CN115197356A - Copolymerization method of C4-C6 alpha-monoolefin and maleic anhydride - Google Patents
Copolymerization method of C4-C6 alpha-monoolefin and maleic anhydride Download PDFInfo
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- CN115197356A CN115197356A CN202210799519.5A CN202210799519A CN115197356A CN 115197356 A CN115197356 A CN 115197356A CN 202210799519 A CN202210799519 A CN 202210799519A CN 115197356 A CN115197356 A CN 115197356A
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- maleic anhydride
- monoolefin
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000007334 copolymerization reaction Methods 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000003068 static effect Effects 0.000 claims abstract description 86
- 238000006243 chemical reaction Methods 0.000 claims abstract description 81
- 229920001577 copolymer Polymers 0.000 claims abstract description 58
- 239000003999 initiator Substances 0.000 claims abstract description 37
- 238000002156 mixing Methods 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- CONKBQPVFMXDOV-QHCPKHFHSA-N 6-[(5S)-5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-2-oxo-1,3-oxazolidin-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C[C@H]1CN(C(O1)=O)C1=CC2=C(NC(O2)=O)C=C1 CONKBQPVFMXDOV-QHCPKHFHSA-N 0.000 description 12
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 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
- 229940117955 isoamyl acetate Drugs 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000007790 solid phase Substances 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- SXAMGRAIZSSWIH-UHFFFAOYSA-N 2-[3-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,2,4-oxadiazol-5-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NOC(=N1)CC(=O)N1CC2=C(CC1)NN=N2 SXAMGRAIZSSWIH-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C=1C=NN(C=1)CC(=O)N1CC2=C(CC1)NN=N2 ZRPAUEVGEGEPFQ-UHFFFAOYSA-N 0.000 description 1
- YJLUBHOZZTYQIP-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=N2 YJLUBHOZZTYQIP-UHFFFAOYSA-N 0.000 description 1
- YCIGYTFKOXGYTA-UHFFFAOYSA-N 4-(3-cyanopropyldiazenyl)butanenitrile Chemical compound N#CCCCN=NCCCC#N YCIGYTFKOXGYTA-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- -1 isoamylene maleic anhydride Chemical compound 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000005673 monoalkenes Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 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 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002455 scale inhibitor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F210/10—Isobutene
-
- 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
- C08F2/01—Processes of polymerisation characterised by special features of the polymerisation apparatus used
-
- 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
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention provides a copolymerization method of C4-C6 alpha-monoolefin and maleic anhydride, which comprises the following steps: (1) In an inert atmosphere, allowing C4-C6 alpha-monoolefin and maleic anhydride solution containing an initiator to stay in a mixer containing a static element for 15-30s for mixing to obtain a blending solution; (2) Introducing the blending solution into at least 2 reaction kettles, carrying out copolymerization reaction for 1-3h under 0.1-10MPa until the reaction is finished, and separating, washing and drying to obtain a copolymer of C4-C6 alpha-monoolefin and maleic anhydride; the temperature in the step (1) is controlled to be 50-100 ℃, the temperature in the step (2) is controlled to be 30-70 ℃, a spiral baffle plate is arranged below a stirring device in the reaction kettle, and the inner diameter of an inlet of the stirring reaction kettle is the same as the inner diameter of a reactor containing a static element. The method can remarkably improve the reaction efficiency by using a mixer containing a static element and combining a reaction kettle with a specific structure to carry out copolymerization reaction.
Description
Technical Field
The invention relates to the technical field of preparation of high polymer materials, in particular to a copolymerization method of C4-C6 alpha-monoolefin and maleic anhydride.
Background
The C4, C5 and C6 alpha-olefin maleic anhydride copolymer is a chemical product with wide application, acid anhydride groups in the copolymer can be subjected to esterification, amidation, imidization, ionization and other reactions, and the obtained product can further expand the application range of the copolymer. For example, the acid anhydride group in the isobutylene maleic anhydride copolymer, and the derivative products of different molecular weights and different functional groups (amide-ammonia type, imide type, crosslinking type, hydrolysis type, ionic type, etc.) obtained by a series of reactions are also different in use. The low molecular weight isobutylene maleic anhydride copolymer can be used as a scale inhibitor, a dispersant and a water reducing agent of cement paste, and the medium and high molecular weight isobutylene maleic anhydride copolymer can be used as an adhesive for wood and paper processing, an emulsion polymerization stabilizer and the like. The aminated isobutylene maleic anhydride copolymer can be used as an adhesive, a water-based coating and the like, the isobutylene maleic anhydride copolymer modified by imine can be used as a polymerization stabilizer and an adhesive latex, and the crosslinked isobutylene maleic anhydride copolymer can be used as a water-absorbent resin and has wide application. The isoamylene maleic anhydride polymer can be used as raw material of pesticide, antioxidant and perfume. Therefore, the alpha-olefin maleic anhydride copolymer from C4 to C6 has wide application, high cost performance and good application prospect.
