CN113956411A - Regulator of conjugated diene and application thereof - Google Patents
Regulator of conjugated diene and application thereof Download PDFInfo
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- CN113956411A CN113956411A CN202010696459.5A CN202010696459A CN113956411A CN 113956411 A CN113956411 A CN 113956411A CN 202010696459 A CN202010696459 A CN 202010696459A CN 113956411 A CN113956411 A CN 113956411A
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- styrene
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- 150000001993 dienes Chemical class 0.000 title claims abstract description 79
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 123
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 85
- 238000005859 coupling reaction Methods 0.000 claims abstract description 72
- 230000008878 coupling Effects 0.000 claims abstract description 71
- 238000010168 coupling process Methods 0.000 claims abstract description 71
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 36
- -1 sodium alkoxide Chemical class 0.000 claims abstract description 32
- 239000003999 initiator Substances 0.000 claims abstract description 31
- 229920001971 elastomer Polymers 0.000 claims abstract description 29
- 239000000806 elastomer Substances 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 18
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 18
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000001979 organolithium group Chemical group 0.000 claims abstract 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 67
- 230000035484 reaction time Effects 0.000 claims description 46
- 229920001577 copolymer Polymers 0.000 claims description 41
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 26
- 238000007334 copolymerization reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical group [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 18
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 17
- 239000005049 silicon tetrachloride Substances 0.000 claims description 17
- 125000000129 anionic group Chemical group 0.000 claims description 16
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 229920005604 random copolymer Polymers 0.000 claims description 10
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 8
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 7
- 150000003440 styrenes Chemical class 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 57
- 229920002554 vinyl polymer Polymers 0.000 abstract description 35
- 230000001105 regulatory effect Effects 0.000 abstract description 31
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 17
- 230000008859 change Effects 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000005062 Polybutadiene Substances 0.000 description 49
- 229920002857 polybutadiene Polymers 0.000 description 49
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- 239000004793 Polystyrene Substances 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000002879 Lewis base Substances 0.000 description 9
- 150000007527 lewis bases Chemical class 0.000 description 9
- 239000011218 binary composite Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- ONTBXMIJJWWZDM-UHFFFAOYSA-N n-ethylpyrrolidin-2-amine Chemical compound CCNC1CCCN1 ONTBXMIJJWWZDM-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 6
- AWXPUWKFOHXUJT-UHFFFAOYSA-N n-butylpyrrolidin-2-amine Chemical compound CCCCNC1CCCN1 AWXPUWKFOHXUJT-UHFFFAOYSA-N 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 239000011115 styrene butadiene Substances 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000007822 coupling agent Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001195 polyisoprene Polymers 0.000 description 5
- 239000005060 rubber Substances 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 3
- VBCKYDVWOPZOBA-UHFFFAOYSA-N 2-(oxolan-2-ylmethoxymethyl)oxolane Chemical compound C1CCOC1COCC1CCCO1 VBCKYDVWOPZOBA-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000003750 conditioning effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229920006132 styrene block copolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 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
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- BJXXCOMGRRCAGN-CLFAGFIQSA-N [2,2-bis(hydroxymethyl)-3-[(z)-octadec-9-enoyl]oxypropyl] (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(CO)(CO)COC(=O)CCCCCCC\C=C/CCCCCCCC BJXXCOMGRRCAGN-CLFAGFIQSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- MXVPZFVOVXXPOB-UHFFFAOYSA-N n-methylpyrrolidin-2-amine Chemical compound CNC1CCCN1 MXVPZFVOVXXPOB-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920002742 polystyrene-block-poly(ethylene/propylene) -block-polystyrene Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Abstract
The invention discloses a regulator of conjugated diene and application thereof, wherein the regulator comprises an asymmetric amine regulator: 2-alkylamino-tetrahydropyrrole having the structural formula:
wherein R is an alkyl group having 1 to 4 carbon atoms. Also comprises a sodium alkoxide regulator, the structural formula of which is as follows:
wherein R is1、R2、R3The hydrogen atoms or alkyl groups having 1 to 4 carbon atoms may be the same or different. The molar ratio of the 2-alkylamino-tetrahydropyrrole regulator to the organic lithium initiator is 0.12-6.2. Molarity of sodium alkoxide regulator with organolithium initiatorThe molar ratio is 0.06-2. The regulating capacity of the regulator is greater than that of the regulator used independently, the molar ratio of vinyl to conjugated diene in the styrene elastomer can be controlled to be 20-80%, and the 1, 2-structure content is slightly changed along with the change of the polymerization temperature. Solves the problems that the styrene elastomer for hydrogenation has unstable structure content of conjugated diene 1,2 during high-temperature and variable-temperature polymerization and can not give consideration to high coupling efficiency in the synthesis of star polymers.
Description
Technical Field
The invention relates to a composite structure regulator for controlling the microstructure of conjugated diene in hydrogenation reaction of styrene elastomers, which belongs to the field of polymer synthesis, and particularly relates to a method for preparing styrene elastomers by adopting an anionic polymerization method.
Background
The microstructure of the conjugated diene (1, 3-butadiene and isoprene) in anionic polymerization mainly refers to a cis-structure, a trans-1, 4-structure, a 1, 2-structure or a 3, 4-structure of a polymer, generally, the polymerization of the conjugated diene is mainly based on 1, 4-structure polymerization, and the content of the 1, 2-structure is low. The 1, 4-structure and 1, 2-structure of the 1, 3-butadiene polymer are decisive for its properties, in particular for its wet skid resistance, the 1, 2-structure content of bulky side groups being increased and the wet skid resistance of the polymer being correspondingly increased. In order to obtain polymers with desirable properties, it is necessary to achieve a microstructure of the polymer that is controllable within a certain range. There are many factors that affect the microstructure of the polymer, such as the type and concentration of the initiator, the solvent and polar additives, and the temperature. Among many factors, the method of adding a polarity modifier to synthesize polymers having different microstructures is the most important method.
