CN1890275A - 用后过渡金属催化剂制备烯烃-丙烯酸属共聚物的方法 - Google Patents
用后过渡金属催化剂制备烯烃-丙烯酸属共聚物的方法 Download PDFInfo
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 25
- 239000003054 catalyst Substances 0.000 title abstract description 17
- 229920006243 acrylic copolymer Polymers 0.000 title abstract 2
- 238000002360 preparation method Methods 0.000 title description 6
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000012190 activator Substances 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 3
- -1 imino- Chemical class 0.000 claims description 17
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 7
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- RUMACXVDVNRZJZ-UHFFFAOYSA-N 2-methylpropyl 2-methylprop-2-enoate Chemical compound CC(C)COC(=O)C(C)=C RUMACXVDVNRZJZ-UHFFFAOYSA-N 0.000 claims description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 claims description 2
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001925 cycloalkenes Chemical class 0.000 claims description 2
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 150000004645 aluminates Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 3
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000126 substance Substances 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical group 0.000 description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 229920006226 ethylene-acrylic acid Polymers 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 238000009512 pharmaceutical packaging Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- JNFRNXKCODJPMC-UHFFFAOYSA-N aniline;boric acid Chemical compound OB(O)O.NC1=CC=CC=C1 JNFRNXKCODJPMC-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明公开一种制备烯烃-丙烯酸属共聚物的方法。方法包括在活化剂和8-10族后过渡金属配合物存在下将烯烃和丙烯酸属单体聚合。后过渡金属催化剂含二氢异吲哚配体。
Description
发明领域
本发明涉及烯烃-丙烯酸属共聚物。更具体地说,本发明涉及用后过渡金属催化剂制备烯烃-丙烯酸属共聚物的方法。
发明背景
目前,特种聚烯烃如乙烯-甲基丙烯酸甲酯(EMA)、乙烯-丙烯酸乙酯(EEA)、乙烯-丙烯酸丁酯(EBA)和乙烯-丙烯酸(EAA)共聚物是通过高温高压自由基聚合反应来制备的。这些聚合物已用于药品包装、一次性手套、电缆复合层、粘合剂和许多其它用途。但这些材料价格昂贵。
自1990年代末以来,已开始研究一些引入后过渡金属(特别是铁、镍或钴)和庞大α-二亚胺配体(或称“双(亚胺)”)的烯烃聚合催化剂。这些后过渡金属催化剂之所以令人感兴趣,是因为与早期的过渡金属茂金属或Ziegler催化剂不同的是,后过渡金属催化剂能够容许并在聚烯烃中引入极性共聚单体。参见美国专利5866663和5955555。
