CN110627934A - Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof - Google Patents
Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof Download PDFInfo
- Publication number
- CN110627934A CN110627934A CN201910888329.9A CN201910888329A CN110627934A CN 110627934 A CN110627934 A CN 110627934A CN 201910888329 A CN201910888329 A CN 201910888329A CN 110627934 A CN110627934 A CN 110627934A
- Authority
- CN
- China
- Prior art keywords
- reaction
- isotactic polypropylene
- raft
- dithiobenzoic acid
- styrene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 polypropylene Polymers 0.000 title claims abstract description 72
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 55
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZGRWZUDBZZBJQB-UHFFFAOYSA-N benzenecarbodithioic acid Chemical compound SC(=S)C1=CC=CC=C1 ZGRWZUDBZZBJQB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 9
- QEZSTBGQYFCJCW-UHFFFAOYSA-N 1-phenylethyl benzenecarbodithioate Chemical compound C=1C=CC=CC=1C(C)SC(=S)C1=CC=CC=C1 QEZSTBGQYFCJCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 13
- 239000011777 magnesium Substances 0.000 claims description 13
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000012968 metallocene catalyst Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000005457 ice water Substances 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 5
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical group C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000006276 transfer reaction Methods 0.000 claims description 2
- 239000000178 monomer Substances 0.000 abstract description 12
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 7
- 229920011250 Polypropylene Block Copolymer Polymers 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 description 18
- 239000012044 organic layer Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229920000098 polyolefin Polymers 0.000 description 12
- 238000001228 spectrum Methods 0.000 description 12
- 229920001400 block copolymer Polymers 0.000 description 10
- 238000005227 gel permeation chromatography Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 6
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 6
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 5
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 5
- 235000010703 Modiola caroliniana Nutrition 0.000 description 5
- 244000038561 Modiola caroliniana Species 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 238000012668 chain scission Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 239000012988 Dithioester Substances 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000205 poly(isobutyl methacrylate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- CFVWNXQPGQOHRJ-UHFFFAOYSA-N 2-methylpropyl prop-2-enoate Chemical compound CC(C)COC(=O)C=C CFVWNXQPGQOHRJ-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- 125000005022 dithioester group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 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
- 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
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- 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
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- 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
- C08F2438/00—Living radical polymerisation
- C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Graft Or Block Polymers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides isotactic polypropylene taking dithiobenzoic acid alpha-methylbenzyl ester as a terminal group, and a preparation method and application thereof, wherein the preparation method of the isotactic polypropylene taking dithiobenzoic acid alpha-methylbenzyl ester as a terminal group comprises the following steps: (1) synthesizing dithiobenzoic acid; (2) synthesizing the isotactic polypropylene with the alpha-methylbenzyl bisthiobenzoate as the terminal group by using the styrene-based end-capped reactive isotactic polypropylene and the dithiobenzoic acid prepared in the step (1). Isotactic polypropylene with di-thio benzoic acid alpha-methyl benzyl ester as a terminal group is used as a novel chain transfer agent for an RATF reaction, and can perform an RAFT reaction with a plurality of free radical polymerization monomers, so that a novel way for preparing a polypropylene block copolymer is provided.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polypropylene high polymer material, and more particularly relates to a polypropylene high polymer material capable of initiating RAFT reaction.
Background
Polyolefin materials (mainly Polyethylene (PE) and polypropylene (PP)) are the largest varieties of current general polymer materials, and have the advantages of good thermal stability, easy processing, excellent mechanical properties, chemical medium resistance, cyclic utilization and the like, so that the polyolefin materials are widely applied to various fields of industry and agriculture, medical treatment and health, military, daily life and the like. Since the discovery of Ziegler-Natta catalysts in the early 50 s of the 20 th century, olefin coordination polymerization has been rapidly developed in terms of polymerization activity, comonomer selection and distribution, and polymer stereoregularity control, driven by the development of more and more recent olefin coordination polymerization catalysts and progressively improved polymerization techniques, resulting in a range of polyolefin products with superior properties. In recent years, in order to further improve the original properties of polyolefins and meet the requirements of different or higher application fields, the high performance and functionalization of polyolefins are the most important direction for the development of polyolefins. However, because the molecular chain structure of polyolefin is relatively single (mainly composed of C, H atoms), and lacks functional groups, how to introduce effective functional groups into the molecular chain to give designable functionality is the key of polyolefin functionalization.