Conventional block copolymers polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS) can be hydrogenated to obtain hydrogenated SBS (SEBS), hydrogenated SIS (SEPS), respectively, by hydrogenation of conjugated diene polymer blocks. The selective hydrogenation of the conjugated diene polymer block can eliminate unsaturated double bonds on the polymer chain segment, so that the product has good stability, aging resistance and wider use temperature. Taking SBS as an example, 1, 4-structure in polybutadiene block is hydrogenated to become ethylene, 1, 2-structure is added to become butylene, and the structural formulas of SBS and SEBS are as follows:
SBS structure
SEBS structural formula
SEBS is a styrene thermoplastic elastomer with excellent performance and wide application, compared with SBS, because the main chain does not contain or contains a small amount of double bonds, SEBS has thermoplastic processability and rubber elasticity, and also has better stability and heat resistance than SBS, the using temperature can reach 120 ℃ (the using temperature of SBS is only 65 ℃), and the SEBS also has excellent outdoor weather resistance such as ozone resistance, ultraviolet resistance and the like. The SEBS performance depends mainly on the structural characteristics of the SBS base rubber. The SBS for hydrogenation is greatly different from the conventional SBS in structure, the 1, 2-structure content of a polybutadiene block in the conventional SBS is between 5 and 10 percent, and the 1, 2-structure content of the polybutadiene block in the SBS for hydrogenation needs to be controlled between 35 and 65 percent. The hydrogenated product of the 1, 4-structure of the polybutadiene is polyethylene, the hydrogenated product of the 1, 2-structure of the polybutadiene is random polybutylene, the hydrogenated product of the polybutadiene block in the SBS is an ethylene-butylene copolymer, and the random arrangement of ethylene and butylene in a molecular chain can inhibit the crystallization caused by a polyethylene long chain sequence. Therefore, the polybutadiene block of the hydrogenated base rubber SBS has to incorporate appropriate butadiene 1, 2-structural units to inhibit crystallization of the hydrogenated product by formation of long-chain polyethylene. Whereas polybutene has a glass transition temperature of-18 ℃ which is high for elastomers, and therefore the butadiene 1, 2-structure cannot be too high either. The proper butadiene 1, 2-structure in the SBS base allows the glass transition temperature rise due to the insertion of the 1, 2-structure to be minimized while minimizing the increase in crystallinity due to the long sequence of the polyethylene. Studies have shown that in the polybutadiene block of SBS, as the 1, 2-structure content of butadiene approaches 50%, the elastomeric block crystallization is substantially suppressed, while the glass transition temperature is significantly increased due to the constraint of butene produced by the hydrogenation of the 1, 2-structure. The actual measurement data show that when the butene structure content is 35-65%, the dynamic hysteresis is at the lowest value, namely the optimal range of the butadiene 1, 2-structure content in the polybutadiene block of the SBS base rubber is 35-65%. Hydrogenation of SIS is similar to SBS, and when 3, 4-structure of isoprene is 35% -65%, the performance of hydrogenation product is optimum. Therefore, it is important to select a suitable structure modifier in the SBS (SIS) base rubber synthesis process.
Structural regulators are mostly polar substances containing heteroatoms (such as oxygen, nitrogen, sulfur, phosphorus, etc.), which are electron-donating Lewis bases. Mainly plays a role in changing the association state of the initiator, changing the microstructure of active species and changing the sequence distribution of the copolymer. Therefore, the addition of the structure regulator has a comprehensive influence on a polymerization system, the microstructure of the polymer can be regulated, the sequence distribution, the molecular weight distribution and the polymerization reaction speed of the polymer can be influenced, and the coupling agent can influence the activity of active species when the star-shaped polymer is prepared, so that the coupling efficiency is greatly reduced.
Lewis bases, such as Tetrahydrofuran (THF), N-Tetramethylethylenediamine (TMEDA), etc., have been reported to control the microstructure of polymers in anionic polymerization of conjugated dienes, and according to the anionic reaction mechanism of conjugated dienes (including 1, 3-butadiene, isoprene) proposed by kuntai, lissaku, etc., during the polymerization of conjugated dienes, active species exist in the form of two structures, i.e., sigma-allyl lithium and pi-allyl lithium, wherein sigma-allyl lithium is mainly responsible for the formation of 1, 4-structures, and pi-allyl lithium is mainly responsible for the formation of 1, 2-structures, which are in thermodynamic equilibrium state under the action of polar solvents, and as the amount of polar additives increases, the equilibrium moves toward the pi-allyl lithium structure, that is, 1, the 2-addition product is increased, and the adjustment of the 1, 2-structure of the poly-conjugated diene between 20 percent and 80 percent can be realized. The single use of Lewis base has the defects of large dosage of the regulator, sensitive microstructure influenced by the addition error of the regulator, very sensitive temperature change in the polymerization process and the like. If tetrahydrofuran is adopted as a structure regulating system, the 1, 2-structure content is in direct proportion to the adding amount of a regulator, and when the molar ratio of the tetrahydrofuran to an initiator is 30, the 1, 2-structure content of the conjugated diene can reach about 50 percent. The microstructure change is easily caused by the addition error of tetrahydrofuran, meanwhile, the solvent recovery is difficult due to the addition of a large amount of tetrahydrofuran, and more importantly, when the tetrahydrofuran is used as a regulator, the 1, 2-structure changes obviously along with the polymerization temperature, the polymerization temperature changes by 20 ℃, and the 1, 2-structure content changes by more than 20%, which brings difficulty to the heat insulation polymerization in industrial production. Kingotai et al [ ZL92114800.3, ZL200510032416.2] developed binary polarity modifier systems for microstructure control. The system adopts Lewis bases with different polarities for compounding, has a microstructure which is insensitive to the content of the added polar reagent, and the microstructure tends to be unchanged when the polar reagent is added to a certain amount, thereby being beneficial