CN116640248A - Method for synthesizing olefin functional polymer - Google Patents
Method for synthesizing olefin functional polymer Download PDFInfo
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- CN116640248A CN116640248A CN202310616893.1A CN202310616893A CN116640248A CN 116640248 A CN116640248 A CN 116640248A CN 202310616893 A CN202310616893 A CN 202310616893A CN 116640248 A CN116640248 A CN 116640248A
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- olefin
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 153
- 238000000034 method Methods 0.000 title claims abstract description 83
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 70
- 229920001002 functional polymer Polymers 0.000 title claims abstract description 53
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 96
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 88
- 239000000178 monomer Substances 0.000 claims abstract description 83
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000002904 solvent Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 238000000926 separation method Methods 0.000 claims abstract description 60
- 239000003999 initiator Substances 0.000 claims abstract description 48
- 238000007599 discharging Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 26
- -1 peroxide compounds Chemical class 0.000 claims description 21
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- 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 claims description 15
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007790 solid phase Substances 0.000 claims description 14
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 11
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000003923 2,5-pyrrolediones Chemical class 0.000 claims description 8
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 8
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 8
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 7
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 7
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000001694 spray drying Methods 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 4
- 125000000041 C6-C10 aryl group Chemical group 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 4
- 238000010908 decantation Methods 0.000 claims description 4
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 4
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 230000005484 gravity Effects 0.000 claims description 2
- SEEYREPSKCQBBF-UHFFFAOYSA-N n-methylmaleimide Chemical compound CN1C(=O)C=CC1=O SEEYREPSKCQBBF-UHFFFAOYSA-N 0.000 claims description 2
- 238000011085 pressure filtration Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000003828 vacuum filtration Methods 0.000 claims description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N Hydrocyanic acid Natural products N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 claims 1
- 125000004093 cyano group Chemical group *C#N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 10
- 238000012673 precipitation polymerization Methods 0.000 abstract description 8
- 238000005265 energy consumption Methods 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 229910052757 nitrogen Inorganic materials 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- 239000004677 Nylon Substances 0.000 description 8
- 229920001778 nylon Polymers 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229940117955 isoamyl acetate Drugs 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- MTLWTRLYHAQCAM-UHFFFAOYSA-N 2-[(1-cyano-2-methylpropyl)diazenyl]-3-methylbutanenitrile Chemical compound CC(C)C(C#N)N=NC(C#N)C(C)C MTLWTRLYHAQCAM-UHFFFAOYSA-N 0.000 description 3
- 229920005603 alternating copolymer Polymers 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- WOLATMHLPFJRGC-UHFFFAOYSA-N furan-2,5-dione;styrene Chemical compound O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 WOLATMHLPFJRGC-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010557 suspension polymerization reaction 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/08—Butenes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention provides a method for synthesizing an olefin functional polymer, which comprises the following steps: the functional monomer, the initiator and the solvent are put into a reactor, and then the low-carbon olefin is introduced into the reactor for pressurizing and heating for polymerization reaction; and (3) carrying out gas-solid-liquid separation on the system after the polymerization reaction, recovering the low-carbon olefin, discharging the rest materials, and carrying out solid-liquid separation to obtain the olefin functional polymer. The method can improve the monomer concentration and the raw material utilization rate by the pressurized reaction of the low-carbon gaseous olefin and the functional monomer and adopting a precipitation polymerization mode, and synthesizes different olefin functional polymers by adjusting the technological parameters, has high reaction efficiency, reduces the difficulty of separating and purifying the product, and simplifies the operation steps; the method is simple to operate, saves energy consumption, has lower cost, can break technical monopoly, and can be suitable for synthesizing the low-carbon olefin functional polymer.
Description
Technical Field
The invention belongs to the technical field of organic polymerization, and relates to a method for synthesizing an olefin functional polymer.
Background
The olefin functional polymer is used as a functional high polymer material, has wide application in the aspects of engineering plastic chain extension, high-performance composite material, nylon infiltration, ink dispersion, microencapsulation, filtration membrane film formation and the like, and is greatly concerned. The molecular chain of the olefin functional polymer has a large number of active groups, can react with various functional groups, such as hydroxyl-terminated or amino-terminated of nylon products, improves the molecular weight of nylon, improves the mechanical properties, solves the problem of rigidity loss of nylon materials due to toughness, and can adjust the viscosity value of nylon by adjusting the addition amount; in addition, the olefin functional polymer can be used for preparing microcapsules, and has good application prospects in the fields of pesticides, fragrances and medicines.
