CN109836524A - Catalyst composition, ethylene- α -olefin polymer and preparation method thereof - Google Patents
Catalyst composition, ethylene- α -olefin polymer and preparation method thereof Download PDFInfo
- Publication number
- CN109836524A CN109836524A CN201711204436.2A CN201711204436A CN109836524A CN 109836524 A CN109836524 A CN 109836524A CN 201711204436 A CN201711204436 A CN 201711204436A CN 109836524 A CN109836524 A CN 109836524A
- Authority
- CN
- China
- Prior art keywords
- olefin
- ethylene
- alpha
- vanadium
- carbon monoxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004711 α-olefin Substances 0.000 title claims abstract description 123
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000003054 catalyst Substances 0.000 title abstract description 21
- 239000000203 mixture Substances 0.000 title abstract description 18
- 230000003197 catalytic effect Effects 0.000 claims abstract description 72
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 67
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 67
- -1 alkyl aluminum halides Chemical class 0.000 claims abstract description 56
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 7
- 239000003446 ligand Substances 0.000 claims abstract description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 59
- 239000005977 Ethylene Substances 0.000 claims description 59
- 229910052799 carbon Inorganic materials 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 35
- 239000012190 activator Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- SJMLNDPIJZBEKY-UHFFFAOYSA-N ethyl 2,2,2-trichloroacetate Chemical compound CCOC(=O)C(Cl)(Cl)Cl SJMLNDPIJZBEKY-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 14
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- 239000004411 aluminium Substances 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical group [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000000460 chlorine Substances 0.000 claims description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 5
- LJVPOYAGTBUSJW-UHFFFAOYSA-N 2,3,4,4-tetrachlorobut-3-enoic acid Chemical compound OC(=O)C(Cl)C(Cl)=C(Cl)Cl LJVPOYAGTBUSJW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- 150000001924 cycloalkanes Chemical class 0.000 claims description 4
- MASXONVJEAXEIV-UHFFFAOYSA-N butyl 2,2-dichloroacetate Chemical compound CCCCOC(=O)C(Cl)Cl MASXONVJEAXEIV-UHFFFAOYSA-N 0.000 claims description 3
- ABQQFYPRVNNXNU-UHFFFAOYSA-N butyl 2,3,4,4-tetrachlorobut-3-enoate Chemical class CCCCOC(=O)C(Cl)C(Cl)=C(Cl)Cl ABQQFYPRVNNXNU-UHFFFAOYSA-N 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical group CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 3
- VFDYKPARTDCDCU-UHFFFAOYSA-N hexachloropropene Chemical group ClC(Cl)=C(Cl)C(Cl)(Cl)Cl VFDYKPARTDCDCU-UHFFFAOYSA-N 0.000 claims description 3
- VHFUHRXYRYWELT-UHFFFAOYSA-N methyl 2,2,2-trichloroacetate Chemical compound COC(=O)C(Cl)(Cl)Cl VHFUHRXYRYWELT-UHFFFAOYSA-N 0.000 claims description 3
- HKMLRUAPIDAGIE-UHFFFAOYSA-N methyl 2,2-dichloroacetate Chemical compound COC(=O)C(Cl)Cl HKMLRUAPIDAGIE-UHFFFAOYSA-N 0.000 claims description 3
- LZJOVWVTJGLPFN-UHFFFAOYSA-N pentyl 2,2,2-trichloroacetate Chemical compound CCCCCOC(=O)C(Cl)(Cl)Cl LZJOVWVTJGLPFN-UHFFFAOYSA-N 0.000 claims description 3
- LJQCONXCOYBYIE-UHFFFAOYSA-N prop-2-enyl 2,2,2-trichloroacetate Chemical compound ClC(Cl)(Cl)C(=O)OCC=C LJQCONXCOYBYIE-UHFFFAOYSA-N 0.000 claims description 3
- AHRFMMRLDGAHBM-UHFFFAOYSA-N propyl 2,2-dichloroacetate Chemical compound CCCOC(=O)C(Cl)Cl AHRFMMRLDGAHBM-UHFFFAOYSA-N 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 3
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 claims description 3
- 229940029284 trichlorofluoromethane Drugs 0.000 claims description 3
- ZBZJXHCVGLJWFG-UHFFFAOYSA-N trichloromethyl(.) Chemical compound Cl[C](Cl)Cl ZBZJXHCVGLJWFG-UHFFFAOYSA-N 0.000 claims description 3
- SECVZLDDYUWJAC-UHFFFAOYSA-N butyl 2,2,2-trichloroacetate Chemical compound CCCCOC(=O)C(Cl)(Cl)Cl SECVZLDDYUWJAC-UHFFFAOYSA-N 0.000 claims description 2
- CMDWNGOTNMWUCD-UHFFFAOYSA-N methyl 2,3,4,4-tetrachlorobut-3-enoate Chemical class COC(=O)C(Cl)C(Cl)=C(Cl)Cl CMDWNGOTNMWUCD-UHFFFAOYSA-N 0.000 claims description 2
- UIFCHGLUUASAAI-UHFFFAOYSA-N pentyl 2,2-dichloroacetate Chemical compound CCCCCOC(=O)C(Cl)Cl UIFCHGLUUASAAI-UHFFFAOYSA-N 0.000 claims description 2
- ILVJSPNNOLUDME-UHFFFAOYSA-N propyl 2,3,4,4-tetrachlorobut-3-enoate Chemical compound C(CC)OC(C(C(=C(Cl)Cl)Cl)Cl)=O ILVJSPNNOLUDME-UHFFFAOYSA-N 0.000 claims description 2
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 229960005215 dichloroacetic acid Drugs 0.000 claims 1
- ZPSUEZJWHBACKQ-UHFFFAOYSA-N ethyl 2-chlorobut-3-enoate Chemical class CCOC(=O)C(Cl)C=C ZPSUEZJWHBACKQ-UHFFFAOYSA-N 0.000 claims 1
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract 3
- 239000000806 elastomer Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 69
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003292 glue Substances 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 229920001577 copolymer Polymers 0.000 description 8
- 150000002431 hydrogen Chemical group 0.000 description 8
- 238000001256 steam distillation Methods 0.000 description 7
- 125000005234 alkyl aluminium group Chemical group 0.000 description 6
- 239000005416 organic matter Substances 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 229910001456 vanadium ion Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005660 chlorination reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229920002943 EPDM rubber Polymers 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 229920006124 polyolefin elastomer Polymers 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- IWYBVQLPTCMVFO-UHFFFAOYSA-N ethyl 2,2-dichloroacetate Chemical compound CCOC(=O)C(Cl)Cl IWYBVQLPTCMVFO-UHFFFAOYSA-N 0.000 description 2
- XBIPWUMRLNQBHL-UHFFFAOYSA-N ethyl 2,3,4,4-tetrachlorobut-3-enoate Chemical class CCOC(=O)C(Cl)C(Cl)=C(Cl)Cl XBIPWUMRLNQBHL-UHFFFAOYSA-N 0.000 description 2
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical compound CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 230000013011 mating Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XEMRAKSQROQPBR-UHFFFAOYSA-N (trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=CC=C1 XEMRAKSQROQPBR-UHFFFAOYSA-N 0.000 description 1
- FEXBEKLLSUWSIM-UHFFFAOYSA-N 2-Butyl-4-methylphenol Chemical compound CCCCC1=CC(C)=CC=C1O FEXBEKLLSUWSIM-UHFFFAOYSA-N 0.000 description 1
- JQEARNLFCSAAPV-UHFFFAOYSA-N 2-chlorobut-3-enoic acid Chemical compound OC(=O)C(Cl)C=C JQEARNLFCSAAPV-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 125000004965 chloroalkyl group Chemical group 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- QAEBVJIVEPSFRK-UHFFFAOYSA-N ethyl 2-(3,4-dichlorophenyl)acetate Chemical compound CCOC(=O)CC1=CC=C(Cl)C(Cl)=C1 QAEBVJIVEPSFRK-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000005649 metathesis reaction Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000009774 resonance method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a catalyst composition, an ethylene- α -olefin polymer and a preparation method thereof, belonging to the field of polyolefin elastomersnClmThe catalyst composition comprises a vanadium-based catalyst, a catalyst component and an activating agent, wherein V is a positive pentavalent central atom of vanadium, OR and Cl are ligands, OR is phenoxy, n is 1, 2 OR 3, m is 0, 1 OR 2, and m + n is 3, the molar ratio of V to the activating agent in Al and vanadium-based catalysts in alkyl aluminum halides is 1-100: 1: 1-20, the vanadium-based catalysts can maintain catalytic activity for a long time by adding the activating agent, and the vanadium-based catalysts and the alkyl aluminum halides act synergistically to enable the catalyst composition to have excellent catalytic effect, reduce the using amount of the catalyst composition and reduce the cost.
