CN117186325A - Method for preparing star polymer by using multifunctional macromolecular initiator based on conjugated olefin polymer - Google Patents
Method for preparing star polymer by using multifunctional macromolecular initiator based on conjugated olefin polymer Download PDFInfo
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- CN117186325A CN117186325A CN202311151635.7A CN202311151635A CN117186325A CN 117186325 A CN117186325 A CN 117186325A CN 202311151635 A CN202311151635 A CN 202311151635A CN 117186325 A CN117186325 A CN 117186325A
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- 229920000642 polymer Polymers 0.000 title claims abstract description 124
- 239000003999 initiator Substances 0.000 title claims abstract description 110
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 24
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 123
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 57
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 39
- -1 alkyl lithium Chemical compound 0.000 claims description 32
- 229910052744 lithium Inorganic materials 0.000 claims description 28
- 239000000178 monomer Substances 0.000 claims description 28
- FZYQHMHIALEGMG-MVOHYUIRSA-N pcbb Chemical compound CCCCOC(=O)CCCC1([C@]23C4=C5C=CC6=C7C=CC8=C9C=CC%10=C%11C=CC%12=C(C=C4)[C@]31C1=C3C4=C2C5=C6C=2C7=C8C5=C9C%10=C(C3=C5C4=2)C%11=C%121)C1=CC=CC=C1 FZYQHMHIALEGMG-MVOHYUIRSA-N 0.000 claims description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 24
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 150000001336 alkenes Chemical class 0.000 claims description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 13
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 12
- 230000000977 initiatory effect Effects 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000003292 glue Substances 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- CCSZEZULHZMGHK-UHFFFAOYSA-N 1-ethenyl-2-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=CC=C1C=C CCSZEZULHZMGHK-UHFFFAOYSA-N 0.000 claims description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- GRFNSWBVXHLTCI-UHFFFAOYSA-N 1-ethenyl-4-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=C(C=C)C=C1 GRFNSWBVXHLTCI-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical group 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 238000010551 living anionic polymerization reaction Methods 0.000 claims description 4
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- LTGJSMARDKHZOY-UHFFFAOYSA-N 1-ethenyl-3-[(2-methylpropan-2-yl)oxy]benzene Chemical compound CC(C)(C)OC1=CC=CC(C=C)=C1 LTGJSMARDKHZOY-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 229910052732 germanium Inorganic materials 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 239000011133 lead Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 abstract description 23
- 230000008878 coupling Effects 0.000 abstract description 20
- 238000010168 coupling process Methods 0.000 abstract description 20
- 238000009826 distribution Methods 0.000 abstract description 20
- 239000007822 coupling agent Substances 0.000 abstract description 15
- 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 abstract description 8
- 239000005049 silicon tetrachloride Substances 0.000 abstract description 8
- PPDADIYYMSXQJK-UHFFFAOYSA-N trichlorosilicon Chemical compound Cl[Si](Cl)Cl PPDADIYYMSXQJK-UHFFFAOYSA-N 0.000 abstract description 8
- 238000010539 anionic addition polymerization reaction Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 125000005843 halogen group Chemical group 0.000 abstract 1
- 229920002521 macromolecule Polymers 0.000 abstract 1
- 230000000192 social effect Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 62
- 229910052786 argon Inorganic materials 0.000 description 31
- 238000003756 stirring Methods 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 26
- 239000000047 product Substances 0.000 description 18
- 238000004458 analytical method Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 229920006112 polar polymer Polymers 0.000 description 11
- 239000000376 reactant Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- FKJPVBLBADLYON-UHFFFAOYSA-N C1(CC1)C(=CC=C)C1=CC=CC=C1 Chemical compound C1(CC1)C(=CC=C)C1=CC=CC=C1 FKJPVBLBADLYON-UHFFFAOYSA-N 0.000 description 4
- CEPJNBWDGVQZTH-UHFFFAOYSA-N C=CC=C(C1CCC1)C1=CC=CC=C1 Chemical compound C=CC=C(C1CCC1)C1=CC=CC=C1 CEPJNBWDGVQZTH-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 4
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000013341 scale-up Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012916 structural analysis Methods 0.000 description 3
- FPWPIVJXMURJKK-UHFFFAOYSA-N (3-ethenylphenoxy)-trimethylsilane Chemical compound C[Si](C)(C)OC1=CC=CC(C=C)=C1 FPWPIVJXMURJKK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UDSTYBSQGGWMII-UHFFFAOYSA-N C(C)C(CCC)[Li] Chemical compound C(C)C(CCC)[Li] UDSTYBSQGGWMII-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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
- 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
- C08F297/023—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 using a coupling agent
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerization Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A method for preparing star polymer based on multi-functional macromolecular initiator of conjugated olefin polymer, star structure polymer is the macromolecule formed by linear polymer arms with outwards extending centers, which has good solubility, lower viscosity, good processability and the like compared with linear polymer, and the star polymer is synthesized by using active anion polymerization, usually Divinylbenzene (DVB), silicon trichloride, silicon tetrachloride and the like are used as coupling agents, because DVB activity is extremely high, silicon trichloride and silicon tetrachloride are limited by the number of low halogen atoms, the prepared star polymer has wider molecular weight distribution, lower coupling efficiency and lower number of arms, the multi-functional macromolecular initiator of conjugated olefin polymer has stable structure, multiple functional sites and can be designed to synthesize multi-arm star polymer, in addition, the multi-arm star polymer prepared by using the multi-functional initiator synthesized by the application has low molecular weight distribution, accurate arm number design, high coupling efficiency and the like, and the method is simple, easy to implement, low in cost, easy to industrialize, wide in application range, and has better economic benefit and social effect.
Description
Technical Field
The application relates to the technical field of synthetic functional polymer materials, in particular to a method for preparing star polymers by using a multifunctional macromolecular initiator based on conjugated olefin polymers.
