CN114426639A - Alpha-olefin-maleic anhydride copolymer and preparation method and application thereof - Google Patents
Alpha-olefin-maleic anhydride copolymer and preparation method and application thereof Download PDFInfo
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- CN114426639A CN114426639A CN202011105716.XA CN202011105716A CN114426639A CN 114426639 A CN114426639 A CN 114426639A CN 202011105716 A CN202011105716 A CN 202011105716A CN 114426639 A CN114426639 A CN 114426639A
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- maleic anhydride
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 90
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000004005 microsphere Substances 0.000 claims abstract description 50
- -1 polypropylene Polymers 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 25
- 239000004743 Polypropylene Substances 0.000 claims abstract description 21
- 229920001155 polypropylene Polymers 0.000 claims abstract description 21
- 229920000098 polyolefin Polymers 0.000 claims abstract description 19
- 150000001335 aliphatic alkanes Chemical group 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000011049 filling Methods 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 54
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 45
- 238000006116 polymerization reaction Methods 0.000 claims description 34
- 239000004711 α-olefin Substances 0.000 claims description 30
- 239000012456 homogeneous solution Substances 0.000 claims description 27
- 239000000178 monomer Substances 0.000 claims description 25
- 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 24
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 229940117955 isoamyl acetate Drugs 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000839 emulsion Substances 0.000 claims description 7
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 claims description 6
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 6
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- XINCECQTMHSORG-UHFFFAOYSA-N Isoamyl isovalerate Chemical compound CC(C)CCOC(=O)CC(C)C XINCECQTMHSORG-UHFFFAOYSA-N 0.000 claims description 4
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 claims description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 claims description 4
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 claims description 4
- PPXUHEORWJQRHJ-UHFFFAOYSA-N ethyl isovalerate Chemical compound CCOC(=O)CC(C)C PPXUHEORWJQRHJ-UHFFFAOYSA-N 0.000 claims description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 4
- PQLMXFQTAMDXIZ-UHFFFAOYSA-N isoamyl butyrate Chemical compound CCCC(=O)OCCC(C)C PQLMXFQTAMDXIZ-UHFFFAOYSA-N 0.000 claims description 4
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001451 organic peroxides Chemical group 0.000 claims description 4
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 2
- 125000006701 (C1-C7) alkyl group Chemical group 0.000 claims description 2
- JLIDRDJNLAWIKT-UHFFFAOYSA-N 1,2-dimethyl-3h-benzo[e]indole Chemical compound C1=CC=CC2=C(C(=C(C)N3)C)C3=CC=C21 JLIDRDJNLAWIKT-UHFFFAOYSA-N 0.000 claims description 2
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- AVMSWPWPYJVYKY-UHFFFAOYSA-N 2-Methylpropyl formate Chemical compound CC(C)COC=O AVMSWPWPYJVYKY-UHFFFAOYSA-N 0.000 claims description 2
- MLLAPOCBLWUFAP-UHFFFAOYSA-N 3-Methylbutyl benzoate Chemical compound CC(C)CCOC(=O)C1=CC=CC=C1 MLLAPOCBLWUFAP-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- DULCUDSUACXJJC-UHFFFAOYSA-N benzeneacetic acid ethyl ester Natural products CCOC(=O)CC1=CC=CC=C1 DULCUDSUACXJJC-UHFFFAOYSA-N 0.000 claims description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 229940007550 benzyl acetate Drugs 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- BLCKNMAZFRMCJJ-UHFFFAOYSA-N cyclohexyl cyclohexyloxycarbonyloxy carbonate Chemical compound C1CCCCC1OC(=O)OOC(=O)OC1CCCCC1 BLCKNMAZFRMCJJ-UHFFFAOYSA-N 0.000 claims description 2
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 2
- 229940094941 isoamyl butyrate Drugs 0.000 claims description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 2
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229940095102 methyl benzoate Drugs 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 61
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000000463 material Substances 0.000 description 13
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 5
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000012673 precipitation polymerization Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229920002292 Nylon 6 Polymers 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005469 granulation Methods 0.000 description 3
- 230000003179 granulation Effects 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920005604 random copolymer Polymers 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241001312741 Gekko swinhonis Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229920005603 alternating copolymer Polymers 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 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
- 239000003365 glass fiber Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
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
- 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
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/18—Spheres
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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 relates to the field of high molecular polymers, and discloses an alpha-olefin-maleic anhydride copolymer, and a preparation method and application thereof. The copolymer comprises a structural unit shown in a formula (1) and a structural unit shown in a formula (2);wherein R is alkane with 6-12 carbon atoms; the molar content of the structural unit shown in the formula (1) is 48-53%, and the molar content of the structural unit shown in the formula (2) is 47-52%, based on the total molar amount of the copolymer. CopolymerThe copolymer microsphere is in a microsphere shape, the surface of the copolymer microsphere is clean and pollution-free, and the microsphere particles are uniform, so that the copolymer microsphere can be used as a filling modification auxiliary agent in polyolefin, particularly polypropylene, and the polymer performance can not be remarkably reduced.