Description
Technical field
The present invention relates to polyolefin elastomer field, in particular to a kind of carbon monoxide-olefin polymeric, ethylene-alpha-olefin polymers
And preparation method thereof.
Background technique
Ethylene-alpha-olefin polymers are a kind of polyolefin elastomers (Polyolefin elastomer, be abbreviated as POE),
It has many advantages, such as that light weight, transparency are high, hardness is low, resilience is good, flexibility is good, good weatherability, alternative EPDM
Rubber (Ethylene-Propylene-Diene Monomer, be abbreviated as EPDM) and be applied to automobile, industry, it is medical, packaging
Equal fields.Also, ethylene-alpha-olefin polymers have easy processing processability, during machine-shaping, do not need addition and appoint
What plasticiser.Based on above-mentioned, it is necessary to synthesize a large amount of ethylene-alpha-olefin polymers come using.Currently, ethene-alpha-olefin is poly-
It closes object mainly to pass through under the action of catalyst, makes ethylene, alpha-olefin that polymerization reaction occur and obtain, therefore it provides a kind of for making
The catalyst of polymerization reaction occurs for ethylene, alpha-olefin or carbon monoxide-olefin polymeric is very necessary.
The prior art provides a kind of carbon monoxide-olefin polymeric, which includes: vanadium oxytrichloride, chlorination alkyl
Aluminium.The molar ratio of vanadium oxytrichloride and chlorination alkyl aluminum is 1:10~20.Ethylene, alpha-olefin are polymerize by solution polymerization process, make second
Alkene, alpha-olefin are dissolved in the polymer solvent in polymeric kettle, and vanadium oxytrichloride, the chlorination of above-mentioned molar ratio are then added into polymeric kettle
Alkyl aluminum, to be catalyzed ethylene, polymerization reaction occurs for alpha-olefin.Wherein, the molar ratio of chlorination alkyl aluminum and alpha-olefin is 1:15.
The inventor finds that the existing technology has at least the following problems:
When carbon monoxide-olefin polymeric catalysis ethylene and alpha-olefine polymerizing that the prior art provides, polymerization obtains ethene-alpha-olefin
The low efficiency of polymer.
Summary of the invention
The technical problem to be solved by the embodiment of the invention is that providing a kind of carbon monoxide-olefin polymeric, ethene-alpha-olefin
Polymer and preparation method thereof can solve the problems, such as that polymerization obtains the low efficiency of ethylene-alpha-olefin polymers.Specific technical solution
It is as follows:
In a first aspect, the carbon monoxide-olefin polymeric includes: vanadium base the embodiment of the invention provides a kind of carbon monoxide-olefin polymeric
Catalyst, alkyl aluminium halide, activator；
The general formula of the catalytic component based on vanadium are as follows: VO (OR)nClm；
Wherein, V is the positive pentavalent central atom of vanadium, and OR, Cl are ligand, and OR is phenoxy group, n 1,2 or 3, m 0,
1 or 2, and m+n=3；
Al in the alkyl aluminium halide, the V in the catalytic component based on vanadium, the activator molar ratio be 1~100:
1:1~20.
Specifically, preferably, the phenoxy group is 2,6- di-t-butyl to methylphenoxy.
Specifically, preferably, the alkyl aluminium halide is two aluminium of ethylaluminum.
Specifically, preferably, the activator is ester chloride with 2~5 chlorine atoms or has 2~5 simultaneously
The chlorohydrocarbon of a carbon atom and 5~8 chlorine atoms.
Specifically, preferably, the ester chloride is selected from methyl trichloroacetate, ethyl trichloroacetate, trichloroacetic acid allyl
Ester, butyl trichloroacetate, trichloroacetic acid pentyl ester, methyl dichloroacetate, ethyl dichloroacetate, dichloroacetic acid butyl ester, dichloroacetic acid
Propyl ester, dichloroacetic acid pentyl ester, 2,3,4,4- tetra- chloro- 3-butenoic acid methyl esters, 2,3,4,4- tetra- chloro- 3-butenoic acid ethyl esters, 2,3,4,
The chloro- 3-butenoic acid propyl ester of 4- tetra-, 2,3,4,4- tetra- chloro- 3-butenoic acid butyl esters, 2,3,4,4- tetra- chloro- 3-butenoic acid chloro propyl ester,
2,3,4,4- tetra- chloro- 3-butenoic acid -2- ethylhexyls, 2,3,4,4- tetra- chloro- 3-butenoic acids are at least one of toluene ester；
The chlorohydrocarbon is selected from least one of trichlorofluoromethane, carbon trichloride, hexachloropropylene, hexacholorocyclopentadiene.
Second aspect, the embodiment of the invention also provides a kind of preparation method of ethylene-alpha-olefin polymers, the methods
Include:
Polymer solvent, alpha-olefin are added into polymeric kettle, is filled with ethylene in Xiang Suoshu polymeric kettle, and add molecular-weight adjusting
Agent makes the ethylene be dissolved to saturation in the polymer solvent；
Carbon monoxide-olefin polymeric described in claim 1 is added into the polymeric kettle, under preset temperature and preset pressure,
Make the ethylene and the alpha-olefin that polymerization reaction occur, obtains polyblend；
Terminator is added into the polyblend, and is successively washed, distilled, dried, ethene-alpha-olefin is obtained
Polymer；
Wherein, the volume ratio of the polymer solvent and the alpha-olefin is 12.5~50:1；
The molar ratio of the ethylene and the molecular weight regulator is 1:0.01~0.03；
Catalytic component based on vanadium in the carbon monoxide-olefin polymeric be dissolved in the molar concentration after the polymer solvent be 0.1~
0.3mmol/L。
Specifically, preferably, the alpha-olefin is 1- butylene, 1- hexene, 1- octene or 1- decene.
Specifically, preferably, the polymer solvent is aliphatic alkane, cycloalkane or aromatic compound；
The molecular weight regulator is diethyl zinc or hydrogen；
The terminator is ethyl alcohol.
Specifically, preferably, the preset temperature is 15 DEG C~60 DEG C, the preset pressure is 0.01MPa~2MPa,
The temperature of the drying is 75 DEG C~85 DEG C.