The existing preparation method of C4 to C6 alpha-olefin maleic anhydride copolymer mainly adopts precipitation polymerization method to synthesize, and usually adopts a mode of directly adding C4 to C6 alpha-monoolefin into maleic anhydride solution to carry out copolymerization reaction, such as: chinese patent document CN111265966A discloses a preparation method of a high-alternance controllable molecular weight maleic anhydride isobutylene copolymer, which specifically comprises the following steps: 1) In an autoclave, under the condition of no oxygen, maleic anhydride and a solvent are stirred and mixed; 2) Introducing isobutene gas and a solvent dissolved with an initiator into the high-pressure kettle to react; 3) Filtering the mixed system obtained by the reaction, taking the filter cake, washing with a polar organic solvent and water, and drying to obtain the maleic anhydride isobutylene copolymer. Chinese patent document CN102690393A discloses a copolymer containing functional groups and prepared from maleic anhydride, which is a C5 blending solution, and a preparation method thereof, and specifically, under the protection of nitrogen, monomer maleic anhydride and initiator Azobisisobutyronitrile (AIBN) are added into an ester medium to be fully dissolved, then the C5 blending solution is added into the system to be dissolved, a milky stable solid-liquid dispersion system of the copolymer of C5 and maleic anhydride is obtained, and a white powdery copolymer of C5 and maleic anhydride is obtained through centrifugal separation and vacuum drying, wherein olefin and diene in the C5 blending solution both react with maleic anhydride. Chinese patent document CN107722177A discloses a method and apparatus for utilizing mixed carbon four, which specifically comprises polymerization equipment, a gas-liquid separator, cracking equipment and a liquid-solid separator. The copolymerization reaction and the steam cracking reaction are combined, so that the mixed carbon four is fully utilized, and the provided polymer containing maleic anhydride functional groups can be further applied as a raw material of a functional material.
The methods disclosed in the above documents all have problems of long dissolution time of C4-C6 alpha-monoolefin and low utilization efficiency. Therefore, how to shorten the dissolution time of the C4-C6 alpha-monoolefin, thereby improving the copolymerization reaction efficiency of the C4-C6 alpha-monoolefin and the maleic anhydride and shortening the reaction time is a technical problem to be solved at present.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of low copolymerization reaction efficiency and long reaction time of the C4-C6 alpha-monoolefin and maleic anhydride in the preparation method of the polar copolymer of the C4-C6 alpha-monoolefin and the maleic anhydride in the prior art, thereby providing a copolymerization method of the C4-C6 alpha-monoolefin and the maleic anhydride.
Therefore, the invention provides the following technical scheme:
a process for the copolymerization of a C4 to C6 α -monoolefin with maleic anhydride comprising the steps of:
(1) In an inert atmosphere, staying C4-C6 alpha-monoolefin and maleic anhydride solution containing an initiator in a reactor containing a static element for 15-30s for mixing to obtain a blending solution;
(2) Introducing the blending solution obtained in the step (1) into at least 2 parallel reaction kettles, carrying out copolymerization reaction for 1-3h under 0.1-10MPa until the reaction is finished, and separating, washing and drying to obtain the copolymer of the C4-C6 alpha-monoolefin and the maleic anhydride;
wherein the temperature of the step (1) is controlled to be 50-100 ℃, the temperature of the step (2) is controlled to be 30-70 ℃, a stirring device is arranged in the reaction kettle, a spiral baffle is arranged below the stirring device, and the inner diameter of an inlet of the reaction kettle is the same as the inner diameter of the reactor containing the static element (the inner diameter of a pipeline connecting the reaction kettle and the reactor containing the static element is the same as the inner diameter of the inlet of the reaction kettle and the inner diameter of the reactor containing the static element).
