CN102336851A - Propylene polymerization catalyst - Google Patents
Propylene polymerization catalyst Download PDFInfo
- Publication number
- CN102336851A CN102336851A CN2010102314700A CN201010231470A CN102336851A CN 102336851 A CN102336851 A CN 102336851A CN 2010102314700 A CN2010102314700 A CN 2010102314700A CN 201010231470 A CN201010231470 A CN 201010231470A CN 102336851 A CN102336851 A CN 102336851A
- Authority
- CN
- China
- Prior art keywords
- dicyclo
- alkene
- catalyzer
- herbaceous plants
- big flowers
- 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
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 28
- 239000002685 polymerization catalyst Substances 0.000 title abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- 239000011777 magnesium Substances 0.000 claims abstract description 46
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 44
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000010936 titanium Substances 0.000 claims abstract description 42
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 14
- 150000002367 halogens Chemical class 0.000 claims abstract description 14
- -1 polypropylene Polymers 0.000 claims abstract description 11
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 150000005690 diesters Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 claims description 84
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 claims description 58
- 238000006116 polymerization reaction Methods 0.000 claims description 45
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 20
- 125000003118 aryl group Chemical group 0.000 claims description 11
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 10
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 9
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229940125904 compound 1 Drugs 0.000 claims description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000003890 succinate salts Chemical class 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 239000004743 Polypropylene Substances 0.000 abstract description 6
- 229920001155 polypropylene Polymers 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 48
- 238000000034 method Methods 0.000 description 30
- 239000000460 chlorine Substances 0.000 description 29
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 28
- 229910052801 chlorine Inorganic materials 0.000 description 28
- 230000000379 polymerizing effect Effects 0.000 description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001035 drying Methods 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012453 solvate Substances 0.000 description 3
- FOSCDBCOYQJHPN-UHFFFAOYSA-M Cl[Mg] Chemical compound Cl[Mg] FOSCDBCOYQJHPN-UHFFFAOYSA-M 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003900 succinic acid esters Chemical class 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 150000003608 titanium Chemical class 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
- SVTBMSDMJJWYQN-RXMQYKEDSA-N (4r)-2-methylpentane-2,4-diol Chemical class C[C@@H](O)CC(C)(C)O SVTBMSDMJJWYQN-RXMQYKEDSA-N 0.000 description 1
- AUEJBKCWXPYRGZ-UHFFFAOYSA-N 1,1'-biphenyl diethoxysilane Chemical compound C(C)O[SiH2]OCC.C1(=CC=CC=C1)C1=CC=CC=C1 AUEJBKCWXPYRGZ-UHFFFAOYSA-N 0.000 description 1
- MVHZHMKEBJJTCH-UHFFFAOYSA-N CN(C)C.CO[SiH3] Chemical compound CN(C)C.CO[SiH3] MVHZHMKEBJJTCH-UHFFFAOYSA-N 0.000 description 1
- WBKFKBYJOWRXRT-UHFFFAOYSA-N CO[Si]OC.C1=CC=CC=C1C1=CC=CC=C1 Chemical compound CO[Si]OC.C1=CC=CC=C1C1=CC=CC=C1 WBKFKBYJOWRXRT-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- RALMAKOEVLJXQO-UHFFFAOYSA-N [Si].COC=1C(=C(C=CC1)C1=CC=CC=C1)OC Chemical compound [Si].COC=1C(=C(C=CC1)C1=CC=CC=C1)OC RALMAKOEVLJXQO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000029305 taxis Effects 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The invention discloses a propylene polymerization catalyst, which comprises magnesium, titanium, halogen and an internal electron donor compound, wherein the internal electron donor compound is a mixture of diester shown in a general formula and succinate shown in a general formula (II), and the weight ratio of the diester to the succinate is 0.5-6.3. Compared with the single use of any electron donor, the obtained catalystHas higher catalytic activity, the product polypropylene keeps wide molecular weight distribution and high stereoregularity, and the catalyst cost is reduced.
Description
Technical field
The present invention provides a kind of catalyst for polymerization of propylene, contains specific electron donor during catalyzer is formed and forms, and makes catalyzer be used for propylene polymerization, can obtain the polymkeric substance that MWD is wide, degree of isotacticity is high.