The synthetic raw materials of the olefin functional polymer mainly comprise olefin and functional monomers, and currently available polymerization methods comprise emulsion polymerization, suspension polymerization and precipitation polymerization, wherein a large amount of stabilizer is needed to be used in the former two methods, and the stabilizer is remained on polymer particles in a physical adsorption or chemical adsorption mode to influence the performance of the polymer particles; while the precipitation polymerization does not require the addition of a stabilizer, the polymerization monomer concentration in the conventional precipitation polymerization system is low, resulting in low polymerization efficiency, and thus, improvement of the polymerization method is required.
Depending on the kind of olefin or functional monomer in the kind of olefin functional polymer synthesis raw material, a corresponding synthesis process is required. CN 101235117a discloses a method for styrene/maleic anhydride copolymerization, which comprises dissolving maleic anhydride monomer, styrene, initiator organic peroxide or azo compound in medium under nitrogen protection, reacting with 60-90 deg.c for 0.25-12 h to obtain dispersion system of polymer microsphere. CN 102212166a discloses a new method for copolymerization of dicyclopentadiene and maleic anhydride, which is to add monomer and initiator into organic medium to dissolve under nitrogen protection, react for 2-12 h at 60-90 deg.c to obtain self-stable dispersion system of monodisperse microsphere of alternating copolymer, and then centrifugally separate and dry to obtain white solid of alternating copolymer of dicyclopentadiene/maleic anhydride.
In the above patents, maleic anhydride is used as a functional monomer to polymerize with an olefin, but the olefin used is usually an olefin of at least C4, and is usually a liquid olefin such as a diene, a cycloolefin or an isoolefin, but the polymerization of a gaseous olefin of at most C4 is not involved. CN 113388123a discloses a preparation method of high-viscosity nylon, which comprises the following steps: the nylon salt prepolymer and the olefin-maleic anhydride copolymer are mixed and subjected to polycondensation reaction to prepare the high-viscosity nylon, and the process method for synthesizing the copolymer by using the olefin-maleic anhydride copolymer in the method is not clear although ethylene-maleic anhydride alternating copolymer and the like can be selected.
In summary, for the synthesis of olefin functional polymers, especially the polymerization of lower olefins with carbon numbers below C4 and functional monomers, a suitable synthesis process is also required to be selected according to the characteristics of the raw materials, so as to improve the production efficiency, simplify the operation, and reduce the cost of the raw materials and the process.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a method for synthesizing an olefin functional polymer, which is characterized in that the method adopts a precipitation polymerization mode to improve the monomer concentration and the raw material utilization rate through the pressurized reaction of low-carbon gaseous olefin and functional monomers, so that the olefin functional polymer is successfully synthesized, the reaction efficiency is high, the subsequent separation steps are simplified, the energy consumption is saved, and the cost is reduced.
To achieve the purpose, the invention adopts the following technical scheme:
the invention provides a method for synthesizing an olefin functional polymer, which comprises the following steps:
(1) The functional monomer, the initiator and the solvent are put into a reactor, and then the low-carbon olefin is introduced into the reactor for pressurizing and heating for polymerization reaction;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials, and carrying out solid-liquid separation to obtain the olefin functional polymer.
In the invention, for the synthesis of olefin functional polymers, the selection of olefin and functional monomers has an important influence on the performance of the polymers, the invention selects low-carbon gaseous olefin to react with liquid functional monomers, the difference of the phases of the low-carbon gaseous olefin and the liquid functional monomers ensures that the difficulty is relatively higher when the low-carbon gaseous olefin and the functional monomers are liquid, and the low-carbon gaseous olefin generally does not contain side chains, and compared with the liquid olefin, the reaction difficulty is higher, the invention improves the concentration of the monomers and the reaction rate through the pressurizing reaction, improves the conversion rate of raw materials and the yield of products, synthesizes different polymers through the adjustment of technological parameters, can avoid the use of assistants such as stabilizers and the like through adopting a precipitation polymerization mode, reduces the difficulty of separation and purification of the products, and simplifies the operation steps; the method is simple to operate, saves energy consumption, has lower cost, can break technical monopoly, and can be suitable for synthesizing the low-carbon olefin functional polymer.
The following technical scheme is a preferred technical scheme of the invention, but is not a limitation of the technical scheme provided by the invention, and the technical purpose and beneficial effects of the invention can be better achieved and realized through the following technical scheme.