If the mixing mode is changed, for example, the initiator and the C4-C6 alpha-monoolefin are mixed in the solvent and then mixed with the maleic anhydride solution in the reactor containing a static element; alternatively, the C4-C6 alpha-monoolefin and maleic anhydride are dissolved in a solvent and then mixed with an initiator in a reactor containing static elements, which will extend the dissolution time of the C4-C6 alpha-monoolefin and reduce the yield of the copolymer of C4-C6 alpha-monoolefin and maleic anhydride. If the temperature in the step (1) is not in a limited temperature range, the reaction yield can be directly reduced, the final yield can only reach about 50 percent, and the analysis reason is probably that the temperature is lower than 50 ℃, and monoolefine and maleic anhydride solution containing an initiator cannot be fully dissolved mutually, and primary polar copolymerization reaction cannot be realized; the temperature is higher than 100 ℃, which can cause excessive initial polar copolymerization reaction and influence the subsequent copolymerization effect in the reaction kettle.
Optionally, the C4-C6 alpha-monoolefin is a monoolefin with a double bond at the end of the molecular chain and has 4-6 carbon atoms.
Optionally, the inert atmosphere is any one of nitrogen, helium, argon, and the like, and the existing inert atmosphere can meet the implementation of the technical scheme of the present invention, but in consideration of cost, nitrogen is generally used.
Optionally, the spiral baffle is arranged 3-6cm below the stirring device, and the spiral baffle is detachably and fixedly connected to the bottom of the reaction kettle; preferably, the spiral baffle is of a steel structure and has a height of 2-5cm.
Optionally, the mixer containing the static element is a static mixer, and both ends of the static mixer at least contain 2 inlets and 2 outlets; preferably, the C4-C6 alpha-monoolefin and the maleic anhydride solution containing the initiator enter the static mixer from different inlets, respectively.
Wherein, the C4-C6 alpha-monoolefin enters the static mixer from one inlet, the maleic anhydride solution containing the initiator enters the static mixer from the other inlet, one outlet is used for discharging the C4-C6 alpha-monoolefin which is not melted into the maleic anhydride solution and returning the C4-C6 alpha-monoolefin to the static mixer for recycling, and the liquid discharged from the other outlet is the blending solution containing the C4-C6 alpha-monoolefin, the initiator and the maleic anhydride.
Preferably, in the step (1), in an inert atmosphere, the C4-C6 alpha-monoolefin with the temperature of 30-70 ℃ and the maleic anhydride solution with the initiator with the temperature of 30-70 ℃ stay in a mixer with a static element for 15-30s for mixing, and the preliminary copolymerization reaction is completed while mixing to obtain the blending solution.
Optionally, the static mixer is selected from any one of an SV type static mixer, an SX type static mixer, and an SK type static mixer.
Optionally, the static mixer has a length of 20-70cm and an inner bore diameter of 3-20cm.
Optionally, the stationary elements are equally spaced apart by a distance of 0.1-0.5cm.
Optionally, the C4-C6 alpha-monoolefin and the maleic anhydride solution containing the initiator may be blended in a static mixer in a laminar, transitional, or turbulent manner.
Optionally, an outlet of the static mixer for discharging the blended solution containing the C4-C6 α -monoolefin, the initiator and the maleic anhydride is communicated with an inlet of the reaction kettle, and preferably, an outlet of the static mixer for discharging the blended solution containing the C4-C6 α -monoolefin, the initiator and the maleic anhydride is communicated with the inlet of the reaction kettle through a buffer tank, a metering pump and a dividing pump.
Optionally, the liquid separated in step (2) contains an excess of unreacted C4-C6 alpha-monoolefin.
Optionally, in the step (1), the pressure of the mixing is 0.1-10MPa;
in the step (1), the mass ratio of the C4-C6 alpha-monoolefin to the maleic anhydride solution containing the initiator is 1: (5-55).
Optionally, in the step (1), the mass ratio of the C4-C6 α -monoolefin to the maleic anhydride is (0.2-5): 1, preferably in a mass ratio of (0.6-3): 1;
in the step (1), the mass ratio of the initiator to the maleic anhydride is (0.01-0.20): 1;
in the step (1), the concentration of the maleic anhydride in the maleic anhydride solution containing the initiator is 3wt% -25wt%.
Optionally, the initiator is a thermal decomposition type initiator, and preferably, the initiator is at least one of dibenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate, dicyclohexyl peroxydicarbonate, azobisisobutyronitrile and azobisisoheptonitrile;
the solvent in the maleic anhydride solution containing the initiator is at least one of organic acid alkyl ester, alkane and aromatic hydrocarbon.
