CN1005716B - Process for preparing supported catalyst system for olefin polymerization - Google Patents
Process for preparing supported catalyst system for olefin polymerization Download PDFInfo
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- CN1005716B CN1005716B CN87101423.8A CN87101423A CN1005716B CN 1005716 B CN1005716 B CN 1005716B CN 87101423 A CN87101423 A CN 87101423A CN 1005716 B CN1005716 B CN 1005716B
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- China
- Prior art keywords
- alcohol
- catalyst system
- magnesium halide
- titanium
- carboxylic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000006116 polymerization reaction Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 150000001336 alkenes Chemical class 0.000 title abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract 2
- 239000010936 titanium Substances 0.000 claims abstract description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- -1 magnesium halide Chemical class 0.000 claims abstract description 38
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 35
- 239000011777 magnesium Substances 0.000 claims abstract description 23
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 10
- 150000005826 halohydrocarbons Chemical class 0.000 claims abstract description 7
- 230000000737 periodic effect Effects 0.000 claims abstract 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 33
- 239000007787 solid Substances 0.000 claims description 24
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000012456 homogeneous solution Substances 0.000 claims description 14
- 150000008065 acid anhydrides Chemical class 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 11
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 3
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 2
- VGGRCVDNFAQIKO-UHFFFAOYSA-N formic anhydride Chemical group O=COC=O VGGRCVDNFAQIKO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000003609 titanium compounds Chemical class 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 150000003961 organosilicon compounds Chemical class 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 239000011949 solid catalyst Substances 0.000 abstract 1
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 17
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000460 chlorine Substances 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 229920001155 polypropylene Polymers 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 229960004756 ethanol Drugs 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 235000010210 aluminium Nutrition 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- 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 3
- 239000012265 solid product Substances 0.000 description 3
- 150000003608 titanium Chemical class 0.000 description 3
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000012662 bulk polymerization Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003701 inert diluent Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- 230000000452 restraining effect Effects 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- HRAQMGWTPNOILP-UHFFFAOYSA-N 4-Ethoxy ethylbenzoate Chemical compound CCOC(=O)C1=CC=C(OCC)C=C1 HRAQMGWTPNOILP-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 1
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 1
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 229960002097 dibutylsuccinate Drugs 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000009730 ganji Substances 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012442 inert solvent Substances 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
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
A process for preparing the magnesium halide supported Ti-contained catalyst system used for polymerizing and copolymerizing olefin includes such steps as preparing the uniform solution of halohydrocarbon from magnesium halide, liquid carboxylic acid anhydride and lower alcohol, treating the solution with titanium halide and carboxylic ester to obtain Ti-contained solid catalyst component , and preparing the catalyst system from the organic compound of metals in groups 1-III in periodic table as component (B) and organosilicon compound (C). The catalyst system has the advantages of high activity, strong orientation capability, good resin performance, no environmental pollution and the like. Because the cheap industrial raw material, namely the low-carbon alcohol, is used, the cost is low, the reaction condition is mild, no special requirements on equipment are required, and the method is easy to popularize.
Description
The invention relates to the preparation method of the used high-effective carrier catalyst system of olefinic polymerization.
The preparation method of the effective catalyst of olefinic polymerization and relevant technologies had many patent documentations, and current catalyst system preferably should push away GB2111066(or the spy opens clear 58,83006).One of its characteristics are magnesium chloride and alcohol (＞C
8) the uniform MgCl of effect generation
2-alcohol adduct solution is used TiCl again
4Obtain containing the crystallization MgCl of titanium chloride etc. after handling with diisobutyl phthalate
2Carried catalyst.This catalyzer has advantages of high catalytic activity, also has very high orientation property simultaneously.But according to said method need under comparatively high temps (130 ℃), to carry out MgCl
2Reaction with alcohol.For lower boiling alcohol,,, do not have other additives and be difficult to and MgCl under existing at normal pressure as ethanol etc.
2In liquid hydrocarbon, react, generate homogeneous solution.The spy opens clear 60,139,707 grades and once used ethanol, Acetyl Chloride 98Min. and MgCl
2Reaction makes catalyzer in inert solvent.But Acetyl Chloride 98Min. is hydrolysis very easily, and operation inconvenience and the catalyzer that makes like this can only be used for vinyl polymerization.The spy opens clear 51-28189 etc. and once used ethanol, ethyl benzoate and MgCl
2, reaction makes catalyst for polymerization of propylene, but because of not making MgCl
2Generate homogeneous solution with ethanol synthesis, therefore the catalyzer that makes has lower catalytic activity.GB2029840A etc. are with MgCl
2Moulding is to reach the purpose of controlling polymers form.Once made ethanol and MgCl
2Reaction, but under elevated pressures, could realize.
Purpose of the present invention makes it under not too high temperature, with anhydrous MgX by adopting the industrial raw material-low-carbon alcohol cheap and easy to get and the mixture of liquid anhydride
2Reaction, in halohydrocarbon, make homogeneous solution, handle through halogenated titanium and carboxylicesters again, obtain titaniferous solid catalytic ingredient (A) with low cost, constitute catalyst system of the present invention jointly with component (B) and component (C), can simplify technology and reduce the cost for preparing the high-effective carrier catalyst system, be convenient to promote suitability for industrialized production.
Preparation method's of the present invention efficient magnesium halide carrier catalyst system contains the solids containing titanium catalyst component (A) of magnesium halide and carboxylicesters; And component (B): periodictable I-III family organometallics; And component (C): silicoorganic compound.Studies show that liquid carboxylic acid's acid anhydride and low-carbon alcohol can generate ester and water, and under certain condition with MgCl
2The complex compound that generates: 2H
2O-MgCl
22RCOOR ' is for being the clear solution of homogeneous, therefore technical characterictic of the present invention be with magnesium halide in halohydrocarbon with liquid carboxylic acid's acid anhydride and low-carbon (LC) (C
1-C
5) mixture reaction of alcohol makes the homogeneous solution of magnesium halide-ester compound halohydrocarbon.This homogeneous solution is handled and is made the solids containing titanium catalyst component (A) that contains magnesium halide and carboxylicesters through the halogenated titanium of liquid state and carboxylicesters again.Concrete steps are: with magnesium halide, it is interior or first with liquid carboxylic acid's acid anhydride that liquid carboxylic acid's acid anhydride, low-carbon alcohol and halohydrocarbon add reactor simultaneously, low-carbon alcohol and halohydrocarbon add reactor, react after 30～60 minutes, add magnesium halide again, temperature of reaction is 40～100 ℃ preferably 60～80 ℃; The mol ratio of magnesium halide and liquid carboxylic acid's acid anhydride is 1: 1～1: 6, preferably 1: 1～1: 2; Magnesium halide is 1: 12～1: 1 with the mol ratio of alcohol, preferably 1: 2～1: 4; Reaction times is 1～6 hour, preferably 2～3 hours.With this homogeneous solution and halogenated titanium or alkoxyl group halogenated titanium-30～-30 ℃ contact after, generate the magnesium halide cenotype of titanium-containing compound, its contact temperature preferably-20～120 ℃ heating and carboxylicesters is handled, and with hexane wash 3-5 time, just obtains solid titanium-containing catalyst component (A).The prepared solid titanium catalyst component of the inventive method (A) has specific surface area 70～250M
2/ g.
The magnesium halide that the present invention adopts is magnesium chloride, magnesium bromide, magnesium iodide and magnesium fluoride.The alcohol that uses is C as straight chain or isomery alcohol
1-C
5Low-carbon alcohol such as methyl alcohol, ethanol, propyl alcohol, Virahol and butanols etc., preferably ethanol.The liquid carboxylic acid's acid anhydride that uses is C as its general formula of fatty acid anhydride
2n(n=1～4); As formic anhydride, diacetyl oxide, propionic anhydride and butyryl oxide etc., preferably diacetyl oxide.Use the mixture and the magnesium halide reaction of liquid carboxylic acid's acid anhydride and alcohol to need in the presence of inert diluent, to carry out.Inert diluent is a halohydrocarbon, mainly is halogenated alkane; As tetracol phenixin, ethylene dichloride, trichloroethane, chloropropane, propylene dichloride, trichloropropane and chlorobutane etc.Halogenated aryl hydrocarbon such as chlorobenzene etc.
Used titanium tetrahalide or the alkoxyl group halogenated titanium general expression of preparation solid titaniferous catalyst component (A) is:
Ti（OR）
nX
4-no≤n≤4
X-halogen R-alkyl
As titanium tetrahalide: TiCl
4, TiBr
4; Alkoxyl group halogenated titanium: Ti(OCH
3) Cl
3, Ti(OCH
3)
2CL
2, Ti(OCH
3)
3Cl, Ti(OC
2H
5) Cl
3, Ti(OC
2H
5)
2Cl
2, Ti(OC
2H
5) Cl, Ti(n-OC
4Hg) Cl
3, Ti(n-OC
4H
8)
2Cl
2, Ti(n-OC
4H
9)
3Cl and Ti(OC
2H
5)
2Br
2Deng, TiCl preferably
4, used carboxylicesters is fat or aromatic series unit and multi-carboxylate; As diethyl succinate, dibutyl succinate, adipic acid dibutylester, n-butyl phthalate, diisobutyl phthalate, di-iso-amyl phthalate ethyl benzoate, ethyl anisate, methyl p-methoxybenzoate, ethyl p-ethoxybenzoate etc.; Diisobutyl phthalate preferably.
(B) used in the present invention component be the periodictable I to III family organometallics, mainly be organo-aluminium compound, its general formula is:
R
nAlX
3-nR is C in the formula
1-C
18Alkyl, mainly be alkyl, X is that halogen mainly is a chlorine, m=1-3, alkyl aluminum compound commonly used have triethyl aluminum, triisobutyl aluminium, aluminium diethyl monochloride, sesquialter ethyl aluminum chloride and ethyl aluminum dichloride etc.When polymerization, the consumption of aluminum alkyls is that the mol ratio of the titanium in aluminium and the solid catalysis group (A) is 3-1000; 50-200 preferably.
(C) used in the present invention component is organic silicide, and its general expression is:
Si（OR
1）
nR
<math><msup><mi>R</mi><msub><mi>2</mi></msup><mi>4-n</mi></msub></math> N=1-3 in the formula, R
1And R
2Be alkyl identical or inequality, dimethyldimethoxysil,ne, trimethylammonium methoxy silane, Union carbide A-162, dimethoxydiphenylsilane, phenyl triethoxysilane etc.When polymerization, the consumption of organic silicide is that the mol ratio of Siliciumatom and aluminium atom in component (B) in the component (C) is 0.01 to 2; Preferably 0.03 to 0.8.
Adopt the prepared catalyst system of the inventive method to be used for the equal polymerization of alkene polymerization together; Solvent polymeric and mass polymerization, its salient features: as catalytic activity, degree of orientation, apparent density etc. except that with present similar catalyst system preferably quite, contrast existing preparation method and also have following advantage:
1, with C
1-C
5Low-carbon alcohol be that one of main raw material prepares catalyst component of the present invention (A), especially adopt to be easy to get and cheap industry anhydrous ethanol, reduced the cost of raw material significantly.
2, in preparation method's technological process of the present invention, the mixture reaction of magnesium halide and liquid fat acid anhydrides and alcohol and year titanium are handled each step and are all carried out at a lower temperature, have reduced energy consumption, can save energy.
3, preparation method of the present invention, the processing condition gentleness, the non-corrosiveness raw material does not have special harsh requirement to equipment, does not have unhappy gas in process of production and produces, and is free from environmental pollution, so the plant factor height, improved operational condition greatly, helps carrying out production strictly in line with rules and regulations.
4, MgCl among the preparation method of the present invention
2The what is called that-ester compound homogeneous solution and titanium compound need add when reacting in no instance helps and analyses agent, can obtain titaniferous solid catalytic ingredient (A).
The preparation method of high-effective carrier catalyst system of the present invention, owing to have an above-mentioned outstanding feature: raw material, cost of equipment is low, and less investment does not have corrosion and free from environmental pollution, easy to operately is easy to promote suitability for industrialized production.
The preparation of example 1, solid titanium-containing catalyst component (A)
Anhydrous MgCl
25 grams (52.5 mmole), 6.20 milliliters of dehydrated alcohols (105.0 mmole), the 1.2-ethylene dichloride of diacetyl oxide 5.85 milliliters (62.0 mmole) and 25 milliliters is chilled to room temperature at 80 ℃ of reactions formation in 2.5 hours homogeneous solution.This solution was added to 180 milliliters of TiCl that keep-20 ℃ in 45 minutes
4In.Slowly be warming up to 100 ℃, add diisobutyl phthalate 3.0 milliliters (11.0 mmoles) and handle after 2 hours, discharge reaction solution, use TiCl
4Wash once, then wash 5 times with dry hexane.Suspension vacuum-drying is got titaniferous solid catalytic ingredient (A): Ti 2.3%, and Mg 17.1%, and Cl 71.0%, diisobutyl phthalate 4.8% and ethyl acetate 2.0%.
Solvent polymeric
Abundant metathetical volume is in 2 liters the autoclave with propylene in (3～5 times) back of finding time repeatedly, add 1 liter of dry hexane (industry), triethyl aluminum 3 mmoles, solid titanium-containing catalyst component (A) 0.02 mmole of dimethoxydiphenylsilane 0.25 mmole and above-mentioned preparation (calculating with titanium) and hydrogenation are to P
N=0.3kg/cm
2Feed propylene and keep 7Kg/cm
2,, get polypropylene 460 grams 70 ℃ of following polymerizations 2 hours.
Catalytic activity 46(myriagram pp/ restrains titanium)
Polypropylene congruence normality 97.2%
Polypropylene melt index 5.7(gram/10 minutes)
Polypropylene apparent density 0.41(grams per milliliter)
Example 2-3
Utilize the solid titanium-containing catalyst component (A) of example 1, polymerization temperature is become 60 ℃ and 80 ℃ of other conditions with example 1, its result lists table 1 in.
Table 1 is annotated: pp is a polypropylene
The active congruent normality apparent density melting index of real polymerization temperature
Example (℃) (myriagram pp/ restrains titanium) (%) (grams per milliliter) (restraining/10 minutes)
1 70 45 97.2 0.41 5.7
2 60 35 96.8 0.41 3.9
3 80 42 97.0 0.36 15
Example 4-5
Utilize the solid titanium-containing catalyst group (A) of example 1, with Al(C
2H
5)
3Consumption changes 4 mmoles and 2 mmoles into, and other conditions are with example 1, and its result lists table 2 in
Table 2
Real Al(C
2H
5)
3Active congruent normality apparent density melting index
Example (mmole number) (myriagram pp/ restrains titanium) (%) (grams per milliliter) (restraining/10 minutes)
4 4 60 96.6 0.40 4.6
5 2 42 97.0 0.39 5.2
The preparation of example 6. solid titanium-containing catalyst components (A)
Anhydrous MgCl
25 grams (52.5 mmole), 6.20 milliliters of dehydrated alcohols (105.0 mmole), diacetyl oxide 5.85 milliliters (62.0 mmoles) and 25 milliliters of 1.2-ethylene dichloride formed homogeneous solution in 2.5 hours 80 ℃ of reactions, were chilled to room temperature.This solution was added to 180 milliliters in 45 minutes ,-20 ℃ TiCl
4In, slowly being warming up to 100 ℃ and adding 3.0 milliliters of diisobutyl phthalates (11.0 mmole) and handle after 2 hours and discharge reaction solution, solid product is with 17* milliliter TiCl
4Handled 2 hours at 100 ℃ with the mixture of 5 milliliters of toluene.Heat filtering is collected solid product, earlier with 30 milliliters of TiCl
4Wash once, then wash 5 times with dry hexane.Suspension vacuum-drying is got titaniferous solid catalytic ingredient (A): Ti 2.1%, and Mg 17.6%, and Cl 54.0%, diisobutyl phthalate 20.4% and ethyl acetate 2.3%.