Background technology
Vestolen PP 7052 is a kind with fastest developing speed in the synthetic resins, in synthetic resins, occupies very outstanding status.At present, all polypropylene products are almost obtained by Ziegler-Natta (Z-N) catalyst propylene polymerization entirely.The Z-N catalyzer develops into present efficient carrier model catalystsystem from the first-generation; Electron donor has played key effect; The multiple electron donor compound that can be used for propylene polymerization is disclosed in the document; Comprise polycarboxylic acid, monobasic or multi-carboxylate, acid anhydrides, ketone, monoether or polyether, alcohol, amine etc. and verivate thereof (like US4971937, US2004014597, EP728769, CN1042547A, CN1143651A, US2003027715, WO03076480, CN1054139A, or the like).In recent years; One type of special dibasic aliphatic carboxylic acid esters and diol-lipid compound receive widely as internal electron donor and paying close attention to; Comprise (referring to US6818583, WO2004024785, CN1313869A, CN1236373A, CN1236374A, CN1552741A, CN1213080C, CN1542024A, CN1552742A and CN1552740A) such as succinate, malonic ester, glutarate, glycol ester, propylene glycol ester, butanediol ester, pentadiol ester and pinakon esters; These electron donor compounds; Not only improved the degree of isotacticity of catalyst activity and polymkeric substance, gained polypropylene molecule amount distributes and also obviously widens.
Summary of the invention
The present invention provides a kind of catalyst for polymerization of propylene on the prior art basis; Adopt diester and the composite electron donor compound of succinate; Single electron donor compound catalyst activity is higher than using, and the molecular weight distribution of acquisition is wideer and degree of isotacticity is high.
Catalyst for polymerization of propylene of the present invention comprises magnesium, titanium, halogen and internal electron donor compound; It is characterized in that the internal electron donor compound is the mixture of succinate of diester and the logical formula II of logical formula I, the weight ratio of diester and succinate is 0.5～6.3.
In formula I and (II), R
1～R
4For carbon number 1～10 alkyl, aryl, aralkyl; R
5, R
6Identical or different, be selected from H, halogen atom, C
1～C
20Straight or branched alkyl, C
3～C
20Naphthenic base, C
6～C
20Aryl or C
7～C
20Aralkyl; R is selected from C
1～C
20Straight or branched alkyl, C
3～C
20Naphthenic base, C
6～C
20Aryl or C
7～C
20Aralkyl.
Two ester compounds in the said formula I are selected from wherein a kind of of diisobutyl phthalate, diethyl phthalate or n-butyl phthalate.
Succinate compounds in the said formula II is selected from dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester, dicyclo (2; 2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester, 7-chloro-dicyclo (2; 2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester or 7-phenyl-dicyclo (2; 2,2) wherein a kind of of certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
Each composition weight of catalyzer consists of:
Electron donor compound 1～10%
Titanium 1～15%
Magnesium 10～25%
Halogen 40～60%.
The preparation of electron donor compound can be adopted prior art, realizes through the esterification of acid anhydrides with alcohol.The compound of logical formula I can directly be purchased acquisition.Logical formula II reference " organic synthesis " (Wang Baoren, Science Press Beijing, method 1981-1985.), with dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the 6-tetracarboxylic dianhydride is dissolved in the alcoholic solvent that structural formula is ROH, and wherein R is an alkyl or aryl; Add p-methyl benzenesulfonic acid again, reflux 24～100 hours, preferred 48～90 hours, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the mol ratio of 6-tetracarboxylic dianhydride and p-methyl benzenesulfonic acid is 100: 1～50, preferred 100: 1～10; Except that after desolvating, obtain the succinate compounds of logical formula II after washing, extraction, the drying.
The acquisition of the titanium during catalyzer is formed, magnesium, halogen is all extensively open in the prior art.Magnesium and halogen are Mg (OR ') by general formula
mX
(2-m)N (R
2OH) spherical magnesium halide alcohol adduct provides, and R ' is C in the formula
1～C
20Alkyl, aralkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜n＜5; R
2Be C
1～C
20Alkyl, aralkyl or aryl.