The organic acid alkyl ester may be selected from any one of isoamyl acetate, ethyl acetate, propyl acetate, and the like;
the alkane may be selected from any of C5-C16 linear or branched liquid alkanes, such as pentane, hexane, heptane and the like;
the aromatic hydrocarbon may be selected from any one of toluene, benzene, etc.
Optionally, in the step (2), the separation mode is filtration or centrifugation, and the separated liquid phase is an organic solvent and can be recycled.
Optionally, in step (2), alcohols, such as ethanol, methanol, isopropanol, and the like, are used for washing.
Optionally, in the step (2), the drying is drying, and the drying temperature is 60-100 ℃.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the copolymerization method of the C4-C6 alpha-monoolefin and the maleic anhydride, provided by the invention, the mixer (static mixer) containing the static element is used, the retention time is limited, the C4-C6 alpha-monoolefin and the maleic anhydride solution containing the initiator can be fully and quickly mutually dissolved, the primary polar copolymerization reaction is completed, and meanwhile, the energy consumption is greatly reduced, and by combining the subsequent copolymerization reaction of the blending solution in 2 reaction kettles which are provided with spiral baffles and have the same inner diameter of an inlet as that of the reactor containing the static element, the C4-C6 alpha-monoolefin dissolving time and the temperature in the preparation process can be obviously reduced, the efficient copolymerization reaction is realized, the energy consumption is greatly reduced, the reaction efficiency is improved, the copolymerization reaction time is shortened, the reaction cost is reduced, and a more feasible method is provided for efficiently producing the C4-C6 alpha-monoolefin maleic anhydride copolymer.
2. Aiming at the characteristic of the reaction of C4-C6 alpha-monoolefin and maleic anhydride, a static mixer of a process enhancement device is introduced into the polar copolymerization reaction, the static mixer can enhance the mass transfer efficiency of the C4-C6 alpha-monoolefin, improve the dissolution degree of the C4-C6 alpha-monoolefin and improve the reaction efficiency of the C4-C6 alpha-monoolefin, and meanwhile, the static mixer does not contain a dynamic element, so that the polar reaction is more energy-saving, environment-friendly and efficient. In order to adapt to the combined use mode of the static mixer and the reaction kettle, the inlet of the reaction kettle is designed to be equivalent to the inner diameter of the static mixer, and a spiral baffle is arranged below the bottom stirring device in the reaction kettle for further accelerating the reaction efficiency.
3. According to the invention, at least two specific reaction kettles are connected in parallel to carry out polar copolymerization reaction, so that the reaction efficiency and the reaction amount are greatly improved, and the industrial production of the product is facilitated compared with the case that two reaction kettles are connected in series, one reaction kettle with a larger volume is adopted, or two conventional reaction kettles connected in parallel.
Drawings
FIG. 1 is a schematic flowsheet showing a process for copolymerizing an α -monoolefin and maleic anhydride according to example 1 of the present invention;
FIG. 2 is an infrared chromatogram of a copolymer of an α -monoolefin and maleic anhydride obtained in example 5-1.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and experimental methods without specific conditions noted in the following examples are generally performed under conventional conditions.
Example 1
FIG. 1 is a schematic flow chart of a copolymerization process of a C4-C6 alpha-monoolefin and maleic anhydride, as follows:
(1) After a static mixer is purged by nitrogen, 4.7g of azodicarbonbutyronitrile and 294g of maleic anhydride are dissolved in 2.1L of isoamyl acetate to obtain a maleic anhydride solution (solution A) containing an initiator, the solution A is subjected to heat exchange to 60 ℃, then the solution A is metered by a metering pump and enters the static mixer through an inlet of the static mixer, alpha-monoolefin (isobutene) is subjected to heat exchange to 60 ℃, then the solution A is metered by the metering pump and enters the static mixer through an inlet of the static mixer, and the mass ratio of the alpha-monoolefin to the solution A in the static mixer is 1: and (3) fully mixing the alpha-monoolefine and the solution A in a static mixer, and carrying out primary reaction to obtain a blending solution. Wherein the inner bore of the static mixer has a diameter of 10cm and a length of 70cm, the stationary elements are equally spaced apart by 0.4cm, and the operating pressure is 0.6MPa.