Background
Multi-arm star polymers (Multi-arm star polymers) are composed of a central core and an outer arm, and methods for synthesizing such polymers are generally classified into a core-before-arm method and a core-before-arm method, wherein the core-before-arm method requires first preparing a Multi-functional initiator with definite structure and number of initiation ends, then preparing a star polymer with controllable number of arms through living polymerization of monomers, for the core-before-arm method, firstly preparing a linear polymer active chain with expected chain length, then adding a coupling agent to a polymerization system to prepare the Multi-arm star polymer, however, the number of arms of the Multi-arm star polymer prepared by the method generally depends on the coupling efficiency of the active chain end and the coupling agent, the method has limitations, at present, the preparation of the Multi-arm star polymer based on the living anionic polymerization generally depends on the core-before-arm method, the coupling agent adopted is Divinylbenzene (DVB), silicon chloride and the like, and the existence of the technical barrier of the coupling agent and the patent are limited, so how to prepare the Multi-arm star polymer based on the living anionic polymerization is a technical solution for preparing the Multi-functional star polymer.
Therefore, in order to solve the deficiencies of the prior art, it is necessary to provide a method for preparing star polymers based on a multifunctional macroinitiator for conjugated olefin polymers.
Disclosure of Invention
The application aims to avoid the defects of the prior art and provide a method for preparing star polymers by using a multifunctional macromolecular initiator based on conjugated olefin polymers, which has the following beneficial effects compared with the prior initiator and coupling agent:
the multi-arm star polymer synthesized by living anion polymerization generally uses Divinylbenzene (DVB), silicon trichloride, silicon tetrachloride coupling agent and the like as coupling agents, wherein DVB monomers have extremely high activity, are extremely easy to generate coupling reaction in nonpolar solvents, so that the addition amount of the DVB monomers needs to be precisely controlled, the silicon trichloride and the silicon tetrachloride are similar to organic lithium and must be stored under anhydrous and anaerobic conditions, and are difficult to industrially scale up due to the rigor of the storage conditions, the multifunctional initiator is prepared based on the fact that conjugated olefin polymer initiates double bonds in the chain of the conjugated olefin polymer through alkyl lithium, and the conjugated double bonds exist in the conjugated olefin polymer/the repeating units in the active chain of the conjugated olefin polymer, therefore, after the alkyl lithium is added, double bonds far away from benzene rings in PCPBB/PCBB/PMEPDB and derivatives thereof are initiated by organic lithium to form a multifunctional macromolecular initiator, and as the polymerization degree of the prepared PCPBB/PCBB/PMEPDB and derivatives thereof is controllable, the multifunctional macromolecular initiator can be directly added to prepare the olefin monomer initiated by the multifunctional macromolecular initiator by the alkyl lithium equivalent to the double bonds in the chain, so that the multi-arm star polymer with accurate arm number can be prepared, in addition, the PCPBB/PCBB/PMEPDB and derivatives thereof can be stored at low temperature after being prepared in large quantity, and the multifunctional initiator can be obtained by directly adding the alkyl lithium to initiate for 10-30min when in use, thereby being convenient for industrial production of the star polymer.
The above object of the present application is achieved by the following means.
The application provides a method for preparing star polymers by using a multifunctional macroinitiator based on conjugated olefin polymers, which comprises the following steps:
s1: preparing PCPBB/PCBB/PMEPDB and derivatives thereof by living anionic polymerization;
s2: preparing a multi-functional macromolecular initiator by PCPBB/PCBB/PMEPDB and derivatives thereof to initiate olefin monomers to synthesize a multi-arm star polymer with single arms being olefin monomers homopolymerized;
s3, preparing a multi-functional initiator by PCPBB/PCBB/PMEPDB and derivatives thereof to initiate olefin monomers to synthesize the multi-arm star polymer with a single arm in a block structure.
Further, S1 includes:
s11: adding an organic solvent, CPBB/CBBB/MEPDB and derivatives thereof and alkyl lithium under an anaerobic environment to form a reaction solution A;
s12: adding the reaction liquid A into a polymerization reactor for heating treatment;
s13: after heating for 3-8 hours, injecting isopropanol into the reaction liquid A to terminate polymerization;
s14: after the polymerization of the reaction solution A is terminated, gum deposition occurs, and gum deposition reaction solution is produced;
s15: adding the glue depositing reaction liquid into a vacuum drying box for drying treatment;
s16: drying to obtain PCPBB/PCBB/PMEPDB and derivatives thereof.
Further, S2 includes:
s21: adding an organic solvent, PCPBB, PCBBB, PMEPDB and derivatives thereof and alkyl lithium under anaerobic environment, and preparing a multifunctional initiator by PCPBB/PCBB/PMEPDB and derivatives thereof with double bonds in an initiating chain for 10min-30 min;
s22: adding a multifunctional initiator A into a polymerization reactor for heating treatment;
s23: heating to-80 deg.c, and injecting regulator into the multifunctional initiator to obtain multifunctional initiator B;
s24: adding olefin monomers into the multifunctional initiator B, and reacting for 3-8 hours to obtain a multifunctional initiator C;
s25: injecting isopropanol into the multifunctional initiator C to terminate polymerization to obtain a multifunctional initiator D;
s26: the polyfunctional initiator D is subjected to polymerization termination and then is subjected to glue precipitation to obtain a polyfunctional initiator F;
s27: adding the multifunctional initiator F after glue precipitation into a vacuum drying box for drying treatment;
s28: and drying to obtain the homo-multi-arm star polymer with the single arm being the olefin monomer.
Further, S3 includes:
s31: adding an organic solvent, a multifunctional initiator F and alkyl lithium in an anaerobic environment, and obtaining a reaction solution B by initiating the multifunctional initiator F containing double bonds in the chain for 10-30 min;
s32: adding the reaction liquid B into a polymerization reactor for heating treatment;
s33: heating to-80 deg.c, and injecting regulator into the reaction liquid to obtain reaction liquid C;
s34: adding olefin monomer into the reaction solution C, and reacting for 3-8 hours to obtain a reaction solution D;
s35: adding olefin monomer into the reaction solution D again, and reacting for 3-8 hours to obtain a reaction solution E;
s36: injecting isopropanol into the reaction solution E to terminate polymerization to obtain a reaction solution F;
s37: after the polymerization of the reaction solution F is terminated, the glue deposition occurs to obtain a reaction solution G;
s38: adding the reaction solution G after glue precipitation into a vacuum drying box for drying treatment;
s39: and drying to obtain the multi-arm star polymer with a single arm in a block structure.