The synthesis of reactive polyolefins with some terminal groups/side groups containing reactive groups and controllable structures is gradually realized, and polyolefin homopolymers and copolymers with different topological structures prepared by using the reactive polyolefins are continuously emerged. The special multi-phase morphology, hydrophilic/hydrophobic property and even unique surface property of the polymers provide a new way for people to synthesize high-molecular materials with high added value and special purposes.
ATRP (atom transfer radical polymerization) is a controlled/living radical polymerization that was discovered independently and rapidly in the middle of the last ninety years, such as Matyjaszewski and Sawamoto, respectively. The reaction is widely applied to the synthesis of novel polymers, and the reaction mechanism is as follows: transition metal compound MtnThe "extraction" of halogen atoms from organic halides by redox reactions, the formation of the oxidized species Mtn+1X and a radical R, followed by a radical R and a mono-radicalAnd reacting the monomer M to generate chain free radical R-M. It is related to Mtn+1X reacts to obtain R-M-X, while the transition metal is reduced to MtnA new round of reaction can be initiated again to continue the chain extension reaction. This is repeated until a polymer of predetermined molecular weight is formed, but the halide is not reactive with the monomer. From Mtn/Mtn+1The catalytic oxidation-reduction process effectively maintains a very low free radical concentration in the system. Meanwhile, chain coupling and disproportionation termination reactions are negligible relative to chain extension reactions, and thus the polymerization reaction is controllable. The ATRP reaction has disadvantages in that the kinds of monomers are limited, and those which readily react with the ligand in the transition metal compound are not suitable, such as carboxyl group-containing monomers; in addition, the removal of transition metals (such as copper ions) after the reaction is finished is troublesome, and the transition metals need to pass through a column or even be dialyzed. Chinese patent publication CN102757542A discloses a block copolymer of polyolefin and phosphorus-containing olefin and a preparation method thereof, wherein a polypropylene with a terminal group as a group capable of initiating controllable/active free radical polymerization is used as an initiator to initiate a specific phosphorus-containing monomer to perform Atom Transfer Radical Polymerization (ATRP) to generate the block copolymer of the polypropylene and the phosphorus-containing olefin with certain flame retardant property, but when the phosphorus-containing polymer is prepared by adopting an ATRP polymerization mode, the problems of low polymerization efficiency, poor structure controllability and the like exist.
Rizzardo et al, 1998, reported a novel living radical polymerization process, i.e., reversible addition-fragmentation chain transfer, RAFT (reversible addition-fragmentation chain transfer). A high-efficiency chain transfer agent (namely a dithioester compound) is introduced into a free radical polymerization system and can perform reversible addition-cracking chain transfer with a growing free radical, so that a polymer with controllable molecular weight and small polydispersity index is obtained. RAFT combines the advantages of a number of polymerisation reactions: the monomer has wide applicability, high polymerization rate and strong molecular design capability, can prepare polymers with structures of high branching, block, grafting, star and the like, and does not have the problem of removing residual ions in atom transfer polymerization. The difficulty in synthesizing the high-efficiency chain transfer agent disulfides causes the defects of the RAFT method in popularization and application.
Therefore, there is a need for a new efficient chain transfer agent for RAFT reactions.
Disclosure of Invention
The invention provides a novel polypropylene macromolecule chain transfer agent for RAFT reaction, which has controllable molecular weight and can be used for carrying out polymerization reaction with a plurality of monomers to prepare a polypropylene block copolymer.
The invention provides isotactic polypropylene taking dithiobenzoic acid alpha-methylbenzyl ester as a terminal group, which has a structure shown in a formula I and is marked as PP-t-RAFT,
the invention provides a preparation method of PP-t-RAFT, which comprises the following steps:
(1) synthesizing dithiobenzoic acid;
(2) and (2) synthesizing isotactic polypropylene taking alpha-methylbenzyl bisthiobenzoate as a terminal group, namely PP-t-RAFT, by using styrene-based end-capped reactive isotactic polypropylene and the dithiobenzoic acid prepared in the step (1).
Weighing magnesium strips with oxide layers removed on the surfaces, adding the magnesium strips into a reaction device, adding iodine, and adding N2Adding the mixed solution of anhydrous THF and bromobenzene under protection, maintaining the temperature in the reaction device at 10-30 deg.C, continuously dropwise adding the mixed solution of anhydrous THF and bromobenzene, keeping the whole reaction system slightly boiling, cooling in ice water bath after the reaction is finished, adding CS2The reaction solution 1 was obtained after the reaction was completed, and dithiobenzoic acid was obtained by separation.