近来已开发出一类含二氢异吲哚配体的新型后过渡金属催化剂。参见待审专利申请09/947745(2001年9月6日申请)。这些催化剂所呈现的活性比双(亚胺)基后过渡金属催化剂更高。并且,这些催化剂较易制备。但是,这些催化剂还未开发用于制备烯烃-丙烯酸属共聚物。
相比传统的自由基聚合方法,后过渡金属催化剂在一些关键的聚合物性能如分子量、结晶度或熔点和多分散度的设计方面具有很高的能力。因此,后过渡金属催化剂能提供更好的产品质量和生产过程的一致性。另外,后过渡金属催化剂不要求高温和高压聚合,避免了使用昂贵的过氧化物。因而过渡金属催化聚合技术能提供比现有自由基技术更安全和更廉价的替代方法。
总之,开发新的制备烯烃-丙烯酸属共聚物的方法对工业生产很重要。更具体地说,该方法将使用新开发的后过渡金属催化剂。理想的话,该催化剂不仅能容许丙烯酸属共聚单体,而且能具有很高活性和易于制备。
发明概述
本发明是一种制备烯烃-丙烯酸属共聚物的方法。本方法使用后过渡金属催化剂。催化剂包括活化剂和含二氢异吲哚配体的后过渡金属配合物。
发明详述
本发明方法包括在活化剂和8-10族后过渡金属配合物存在下将烯烃和丙烯酸属单体聚合。配合物含二氢异吲哚配体。活化剂与配合物相互作用生成催化活性种。
适宜的后过渡金属配合物包括如下通式结构的配合物:
L-M-(X)n
M是8-10族后过渡金属,L是二氢异吲哚配体,X是不稳定配体,n为X配体的数目,大于或等于1。
优选M选自Fe、Co、Ni、Cu和Zn,更优选M选自Fe、Co和Ni,最优选M是Fe。
二氢异吲哚配体优选具有如下通式:
当形成后过渡金属配合物时,N-H基团的氢可移出,在氮和后过渡金属间形成一个离子键。任选上述结构的芳环氢原子独立被取代。适宜的环取代基包括烷基、芳基、芳烷基、甲硅烷基、卤素、烷氧基、甲硅烷氧基、硝基、二烷基氨基、二芳基氨基等。
A是芳基和杂芳基。当A是芳基时,优选为苯基取代的或烷基取代的如4-甲基苯基和2,4,6-三甲基苯基(2-基)。当A是杂芳基时,优选是2-吡啶基、2-嘧啶基、4-嘧啶基、2-吡嗪基、2-咪唑基、2-噻唑基或2-唑基。芳基和杂芳基可与其它环稠合如2-萘基、2-苯并噻唑基或2-苯并咪唑基情形。
一些增添例性二氢异吲哚如下:
优选X独立选自氢和卤素,更优选X是卤素,最优选X是氯。
适宜的活化剂包括铝氧烷和烷基铝化合物。适宜的铝氧烷化合物的实例包括甲基铝氧烷(MAO)、聚合型MAO(PMAO)、乙基铝氧烷、二异丁基铝氧烷等。适宜的烷基铝化合物的实例包括三乙基铝、二乙基氯化铝、三甲基铝、三异丁基铝等。适宜的铝氧烷化合物还包括改性铝氧烷。铝氧烷的改性方法是众所周知的。例如,美国专利4990640中提出用含活性氢的化合物如乙二醇改性铝氧烷的方法。美国专利6340771提出用糖改性MAO来制备“甜”MAO。另外,美国专利5543377提出用酮醇和β-二酮来改性铝氧烷。
适宜的活化剂还包括含非亲核阴离子的酸盐。这些化合物通常是由庞大配体连接硼或铝构成。实例包括四(五氟苯基)硼酸锂、四(五氟苯基)铝酸锂、四(五氟苯基)硼酸苯胺盐。
适宜的活化剂还包括有机硼烷,是硼和一或多个烷基、芳基或烷芳基的化合物。适宜的有机硼烷包括取代或未取代的三烷基和三芳基硼烷如三(五氟苯基)硼烷、三苯基硼烷、三正辛基硼烷等。适宜的有机硼烷活化剂描述于美国专利5153157、5198401和5241025。适宜的活化剂还包括铝硼酸盐,是烷基铝化合物与有机硼酸的反应产物。这些活化剂描述于美国专利5414180和5648440。
任选将后过渡金属配合物、活化剂或二者负载于无机固体或有机聚合物载体。适宜的载体包括氧化硅、氧化铝、氧化硅-氧化铝、氧化镁、氧化钛、粘土、沸石或类似物。优选载体在使用前经热、化学或二者处理,来降低表面羟基的浓度。热处理是使用前将载体在干燥气氛和升温条件、优选大于约100℃且更优选约150-600℃下进行加热(或称“焙烧”)处理。可使用各种不同的化学处理法,包括与有机铝、有机镁、有机硅、或有机硼化合物反应。例如参见美国专利6211311描述的技术。
适宜的烯烃包括α-烯烃、环烯烃、共轭二烯及它们的混合物。优选C2-C20α-烯烃。特别优选乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯及其混合物。最优选乙烯和丙烯。
适宜的丙烯酸属单体包括丙烯酸C1-C20烷基酯、甲基丙烯酸C1-C20烷基酯、丙烯酸C6-C20芳基酯、甲基丙烯酸C6-C20芳基酯等及其它们的混合物。适宜的丙烯酸属单体的实例是丙烯酸正丁酯、甲基丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸叔丁酯、甲基丙烯酸异丁酯、甲基丙烯酸苄酯、甲基丙烯酸环己酯及它们的混合物。