The third aspect, the embodiment of the invention also provides a kind of ethylene-alpha-olefin polymers, are prepared using the method
It obtains.
Technical solution provided in an embodiment of the present invention has the benefit that
On the one hand carbon monoxide-olefin polymeric provided in an embodiment of the present invention can make catalytic component based on vanadium by adding activator
Catalytic activity is persistently kept, moreover, catalytic component based on vanadium and alkyl aluminium halide synergistic effect, have the carbon monoxide-olefin polymeric excellent
Catalytic effect.On the other hand, the price of activator is lower than catalytic component based on vanadium and alkyl aluminium halide, and can improve the catalyst group
The catalytic effect for closing object reduces the usage amount of catalytic component based on vanadium and alkyl aluminium halide in the carbon monoxide-olefin polymeric, and then reduces
Cost.Using the ethylene-α-alkene that is high-efficient, and obtaining for the ethylene-alpha-olefin polymers that the catalyst combination polymerize
Hydrocarbon polymer has the characteristics that excellent resilience, flexibility, Mooney viscosity.
Specific embodiment
Unless otherwise defined, all technical terms used in the embodiment of the present invention all have usual with those skilled in the art
The identical meaning understood.It to make the object, technical solutions and advantages of the present invention clearer, below will be to embodiment party of the present invention
Formula is described in further detail.
In a first aspect, the carbon monoxide-olefin polymeric includes: that vanadium base is urged the embodiment of the invention provides a kind of carbon monoxide-olefin polymeric
Agent, alkyl aluminium halide, activator；
The general formula of catalytic component based on vanadium are as follows: VO (OR)nClm；
Wherein, V is the positive pentavalent central atom of vanadium, and OR, Cl are ligand, and OR is phenoxy group, n 1,2 or 3, m 0,
1 or 2, and m+n=3；
The molar ratio of the V in Al, catalytic component based on vanadium, activator in alkyl aluminium halide are 1~100:1:1~20.
On the one hand carbon monoxide-olefin polymeric provided in an embodiment of the present invention can make catalytic component based on vanadium by adding activator
Catalytic activity is persistently kept, moreover, catalytic component based on vanadium and alkyl aluminium halide synergistic effect, have the carbon monoxide-olefin polymeric excellent
Catalytic effect.On the other hand, the price of activator is lower than catalytic component based on vanadium and alkyl aluminium halide, and can improve the catalyst group
The catalytic effect for closing object reduces the usage amount of catalytic component based on vanadium and alkyl aluminium halide in the carbon monoxide-olefin polymeric, and then reduces
Cost.Using the ethylene-α-alkene that is high-efficient, and obtaining for the ethylene-alpha-olefin polymers that the catalyst combination polymerize
Hydrocarbon polymer has the characteristics that excellent resilience, flexibility, Mooney viscosity.
Specifically, the Al in alkyl aluminium halide, the V in catalytic component based on vanadium, activator molar ratio be can be 1:1:1,
10:1:2,15:1:5,20:1:8,25:1:10,30:1:11,35:1:12,40:1:13,45:1:14,50:1:15,60:1:16,
70:1:17,80:1:18,90:1:19,100:1:20 etc..
The molar ratio of Al, the V in catalytic component based on vanadium, activator in such setting alkyl aluminium halide, are reducing cost
Under the premise of, it mutually acts synergistically between above-mentioned three kinds of components, assigns the carbon monoxide-olefin polymeric excellent catalytic effect, applied
In ethylene, alpha-olefin polymerization in, polymerization obtains the high-efficient of ethylene-alpha-olefin polymers, and reduces production cost.
As a kind of optional example, the molar ratio of the V in Al and catalytic component based on vanadium in alkyl aluminium halide is 5~40:1.
Further, it is preferable to which the molar ratio of the V in Al and catalytic component based on vanadium in alkyl aluminium halide is 10~15:1.
The molar ratio of the V in the Al and catalytic component based on vanadium in alkyl aluminium halide is arranged such, makes alkyl aluminium halide and vanadium base
Mating reaction between catalyst is good, can play efficient catalytic action.
As another optional example, the molar ratio of V and activator in catalytic component based on vanadium are 1:1~20.Further,
It is preferred that the molar ratio of V and activator in catalytic component based on vanadium are 1:3~5.
The molar ratio of the V in catalytic component based on vanadium and activator is arranged such, under the premise of saving raw material, activator makes vanadium
Base catalyst persistently keeps catalytic activity, and then polymerize convenient for catalytic component based on vanadium efficient catalytic ethylene with alpha-olefin.
Specifically, catalytic component based on vanadium is complex, positive pentavalent vanadium be center atom, OR, Cl be ligand, with vanadium from
It is keyed between son.Ligand is arranged such, convenient for making the organic matters such as the catalytic component based on vanadium and polymer solvent, alpha-olefin dissolve each other,
And then catalytic action is given full play to convenient for the catalytic component based on vanadium.
When catalytic action occurs, the transformation of positive pentavalent vanadium ion is positive trivalent vanadium ion catalytic component based on vanadium, positive trivalent vanadium from
Son promotes catalysis reaction and becomes positive divalent vanadium ion, and positive divalent vanadium ion loses catalytic activity, in the activation of activator
Under, positive divalent vanadium ion changes the trivalent vanadium ion that is positive, and then the catalytic component based on vanadium is made to continue to keep catalytic activity.
Under the premise of based on preparation acquisition catalytic component based on vanadium is easy, the phenoxy group in catalytic component based on vanadium is the tertiary fourth of 2,6- bis-
Base is to methylphenoxy.
The catalytic component based on vanadium can be made by way of synthesis, as a kind of optional mode, in the item of anhydrous and oxygen-free
Under part, vanadium oxytrichloride is added in dry hexane, is then slowly dropped into 2,6-, bis- uncle with dry hexane dissolution at low temperature
Butyl p-methyl phenol is bubbled when being added dropwise with high pure nitrogen, and catalytic component based on vanadium is made to blow out the hydrogen chloride that reaction generates, claims
It is 2,6- di-t-butyl to methyl oxygroup dichloro vanadyl.
It can play the role of the vanadium mating reaction in co-catalyst, with catalytic component based on vanadium in alkyl aluminium halide, form polymerization
Activated centre enhances the catalytic performance of the carbon monoxide-olefin polymeric, efficiently to make ethylene and alpha-olefine polymerizing.Wherein, halogenation
Alkyl aluminum can be kelene base aluminium, bromination alkyl aluminum or iodate alkyl aluminum etc..Based on be easy obtain, it is cheap, with
Under the premise of other components compatibility is good, alkyl aluminium halide is two aluminium of ethylaluminum.
Activator and catalytic component based on vanadium, alkyl aluminium halide act synergistically, and catalytic component based on vanadium is enable to continue that catalysis is kept to live
Property, and act synergistically with alkyl aluminium halide, co-catalysis ethylene, alpha-olefine polymerizing generate ethylene alpha-olefin polymer.Activator
A variety of chemical reagent with the activity function can be selected as, based on easy and catalytic component based on vanadium, alkyl aluminium halide, α-alkene
Hydrocarbon, polymer solvent etc. dissolve each other, and under the premise of cheap, activator is ester chloride with 2~5 chlorine atoms or simultaneously
Chlorohydrocarbon with 2~5 carbon atoms and 5~8 chlorine atoms.
For example, activator can be the ester chloride with 2,3,4,5 chlorine atoms, or have 2 simultaneously
It is a, 3,4, it is any in 5 carbon atoms, and there is the chlorohydrocarbon of 5,6,7,8 chlorine atoms simultaneously.