Magnesium halide specifically is selected from wherein a kind of of magnesium chloride, magnesium bromide, chloro magnesium methylate or chloro magnesium ethylate, preferred magnesium chloride.Used alcohol is selected from wherein a kind of of methyl alcohol, ethanol, propyl alcohol, Virahol, butanols or isopropylcarbinol, preferred alcohol.
The donor of said titanium is that general formula is Ti (OR)
nX
(4-n)Compound, R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.Specifically be selected from wherein a kind of of purity titanium tetraethoxide, four titanium butoxide, dichloro dialkoxy titanium, chloro tri-alkoxy titanium, titanium tetrachloride or titanium tetrabromide, preferred titanium tetrachloride.
The Preparation of catalysts process can adopt existing method.The present invention just lists act a kind of method wherein; Specifically comprise: 1) spherical magnesium halide alcohol adduct particle is joined in the halogenated titanium liquid temperature of reaction-50～20 ℃, preferred-30～0 ℃; Reacted 1～6 hour; Preferred 1～4 hour, the mol ratio of magnesium and titanium was 1: 5～1: 100, preferred 1: 10～1: 50; 2) be warming up to 30～80 ℃, after preferred 40～60 ℃, add the internal electron donor mixture; Be warming up to 100～140 ℃ again, preferred 110～130 ℃, reacted 1～6 hour; Preferred 1～4 hour, the mol ratio of magnesium and internal electron donor compound was 2: 1～20: 1, preferred 2: 1～12: 1; 3) add halogenated titanium liquid with the first step same amount after filtering again,, after filtration, washing, drying, obtain catalyzer in 100～140 ℃ of reactions 1～4 hour.
Catalyzer of the present invention also need add a certain amount of alkylaluminium cpd auxiliary agent in use, and the aluminum alkyls general formula is AlRnX
(3-n)R is alkyl, the aryl or aralkyl of Cl～C20 in the formula; X is a halogen; N is the integer of 0≤n≤3.Specifically be selected from a kind of in trimethylaluminium, triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride or the chloro-di-isobutyl aluminum, preferred triethyl aluminum or triisobutyl aluminium.
For obtaining high isotatic polypropylene, the further adding of suggestion general formula is R during polymerization
nSi (OR
*)
4-nSilicoorganic compound as external electron donor, 0≤n in the formula≤3, R and R
*Be of the same race or different alkyl, naphthenic base, aryl, haloalkyl, R also can be halogen and Wasserstoffatoms.It is wherein a kind of specifically to be selected from trimethylammonium methoxy silane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethoxydiphenylsilane or phenylbenzene diethoxy silane, preferred phenylbenzene dimethoxy silicon.
The consumption of catalyzer, aluminum alkyls and silicoorganic compound is with transition metal: aluminium: the molar ratio computing between the silicon is 1: 1～2000: 1～50, preferred 1: 1～500: 1～30.
Catalyst propylene polymerization provided by the invention can adopt disclosed the whole bag of tricks, does not have special qualification, and polymerization temperature is generally 0～80 ℃, preferred 40～60 ℃.Only be example with the slurry polymerization here, the use that the brief description catalyzer is basic: at 250 milliliters through vacuum drying treatment, and with adding 100 milliliters of heptane of handling through anhydrous and oxygen-free in nitrogen and the abundant metathetical reactor drum of propylene gas; Pressure is 1 normal atmosphere in the maintenance bottle, adds triethyl aluminum and dimethoxy phenylbenzene silicon, stirs after 5 minutes, adds catalyzer of the present invention; Polyreaction 1 hour, with acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
Compared with prior art; It is composite to adopt two kinds of internal electron donors to carry out in the catalyzer provided by the invention, and than any electron donor of single use, catalyzer has more high catalytic activity; The product Vestolen PP 7052 keeps wide molecular weight distribution and high taxis, and the catalyzer cost reduces.
Embodiment
Embodiment 1
(1) dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dimethyl ester
With 10g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3; 5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate, adds the 0.2g p-methyl benzenesulfonic acid, refluxes 60 hours at 80 ℃; Decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium hydrogencarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 8.2g white crystal dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2 after the drying again; 3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 3.39 (s, 12H, CH3); δ 2.96 (m, 4H, CH): δ 2.37 (m, 2H, CH); δ 5.59 (m, 2H, CH).