本方法可以淤浆、溶液、气相或本体或组合方式操作。优选溶液和淤浆工艺。聚合反应可在很宽温度范围操作,如约-30℃到约280℃。更优选的范围为约30℃-180℃,最优选的范围是约50℃-150℃。
烯烃/丙烯酸属单体的摩尔比优选在99/1到50/50范围内。更优选该比例在95/5到75/25范围内。本发明方法所制聚合物作为丙烯酸属功能聚烯烃有很多用途。它们可用来制造薄膜,也可用于粘合剂。
可由本发明方法制备的烯烃-丙烯酸属共聚物的实例包括乙烯-甲基丙烯酸甲酯(EMA)、乙烯-丙烯酸乙酯(BEA)、乙烯-丙烯酸丁酯(EBA)和丙烯-甲基丙烯酸甲酯共聚物等。已发现这些聚合物有很多应用如药品包装、一次性手套和电缆复合层。
下列实施例仅仅是例示说明本发明。本领域技术人员应能认识到在本发明精神和权利要求范围内的许多变化。
实施例1
使用1,3-二(2-基亚氨基)二氢异吲哚合铁(II)配合物和MAO活化剂的乙烯与丙烯酸正丁酯共聚反应
催化剂制备
在一个装配氮气进管和内置烧结玻璃过滤器的100ml圆底烧瓶中加入邻苯二甲酰亚胺(2.94g,20.0mmol)和乙酸乙酯(60ml)。(烧结玻璃过滤器接到一个穿过橡胶隔片插入反应器的玻璃管底部,过滤器易于升至或降至反应器液面的上下)。将2,4,6-三甲基苯胺(5.41g,40.0mmol,2.0当量)和氯化铁(II)(2.54g,20.0mmol)加入烧瓶,氮气和室温条件下将混合物搅拌1小时。将黄色混合物加热回流(77℃)10小时,然后室温下搅拌32小时。形成棕色沉淀物。通过在氮气流下汽提出乙酸乙酯来浓缩反应混合物。向残留物中加入冷乙醚(30ml),搅拌混合物来洗涤残留物。将玻璃过滤器浸入液相,然后在减压条件下经内过滤器将液相移出。固体真空干燥2小时,得到一棕色粉末。收率:10.11g(99.4%)。
聚合
聚合反应在一个Endeavor(AdvantageTM系列3400 ProcessChemistry Workstation,Argonaut技术有限公司制造)内进行。Endeavor包含8个温度、压力、搅拌和注入控制各自独立的压力反应器管。Endeavor放入手套箱内便于手工操作且处于惰性氮气氛中。预定程序的计算机监测和收集压力、温度、每一反应器管内的乙烯耗量与时间的关系。
反应器管(10ml)装入丙烯酸正丁酯(4ml)、三异丁基铝(0.1ml,1.0M己烷溶液),MAO(0.08ml,1.0M甲苯溶液),和催化剂(0.2ml,1.0M甲苯溶液)。然后将反应器管密封。反应器用乙烯加压到400psig并加热到100℃。在此温度和压力读数下,连续送入乙烯使聚合反应持续约1小时。乙烯耗量约0.73g(0.026mol)。聚合后,真空移出未反应的丙烯酸酯,得到1.8g聚合物。聚合物的丙烯酸酯/乙烯摩尔比:1∶3.1(按单体耗量计算),Mw:2.1×105,Mn:8.8×103。
实施例2
使用1,3-二(2-吡啶基亚氨基)二氢异吲哚合铁(II)配合物和MAO活化剂的乙烯与丙烯酸正丁酯共聚反应
催化剂制备
在一个装配氮气进管和内置烧结玻璃过滤器的100ml圆底烧瓶中加入邻苯二甲酰亚胺(2.94g,20.0mmol)和乙酸乙酯(50ml)。将2-氨基吡啶(3.77g,40.0mmol,2.1当量)和氯化铁(II)(2.54g,20.0mmol)加入烧瓶,氮气和室温条件下将混合物搅拌1小时。混合物室温下搅拌120小时。得到一白色沉淀物。
24、48和120小时时从烧瓶底部取样,每一样品真空干燥0.5小时,每个样品取一小部分(40mg)溶解于甲苯(20ml)中并在乙烯聚合试验中进行测试。(24小时样品的聚合结果示于表1)。其余的反应混合物在120小时搅拌后进行真空汽提。用冷乙醚(3×20ml)洗涤后,将白色固体真空干燥1小时。总收率:8.40g(98.6%)。
聚合
按实施例1的聚合步骤。乙烯耗量0.59g(0.021mol),收集到1.7g聚合物。聚合物的丙烯酸酯/乙烯摩尔比:1∶2.4,Mw:1.9×105,Mn:8.5×103。
实施例3
使用1,3-二(2-基亚氨基)二氢异吲哚合镍(II)配合物和MAO活化剂的乙烯与丙烯酸正丁酯共聚反应
催化剂制备
在一个如上装配的100ml圆底烧瓶中加入邻苯二甲酰亚胺(2.94g,20.0mmol)和乙酸乙酯(60ml)。将2,4,6-三甲基苯胺(5.41g,40.0mmol,2.0当量)和氯化镍(II)(2.63g,20.0mmol)加入烧瓶,氮气和室温条件下将混合物搅拌24小时,形成棕色沉淀物。通过在氮气流下汽提出乙酸乙酯来浓缩反应混合物。向残留物中加入冷乙醚(30ml),搅拌混合物来洗涤残留物。减压条件下经内过滤器将液相移出。固体真空干燥2小时,得到一棕色粉末。收率:9.60g(93.8%)。
聚合
按实施例1的聚合步骤。乙烯耗量0.84g(0.03mol),收集到2.16g聚合物。聚合物的丙烯酸酯/乙烯摩尔比:1∶3.0,Mw:2.0×105,Mn:7.6×103。