As an example, ester chloride is selected from methyl trichloroacetate, ethyl trichloroacetate, allyl trichloroacetate, trichlorine
Butyl acetate, trichloroacetic acid pentyl ester, methyl dichloroacetate, ethyl dichloroacetate, dichloroacetic acid butyl ester, dichloroacetic acid propyl ester, two
N-amyl chloroacetate, 2, it is 3,4,4- tetra- chloro- 3-butenoic acid methyl esters, 2,3,4,4- tetra- chloro- 3-butenoic acid ethyl esters, 2,3,4,4- tetra- chloro-
3-butenoic acid propyl ester, 2,3,4,4- tetra- chloro- 3-butenoic acid butyl esters, 2,3,4,4- tetra- chloro- 3-butenoic acid chloro propyl ester, 2,3,4,4-
Four chloro- 3-butenoic acid -2- ethylhexyls, 2,3,4,4- tetra- chloro- 3-butenoic acids are at least one of toluene ester.For example, chlorination
Ester can selected from any one in above-mentioned a variety of ester chlorides, two kinds, three kinds ... or whole ester chloride.When ester chloride is
When mixture, the ratio of each component is not especially limited.
Chlorohydrocarbon is selected from least one of trichlorofluoromethane, carbon trichloride, hexachloropropylene, hexacholorocyclopentadiene.For example,
Chlorohydrocarbon in above-mentioned a variety of chlorohydrocarbons any one, two kinds, three kinds ... or whole chlorohydrocarbon.When chlorohydrocarbon is
When mixture, the ratio of each component is not especially limited.
The effect of above-mentioned ester chloride and chlorohydrocarbon activation catalytic component based on vanadium is good and cheap, is easy to obtain.
Preferably, activator is ethyl trichloroacetate, ethyl trichloroacetate it is cheap, be easy to obtain, and can be with
The organic matters such as polymer solvent, the alpha-olefin of a variety of different components dissolve each other.
In addition, activator can also be the alkyl-substituted aromatic hydrocarbons of chloro, and there are 2~5 chlorine atoms in chloro alkyl, such as
Benzotrichloride.Activator can also be the phenyl derivatives of ester race chloro, such as 3,4- dichlorophenylacetic acid ethyl ester.In the present invention
In embodiment, the ingredient of activator is not especially limited, can be improved the organic matter of ethylene ' alpha '-olefin Copolymerization activity.
Second aspect, the embodiment of the invention provides a kind of preparation method of ethylene-alpha-olefin polymers, this method packets
It includes:
Polymer solvent, alpha-olefin are added into polymeric kettle, ethylene is filled with into polymeric kettle, and add molecular weight regulator,
Ethylene is set to be dissolved to saturation in polymer solvent；
Above-mentioned carbon monoxide-olefin polymeric is added into polymeric kettle, under preset temperature and preset pressure, makes ethylene and alpha-olefin
Polymerization reaction occurs, obtains polyblend；
Terminator is added into polyblend, and is successively washed, distilled, dried, ethene-alpha-olefin polymerization is obtained
Object；
Wherein, the volume ratio of polymer solvent and alpha-olefin is 12.5~50:1；
The molar ratio of ethylene and molecular weight regulator is 1:0.01~0.03；
It is 0.1~0.3mmol/L that catalytic component based on vanadium in carbon monoxide-olefin polymeric, which is dissolved in the molar concentration after polymer solvent,.
Above-mentioned preparation method is simple, and can be efficiently prepared ethene-alpha-olefin polymerization using the carbon monoxide-olefin polymeric
Object, and obtained ethylene-alpha-olefin polymers have the characteristics that excellent resilience, flexibility, Mooney viscosity, convenient for being applied to
The fields such as automobile, industry, medical, packaging.
Specifically, in order to avoid generating other impurities in polymerization process, polymer solvent is being added into polymeric kettle
Before, it is vacuum-treated polymeric kettle, or using the gas in nitrogen metathesis polymerizable kettle.
Specifically, alpha-olefin can be a variety of olefin compounds, for the ease of obtaining resilience, flexibility, Mooney viscosity
Excellent ethylene-alpha-olefin polymers, alpha-olefin are 1- butylene, 1- hexene, 1- octene or 1- decene.Correspondingly, ethylene-
Alpha-olefine polymers are ethylene -1- butene polymers, ethylene -1- hexene oligomerization object, ethylene -1- octene polymer, the ethylene -1- last of the ten Heavenly stems
Alkene polymer.
When preparing ethylene-alpha-olefin polymers, using the method for polymerisation in solution, convenient for make alpha-olefin, catalytic component based on vanadium,
Alkyl aluminium halide, activator equably interact in polymeric solution, and then alpha-olefin is promoted steadily to send out with ethylene
Raw polymerization reaction.Polymer solvent can be gas chromatography, obtain based on easy, the good premise with other components intermiscibility
Under, polymer solvent is aliphatic alkane, cycloalkane or aromatic compound.For example, polymer solvent can for hexane, butane,
The aliphatic alkanes such as iso-butane, the cycloalkane such as hexamethylene, pentamethylene, the aromatic compounds such as toluene, dimethylbenzene, benzene.In price
It is cheap, with other components intermiscibility it is good under the premise of, polymer solvent is preferably aliphatic alkane.Further, polymer solvent is excellent
The hexane being selected as in aliphatic alkane.
Molecular weight regulator plays the role of adjusting molecular weight, so that the ethylene-alpha-olefin polymers being prepared have
Suitable molecular chain length, and then assign the excellent resilience of ethylene-alpha-olefin polymers, flexibility.Molecular weight regulator can
It is a variety of to be selected as, it is being suitable for ethylene, alpha-olefin, catalytic component based on vanadium, alkyl aluminium halide, activator system, and cheap
Under the premise of, molecular weight regulator is diethyl zinc or hydrogen.Further, it is preferable to which molecular weight regulator is hydrogen, using
When, hydrogen is filled in polymeric kettle after can mixing with ethylene gas.
When molecular weight regulator is hydrogen, hydrogen volume ratio shared in the mixed gas of hydrogen and ethylene is
0.5%~20%, such as can be 0.5%, 1.5%, 5.5%, 10.5%, 15.5%, 18.5%, 20.5% etc..
For the ease of obtaining the good ethylene-alpha-olefin polymers of resilience, flexibility, mixing of the hydrogen in hydrogen and ethylene
Shared volume ratio is 1%~10% in gas.Further, hydrogen volume shared in the mixed gas of hydrogen and ethylene
Than being 2%~5%.
After ethylene, alpha-olefin polymerization preset time, such as after 10~180min, further preferably 20~
60min, even if after taking out the polyblend by polymeric kettle, cannot guarantee that ethylene and alpha-olefin stop polymerization reaction, therefore
It needs to add terminator and terminates polymerization reaction.Terminator can select a variety of chemical reagent for having and terminating polymerization reaction effect,
Preferably, terminator is ethyl alcohol.Cheap, the easy acquisition of ethyl alcohol.
It is above-mentioned prepare ethylene-alpha-olefin polymers during, preset temperature be 15 DEG C~60 DEG C, such as can be 15
DEG C, 25 DEG C, 35 DEG C, 45 DEG C, 55 DEG C, 60 DEG C etc., preset pressure is 0.01MPa~2MPa, for example, can for 0.01MPa,
0.11MPa、0.21MPa、0.41MPa、0.61MPa、0.81MPa、1.1MPa、1.2MPa、1.3MPa、1.4MPa、1.5MPa、
1.6MPa, 1.7MPa, 1.8MPa, 1.9MPa, 2.0MPa etc..Preset temperature, preset pressure is arranged such, convenient for making the catalyst
Composition efficiently plays catalytic action, and obtained ethylene-alpha-olefin polymers have resilience, flexibility, Mooney viscosity etc.