Description
Technical Field
The invention relates to the field of high molecular polymers, in particular to an alpha-olefin-maleic anhydride copolymer microsphere and a preparation method and application thereof.
Background
In the prior art, the maleic anhydride-containing copolymers are mostly prepared by solution or conventional precipitation polymerization. Shenrong et al in "Styrene-maleic anhydride copolymerization in different solvents" disclose that maleic anhydride and styrene were reacted in ethyl acetate and N, N-dimethylformamide, and after completion of the reaction, a polymer of maleic anhydride and styrene was prepared by using ethanol as a precipitant (proceedings of Wuhan engineering university, 2019, 41 (1): 65-68).
In "Synthesis of styrene-maleic anhydride alternating copolymer with Low relative molecular weight" in Liuting nations et al, styrene-maleic anhydride copolymer was synthesized in toluene by precipitation polymerization.
Synthesis and characterization of styrene-maleic anhydride random copolymer in Green solvent of Gekko Swinhonis et al (plastics science 2019, 47(2):24-28) styrene-maleic anhydride random copolymer was prepared by solution polymerization using dimethyl carbonate as a Green solvent.
Multipolymers of maleic anhydride have many uses. The study of Liangshujun et al on' alpha-methylstyrene/styrene/maleic anhydride hexene copolymer functionalized polypropylene and compatibilized polypropylene/nylon 6 blending system, reported in macromolecules 2011, 2: 180-185' uses butanone as solvent to synthesize hexene copolymer of maleic anhydride, styrene and alpha methyl styrene, and the hexene copolymer has in-situ compatibilization effect on polypropylene/nylon 6 blending system, so that the particle size of dispersed phase nylon 6 is obviously reduced.
The common filling modified materials of the polyolefin are inorganic materials such as calcium carbonate, talcum powder, glass fiber and the like, and the inorganic materials have larger surface property difference with the polyolefin, so that even if the corresponding surface treatment auxiliary agent is added during blending with the polyolefin, the dispersion is still uneven, and the performance of the polymer is reduced. There is therefore a need to develop a filler modification aid which is more compatible and does not cause a decrease in the properties of the polyolefin.
Disclosure of Invention
The invention aims to overcome the problem that the performance of polyolefin is reduced by using an inorganic filling modification auxiliary agent for polyolefin in the prior art, and provides an alpha-olefin-maleic anhydride copolymer, a preparation method and application thereof.
In order to achieve the above object, a first aspect of the present invention provides an α -olefin-maleic anhydride copolymer characterized in that the copolymer comprises a structural unit represented by formula (1) and a structural unit represented by formula (2);
wherein R is alkane with 6-12 carbon atoms;
the molar content of the structural unit shown in the formula (1) is 48-53%, and the molar content of the structural unit shown in the formula (2) is 47-52%, based on the total molar amount of the copolymer.
The second aspect of the present invention provides a method for producing an α -olefin-maleic anhydride copolymer, characterized in that the method comprises the steps of:
(1) dissolving a polymerization monomer and an initiator in an organic medium in an inert atmosphere to form a homogeneous solution;
(2) after the homogeneous solution is subjected to polymerization reaction to obtain copolymer emulsion suspension, performing solid-liquid separation to obtain the alpha-olefin-maleic anhydride copolymer;
wherein the polymerized monomers are maleic anhydride and alpha-olefin shown in a formula (3); the molar content of the maleic anhydride is 48 to 53% and the molar content of the alpha-olefin is 47 to 52%, based on the total mass of the polymerized monomers;
wherein R is alkane with 6-12 carbon atoms.