(2) Respectively introducing the blending solution obtained in the step (1) into two parallel reaction kettles through a buffer tank, a metering pump and a shunt pump to continuously carry out copolymerization reaction, wherein the reaction temperature is 60 ℃, the reaction pressure is 1MPa, and the reaction lasts for 3 hours until the reaction is finished; and then filtering and separating the obtained liquid-solid blend, washing the obtained solid phase with absolute ethyl alcohol, and drying at 70 ℃ to obtain the copolymer of the alpha-monoolefin and the maleic anhydride, wherein stirrers are respectively arranged in the two reaction kettles, the stirring speed is 500r/min, a spiral baffle is arranged at the position 5cm below the stirrer, and the height of the spiral baffle is 3cm.
Table 1 below shows the production and number average molecular weight of the copolymer finally obtained, according to the above-mentioned test conditions, varying the length of the static mixer and the residence time of the alpha-monoolefin and the solution A in the static mixer.
TABLE 1
| Static mixer length | Residence time | Quality of the copolymer | Number average molecular weight of copolymer | |
| Examples 1 to 1 | 70cm | 20s | 417g | 102000 |
| Examples 1 to 2 | 20cm | 25s | 372g | 81000 |
Example 2
Example 2 is similar to example 1-1 except that the mass ratio of the α -monoolefin to the solution A in the static mixer in step (1) is different, and the mass ratio of the α -monoolefin to the solution A in the static mixer in step (1) of example 2 and the mass and number average molecular weight of the copolymer are specifically shown in the following table.
TABLE 2
Example 3
Example 3 is similar to example 1-1 except that the operating pressure of the static mixer in step (1) is different, and the operating pressure of the static mixer in step (1) of example 3 and the mass and number average molecular weight of the copolymer are specifically shown in the following table.
TABLE 3
| Operating pressure of static mixer | Quality of the copolymer | Number average molecular weight of copolymer | |
| Example 3-1 | 0.1Mpa | 369g | 91000 |
| Examples 3 to 2 | 1Mpa | 422g | 98000 |
Example 4
Example 4 is similar to example 1-1, except that the temperature of the α -monoolefin and solution A after heat exchange in step (1) is different, the temperature of the α -monoolefin and solution A after heat exchange in step (1) of example 4 is the same, and the specific temperature after heat exchange and the mass and number average molecular weight of the copolymer are specified in the following table.
TABLE 4
Example 5
Example 5 is similar to example 4-1, differing only in the reaction temperature of step (2),
the reaction temperature in step (2) of example 5 and the mass and number average molecular weight of the copolymer are specifically shown in the following table.
TABLE 5
| Reaction temperature | Quality of the copolymer | Number average molecular weight of copolymer | |
| Example 5-1 | 30℃ | 386g | 80000 |
| Example 5-2 | 60℃ | 424g | 85000 |
| Examples 5 to 3 | 70℃ | 423g | 85000 |
As shown in FIG. 2, the IR spectrum of the copolymer of α -monoolefin and maleic anhydride obtained in example 5-1 is shown, in which 1771.06cm -1 And 1852.62cm -1 Is C = O stretching vibration absorption peak of acid anhydride, 2900cm -1 The vicinity is the stretching vibration absorption peak of methyl and methylene.
Example 6
Example 6 is similar to example 5-1 except that the reaction pressure in step (2) is different, and the reaction pressure in step (2) of examples 11-12 and the mass and number average molecular weight of the copolymer are specifically shown in the following table.
TABLE 6
| Reaction pressure | Quality of the copolymer | Number average molecular weight of copolymer | |
| Example 6-1 | 0.2Mpa | 396g | 61000 |
| Example 6-2 | 3Mpa | 417g | 85000 |
| Examples 6 to 3 | 8Mpa | 418g | 79000 |
Example 7
Example 7 is similar to example 5-1 except that the amount of initiator used in step (1) is different and the amount of initiator used in step (1) of example 7 and the mass and number average molecular weight of the copolymer are specified in the following table.
TABLE 7
| Mass of initiator | Quality of the copolymer | Number average molecular weight of copolymer | |
| Example 7-1 | 23g | 433g | 64000 |
| Example 7-2 | 50g | 438g | 41000 |
Example 8
Example 8 is similar to example 5-1 except that the amount of maleic anhydride used in step (1) is different, and the amounts of maleic anhydride used and the mass and number average molecular weights of the copolymers in step (1) of examples 15-16 are specifically shown in the following table.