Performance, application easy to process.Moreover, the condition of above-mentioned preset temperature and preset pressure is easy to reach, the energy is saved, it is convenient
The ethylene-alpha-olefin polymers are prepared, production cost is reduced.
In order to make ethylene and alpha-olefin that polymerization reaction efficiently occur, preferably preset temperature is 25 DEG C~45 DEG C, preset pressure
For 0.1MPa~1MPa.
After terminator is added into polyblend, polyblend is washed by using alkaline reagent, with
Make the organic matter and inorganic matter layering in polyblend.After organic matter is separated, glue further can be obtained by steam distillation
The ethylene-alpha-olefin polymers of state.By being dried to obtain gelatinous ethylene-alpha-olefin polymers.
Wherein, dry temperature is 75 DEG C~85 DEG C, such as can be 75 DEG C, 77 DEG C, 79 DEG C, 81 DEG C, 83 DEG C, 85 DEG C
Deng.Dry temperature is arranged such, reduces the bubble in ethylene-alpha-olefin polymers dry glue, keeps ethylene-alpha-olefin polymers dry
The density of glue is uniform.
The third aspect, the embodiment of the invention also provides a kind of ethylene-alpha-olefin polymers, which utilizes above-mentioned side
Method is prepared.
Have excellent resilience, flexibility, Mooney viscous by the ethylene-alpha-olefin polymers that the above method is prepared
The features such as spending, convenient for applied to the fields such as automobile, industry, medical, packaging.
Hereinafter the present invention will be further described through by specific embodiment.
In following specific embodiments, condition person is not specified in related operation, according to normal conditions or manufacturer
It is recommended that condition carry out.It is raw materials used production firm is not specified and specification person be can be with conventional products that are commercially available.
Ethylene, hydrogen are purchased from Jilin Petrochemical company；Hexane is purchased from Jilin Petrochemical company；1- octene, 1- hexene are purchased from carat
Ma Er company；Two aluminium of ethylaluminum is great along Biotechnology Co., Ltd purchased from Shanghai；Ethyl trichloroacetate is purchased from the vast think of in Shanghai
Chemical Co., Ltd..
Embodiment 1
A kind of ethylene-alpha-olefin polymers are present embodiments provided, which makes by the following method
It is standby to obtain: to be uniformly mixed the ethylene of molar ratio 1:0.02, hydrogen by recycle compressor.Volume is true for the polymeric kettle of 5L
1h is managed in vacancy, and 2000mL hexane, the 1- octene of 100mL are then added in polymeric kettle.Start recycle compressor, into polymeric kettle
It is passed through the mixture of ethylene, hydrogen, ethylene is dissolved in hexane and reaches saturation.Then 10mL is added into polymeric kettle to contain
Hexane solution, 4mmol ethylaluminum two aluminium, 2mmol tri- of the 0.4mmol 2,6- di-t-butyl to methyl oxygroup dichloro vanadyl
Ethyl chloroacetate, and make Al in alkyl aluminium halide, in catalytic component based on vanadium V, ethyl trichloroacetate molar ratio 10:1:5, control
The temperature of polymeric kettle processed is 50 DEG C, pressure 0.5MPa, and polymerization reaction time 45min obtains polyblend.Then will gather
It closes mixture and one container is discarded to by the pipeline of polymeric kettle lower part, and ethyl alcohol is added into container and terminates reaction, then with 2%
Sodium hydroxide solution washs 2 times, and the organic matters such as ethylene-alpha-olefin polymers and inorganic matter are layered, by ethylene-alpha-olefin polymers
Equal organic matters are separated, and then ethene-alpha-olefin copolymer is precipitated by the method for steam distillation.Further, will
Ethene-alpha-olefin copolymer precipitate is placed in drying in 80 DEG C of vacuum oven, obtains 96g ethene-alpha-olefin copolymer, i.e.,
The dry glue of ethylene-l-octane copolymer.
Embodiment 2
A kind of ethylene-alpha-olefin polymers are present embodiments provided, which makes by the following method
It is standby to obtain: to be uniformly mixed the ethylene of molar ratio 1:0.01, hydrogen by recycle compressor.Volume is true for the polymeric kettle of 5L
1h is managed in vacancy, and 2000mL hexane, the 1- octene of 100mL are then added in polymeric kettle.Start recycle compressor, into polymeric kettle
It is passed through the mixture of ethylene, hydrogen, ethylene is dissolved in hexane and reaches saturation.Then 10mL is added into polymeric kettle to contain
Hexane solution, 4mmol ethylaluminum two aluminium, 1.2mmol of the 0.4mmol 2,6- di-t-butyl to methyl oxygroup dichloro vanadyl
Ethyl trichloroacetate, and make Al in alkyl aluminium halide, V, ethyl trichloroacetate molar ratio 10:1:3 in catalytic component based on vanadium, control
The temperature of polymeric kettle processed is 55 DEG C, pressure 0.7MPa, and polymerization reaction time 55min obtains polyblend.Then will gather
Close mixture and container be discarded to by the pipeline of polymeric kettle lower part, and ethyl alcohol is added into container and terminates reaction, then with 2% hydrogen
Sodium hydroxide solution is washed 3 times, and the organic matters such as ethylene-alpha-olefin polymers and inorganic matter are layered, by ethylene-alpha-olefin polymers etc.
Organic matter is separated, and then ethene-alpha-olefin copolymer is precipitated by the method for steam distillation.Further, by second
Alkene-alpha olefin copolymer precipitate is placed in drying in 80 DEG C of vacuum oven, obtains 118g ethene-alpha-olefin copolymer, i.e.,
The dry glue of ethylene-l-octane copolymer.
Embodiment 3
A kind of ethylene-alpha-olefin polymers are present embodiments provided, which makes by the following method
It is standby to obtain: to be uniformly mixed the ethylene of molar ratio 1:0.03, hydrogen by recycle compressor.Volume is true for the polymeric kettle of 5L
1h is managed in vacancy, and 2000mL hexane, the 1- octene of 100mL are then added in polymeric kettle.Start recycle compressor, into polymeric kettle
It is passed through the mixture of ethylene, hydrogen, ethylene is dissolved in hexane and reaches saturation.Then 10mL is added into polymeric kettle to contain
Hexane solution, 4mmol ethylaluminum two aluminium, 1.6mmol of the 0.4mmol 2,6- di-t-butyl to methyl oxygroup dichloro vanadyl
Ethyl trichloroacetate, and make Al in alkyl aluminium halide, in catalytic component based on vanadium V, ethyl trichloroacetate molar ratio 10:1:4,
The temperature for controlling polymeric kettle is 45 DEG C, pressure 1MPa, and polymerization reaction time 65min obtains polyblend.Then will gather
Close mixture and container be discarded to by the pipeline of polymeric kettle lower part, and ethyl alcohol is added into container and terminates reaction, then with 2% hydrogen
Sodium hydroxide solution is washed 1 time, and the organic matters such as ethylene-alpha-olefin polymers and inorganic matter are layered, by ethylene-alpha-olefin polymers etc.