As a preferred embodiment of the present invention, the functional monomer in step (1) includes any one or a combination of at least two of maleic anhydride, maleimide or maleimide derivatives, and typical but non-limiting examples of such combinations are: combinations of maleic anhydride and maleimide, combinations of maleimide and maleimide derivatives, combinations of maleic anhydride, maleimide and maleimide derivatives, and the like.
Preferably, the maleimide derivative comprises N-methylmaleimide and/or N-phenylmaleimide.
Preferably, the initiator of step (1) comprises azo compounds and/or peroxide compounds.
Preferably, the azo-based compound includes any one or a combination of at least two of azobisisobutyronitrile, azobisisovaleronitrile, azobisisoheptonitrile, azobicyclohexylcarbonitrile, or dimethyl azobisisobutyrate, typical but non-limiting examples of such combinations are: a combination of azobisisobutyronitrile and azobisisovaleronitrile, a combination of azobisisobutyronitrile and azobisisoheptonitrile, a combination of azobisisobutyronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate, a combination of azobisisovaleronitrile, azobisisoheptonitrile and dimethyl azobisisobutyrate, and the like.
Preferably, the peroxide-based compound comprises any one or a combination of at least two of dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide or diisopropyl peroxydicarbonate, typical but non-limiting examples of such combinations being: a combination of dibenzoyl peroxide and lauroyl peroxide, a combination of lauroyl peroxide and dicumyl peroxide, a combination of benzoyl peroxide, dicumyl peroxide and diisopropyl peroxydicarbonate, a combination of dibenzoyl peroxide, lauroyl peroxide and diisopropyl peroxydicarbonate, and the like.
As a preferred embodiment of the present invention, the solvent in step (1) includes any one or a combination of at least two of an alkane compound, an organic alkanoate compound, and an aromatic hydrocarbon compound, and typical, but non-limiting examples of the combination are: a combination of an alkane compound and an organic alkanoate compound, a combination of an organic alkanoate compound and an aromatic hydrocarbon compound, a combination of an alkane compound, an organic alkanoate compound and an aromatic hydrocarbon compound, and the like.
Preferably, the alkanes include any one or a combination of at least two of cyclohexane, n-hexane, n-pentane, n-heptane, n-octane, or n-decane, typical but non-limiting examples of such combinations are: a combination of cyclohexane and n-hexane, a combination of n-hexane and n-heptane, a combination of n-heptane and n-octane, a combination of cyclohexane, n-hexane and n-heptane, and the like.
Preferably, the structural general formula of the organic alkyl acid ester compound isWherein R1 is any one of H, C1-C20 alkyl or C6-C10 aryl, and R2 is any one of C1-C20 alkyl or C6-C10 aryl.
Preferably, the organic alkanoate compound includes any one or a combination of at least two of ethyl acetate, isoamyl acetate, or butyl acetate, typical but non-limiting examples of which are: a combination of ethyl acetate and butyl acetate, a combination of ethyl acetate and isoamyl acetate, a combination of ethyl acetate, isoamyl acetate and butyl acetate, and the like.
Preferably, the aromatic compounds include any one or a combination of at least two of benzene, toluene, ethylbenzene or xylene, typical but non-limiting examples of which are: benzene and ethylbenzene, benzene and toluene, ethylbenzene and xylene, benzene, ethylbenzene and xylene, and the like.
As a preferable technical scheme of the invention, the functional monomer, the initiator and the solvent in the step (1) are mixed and then put into a reactor or respectively put into the reactor and then mixed.
Preferably, the reactor of step (1) comprises an autoclave.
Preferably, the molar ratio of initiator to functional monomer in step (1) is (0.001-0.01): 1, e.g. 0.001:1, 0.002:1, 0.003:1, 0.005:1, 0.007:1, 0.008:1 or 0.01:1, etc., but is not limited to the recited values, and other non-recited values within this range of values are equally applicable.
Preferably, the mass ratio of the solvent to the functional monomer in step (1) is (10-50): 1, such as 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1 or 50:1, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the low-carbon olefin in step (1) includes any one or a combination of at least two of ethylene, propylene, butene or butadiene, and typical, but non-limiting examples of the combination are: a combination of ethylene and propylene, a combination of propylene and butene, a combination of ethylene, propylene and butene, and the like, wherein the butene comprises 1-butene, 2-butene, or an isomer of isobutene, and the like.
Preferably, before the light olefins are introduced in the step (1), the reactor is vacuumized and then is replaced by introducing a protecting gas, wherein the protecting gas can be nitrogen or inert gas.
Preferably, the step (1) is carried out by introducing low-carbon olefin and pressurizing to the reaction pressure.