Specifically, the CPBB derivative/CBBB derivative/MEPDB derivative contains an amine group, a dimethylamino group, an alkoxy group, a tert-butyl group, a long carbon chain alkyl group, a cyano group, a hydroxyl group, a triisopropoxyl group, a hydrosilylation group, an alkynyl group, a mercapto group, a fluorine atom, a chlorine atom, and a bromine atom.
Specifically, the olefin monomers include styrene, butadiene, isoprene, α -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2-vinylpyridine, 4-vinylpyridine, methyl methacrylate, n-butyl methacrylate, 2-t-butoxystyrene, 3-t-butoxystyrene, 4-t-butoxystyrene, silane, trimethylsilane, 3-vinylcatechol acetone, 4-vinylcatechol acetone, 1.4-divinylbenzene, 1.2-divinylbenzene, 1.3-divinylbenzene.
Specifically, the alkyl lithium initiator includes: and one or a mixture of a plurality of monofunctional lithium initiators in RLi and TRLi, wherein R is a hydrocarbon group, an alkane group and an arene group with 2-20 carbon atoms, and T is a metal atom and a nitrogen atom, and the metal atom is tin, silicon, lead, titanium and germanium.
Specifically, the organic solvent comprises nonpolar aromatic hydrocarbon and nonpolar aliphatic hydrocarbon, the organic solvent used for polymerization at 30-80 ℃ comprises benzene, toluene, hexane, cyclohexane and n-hexane, and the organic solvent used for polymerization at-80-0 ℃ comprises mixed solution of tetrahydrofuran, tetrahydrofuran and n-hexane.
Specifically, the process of preparing PCPBB/PCBB/PMEPDB and its derivatives is carried out at 30-80 deg.c and the process of preparing multi-arm star polymer at-80 deg.c.
In particular, the modifier comprises a mixture of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and metal alkoxides.
Compared with the existing initiator and coupling agent, the application has the following beneficial effects:
the multi-arm star polymer synthesized by living anion polymerization generally uses Divinylbenzene (DVB), silicon trichloride, silicon tetrachloride coupling agent and the like as coupling agents, wherein DVB monomers have extremely high activity, are extremely easy to generate coupling reaction in nonpolar solvents, so that the addition amount of the DVB monomers needs to be precisely controlled, the silicon trichloride and the silicon tetrachloride are similar to organic lithium and must be stored under anhydrous and anaerobic conditions, and are difficult to industrially scale up due to the rigor of the storage conditions, the multifunctional initiator is prepared based on the fact that conjugated olefin polymer initiates double bonds in the chain of the conjugated olefin polymer through alkyl lithium, and the conjugated double bonds exist in the conjugated olefin polymer/the repeating units in the active chain of the conjugated olefin polymer, therefore, after the alkyl lithium is added, double bonds far away from benzene rings in PCPBB/PCBB/PMEPDB and derivatives thereof are initiated by organic lithium to form a multifunctional macromolecular initiator, and as the polymerization degree of the prepared PCPBB/PCBB/PMEPDB and derivatives thereof is controllable, the multifunctional macromolecular initiator can be directly added to prepare the olefin monomer initiated by the multifunctional macromolecular initiator by the alkyl lithium equivalent to the double bonds in the chain, so that the multi-arm star polymer with accurate arm number can be prepared, in addition, the PCPBB/PCBB/PMEPDB and derivatives thereof can be stored at low temperature after being prepared in large quantity, and the multifunctional initiator can be obtained by directly adding the alkyl lithium to initiate for 10-30min when in use, thereby being convenient for industrial production of the star polymer.
Drawings
The application is further illustrated by the accompanying drawings, which are not to be construed as limiting the application in any way.
FIG. 1 is a structural formula of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) and 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB), (3-methylenepenta-1, 4-dien-1-yl) benzene (MEPDB).
FIG. 2 is a structural formula of homopolymers of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) and 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB), (3-methylenepenta-1, 4-dien-1-yl) benzene (MEPDB).
Detailed Description
The present application is further illustrated by the following examples, which are not intended to limit the scope of the claims herein, by analyzing polymer structure by nuclear magnetic resonance spectroscopy, by molecular weight and molecular weight distribution index (ratio of weight average molecular weight to number average molecular weight) of the polymer by gel permeation chromatography, and by analyzing the arm number of the multi-arm star polymer.
Example 1.
Shown in FIG. 1 are structural formulas of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) and 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB), (3-methylenepenta-1, 4-dien-1-yl) benzene (MEPDB).
In FIG. 2 are structural formulas of homopolymers of 1-cyclopropyl-1-phenyl-1, 3-butadiene (CPBB) and 1-cyclobutyl-1-phenyl-1, 3-butadiene (CBBB), (3-methylenepenta-1, 4-dien-1-yl) benzene (MEPDB).
Under the protection of argon, adding 100ml of benzene, 900ml of normal hexane and 100g of CPBB into a polymerization reactor, heating to 30 ℃, opening and stirring, adding an initiator n-butyllithium according to the designed PCPBB polymerization degree of 4, reacting for 8 hours, adding isopropanol to terminate, precipitating reactants in excessive anhydrous methanol, drying the obtained polymer in a vacuum oven until the weight is constant, testing and analyzing that the molecular weight of PCPBB is 740g/mol, the polymerization degree is 4.0, adding 1g of PCPBB and 1000ml of THF into the polymerization reactor under the protection of the argon, setting the temperature to-80 ℃, opening and stirring, adding sec-butyllithium according to the double bond/initiator ratio in PCPBB chain of 0.5, preparing a multifunctional initiator for 30 minutes, then adding 0.6g of THF, rapidly adding 100g of 2-vinyl pyridine, initiating polymerization for 8 hours, adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive anhydrous ethanol, drying the obtained polymer in the vacuum oven until the weight is constant, and analyzing the structure of the product is as follows: the number average molecular weight of the polymer was 1.6kg/mol, the molecular weight distribution was 1.05, the number of polymer arms was 3.8, and the coupling efficiency was 95.0%.