Claims (19)
1.一种包括在活化剂和含二氢异吲哚配体的8-10族后过渡金属配合物存在下将烯烃和丙烯酸属单体聚合的方法。
2.权利要求1的方法,其中配合物具有如下通式结构:
L-M-(X)n
其中M是8-10族后过渡金属,L是二氢异吲哚配体,X是不稳定配体,n为X配体的数目,大于或等于1。
4.权利要求3的方法,其中A和A’相同且选自芳基。
5.权利要求3的方法,其中A和A’相同且选自杂芳基。
6.权利要求2的方法,其中M选自Ni、Co和Fe。
7.权利要求2的方法,其中M是Fe。
8.权利要求2的方法,其中X独立选自氢和卤素。
9.权利要求2的方法,其中X独立选自卤素。
10.权利要求1的方法,其中配合物包括Fe和1,3-二(2-基亚氨基)二氢异吲哚配体。
11.权利要求1的方法,其中配合物包括Fe和1,3-二(2-吡啶基亚氨基)二氢异吲哚配体。
12.权利要求1的方法,其中活化剂选自烷基铝氧烷、烷基铝化合物、铝硼酸盐、有机硼烷、离子型硼酸盐和离子型铝酸盐。
13.权利要求1的方法,其中活化剂是铝氧烷。
14.权利要求1的方法,其中烯烃选自C2-C10α-烯烃、环烯烃、二烯烃及它们的混合物。
15.权利要求1的方法,其中烯烃选自乙烯、丙烯、1-丁烯、1-戊烯、1-己烯、1-辛烯及其混合物。
16.权利要求1的方法,其中烯烃是乙烯。
17.权利要求1的方法,其中丙烯酸属单体选自丙烯酸C1-C20烷基酯、甲基丙烯酸C1-C20烷基酯、丙烯酸C6-C20芳基酯、甲基丙烯酸C6-C20芳基酯及其混合物。
18.权利要求1的方法,其中丙烯酸属单体选自丙烯酸正丁酯、甲基丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸叔丁酯、甲基丙烯酸异丁酯、甲基丙烯酸苄酯、甲基丙烯酸环己酯及其混合物。
19.权利要求1的方法,其中烯烃是乙烯且丙烯酸属单体是丙烯酸正丁酯。
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CN114206956A (zh) * | 2019-08-20 | 2022-03-18 | 陶氏环球技术有限责任公司 | 用于乙烯和丙烯酸酯单体共聚的双(膦基)-苯氧基镍(ii)催化剂 |
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Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
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US5153157A (en) | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US5198401A (en) | 1987-01-30 | 1993-03-30 | Exxon Chemical Patents Inc. | Ionic metallocene catalyst compositions |
US5241025A (en) | 1987-01-30 | 1993-08-31 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
KR930002411B1 (ko) | 1988-09-14 | 1993-03-30 | 미쓰이세끼유 가가꾸고오교오 가부시끼가이샤 | 벤젠불용성 유기알루미늄 옥시화합물 및 그 제조방법 |
US5449650A (en) | 1992-12-08 | 1995-09-12 | Mitsubishi Petrochemical Company Limited | Catalyst components for polymerization of olefins and use thereof |
US5414180A (en) | 1993-07-14 | 1995-05-09 | Phillips Petroleum Company | Organo-aluminoxy product and use |
CA2129794A1 (en) | 1993-08-10 | 1995-02-11 | Toshiyuki Tsutsui | Olefin polymerization catalysts and methods of olefin polymerization |
US5880241A (en) | 1995-01-24 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Olefin polymers |
US5714556A (en) | 1995-06-30 | 1998-02-03 | E. I. Dupont De Nemours And Company | Olefin polymerization process |