TABLE 8
| The amount of maleic anhydride used | Quality of the copolymer | Number average molecular weight of copolymer | |
| Example 8-1 | 98g | 127g | 56000 |
| Example 8 to 2 | 525g | 431g | 86000 |
Examples 9 to 12
Examples 9-12 are similar to example 5-1 except that the type of α -monoolefin and the mass ratio of α -monoolefin to solution A in step (1) are different, and the specific examples of the type of α -monoolefin, the mass ratio of α -monoolefin to solution A and the mass and number average molecular weight of the copolymer in step (1) of examples 9-12 are shown in the following tables.
TABLE 9
Comparative example 1
Dissolving 4.7g of azobisbutyronitrile and 294g of maleic anhydride in 2.1L of isoamyl acetate to obtain a maleic anhydride solution (solution A) containing an initiator, wherein after the solution A is subjected to heat exchange to 70 ℃, after the alpha-monoolefin (isobutene) is subjected to heat exchange to 70 ℃, the alpha-monoolefin and the solution A are mixed according to a mass ratio of 1:12 respectively passing through a buffer tank, a metering pump and a shunt pump, and then respectively introducing into two parallel reaction kettles (the insides of the kettles are both provided with a stirrer, the stirring speed is 500r/min, the positions 5cm below the stirrers are both provided with spiral baffles, the heights of the spiral baffles are both 3 cm) to continuously carry out copolymerization reaction, the reaction temperature is 70 ℃, the reaction pressure is 1MPa, and the reaction time is 3h; and then filtering and separating the obtained liquid-solid blend, washing the obtained solid phase by using absolute ethyl alcohol, and drying at 70 ℃ to obtain the alpha-monoolefine and maleic anhydride copolymer.
This comparative example produced 305g of a white isobutylene-maleic anhydride copolymer having a number average molecular weight of 73000.
As is clear from this comparative example compared with example 5-1, the same other conditions were used except that the conditions for intensive blending and preliminary reaction in the static mixer were omitted, and the yield of the copolymer of isobutylene and maleic anhydride finally obtained was lowered.
Comparative example 2
(1) After a static mixer is purged by nitrogen, 4.7g of azodicarbonbutyronitrile and 294g of maleic anhydride are dissolved in 2.1L of isoamyl acetate to obtain a maleic anhydride solution (solution A) containing an initiator, the solution A is subjected to heat exchange to 70 ℃, then the solution A is metered by a metering pump and enters the static mixer through an inlet of the static mixer, alpha-monoolefine (isobutene) is subjected to heat exchange to 70 ℃, then the solution A is metered by the metering pump and enters the static mixer through an inlet of the static mixer, and the mass ratio of the alpha-monoolefine to the solution A in the static mixer is 1: the alpha-monoolefin and the solution A were thoroughly mixed in a static mixer and subjected to preliminary reaction (residence time 20 s) to give a blended solution. Wherein the inner bore diameter of the static mixer is 10cm, the static elements are equally spaced, the spacing distance is 0.4cm, the length is 70cm, and the operating pressure is 0.6Mpa.
(2) Introducing the blending solution obtained in the step (1) into a reaction kettle (the volume of the reaction kettle is the sum of the volumes of two reaction kettles connected in parallel in the embodiment 5-1, a stirrer is arranged in the reaction kettle, the stirring speed is 500r/min, a spiral baffle is arranged at the position 5cm below the stirrer, the height of the spiral baffle is 3 cm), and continuously carrying out copolymerization reaction, wherein the reaction temperature is 70 ℃, the reaction pressure is 1MPa, and the reaction time is 3h; then, the obtained liquid-solid blend is filtered and separated, the obtained solid phase is washed by absolute ethyl alcohol and dried at 70 ℃, and 345g of copolymer of alpha-monoolefin and maleic anhydride with the number average molecular weight of 81000 is obtained.
As is clear from this comparative example compared with example 5-1, under the same other conditions except that two parallel reaction vessels were replaced with one reaction vessel, the yield of the copolymer of isobutylene and maleic anhydride finally obtained was lowered.