Example 2.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 200ml of toluene, 800ml of cyclohexane and 100g of CPBB are firstly added into a polymerization reactor, the temperature is raised to 40 ℃, stirring is started, initiator ethyl lithium is added according to the designed PCPBB polymerization degree of 8, reaction is carried out for 7h, isopropanol is added for termination, reactants are precipitated in excessive anhydrous methanol, the obtained polymer is dried in a vacuum oven to constant weight, the molecular weight of PCPBB is 1600g/mol after test analysis, the polymerization degree is 8, under the protection of argon, 0.083g of PCPBB, 900ml of THF and 100ml of normal hexane are added into the polymerization reactor, the temperature is set to-40 ℃, stirring is started, n-butyllithium is added according to the proportion of double bonds/initiator in PCPBB chain of 0.5, a multifunctional initiator is prepared for 25min, then 0.5g of tetramethyl ethylenediamine (TMEDA) is added, 100g of methyl methacrylate is rapidly added, polymerization is initiated for 7h, polymerization is terminated by adding degassed isopropanol, the reaction solution is precipitated in excessive anhydrous ethanol, and the obtained polymer is dried in the vacuum oven to constant weight, the product structure analysis result is as follows: the number average molecular weight of the polymer was 7.0kg/mol, the molecular weight distribution was 1.08, the number of polymer arms was 7.9, and the coupling efficiency was 95.2%.
Example 3.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 300ml of ethylbenzene, 700ml of cyclopentane and 100g of MEPDB are firstly added into a polymerization reactor, the temperature is raised to 40 ℃, stirring is started, the initiator tert-butyllithium is added according to the design PMEPDB polymerization degree of 12, the reaction is carried out for 6 hours, isopropanol is added for termination, the reactant is precipitated in excessive anhydrous methanol, the obtained polymer is dried to constant weight in a vacuum oven, the molecular weight of PMEPDB is 1900g/mol and the polymerization degree is 12.5 through test analysis,
under the protection of argon, 0.042g of PMEPDB, 800ml of THF and 200ml of n-hexane are added into a polymerization reactor, the temperature is set to 0 ℃, stirring is started, the ethyl butyl lithium is added according to the proportion of double bonds/initiator in the PMEPDB chain of 0.5, a multifunctional initiator is prepared for 20min, then 0.8g of potassium tert-butoxide is added, 100g of 2-tert-butoxide styrene is quickly added, polymerization is initiated for 6h, degassed isopropanol is added to terminate polymerization, the reaction solution is precipitated in excessive absolute ethyl alcohol, the obtained polymer is dried to constant weight in a vacuum oven, and the structural analysis result of the product is as follows: the number average molecular weight of the polymer was 12.0kg/mol, the molecular weight distribution was 1.05, the number of polymer arms was 12.1, and the coupling efficiency was 96.8%.
Example 4.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 400ml of dimethylbenzene, 600ml of heptane and 100g of CPBB-OCH3 are firstly added into a polymerization reactor, the temperature is raised to 50 ℃, stirring is started, sec-butyllithium serving as an initiator is added according to the designed polymerization degree of CPBB-OCH3 of 16, reaction is carried out for 5h, isopropanol is added for termination, reactants are precipitated in excessive anhydrous methanol, the obtained polymer is dried in a vacuum oven until the constant weight, the molecular weight of PCPBB-OCH3 is 3400g/mol after test analysis, the polymerization degree is 15.9, 0.014g of CPBB-OCH3 and 100ml of normal hexane are added into the polymerization reactor under the protection of argon, the temperature is set to 40 ℃, stirring is started, isopropyl lithium is added according to the proportion of double bonds/initiator in CPBB-OCH3 chains of 0.5, the multifunctional initiator is prepared for 20min, then 1.2g of potassium tert-pentoxy is added, 100g of styrene is rapidly added, polymerization is initiated for 5.5h, the isopropanol after the addition is carried out, polymerization is terminated in the anhydrous ethanol, the obtained polymer solution is precipitated in the vacuum oven until the constant weight is dried until the structure analysis results are obtained, and the product is dried in the oven after the following steps: the number average molecular weight of the polymer was 36.5kg/mol, the molecular weight distribution was 1.08, the number of polymer arms was 15.5, and the coupling efficiency was 98.7%.
Example 5.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 300ml of cyclohexane, 700ml of heptane and 100g of CBBB-yne are firstly added into a polymerization reactor, the temperature is raised to 60 ℃, stirring is started, n-butyllithium initiator is added according to the designed polymerization degree of PCBB-yne of 20, reaction is carried out for 4 hours, isopropanol is added for termination, reactants are precipitated in excessive anhydrous methanol, the obtained polymer is dried in a vacuum oven until the constant weight is reached, the molecular weight of the PCBB-yne is 6400g/mol after test analysis, the polymerization degree is 19.4, under the protection of argon, 0.0075g,THF 500ml of PCBB-yne and 500ml of n-hexane are added into the polymerization reactor, the temperature is set to 80 ℃, stirring is started, n-butyllithium initiator is added according to the proportion of double bonds/initiator in PCBB-yne chain of 0.5, the multifunctional initiator is prepared for 10 minutes, then 1.5g of crown ether is added, 100g of 4-tertiary butoxystyrene is rapidly added, the polymerization is initiated for 3 hours, the polymerization is terminated after the added isopropanol is dried in the vacuum oven, the obtained polymer is precipitated in excessive anhydrous ethanol, the obtained polymer is dried until the constant weight is reached, the structure analysis result is as follows: the number average molecular weight of the polymer was 66.5kg/mol, the molecular weight distribution was 1.12, the number of polymer arms was 19.1, and the coupling efficiency was 98.4%.