Preferably, the low-carbon olefin in the step (1) is introduced above the solution for reaction, and stirring is performed in the reaction process.
In the invention, the low-carbon olefin is introduced above the solution in the reaction kettle to provide the reaction pressure in the reaction kettle; according to the type and solubility difference of the low-carbon olefin, the ethylene solubility is not large, and the propylene and the butene are mainly reacted on the solution interface by pressurization, and are dissolved in the solvent for reaction.
In a preferred embodiment of the present invention, the polymerization reaction in the step (1) is carried out at a temperature of 40 to 150 ℃, for example, 40 ℃, 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃, 150 ℃ or the like, but the polymerization reaction is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable, and preferably 50 to 120 ℃.
Preferably, the pressure of the polymerization reaction in the step (1) is 0.1 to 10MPa, for example, 0.1MPa, 0.5MPa, 1MPa, 3MPa, 5MPa, 6MPa, 8MPa or 10MPa, etc., but the polymerization reaction is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable, and preferably 2 to 6MPa.
Preferably, the polymerization reaction in step (1) is carried out for a period of time ranging from 0.5 to 20 hours, for example, from 0.5 hours, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 13.5 hours, 15 hours, 18 hours or 20 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the pressure is maintained by continuously introducing the low-carbon olefin in the polymerization reaction process in the step (1).
Preferably, microspheroidal particles are formed during the polymerization reaction of step (1).
The particle diameter of the microspheroidal particles is preferably 10 to 50. Mu.m, for example, 10 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm or 50 μm, etc., but is not limited to the values recited, and other values not recited in the range of values are equally applicable.
In the preferred technical scheme of the invention, the residual low-carbon olefin is discharged in the gas-solid-liquid separation process in the step (2), and is replaced by the shielding gas.
In the invention, the low-carbon olefin discharged after the reaction can be recycled after being pressurized.
Preferably, the residual materials after the low-carbon olefin is recovered in the step (2) are discharged in a solid-liquid mode.
Preferably, the method of solid liquid separation of step (2) comprises any one or a combination of at least two of decantation, filtration or centrifugation, typical but non-limiting examples of which are: a combination of decantation and filtration, a combination of filtration and centrifugation, a combination of decantation, filtration and centrifugation, and the like.
Preferably, the filtration comprises any one of gravity filtration, vacuum filtration or pressure filtration.
Preferably, the filter used for the filtration includes any one of an atmospheric filter, a vacuum filter, and a pressurized filter.
Preferably, the solid phase product obtained by the solid-liquid separation is washed and dried in sequence to obtain the olefin functional polymer.
As a preferred embodiment of the present invention, the washing is performed using the solvent of step (1).
Preferably, the drying mode is any one of vacuum drying, forced air drying, spray drying or fluidized bed drying.
Preferably, the drying temperature is 30 to 120 ℃, for example, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, or the like, but not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable; the time is 1 to 72 hours, for example, 1 hour, 6 hours, 12 hours, 24 hours, 36 hours, 48 hours, 60 hours or 72 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the pressure is 0.1 to 101kPa, for example, 0.1kPa, 1kPa, 10kPa, 20Pa, 40kPa, 60kPa, 80kPa, 101kPa, or the like, but is not limited to the values recited therein, and other values not recited therein are similarly applicable.
As a preferred technical solution of the present invention, the method comprises the steps of:
(1) The method comprises the steps of (1) putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer comprises any one or a combination of at least two of maleic anhydride, maleimide or maleimide derivatives, the initiator comprises azo compounds and/or peroxide compounds, and the solvent comprises any one or a combination of at least two of alkane compounds, organic alkanoate compounds or aromatic hydrocarbon compounds; the molar ratio of the initiator to the functional monomer is (0.001-0.01): 1, the mass ratio of the solvent to the functional monomer is (10-50): 1, the high-pressure reaction kettle is vacuumized and then is replaced by the protective gas, then the low-carbon olefin is introduced into the high-pressure reaction kettle to be pressurized to the reaction pressure, the low-carbon olefin comprises any one or the combination of at least two of ethylene, propylene, butylene or butadiene, the temperature is raised to carry out the polymerization reaction, the temperature of the polymerization reaction is 40-150 ℃, the pressure is 0.1-10 MPa, and the time is 0.5-20 h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process, wherein the particle size of the microspherical particles is 10-50 mu m;
(2) And (3) performing gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), discharging residual low-carbon olefin in the gas-solid-liquid separation process, replacing the residual low-carbon olefin by using a protective gas, discharging the residual material in a solid-liquid mode, performing solid-liquid separation, and sequentially washing and drying the solid-phase product obtained after the solid-liquid separation, wherein the washing is performed by adopting the solvent in the step (1), the drying mode is any one of vacuum drying, forced air drying, spray drying or fluidized bed drying, the drying temperature is 30-120 ℃, the time is 1-72 h, and the pressure is 0.1-101 kPa, so as to obtain the olefin functional polymer.