Comparative example 3
(1) After a static mixer is purged by nitrogen, 4.7g of azodicarbonbutyronitrile and 294g of maleic anhydride are dissolved in 2.1L of isoamyl acetate to obtain a maleic anhydride solution (solution A) containing an initiator, the solution A is subjected to heat exchange to 70 ℃, then the solution A is metered by a metering pump and enters the static mixer through an inlet of the static mixer, alpha-monoolefine (isobutene) is subjected to heat exchange to 70 ℃, then the solution A is metered by the metering pump and enters the static mixer through an inlet of the static mixer, and the mass ratio of the alpha-monoolefine to the solution A in the static mixer is 1: the alpha-monoolefin and the solution A were thoroughly mixed in a static mixer and subjected to preliminary reaction (residence time 20 s) to obtain a blended solution. Wherein the length of the static mixer is 70cm, the diameter of the inner hole is 10cm, the static elements are equally spaced, the spacing distance is 0.4cm, and the operating pressure is 0.6MPa.
(2) Introducing the blending solution obtained in the step (1) into two conventional reaction kettles connected in parallel after passing through a buffer tank, a metering pump and a shunt pump (the capacity of 2 reaction kettles is the same as that of 2 reaction kettles in the example 5-1, the stirring speed is 500r/min, only no spiral baffle is arranged under a stirrer), and continuously carrying out copolymerization reaction at the reaction temperature of 70 ℃, the reaction pressure of 1MPa and the reaction time of 3h; and then filtering and separating the obtained liquid-solid blend, washing the obtained solid phase with ethanol, and drying at 70 ℃ to obtain the alpha-monoolefin and maleic anhydride copolymer.
The comparative example produced 355g of a white isobutylene/maleic anhydride copolymer having a number average molecular weight of 90000.
As is clear from this comparative example compared with example 5-1, under otherwise identical conditions except that the two reaction vessels were replaced with 2 conventional reaction vessels with only stirring, the yield of the finally obtained copolymer of isobutylene and maleic anhydride was lowered.
Comparative examples 4 to 5
(1) After a static mixer is purged by nitrogen, 4.7g of azodicarbonbutyronitrile and 294g of maleic anhydride are dissolved in 2.1L of isoamyl acetate to obtain a maleic anhydride solution (solution A) containing an initiator, the solution A is subjected to heat exchange to 70 ℃, then metered by a metering pump and enters the static mixer through an inlet of the static mixer, alpha-monoolefin (1-heptene or 1-octene) is subjected to heat exchange to 70 ℃, then metered by the metering pump and enters the static mixer through an inlet of the static mixer, and the mass ratio of the alpha-monoolefin to the solution A in the static mixer is 1: the alpha-monoolefin and the solution A were thoroughly mixed in a static mixer and subjected to preliminary reaction (residence time 20 s) to give a blended solution. Wherein the inner bore diameter of the static mixer is 10cm, the static elements are equally spaced, the spacing distance is 0.4cm, the length is 70cm, and the operating pressure is 0.6Mpa.
(2) The blending liquid respectively passes through a buffer tank, a metering pump and a shunt pump and then is respectively introduced into two reaction kettles connected in parallel at a speed rate (the inner parts of the reaction kettles are respectively provided with a stirrer, the stirring speed is 500r/min, the positions 5cm below the stirrers are respectively provided with a spiral baffle, the height of the spiral baffle is 3 cm), copolymerization reaction is continuously carried out, the reaction temperature is 30 ℃, the reaction pressure is 1MPa, and the reaction time is 3h; then, the obtained liquid-solid blend is filtered and separated, the obtained solid phase is washed by absolute ethyl alcohol and dried at 70 ℃ to obtain 225g of copolymer of 1-heptene and maleic anhydride with the number average molecular weight of 21000; 228g of copolymer of 1-octene and maleic anhydride, and the number average molecular weight of the copolymer is 20000.
As can be seen from this comparative example, compared with example 5-1, under otherwise identical conditions, except that C7 and C8 alpha-monoolefins were used, the yield of the resulting copolymer of isobutylene and maleic anhydride was reduced.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (10)
1. A process for the copolymerization of a C4 to C6 alpha-monoolefin with maleic anhydride comprising the steps of:
(1) In an inert atmosphere, staying C4-C6 alpha-monoolefin and maleic anhydride solution containing an initiator in a reactor containing a static element for 15-30s for mixing to obtain a blending solution;
(2) Introducing the blending solution obtained in the step (1) into at least 2 parallel reaction kettles, carrying out copolymerization reaction for 1-3h under 0.1-10MPa until the reaction is finished, and separating, washing and drying to obtain a copolymer of C4-C6 alpha-monoolefin and maleic anhydride;
wherein the temperature of the step (1) is controlled to be 50-100 ℃, the temperature of the step (2) is controlled to be 30-70 ℃, a stirring device is arranged in the reaction kettle, a spiral baffle is arranged below the stirring device, and the inner diameter of an inlet of the reaction kettle is the same as the inner diameter of the reactor containing the static element.