(2) Preparation of catalysts
Under the anhydrous and oxygen-free condition, (make by oneself, preparation process is with document CN1110281A, and mean particle size is 110 μ m, and specific surface is 150-230M with 5.0g microspheroidal magnesium chloride alcohol adduct particle
2/ g, alcohol is 2.85: 1 with the mol ratio of content of magnesium chloride, molecular formula: MgCl
22.85CH
3CH
2OH) join in 140 milliliters of titanium tetrachloride liquid of-20 ℃, react after 2 hours, be warming up to 60 ℃ gradually; Add 0.55g diisobutyl phthalate and 0.17g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.Be warming up to 120 ℃ gradually, reacted 2 hours, filter; Add 140 milliliters of titanium tetrachlorides again, in 120 ℃ of reactions 2 hours and filtration; In 60 ℃ of washings 5 times, at room temperature use 50 milliliters of hexane wash once with 100 milliliters of hexanes, obtain catalyzer after the vacuum-drying.
The weight content of catalyzer each component is: titanium 2.89%, diisobutyl phthalate 7.93%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 1.93%, magnesium 13.57%, chlorine 51.21%.
(3) propylene polymerization
250 milliliters through vacuum drying treatment and with nitrogen and the abundant metathetical reaction flask of propylene gas in; Add 100 milliliters of heptane of handling through anhydrous and oxygen-free, pressure is 1 normal atmosphere in the maintenance bottle, and temperature is 50 ℃; Add the 6mmol triethyl aluminum; Stir after 5 minutes, add the above-mentioned ingredient of solid catalyst of 0.1g, the mol ratio of titanium and triethyl aluminum is 1: 100 in the ingredient of solid catalyst.Polyreaction 1 hour, with acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
Polymerization result is listed in table 1.
Embodiment 2
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.41g diisobutyl phthalate and 0.34g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.57%, diisobutyl phthalate 4.53%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 3.11%, magnesium 13.27%, chlorine 50.21%.
(2) propylene polymerization
Except adding the 5.4mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Polymerization result is listed in table 1.
Embodiment 3
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.34g diisobutyl phthalate and 0.42g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.73%, diisobutyl phthalate 2.8%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 2.22%, magnesium 15.01%, chlorine 50.13%.
(2) propylene polymerization
Except adding the 5.7mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Polymerization result is listed in table 1.
Embodiment 4
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.28g diisobutyl phthalate and 0.51g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 3.15%, diisobutyl phthalate 2.98%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 3.34%, magnesium 14.12%, chlorine 51.13%.
(2) propylene polymerization
Except adding the 6.5mmol triethyl aluminum, other polymerizing condition is with embodiment 1.Polymerization result is listed in table 1.
Polymerization result is listed in table 1.
Embodiment 5
(1) dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dibenzyl ester
With 10g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3; 5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL benzylalcohol solvent, adds the 0.2g p-methyl benzenesulfonic acid, refluxes 60 hours at 100 ℃; Decompression remove add again behind the Virahol 50mL contain the aqueous solution of 0.1g sodium hydrogencarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 8.1g white crystal dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2 after the drying again; 3,5,6-tetracarboxylic acid dibenzyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 4.12 (m, 8H, CH
2); δ 2.18 (m, 4H, CH); δ 2.78 (m, 2H, CH); δ 5.59 (m, 2H, CH); δ 7.26 (m, 10H, C
6H
5).
(2) Preparation of catalysts
Except the internal electron donor compound changes 0.62g diisobutyl phthalate and dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dibenzyl ester 0.16g, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.24%, diisobutyl phthalate 6.98%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 1.34%, magnesium 14.57%, chlorine 51.21%.
(3) propylene polymerization
Except adding the 4.7mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 6
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.55g diisobutyl phthalate and 0.32g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dibenzyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.58%, diisobutyl phthalate 5.68%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 2.35%, magnesium 14.33%, chlorine 51.28%.
(2) propylene polymerization
Except adding the 5.4mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 7
(1) preparation of catalyst component
Except the internal electron donor compound changes 0.41g diisobutyl phthalate and 0.64g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dibenzyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.78%, diisobutyl phthalate 4.25%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 3.10%, magnesium 15.44%, chlorine 50.28%.