Compared with the prior art, the invention has the following beneficial effects:
(1) The method can improve the monomer concentration and the raw material utilization rate by the pressurized reaction of the low-carbon gaseous olefin and the functional monomer and adopting a precipitation polymerization mode, and synthesizes different olefin functional polymers by adjusting the technological parameters, has high reaction efficiency, reduces the difficulty of separating and purifying the product, and simplifies the operation steps;
(2) The method disclosed by the invention is simple to operate, saves energy consumption, is low in cost, can break technical monopoly, and can be suitable for synthesizing the low-carbon olefin functional polymer.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
The present invention provides in part a method for synthesizing an olefin functional polymer, the method comprising the steps of:
(1) The functional monomer, the initiator and the solvent are put into a reactor, and then the low-carbon olefin is introduced into the reactor for pressurizing and heating for polymerization reaction;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering the low-carbon olefin, discharging the rest materials, and carrying out solid-liquid separation to obtain the olefin functional polymer.
The following are exemplary but non-limiting examples of the invention:
example 1:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleic anhydride, the initiator is azodiisobutyronitrile, the solvent is cyclohexane and butyl acetate with the volume ratio of 1:1, the molar ratio of the initiator to the functional monomer is 0.008:1, the mass ratio of the solvent to the functional monomer is 10:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for three times, introducing low-carbon olefin into the high-pressure reaction kettle, pressurizing to 3.5MPa, heating the low-carbon olefin to ethylene, and carrying out polymerization reaction, wherein the temperature of the polymerization reaction is 80 ℃, the pressure is 3.5MPa, and the time is 10h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, filtering and separating, discharging the rest low-carbon olefin in the gas-solid-liquid separation process, replacing the rest low-carbon olefin with nitrogen, and washing and drying the solid-phase product obtained after filtering and separating in sequence, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is vacuum drying, the drying temperature is 110 ℃, the time is 36h, and the pressure is 80kPa, so that the olefin functional polymer is obtained.
Example 2:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleic anhydride, the initiator is dibenzoyl peroxide, the solvent is n-hexane and benzene with the volume ratio of 1:1, the molar ratio of the initiator to the functional monomer is 0.007:1, the mass ratio of the solvent to the functional monomer is 20:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for three times, introducing low-carbon olefin into the high-pressure reaction kettle, pressurizing to the pressure of 4.5MPa, heating the low-carbon olefin to ethylene, and carrying out polymerization reaction, wherein the temperature of the polymerization reaction is 110 ℃, the pressure is 4.5MPa, and the time is 9h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out centrifugal separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process, replaced by nitrogen, and the solid phase product obtained after centrifugal separation is washed and dried sequentially, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is vacuum drying, the drying temperature is 70 ℃, the time is 48h, and the pressure is 60kPa, so that the olefin functional polymer is obtained.
Example 3:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleic anhydride, the initiator is azo-diisoheptonitrile, the solvent is dimethylbenzene, the molar ratio of the initiator to the functional monomer is 0.01:1, the mass ratio of the solvent to the functional monomer is 30:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for replacement twice, introducing low-carbon olefin into the high-pressure reaction kettle, pressurizing to 4MPa, wherein the low-carbon olefin is ethylene, heating for polymerization, and the polymerization temperature is 70 ℃, the pressure is 4MPa, and the time is 15h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, filtering and separating, discharging the rest low-carbon olefin in the gas-solid-liquid separation process, replacing the rest low-carbon olefin with nitrogen, and washing and drying the solid-phase product obtained after filtering and separating in sequence, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is air blast drying, the drying temperature is 120 ℃, the time is 12h, and the pressure is 101kPa, thus obtaining the olefin functional polymer.