to realizing the structural stability of a polymer product. However, the system also has the problem of reduced regulating capacity of the binary regulator, namely the content of the 1, 2-structure of the conjugated diene when the binary regulator is used is lower than that of the 1, 2-structure of the conjugated diene when a strong polar reagent is used alone, and the using amount of the binary regulator is larger. The Lewis base with multi-polar groups has higher regulating capacity to the content of the 1, 2-structure of the conjugated diene and has better effect in the synthesis of the conjugated diene polymer with the high content of the 1, 2-structure. However, most of these organic compounds have symmetrical structures, which are produced during anionic polymerization as follows: serious side reaction, adverse effect on the reaction of active species and coupling agents such as silicon tetrachloride and the like, and the like. ZL200510032416.2 reports a process for regulating the vinyl content of polybutadiene over a wide range using a binary regulator of pentamethyldiethylenetriamine in combination with tetrahydrofuran. However, in practical application, the problems of low polymerization rate, low coupling efficiency in the preparation of star polymers and the like exist. ZL200610081110.0 reports a method of regulating the microstructure of conjugated diene homo-and copolymers by compounding an organic salt with a Lewis base. The method has higher regulating capacity on the microstructure of the poly-conjugated diene than that of each polarity regulator, can enable the content of the 1, 2-structure of the conjugated diene to be higher, but the symmetrical Lewis base adopted by the regulating system can lead part of active chains to be deactivated at the final stage of polymerization, which can definitely reduce the coupling efficiency during coupling. Therefore, it is one of the hot spots to study how to simultaneously achieve high coupling efficiency while increasing the content of the 1, 2-structure of the conjugated diene.
In order to achieve the high 1, 2-structure content and the high coupling efficiency of the conjugated diene at the same time, the asymmetric ether structure regulator is rapidly developed, and structurally, the asymmetric ether is developed from the symmetric ether, so that the conversion rate of the reaction, the subsequent coupling reaction and the like are not influenced by the addition of the regulator. "modifier for synthesizing vinyl polybutadiene by anion polymerization" [ synthetic rubber industry, 2006, 29 (5): 387] have reported Lewis bases of asymmetric structure as polarity regulators for butadiene homopolymers or copolymers. The asymmetric ether as a structure regulator can effectively improve the coupling efficiency, has the defects of limited regulating range of the 1, 2-structure content of the conjugated diene, can not prepare the conjugated diene homo/copolymer with high 1, 2-structure content, is particularly sensitive to the change of temperature, and greatly reduces the 1, 2-structure content when the polymerization temperature is increased. In industrial production, a near adiabatic polymerization mode is generally adopted, the polymerization temperature generally varies from 50 ℃ to 100 ℃, and the microstructure of the polymer is changed when the polymerization temperature varies, so that the stability of the product performance is not facilitated. There is a need in the art to develop a structural regulation system with less change in the 1, 2-structural content of the conjugated diene at higher temperature changes.
Disclosure of Invention
The invention aims to solve the problems that the prior art has large dosage of a microstructure regulator of conjugated diene (1, 3-butadiene and isoprene) in a styrene elastomer for hydrogenation, low coupling efficiency and large content change of the structure of the conjugated diene (1, 2-structure of butadiene and 3, 4-structure of isoprene) when the polymerization temperature changes. The system adopts a composite regulating system comprising an asymmetric amine structure regulator and a sodium alkoxide regulator, and when the polymerization temperature of the regulating system changes by 20 ℃, the change of 1, 2-% structural content of conjugated diene is only within 5 percent, so that the regulating system is insensitive to the change of the polymerization temperature. Meanwhile, the regulating system has small dosage, does not cause the phenomenon of 'inactivation' in the later polymerization stage, and has coupling efficiency of over 85 percent. The regulating capacity of the regulating system is larger than that of the regulating system when the regulating system and the polydiene are used independently, and the content of the 1, 2-structure in the polydiene is controlled to be 20-80%, and the optimal content is 35-65%.
A binary composite regulating system for controlling the microstructure of conjugated diene (butadiene and isoprene) in a styrene elastomer for hydrogenation comprises 2-alkylamino-tetrahydropyrrole and a sodium alkoxide regulator, wherein the molar ratio of the 2-alkylamino-tetrahydropyrrole regulator to an organic lithium initiator is 0.12-6.2; the molar ratio of the sodium alkoxide regulator to the organic lithium initiator is 0.06-2. The 2-alkyl amino-tetrahydropyrrole is mainly used for adjusting the microstructure of the conjugated diene, and the sodium alkoxide is mainly used for adjusting the reactivity ratio during the copolymerization of the butylbenzene.
The structural formula of the 2-alkylamino-tetrahydropyrrole is as follows:
wherein R is an alkyl group having 1 to 4 carbon atoms;
the structural formula of the sodium alkoxide is as follows:
wherein R is1、R2、R3The hydrogen atoms or the alkyl groups having 1 to 4 carbon atoms may be the same or different.
The binary composite regulating system is suitable for the anionic copolymerization of common conjugated diene (butadiene and isoprene) and styrene.
The binary composite regulating system can also synthesize a star-structured styrene-conjugated diene-styrene block copolymer. Firstly, adding a hydrocarbon solvent and all styrene monomers into a polymerization kettle, metering two regulators, then adding a metered organic lithium initiator, wherein the polymerization temperature is 40-90 ℃, the reaction time is 0.5-1 hour, and firstly, generating a styrene section; then adding a conjugated diene monomer, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-1 hour, so as to generate a styrene-conjugated diene section; finally, adding silicon tetrachloride for coupling, wherein the coupling temperature is 40-80 ℃, and the coupling time is 0.2-1 h, so as to obtain the star block structure styrene-butadiene-styrene copolymer.
