer in vacuum oven to constant temperatureAnd (4) heavy. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.6 percent, the mass percent of the isoprene content is 22.6 percent, and the mass percent of the butadiene content is 57.8 percent; the number average molecular weight is 411.2kg/mol, and the molecular weight distribution is 1.19; the content of 3.4-polyisoprene was 76.2%, the content of 1, 2-polybutadiene was 62.0%, the number of polymer arms was 4.11, and the coupling efficiency was 93.0%.
Example 13
Under the protection of argon, 100ml of benzene and 900ml of N-hexane which are solvents are sequentially added into a 2L polymerization reactor vacuumized and gas-supplemented for three times, an initiator N-butyllithium is added according to a designed molecular weight of 80kg/mol, and 1, 1' -bis [4- (N, N-dimethylamino) phenyl ] ethylene is added according to a ratio of a functionalized diphenylethylene monomer to the initiator of 1.0]Ethylene DPE- (NMe)2)2Reacting for 2 hours; adding dipiperidine ethane, 20g of styrene, 60g of isoprene and 20g of butadiene according to the ratio of the regulator to the initiator of 1.0, reacting for 18h at 30 ℃, and adding a coupling agent SiCl according to the ratio of the initiator to the coupling agent of 4.04After 24 hours of reaction at 40 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 19.4 percent, the mass percent of the isoprene content is 59.6 percent, and the mass percent of the butadiene content is 21.0 percent; the number average molecular weight is 320.8kg/mol, and the molecular weight distribution is 1.16; the content of 3.4-polyisoprene was 76.2%, the content of 1, 2-polybutadiene was 72.3%, the number of polymer arms was 4.01, and the coupling efficiency was 93.9%.
Molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the copolymer.
Example 14
Under the protection of argon, 100ml of benzene and 900ml of cyclohexane as solvents are sequentially added into a 2L polymerization reactor which is vacuumized and gas-supplemented for three times, an initiator N-butyllithium is added according to a designed molecular weight of 80kg/mol, and 1- [4- (N, N-dimethylamino) phenyl ] ethylene is added according to a ratio of a functionalized diphenylethylene monomer/initiator of 1.0]-1’-phenylethene (DPE-NMe)2) Reacting for 1 h; adding Tetramethylethylenediamine (TMEDA), styrene 20g, isoprene 40g and butadiene 40g according to the ratio of regulator/initiator of 1.0, reacting at 20 ℃ for 24h, and adding coupling agent Si according to the ratio of initiator/coupling agent of 6.02Cl6After 24 hours of reaction at 30 ℃, degassed isopropanol was added to terminate the polymerization, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The results of the product structure analysis are as follows: based on 100 percent of the polymer, the mass percent of the combined styrene content in the copolymer is 20.4 percent, the mass percent of the isoprene content is 39.6 percent, and the mass percent of the butadiene content is 40.0 percent; the number average molecular weight is 491.2kg/mol, and the molecular weight distribution is 1.16; the 3.4-polyisoprene content was 76.2%, the 1, 2-polybutadiene content was 62.0%, the number of polymer arms was 6.14, and the coupling efficiency was 82.0%.
The foregoing are merely exemplary embodiments of the present invention to enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The nitrogen-containing functionalized SIBR integrated rubber with a star-shaped coupling structure is a tetrapolymer prepared by copolymerizing a nitrogen-containing functional group 1, 1-diphenylethylene functional monomer with styrene, butadiene and isoprene by adopting alkyl lithium initiation and multi-arm star-shaped coupling agent coupling; the number average molecular weight of the nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure is 9 multiplied by 104-50×104g/mol；
The coupling agent is SiCl3CH3、SiCl4、SnCl3CH3、SnCl4、Si2Cl6Is selected from monofunctional alkyllithium, which is a mixture of one or more initiators disclosed in the prior art for anionic polymerization of butadiene and styrene, including but not limited to n-butyllithium and sec-butyllithium;
based on the mass of the quadripolymer as 100 percent, the mass of styrene accounts for 10 to 30 percent, the mass of isoprene accounts for 20 to 60 percent, and the mass of butadiene accounts for 20 to 60 percent;
the initiating end or chain of the quadripolymer at least contains 1 functional monomer of the 1, 1-diphenylethylene, and the number of arms of the quadripolymer is between 3.0 and 6.0.