Uniformly mixing 15-45mL of anhydrous THF and 3.4-6.1mL of bromobenzene to obtain a mixed solution 1, weighing 0.8-2.1g of magnesium strip with the surface being removed of an oxide layer, placing the magnesium strip into a three-necked bottle, adding 0.1-1g of iodine, and adding N2Adding 2-7mL of mixed solution 1 under protection, maintaining the temperature at 10-30 deg.C, dropwise adding the rest of mixed solution 1 after reaction, maintaining the temperature at 30-60 deg.C for 0.5-1.5 hr to obtain dark green reaction solution, cooling in ice water bath, and dropwise adding CS with concentration of 0.2mmol/mL2The reaction solution was changed to a dark red color in 10-100mL of THF solution, and the mixture was added dropwiseAfter the reaction is finished, heating to 30-60 ℃ and maintaining for 0.5-1.5 hours to obtain reaction liquid 1; removing unreacted magnesium strips in the reaction solution 1, vacuumizing to remove THF to obtain a reaction solution 2, sequentially adding 60-100mL of diethyl ether and 60-100mL of 6M HCl aqueous solution at the temperature of-10-10 ℃ to the reaction solution 2, extracting and separating an upper mauve organic layer, adding 80-120mL of 0.4M NaOH aqueous solution to the mauve organic layer, acidifying with 60-100mL of 6M HCl, extracting and separating the upper mauve organic layer, repeating for three times, drying the mauve organic layer with anhydrous magnesium sulfate for 1-4 hours, filtering, and removing the solvent in vacuum at room temperature to obtain the mauve dithiobenzoic acid.
And (2) drying the styrene-terminated reactive isotactic polypropylene, adding carbon tetrachloride, adding the dithiobenzoic acid prepared in the step (1), after the reaction is finished, pouring the obtained product into ethanol for precipitation, washing the precipitate with distilled water and ethanol, filtering and drying to obtain the isotactic polypropylene (PP-t-RAFT) with the dithiobenzoic acid alpha-methylbenzyl ester as the terminal group.
In the step (2), dithiobenzoic acid is 1.1-10(mol/mol) times of terminal styrene group.
In the step (2), 1 to 5g of styrene-based-terminated reactive isotactic polypropylene (terminal styrene group content: 0.4 to 0.8 mol%, Mn: 1.2 to 1.8X 10)4PDI is 2.1-2.5), vacuum drying is carried out in oil bath at the temperature of 40-70 ℃ for 2-6h, then 160mL of carbon tetrachloride is added, stirring is carried out for 0.5-2.5h, the dithiobenzoic acid synthesized in the step (1) is added, wherein the added substance amount of the dithiobenzoic acid is 1.1-10 times of that of the terminal styrene group, after reaction is carried out for 3-10h, the dithiobenzoic acid is poured into ethanol for precipitation, washed by distilled water and ethanol, the polymer is filtered, and drying is carried out at the temperature of 40-70 ℃ until constant weight is achieved, so that PP-t-RAFT is obtained.
And (3) synthesizing the styrene-based end-capped reactive isotactic polypropylene through olefin coordination chain transfer reaction in the step (2).
And (2) vacuumizing the polymerization kettle, introducing a mixed gas of hydrogen and nitrogen, sequentially adding toluene, a chain transfer agent, a cocatalyst and a toluene solution of a metallocene catalyst, and introducing propylene for polymerization to obtain the styrene-terminated reactive isotactic polypropylene.
In the step (2), the chain transfer agent is 1, 4-divinylbenzene, the cocatalyst is methylaluminoxane, and the metallocene catalyst is rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2。
In the step (2), after a 500ML high-pressure reaction kettle is vacuumized, mixed gas of hydrogen and nitrogen is introduced into the kettle at the temperature of between 20 and 40 ℃ to form a 0.5 to 3bar mixture, and 30 to 60mL of toluene, 1 to 5mL of 1, 4-divinylbenzene, methylaluminoxane and metallocene catalyst rac-Me are sequentially added2Si[2-Me-4-Ph(Ind)]ZrCl2Wherein the amount of the metallocene catalyst added is [ Zr ] in terms of the amount of Zr]1-3 μmol; the amount of methylaluminoxane added was [ Al ] in terms of the amount of Al species]/[Zr]3000(mol/mol) 100-; introducing propylene at 30 ℃, reacting for 10-20min under the pressure of 1-10bar, releasing pressure, stopping the reaction by using ethanol containing 8-15 wt% of hydrochloric acid, washing by using tetrahydrofuran, water and ethanol for a plurality of times, putting into a vacuum oven, and drying at 35-60 ℃ to constant weight to obtain the styrene-terminated reactive isotactic polypropylene.
The PP-t-RAFT is applied to RAFT reaction.
And the PP-t-RAFT and one or more free radical polymerization monomers of 4-vinyl benzyl diethyl phosphate, styrene, isobutyl methacrylate and methyl acrylate are subjected to RAFT reaction.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention provides a novel chain transfer agent for an RATF reaction, and the chain transfer agent can perform an RAFT reaction with a plurality of free radical polymerization monomers, so that a novel way for preparing a polypropylene block copolymer is provided.
(2) The invention provides isotactic polypropylene taking dithiobenzoic acid alpha-methylbenzyl ester as a terminal group, which is convenient for preparing polypropylene block copolymer through RAFT reaction.
Drawings
FIG. 1 shows nuclear magnetic spectra of styrene-based end-capped reactive isotactic polypropylene and isotactic polypropylene with alpha-methylbenzyl bisthiobenzoate as a terminal group.
FIG. 2 is a gel permeation chromatogram of styrene-based end-capped reactive isotactic polypropylene, isotactic polypropylene with alpha-methylbenzyl bisthiobenzoate as a terminal group, with the abscissa being the weight average molecular weight of the compound.
FIG. 3 is a nuclear magnetic spectrum of a block copolymer of propylene and diethyl 4-vinylbenzylphosphate prepared at different reaction times.
FIG. 4 shows the nuclear magnetic spectra of the block copolymers of propylene and isobutyl methacrylate prepared at different reaction times.
Detailed Description
EXAMPLE 1 preparation of PP-t-RAFT
(1)30mL of anhydrous THF and 4.9mL of bromobenzene are uniformly mixed to obtain a mixed solution 1, 1.32g of magnesium strip with the oxide layer removed on the surface is weighed and put into a three-necked bottle, 0.5g of iodine is added into the mixed solution, and the mixed solution is added into N2Adding 5mL of mixed solution 1 under protection, maintaining the dimension at 20 deg.C, reacting, adding dropwise the rest of mixed solution 1, maintaining at 50 deg.C for 1 hr to obtain dark green reaction solution, cooling in ice water bath, and adding 0.2mmol/mL CS2The THF solution is 50mL, the reaction solution turns into dark red, after the dropwise addition is finished, the temperature is raised to 50 ℃ and maintained for l hours, and a reaction solution 1 is obtained; removing unreacted magnesium strips in the reaction solution 1, and vacuumizing to remove THF to obtain a reaction solution 2; adding 80mL of diethyl ether and 80mL of 6M HCl aqueous solution at the temperature of 3 ℃ into the reaction solution 2 in sequence, and extracting and separating an upper purple red organic layer; adding 100mL of 0.4M NaOH aqueous solution into the purple organic layer, acidifying with 80mL of 6M HCl, extracting and separating the upper purple organic layer, repeating the extraction for three times, drying with anhydrous magnesium sulfate for 2 hours, filtering, and removing the solvent in vacuum at room temperature to obtain the purple dithiobenzoic acid.
(2) Vacuumizing a 450mL polymerization kettle with mechanical stirring for 30min, introducing mixed gas lbar of hydrogen and nitrogen with the volume ratio of 1:1 at 30 ℃, and sequentially adding toluene, 1, 4-divinylbenzene, methylaluminoxane and metallocene catalyst rac-Me2Si[2-Me-4-Ph(lnd)]2ZrCl2The total volume of the reaction system was 50 mL. Then introducing propylene, andthe polymerization was carried out maintaining propylene at a pressure of 2 bar. After reacting for 15min, releasing the pressure, stopping the reaction by using ethanol containing 10 wt% of hydrochloric acid, washing the reaction by using tetrahydrofuran, water and ethanol for a plurality of times in sequence, and drying the reaction product in a vacuum oven at 50 ℃ to constant weight to obtain the styrene-terminated reactive isotactic polypropylene.
2.5g of a styrene-based-terminated reactive isotactic polypropylene (terminal styrene group content 0.65 mol%, Mn 1.59X 10%4PDI 2.31(GPC)), was charged into a 250mL flask equipped with a magnetic rotor, dried by vacuum in an oil bath at 60 ℃ for 4 hours, then added with 120mL of carbon tetrachloride, stirred for 1 hour, and then added with the synthetic dithiobenzoic acid of step (1) to ensure that the dithiobenzoic acid is 1.1 times the terminal styrene group. After 8 hours of reaction, the mixture was poured into ethanol for precipitation, washed with distilled water and ethanol, and the polymer was filtered and dried at 60 ℃ to a constant weight, thereby obtaining 2.4g of isotactic polypropylene (PP-t-RAFT) having α -methylbenzyl dithiobenzoate as a terminal group. Nuclear magnetic hydrogen spectrum of isotactic polypropylene using synthesized dithiobenzoic acid alpha-methylbenzyl ester as end group and styrene group end-capped reactive isotactic polypropylene (1HNMR) (fig. 1), Gel Permeation Chromatography (GPC) (fig. 2).
As can be seen from fig. 1: the styrene-terminated reactive isotactic polypropylene exhibited distinct styrene methylene peaks at 5.2 and 5.7ppm delta, whereas these two peaks in the product PP-t-RAFT disappeared completely, instead of the characteristic benzyl dithioester peak at 5.3ppm delta, and the relative integrated area of this peak corresponded completely to the styrene methylene peak, indicating that the terminal styrene groups in the styrene-terminated reactive isotactic polypropylene were all converted to benzyl dithioester groups.
As can be seen from fig. 2: the relative molecular weight and molecular weight distribution of the polymer before and after the reaction in the step (2) are hardly changed, which indicates that chain scission is not caused by the reaction.
EXAMPLE 2 preparation of PP-t-RAFT
(1)15mL of anhydrous THF and 3.4mL of bromobenzene are uniformly mixed to obtain a mixed solution 1, 0.8g of magnesium strip with the oxide layer removed on the surface is weighed and put into a three-necked bottle, 0.1g of iodine is added, and the mixture is added into N2Adding 2mL of mixed solution 1 under protection, maintaining the dimensionality at 10 ℃, and dripping after the reactionAdding the rest of the mixed solution 1, maintaining at 30 deg.C for 0.5 hr to obtain dark green reaction solution, cooling in ice water bath, and adding 0.2mmol/mL CS2The reaction solution is changed into dark red by 10mL of THF solution, and after the dropwise addition is finished, the temperature is increased to 30 ℃ and maintained for 0.5 hour, so that a reaction solution 1 is obtained; removing unreacted magnesium strips in the reaction solution 1, and vacuumizing to remove THF to obtain a reaction solution 2; adding 60mL of diethyl ether and 60mL of 6M HCl aqueous solution at the temperature of minus 10 ℃ into the reaction solution 2 in sequence, and extracting and separating an upper purple red organic layer; adding 80mL of 0.4M NaOH aqueous solution into the purple organic layer, acidifying with 60mL of 6M HCl, extracting to separate out the upper purple organic layer, repeating the extraction for three times, drying with anhydrous magnesium sulfate for 1 hour, filtering, and removing the solvent in vacuum at room temperature to obtain the purple dithiobenzoic acid.
(2) 1g of styrene-based-terminated reactive isotactic polypropylene (terminal styrene group content: 0.4 mol%, Mn: 1.2X 10)4PDI 2.1(GPC)), into a 250mL flask equipped with a magnetic rotor, vacuum-dried for 6 hours in an oil bath at 40 ℃, then added with 100mL of carbon tetrachloride, stirred for 0.5 hour, and added with the synthetic dithiobenzoic acid of step (1) to ensure that the dithiobenzoic acid is 2 times the terminal styrene group. After reacting for 3 hours, pouring the mixture into ethanol for precipitation, washing the precipitate with distilled water and ethanol, filtering the polymer, and drying the polymer at 40 ℃ to constant weight to obtain the isotactic polypropylene (PP-t-RAFT) with the dithiobenzoic acid alpha-methylbenzyl ester as the terminal group. Nuclear magnetic hydrogen spectrum (1HNMR) and Gel Permeation Chromatography (GPC) were performed on styrene-terminated reactive isotactic polypropylene and synthesized isotactic polypropylene with α -methylbenzyl bisthiobenzoate as a terminal, and the results of the spectra were similar to those of example 1, and the results also show that: the molecular weight of the PP-t-RAFT is consistent with that of the styrene-terminated reactive isotactic polypropylene, chain scission of molecular chains does not occur in the modification process, and nuclear magnetic analysis also proves the success of PP-t-RAFT synthesis.
EXAMPLE 3 preparation of PP-t-RAFT
(1)45mL of anhydrous THF and 6.1mL of bromobenzene are uniformly mixed to obtain a mixed solution 1, 2.1g of magnesium strip with the oxide layer removed on the surface is weighed and put into a three-necked bottle, 1g of iodine is added, and the mixture is added into N2Under protection, adding 7mL of mixed solution 1, maintaining the dimension at 30 ℃, after the reaction,dropwise adding the rest of the mixed solution 1, maintaining at 60 deg.C for 1.5 hr to obtain dark green reaction solution, cooling in ice water bath, and dropwise adding 0.2mmol/mL CS2Changing the reaction solution into dark red by using 100mL of THF solution, and after the dropwise addition is finished, heating to 60 ℃ and maintaining for 1.5 hours to obtain reaction solution 1; removing unreacted magnesium strips in the reaction solution 1, and vacuumizing to remove THF to obtain a reaction solution 2; adding 100mL of diethyl ether and 100mL of 6M HCl aqueous solution at 10 ℃ into the reaction solution 2 in sequence, and extracting and separating an upper purple organic layer; adding 120mL of 0.4M NaOH aqueous solution into the purple organic layer, then acidifying with 100mL of 6M HCl, extracting and separating the upper purple organic layer, repeating the extraction for three times, drying with anhydrous magnesium sulfate for 4 hours, filtering, and removing the solvent in vacuum at room temperature to obtain the purple dithiobenzoic acid.
(2) 5g of styrene-based-terminated reactive isotactic polypropylene (terminal styrene group content: 0.8 mol%, Mn: 1.8X 10)4PDI 2.5(GPC)), dried in oil bath at 70 ℃ under vacuum for 2h, then added with 160mL of carbon tetrachloride, stirred for 2.5h, and added with the dithiobenzoic acid synthesized in step (1), ensuring that the dithiobenzoic acid is 10 times of the terminal styrene group. After reacting for 10 hours, pouring the mixture into ethanol for precipitation, washing the precipitate with distilled water and ethanol, filtering the polymer, and drying the polymer at 70 ℃ to constant weight to obtain the isotactic polypropylene (PP-t-RAFT) with the dithiobenzoic acid alpha-methylbenzyl ester as the terminal group. Nuclear magnetic hydrogen spectrum (1HNMR) and Gel Permeation Chromatography (GPC) were performed on styrene-terminated reactive isotactic polypropylene and synthesized isotactic polypropylene with α -methylbenzyl bisthiobenzoate as a terminal, and the results of the spectra were similar to those of example 1, and the results also show that: the molecular weight of the PP-t-RAFT is consistent with that of the styrene-terminated reactive isotactic polypropylene, chain scission of molecular chains does not occur in the modification process, and nuclear magnetic analysis also proves the success of PP-t-RAFT synthesis.
Example 4 application of PP-t-RAFT
PP-t-RAFT initiated polymerization of diethyl 4-vinylbenzylphosphate
2.5g of PP-t-RAFT prepared in example 1 and 8.9mg of AIBN (azobisisobutyronitrile) were charged into a 100mL flask equipped with a magnet rotor, and vacuum-dried in an oil bath at 60 ℃ for 4 hours. Adding 30mL of toluene, stirring for 15min, adding 4mL of 4-vinyl benzyl diethyl phosphate, and treating the system for three times by a method of liquid nitrogen freezing, vacuumizing, nitrogen filling and unfreezing under the protection of nitrogen. After reaction for 2h at 90 ℃, the product is poured into ethanol for precipitation, filtered, then dichloromethane is added for swelling and washing the polymer, then hexane is used for precipitating the polymer, and after filtration, drying is carried out at 60 ℃ until the weight is constant, thus obtaining the pure block copolymer of propylene and 4-vinyl benzyl diethyl phosphate.
FIG. 3 shows the nuclear magnetic spectra of block copolymer prepared from polypropylene and diethyl 4-vinylbenzylphosphate at different reaction times, wherein the reaction times are 1, 2, 4 and 8h from top to bottom, and the peak at delta of 3.2ppm is-C6H4-CH2A characteristic peak of-P-, a peak at 4.0ppm of delta being-O-CH2-CH3It can be seen that the peak intensity of the characteristic peaks of the phosphate group at δ of 3.2 and 4.0pmm increases with the increase of the polymerization time, indicating that the content of diethyl 4-vinylbenzylphosphate units in the block copolymer of propylene and diethyl 4-vinylbenzylphosphate increases.
Example 5 application of PP-t-RAFT
PP-t-RAFT initiated polymerization of isobutyl methacrylate
2.5g of PP-t-RAFT prepared in example 2 and 8.9mg of AIBN were charged into a 50mL flask equipped with a magnet rotor, and vacuum-dried in an oil bath at 60 ℃ for 4 hours. Adding 50 mL; stirring the toluene for 15min, adding 10mmol of isobutyl methacrylate monomer, and treating the system for three times by using a method of liquid nitrogen freezing, vacuumizing, filling nitrogen and unfreezing under the protection of nitrogen. After the reaction is carried out for 10min at the temperature of 90 ℃, the product is poured into ethanol for precipitation, filtered, added with dichloromethane for swelling and washing the polymer, then the polymer is precipitated by ethanol, and dried to constant weight at the temperature of 60 ℃ to obtain the pure block copolymer of polypropylene and isobutyl methacrylate.
FIG. 4 is a nuclear magnetic spectrum of a block copolymer prepared from propylene and isobutyl methacrylate at different reaction times, wherein the reaction time is 10/20/30/40min from top to bottom, and it can be seen from the graph that after ten minutes of reaction, the nuclear magnetic spectrum of the product shows an obvious peak of isobutyl polymethacrylate at 3.7ppm, which indicates that PP-t-RAFT has active chemical properties and strong reactivity, and the polymerization of isobutyl acrylate monomer is rapidly initiated within 10min from the beginning of the reaction. From the nuclear magnetic spectrum, the peak of the polyisobutyl methacrylate is gradually enhanced along with the prolonging of the reaction time, the reaction is carried out for 20min, and after 30min, the content of the polyisobutyl methacrylate in the block copolymer is increased to 10 percent and 31 percent.
Claims (10)
1. Isotactic polypropylene taking dithiobenzoic acid alpha-methylbenzyl ester as a terminal group is characterized in that: the structure is shown as formula I and is marked as PP-t-RAFT,
2. the method of preparing PP-t-RAFT according to claim 1, characterized by comprising the steps of:
(1) synthesizing dithiobenzoic acid;
(2) and (2) synthesizing isotactic polypropylene taking alpha-methylbenzyl bisthiobenzoate as a terminal group, namely PP-t-RAFT, by using styrene-based end-capped reactive isotactic polypropylene and the dithiobenzoic acid prepared in the step (1).
3. The method of claim 2, wherein: weighing magnesium strips with oxide layers removed on the surfaces, adding the magnesium strips into a reaction device, adding iodine, and adding N2Adding the mixed solution of anhydrous THF and bromobenzene under protection, maintaining the temperature in the reaction device at 10-30 deg.C, continuously dropwise adding the mixed solution of anhydrous THF and bromobenzene, keeping the whole reaction system slightly boiling, cooling in ice water bath after the reaction is finished, adding CS2The reaction solution 1 was obtained after the reaction was completed, and dithiobenzoic acid was obtained by separation.
4. The method of claim 2, wherein: and (2) drying the styrene-terminated reactive isotactic polypropylene, adding carbon tetrachloride, adding the dithiobenzoic acid prepared in the step (1), after the reaction is finished, pouring the obtained product into ethanol for precipitation, washing the precipitate with distilled water and ethanol, filtering and drying to obtain the isotatic polypropylene taking the dithiobenzoic acid alpha-methylbenzyl ester as the terminal group.
5. The method of claim 2, wherein: the amount of the dithiobenzoic acid substance in the step (2) is 1.1-10 times of the terminal styrene group in the styrene-terminated reactive isotactic polypropylene.
6. The method of claim 2, wherein: and (3) synthesizing the styrene-based end-capped reactive isotactic polypropylene through olefin coordination chain transfer reaction in the step (2).
7. The method of claim 6, wherein: and (2) vacuumizing the polymerization kettle, introducing a mixed gas of hydrogen and nitrogen, sequentially adding toluene, a chain transfer agent, a cocatalyst and a toluene solution of a metallocene catalyst, and introducing propylene for polymerization to obtain the styrene-terminated reactive isotactic polypropylene.
8. The method of claim 7, wherein: in the step (2), the chain transfer agent is 1, 4-divinylbenzene, the cocatalyst is methylaluminoxane, and the metallocene catalyst is rac-Me2Si[2-Me-4-Ph(Ind)]2ZrCl2。
9. Use of a PP-t-RAFT according to claim 1 in a RAFT reaction.
10. Use of a PP-t-RAFT prepared according to any one of claims 2 to 8 in a RAFT reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910888329.9A CN110627934A (en) | 2019-09-19 | 2019-09-19 | Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910888329.9A CN110627934A (en) | 2019-09-19 | 2019-09-19 | Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110627934A true CN110627934A (en) | 2019-12-31 |
Family
ID=68971730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910888329.9A Pending CN110627934A (en) | 2019-09-19 | 2019-09-19 | Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110627934A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101544709A (en) * | 2009-04-30 | 2009-09-30 | 复旦大学 | Active free radical polymerization adjusting and controlling agent and preparation thereof |
| CN101851305A (en) * | 2009-04-03 | 2010-10-06 | 中国科学院化学研究所 | Isotactic polypropylene capped with styrene group and preparation method thereof |
| CN107973886A (en) * | 2016-10-24 | 2018-05-01 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation of thermal reversion self-healing polymers material and restorative procedure |
-
2019
- 2019-09-19 CN CN201910888329.9A patent/CN110627934A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851305A (en) * | 2009-04-03 | 2010-10-06 | 中国科学院化学研究所 | Isotactic polypropylene capped with styrene group and preparation method thereof |
| CN101544709A (en) * | 2009-04-30 | 2009-09-30 | 复旦大学 | Active free radical polymerization adjusting and controlling agent and preparation thereof |
| CN107973886A (en) * | 2016-10-24 | 2018-05-01 | 中国林业科学研究院林产化学工业研究所 | A kind of preparation of thermal reversion self-healing polymers material and restorative procedure |
Non-Patent Citations (1)
| Title |
|---|
| KYRIAKI S. PAFITI等: "《End-Linked Poly[2-(dimethylamino)ethyl Methacrylate] Poly(methacrylic acid) Polyampholyte Conetworks: Synthesis by Sequential RAFT》", 《MACROMOLECULES》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Varshney et al. | Anionic polymerization of (meth) acrylic monomers. 4. Effect of lithium salts as ligands on the" living" polymerization of methyl methacrylate using monofunctional initiators | |
| US7160965B2 (en) | Cyclopentadienyl-containing low-valent early transition metal olefin polymerization catalysts | |
| Kim et al. | Preparation of polystyrene–polyolefin multiblock copolymers by sequential coordination and anionic polymerization | |
| Miyake et al. | Coordination polymerization of renewable butyrolactone-based vinyl monomers by lanthanide and early metal catalysts | |
| JPWO2007011017A1 (en) | Method for obtaining (meth) acrylic acid ester polymer from reaction solution | |
| CN101691417A (en) | Star poly-(methyl)acrylate long-chain ester polymer and preparation method thereof | |
| EP1290037A1 (en) | Polymerisation initiator and use | |
| AU2001274216A1 (en) | Polymerisation initiator and use | |
| CN110627934A (en) | Isotactic polypropylene with dithiobenzoic acid alpha-methylbenzyl ester as end group, and preparation method and application thereof | |
| Hwu et al. | Synthesis and application of functional polyethylene graft copolymers by atom transfer radical polymerization | |
| JP3221755B2 (en) | New functionalized polyolefins | |
| EP1165628A1 (en) | Use of an initiator for controlled polymerisation reactions | |
| Wang et al. | Catalytic synthesis and characterization of well-defined polypropylene graft copolymers | |
| EP1095074A1 (en) | A living polymerisation process | |
| Malins et al. | Utilising alternative modifications of α-olefin end groups to synthesise amphiphilic block copolymers | |
| CN113683716B (en) | Ethylene polymerization catalyst, preparation method thereof and preparation method of ethylene-isobutylene copolymer | |
| Mathers et al. | Overview of controlled/living polymerization methods of vinyl monomers | |
| EP1165629A1 (en) | Catalyst composition and method for making a polymer or copolymer | |
| EP1095073B1 (en) | A polymerisation process | |
| Xiao et al. | SYNTHESIS OF POLY (ETHYLENE OXIDE)-B-POLYSTYRENE-BPOLY (4-VINYLPYRIDINE) ABC TRIBLOCK COPOLYMERS BY TWO-STEP ATOM TRANSFER RADICAL POLYMERIZATION | |
| DE60302320T2 (en) | Process for the living radical polymerization of olefinically unsaturated monomers | |
| MOHAJERI et al. | Structural characteristics and thermal properties of poly (methyl methacrylate) and atactic polystyrene grafted onto metallocene based ethylene-allylbenzene copolymer | |
| WO2021099947A1 (en) | Catalyst composition and a process for preparation thereof | |
| CN117222677A (en) | Functional copolymers of 1, 3-dienes with ethylene or functional copolymers of 1, 3-dienes, ethylene with alpha-mono-olefins | |
| CN114269796A (en) | Polyethylene and chlorinated polyethylene thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191231 |
|
| WD01 | Invention patent application deemed withdrawn after publication |