The binary composite regulating system can synthesize a star-structured styrene-butadiene-styrene random copolymer: firstly, adding a hydrocarbon solvent, all styrene and conjugated diene monomers, a 2-alkylamino-tetrahydropyrrole regulator and a sodium alkoxide regulator into a polymerization kettle, and then adding an organic lithium initiator, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-2 hours, so as to generate a linear styrene-conjugated diene random copolymer; finally, adding silicon tetrachloride for coupling, wherein the coupling temperature is 40-80 ℃, and the reaction time is 0.2-1 hour, so as to obtain the star-shaped styrene-conjugated diene random copolymer.
The binary composite regulating system can synthesize a styrene-conjugated diene-styrene block copolymer with a linear structure: for example, firstly, a hydrocarbon solvent and part of styrene monomer are added into a polymerization kettle, a 2-alkylamino-tetrahydropyrrole regulator and a sodium alkoxide regulator are metered, then a metered organic lithium initiator is added, the polymerization temperature is 40-90 ℃, the reaction time is 0.5-1 hour, and a styrene section is generated firstly; then adding a conjugated diene monomer, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-1 hour, so as to generate a styrene-conjugated diene section; and finally, adding the residual styrene monomer, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-1 hour, so as to generate the styrene-butadiene-styrene block copolymer with the linear structure.
In the anionic copolymerization method of the styrene elastomer for hydrogenation, the styrene accounts for 10 to 60 weight percent of the total amount of the styrene and the conjugated diene monomers.
In the method for anionic copolymerization of a hydrogenated styrene-based elastomer of the present invention, the conjugated diene is selected from butadiene and isoprene.
According to the anionic copolymerization method of the styrene elastomer for hydrogenation, the dosage of the organic lithium initiator is 0.1-4 mmol per 100g of total amount of styrene and conjugated diene monomers.
According to the anionic copolymerization method of the styrene elastomer for hydrogenation, the organic lithium initiator is n-butyllithium or isobutyllithium.
The invention relates to an anionic copolymerization method of a styrene elastomer for hydrogenation, wherein a hydrocarbon solvent is cyclohexane, normal hexane or a mixed solvent of cyclohexane and normal hexane, and the addition amount of the hydrocarbon solvent is 500-1200 wt% of the total amount of styrene and conjugated diene monomers.
According to the anionic copolymerization method of the styrene elastomer for hydrogenation, disclosed by the invention, the composite regulator can control the molar ratio of vinyl to conjugated diene in the styrene elastomer to be 20-80% based on the conjugated diene participating in copolymerization.
The binary regulating system is used for controlling the microstructure of the conjugated diene in the styrene elastomer for hydrogenation and can also be used for styrene/conjugated diene anion copolymerization to obtain a random copolymer with controllable microstructure.
The adjusting capacity of the binary adjusting system is larger than that of the binary adjusting system when the binary adjusting system and the conjugated diene are used independently, the composite adjusting system is small in using amount and small in influence of polymerization temperature, the polymerization temperature is increased by 20 ℃, the content of the 1, 2-structure of the conjugated diene is changed within 5%, the higher the temperature is, the smaller the reduction range is, and the influence on the reaction activity is small, so that the industrial production is facilitated.
When the conjugated diene monomer is copolymerized with styrene, the molecular weight of the obtained polymer is 50,000-400,000, and the molecular weight distribution is 1.1-1.8.
The 2-alkylamino-tetrahydropyrrole belongs to Lewis base of asymmetric amines, can realize the regulation and control of high-efficiency 1, 2-structure content, has small steric hindrance on monomer insertion and reaction of active species and a coupling agent in the polymerization process, reduces the inactivation benefit of an active chain in the polymerization process, and increases the coupling efficiency of later-stage coupling. The addition of sodium alkoxide regulator makes the system contain more metal ions (Li)+、Na+) The nucleophilic ability of carbanion is weakened, the temperature change of the complexation reaction of the active chain is smaller, the polymerization temperature is increased, and the 1, 2-structure content change of the conjugated diene is smaller.
The invention adopts a binary composite regulating system of a 2-alkylamino-tetrahydropyrrole regulator and a sodium alkoxide regulator to control the 1, 2-structure content of the conjugated diene and styrene copolymer, the regulating capability of the binary composite regulating system is greater than that of the conjugated diene and styrene copolymer when the conjugated diene and styrene copolymer are used independently, the 1, 2-structure content can be controlled to be between 20 and 80 percent, the coupling efficiency in the preparation of star polymers can be improved, and the star polymer product with the coupling efficiency of 85 percent can be prepared when silicon tetrachloride is used as the coupling agent. The binary composite regulator system of the invention has little dosage, can reduce side reaction, has insensitivity to temperature, can greatly solve the problem that the 1, 2-structure content is influenced by large dosage of the regulator and large fluctuation of polymerization temperature in industry, has little influence on reaction activity and has great industrial application value.
Drawings
FIG. 1 is a graph showing the trend of vinyl content (1, 2-structure) versus polymerization temperature.
FIG. 2 is a phase separation TEM photograph of the synthesized copolymer of example 1.
FIG. 3 shows the nuclear magnetic spectrum of the vinyl content test in example 1.
Detailed Description
The following examples are intended to further illustrate the process of the present invention but should not be construed as limiting thereof.