Example 6.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 100ml of toluene, 900ml of cyclohexane and 100g of MEPDB-NMe2 are firstly added into a polymerization reactor, the temperature is raised to 30 ℃, stirring is started, initiator ethyl lithium is added according to the designed polymerization degree of PMEPDB-NMe2 of 4, the reaction is carried out for 8 hours, isopropanol is added for termination, the reactant is precipitated in excessive anhydrous methanol, the obtained polymer is dried in a vacuum oven until the constant weight, the molecular weight of PMEPDB-NMe2 is 720g/mol after test analysis, the polymerization degree is 3.9, under the protection of argon, 0.17g of PMEPDB-NMe2 and 1000ml of THF are added into the polymerization reactor, the temperature is set to-80 ℃, stirring is started, isopropyl lithium is added according to the proportion of double bonds/initiator in the PMEPDB-NMe2 chain of 0.5, the polyfunctional initiator is prepared for 30 minutes, then 2.5g of dipiperidine ethane (DPE) is added, 50g of 2-vinylpyridine (2-VP) is quickly added for initiation polymerization, 50g of Methyl Methacrylate (MMA) is quickly added after 8 hours, the polymerization is carried out for 8 hours, the obtained polymer solution is dehydrated after the polymerization is dehydrated in the vacuum oven until the excessive polymerization is stopped, the obtained is dehydrated, the polymer solution is dehydrated after the polymerization structure is dehydrated, and the polymer is dehydrated in the oven is dehydrated, the product is completely dehydrated: the number average molecular weight of the polymer is 3.1kg/mol, the molecular weight distribution is 1.06, the number of polymer arms is 3.7, the coupling efficiency is 94.8%, and the prepared star polar polymer has single arm of
P (2-VP) -block-PMMA structure.
Example 7.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 300ml of octane, 700ml of normal hexane and 100g of CPBB-NMe2 are firstly added into a polymerization reactor, the temperature is raised to 50 ℃, stirring is started, an initiator n-butyllithium is added according to the designed polymerization degree of PCPBB-NMe2 of 9, the reaction is carried out for 6 hours, isopropanol is added for termination, the reactant is precipitated in excessive anhydrous methanol, the obtained polymer is dried to constant weight in a vacuum oven, the molecular weight of PCPBB-NMe2 is 1800g/mol after test analysis, the polymerization degree is 8.2, under the protection of argon, 0.045g of PCPBB-NMe2, 800ml of THF and 200ml of normal hexane are added into the polymerization reactor, the temperature is set to-70 ℃, the stirring is started, the ratio of double bond/initiator in PCPBB-NMe2 chain is 0.5, the polyfunctional initiator is prepared for 25 minutes, then 1.7g of hexamethylphosphoric triamide (HMPA) is added, 50g of 4-vinyl pyridine (4-VP) is rapidly added, the polymerization is initiated, 7 hours, methyl acrylate is rapidly added into the methyl acrylate is rapidly added to the product after 7 hours, the methyl acrylate is dehydrated, the obtained is dehydrated, the product is dried after the polymerization is dehydrated in the vacuum oven, the obtained is dehydrated, the product is dehydrated, and the structure is completely dehydrated, and the product is dried to constant weight is analyzed: the number average molecular weight of the polymer is 11.0kg/mol, the molecular weight distribution is 1.18, the number of polymer arms is 7.9, the coupling efficiency is 96.3%, and the prepared star polar polymer has single arm of
P (4-VP) -block-PMMA structure.
Example 8.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, adding 100ml of benzene, 900ml of normal hexane and 100g of CPBB into a polymerization reactor, heating to 30 ℃, opening and stirring, adding an initiator n-butyllithium according to the designed PCPBB polymerization degree of 4, reacting for 8 hours, adding isopropanol, stopping precipitation of reactants in excessive anhydrous methanol, drying the obtained polymer in a vacuum oven until the weight is constant, testing and analyzing that the molecular weight of CPBB is 820g/mol, the polymerization degree is 4.2, adding 0.16g of CPBB and 1000ml of THF into the polymerization reactor under the protection of argon, setting the temperature to-80 ℃, opening and stirring, adding n-butyllithium according to the proportion of double bonds/initiator in CPBB chain of 0.5, preparing a multifunctional initiator for 30 minutes, then adding 3.6g of Tetrahydrofuran (THF), rapidly adding 50g of 2-vinyl pyridine (2-VP), initiating polymerization, rapidly adding 30g of 4-vinyl pyridine (4-VP), rapidly adding 20g of 2-tert-butoxystyrene (2-BOS) after 8 hours, rapidly adding the obtained polymer into the dried polymer until the weight is constant, and analyzing the structure of the obtained polymer solution in the vacuum oven until the weight is constant, drying the obtained polymer solution is not subjected to the dry after the polymerization is subjected to the polymerization, and the structure is constant, and the dry, and the product is dried: the number average molecular weight of the polymer is 3.2kg/mol, the molecular weight distribution is 1.15, the number of polymer arms is 3.9, the coupling efficiency is 92.9%, and the prepared star polar polymer has single arms:
p (2-VP) -block-P (4-VP) -block-P (2-BOS) structure.
Example 9.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 500ml of toluene, 500ml of normal hexane and 100g of CBBB are added into a polymerization reactor, the temperature is raised to 80 ℃, stirring is started, an initiator ethyl lithium is added according to the designed PCBB polymerization degree of 20, the reaction is carried out for 8 hours, isopropanol is added for termination, the reactant is precipitated in excessive anhydrous methanol, and the obtained polymer is dried to constant weight in a vacuum oven. The molecular weight of PCBB is 3700g/mol and the polymerization degree is 19.5. Under the protection of argon, 300ml of PCBB 0.0056g,THF 700ml and normal hexane are added into a polymerization reactor, the temperature is set to be minus 20 ℃, stirring is started, ethyl lithium is added according to the proportion of double bonds/initiator in PCBB chain of 0.5, a multifunctional initiator is prepared for 10min, and then 4.0g of Tetrahydrofuran (THF) is added. 30g of 4-t-butoxystyrene (4-BOS) was rapidly added to initiate polymerization. After 3h, 40g of trimethyl (3-vinylphenoxy) silane (3-TMSOS) was added rapidly. After 3h, 30g of 4-vinylcatechol acetone (4-VCA) were added rapidly. The polymerization was terminated by adding degassed isopropanol, the reaction solution was precipitated in excess absolute ethanol, and the resulting polymer was dried in a vacuum oven to constant weight. The product structure analysis results are as follows: the number average molecular weight of the polymer is 88.9kg/mol, the molecular weight distribution is 1.20, the number of polymer arms is 19.0, the coupling efficiency is 96.9%, and the prepared star polar polymer has single arms:
p (4-BOS) -block-P (3-TMSOS) -block-P (4-VCA) structure.