The third aspect of the present invention provides an α -olefin-maleic anhydride copolymer produced by the above production method.
In a fourth aspect, the present invention provides the use of the above-mentioned α -olefin-maleic anhydride copolymer as a filling modification aid in a polyolefin, preferably, the polyolefin is polypropylene.
By the technical scheme, the alpha-olefin-maleic anhydride copolymer and the preparation method and application thereof provided by the invention have the following beneficial effects:
the alpha-olefin-maleic anhydride copolymer provided by the invention contains specific contents of maleic anhydride and long-chain alpha-olefin, so that the obtained copolymer is microspherical, and the microspherical copolymer has uniform particle size and clean and pollution-free surface.
Furthermore, in the preparation method provided by the invention, a specific organic medium is selected and matched with a specific amount of monomers to realize self-stabilization precipitation polymerization reaction of maleic anhydride and long-chain alpha-olefin, no stabilizer or co-stabilizer is required to be added in a polymerization reaction system, a self-stabilization dispersion effect is realized, and copolymer microspheres with the average particle size of 500-1600nm can be prepared.
Further, the alpha-olefin-maleic anhydride copolymer provided by the invention is used as a filling modification auxiliary agent for polyolefin, particularly polypropylene, does not cause remarkable reduction of polymer performance, and can adjust the polarity of the polyolefin and reduce the cost.
Drawings
FIG. 1 is the FI-IR chart of the copolymer prepared in example 1;
FIG. 2 is a scanning electron micrograph of the copolymer obtained in example 1.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides an α -olefin-maleic anhydride copolymer characterized in that the copolymer comprises a structural unit represented by formula (1) and a structural unit represented by formula (2);
wherein R is alkane with 6-12 carbon atoms;
the molar content of the structural unit shown in the formula (1) is 48-53%, and the molar content of the structural unit shown in the formula (2) is 47-52%, based on the total molar amount of the copolymer.
In the present invention, the total content of the structural unit represented by the formula (1) and the structural unit represented by the formula (2) is 100%.
In the invention, the copolymer contains structural units derived from maleic anhydride and structural units derived from alpha-olefin in specific contents, so that the obtained copolymer is microspherical, and the copolymer microsphere has the characteristics of uniform particle size, clean surface and no pollution.
Further, in the invention, the copolymer contains a structural unit derived from maleic anhydride and a structural unit derived from long-chain alpha-olefin, so that the obtained copolymer has the performance characteristic of stronger polarity and better compatibility with polyolefin.
Further, in order to obtain an α -olefin-maleic anhydride copolymer having more excellent overall properties, the molar content of the structural unit represented by the formula (1) is 49 to 52%, and the molar content of the structural unit represented by the formula (2) is 48 to 51%, based on the total molar amount of the copolymer.
In the present invention, the molar content of each structural unit in the copolymer is used1H NMR is used for testing, and the testing method is to pass1And calculating the ratio of the peak area corresponding to the characteristic hydrogen in the corresponding structural unit in H NMR.
According to the invention, in the formula (2), R is an alkane with 6-8 carbon atoms.
According to the invention, the alpha-olefin-maleic anhydride copolymer is in the form of microspheres.
Further, the average particle diameter of the alpha-olefin-maleic anhydride copolymer is 500 to 1600nm, preferably 700 to 1600 nm.
In the present invention, the average particle diameter of the copolymer microspheres is measured by a scanning electron microscope method.
The second aspect of the present invention provides a method for preparing an α -olefin-maleic anhydride copolymer, wherein the method comprises the steps of:
(1) dissolving a polymerization monomer and an initiator in an organic medium in an inert atmosphere to form a homogeneous solution;
(2) after the homogeneous solution is subjected to polymerization reaction to obtain copolymer emulsion suspension, performing centrifugal separation to obtain the alpha-olefin-maleic anhydride copolymer;
wherein the polymerized monomers are maleic anhydride and alpha-olefin shown in a formula (3); the molar content of the maleic anhydride is 48 to 53% and the molar content of the alpha-olefin is 47 to 52%, based on the total mass of the polymerized monomers;
wherein R is alkane with 6-12 carbon atoms.