FIG. 1 is a graph of vinyl content (1, 2-structure) versus polymerization temperature trend; FIG. 2 is a phase separation TEM photograph of the synthesized copolymer of example 1; FIG. 3 is a nuclear magnetic spectrum of vinyl content measurement in example 1, wherein signals are present at 2.05-2.06 positions of acetylmethyl groups in polybutadiene, signals are present at 2.45-3.0 positions of methine groups in polybutadiene, signals are present at 3.84-4.16 positions of methylene groups connected with acetyl groups in polybutadiene, and signals are present at 5.30-5.55 positions of double bond hydrogen in polybutadiene. Table 1 shows a comparison table of the structure control and coupling efficiency in examples 1 to 10 and comparative examples 1 to 10.
The polymerizer was subjected to baking at high temperature and nitrogen substitution three or more times before the experiment.
The 1, 2-structure content of the polymer samples was characterized analytically using nuclear magnetic resonance NMR and the molecular weight (Mn), Molecular Weight Distribution (MWD) and coupling efficiency of the polymer samples were characterized analytically using gel permeation chromatography.
Example 1
Adding 35g of styrene monomer and 820g of cyclohexane into a polymerization bottle, adding 2.9mmol of 2-ethylamino-tetrahydropyrrole and 0.96mmol of sodium 2, 3-dimethylpentanoate, then adding 1.6mmol of n-butyllithium initiator, wherein the polymerization temperature is 50 ℃ and the reaction time is 1 hour to obtain a styrene section; then adding 57g of butadiene monomer, wherein the polymerization temperature is 50 ℃, and the reaction time is 1 hour, so as to obtain a styrene-butadiene section; finally adding silicon tetrachloride for coupling, wherein the coupling temperature is 80 ℃, the reaction time is 0.5 hour, and the polymer is precipitated and dried in vacuum to obtain the star block structure styrene-butadiene-styrene copolymer.
The vinyl content of the polybutadiene block in the copolymer was determined to be 45%, the number average molecular weight of the single-arm polymer base of polystyrene-polybutadiene was 60000, the MWD was 1.24, and the coupling efficiency was 75%.
Comparative example 1
The other conditions were the same as in example 1 except that 2-ethylamino-tetrahydropyrrole was used as the modifier in an amount of 3.86 mmol.
The vinyl content of the polybutadiene block in the copolymer was determined to be 42%, the polystyrene-polybutadiene single-arm polymer molecular weight was determined to be 60000, the MWD was 1.22, and the coupling efficiency was determined to be 74%.
Example 2
Other conditions were the same as in example 1, and the polymerization temperatures in both stages were 70 ℃.
The vinyl content of the polybutadiene block in the copolymer was determined to be 44%, the polystyrene-polybutadiene single-arm polymer molecular weight was 60000, the MWD was 1.24, and the coupling efficiency was 75%.
Comparative example 2
The other conditions were the same as in example 2 except that only sodium 2, 3-dimethylpentanolate was used as the conditioning agent in an amount of 3.86 mmol.
The vinyl content of the polybutadiene block in the copolymer was determined to be 28%, the polystyrene-polybutadiene single-arm polymer molecular weight was determined to be 60000, the MWD was 1.23, and the coupling efficiency was determined to be 73%.
Example 3
Adding 30g of styrene and 800g of cyclohexane into a polymerization bottle, adding 2.1mmol of 2-methylamino-tetrahydropyrrole and 0.3mmol of 2, 3-dimethyl sodium octylate, then adding 0.8mmol of isobutyl lithium initiator, wherein the polymerization temperature is 70 ℃, and the reaction time is 1 hour to obtain a styrene section; then adding 70g of butadiene, wherein the polymerization temperature is 70 ℃, and the reaction time is 0.5h to obtain a styrene-butadiene section; finally adding silicon tetrachloride for coupling, wherein the coupling temperature is 70 ℃, the reaction time is 0.8 hour, and the polymer is precipitated and dried in vacuum to obtain the star block structure styrene-butadiene-styrene copolymer.
The vinyl content of the polybutadiene block in the copolymer was 75%, and the polystyrene-polybutadiene single-arm polymer was measured to have a molecular weight of 130000, an MWD of 1.45, and a coupling efficiency of 62%.
Comparative example 3
The other conditions were the same as in example 3 except that tetrahydrofuran and tetramethylethylenediamine were used as the regulators in amounts of 2.1mmol and 0.3mmol, respectively.
The vinyl content of the polybutadiene block in the polystyrene/butadiene copolymer was determined to be 74%, the polystyrene-polybutadiene copolymer had a one-armed molecular weight of 135000, the MWD was 1.30, and the coupling efficiency was 51%.
Example 4
Other conditions were the same as in example 3, and the polymerization temperatures in both stages were 90 ℃.
The vinyl content of the polybutadiene block in the copolymer was 72%, and the polystyrene-polybutadiene single-arm polymer was measured to have a molecular weight of 130000, an MWD of 1.45, and a coupling efficiency of 61%.
Comparative example 4
The other conditions were the same as in example 4 except that tetrahydrofuran and tetramethylethylenediamine were used as the regulators in amounts of 2.1mmol and 0.3mmol, respectively.
The vinyl content of the polybutadiene block in the copolymer is 58%, and the molecular weight of the polystyrene-polybutadiene single-arm polymer is determined to be 130000, the MWD is 1.45, and the coupling efficiency is 58%.
Example 5
Adding 20g of styrene monomer and 800g of cyclohexane into a polymerization bottle, adding 0.29mmol of 2-butylamino-tetrahydropyrrole and 0.96mmol of 2, 3-dimethyl sodium pentol, then adding 1.6mmol of n-butyl lithium initiator, the polymerization temperature is 50 ℃, the reaction time is 1 hour, then adding 60g of butadiene monomer, the polymerization temperature is 50 ℃, the reaction time is 1 hour, finally adding a silicon tetrachloride coupling agent, the coupling temperature is 50 ℃, the reaction time is 1 hour, and precipitating and vacuum drying the polymer to obtain the star block structure styrene-butadiene-styrene copolymer.