Polymerization is as follows with example 1 its result:
Catalytic activity 520,000 (gram pp/ gram titanium), congruent normality 94.7%, melting index 21.2(gram/10 minutes), apparent density 0.37(grams per milliliter)
The preparation of example 7 solid titanium-containing catalyst components (A)
Anhydrous MgCl
25 grams (52.5 mmole), 6.20 milliliters of (105.0 mmole) diacetyl oxides of dehydrated alcohol 5.85 milliliters (62 mmoles) and 25 milliliters of 1.2-ethylene dichloride formed homogeneous solution in 2.5 hours 80 ℃ of reactions, were chilled to room temperature.This solution was added to 180 milliliters 5 ℃ TiCl in 45 minutes
4In, slowly be warming up to 100 ℃, add diisobutyl phthalate 3.0 milliliters (11.0 mmoles) and handle discharge reaction solution TiCl after 2 hours
4100 ℃ of re-treatments once.Heat filtering is collected solid product, earlier with 30 milliliters of TiCl
4Wash once, then wash 5 times with dry hexane.Suspension vacuum-drying is got titaniferous solid catalytic ingredient (A).* the method for closing is with example 1, and the following active 48 myriagram pp/ of its result restrain titanium, congruent normality 96* apparent density 0.38(grams per milliliter), melting index 1.9(gram/10 minutes)
The preparation of example 8 solid titanium-containing catalyst components (A)
Anhydrous MgCl gram (52.5 mmole), 6.20 milliliters of dehydrated alcohols (105.2 mmole), diacetyl oxide 5.85 milliliters (62.0 mmoles) and 25 milliliters of 1.2-ethylene dichloride formed homogeneous solution in 2 hours 80 ℃ of reactions, were chilled to room temperature.This liquid was added drop-wise to 160 milliliters of TiCl that remain on-20 ℃ in 45 minutes
4In the mixed solution of 20 milliliters of toluene, slowly be warming up to 100 ℃, the diisobutyl phthalate that adds 3.0 milliliters (11.0 mmoles) handles that discharge after 2 hours should anti-liquid.Re-treatment once under these conditions.Wash five times with Ganji's alkane, suspension vacuum-drying is got titaniferous solid catalysis component (A).Polymerization process is with example 1.Its result is as follows: active 46(myriagram pp/ gram titanium), congruent normality 94.7%, apparent density 0.38(grams per milliliter) and melting index 21.2(restrain/10 minutes)
The preparation of example 9 solid titanium-containing catalyst parts (A)
With the dehydrated alcohol of 9.6 milliliters of (105.0 mmole) propyl carbinols replacements in example 1, other conditions are with example 1.Its result is as follows: active 33 myriagram pp/ gram titanium, congruent normality 96.2%, apparent density 0.24 grams per milliliter and melting index 0.1(gram/10 minutes)
The preparation of example 10 solid titanium-containing catalyst components (A)
Dehydrated alcohol with 3.1 milliliters (52.5 mmoles) replaces 6.20 milliliters of (105.0 mmole) dehydrated alcohols in the example 1, and other condition is with 1.Its result is as follows.
Active 20(myriagram pp/ gram titanium), congruent normality 98.0%, apparent density 0.35(grams per milliliter) and melting index 3.9(restrain/10 minutes)
The preparation of example 11 solid titanium-containing catalyst components (A)
With the diacetyl oxide in the propionic anhydride replacement example 1 of 8 milliliters (62.0 mmoles), other conditions are with example 1, and its result is as follows:
Active 35(myriagram pp/ gram titanium), congruent normality 96.2%, apparent density 0.37(grams per milliliter) and melting index 2.9(restrain/10 minutes)
Example 12 mass polymerizations
Abundant metathetical volume is in the autoclave of 5 liters with propylene in (3-5 time) back finding time repeatedly, add 3 liter liquid propenes, add 4 moles of triethyl aluminums more successively, solid titanium-containing catalyst component (A) 0.02 mmole in dimethoxydiphenylsilane 0.25 mmole and the example 1 (calculating) with titanium.Be warming up to 70 ℃, polymerization 2 hours, its result is as follows:
Catalytic activity 153(myriagram pp)/the gram titanium
Polypropylene congruence normality 97.4%
Polypropylene apparent density 0.41(grams per milliliter)
Polypropylene melt index 5.2(gram/10 minutes)
Claims (15)
1, a kind of preparation method who is used for the supported catalyst system of olefinic polymerization, described catalyst system contains (A), (B), (C) three components:
(A) being is the titaniferous of carrier and the solid catalytic ingredient of carboxylicesters with the magnesium halide, and the titanium compound general formula is Ti(OR)
nX
1-n, wherein R is an alkyl, X is a halogen, 0≤n≤4;
(B) be that I mainly is an alkylaluminium cpd to III family organometallic compound in the periodic table of elements, its general formula is: R*ALX
3-nWherein R is C
1-C
18Alkyl, X is a halogen, m=1～3
(C) be silicoorganic compound, its general formula is
Si（OR
1）
n <math><msup><mi>R</mi><msub><mi>2</mi></msup><mi>4-n</mi></msub></math> N=1～3 R
1And R
2Be alkyl identical or inequality.
Use MgCl
2In hydrocarbon, react the generation homogeneous solution with alcohol, use TiCl again
4Make (A) component after handling with carboxylicesters, it is characterized in that
(1.1) by magnesium halide in halohydrocarbon with liquid carboxylic acid's acid anhydride and C
1～C
5Any pure mixture reaction form the homogeneous solution of magnesium halide one ester compound halohydrocarbon, its temperature of reaction is 40～100 ℃, optimal reaction temperature is 60～80 ℃,
(1.2) then magnesium halide one ester compound halohydrocarbon homogeneous solution is contacted at-30～+ 30 ℃ with titanium tetrahalide, be preferably in-20～+ 15 ℃, heat down and handle with carboxylicesters at 60～120 ℃ again, optimum treatmenting temperature is 100～110 ℃,
(1.3) mole ratio of magnesium halide and liquid carboxylic acid's acid anhydride is 1: 1～1: 6, and optimum proportion is 1: 1～1: 2,
(1.4) magnesium halide is 1: 12～1: 1 with the mole ratio of alcohol, and optimum proportion is 1: 2～1: 4,
(1.5) reaction times is 1～6 hour, preferably 2～3 hours,
2, catalyst system preparation method as claimed in claim 1 is characterized in that described liquid carboxylic acid's acid anhydride is formic anhydride, diacetyl oxide, propionic anhydride and butyryl oxide.
3, catalyst system preparation method as claimed in claim 1 is characterized in that preferably diacetyl oxide of described liquid carboxylic acid's acid anhydride.
4, catalyst system preparation method as claimed in claim 1 is characterized in that described C
1～C
5Alcohol be straight chain alcohol or isomery alcohol, they are methyl alcohol, ethanol, propyl alcohol, butanols and isopropylcarbinol.
5, catalyst system preparation method as claimed in claim 1 is characterized in that described C
1～C
5Alcohol be straight chain alcohol or isomery alcohol, preferably ethanol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101423.8A CN1005716B (en) | 1987-11-20 | 1987-11-20 | Process for preparing supported catalyst system for olefin polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87101423.8A CN1005716B (en) | 1987-11-20 | 1987-11-20 | Process for preparing supported catalyst system for olefin polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034548A CN1034548A (en) | 1989-08-09 |
| CN1005716B true CN1005716B (en) | 1989-11-08 |
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ID=4813412
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87101423.8A Expired CN1005716B (en) | 1987-11-20 | 1987-11-20 | Process for preparing supported catalyst system for olefin polymerization |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004005360A2 (en) * | 2002-07-09 | 2004-01-15 | Basell Polyolefine Gmbh | Catalyst system for the polymerization of olefins |
| CN100390206C (en) * | 2005-02-02 | 2008-05-28 | 北京金鼎科化工科技有限公司 | Catalyst active constituent and catalyst containing same |
| KR102292650B1 (en) | 2016-08-19 | 2021-08-23 | 인스티튜트 오브 케미스트리, 차이니즈 아카데미 오브 사이언시즈 | Ultra-high molecular weight, ultra-fine particle size polyethylene, preparation method therefor and use thereof |
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1987
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| CN1034548A (en) | 1989-08-09 |
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