(2) propylene polymerization
Except adding the 5.8mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 8
(1) 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dimethyl ester
With 10g7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3; 5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate, adds the 0.2g p-methyl benzenesulfonic acid, refluxes 60 hours at 80 ℃; Decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium hydrogencarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 7.6g white crystal 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2 after the drying again; 3,5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 3.39 (s, 12H, CH
3); δ 2.55 (m, 4H, CH); δ 2.37 (m, 2H, CH); δ 5.31 (m, 1H, CH).
(2) Preparation of catalysts
Except the internal electron donor compound changes 0.55g diisobutyl phthalate and 0.19g 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.54%, diisobutyl phthalate 6.25%, 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 2.89%, magnesium 20.54%, chlorine 52.14%.
(3) propylene polymerization
Except adding the 5.3mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 9
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.41g diisobutyl phthalate and 0.37g 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.88%, diisobutyl phthalate 4.35%, 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 3.88%, magnesium 20.44%, chlorine 50.78%.
(2) propylene polymerization
Except adding the 6.0mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 10
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.28g diisobutyl phthalate and 0.56g 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.90%, diisobutyl phthalate 3.78%, 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 5.15%, magnesium 20.01%, chlorine 50.22%.
(2) propylene polymerization
Except adding the 6.0mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 11
(1) 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5, the preparation of 6-tetracarboxylic acid dimethyl ester
With 10g 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2; 3,5,6-tetracarboxylic dianhydride (Alfa Aesar reagent) is dissolved in the 80mL methanol solvate; Add the 0.2g p-methyl benzenesulfonic acid, refluxed 60 hours at 80 ℃, decompression remove add behind the methyl alcohol 50mL contain the aqueous solution of 0.1g sodium hydrogencarbonate, with 3 * 50mL extracted with diethyl ether, anhydrous magnesium sulfate drying, filter, remove ether, obtain 6.5g white crystal 7-phenyl-dicyclo (2 after the drying again; 2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3; 5,6-tetracarboxylic acid dimethyl ester.
1H NMR (CDCl
3, 300MHz) analytical results: δ 3.50 (s, 12H, CH
3); δ 2.33 (m, 4H, CH); δ 2.78 (m, 2H, CH); δ 5.37 (m, 1H, CH); δ 7.26 (s, 5H, C
6H
5).
(2) Preparation of catalysts
Except the internal electron donor compound changes 0.62g diisobutyl phthalate and 0.10g 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.67%, diisobutyl phthalate 6.25%, 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 2.89%, magnesium 19.89%, chlorine 50.69%.
(3) propylene polymerization
Except adding the 5.6mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 12
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.55g diisobutyl phthalate and 0.21g 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.78%, diisobutyl phthalate 5.60%, 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 2.15%, magnesium 21.01%, chlorine 50.28%.
(2) propylene polymerization
Except adding the 5.8mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 13
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.34g diisobutyl phthalate and 0.52g 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.15%, diisobutyl phthalate 3.60%, 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 4.15%, magnesium 19.01%, chlorine 51.28%.
(2) propylene polymerization
Except adding the 4.5mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 14
(1) Preparation of catalysts
Except changing into, the internal electron donor compound adds 0.44g diethyl phthalate and 0.17g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester, and all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.59%, diethyl phthalate 7.23%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 2.03%, magnesium 13.67%, chlorine 51.51%.
(2) propylene polymerization
Except adding the 5.4mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
Embodiment 15
(1) Preparation of catalysts
Except the internal electron donor compound changes 0.28g diethyl phthalate and 0.42g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5 into, 6-tetracarboxylic acid dimethyl ester, all the other conditions are identical with embodiment 1 condition.The content of each component is in the catalyzer: titanium 2.71%, diethyl phthalate 2.18%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 2.76%, magnesium 15.31%, chlorine 50.06%.
(2) propylene polymerization
Except adding the 5.7mmol triethyl aluminum, other polymerizing condition is with embodiment 1.
Polymerization result is listed in table 1.
The comparative example 1
Preparation of catalysts method and propene polymerizing method just only add the 1.03g diisobutyl phthalate with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.85%, diisobutyl phthalate 7.62%, magnesium 15.09%, chlorine 50.41%.
Test-results is as shown in table 1.
The comparative example 2
Preparation of catalysts method and propene polymerizing method just only add 1.47g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.68%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 10.83%, magnesium 14.41%, chlorine 51.23%.
Test-results is as shown in table 1.
The comparative example 3
Preparation of catalysts method and propene polymerizing method just add 0.07g diisobutyl phthalate and 0.76g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.95%, diisobutyl phthalate 1.08%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 6.14%, magnesium 14.52%, chlorine 51.2%.
Test-results is as shown in table 1.
The comparative example 4
Preparation of catalysts method and propene polymerizing method just add 0.62g diisobutyl phthalate and 0.08g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer:: titanium 2.75%, diisobutyl phthalate 7.08%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 1.24%, magnesium 15.52%, chlorine 50.21%.
Test-results is as shown in table 1.
The comparative example 5
Preparation of catalysts method and propene polymerizing method just only add 1.60g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester with embodiment 5 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.78%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester 7.83%, magnesium 14.62%, chlorine 51.33%.
Test-results is as shown in table 1.
The comparative example 6
Preparation of catalysts method and propene polymerizing method just add 0.14g diisobutyl phthalate and 1.28g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.55%, diisobutyl phthalate 1.88%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 6.79%, magnesium 15.05%, chlorine 51.28%.
Test-results is as shown in table 1.
The comparative example 7
Preparation of catalysts method and propene polymerizing method just only add 0.93g 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.52%, 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 8.55%, magnesium 15.62%, chlorine 50.33%.
Test-results is as shown in table 1.
The comparative example 8
Preparation of catalysts method and propene polymerizing method just add 0.62g diisobutyl phthalate and 0.09g7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 8 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.57%, diisobutyl phthalate 7.88%, 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 1.79%, magnesium 15.08%, chlorine 51.29%.
Test-results is as shown in table 1.
The comparative example 9
Preparation of catalysts method and propene polymerizing method just add 0.14g diisobutyl phthalate and 0.74g7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.67%, diisobutyl phthalate 1.58%, 7-chloro-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 6.89%, magnesium 15.18%, chlorine 50.29%.
Test-results is as shown in table 1.
The comparative example 10
Preparation of catalysts method and propene polymerizing method just only add 1.03g 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.55%, 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 7.15%, magnesium 15.32%, chlorine 51.33%.
Test-results is as shown in table 1.
The comparative example 11
Preparation of catalysts method and propene polymerizing method just add 0.14g diisobutyl phthalate and 0.82g 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.55%, diisobutyl phthalate 1.08%, 7-phenyl-dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 6.38%, magnesium 15.52%, chlorine 50.37%.
Test-results is as shown in table 1.
The comparative example 12
Preparation of catalysts method and propene polymerizing method just only add the 0.55g diethyl phthalate with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer: titanium 2.75%, diethyl phthalate 7.52%, magnesium 14.39%, chlorine 50.01%.
Test-results is as shown in table 1.
The comparative example 13
Preparation of catalysts method and propene polymerizing method just add 0.22g diethyl phthalate and 0.51g dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester with embodiment 1 in catalyst preparation process.The content of each component is in the catalyzer:: titanium 2.55%, diethyl phthalate 3.18%, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester 5.21%, magnesium 15.12%, chlorine 50.01%.
Test-results is as shown in table 1.
Table 1 polymerizing condition and experimental result
Claims (7)
1. catalyst for polymerization of propylene comprises magnesium, titanium, halogen and internal electron donor compound, it is characterized in that the internal electron donor compound is the mixture of succinate of diester and the logical formula II of logical formula I:
In formula I and (II), R
1～R
4For carbon number 1～10 alkyl, aryl, aralkyl; R
5, R
6Identical or different, be H, halogen atom, C
1～C
20Straight or branched alkyl, C
3～C
20Naphthenic base, C
6～C
20Aryl or C
7～C
20Aralkyl; R is C
1～C
20Straight or branched alkyl, C
3～C
20Naphthenic base, C
6～C
20Aryl or C
7～C
20Aralkyl;
Each composition weight of catalyzer consists of:
Electron donor compound 1～10%
Titanium 1～15%
Magnesium 10～25%
Halogen 40～60%,
The weight ratio of diester and succinate electron donor compound is 0.5～6.3.