ES2151279T3 (es) | 1996-06-17 | 2000-12-16 | Exxon Chemical Patents Inc | Procesos de polimerizacion a presion elevada con sistemas de catalizadores de metales de transicion retardada |
IL129929A0 (en) | 1996-12-17 | 2000-02-29 | Du Pont | Polymerization of ethylene with specific iron or cobalt complexes novel pyridinebis (imines) and novel complexes of pyridinebis(imines) with iron and cobalt |
US6410660B1 (en) | 1998-03-27 | 2002-06-25 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US6211311B1 (en) | 1999-05-25 | 2001-04-03 | Equistar Chemicals, L.P. | Supported olefin polymerization catalysts |
US6310165B1 (en) | 1999-11-18 | 2001-10-30 | Eastman Kodak Company | Polymerization process with novel catalyst system |
US6340771B1 (en) | 1999-12-22 | 2002-01-22 | Nova Chemicals (International) S. A. | “Sweet” MAO |
US6501000B1 (en) | 2000-04-04 | 2002-12-31 | Exxonmobil Research And Engineering Company | Late transition metal catalyst complexes and oligomers therefrom |
US6506859B1 (en) | 2000-08-18 | 2003-01-14 | Exxonmobil Research And Engineering Company | Polymerization using late transition metal catalyst complexes formed in situ |
US6562973B1 (en) | 2001-08-15 | 2003-05-13 | Equistar Chemicals, Lp | Method for making late transition metal catalysts for olefin polymerization |
US6693154B2 (en) * | 2001-09-06 | 2004-02-17 | Equistar Chemicals, Lp | Transition metal catalysts for olefin polymerization |
US6515071B1 (en) | 2002-05-22 | 2003-02-04 | Ashland Inc. | Process for the preparation of dicyclopentadiene modified polyester resins |
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CN111163863A (zh) * | 2018-03-21 | 2020-05-15 | Lg化学株式会社 | 制备过渡金属配合物的方法 |
US11414504B2 (en) | 2018-03-21 | 2022-08-16 | Lg Chem, Ltd. | Method for preparing transition metal complex |
CN111163863B (zh) * | 2018-03-21 | 2022-10-21 | Lg化学株式会社 | 制备过渡金属配合物的方法 |
CN114206956A (zh) * | 2019-08-20 | 2022-03-18 | 陶氏环球技术有限责任公司 | 用于乙烯和丙烯酸酯单体共聚的双(膦基)-苯氧基镍(ii)催化剂 |
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