Example 10.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, firstly adding 2.0ml of toluene, 8.0ml of cyclohexane and 1.0g of CPBB into a polymerization reactor, heating to 40 ℃, opening stirring, adding an initiator ethyl lithium according to the designed PCPBB polymerization degree of 4, reacting for 7h, under the protection of argon, injecting the PCPBB-Li with an active terminal into a polymerization reactor filled with 900ml of THF and 100ml of n-hexane, setting the temperature to-80 ℃, opening stirring, adding n-butyl lithium according to the double bond/initiator ratio of PCPBB-Li chain of 0.5, preparing a multifunctional initiator for 25min, then adding 5.5g of ethylene glycol diethyl ether, quickly adding 100g of 4-vinylpyridine, initiating polymerization for 7h, adding degassed isopropanol to terminate polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, drying the obtained polymer in a vacuum oven until the weight is constant, and analyzing the product structure is as follows: the number average molecular weight of the polymer was 5.0kg/mol, the molecular weight distribution was 1.18, the number of polymer arms was 3.9, and the coupling efficiency was 97.5%.
Example 11.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, adding 3.0ml of octane, 7.0ml of normal hexane and 0.2g of CBBB into a polymerization reactor, heating to 80 ℃, opening stirring, adding an initiator sec-butyllithium according to the designed PCBB polymerization degree of 20, reacting for 3 hours, injecting the PCBB-Li with an active tail end into the polymerization reactor filled with 800ml of THF and 200ml of normal hexane under the protection of the argon, setting the temperature to-40 ℃, opening stirring, adding isopropyl lithium according to the double bond/initiator ratio of PCBB-Li chain of 0.5, preparing a multifunctional initiator for 10 minutes, then adding 2.1g of diethylene glycol dibutyl ether, quickly adding 30g of 4-vinylpyridine (4-VP), initiating polymerization, quickly adding 70g of Methyl Methacrylate (MMA) after 3 hours, adding degassed isopropanol after 3 hours, terminating the polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven to constant weight, wherein the structural analysis result is as follows: the number average molecular weight of the polymer is 95.8kg/mol, the molecular weight distribution is 1.17, the number of polymer arms is 19.6, the coupling efficiency is 98.0%, and the prepared star polar polymer has single arm of
P (4-VP) -block-PMMA structure.
Example 12.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, firstly adding 1.0ml of benzene, 9.0ml of normal hexane and 1.0g of MEPDB into a polymerization reactor, heating to 30 ℃, opening stirring, adding an initiator n-butyllithium according to the designed PMEPDB polymerization degree of 4, reacting for 8 hours, under the protection of argon, injecting 1000ml of PMEPDB-Li with an active end into THF, adding into the polymerization reactor, setting the temperature to 0 ℃, opening stirring, adding n-butyllithium according to the double bond/initiator ratio in the PMEPDB-Li chain of 0.5, preparing a multifunctional initiator for 30 minutes, then adding 2.6g of triethylamine, quickly adding 30g of 2-vinylpyridine (2-VP), initiating polymerization, quickly adding 50g of 2-tert-butoxystyrene (2-BOS) after 8 hours, stopping polymerization by adding the degassed isopropanol, precipitating the reaction solution in absolute ethyl alcohol, and drying the obtained polymer in a vacuum oven until the weight is constant, wherein the structure analysis result is as follows: the number average molecular weight of the polymer is 3.2kg/mol, the molecular weight distribution is 1.15, the number of polymer arms is 3.9, the coupling efficiency is 97.6%, and the prepared star polar polymer has single arm of
P (2-VP) -block-P (4-VP) -block-P (2-BOS) structure.
Example 13.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 4.0ml of toluene, 6.0ml of cyclohexane and 0.3g of CPBB-OH are firstly added into a polymerization reactor, the temperature is raised to 80 ℃, stirring is started, an initiator ethyl lithium is added according to the designed PCPBB-OH polymerization degree of 20, the reaction is carried out for 3 hours, under the protection of argon, the PCPBB-OH-Li with an active end is injected into the reactor filled with 600ml of THF, 400ml of n-hexane and the temperature is set to-20 ℃, stirring is started, the n-butyl lithium is added according to the proportion of double bonds/initiator in the PCPBB-OH-Li chain of 0.5, the polyfunctional initiator is prepared for 10 minutes, then 2.8g of triethylamine is added, 10g of 4-vinyl pyridine (2-VP) is quickly added, polymerization is initiated, after 3 hours, 20g of Methyl Methacrylate (MMA) is quickly added, after 3 hours, 70g of 2-tert-butoxystyrene (2-BOS) is quickly added, the polymerization is terminated after the addition, the reaction solution is precipitated in absolute ethyl alcohol, the polymer is dried in a constant weight oven until the product is obtained, and the structure is analyzed under the following conditions: the number average molecular weight of the polymer is 89.6kg/mol, the molecular weight distribution is 1.25, the number of polymer arms is 19.9, the coupling efficiency is 95.6%, and the prepared star polar polymer has single arm of
P (4-VP) -block-PMMA-block-P (2-BOS) structure.
Example 14.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 500ml of normal hexane, 500ml of heptane and 100g of CBBB-SiH are firstly added into a polymerization reactor, the temperature is raised to 30 ℃, stirring is turned on, tert-butyllithium initiator is added according to the designed PCBB-SiH polymerization degree of 4, reaction is carried out for 8h, isopropanol is added for termination, reactants are precipitated in excessive anhydrous methanol, the obtained polymer is dried in a vacuum oven until the constant weight, the molecular weight of PCBB-SiH is 1200g/mol after test analysis, the polymerization degree is 4.5, under the protection of argon, 0.022g of PCBB-SiH, 600ml of THF and 400ml of normal hexane are added into the polymerization reactor, the temperature is set to-80 ℃, tert-butyllithium initiator is added according to the designed PCBB-SiH chain proportion of 0.5, the multifunctional initiator is prepared, then 4.6g of triethylamine is added, 2-tert-butoxystyrene (2-BOS) is rapidly added for 20g, polymerization is initiated, after 8h, trimethyl (3-vinylphenoxy) silane (3-TMSS) is rapidly added for 20g, 4-TMSS is rapidly added into the obtained after the rapid polymerization is carried out for 20 h, the following the rapid polymerization is carried out, 4-vinyl pyridine is rapidly added into the obtained after the vacuum oven until the constant weight is dehydrated, the obtained product is rapidly added into the solution is dehydrated after the vacuum is dehydrated (40 g of isopropyl alcohol) is dehydrated, the obtained after the polymerization is rapidly dried, the product is dehydrated, and the product is dehydrated, is subjected to 8h to the following the vacuum analysis to 20g to the vacuum reaction is subjected to the vacuum to the final to the polymerization reaction to the final product: the number average molecular weight of the polymer is 45.6kg/mol, the molecular weight distribution is 1.08, the number of polymer arms is 4.3, the coupling efficiency is 95.6%, and the prepared star polar polymer has single arm of
P (2-BOS) -block-P (3-TMSOS) -block-P (4-VP) -block-PMMA structure.