In the invention, in the presence of an organic medium, maleic anhydride and alpha-olefin shown in a formula (3) are copolymerized according to the method defined by the invention in a copolymerization mode, and in a polymerization monomer, the molar contents of the maleic anhydride and the alpha-olefin shown in the formula (3) are regulated, when the molar contents of the maleic anhydride and the alpha-olefin shown in the formula (3) meet the range, the self-stable dispersion of a polymerization system can be realized, the prepared polymer is microspherical, in addition, no auxiliary agents such as a stabilizing agent, a precipitating agent and the like are additionally added in the polymerization process, the obtained copolymer microsphere has the characteristic of clean surface, the dispersibility in the medium is good, and the aggregation does not occur.
Further, in order to obtain a copolymer having more excellent properties, the inventors have studied the molar contents of maleic anhydride and α -olefin represented by formula (3) during the polymerization process, and have found that when the molar content of maleic anhydride is 49 to 52% and the molar content of α -olefin is 48 to 51% based on the total amount of the polymeric monomers, copolymer microspheres having a clean particle surface can be obtained, and that when the obtained copolymer microspheres are used as a filling modification aid for polyolefins, particularly polypropylene, no significant decrease in polymer properties is caused.
According to the invention, in formula (3), R is an alkane having 6 to 8 carbon atoms.
According to the invention, the mass concentration of the polymerized monomers is from 3 to 22% by weight, preferably from 4 to 21% by weight, more preferably from 6 to 20% by weight, based on the total weight of the homogeneous solution.
According to the invention, the initiator is an organic peroxide and/or an azo compound.
According to the present invention, the organic peroxide is at least one selected from the group consisting of dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate.
According to the invention, the azo compound is selected from azobisisobutyronitrile and/or azobisisoheptonitrile.
According to the invention, the initiator is present in a mass concentration of 0.12 to 2.4% by weight, preferably 0.6 to 2% by weight, more preferably 1 to 2% by weight, based on the total weight of the homogeneous solution
According to the invention, the organic medium is a mixture of an organic acid alkyl ester and hexane.
In the invention, organic acid alkyl ester and hexane are selected as organic media, and can be matched with maleic anhydride and alpha-olefin shown in a formula (3) with specific dosage, so that the self-stabilization precipitation polymerization reaction of the maleic anhydride and the alpha-olefin shown in the formula (3) can be realized, no stabilizer or co-stabilizer is required to be added in a polymerization reaction system, the self-stabilization dispersion effect is realized, and the obtained copolymer microsphere has a clean and pollution-free surface.
According to the invention, the weight ratio of the organic acid alkyl ester to the hexane is 0.6-0.9: 1.
In the present invention, when the weight ratio of the organic acid alkyl ester to hexane in the organic medium satisfies the above range, it is more advantageous for the polymerization system to form a self-stabilized dispersion system, and thus the copolymer microspheres obtained have more advantageous surface morphology.
Further, when the weight ratio of the organic acid alkyl ester to the hexane is 0.7 to 0.9:1, the comprehensive effect of the prepared copolymer microspheres is more excellent.
According to the invention, the organic acid alkyl ester has the general formula R1COOR2Wherein R is1Selected from H, C1-4At least one of alkyl, phenyl and benzyl of (A), R2Is C1-10Alkyl group of (1).
Preferably, R1Is C1-4Alkyl and/or phenyl of R2Is C1-7Alkyl group of (1).
According to the invention, the reaction medium is selected from at least one of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate.
In the present invention, the polymerization reaction is carried out in an inert atmosphere, which may be provided by an inert gas, such as nitrogen, which is conventional in the art.
In the present invention, in order to achieve self-stabilization of the polymerization system and further to prepare copolymer microspheres having uniform particle size and showing cleanness and no pollution, the inventors have studied the conditions of the polymerization reaction. Research shows that when the polymerization temperature is 60-95 ℃ and the polymerization time is 2-24h, the polymerization system forms a stable self-stabilization system, in the system, polymerization monomers, namely maleic anhydride and long-chain alpha-olefin, are polymerized to form microspheres, and the microspheres are not aggregated in a medium and have good dispersibility.
Further, the polymerization temperature is 66-75 ℃, and the polymerization time is 6-12 h.
The third aspect of the present invention provides an α -olefin-maleic anhydride copolymer produced by the above production method.
According to the present invention, the copolymer is in the form of microspheres, and further, the average particle diameter of the copolymer is 500 to 1600nm, preferably 700 to 1600 nm.
In the present invention, the molar content of the structural unit provided by maleic anhydride is 48 to 53% and the molar content of the structural unit provided by the α -olefin represented by the formula (3) is 47 to 52%, based on the total molar amount of the copolymer.
Further, in the invention, the copolymer contains a structural unit derived from maleic anhydride and a structural unit derived from long-chain alpha-olefin, so that the obtained copolymer has the performance characteristic of stronger polarity and better compatibility with polyolefin.
Further, when the molar content of the structural unit provided by maleic anhydride is 49 to 52% and the molar content of the structural unit provided by the α -olefin represented by the formula (3) is 48 to 51% based on the total molar amount of the copolymer, the copolymer has more excellent overall properties.
In a fourth aspect, the present invention provides the use of the above-mentioned α -olefin-maleic anhydride copolymer as a filling modification aid in a polyolefin, preferably, the polyolefin is polypropylene.
In the invention, at 230 ℃ and under the load of 2.16kg, the melt index of the polypropylene is 10g/10min, and the melt index of the polypropylene obtained after adding the microspheres is 7-10g/10 min.
In the present invention, the α -olefin-maleic anhydride copolymer is used in an amount of 0.2 to 1.5 wt%, preferably 0.4 to 0.9 wt%, relative to the total weight of the polyolefin.
The present invention will be described in detail below by way of examples. In the following examples of the present invention,
the polymerization yield (C) was determined by the following formulap) Perform calculation
Cp=Mp×100%/Mm
Wherein Mp is the mass of the resulting polymer; mm is the total mass of the monomers added;
observing and measuring the shape and the size of the copolymer microsphere by adopting a Scanning Electron Microscope (SEM);
the infrared spectrogram of the copolymer is tested by FI-IR;
the content of each structural unit in the copolymer is adopted1H NMR is used for testing, and the testing method is to pass1Measuring the content of each structural unit according to the ratio of the peak areas corresponding to the characteristic hydrogen in the corresponding structural unit in H NMR;
polypropylene, grade 1647, melt index 10g/10 min;
and testing the performance of the modified polypropylene according to the method GB/T1843-2008.
Examples and comparative examples all other materials were commercially available.
Example 1
Adding 11g of maleic anhydride, 0.6g of azobisisobutyronitrile, 8.4g of hexene, 90mL of hexane and 87.8g of isoamyl acetate into a 500mL three-neck flask, uniformly mixing the materials to obtain a homogeneous solution, introducing nitrogen for 20 minutes, transferring the three-neck flask into a water bath at 60 ℃, reacting for 24 hours, and after the reaction is finished, centrifugally separating the obtained polymer milky suspension by a centrifuge at the rotating speed of 2000rad/min for 20 minutes to obtain polymer solid A19.7g, wherein the yield of the corresponding polymer is 50%. The particle size of the polymer microsphere is 1600 nanometers. Wherein the concentration of the polymerization monomer is 11.6 wt% and the concentration of the initiator is 0.36 wt% based on the total weight of the homogeneous solution.
Subjecting the polymer microsphere A1 to1H NMR measurement determined that the molar content of the structural unit provided by maleic anhydride was 50% and the molar content of the structural unit provided by α -olefin was 50% in the polymer.
FI-IR chart of copolymer microspheres as shown in FIG. 1, 1785cm-1、1850cm-1Characteristic absorption peaks for anhydride groups.
As shown in the SEM image of the copolymer microsphere in FIG. 2, it can be seen that the particles of the copolymer microsphere are uniform and the surface of the particles is clean and not contaminated.
Example 2
Adding 20g of maleic anhydride, 0.2g of azobisisobutyronitrile, 70mL of hexane, 17.2g of hexene and 87.8g of butyl butyrate into a 500mL three-neck flask, uniformly mixing the materials to obtain a homogeneous solution, introducing nitrogen for 20 minutes, moving the three-neck flask into a water bath at 95 ℃, reacting for 2 hours, and after the reaction is finished, centrifuging the obtained polymer emulsion suspension by a centrifuge at the rotating speed of 2000rad/min for 20 minutes to obtain polymer solid A28.9g, wherein the corresponding polymer yield is 48%. The particle size of the polymer microsphere is 1500 nanometers. Wherein the concentration of the polymerization monomer is 21.6 wt% and the concentration of the initiator is 0.12 wt% based on the total weight of the homogeneous solution.