Organic matter is separated, and then ethene-alpha-olefin copolymer is precipitated by the method for steam distillation.Further, by second
Alkene-alpha olefin copolymer precipitate is placed in drying in 82 DEG C of vacuum oven, obtains 120g ethene-alpha-olefin copolymer, i.e.,
The dry glue of ethylene-l-octane copolymer.
Embodiment 4
A kind of ethylene-alpha-olefin polymers are present embodiments provided, which makes by the following method
It is standby to obtain: to be uniformly mixed the ethylene of molar ratio 1:0.03, hydrogen by recycle compressor.Volume is true for the polymeric kettle of 5L
1h is managed in vacancy, and 2000mL hexane, the 1- hexene of 100mL are then added in polymeric kettle.Start recycle compressor, into polymeric kettle
It is passed through the mixture of ethylene, hydrogen, ethylene is dissolved in hexane and reaches saturation.Then 10mL is added into polymeric kettle to contain
Hexane solution, 4mmol ethylaluminum two aluminium, 2mmol tri- of the 0.4mmol 2,6- di-t-butyl to methyl oxygroup dichloro vanadyl
Ethyl chloroacetate, and make Al in alkyl aluminium halide, in catalytic component based on vanadium V, ethyl trichloroacetate molar ratio 10:1:5, control
The temperature of polymeric kettle processed is 45 DEG C, pressure 1MPa, and polymerization reaction time 65min obtains polyblend.It then will polymerization
Mixture is discarded to container by the pipeline of polymeric kettle lower part, and into container be added ethyl alcohol terminate reaction, then with 2% hydrogen-oxygen
Change sodium solution washing several times, the organic matters such as ethylene-alpha-olefin polymers and inorganic matter are layered, by ethylene-alpha-olefin polymers etc.
Organic matter is separated, and then ethene-alpha-olefin copolymer is precipitated by the method for steam distillation.Further, by second
Alkene-alpha olefin copolymer precipitate is placed in drying in 82 DEG C of vacuum oven, obtains 121g ethene-alpha-olefin copolymer, i.e.,
The dry glue of ethylene -1- hexene copolymer.
Embodiment 5
A kind of ethylene-alpha-olefin polymers are present embodiments provided, which makes by the following method
It is standby to obtain: to be uniformly mixed the ethylene of molar ratio 1:0.02, hydrogen by recycle compressor.Volume is true for the polymeric kettle of 5L
1h is managed in vacancy, and 2000mL hexane, the 1- hexene of 100mL are then added in polymeric kettle.Start recycle compressor, into polymeric kettle
It is passed through the mixture of ethylene, hydrogen, ethylene is dissolved in hexane and reaches saturation.Then 10mL is added into polymeric kettle to contain
Hexane solution, 4mmol ethylaluminum two aluminium, 1.6mmol of the 0.4mmol 2,6- di-t-butyl to methyl oxygroup dichloro vanadyl
Ethyl trichloroacetate, and make Al in alkyl aluminium halide, in catalytic component based on vanadium V, ethyl trichloroacetate molar ratio 10:1:4,
The temperature for controlling polymeric kettle is 50 DEG C, pressure 0.08MPa, and polymerization reaction time 45min obtains polyblend.Then
Polyblend is discarded to container by the pipeline of polymeric kettle lower part, and ethyl alcohol is added into container and terminates reaction, then with 2%
Sodium hydroxide solution washing several times, the organic matters such as ethylene-alpha-olefin polymers and inorganic matter are layered, and ethene-alpha-olefin is gathered
It closes the organic matters such as object to separate, then ethene-alpha-olefin copolymer is precipitated by the method for steam distillation.Further
The precipitate that ethene-alpha-olefin is copolymerized is placed in drying in 81 DEG C of vacuum oven, it is total to obtain 126g ethene-alpha-olefin by ground
Polymers, the i.e. dry glue of ethylene -1- hexene copolymer.
Embodiment 6
A kind of ethylene-alpha-olefin polymers are present embodiments provided, which makes by the following method
It is standby to obtain: to be uniformly mixed the ethylene of molar ratio 1:0.02, hydrogen by recycle compressor.Volume is true for the polymeric kettle of 5L
1h is managed in vacancy, and 2000mL hexane, the 1- hexene of 100mL are then added in polymeric kettle.Start recycle compressor, into polymeric kettle
It is passed through the mixture of ethylene, hydrogen, ethylene is dissolved in hexane and reaches saturation.Then 10mL is added into polymeric kettle to contain
Hexane solution, 4mmol ethylaluminum two aluminium, 1.2mmol of the 0.4mmol 2,6- di-t-butyl to methyl oxygroup dichloro vanadyl
Ethyl trichloroacetate and make Al in alkyl aluminium halide, in catalytic component based on vanadium V, ethyl trichloroacetate molar ratio 10:1:3,
The temperature for controlling polymeric kettle is 50 DEG C, pressure 0.09MPa, and polymerization reaction time 53min obtains polyblend.Then
Polyblend is discarded to container by the pipeline of polymeric kettle lower part, and ethyl alcohol is added into container and terminates reaction, then with 2%
Sodium hydroxide solution wash 2 times, the organic matters such as ethylene-alpha-olefin polymers and inorganic matter are layered, and ethene-alpha-olefin is polymerize
The organic matters such as object are separated, and then ethene-alpha-olefin copolymer is precipitated by the method for steam distillation.Further,
Ethene-alpha-olefin copolymer precipitate is placed in drying in 78 DEG C of vacuum oven, obtains the copolymerization of 124g ethene-alpha-olefin
Object, the i.e. dry glue of ethylene -1- hexene copolymer.
Comparative example 1
The comparative example is identical as the preparation method of embodiment 1, the difference is that only: not adding ethyl trichloroacetate, obtains
To the dry glue of 5g ethene-alpha-olefin copolymer, the i.e. dry glue of ethylene-l-octane copolymer.
Comparative example 2
The comparative example is identical as the preparation method of embodiment 4, the difference is that only: not adding ethyl trichloroacetate, obtains
To the dry glue of 17g ethene-alpha-olefin copolymer, the i.e. dry glue of ethylene -1- hexene copolymer.
Application Example
The ethene-alpha-olefin that the present embodiment provides 1~embodiment of embodiment 6 and comparative example 1 and comparative example 2 polymerize
The performances such as object melt index, density, Mooney viscosity and the carbon monoxide-olefin polymeric in corresponding embodiment and comparative example are urged
Change performance to be evaluated.Specific evaluation procedure are as follows: detected by magnetic nuclear resonance method in each ethylene-alpha-olefin polymers
In conjunction with the mass percent of alpha-olefin.Pass through " GB/T3682-2000 thermoplastic elastomer (TPE) melt mass flow rate and melt body
The measurement of product flow rate " method that provides of standard provides 1~embodiment of embodiment 6 and comparative example 1 and comparative example 2
Ethylene-alpha-olefin polymers melt index, density, Mooney viscosity are detected, and relevant parameter is reported in Table 1 below.Pass through formula
(1) catalytic efficiency is calculated to evaluate the catalytic performance of carbon monoxide-olefin polymeric, and relevant parameter is reported in Table 1 below.It will
The test that the above-mentioned ethylene-alpha-olefin polymers provided 1~embodiment of embodiment 6 and comparative example 1 and comparative example 2 carry out
Sequentially number is No. 1, No. 2, No. 3, No. 4, No. 5, No. 6, No. 7, No. 8.
Wherein, w is the catalytic efficiency of carbon monoxide-olefin polymeric, m1For the quality of ethylene-alpha-olefin polymers dry glue, unit is
g；m2For the quality of vanadium in catalytic component based on vanadium, unit g.