2. catalyzer according to claim 1 is characterized in that two ester compounds in the formula I are wherein a kind of of diisobutyl phthalate, diethyl phthalate or n-butyl phthalate.
3. catalyzer according to claim 1 is characterized in that the succinate compounds in the formula II is dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5; 6-tetracarboxylic acid dimethyl ester, dicyclo (2,2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dibenzyl ester, 7-chloro-dicyclo (2; 2,2) certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester or 7-phenyl-dicyclo (2; 2,2) wherein a kind of of certain herbaceous plants with big flowers alkane-7-alkene-2,3,5,6-tetracarboxylic acid dimethyl ester.
4. the catalyzer one of said according to claim 1-3, it is characterized in that catalyzer form in magnesium and halogen by general molecular formula Mg (OR ')
mX
(2-m)N (R
2OH) spherical magnesium halide alcohol adduct provides, and R ' is C in the formula
1～C
20Alkyl, aralkyl or aryl; X is a halogen; M is the integer of 0≤m＜2; N is the decimal or the integer of 0＜n＜5; R
2Be C
1～C
20Alkyl, aralkyl or aryl.
5. catalyzer according to claim 4 is characterized in that the magnesium halide in the magnesium halide alcohol adduct is a magnesium chloride.Described alcohol is ethanol.
6. the catalyzer one of said according to claim 1-3, the donor that it is characterized in that titanium is that general formula is Ti (OR)
nX
(4-n)Compound, R is C in the formula
1～C
20Alkyl, aryl or aralkyl; X is a halogen; N is the integer of 0≤n＜4.
7. catalyzer according to claim 5 is characterized in that titanium compound is a titanium tetrachloride.
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| CN201010231470.0A Active CN102336851B (en) | 2010-07-14 | 2010-07-14 | Propylene polymerization catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627712A (en) * | 2012-03-29 | 2012-08-08 | 中国科学院长春应用化学研究所 | Preparation method and application of Ziegler Natta catalyst for propylene polymerization |
| CN103483472A (en) * | 2012-06-13 | 2014-01-01 | 中国石油天然气股份有限公司 | Supported polypropylene catalyst and preparation method thereof |
| CN103665209A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Polypropylene catalyst and preparation method thereof |
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| CN1597714A (en) * | 2003-09-18 | 2005-03-23 | 中国石油化工股份有限公司 | Method of producing olefine polymer and its polymer |
| CN101068853A (en) * | 2004-09-24 | 2007-11-07 | 富士胶片株式会社 | Polymer, method for producing the polymer, optical film, and image display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1597714A (en) * | 2003-09-18 | 2005-03-23 | 中国石油化工股份有限公司 | Method of producing olefine polymer and its polymer |
| CN101068853A (en) * | 2004-09-24 | 2007-11-07 | 富士胶片株式会社 | Polymer, method for producing the polymer, optical film, and image display device |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627712A (en) * | 2012-03-29 | 2012-08-08 | 中国科学院长春应用化学研究所 | Preparation method and application of Ziegler Natta catalyst for propylene polymerization |
| CN102627712B (en) * | 2012-03-29 | 2014-02-12 | 中国科学院长春应用化学研究所 | Preparation method and application of Ziegler-Natta catalyst for propylene polymerization |
| CN103483472A (en) * | 2012-06-13 | 2014-01-01 | 中国石油天然气股份有限公司 | Supported polypropylene catalyst and preparation method thereof |
| CN103483472B (en) * | 2012-06-13 | 2015-09-23 | 中国石油天然气股份有限公司 | Supported polypropylene catalyst and preparation method thereof |
| CN103665209A (en) * | 2012-09-18 | 2014-03-26 | 中国石油天然气股份有限公司 | Polypropylene catalyst and preparation method thereof |
| CN103665209B (en) * | 2012-09-18 | 2017-03-15 | 中国石油天然气股份有限公司 | Polypropylene catalyst and preparation method thereof |
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| CN102336851B (en) | 2014-04-02 |
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