Subjecting the polymer microsphere A2 to1H NMR measurement determined that the molar content of structural units provided by maleic anhydride was 48% and the molar content of structural units provided by α -olefin was 52% in the polymer.
Example 3
Adding 10.2g of maleic anhydride, 0.7g of azobisisobutyronitrile, 80mL of hexane, 8.6g of hexene and 80g of butyl benzoate into a 500mL three-neck flask, uniformly mixing the materials to obtain a homogeneous solution, introducing nitrogen for 20 minutes, moving the three-neck flask into a water bath at 80 ℃, reacting for 5 hours, and centrifugally separating the obtained polymer milky suspension by a centrifuge at the rotating speed of 2000rad/min for 20 minutes to obtain a polymer solid A39 g, wherein the yield of the corresponding polymer is 48%. The particle size of the polymer was 1400 nm. Wherein the concentration of the polymerization monomer is 12.3 wt% and the concentration of the initiator is 0.46 wt% based on the total weight of the homogeneous solution.
Subjecting the polymer microsphere A3 to1H NMR measurement determined that the molar content of the structural unit provided by maleic anhydride was 53% and the molar content of the structural unit provided by α -olefin was 47% in the polymer.
Example 4
9.6g of maleic anhydride, 4g of azobisisobutyronitrile, 80mL of hexane, 11.2g of octene and 85.8g of butyl acetate are added into a 500mL three-neck flask, the materials are uniformly mixed to obtain a homogeneous solution, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a water bath at 65 ℃ for reaction for 5 hours, and after the reaction is finished, the obtained polymer milky suspension is centrifugally separated for 20 minutes by a centrifuge at the rotating speed of 2000rad/min to obtain polymer solid A48 g, wherein the corresponding polymer yield is 38%. The particle size of the polymer microsphere is 1500 nanometers. Wherein the concentration of the polymerization monomer is 13 wt% and the concentration of the initiator is 2.4 wt% based on the total weight of the homogeneous solution.
Subjecting the polymer microsphere A4 to1H NMR measurement determined that the molar content of structural units provided by maleic anhydride was 48% and the molar content of structural units provided by α -olefin was 52% in the polymer.
Example 5
9.5g of maleic anhydride, 0.89g of azobisisobutyronitrile, 70mL of hexane, 16.8g of dodecene and 82.8g of isoamyl acetate are added into a 500mL three-neck flask, the materials are uniformly mixed to obtain a homogeneous solution, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a 75 ℃ water bath for reaction for 5 hours, and after the reaction is finished, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifuge at the rotating speed of 2000rad/min to obtain polymer solid A59.8g, wherein the corresponding polymer yield is 37%. The particle size of the polymer microspheres is 1200 nm. Wherein the concentration of the polymerized monomer is 16.8 wt% and the concentration of the initiator is 0.57 wt% based on the total weight of the homogeneous solution.
Subjecting the polymer microsphere A5 to1H NMR measurement of the polymer, it was determined that the structural unit provided by maleic anhydride was present in the polymerThe molar content of elements is 50% and the molar content of structural units provided by the alpha-olefins is 50%.
Example 6
9.6g of maleic anhydride, 0.69g of azobisisobutyronitrile, 70mL of hexane, 8.6g of hexene and 86.8g of isoamyl acetate are added into a 500mL three-neck flask, the materials are uniformly mixed to obtain a homogeneous solution, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a 75 ℃ water bath for reaction for 3 hours, and after the reaction is finished, the obtained polymer emulsion suspension is centrifugally separated for 20 minutes by a centrifuge at the rotating speed of 2000rad/min to obtain polymer solid A67.3g, the corresponding polymer yield is 40%, and the particle size of the polymer microspheres is 1350 nanometers. Wherein, based on the total weight of the homogeneous phase solution, the concentration of the polymerization monomer is 12 wt%, and the concentration of the initiator is 0.45 wt%.
Subjecting the polymer microsphere A6 to1H NMR measurement revealed that the molar content of the structural unit derived from maleic anhydride was 51% and the molar content of the structural unit derived from alpha-olefin was 49% in the polymer
Example 7
9.8g of maleic anhydride, 0.79g of azobisisobutyronitrile, 80mL of hexane, 8.6g of hexene and 88.8g of isoamyl acetate are added into a 500mL three-neck flask, the materials are uniformly mixed to obtain a homogeneous solution, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a water bath at 72 ℃ for reaction for 5 hours, after the reaction is finished, the obtained polymer milky suspension is centrifugally separated for 20 minutes by a centrifuge at the rotating speed of 2000rad/min to obtain polymer solid A77.5g, the corresponding polymer yield is 41%, and the particle size of the polymer microspheres is 1250 nanometers. Wherein the concentration of the polymerization monomer is 11.4 wt% and the concentration of the initiator is 0.49 wt% based on the total weight of the homogeneous solution.
Subjecting the polymer microsphere A7 to1H NMR measurement determined that the molar content of structural units provided by maleic anhydride was 49% and the molar content of structural units provided by α -olefin was 51% in the polymer.
Example 8
2.45g of maleic anhydride, 0.89g of azobisisobutyronitrile, 70mL of hexane, 2.3g of hexene and 87.8g of isoamyl acetate are added into a 500mL three-neck flask, the materials are uniformly mixed to obtain a homogeneous solution, nitrogen is introduced for 20 minutes, the three-neck flask is moved into a 70 ℃ water bath for reaction for 5 hours, and after the reaction is finished, the obtained polymer emulsion suspension is centrifugally separated by a centrifuge at the rotating speed of 2000rad/min for 20 minutes to obtain polymer solid A81.4g, wherein the corresponding polymer yield is 29%. The particle size of the polymer microspheres is 600 nanometers. Wherein the concentration of the polymerization monomer is 3.4 wt% and the concentration of the initiator is 0.64 wt% based on the total weight of the homogeneous solution.
Subjecting the polymer microsphere A8 to1H NMR measurement determined that the molar content of the structural unit provided by maleic anhydride was 50% and the molar content of the structural unit provided by α -olefin was 50% in the polymer.
Comparative example 1
Copolymer microspheres were prepared according to the method of example 1, except that: the amounts of alkyl esters of organic acids and hexane used differ from the examples, in particular: adding 11g of maleic anhydride, 0.6g of azobisisobutyronitrile, 8.4g of hexene, 20mL of hexane and 87.8g of isoamyl acetate into a 500mL three-neck flask, uniformly mixing the materials to obtain a homogeneous solution, introducing nitrogen for 20 minutes, transferring the three-neck flask into a water bath at 60 ℃, reacting for 24 hours, and obtaining a polymer transparent solution after the reaction is finished without forming microsphere particles.
Comparative example 2
Copolymer microspheres were prepared according to the method of example 1, except that: the polymerization system contained no hexane.
Adding 11g of maleic anhydride, 0.6g of azobisisobutyronitrile, 8.4g of hexene and 87.8g of isoamyl acetate into a 500mL three-neck flask, uniformly mixing the materials to obtain a homogeneous solution, introducing nitrogen for 20 minutes, transferring the three-neck flask into a water bath at 60 ℃, reacting for 24 hours to obtain a transparent polymer solution without microsphere particles after the reaction is finished.
Test example
Extrusion granulation
The polymer microspheres prepared in the examples were added to high-pressure polypropylene in the amounts shown in table 1, respectively, and subjected to extrusion granulation to obtain polypropylene particles, wherein the experimental conditions of the granulation were as follows: a feeding section is 150-170 ℃; a plasticizing section of 175-220 ℃; the homogenizing section is 165-200 ℃; the die head is 160-180 ℃ and the rotating speed is 90-120 rad/min.
And (3) performance testing: and testing the performance of the modified polypropylene according to the method GB/T1843-2008.
The performance results of the material obtained after adding the polymeric microspheres to polypropylene are shown in table 1.
Test example 11 is the performance of polypropylene without microsphere polymer addition.
TABLE 1
As shown in Table 1, when the copolymer microspheres provided by the invention are added to polypropylene as a filler, the low-temperature impact toughness and the normal-temperature impact toughness of the obtained polypropylene are not reduced, and the toughness is slightly improved compared with that of pure polypropylene.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (11)
1. An α -olefin-maleic anhydride copolymer characterized in that the copolymer comprises a structural unit represented by formula (1) and a structural unit represented by formula (2);
wherein R is alkane with 6-12 carbon atoms;
the molar content of the structural unit shown in the formula (1) is 48-53%, and the molar content of the structural unit shown in the formula (2) is 47-52%, based on the total molar amount of the copolymer.
2. The α -olefin-maleic anhydride copolymer according to claim 1, wherein in formula (2), R is an alkane having 6 to 8 carbon atoms;
preferably, the molar content of the structural unit represented by the formula (1) is 49 to 52% and the molar content of the structural unit represented by the formula (2) is 48 to 51%, based on the total molar amount of the copolymer.
3. The alpha-olefin-maleic anhydride copolymer according to claim 1 or 2, wherein the alpha-olefin-maleic anhydride copolymer is in a microspheric shape;
preferably, the average particle size of the alpha-olefin-maleic anhydride copolymer is 500 to 1600nm, preferably 700 to 1600 nm.
4. A method for preparing an alpha-olefin-maleic anhydride copolymer, comprising the steps of:
(1) dissolving a polymerization monomer and an initiator in an organic medium in an inert atmosphere to form a homogeneous solution;
(2) after the homogeneous solution is subjected to polymerization reaction to obtain copolymer emulsion suspension, performing solid-liquid separation to obtain the alpha-olefin-maleic anhydride copolymer;
wherein the polymerized monomers are maleic anhydride and alpha-olefin shown in a formula (3); the molar content of the maleic anhydride is 48 to 53% and the molar content of the alpha-olefin is 47 to 52%, based on the total mass of the polymerized monomers;
wherein R is alkane with 6-12 carbon atoms.
5. The production process according to claim 4, wherein, in the formula (3), R is an alkane having 6 to 8 carbon atoms;
preferably, the mass concentration of the polymerized monomer is from 3 to 22 wt%, preferably from 4 to 21 wt%, more preferably from 6 to 20 wt%, based on the total weight of the homogeneous solution;
preferably, the molar content of the maleic anhydride is 49 to 52% and the molar content of the alpha-olefin is 48 to 51%, based on the total mass of polymerized monomers.
6. The production method according to claim 4 or 5, wherein the initiator is an organic peroxide and/or an azo compound;
preferably, the organic peroxide is selected from at least one of dibenzoyl peroxide, dicumyl peroxide, ditert-butyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate;
preferably, the azo compound is selected from azobisisobutyronitrile and/or azobisisoheptonitrile;
preferably, the mass concentration of the initiator is from 0.12 to 2.4 wt%, preferably from 0.6 to 2 wt%, more preferably from 1 to 2 wt%, based on the total weight of the homogeneous solution.
7. The production method according to any one of claims 4 to 6, wherein the organic medium is a mixture of an organic acid alkyl ester and hexane;
preferably, the weight ratio of the organic acid alkyl ester to the hexane is 0.6-0.9:1, preferably 0.7-0.9: 1;
preferably, the organic acid alkyl ester has the general formula R1COOR2Wherein R is1Selected from H, C1-4At least one of alkyl, phenyl and benzyl of (A), R2Is C1-10Alkyl groups of (a);
more preferably, R1Is C1-4Alkyl and/or phenyl of R2Is C1-7Alkyl groups of (a);
more preferably, the organic medium is selected from at least one of ethyl formate, propyl formate, isobutyl formate, pentyl formate, ethyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isoamyl butyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate.
8. The production method according to any one of claims 4 to 7, wherein the conditions of the polymerization reaction include: the polymerization temperature is 60-95 ℃, preferably 65-75 ℃; the polymerization time is 2 to 24 hours, preferably 6 to 12 hours.
9. An α -olefin-maleic anhydride copolymer produced by the production method according to any one of claims 4 to 8.
10. The alpha-olefin-maleic anhydride copolymer according to claim 9, wherein the copolymer is in the form of microspheres;
preferably, the average particle size of the copolymer is from 500 to 1600nm, preferably from 700 to 1600 nm.
11. Use of an alpha-olefin-maleic anhydride copolymer according to any of claims 1-3 and 9-10 as a filling modification aid in a polyolefin, preferably the polyolefin is polypropylene.
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