Table 1
Wherein, in conjunction with the mass percent of alpha-olefin between 28.1%~35.2%, ethylene-alpha-olefin polymers are returned
Elasticity, flexility are better.Melt index is bigger, indicates that the processing fluidity of the ethylene-alpha-olefin polymers is better, conversely,
It is then poorer.The density of ethylene-alpha-olefin polymers is in 0.865~0.879g/m3, compared to density in 0.856~0.858g/m3
With excellent resilience performance.Mooney viscosity is in (ML1+4 120℃) 26~35 ethylene-alpha-olefin polymers processing performance it is good.
As shown in Table 1, α-alkene is combined in the ethylene-alpha-olefin polymers of 1~embodiment of embodiment 6 (No. 1~No. 6) offers
The mass percent of hydrocarbon is between 28.1%~35.2%, and the ethylene-α-of comparative example 1 and comparative example 2 (No. 7~No. 8) offers
The mass percent that alpha-olefin is combined in olefin polymer is 46%, 42%, so the ethylene-that 1~embodiment of embodiment 6 provides
The flexility of alpha-olefine polymers is good.The melt index of ethylene-alpha-olefin polymers that 1~embodiment of embodiment 6 provides is
The ethylene-alpha-olefin polymers that 0.6-1.6, density ratio comparative example 1 and comparative example 2 provide are big, have excellent resilience performance.It is real
The Mooney viscosity of the ethylene-alpha-olefin polymers of the offer of 1~embodiment of example 2 is applied in (ML1+4 120℃) between 26~35, processability
It can be good.And the catalytic efficiency of the corresponding carbon monoxide-olefin polymeric used is apparently higher than comparative example 1 and ratio in 1~embodiment of embodiment 6
Compared with carbon monoxide-olefin polymeric used in example 2.As it can be seen that there is carbon monoxide-olefin polymeric provided in an embodiment of the present invention excellent catalysis to imitate
Fruit, and there is excellent resilience, flexibility, easy processing etc. using ethylene-alpha-olefin polymers made from the catalyst combination
Performance meets the requirement of the multiple fields such as automobile, medical.
The foregoing is merely presently preferred embodiments of the present invention, the protection scope being not intended to limit the invention, all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.
Claims (10)
1. a kind of carbon monoxide-olefin polymeric, which is characterized in that the carbon monoxide-olefin polymeric include: catalytic component based on vanadium, alkyl aluminium halide,
Activator；
The general formula of the catalytic component based on vanadium are as follows: VO (OR)nClm；
Wherein, V is the positive pentavalent central atom of vanadium, and OR, Cl are ligand, and OR is phenoxy group, n 1,2 or 3, m 0,1 or
2, and m+n=3；
Al in the alkyl aluminium halide, the V in the catalytic component based on vanadium, the activator molar ratio be 1~100:1:1~
20。
2. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that the phenoxy group is 2,6- di-t-butyl to first
Phenoxyl.
3. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that the alkyl aluminium halide is ethylaluminum two
Aluminium.
4. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that the activator is with 2~5 chlorine atoms
Ester chloride or there is the chlorohydrocarbons of 2~5 carbon atoms and 5~8 chlorine atoms simultaneously.
5. carbon monoxide-olefin polymeric according to claim 4, which is characterized in that the ester chloride be selected from methyl trichloroacetate,
Ethyl trichloroacetate, allyl trichloroacetate, butyl trichloroacetate, trichloroacetic acid pentyl ester, methyl dichloroacetate, dichloroacetic acid second
Ester, dichloroacetic acid butyl ester, dichloroacetic acid propyl ester, dichloroacetic acid pentyl ester, 2,3,4,4- tetra- chloro- 3-butenoic acid methyl esters, 2,3,4,4-
Four chloro- 3-butenoic acid ethyl esters, 2,3,4,4- tetra- chloro- 3-butenoic acid propyl ester, 2,3,4,4- tetra- chloro- 3-butenoic acid butyl esters, 2,3,4,
The chloro- 3-butenoic acid chloro propyl ester of 4- tetra-, 2,3,4,4- tetra- chloro- 3-butenoic acid -2- ethylhexyls, 2,3,4,4- tetra- chloro- 3- butylene
Acid is at least one of toluene ester；
The chlorohydrocarbon is selected from least one of trichlorofluoromethane, carbon trichloride, hexachloropropylene, hexacholorocyclopentadiene.
6. a kind of preparation method of ethylene-alpha-olefin polymers, which is characterized in that the described method includes:
Polymer solvent, alpha-olefin are added into polymeric kettle, is filled with ethylene in Xiang Suoshu polymeric kettle, and add molecular weight regulator,
The ethylene is set to be dissolved to saturation in the polymer solvent；
The described in any item carbon monoxide-olefin polymerics of Claims 1 to 5 are added into the polymeric kettle, in preset temperature and default pressure
Under power, makes the ethylene and the alpha-olefin that polymerization reaction occur, obtain polyblend；
Terminator is added into the polyblend, and is successively washed, distilled, dried, ethene-alpha-olefin polymerization is obtained
Object；
Wherein, the volume ratio of the polymer solvent and the alpha-olefin is 12.5~50:1；
The molar ratio of the ethylene and the molecular weight regulator is 1:0.01~0.03；
It is 0.1~0.3mmol/ that catalytic component based on vanadium in the carbon monoxide-olefin polymeric, which is dissolved in the molar concentration after the polymer solvent,
L。
7. according to the method described in claim 6, it is characterized in that, the alpha-olefin be 1- butylene, 1- hexene, 1- octene or
Person's 1- decene.
8. according to the method described in claim 6, it is characterized in that, the polymer solvent be aliphatic alkane, cycloalkane or
Aromatic compound；
The molecular weight regulator is diethyl zinc or hydrogen；
The terminator is ethyl alcohol.
9. according to the method described in claim 6, it is characterized in that, the preset temperature be 15 DEG C~60 DEG C, the default pressure
Power is 0.01MPa~2MPa, and the temperature of the drying is 75 DEG C~85 DEG C.