2. The copolymerization method according to claim 1, wherein the spiral baffle is arranged 3-6cm below the stirring device, and the spiral baffle is detachably connected and fixed at the bottom of the reaction kettle.
3. The copolymerization process of claim 1, wherein the mixer containing static elements is a static mixer having at least 2 inlets and 2 outlets at each end.
4. The copolymerization method according to claim 3, wherein the static mixer is selected from any one of an SV type static mixer, an SX type static mixer, and an SK type static mixer.
5. The copolymerization process of claim 3, wherein the static mixer has a length of 20 to 70cm and an internal bore diameter of 3 to 20cm.
6. The copolymerization process of claim 1, wherein the stationary elements are equally spaced apart by a distance of 0.1 to 0.5cm.
7. The copolymerization process according to claim 1, wherein in step (1), the pressure of mixing is from 0.1 to 1MPa; and/or
In the step (1), the mass ratio of the C4-C6 alpha-monoolefin to the maleic anhydride solution containing the initiator is 1: (5-55).
8. The copolymerization process according to claim 1, wherein in step (1), the mass ratio of the C4-C6 α -monoolefin to maleic anhydride is (0.2-5): 1.
9. the copolymerization process according to claim 1, wherein in step (1), the mass ratio of the initiator to maleic anhydride is (0.01-0.20): 1; and/or
In the step (1), the concentration of the maleic anhydride in the maleic anhydride solution containing the initiator is 3wt% -25wt%.
10. The copolymerization method according to claim 1, wherein the initiator is a thermal decomposition type initiator; and/or
The solvent in the maleic anhydride solution containing the initiator is at least one of organic acid alkyl ester, alkane and aromatic hydrocarbon.
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|---|---|---|---|---|
| EP0303057A2 (en) * | 1987-08-11 | 1989-02-15 | S.C. Johnson & Son, Inc. | Continous process and system for producing polymers maleic anhydride & certain alpha-olefins |
| US5003014A (en) * | 1990-05-21 | 1991-03-26 | Gaf Chemicals Corporation | Process for making copolymers of maleic anhydride and a C1 -C4 alkyl vinyl ether having a predetermined specific viscosity |
| JPH03215507A (en) * | 1990-01-18 | 1991-09-20 | Showa Denko Kk | Production of ethylenic copolymer |
| US5548031A (en) * | 1993-11-19 | 1996-08-20 | Tosoh Corporation | Copolymer production process |
| US20050148745A1 (en) * | 2002-01-28 | 2005-07-07 | Benthem Van Rudolfus Antonius Theodorus M. | Process for the preparation of a copolymer of maleic anhydride and an alkyl vinyl ether, copolymers of maleic anhydride and an alkyl vinyl ether and an apparatus |
| CN107537420A (en) * | 2016-06-28 | 2018-01-05 | 华茂东 | Reactor solid stirring structure |
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2022
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0303057A2 (en) * | 1987-08-11 | 1989-02-15 | S.C. Johnson & Son, Inc. | Continous process and system for producing polymers maleic anhydride & certain alpha-olefins |
| JPH03215507A (en) * | 1990-01-18 | 1991-09-20 | Showa Denko Kk | Production of ethylenic copolymer |
| US5003014A (en) * | 1990-05-21 | 1991-03-26 | Gaf Chemicals Corporation | Process for making copolymers of maleic anhydride and a C1 -C4 alkyl vinyl ether having a predetermined specific viscosity |
| US5548031A (en) * | 1993-11-19 | 1996-08-20 | Tosoh Corporation | Copolymer production process |
| US20050148745A1 (en) * | 2002-01-28 | 2005-07-07 | Benthem Van Rudolfus Antonius Theodorus M. | Process for the preparation of a copolymer of maleic anhydride and an alkyl vinyl ether, copolymers of maleic anhydride and an alkyl vinyl ether and an apparatus |
| CN107537420A (en) * | 2016-06-28 | 2018-01-05 | 华茂东 | Reactor solid stirring structure |
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