Example 15.
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, 5.0ml of ethylbenzene, 5.0ml of octane and 0.2g of CBBB-SiOEt are firstly added into a polymerization reactor, the temperature is raised to 80 ℃, stirring is started, initiator tert-butyllithium is added according to the designed polymerization degree of PCBB-SiOEt of 20, reaction is carried out for 3h, under the protection of argon, 700ml of THF and 300ml of n-hexane are filled into the polymerization reactor, the temperature is set to-20 ℃, stirring is started, and n-butyllithium is added according to the proportion of double bonds/initiator in PCBB-SiOEt-Li chains of 0.5, preparation of a multifunctional initiator for 10min, followed by addition of 2.6g hexamethylphosphoric triamide (HMPA), rapid addition of 10g of 4-vinylpyridine (4-VP) to initiate polymerization, after 3h, rapid addition of 20g of Methyl Methacrylate (MMA), after 3h, rapid addition of 10g of 2-tert-butoxystyrene (2-BOS), after 3h, rapid addition of 60g of 4-vinylcatechol acetone (4-VCA), after 3h, addition of degassed isopropanol to terminate polymerization, precipitation of the reaction solution in excess absolute ethanol, drying of the resulting polymer in a vacuum oven to constant weight, and structural analysis of the product was as follows: the number average molecular weight of the polymer is 99.6kg/mol, the molecular weight distribution is 1.15, the number of polymer arms is 19.2, the coupling efficiency is 96.0%, and the prepared star polar polymer has single arm of
P (4-VP) -block-PMMA-block-P (2-BOS) -block-P (4-VCA) structure.
Comparative example 1
Compared with example 1, the characteristics are the same as example 1 except that: under the protection of argon, adding 3.0ml of octane, 7.0ml of normal hexane and 0.2g of DVB into a polymerization reactor, heating to 80 ℃, opening stirring, adding n-butyllithium according to the molar ratio of DVB/initiator of 20.0, reacting for 5min, then injecting the mixture into the polymerization reactor filled with 800ml of THF and 200ml of normal hexane, setting the temperature to-20 ℃, opening stirring, rapidly adding 30g of 4-vinylpyridine (4-VP), initiating polymerization, rapidly adding 70g of Methyl Methacrylate (MMA) after 3h, adding degassed isopropanol after 3h for terminating polymerization, precipitating the reaction solution in excessive absolute ethyl alcohol, drying the obtained polymer in a vacuum oven to constant weight, and analyzing the structure of the product as follows: the number average molecular weight of the polymer is 95.8kg/mol, the molecular weight distribution is 1.37, the number of polymer arms is 17.8, the coupling efficiency is 89.0%, and the prepared star-shaped polar polymer has a single-arm P (4-VP) -block-PMMA structure.
In comparison with comparative example 1, the polymerization reaction solution, temperature, time and reacted olefin monomer were identical, and in comparative example 1, DVB was used as a coupling agent to prepare star-shaped polar polymer, and in example 15, PCBB-Li multifunctional initiator was used. Because PCBB-Li multifunctional initiator has stable structure and is not easy to crosslink, the multi-arm star polymer prepared in example 11 has narrower molecular weight distribution than that in comparative example 1. In addition, the efficiency of the PCBB-Li multifunctional initiator for re-initiating monomer polymerization is higher than that of DVB coupling, and the structure of the prepared multi-arm star polymer is more perfect.
Compared with the existing initiator and coupling agent, the application has the following beneficial effects:
the multi-arm star polymer synthesized by living anion polymerization generally uses Divinylbenzene (DVB), silicon trichloride, silicon tetrachloride coupling agent and the like as coupling agents, wherein DVB monomers have extremely high activity, are extremely easy to generate coupling reaction in nonpolar solvents, so that the addition amount of the DVB monomers needs to be precisely controlled, the silicon trichloride and the silicon tetrachloride are similar to organic lithium and must be stored under anhydrous and anaerobic conditions, and are difficult to industrially scale up due to the rigor of the storage conditions, the multifunctional initiator is prepared based on the fact that conjugated olefin polymer initiates double bonds in the chain of the conjugated olefin polymer through alkyl lithium, and the conjugated double bonds exist in the conjugated olefin polymer/the repeating units in the active chain of the conjugated olefin polymer, therefore, after the alkyl lithium is added, double bonds far away from benzene rings in PCPBB/PCBB/PMEPDB and derivatives thereof are initiated by organic lithium to form a multifunctional macromolecular initiator, and as the polymerization degree of the prepared PCPBB/PCBB/PMEPDB and derivatives thereof is controllable, the multifunctional macromolecular initiator can be directly added to prepare the olefin monomer initiated by the multifunctional macromolecular initiator by the alkyl lithium equivalent to the double bonds in the chain, so that the multi-arm star polymer with accurate arm number can be prepared, in addition, the PCPBB/PCBB/PMEPDB and derivatives thereof can be stored at low temperature after being prepared in large quantity, and the multifunctional initiator can be obtained by directly adding the alkyl lithium to initiate for 10-30min when in use, thereby being convenient for industrial production of the star polymer.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the scope of the present application, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present application without departing from the spirit and scope of the technical solution of the present application.
Claims (10)
1. A method for preparing star polymers based on a multifunctional macroinitiator of conjugated olefin polymers, characterized by comprising the steps of:
s1: preparing PCPBB/PCBB/PMEPDB and derivatives thereof by living anionic polymerization;
s2: preparing a multi-functional macromolecular initiator by PCPBB/PCBB/PMEPDB and derivatives thereof to initiate olefin monomers to synthesize a multi-arm star polymer with single arms being olefin monomers homopolymerized;
s3, preparing a multi-functional initiator by PCPBB/PCBB/PMEPDB and derivatives thereof to initiate olefin monomers to synthesize the multi-arm star polymer with a single arm in a block structure.
2. The method for preparing star polymers from a class of polyfunctional macroinitiators for conjugated olefin polymers according to claim 1, wherein: s1 comprises the following steps:
s11: adding an organic solvent, CPBB/CBBB/MEPDB and derivatives thereof and alkyl lithium under an anaerobic environment to form a reaction solution A;
s12: adding the reaction liquid A into a polymerization reactor for heating treatment;
s13: after heating for 3-8 hours, injecting isopropanol into the reaction liquid A to terminate polymerization;
s14: after the polymerization of the reaction liquid A is stopped, gum deposition occurs, and gum deposition reaction liquid is produced;
s15: adding the glue depositing reaction liquid into a vacuum drying box for drying treatment;
s16: drying to obtain PCPBB/PCBB/PMEPDB and derivatives thereof.
3. The method for preparing star polymers from a class of polyfunctional macroinitiators for conjugated olefin polymers according to claim 1, wherein: s2 comprises the following steps:
s21: adding an organic solvent, PCPBB, PCBBB, PMEPDB and derivatives thereof and alkyl lithium under anaerobic environment, and preparing a multifunctional initiator by PCPBB/PCBB/PMEPDB and derivatives thereof with double bonds in an initiating chain for 10min-30 min;
s22: adding a multifunctional initiator A into a polymerization reactor for heating treatment;
s23: heating to-80 ℃ and then injecting a regulator into the multifunctional initiator A to obtain a multifunctional initiator B;
s24: adding olefin monomers into the multifunctional initiator B, and reacting for 3-8 hours to obtain a multifunctional initiator C;
s25: injecting isopropanol into the multifunctional initiator C to terminate polymerization to obtain a multifunctional initiator D;
s26: the multifunctional initiator D is subjected to polymerization termination and then is subjected to glue precipitation to obtain a multifunctional initiator F;
s27: adding the multifunctional initiator F after glue precipitation into a vacuum drying box for drying treatment;
s28: and drying to obtain the homo-multi-arm star polymer with the single arm being the olefin monomer.
4. The method for preparing star polymers from a class of polyfunctional macroinitiators for conjugated olefin polymers according to claim 1, wherein: s3 comprises the following steps:
s31: adding the organic solvent, the multifunctional initiator F and alkyl lithium in an anaerobic environment, and obtaining a reaction solution B after the multifunctional initiator F containing double bonds in an initiation chain is added for 10-30 min;
s32: adding the reaction liquid B into a polymerization reactor for heating treatment;
s33: heating to-80 ℃ and then injecting a regulator into the reaction liquid B to obtain a reaction liquid C;
s34: adding olefin monomers into the reaction solution C, and reacting for 3-8 hours to obtain a reaction solution D;
s35: adding olefin monomer into the reaction solution D again, and reacting for 3-8 hours to obtain a reaction solution E;
s36: injecting isopropanol into the reaction solution E to terminate polymerization to obtain a reaction solution F;
s37: after the polymerization of the reaction solution F is terminated, the reaction solution G is obtained by glue precipitation;
s38: adding the reaction solution G after glue precipitation into a vacuum drying box for drying treatment;
s9: and drying to obtain the multi-arm star polymer with a single arm in a block structure.
5. The method for preparing star polymers from a class of polyfunctional macroinitiators for conjugated olefin polymers according to claim 1, wherein: the CPBB derivative/CBBB derivative/MEPDB derivative comprises an amino group, a dimethylamino group, an alkoxy group, a tertiary butyl group, a long carbon chain alkyl group, a cyano group, a hydroxyl group, a triisopropoxyl group, a hydrosilyl group, an alkynyl group, a mercapto group, a fluorine atom, a chlorine atom and a bromine atom.
6. A process for preparing star polymers based on polyfunctional macroinitiators of conjugated olefinic polymers according to claim 2, characterized in that: the olefin monomers include styrene, butadiene, isoprene, alpha-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2-vinylpyridine, 4-vinylpyridine, methyl methacrylate, n-butyl methacrylate, 2-t-butoxystyrene, 3-t-butoxystyrene, 4-t-butoxystyrene, silane, trimethylsilane, 3-vinylcatechol acetone, 4-vinylcatechol acetone, 1.4-divinylbenzene, 1.2-divinylbenzene, 1.3-divinylbenzene.
7. A process for preparing star polymers based on polyfunctional macroinitiators of conjugated olefinic polymers according to claim 2, characterized in that: the alkyl lithium initiator includes: and one or a mixture of a plurality of monofunctional lithium initiators in RLi and TRLi, wherein R is a hydrocarbon group, an alkane group and an arene group with 2-20 carbon atoms, and T is a metal atom and a nitrogen atom, and the metal atom is tin, silicon, lead, titanium and germanium.
8. A process for preparing star polymers based on polyfunctional macroinitiators of conjugated olefinic polymers according to claim 2, characterized in that: the organic solvent comprises nonpolar aromatic hydrocarbon and nonpolar aliphatic hydrocarbon, the organic solvent used for polymerization at 30-80 ℃ comprises benzene, toluene, hexane, cyclohexane and n-hexane, and the organic solvent used for polymerization at-80-0 ℃ comprises tetrahydrofuran, mixed solution of tetrahydrofuran and n-hexane.
9. The method for preparing star polymers from a class of polyfunctional macroinitiators for conjugated olefin polymers according to claim 1, wherein: the process for preparing PCPBB/PCBB/PMEPDB and derivatives thereof is carried out at 30-80 ℃, and the process for preparing the multi-arm star polymer is carried out at-80 ℃.
10. A process for preparing star polymers from a class of polyfunctional macroinitiators for conjugated olefinic polymers according to claim 3, characterized in that: the regulator comprises a mixture of oxygen-containing, nitrogen-containing, sulfur-containing, phosphorus-containing polar compounds and metal alkoxide compounds.
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