10. a kind of ethylene-alpha-olefin polymers are prepared using the described in any item methods of claim 6~9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711204436.2A CN109836524B (en) | 2017-11-27 | 2017-11-27 | Catalyst composition, ethylene-alpha-olefin polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711204436.2A CN109836524B (en) | 2017-11-27 | 2017-11-27 | Catalyst composition, ethylene-alpha-olefin polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109836524A true CN109836524A (en) | 2019-06-04 |
| CN109836524B CN109836524B (en) | 2022-03-29 |
Family
ID=66880133
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711204436.2A Active CN109836524B (en) | 2017-11-27 | 2017-11-27 | Catalyst composition, ethylene-alpha-olefin polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109836524B (en) |
Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059034A1 (en) * | 1981-02-04 | 1982-09-01 | Sumitomo Chemical Company, Limited | A process for producing copolymers of ethylene with alpha-olefins |
| CN85108910A (en) * | 1984-12-12 | 1986-08-06 | 埃克森研究工程公司 | Polymerizing catalyst and preparation thereof and use |
| EP0371411A2 (en) * | 1988-11-26 | 1990-06-06 | Sumitomo Chemical Company, Limited | A method for producing olefin polymers |
| EP0546629A1 (en) * | 1991-12-10 | 1993-06-16 | ENICHEM ELASTOMERI S.r.l. | Process for preparing elastomeric copolymers of ethylene with a high tensile strength of the crude product |
| CN1073453A (en) * | 1991-11-22 | 1993-06-23 | 希蒙特公司 | Spherical component and catalyst for olefin polymerization |
| CN1100433A (en) * | 1993-06-28 | 1995-03-22 | 联合碳化化学品及塑料技术公司 | Ethylene/propylene copolymer |
| CN1280138A (en) * | 1999-06-14 | 2001-01-17 | 联合碳化化学品及塑料技术公司 | Method for reducing low polymer forming in poly olefines |
| EP1113028A1 (en) * | 1999-12-17 | 2001-07-04 | Bayer Inc. | Process for production of olefin polymer with long chain branching |
| CN1108316C (en) * | 1995-06-30 | 2003-05-14 | 埃尼凯姆埃拉斯托麦里公司 | Process for preparation of ethylene-propylene copolymers |
| CN1489603A (en) * | 2001-02-07 | 2004-04-14 | 沙特基础工业公司 | Catalyst composition for polymerization of olefins and method for preparing same |
| EP2289950A1 (en) * | 2009-08-25 | 2011-03-02 | Borealis AG | Improved ethylene polymerization catalyst composition |
| CN102532383A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Gel inhibiting method for ethylene-alphaolefin-non-conjugated diene terpolymer |
| CN103374089A (en) * | 2012-04-20 | 2013-10-30 | 中国石油化工股份有限公司 | Method for removing catalysts from ethylene-alpha olefin copolymer solution and preparation method of copolymer |
| US20140249282A1 (en) * | 2011-11-25 | 2014-09-04 | Versalis S.P.A. | Process for the preparation of a copolymer of ethylene |
| CN104418964A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Preparation method of ethylene-propylene-non-conjugated diene random copolymer |
| CN106916243A (en) * | 2015-12-25 | 2017-07-04 | 中国石油天然气股份有限公司 | Process for producing ethylene random copolymer |
| CN106977633A (en) * | 2016-01-18 | 2017-07-25 | 北京引发科技有限公司 | A kind of vanadium-based catalyst systems for olefinic polymerization |
-
2017
- 2017-11-27 CN CN201711204436.2A patent/CN109836524B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0059034A1 (en) * | 1981-02-04 | 1982-09-01 | Sumitomo Chemical Company, Limited | A process for producing copolymers of ethylene with alpha-olefins |
| CN85108910A (en) * | 1984-12-12 | 1986-08-06 | 埃克森研究工程公司 | Polymerizing catalyst and preparation thereof and use |
| EP0371411A2 (en) * | 1988-11-26 | 1990-06-06 | Sumitomo Chemical Company, Limited | A method for producing olefin polymers |
| CN1073453A (en) * | 1991-11-22 | 1993-06-23 | 希蒙特公司 | Spherical component and catalyst for olefin polymerization |
| EP0546629A1 (en) * | 1991-12-10 | 1993-06-16 | ENICHEM ELASTOMERI S.r.l. | Process for preparing elastomeric copolymers of ethylene with a high tensile strength of the crude product |
| CN1100433A (en) * | 1993-06-28 | 1995-03-22 | 联合碳化化学品及塑料技术公司 | Ethylene/propylene copolymer |
| CN1108316C (en) * | 1995-06-30 | 2003-05-14 | 埃尼凯姆埃拉斯托麦里公司 | Process for preparation of ethylene-propylene copolymers |
| CN1280138A (en) * | 1999-06-14 | 2001-01-17 | 联合碳化化学品及塑料技术公司 | Method for reducing low polymer forming in poly olefines |
| EP1113028A1 (en) * | 1999-12-17 | 2001-07-04 | Bayer Inc. | Process for production of olefin polymer with long chain branching |
| CN1489603A (en) * | 2001-02-07 | 2004-04-14 | 沙特基础工业公司 | Catalyst composition for polymerization of olefins and method for preparing same |
| EP2289950A1 (en) * | 2009-08-25 | 2011-03-02 | Borealis AG | Improved ethylene polymerization catalyst composition |
| CN102532383A (en) * | 2010-12-30 | 2012-07-04 | 中国石油化工股份有限公司 | Gel inhibiting method for ethylene-alphaolefin-non-conjugated diene terpolymer |
| US20140249282A1 (en) * | 2011-11-25 | 2014-09-04 | Versalis S.P.A. | Process for the preparation of a copolymer of ethylene |
| CN104053686A (en) * | 2011-11-25 | 2014-09-17 | 维尔萨利斯股份公司 | Process for preparation of copolymer of ethylene |
| CN103374089A (en) * | 2012-04-20 | 2013-10-30 | 中国石油化工股份有限公司 | Method for removing catalysts from ethylene-alpha olefin copolymer solution and preparation method of copolymer |
| CN104418964A (en) * | 2013-08-23 | 2015-03-18 | 中国石油天然气股份有限公司 | Preparation method of ethylene-propylene-non-conjugated diene random copolymer |
| CN106916243A (en) * | 2015-12-25 | 2017-07-04 | 中国石油天然气股份有限公司 | Process for producing ethylene random copolymer |
| CN106977633A (en) * | 2016-01-18 | 2017-07-25 | 北京引发科技有限公司 | A kind of vanadium-based catalyst systems for olefinic polymerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109836524B (en) | 2022-03-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| RU2727776C1 (en) | Polyethylenes and ethylene copolymers for extrusion blowing film | |
| JP4794293B2 (en) | Metal compound, vinyl monomer polymerization catalyst composition using the same, and use of the vinyl monomer for polymerization using the composition | |
| CN1282274A (en) | Nickel diimine catalysts with methylalumoxane as cocatalyst, method of polymerization of olefins therewith and polymers produced | |
| CN1303399A (en) | Copolymerization of olefins | |
| US10280239B2 (en) | Method for preparing polyolefin polymer for fiber production | |
| JP2017518267A (en) | Silylbis (hexamethylindenyl) complexes of Group IVA metals as polymerization catalysts | |
| US6521724B2 (en) | Polymerization process | |
| KR19990006927A (en) | Ethylene Polymerization Method and Heterogeneous Catalyst System | |
| CN110914316B (en) | Polypropylene and preparation method thereof | |
| KR102272244B1 (en) | Process for preparing a catalyst for polymerizing an olefin, catalyst for polymerizing an olefin, and polyolefin | |
| CN109836523A (en) | Catalyst composition, ethylene- α -olefin polymer and preparation method thereof | |
| CN114380960B (en) | Poly (norbornene-b-polar functionalized norbornene) and preparation method thereof | |
| CN114456333B (en) | Poly (norbornene-b-vinyl norbornene) and preparation method thereof | |
| CN109836524A (en) | Catalyst composition, ethylene- α -olefin polymer and preparation method thereof | |
| CN109312026A (en) | Catalyst composition | |
| CN113164946A (en) | Method for stabilizing hydrogenation catalyst | |
| CN112292407A (en) | Catalyst composition and method for preparing polyolefin using the same | |
| KR20140143686A (en) | A supported nonmetallocene catalyst, preparation and use thereof | |
| KR20190143016A (en) | Catalyst composition for producing polyolefin resin and polyolefin resin polymerization method using the same | |
| CN114853964B (en) | Cycloolefin block copolymer and process for producing the same | |
| CN107880162B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| EP1713836B1 (en) | Preparation method of polymerisation catalyst for production of polyethylene with broad molecular weight distribution | |
| CN107880163B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN107880186B (en) | Catalyst component for olefin polymerization and preparation and application thereof | |
| CN1119357C (en) | Titanium-nickel modified ethylene polymerizing chromium series catalyst and preparation process thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |