CN1539857A - Propylene polymerized catalyst system, preparationmethod and usage - Google Patents
Propylene polymerized catalyst system, preparationmethod and usage Download PDFInfo
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- CN1539857A CN1539857A CNA031229786A CN03122978A CN1539857A CN 1539857 A CN1539857 A CN 1539857A CN A031229786 A CNA031229786 A CN A031229786A CN 03122978 A CN03122978 A CN 03122978A CN 1539857 A CN1539857 A CN 1539857A
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Abstract
A catalyst system for the polymerization of propylene is composed of primary catalyst and secondary catalyst which is alkyl aluminium compound. Said primary catalyst is prepared through reaction between microspheric magnesium chloride-alcohol addition, titanium halide solution and 1,3-diether, filtering, washing and drying. Its advantages are high activity and high stereostructure regularity.
Description
Technical field
The present invention relates to a kind of catalyst system that is used for propylene polymerization.
The invention still further relates to a kind of preparation method who is used for the catalyst system of propylene polymerization.
Background technology
In recent ten years, the research of olefinic polymerization catalyst system therefor has had bigger development, and the catalyst performance of being produced also constantly is improved.Simultaneously, also more and more higher to the polymer processing performance demands, this just requires the better polyolefin catalyst of performance.
US 4298718 has described this class catalyzer first, and this catalyzer is downloaded on the magnesium halide in active by titanium tetrachloride and forms.Although this catalyzer has high reactivity in propylene polymerization, there is not good stereospecificity.
GB 2111066 contacts magnesium chloride alcohol adduct homogeneous solution with liquid titanium compound, add a kind of electron donor (as phthalic ester) simultaneously, forms solid titanium catalyst.When olefinic polymerization, need to add another electron donor (alkoxy-silicon compound) and just can obtain high normal polypropylene.The polymerization technique complexity of this catalyzer, and have only the suitable interior external electron donor of selection just can play synergy, the catalyzer of synthetic high reactivity and stereospecificity, and this catalyzer is not suitable for gas phase polymerization.
EP 0361494 is when the preparation catalyzer, and adding a kind of special ether is internal electron donor.When polymerization, need not to add external electron donor and can obtain high normal polypropylene and higher activity is arranged.Subsequently, be purpose with the performance of improving or improve above-mentioned catalyzer, applied for a lot of patents.Yet in existing numerous patents and scientific and technical literature, with containing 1 of tetra-atomic ring structure, the 3-diether is that the catalyzer with high reactivity and stereospecificity that unique electron donor obtains sees that never the people reported.
Summary of the invention
The object of the present invention is to provide a kind of catalyst system that is used for propylene polymerization, thereby this catalyzer has overcome and will obtain high normal polymkeric substance in the prior art and just must cause with the cooperation of external electron donor and active descend the shortcoming of polymerization technique complexity; This catalyzer adds a kind of novel 1 in preparation, and the 3-diether need not to add external electron donor when polymerization, promptly show high reactivity and stereospecificity, has simplified production technique.
The catalyst system that the present invention is used for propylene polymerization is made of Primary Catalysts and promotor.
Primary Catalysts is to obtain spherical magnesium halide alcohol adduct by magnesium halide and alcohol reaction, mixes with titanium-containing compound, adds and contains 1 of tetra-atomic ring, and the 3-diether obtains comprising titanium, magnesium, halogen and 1, the solid catalyst of 3-diether.Concrete operations are as follows: microspheric magnesium chloride alcohol adduct particle is joined in-50～30 ℃ of titanium tetrachloride liquid preferably-30～0 ℃, and the mol ratio of magnesium chloride and titanium tetrachloride is 1: 10-1: 100, be preferably 1: 20-1: 60; Reaction times is 10 minutes to 5 hours, is preferably 1～3 hour; Slowly be warming up to 40～120 ℃, be preferably 50-90 ℃ and add ether compound, the mol ratio of magnesium chloride and ether compound is 2: 1～20: 1, is preferably 2: 1～12: 1; Continue to be warming up to 100～140 ℃, be preferably 110～130 ℃ of reactions 1～4 hour, add halogenated titanium after filtering again, the mol ratio of magnesium and titanium is 1: 10-1: 100,110～130 ℃ of reactions 1～4 hour, filter, washing, drying obtains magnesium chloride load type catalyzer, and its weight is composed as follows:
Magnesium 10-25%
Titanium 0.5-8%
Chlorine 40-70%
1,3-diether 1-25%
The general formula of the magnesium halide alcohol adduct that the present invention adopts: Mg (OR
1)
mX
(2-m)In the formula, R
1Be the alkyl of carbonatoms 1-20, aralkyl, aryl; X is a halogen; M is the integer of 0≤m≤2.Concrete as: magnesium chloride, magnesium bromide, chloro magnesium methylate, chloro magnesium ethylate, chloro butoxy magnesium etc., preferred magnesium chloride.Alcohol general formula: R
2In the OH formula, R
2Be the alkyl of carbonatoms 1-20, aralkyl, aryl.Concrete as: methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, 2-ethyl butanol, 2-Ethylhexyl Alcohol, preferred alcohol.After compound heating for dissolving such as magnesium chloride and ethanol, high pressure ejection or high-speed stirring are solidified into microsphere particle in heat-eliminating medium, promptly obtain the magnesium chloride alcohol adduct.
Its general formula: Mg (OR
1)
mX
(2-m)N (R
2OH), n is the integer or the decimal of 0＜n＜4.
Magnesium halide alcohol adduct of the present invention is extensively disclosed in CN 1034736C.
Titanium-containing compound general formula of the present invention is Ti (OR)
nX
(4-n), R is the alkyl of hydrogen or carbonatoms 1-20 in the formula, aralkyl, aryl; X is a halogen; N is the integer of 0≤n≤4; As tetracol phenixin, titanium tetrabromide, four titanium butoxide, purity titanium tetraethoxide, trichlorine titan-alkoxide, dichloro dialkoxy titanium or chloro tri-alkoxy titanium, preferred tetracol phenixin.
Titanium-containing compound of the present invention is extensively disclosed in CN 85100997.
Promotor of the present invention is an alkylaluminium cpd, and its general formula is AlR
nX
(3-n), R is the alkyl of carbonatoms 1-20 in the formula, aralkyl, aryl; X is a halogen; N is the integer of 0≤n≤3; As: trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum or ethyl aluminum dichloride, preferred triethyl aluminum, triisobutyl aluminium.
The ether compound that the present invention adopts is that quaternary is cyclosubstituted 1, the 3-diether, and its structural formula is:
Substituent R in the formula
1, R
2, R
3, R
4, R
5, R
6Be hydrogen, halogen, C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20A kind of in the aryl;
Substituent R in the formula
7, R
8Be C
1-C
20The alkyl of straight or branched.
Described 1, the 3-diether has:
1, two (the methoxymethyl)-tetramethylene of 1-
1, two (the methoxymethyl)-2-methyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-ethyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-propyl group-tetramethylene of 1-
1, two (the methoxymethyl)-2-butyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-cyclopropyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-chloro-tetramethylene of 1-
1, two (the methoxymethyl)-2-fluoro-tetramethylene of 1-
1, two (the methoxymethyl)-2-methoxyl group-tetramethylene of 1-
1, two (the methoxymethyl)-3-methyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-ethyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-propyl group-tetramethylene of 1-
1, two (the methoxymethyl)-3-butyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-amyl group-tetramethylene of 1-
1, two (the methoxymethyl)-3-chloro-tetramethylene of 1-
1, two (the methoxymethyl)-3-fluoro-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclopropyl methylene radical-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclobutyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclopentyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclohexyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclohexenyl-tetramethylene of 1-
1, two (methoxymethyl)-3 of 1-, 3-two chloro-tetramethylene
1, two (methoxymethyl)-3 of 1-, 3-two fluoro-tetramethylene
1, two (methoxymethyl)-2 of 1-, 2-two chloro-tetramethylene
1, two (methoxymethyl)-2 of 1-, 2-two fluoro-tetramethylene
1, two (the methoxymethyl)-2-methoxyl groups-3 of 1-, 3-dimethyl-tetramethylene
1, two (the butoxymethyl)-tetramethylene of 1-
1, two (isopropoxy the methyl)-tetramethylene of 1-
1, two (the phenoxymethyl)-tetramethylene of 1-
1, two (the benzyloxymethyl)-tetramethylene of 1-
1, two (1-the methoxy ethyl)-tetramethylene of 1-
The present invention synthesizes 1 first, two (the methoxymethyl)-tetramethylene of 1-:
At first with 1,1-tetramethylene dioctyl phthalate ethyl ester is a raw material, is catalyzer with sulfuric acid, carries out the hydrolysis of ester, obtains 1,1-tetramethylene dioctyl phthalate; Make it be reduced to 1 with lithium aluminum hydride then, 1-tetramethylene dimethanol; Last and iodomethane reaction obtains 1, two (the methoxymethyl)-tetramethylene of 1-.
The H-NMR solvent is CDCl
3
1,1-tetramethylene dimethanol:
1.806ppm multiplet 4H tetramethylene
1.904ppm multiplet 2H tetramethylene
3.698ppm unimodal 4H OH
4.146ppm unimodal 2H CH
2
1, two (the methoxymethyl)-tetramethylene of 1-:
1.850ppm multiplet 6H tetramethylene
3.373ppm unimodal 4H CH
2+ 6H CH
3
The method that a kind of catalyst for polymerization of propylene of the present invention is used for propylene polymerization is as follows:
Titanium during polymerization in the Primary Catalysts and the mol ratio of the aluminium in the promotor 1: 1～1: 2000 are preferably 1: 1～1: 500; Polymerization temperature is 20～150 ℃, and preferred 30～100 ℃, for the molecular weight of telomerized polymer, can adopt hydrogen is molecular weight regulator.
Slurry polymerization:
At 250 milliliters through vacuum drying treatment, and use nitrogen, in the abundant metathetical reaction flask of propylene gas, add 100 milliliters of heptane of handling through anhydrous and oxygen-free, keeping the pressure in the bottle is 1 normal atmosphere, add alkyl aluminum solutions, stir after 5 minutes, adding catalyzer, polyreaction 1 hour, with acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.
Mass polymerization:
2 liters autoclaves after thorough drying, are used nitrogen, and the propylene displacement for several times, add 0.5～0.8 liter propylene and an amount of triethyl aluminium solution, stir the back and add catalyzer, and then add 0.4～0.8 liter of propylene, react and emit unreacted propylene after 2 hours, obtain polymkeric substance.
Vapour phase polymerization:
Adopt first body prepolymerization earlier, gas phase polymerization process again, through 2 liters of autoclaves of thorough drying, use nitrogen, after the propylene displacement for several times, the propylene that adds 0.2 liter, triethyl aluminum and 3～8 milligrams of catalyzer are raised to 70 ℃ of pre-polymerizations 20～30 minutes with temperature, and the pressure that keeps reactor was 13～18 normal atmosphere polymerizations 1.5 hours, close propylene, obtain polymkeric substance.
Embodiment
Embodiment 1
Preparation of catalysts
The microspheric magnesium chloride alcohol adduct particles of 4.3 grams are joined in-20 ℃ 140 milliliters the titanium tetrachloride liquid, reacted 1.5 hours, slowly be warming up to 40 ℃ and add 0.5 gram 1, two (the methoxymethyl)-tetramethylene of 1-, 120 ℃ of reactions 2 hours, filter, add 140 milliliters of titanium tetrachlorides again, 120 ℃ of reactions 2 hours, filter, 60 ℃ of washings five times, at room temperature use 100 milliliters of hexane wash once with 100 milliliters of hexanes, obtain magnesium chloride load type catalyzer after the vacuum-drying, more than operation is all finished under the anhydrous and oxygen-free condition.
Slurry polymerization
250 milliliters through vacuum drying treatment, and use nitrogen, in the abundant metathetical reaction flask of propylene gas, add 100 milliliters of heptane of handling through anhydrous and oxygen-free, keeping the pressure in the bottle is 1 normal atmosphere, and temperature remains on 40 ℃, add alkyl aluminum solutions, stir after 5 minutes, add above-mentioned catalyzer again, the titanium in the Primary Catalysts and the mol ratio of the aluminium in the promotor are 1: 60, polyreaction 1 hour, with acidifying ethanol termination reaction, suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.The polymerization relevant data is listed in table 1.
Embodiment 2
Remove when the preparation Primary Catalysts, 1, the amount of two (the methoxymethyl)-tetramethylene of 1-is become outside 0.75 gram by 0.5 gram, and other are identical with embodiment 1.
The polymerization relevant data is listed in table 1.
Embodiment 3～5
Press the polymerization process of embodiment 1, the titanium in the Primary Catalysts and the mol ratio of the aluminium in the promotor were respectively 1: 40/20/100, and other are identical with embodiment 1.
The polymerization relevant data is listed in table 1.
Embodiment 6～9
Press the polymerization process of embodiment 1, polymerization temperature is respectively 30,50, and 60,70 ℃, other are identical with embodiment 1.
The polymerization relevant data is listed in table 1.
Embodiment 10
Synthesizing with embodiment 1 of catalyzer, polymerization process adopts mass polymerization.
2 liters autoclave is after thorough drying, use nitrogen, the propylene displacement for several times, add 0.8 liter propylene and an amount of alkyl aluminum solutions, stir the back and add 10 milligrams of catalyzer, and then add 0.7 liter of propylene, be warmed up to 70 ℃ rapidly, react and emit unreacted propylene after 2 hours, obtain polymkeric substance, its activity is 1.31 * 10
6GPP/gTih.
The polymerizing condition of table 1 embodiment 1～9 and polymerization result
The active Mw degree of isotacticity of sequence number Al/Ti T
(mol ratio) (℃) (* 10
3(* 10
5) (%)
gPP/gTi·h)
1 60 40 2.691 1.363 93.3
2 60 40 2.200 1.250 93.0
3 40 40 3.493 1.464 94.0
4 20 40 2.259 1.539 92.8
5 100 40 2.060 1.474 91.5
6 60 30 1.954 1.954 93.7
7 60 50 1.229 1.191 93.2
8 60 60 1.017 1.056 92.7
9 60 70 0.954 1.412 91.5
Claims (6)
1. the catalyst system of a propylene polymerization comprises Primary Catalysts and promotor, it is characterized in that described Primary Catalysts is the supported solid titanium catalyst, and its weight is composed as follows:
Magnesium 10-25%
Titanium 0.5-8%
Chlorine 40-70%
1,3-diether 1-25%
Described 1, the 3-diether has following structure:
Substituent R in the formula
1, R
2, R
3, R
1, R
5, R
6Be hydrogen, halogen, C
1-C
20The alkyl of straight or branched, C
3-C
20Cycloalkyl, C
6-C
20Aryl a kind of;
Substituent R in the formula
7, R
8Be C
1-C
20The alkyl of straight or branched.
Promotor is an alkylaluminium cpd, and its general formula is AlR
nX
(3-n), R is the alkyl of carbonatoms 1-20 in the formula, aralkyl, aryl; X is a halogen; N is the integer of 0≤n≤3; Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, trioctylaluminum, a hydrogen diethyl aluminum, a hydrogen diisobutyl aluminum, aluminium diethyl monochloride, a chloro-di-isobutyl aluminum or ethyl aluminum dichloride.
2. the catalyst system of propylene polymerization according to claim 1 is characterized in that describedly 1, and the 3-diether has:
1, two (the methoxymethyl)-tetramethylene of 1-
1, two (the methoxymethyl)-2-methyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-ethyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-propyl group-tetramethylene of 1-
1, two (the methoxymethyl)-2-butyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-cyclopropyl-tetramethylene of 1-
1, two (the methoxymethyl)-2-chloro-tetramethylene of 1-
1, two (the methoxymethyl)-2-fluoro-tetramethylene of 1-
1, two (the methoxymethyl)-2-methoxyl group-tetramethylene of 1-
1, two (the methoxymethyl)-3-methyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-ethyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-propyl group-tetramethylene of 1-
1, two (the methoxymethyl)-3-butyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-amyl group-tetramethylene of 1-
1, two (the methoxymethyl)-3-chloro-tetramethylene of 1-
1, two (the methoxymethyl)-3-fluoro-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclopropyl methylene radical-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclobutyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclopentyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclohexyl-tetramethylene of 1-
1, two (the methoxymethyl)-3-cyclohexenyl-tetramethylene of 1-
1, two (methoxymethyl)-3 of 1-, 3-two chloro-tetramethylene
1, two (methoxymethyl)-3 of 1-, 3-two fluoro-tetramethylene
1, two (methoxymethyl)-2 of 1-, 2-two chloro-tetramethylene
1, two (methoxymethyl)-2 of 1-, 2-two fluoro-tetramethylene
1, two (the methoxymethyl)-2-methoxyl groups-3 of 1-, 3-dimethyl-tetramethylene
1, two (the butoxymethyl)-tetramethylene of 1-
1, two (isopropoxy the methyl)-tetramethylene of 1-
1, two (the phenoxymethyl)-tetramethylene of 1-
1, two (the benzyloxymethyl)-tetramethylene of 1-
1, two (1-the methoxy ethyl)-tetramethylene of 1-.
3. the preparation method of the catalyst system of propylene polymerization according to claim 1, it is characterized in that the supported solid titanium catalyst is that step is carried out in the following order: microspheric magnesium chloride alcohol adduct particle is joined in-50～30 ℃ the halogenated titanium liquid, the mol ratio of magnesium and titanium is 1: 10-1: 100, reaction times is 10 minutes to 5 hours, slowly be warming up to 40～120 ℃, add 1, the 3-diether compound, the mol ratio of magnesium and ether compound is 2: 1～20: 1, continue to be warming up to 100～140 ℃, reacted 1～4 hour, and added halogenated titanium after filtering again, the mol ratio of magnesium and titanium is 1: 10-1: 100,110～130 ℃ of reactions 1～4 hour, filter, washing, drying obtains the supported solid titanium catalyst.
4. the preparation method of the catalyst system of propylene polymerization according to claim 3 is characterized in that described halogenated titanium is a titanium tetrachloride, trichlorine titan-alkoxide, dichloro dialkoxy titanium or chloro tri-alkoxy titanium.
5. the preparation method of the catalyst system of propylene polymerization according to claim 3, the general formula that it is characterized in that described magnesium halide alcohol adduct is Mg (OR
1)
mX
(2-m)N (R
2OH) R in the formula
1Be the alkyl of carbonatoms 1-20, aralkyl, aryl; X is a halogen; M is the integer of 0≤m≤2; R
2Be the alkyl of carbonatoms 1-20, aralkyl, aryl; N is the integer or the decimal of 0＜n＜4.
6. the purposes of the catalyst system of propylene polymerization according to claim 1 is characterized in that and can intermittently or carry out polymerization continuously, can adopt slurry polymerization, mass polymerization or vapour phase polymerization.
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|---|---|---|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195668B (en) * | 2006-12-06 | 2010-05-19 | 中国石油天然气股份有限公司 | Load type main catalyst for propylene polymerization and method for producing the same |
| CN103059175A (en) * | 2012-11-22 | 2013-04-24 | 中国科学院化学研究所 | Solid catalyst composition for olefinic polymerization and preparation method thereof |
| CN109563203A (en) * | 2016-06-30 | 2019-04-02 | 陶氏环球技术有限责任公司 | It can be used for the procatalyst compositions and preparation method thereof of low comonomer incorporation |
| CN110511304A (en) * | 2019-09-19 | 2019-11-29 | 营口风光新材料股份有限公司 | A kind of preparation method and application of the high-efficiency activated Ziegler-Natta catalyst for propylene polymerization |
| CN112824433A (en) * | 2019-11-20 | 2021-05-21 | 中国石油化工股份有限公司 | Propylene and 1-butene random copolymer, polypropylene composition and preparation method of each |
-
2003
- 2003-04-23 CN CN 03122978 patent/CN1247627C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195668B (en) * | 2006-12-06 | 2010-05-19 | 中国石油天然气股份有限公司 | Load type main catalyst for propylene polymerization and method for producing the same |
| CN103059175A (en) * | 2012-11-22 | 2013-04-24 | 中国科学院化学研究所 | Solid catalyst composition for olefinic polymerization and preparation method thereof |
| CN103059175B (en) * | 2012-11-22 | 2014-11-26 | 中国科学院化学研究所 | Solid catalyst composition for olefinic polymerization and preparation method thereof |
| CN109563203A (en) * | 2016-06-30 | 2019-04-02 | 陶氏环球技术有限责任公司 | It can be used for the procatalyst compositions and preparation method thereof of low comonomer incorporation |
| CN110511304A (en) * | 2019-09-19 | 2019-11-29 | 营口风光新材料股份有限公司 | A kind of preparation method and application of the high-efficiency activated Ziegler-Natta catalyst for propylene polymerization |
| CN112824433A (en) * | 2019-11-20 | 2021-05-21 | 中国石油化工股份有限公司 | Propylene and 1-butene random copolymer, polypropylene composition and preparation method of each |
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|---|---|
| CN1247627C (en) | 2006-03-29 |
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