Example 4:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into an autoclave, wherein the functional monomer is maleic anhydride, the initiator is azobisisobutyronitrile and dicumyl peroxide with a molar ratio of 1:1, the solvent is isoamyl acetate, the molar ratio of the initiator to the functional monomer is 0.006:1, the mass ratio of the solvent to the functional monomer is 50:1, vacuumizing the autoclave, introducing argon gas for replacement twice, introducing low-carbon olefin into the autoclave, pressurizing to a pressure of 8MPa, heating the low-carbon olefin to propylene, and carrying out polymerization reaction, wherein the temperature of the polymerization reaction is 100 ℃, the pressure is 8MPa, and the time is 10h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out filter pressing separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process, replaced by argon, and the solid-phase product obtained after the filter pressing separation is washed and dried in sequence, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is spray drying, the drying temperature is 100 ℃, the time is 36h, and the pressure is 101kPa, so that the olefin functional polymer is obtained.
Example 5:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleimide, the initiator is azodiisobutyronitrile, the solvent is cyclohexane and butyl acetate with the volume ratio of 1:1, the molar ratio of the initiator to the functional monomer is 0.01:1, the mass ratio of the solvent to the functional monomer is 25:1, vacuumizing the high-pressure reaction kettle, introducing argon for three times, introducing low-carbon olefin into the high-pressure reaction kettle, pressurizing to the pressure of 5MPa, heating the low-carbon olefin to propylene, and carrying out polymerization reaction, wherein the temperature of the polymerization reaction is 50 ℃, the pressure is 5MPa, and the time is 8h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out centrifugal separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process and replaced by argon, and the solid phase product obtained after centrifugal separation is washed and dried sequentially, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is vacuum drying, the drying temperature is 70 ℃, the time is 72h, and the pressure is 10kPa, so that the olefin functional polymer is obtained.
Example 6:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleimide, the initiator is lauroyl peroxide, the solvent is benzene and xylene in a volume ratio of 1:1, the molar ratio of the initiator to the functional monomer is 0.002:1, the mass ratio of the solvent to the functional monomer is 40:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for three times, introducing low-carbon olefin into the high-pressure reaction kettle, pressurizing to a pressure of 5MPa, heating the low-carbon olefin to be 1-butene, and carrying out polymerization reaction, wherein the temperature of the polymerization reaction is 120 ℃, the pressure is 5MPa, and the time is 2h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out filter pressing separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process, replaced by nitrogen, and the solid-phase product obtained after the filter pressing separation is washed and dried sequentially, the washing is carried out by adopting the solvent in the step (1), the drying mode is vacuum drying, the drying temperature is 100 ℃, the time is 60h, and the pressure is 30kPa, so that the olefin functional polymer is obtained.
Example 7:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleic anhydride, the initiator is dibenzoyl peroxide, the solvent is butyl acetate, the molar ratio of the initiator to the functional monomer is 0.002:1, the mass ratio of the solvent to the functional monomer is 35:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for three times, introducing low-carbon olefin into the high-pressure reaction kettle, pressurizing to the pressure of 2MPa, heating the low-carbon olefin to ethylene, and carrying out polymerization reaction, wherein the temperature of the polymerization reaction is 150 ℃, the pressure is 2MPa, and the time is 7h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out filter pressing separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process, replaced by nitrogen, and the solid-phase product obtained after the filter pressing separation is washed and dried in sequence, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is vacuum drying, the drying temperature is 80 ℃, the time is 48h, and the pressure is 90kPa, so that the olefin functional polymer is obtained.
Example 8:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleic anhydride, the initiator is dibenzoyl peroxide, the solvent is butyl acetate, the molar ratio of the initiator to the functional monomer is 0.003:1, the mass ratio of the solvent to the functional monomer is 20:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for three times, introducing low-carbon olefin into the high-pressure reaction kettle, pressurizing to 4.0MPa, heating to perform polymerization, wherein the temperature of the polymerization is 100 ℃, the pressure is 4MPa, and the time is 11h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out filter pressing separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process, replaced by nitrogen, and the solid-phase product obtained after the filter pressing separation is washed and dried in sequence, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is fluidized bed drying, the drying temperature is 100 ℃, the time is 24h, and the pressure is 100kPa, so that the olefin functional polymer is obtained.
Example 9:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleic anhydride, the initiator is azodiisobutyronitrile, the solvent is isoamyl acetate, the molar ratio of the initiator to the functional monomer is 0.004:1, the mass ratio of the solvent to the functional monomer is 25:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for three times for replacement, introducing low-carbon olefin into the high-pressure reaction kettle for pressurization until the pressure is 5.5MPa, the low-carbon olefin is ethylene, and heating for polymerization, wherein the temperature of the polymerization is 80 ℃, the pressure is 5.5MPa, and the time is 10h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out filter pressing separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process, replaced by nitrogen, and the solid-phase product obtained after the filter pressing separation is washed and dried sequentially, the washing is carried out by adopting the solvent in the step (1), the drying mode is vacuum drying, the drying temperature is 60 ℃, the time is 54h, and the pressure is 50kPa, so that the olefin functional polymer is obtained.
Example 10:
the present embodiment provides a method for synthesizing an olefin functional polymer, comprising the steps of:
(1) Putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer is maleic anhydride, the initiator is azodiisobutyronitrile, the solvent is isoamyl acetate, the molar ratio of the initiator to the functional monomer is 0.007:1, the mass ratio of the solvent to the functional monomer is 30:1, vacuumizing the high-pressure reaction kettle, introducing nitrogen for three times for replacement, introducing low-carbon olefin into the high-pressure reaction kettle for pressurization until the pressure is 10MPa, heating the low-carbon olefin to ethylene, and carrying out polymerization reaction, wherein the temperature of the polymerization reaction is 60 ℃, the pressure is 10MPa, and the time is 15h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), simultaneously recovering low-carbon olefin, discharging the rest materials in a solid-liquid mode, and carrying out filter pressing separation, wherein the rest low-carbon olefin is discharged in the gas-solid-liquid separation process, replaced by nitrogen, and the solid-phase product obtained after the filter pressing separation is washed and dried in sequence, wherein the washing is carried out by adopting the solvent in the step (1), the drying mode is vacuum drying, the drying temperature is 120 ℃, the time is 8h, and the pressure is 1kPa, so that the olefin functional polymer is obtained.
The conversion of the functional monomer, the yield of the olefin functional polymer and the acid anhydride value were calculated from the detection of the raw material monomer and the olefin functional polymer in the above examples, and the polymer particle size was measured, and the results are shown in table 1.
TABLE 1 data on the results of the polymerization reactions in examples 1-10
As shown in Table 1, the functional olefin polymer synthesized by the method of the invention has the technical parameters regulated, the conversion rate of the functional monomer can reach more than 82%, the yield of the polymer can reach more than 80%, the anhydride value of the polymer is more than 60%, and the particle size range is about 10-50 μm.
According to the method, the low-carbon gaseous olefin and the functional monomer are subjected to pressurized reaction, a precipitation polymerization mode is adopted, so that the monomer concentration and the raw material utilization rate can be improved, different olefin functional polymers are synthesized by regulating and controlling the technological parameters, the reaction efficiency is high, the difficulty of separating and purifying the product is reduced, and the operation steps are simplified; the method is simple to operate, saves energy consumption, has lower cost, can break technical monopoly, and can be suitable for synthesizing the low-carbon olefin functional polymer.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions for the method of the present invention, addition of auxiliary steps, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
Claims (10)
1. A method of synthesizing an olefin functional polymer, the method comprising the steps of:
(1) The functional monomer, the initiator and the solvent are put into a reactor, and then the low-carbon olefin is introduced into the reactor for pressurizing and heating for polymerization reaction;
(2) And (3) carrying out gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), recovering the low-carbon olefin, discharging the rest materials, and carrying out solid-liquid separation to obtain the olefin functional polymer.
2. The method of claim 1, wherein the functional monomer of step (1) comprises any one or a combination of at least two of maleic anhydride, maleimide, or maleimide derivatives;
preferably, the maleimide derivative comprises N-methylmaleimide and/or N-phenylmaleimide;
preferably, the initiator of step (1) comprises azo compounds and/or peroxide compounds;
preferably, the azo compound comprises any one or a combination of at least two of azodiisobutyronitrile, azodiisovaleronitrile, azodiisoheptanenitrile, azodicyclohexyl carbonitrile or dimethyl azodiisobutyrate;
preferably, the peroxide compound comprises any one or a combination of at least two of dibenzoyl peroxide, lauroyl peroxide, dicumyl peroxide or diisopropyl peroxydicarbonate.
3. The method according to claim 1 or 2, wherein the solvent of step (1) comprises any one or a combination of at least two of an alkane, an organic alkanoate, or an aromatic hydrocarbon;
preferably, the alkane compound comprises any one or a combination of at least two of cyclohexane, n-hexane, n-pentane, n-heptane, n-octane and n-decane;
preferably, the structural general formula of the organic alkyl acid ester compound isWherein R1 is any one of H, C1-C20 alkyl or C6-C10 aryl, and R2 is any one of C1-C20 alkyl or C6-C10 aryl;
preferably, the aromatic hydrocarbon compound comprises any one or a combination of at least two of benzene, toluene, ethylbenzene or xylene.
4. A process according to any one of claims 1 to 3, wherein the functional monomer, initiator and solvent of step (1) are mixed and fed into the reactor or separately fed into the reactor and then mixed;
preferably, the reactor of step (1) comprises a high pressure reactor;
preferably, the molar ratio of the initiator to the functional monomer in the step (1) is (0.001-0.01): 1;
preferably, the mass ratio of the solvent to the functional monomer in the step (1) is (10-50): 1.
5. The method of any one of claims 1-4, wherein the low carbon olefin of step (1) comprises any one or a combination of at least two of ethylene, propylene, butene, or butadiene;
preferably, before the light olefins are introduced in the step (1), the reactor is vacuumized and then is replaced by a protective gas;
preferably, the step (1) is to introduce low-carbon olefin and pressurize to the reaction pressure;
preferably, the low-carbon olefin in the step (1) is introduced above the solution for reaction, and stirring is performed in the reaction process.
6. The process according to any one of claims 1 to 5, wherein the temperature of the polymerization reaction of step (1) is 40 to 150 ℃, preferably 50 to 120 ℃;
preferably, the pressure of the polymerization reaction in the step (1) is 0.1-10 MPa, preferably 2-6 MPa;
preferably, the polymerization reaction in step (1) takes 0.5 to 20 hours.
7. The method according to any one of claims 1 to 4, wherein the pressure is maintained by continuously introducing the low-carbon olefin during the polymerization reaction in step (1);
preferably, microspheroidal particles are formed during the polymerization of step (1);
preferably, the microspheroidal particles have a particle size of from 10 to 50 μm.
8. The process according to any one of claims 1 to 7, wherein the remaining lower olefins are discharged during the gas-solid-liquid separation in step (2) and replaced with a shielding gas;
preferably, the residual materials after the low-carbon olefin is recovered in the step (2) are discharged in a solid-liquid mode;
preferably, the method of solid-liquid separation of step (2) comprises any one or a combination of at least two of decantation, filtration or centrifugation;
preferably, the filtration comprises any one of gravity filtration, vacuum filtration or pressure filtration;
preferably, the filter used for filtering comprises any one of an atmospheric filter, a vacuum filter or a pressurized filter;
preferably, the solid phase product obtained by the solid-liquid separation is washed and dried in sequence to obtain the olefin functional polymer.
9. The method of claim 8, wherein the washing is performed with the solvent of step (1);
preferably, the drying mode is any one of vacuum drying, forced air drying, spray drying or fluidized bed drying;
preferably, the drying temperature is 30-120 ℃, the time is 1-72 h, and the pressure is 0.1-101 kPa.
10. The method according to any one of claims 1-9, characterized in that the method comprises the steps of:
(1) The method comprises the steps of (1) putting a functional monomer, an initiator and a solvent into a high-pressure reaction kettle, wherein the functional monomer comprises any one or a combination of at least two of maleic anhydride, maleimide or maleimide derivatives, the initiator comprises azo compounds and/or peroxide compounds, and the solvent comprises any one or a combination of at least two of alkane compounds, organic alkanoate compounds or aromatic hydrocarbon compounds; the molar ratio of the initiator to the functional monomer is (0.001-0.01): 1, the mass ratio of the solvent to the functional monomer is (10-50): 1, the high-pressure reaction kettle is vacuumized and then is replaced by the protective gas, then the low-carbon olefin is introduced into the high-pressure reaction kettle to be pressurized to the reaction pressure, the low-carbon olefin comprises any one or the combination of at least two of ethylene, propylene, butylene or butadiene, the temperature is raised to carry out the polymerization reaction, the temperature of the polymerization reaction is 40-150 ℃, the pressure is 0.1-10 MPa, and the time is 0.5-20 h; continuously introducing low-carbon olefin in the polymerization reaction process to maintain pressure, and generating microspherical particles in the polymerization reaction process, wherein the particle size of the microspherical particles is 10-50 mu m;
(2) And (3) performing gas-solid-liquid separation on the system obtained after the polymerization reaction in the step (1), discharging residual low-carbon olefin in the gas-solid-liquid separation process, replacing the residual low-carbon olefin by using a protective gas, discharging the residual material in a solid-liquid mode, performing solid-liquid separation, and sequentially washing and drying the solid-phase product obtained after the solid-liquid separation, wherein the washing is performed by adopting the solvent in the step (1), the drying mode is any one of vacuum drying, forced air drying, spray drying or fluidized bed drying, the drying temperature is 30-120 ℃, the time is 1-72 h, and the pressure is 0.1-101 kPa, so as to obtain the olefin functional polymer.
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