2. The nitrogen-containing functionalized SIBR integral rubber in star coupling structure according to claim 1, wherein the nitrogen-containing functional group 1, 1-diphenylethylene functional monomer comprises 1,1 '-bis [4- (N, N-dimethylamino) phenyl ] ethylene, 1, 1' -bis [4- (N, N-diethylamino) phenyl ] ethylene, 1,1 '-bis [4- (N, N-di-tert-butylamino) phenyl ] ethylene, 1- [4- (N, N-dimethylamino) phenyl ] -1' -phenylethene, 1- [4- (N, N-diethylamino) phenyl ] -1 '-phenylethene, 1- [4- (N, N-di-tert-butylamino) phenyl ] -1' -phenylethene, 1- [4- (N, N-methyl trimethylsilyl amino) phenyl ] -1 '-phenylethene, 1- [4- (N, N-ethyl trimethylsilyl amino) phenyl ] -1' -phenylethene, 1- [4- (N, N-tert-butyl trimethylsilyl amino) phenyl ] -1 '-phenylethene, and one or more amino functionalized monomers of 1- [4- (N, N-di-trimethylsilyl amino) phenyl ] -1' -phenylethene; preferably at least one of 1,1 '-bis [4- (N, N-dimethylamino) phenyl ] ethylene and 1- [4- (N, N-dimethylamino) phenyl ] -1' -phenylethene.
3. The nitrogen-containing functionalized SIBR integrated rubber of claim 1, wherein the mass ratio of styrene is 15 to 25%, the mass ratio of isoprene is 25 to 50%, and the mass ratio of butadiene is 25 to 50%, based on 100% by mass of the tetrapolymer.
4. The nitrogen-containing functionalized SIBR integrated rubber according to claim 3, wherein the tetrapolymer comprises 1 nitrogen-containing functional group-1, 1-diphenylethylene functional monomer at both the initiation end and the chain, and the number of arms of the tetrapolymer is 4.0-5.0.
5. A method for preparing the nitrogen-containing functionalized SIBR integrated rubber with a star-shaped coupling structure according to any of claims 1 to 4, comprising the steps of:
s1, weighing a certain amount of the 1, 1-diphenylethylene functional monomer containing the nitrogen functional group in the nitrogen-containing functional group SIBR integrated rubber with the star-shaped coupling structure, styrene, isoprene and butadiene according to the designed mass ratio, adding an organic solvent, an alkyl lithium initiator and a polarity regulator into a container, and reacting for 1-3 h; the molar ratio of the polarity modifier to the amount of the alkyllithium initiator is 1: 1-100;
s2, adding styrene, isoprene and butadiene according to the designed mass ratio, and reacting for 12-24h at 20-90 ℃;
s3, adding a coupling agent, and reacting at 20-90 ℃ for 12-24 h; the dosage ratio of the initiator to the coupling agent is 1: 3-6;
and S4, adding isopropanol to terminate the reaction, settling in ethanol, and drying to obtain the nitrogen-containing functionalized SIBR integrated rubber with a star-shaped coupling structure.
6. The method for preparing the nitrogen-containing functionalized SIBR integrated rubber of star coupling structure according to claim 5, wherein the ratio of the nitrogen-containing functional group 1, 1-diphenylethylene functional monomer to the initiator is 1: 1, the functional group of the prepared nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure is positioned at the chain end.
7. The method for preparing the nitrogen-containing functionalized SIBR integrated rubber of star coupling structure according to claim 5, wherein the ratio of the nitrogen-containing functional group 1, 1-diphenylethylene functional monomer to the initiator is 1: 1-500 hours later, the functional group of the prepared nitrogen-containing functionalized SIBR integrated rubber with the star-shaped coupling structure is positioned in a chain.
8. The method for preparing the nitrogen-containing functionalized SIBR integral rubber with a star-coupled structure according to claim 5, wherein the alkyl lithium initiator is selected from the group consisting of monofunctional alkyl lithium initiators which are one or a mixture of several initiators for butadiene and styrene anionic polymerization disclosed in the prior art; the organic solvent is selected from one or a mixture of several of nonpolar aromatic hydrocarbon and nonpolar aliphatic hydrocarbon, including but not limited to n-hexane, cyclohexane and cyclopentane.
9. The process of claim 5, wherein the polar modifier is selected from the group consisting of oxygen-containing, sulfur-containing, phosphorus-containing polar compounds and metal alkoxide compounds.
10. The method of claim 5, wherein the coupling agent is SiCl3CH3、SiCl4、SnCl3CH3、SnCl4,Si2Cl6At least one of (1).
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