The vinyl content of the polybutadiene block in the copolymer was 53%, and the polystyrene-polybutadiene single-arm polymer was measured to have a molecular weight of 78000, an MWD of 1.50, and a coupling efficiency of 76%.
Comparative example 5
The other conditions were the same as in example 5 except that 2-butylamino-tetrahydropyrrole was used as the modifier in an amount of 0.29 mmol.
The vinyl content of the polybutadiene block in the copolymer was 42%, and the polystyrene-polybutadiene single-arm polymer was measured to have a molecular weight of 78000, an MWD of 1.4, and a coupling efficiency of 68%.
Example 6
Adding 40g of styrene monomer and 800g of cyclohexane into a polymerization bottle, adding 0.29mmol of 2-butylamino-tetrahydropyrrole and 0.64mmol of 2, 3-dimethyl sodium octoate, then adding 0.8mmol of n-butyllithium initiator, the polymerization temperature is 50 ℃, the reaction time is 0.8 hour, then adding 60g of isoprene monomer, the polymerization temperature is 50 ℃, the reaction time is 1 hour, finally adding silicon tetrachloride for coupling, the coupling temperature is 80 ℃, the reaction time is 0.5 hour, and precipitating and vacuum drying the polymer to obtain the styrene-isoprene-styrene copolymer with the star-shaped block structure.
The vinyl content of the polyisoprene block in the copolymer was 70%, the polystyrene-polyisoprene one-armed polymer molecular weight was determined to be 128000, the MWD was 1.45, and the coupling efficiency was 67%.
Comparative example 6
The other conditions were the same as in example 6 except that sodium 2, 3-dimethyloctanol was used as the conditioning agent in an amount of 0.64 mmol.
The vinyl content of the polyisoprene block in the copolymer was 71%, the polystyrene-polyisoprene one-armed polymer molecular weight was determined to be 128000, the MWD was 1.42, and the coupling efficiency was 49%.
Example 7
Adding 20g of styrene monomer and 800g of cyclohexane into a polymerization bottle, adding 0.217mmol of 2-butylamino-tetrahydropyrrole and 0.15mmol of 2, 3-dimethyl sodium octoate, then adding 1.8mmol of n-butyl lithium initiator, the polymerization temperature is 50 ℃, the reaction time is 1 hour, then adding 60g of butadiene monomer, the polymerization temperature is 50 ℃, the reaction time is 1 hour, finally adding silicon tetrachloride for coupling, the coupling temperature is 80 ℃, the reaction time is 1 hour, and precipitating and vacuum drying the polymer to obtain the styrene-butadiene-styrene copolymer with the star-shaped block structure.
The vinyl content of the polybutadiene block in the copolymer is 35%, and the molecular weight of the polystyrene-polybutadiene single-arm polymer is measured to be 60000, the MWD is 1.43, and the coupling efficiency is 82%.
Comparative example 7
The other conditions were the same as in example 7 except that tetrahydrofuran and tetrahydrofurfuryl ether were used as the regulators in amounts of 0.217mmol and 0.15mmol, respectively.
The vinyl content of the polybutadiene block in the copolymer is 36%, and the molecular weight of the polystyrene-polybutadiene single-arm polymer is measured to be 60000, the MWD is 1.42, and the coupling efficiency is 61%.
Example 8
Adding 30g of styrene and 800g of cyclohexane into a polymerization bottle, adding 0.06mmol of 2-butylamino-tetrahydropyrrole and 0.03mmol of 2, 3-dimethyl sodium octoate, then adding 0.5mmol of n-butyllithium initiator, wherein the polymerization temperature is 60 ℃, the reaction time is 1 hour, then adding 70g of butadiene, the polymerization temperature is 60 ℃, the reaction time is 1 hour, finally adding silicon tetrachloride for coupling, wherein the coupling temperature is 80 ℃, the reaction time is 1 hour, and precipitating and vacuum drying the polymer to obtain the styrene-butadiene-styrene copolymer product with the star-shaped block structure.
The vinyl content of the butadiene segment in the copolymer was determined to be 21%, the polystyrene-polybutadiene single-arm polymer molecular weight was 205000, the MWD was 1.30, and the coupling efficiency was 80%.
Comparative example 8
The other conditions were the same as in example 8 except that tetrahydrofurfuryl ether and pentamethylvinyltriamine were used as the regulators in amounts of 0.06mmol and 0.03mmol, respectively.
The vinyl content of the butadiene segment in the copolymer was determined to be 21%, the polystyrene-polybutadiene single-arm polymer molecular weight was 205000, the MWD was 1.30, and the coupling efficiency was 68%.
Example 9
Adding 30g of styrene and 800g of cyclohexane into a polymerization bottle, adding 1.15mmol of 2-ethylamino-tetrahydropyrrole and 0.65mmol of 2, 3-dimethyl sodium octoate, then adding 4.0mmol of n-butyl lithium initiator, wherein the polymerization temperature is 80 ℃, the reaction time is 0.5 hour, then adding 70g of butadiene, the polymerization temperature is 80 ℃, the reaction time is 1 hour, finally adding silicon tetrachloride for coupling, the coupling temperature is 80 ℃, the reaction time is 0.5 hour, and precipitating and vacuum drying the polymer to obtain the styrene-butadiene-styrene copolymer with the star-shaped block structure.
The vinyl content of the polybutadiene block in the copolymer was 30%, and the polystyrene-polybutadiene single-arm polymer was measured to have a molecular weight of 128000, an MWD of 1.50, and a coupling efficiency of 78%.
Comparative example 9
The other conditions were the same as in example 9 except that tetrahydrofuran and tetramethylethylenediamine were used as the regulators in amounts of 1.15mmol and 0.65mmol, respectively.
The vinyl content of the butadiene segment in the polystyrene/butadiene copolymer was determined to be 29%, the polystyrene-polybutadiene single-arm polymer molecular weight was 128000, the MWD was 1.40, and the coupling efficiency was 68%.
Example 10
Adding 90g of butadiene, 10g of styrene, 500g of cyclohexane and 100g of n-hexane into a polymerization bottle, adding 0.6mmol of 2-ethylamino-tetrahydropyrrole and 0.6mmol of sodium 2, 3-dimethyloctanol, then adding 0.8mmol of isobutyllithium initiator, carrying out polymerization at 80 ℃ for 1 hour, and finally adding silicon tetrachloride for coupling, wherein the coupling temperature is 80 ℃ and the reaction time is 0.5 hour. The polymer is precipitated and dried in vacuum to obtain the star-structured polystyrene/butadiene random copolymer.
The vinyl content of the polybutadiene block in the copolymer was 65%, the polystyrene/butadiene one-armed polymer molecular weight was determined to be 120000, the MWD was 1.40, and the coupling efficiency was 70%.
Comparative example 10
The other conditions were the same as in example 10 except that tetrahydrofuran and sodium dodecylbenzenesulfonate were used as regulators in an amount of 0.6mmol in each case.
The vinyl content of the butadiene segment in the polystyrene/butadiene copolymer was determined to be 64%, the polystyrene/butadiene single-arm polymer molecular weight was 120000, the MWD was 1.40, and the coupling efficiency was 60%.
Example 11
Adding 45g of butadiene, 5g of styrene, 250g of cyclohexane and 50g of n-hexane into a polymerization bottle, adding 2.05mmol of 2-ethylamino-tetrahydropyrrole and 0.6mmol of sodium 2, 3-dimethyloctanol, then adding 0.4mmol of isobutyl lithium initiator, carrying out polymerization at 80 ℃ for 0.6 h, and finally adding silicon tetrachloride for coupling, wherein the coupling temperature is 70 ℃ and the reaction time is 0.7 h. The polymer is precipitated and dried in vacuum to obtain the star-structured polystyrene-butadiene random copolymer product.
The vinyl content of the polybutadiene block in the copolymer was 78%, and the molecular weight of the styrene-butadiene single-arm copolymer was determined to be 118000, the MWD was 1.38, and the coupling efficiency was 78%.
Example 12
40g of butadiene, 10g of styrene, 250g of cyclohexane and 50g of n-hexane are added into a polymerization bottle, 0.05mmol of 2-ethylamino-tetrahydropyrrole and 0.025mmol of sodium 2, 3-dimethyloctanol are added, 0.4mmol of isobutyllithium initiator is added, the polymerization temperature is 80 ℃, the reaction time is 1 hour, and finally silicon tetrachloride is added for coupling, the coupling temperature is 70 ℃, and the reaction time is 0.7 hour. The polymer is precipitated and dried in vacuum to obtain the star-structured polystyrene-butadiene random copolymer product.
The vinyl content of the polybutadiene block in the copolymer was 20%, and the molecular weight of the styrene-butadiene single-arm copolymer was measured to be 124000, the MWD was 1.33, and the coupling efficiency was 72%.
Example 13
180g of butadiene, 20g of styrene, 1000g of cyclohexane and 200g of n-hexane are added into a polymerization bottle, 0.65mmol of 2-ethylamino-tetrahydropyrrole and 0.31mmol of sodium 2, 3-dimethyloctanol are added, 0.36mmol of isobutyllithium initiator is added, the polymerization temperature is 80 ℃, the reaction time is 1 hour, and finally silicon tetrachloride is added for coupling, the coupling temperature is 70 ℃, and the reaction time is 0.7 hour. The polymer is precipitated and dried in vacuum to obtain the star-structured polystyrene-butadiene random copolymer product.
The vinyl content of the polybutadiene block in the copolymer was 23%, and the molecular weight of the styrene-butadiene single-arm copolymer was determined to be 118000, the MWD was 1.35, and the coupling efficiency was 68%.
Example 14
150g of isoprene, 20g of styrene and 1600g of cyclohexane are added into a polymerization bottle, 3.8mmol of 2-ethylamino-tetrahydropyrrole and 0.9mmol of sodium 2, 3-dimethyl octanol are added, then 0.8mmol of n-butyl lithium initiator is added, the polymerization temperature is 60 ℃, the reaction time is 1 hour, and the obtained polymer is precipitated and dried in vacuum to obtain the linear polystyrene/isoprene random copolymerization product.
The vinyl content of the polyisoprene block in the copolymer was 73%, the polystyrene-isoprene molecular weight was determined to be 236000, and the MWD was 1.18.
Example 15
Adding 15g of styrene monomer and 800g of cyclohexane into a polymerization bottle, adding 0.45mmol of 2-butylamino-tetrahydropyrrole and 0.38mmol of 2, 3-dimethyl sodium octoate, then adding 1.06mmol of n-butyl lithium initiator, the polymerization temperature is 50 ℃, the reaction time is 1 hour, then adding 60g of butadiene monomer, the polymerization temperature is 60 ℃, the reaction time is 1 hour, finally adding 15g of styrene monomer, the reaction temperature is 60 ℃, the reaction time is 1 hour, and precipitating and vacuum drying the polymer to obtain the linear styrene-butadiene-styrene block copolymer.
The vinyl content of the polybutadiene block in the test copolymer was 38%, the molecular weight of the styrene-butadiene one-armed copolymer was 218000, and the MWD was 1.38.
Examples 1,2, 3,4 and comparative examples 1,2, 3,4 show that the vinyl content of butadiene is changed little when the polymerization temperature is changed by using the composite regulating system of the present invention, while the vinyl content of butadiene is changed greatly when the polymerization temperature is changed by using other regulating agents or a single regulating agent, and examples 5, 6, 7, 8, 9, 10 and comparative examples 5, 6, 7, 8, 9, 10 show that the coupling efficiency can be remarkably improved by using the composite regulating agent of the present invention, thereby reducing the presence of a small molecular weight polymer (a small molecular weight polystyrene or a small molecular weight polystyrene-butadiene block copolymer) and improving the mechanical properties, particularly tensile strength of the product. Examples 10 to 14 are the copolymerization of styrene and conjugated diene, which show that the composite modifier of the present invention can also be used for isoprene/styrene random copolymerization. Example 15 is the copolymerization of styrene and a conjugated diene to give a linear block copolymer.
TABLE 1 structural control and coupling efficiency of examples and comparative examples
Claims (10)
1. The regulator for conjugated diene is characterized by comprising a 2-alkylamino-tetrahydropyrrole regulator and a sodium alkoxide regulator, wherein the molar ratio of the 2-alkylamino-tetrahydropyrrole regulator to an organic lithium initiator is 0.12-6.2, the molar ratio of the sodium alkoxide regulator to the organic lithium initiator is 0.06-2, the 2-alkylamino-tetrahydropyrrole regulator is an asymmetric amine regulator, and the structural formula is as follows:
wherein R is an alkyl group having 1 to 4 carbon atoms;
the structural formula of the sodium alkoxide regulator is as follows:
wherein R is1、R2、R3Is a hydrogen atom or an alkyl group of 1 to 4 carbons, R1、R2、R3The same or different.
2. Use of a regulator of conjugated diolefins according to claim 1 in a process for the anionic copolymerization of hydrogenated styrenic elastomers, characterized in that it comprises the following steps:
firstly, adding a hydrocarbon solvent, a styrene monomer, a 2-alkylamino-tetrahydropyrrole regulator and a sodium alkoxide regulator into a polymerization kettle, and then adding an organic lithium initiator, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-1 hour, so as to generate a styrene section; then adding a conjugated diene monomer, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-1 hour, so as to generate a styrene-conjugated diene section; finally, adding silicon tetrachloride for coupling, wherein the coupling temperature is 40-80 ℃, and the reaction time is 0.2-1 hour, so as to obtain the star block structure styrene-butadiene-styrene copolymer.
3. Use of a regulator of conjugated diolefins according to claim 1 in a process for the anionic copolymerization of hydrogenated styrenic elastomers, characterized in that it comprises the following steps:
firstly, adding a hydrocarbon solvent, a styrene monomer, a conjugated diene monomer, a 2-alkylamino-tetrahydropyrrole regulator and a sodium alkoxide regulator into a polymerization kettle, and then adding an organic lithium initiator, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-2 hours, so as to generate a linear styrene-conjugated diene random copolymer; finally, adding silicon tetrachloride for coupling, wherein the coupling temperature is 40-80 ℃, and the reaction time is 0.2-1 hour, so as to obtain the star-shaped styrene-conjugated diene random copolymer.
4. Use of a regulator of conjugated diolefins according to claim 1 in a process for the anionic copolymerization of hydrogenated styrenic elastomers, characterized in that it comprises the following steps:
firstly, adding a hydrocarbon solvent, a styrene monomer, a 2-alkylamino-tetrahydropyrrole regulator and a sodium alkoxide regulator into a polymerization kettle, and then adding an organic lithium initiator, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-1 hour, so as to generate a styrene section; then adding a conjugated diene monomer, wherein the polymerization temperature is 40-90 ℃, and the reaction time is 0.5-1 hour, so as to generate a styrene-conjugated diene section; finally, styrene monomer is added, the polymerization temperature is 40-90 ℃, the reaction time is 0.5-1 hour, and the linear styrene-conjugated diene-styrene segmented copolymer is generated.
5. The use of the modifier for conjugated diene as claimed in any one of claims 2 to 4 in the anionic copolymerization process of hydrogenated styrene-based elastomer, wherein the amount of styrene monomer is 10 to 60 wt% based on the total amount of styrene monomer and conjugated diene monomer.
6. Use of the regulator of conjugated diolefins according to any of claims 2 to 4 in a process for the anionic copolymerization of hydrogenated styrenic elastomers, characterized in that the conjugated diolefin monomers are selected from butadiene, isoprene.
7. The use of the regulator of conjugated diolefins as claimed in any one of claims 2 to 4 in the anionic copolymerization of hydrogenated styrenic elastomers, wherein said organolithium initiator is used in an amount of 0.1 to 4mmol per 100g of the total amount of styrene monomer and conjugated diolefin monomer.
8. The use of the regulator of conjugated diolefins as claimed in any one of claims 2 to 4 in the anionic copolymerization process of hydrogenated styrenic elastomers, wherein said organolithium initiator is n-butyllithium or isobutyllithium.
9. The use of the regulator of conjugated diene as claimed in any one of claims 2 to 4, wherein the hydrocarbon solvent is at least one of cyclohexane and n-hexane, and the amount of the hydrocarbon solvent added is 500 wt% to 1200 wt% of the total amount of the styrene monomer and the conjugated diene monomer.
10. The use of the regulator of conjugated diolefin as claimed in any one of claims 2 to 4 in the anionic copolymerization of hydrogenated styrene-based elastomer, wherein the molar ratio of vinyl groups to conjugated diolefin in the styrene-based elastomer is controlled to 20% to 80% by weight based on the conjugated diolefin monomer participating in the copolymerization.
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