CN1315459A - Catalyst system for ether-type olefine polymerization and its preparing process - Google Patents
Catalyst system for ether-type olefine polymerization and its preparing process Download PDFInfo
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- CN1315459A CN1315459A CN 00103538 CN00103538A CN1315459A CN 1315459 A CN1315459 A CN 1315459A CN 00103538 CN00103538 CN 00103538 CN 00103538 A CN00103538 A CN 00103538A CN 1315459 A CN1315459 A CN 1315459A
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- ether
- dimethyl acetal
- propanal dimethyl
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Abstract
A catalyst system for the ether-type olefin polymerization has a master catalyst which is a solid one prepared by carrying 4-valence Ti compound and ether compound on magnesium halide carrier and a cocatalyst which is an organic compound of metal, and is prepared through mixing magnesium halide, inertial disperser and alcohol and reaction with 4-valence Ti compound and ether compound to obtain solid catalyst. Its advantages include high activity.
Description
The invention relates to the catalyst system of synthesis of polyolefins.With magnesium halide is carrier loaded tetravalent titanium compound, and promotor is an organometallics, need not to add the catalyst system of electron donor during olefinic polymerization.
The high-effective carrier catalyst that is used for olefinic polymerization at present mainly is carrier with the magnesium halide, the titanic complex phase catalyst system of load.GB211066 and Te Kai clear 5883006 is that magnesium halide is dissolved in the uniform solution of alcohol generation, then with magnesium halide alcoholic solution and low temperature titanium tetrachloride and internal electron donor effect, obtain titaniferous magnesium halide carrier catalyzer when magnesium halide is separated out, internal electron donor is a phthalate compound.When but such catalyzer is used for olefinic polymerization, need to add external electron donor-alkoxy-silicon compound, could generate high normal polyolefine, the polymerization technique complexity.In the selection of inside and outside electron donor, have only the suitable inside and outside electron donor of selection just can play synergy in addition, synthesize highly active catalyzer and polymerize high normal polyolefine.Its form of catalyzer and the size of this method preparation are difficult to control, and the polymer morphology that obtains is poor, and apparent density is little, and the selection of inside and outside electron donor is restricted.
In addition, magnesium halide carrier is at first activated and make the particle (as ball-type etc.) of definite shape,, obtain the titanic catalyzer of load then with the magnesium halide carrier and titanium compound and the internal electron donor effect that form.The internal electron donor that adopts is still carboxylic acid ester compound, as dibutyl phthalate etc.The method for preparing the moulding magnesium halide carrier has spray method, high-speed mixing method, and methods such as high pressure ejection method prepare carrier.As CN1034736C, US4399054 is with magnesium chloride and ethanol, and after the heating for dissolving, high pressure ejection or high-speed stirring are solidified into microparticle in heat-eliminating medium, obtain catalyzer behind the load titanium compound together for silicone oil, mineral oil.When being used for olefinic polymerization, this catalyzer still need add external electron donor, as alkoxy-silicon compound.
When synthesizing the magnesium halide loaded catalyst, can when synthetic catalyst, only use a kind of electron donor, or use a kind of electron donor, can both obtain the catalyzer of high reactivity and high stereospecificity with promotor.This electron donor is an ether compound, and EP0361494 A2 and US4971931 replace the third diether effect with magnesium chloride support and titanium tetrachloride and two to prepare catalyzer.The magnesium chloride support activation is under nitrogen, after a certain proportion of magnesium chloride, diether and the activation of chloroparaffin mixing and ball milling, carries out the titanium tetrachloride load again, the preparation catalyzer.Be used for olefinic polymerization, the polyolefine degree of isotacticity of generation is higher, but active low, and activity of such catalysts and form are difficult to control.The polymer morphology that generates is also relatively poor, and apparent density is little.
It is low that the present invention has overcome in the prior art catalyst activity, need add external electron donor during polyreaction, the shortcoming of polymerization technique complexity, and a kind of catalyst system for ether-type olefine polymerization and preparation method are provided.
A kind of catalyst system for ether-type olefine polymerization of the present invention contains Primary Catalysts and promotor.Primary Catalysts is a kind of solid catalyst that magnesium halide carrier load tetravalent titanium compound and ether compound are formed.Wherein the mole proportioning of magnesium halide carrier and ether compound is 50: 1～1: 1, is preferably 20: 1～2: 1.Adopting the compound general formula of magnesium is Mg (OR)
nX
2-n(n=0～2), wherein R is C
1～C
10Alkyl, be preferably C
2～C
4Alkyl, as magnesium ethylate, magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride etc.Promotor is an I A-III A family organometallics, and general formula is R
nMeX
3-n, R is hydrogen or C
1-C
20Alkyl, X represents halogen, Me is a metal, n=1-3.As Al (CH
3)
3, Al (C
2H
5)
3, Al (C
4H
9)
3, Al (iC
4H
9)
3, Al (C
2H
5)
2Cl, Al (C
2H
5) Cl
2Deng, best is triethyl aluminum and triisobutyl aluminium.During olefinic polymerization, the mol ratio of titanium content is 10～2000 in the consumption of aluminum alkyls and the catalyzer, is preferably 40～800.Above-mentioned tetravalent titanium compound is Ti (OR)
nX
4-n(n=0～4), X is a halogen.R is C
1～C
10Alkyl, R can be identical, also can be different, be preferably C
2～C
5Alkyl.As TiCl
4, TiBr
4, TiI
4, Ti (OEt) Cl
3, Ti (OEt)
2Cl
2, Ti (OBu)
4, Ti (OiBuO)
4, be preferably TiCl
4
The general formula of the ether compound that the present invention adopts is:
1.R
1, R
2, R
3, R
4Be to contain C
1～C
10Straight or branched alkyl, cyclic hydrocarbon radical or hydrogen atom etc.R
1, R
2, R
3, R
4Can be identical, also can be different, as hydrogen atom, methyl, ethyl, propyl group etc. are preferably hydrogen atom and methyl.2.X
1, X
2, X
3, X
4Can all be-oxyl, can partly be-oxyl also, but at least wherein two must be-oxyl.As methoxyl group, oxyethyl group, propoxy-, butoxy, isobutoxy, pentyloxy, hexyloxy, octyloxy, different octyloxy, phenoxy group, benzyloxy, substituent phenoxy, substituted benzyloxy etc., two necessary-oxyls are preferably methoxyl group, oxyethyl group.3.X
1, X
2, X
3, X
4Can partly be alkyl, can only be at most wherein two for alkyl, as methyl, ethyl, propyl group, butyl, isobutyl-, amyl group, cyclopentyl, hexyl, cyclohexyl, octyl group, iso-octyl, phenyl, benzyl, substituted-phenyl, substituted benzyl etc.4. the structural formula central carbon atom also can be used as the bridge carbon atom and alkyl is connected to ring, as fatty six membered ring, and seven Yuans rings of fat, cyclopentadiene ring, indenes ring, fluorenes ring etc.
The ether compound that is adopted has: 1. the substituent X of diether compound
3And X
4Be alkyl or aryl.The alkyl diether is: 2, and 2-dimethyl-1,3-Propanal dimethyl acetal, 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-di-isopropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-diamyl-1,3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal.The aryl diether is: 2, and 2-phenylbenzene-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal.2. the substituent X of three ether compounds
1, X
2, X
3Be alkoxyl group, X
4Be alkyl or aryl.Three ether compounds are: 2-benzyl trihydroxybutane three methyl ethers, 2-isobutyl-trihydroxybutane three methyl ethers, 2-indenyl trihydroxybutane three methyl ethers, 2-fluorenyl trihydroxybutane three methyl ethers, 2-benzyl-2-benzyloxymethyl-1,3-Propanal dimethyl acetal etc.3. tetraether compounds: tetramethylolmethane tetramethyl ether, tetramethylolmethane tetrem ether, 2,2-diisopropoxy methyl isophthalic acid, 3-Propanal dimethyl acetal, 2-benzyloxymethyl trihydroxybutane three methyl ethers, 2,2-benzyloxy methyl isophthalic acid, 3-Propanal dimethyl acetal etc.
Catalyst system for ether-type olefine polymerization of the present invention is used for olefinic polymerization and copolymerization has following characteristics: when catalyst system of the present invention is used for olefinic polymerization, need not external electron donor 1..2. the catalyst activity height is 3.5～150,000 gPP/gCat. under bulk polymerization conditions.3. this catalyst system adaptability is good, can be used for liquid-phase bulk polymerization, slurry polymerization and gas phase polymerization system, can also interrupter method or continuous processing carry out the polymerization and the copolymerization of alkene.4. select suitable ether compound, make not contain aryl in catalyzer and the polymkeric substance, can be used for biomaterial and food storage.5. catalyzer and polymer beads are even, narrow particle size distribution, and the polymkeric substance apparent density is big, and can regulate and control within the specific limits.
The preparation method of a kind of catalyst system for ether-type olefine polymerization of the present invention carries out in the following order: 1. the preparation method 1 of magnesium compound alcoholic solution) in the reactor after fully replacing with rare gas element, add magnesium halide, inertia dispersion agent and alcohol successively.Alcohol is 1～10 with the mol ratio of magnesium halide, and best mol ratio is 2～5.Heated and stirred in 80～150 ℃ of reactions 1～8 hour, is preferably 100～135 ℃ of reactions 2～4 hours.The concentration of magnesium halide in dispersion agent is 5～30g/l, is preferably 10～20g/l, is cooled to 25 ℃, obtains the magnesium halide alcoholic solution.Method 2) in the reactor after fully replacing with rare gas element, add compound, inertia dispersion agent and the alcohol of magnesium halide successively, alcohol is 1～10 with the mol ratio of magnesium halide, and best mol ratio is 2～5.Heated and stirred in 80～150 ℃ of reactions 1～8 hour, is preferably 100～135 ℃ of reactions 2～4 hours.The concentration of magnesium halide in dispersion agent is 5～30g/1, is preferably 10～20g/l.Be cooled to 20～80 ℃ and add ether compound, the mol ratio of magnesium halide and ether compound is 50～0, is preferably 20～0, is cooled to 25 ℃, obtains the magnesium halide alcoholic solution.2. the Preparation of catalysts method 1) the halogenated magnesium compound alcoholic solution of above-mentioned preparation, in splashing into-25～0 ℃ the solution of titanium compound in 0.5～3 hour, and under this temperature, stirred 1～3 hour, be warming up to 40～100 ℃ and add ether compound, the mol ratio of magnesium halide and ether compound 20: 1～2: 1.Be warming up to 100～135 ℃ of reactions 1～4 hour, the solid after the filtration uses titanium tetrachloride in 100～135 ℃ of processing 1～4 hour again, filters, and uses anhydrous hexane 1～6 time, and vacuum-drying gets solid catalyst.Method 2) gets magnesium chloride alcohol adduct MgCl
2.xROH (x=0～5, R=C
2～C
6) shaping carrier, slowly join in-25～0 ℃ the titanium tetrachloride, be warming up to 100～140 ℃ in 1～4 hour.When being warming up to 40～100 ℃, add ether compound, the mol ratio of magnesium halide and ether compound 20: 1～2: 1 was 100～135 ℃ of reactions 2 hours.Add TiCl in the solid after filtering
4, 100～135 ℃ of reactions 2 hours.After the filtration, use hexane wash 1～5 time, vacuum-drying gets solid catalyst.
The reagent that synthetic above-mentioned catalyzer uses has: alcohol is C
1～C
10Straight chain and the alcohol of side chain, as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, primary isoamyl alcohol, hexanol, enanthol, octanol, isooctyl alcohol, nonyl alcohol, certain herbaceous plants with big flowers alcohol etc., that best is C
5～C
8Branched alkanol.Above-mentioned inertia dispersion agent is for containing C
7～C
30Aliphatic hydrocarbon and halogenated aromatic.Comprise kerosene, vaseline oil, white oil, chlorobenzene etc., preferably C
9～C
15Aliphatic hydrocarbon.
The concrete high reactivity of catalyst system for ether-type olefine polymerization of the present invention need not external electron donor during polyreaction, can be used for vapour phase polymerization, slurry polymerization or the mass polymerization of alkene, also can be used for the copolymerization of alkene, can carry out pre-polymerization repolymerization or direct polymerization earlier.Adopt hydrogen to make the polymericular weight conditioning agent, polymerization temperature is 20 ℃～90 ℃, and is best with 40 ℃～80 ℃.
It is as follows that the present invention is used for olefine polymerizing process: slurry polymerization: also use nitrogen, the abundant metathetical reaction flask of propylene at 250 milliliters through vacuum-drying, add 100 milliliters of hexanes of handling through anhydrous and oxygen-free, keeping the alkene pressure in the bottle is 770 mmhg, is controlled at certain temperature, adds AlR
3N-heptane solution stirred after 5 minutes, added catalyzer, and polyreaction 1 hour adds 100 milliliters of termination reactions of acidifying ethanol, and suction filtration is also used washing with alcohol, and vacuum-drying gets polymkeric substance.Mass polymerization: press in the reactor in 2 risings, after thorough drying, after nitrogen, propylene are fully replaced, add the propylene that 0.5-0.8 rises again.Add AlR
3N-heptane solution, stir the back and add catalyzer.Add propylene 0.4-0.6 liter again, rapidly temperature is elevated to certain temperature, polymerization is 2 hours under this temperature, emits unreacted propylene, obtains polymkeric substance.
Embodiment
Embodiment 1. catalyzer are synthetic: with adding Magnesium Chloride Anhydrous 18 grams, 80 milliliters of decane, kerosene 70ml, 30 milliliters of isooctyl alcohol and ethanol 20ml in the abundant metathetical reactor of nitrogen successively.Be heated to 100 ℃ of reactions 3 hours under stirring, solid is cooled to 25 ℃ after all dissolving, and splashes in 2 hours in 0 ℃ of 620 milliliters of titanium tetrachloride and the 100ml chlorobenzene.Be warming up to 100 ℃ in 2 hours, when being warming up to 60 ℃, add 2,2-dipropyl-1,4.8 milliliters of 3-Propanal dimethyl acetals, 100 ℃ were reacted 2 hours.After the filtration, add 450 milliliters of chlorobenzene 100ml and titanium tetrachlorides, 120 ℃ were reacted 2 hours.Behind the suction filtration, with 100 milliliters of hexanes in 55 ℃ of washings five times, 25 ℃ of 100ml hexane wash 1 time.Behind the suction filtration, vacuum-drying gets solid catalyst 23.4g gram, and titanium content is 3.06%.Olefinic polymerization: the 250ml there-necked flask after fully exchanging with nitrogen with after the propylene exchange three times, adds the heptane 100ml that handles through anhydrous and oxygen-free again.Stir down, temperature is 70 ℃, adds the n-heptane solution (3.6mmol/ml) of triethyl aluminum, adds above-mentioned catalyzer again.At propylene pressure is under the condition of 770mmHg, carries out polyreaction 1 hour, adds acidifying ethanol termination reaction, and uses the washing with alcohol polymkeric substance, and vacuum-drying obtains polymkeric substance.Operational condition and polymer property are listed in table 1.
Embodiment 2 catalyzer are synthetic: with adding Magnesium Chloride Anhydrous 22 grams, kerosene 210ml and ethanol 45ml in the abundant metathetical reactor of nitrogen successively.Be heated to 100 ℃ of reactions 2.5 hours under stirring.After the solid dissolving, be cooled to 40 ℃ and add 2,2-diisobutyl-1,5.5 milliliters of 3-Propanal dimethyl acetals reacted 1 hour again, were cooled to 25 ℃.In 1.5 hours, splash in-22 ℃ 785 milliliters the titanium tetrachloride.Be warming up to 120 ℃ in 2 hours, reacted 3 hours, in 55 ℃ of washings five times, the 100ml hexane wash is 1 time under the room temperature with 120 milliliters of hexanes.Behind the suction filtration, vacuum-drying gets solid catalyst 26.7g gram, and titanium content is 2.33%.Olefinic polymerization: the method for propylene polymerization is with embodiment 1, and operational condition and polymer property are listed in table 1.
Embodiment 3 catalyzer are synthetic: with adding Magnesium Chloride Anhydrous 11.5 grams in the abundant metathetical reactor of nitrogen successively, white vaseline oil 135ml, isooctyl alcohol 55ml.Stir and to be heated to 135 ℃ of reactions 2 hours down, solid is cooled to 25 ℃ after dissolving, and splashes in 2 hours in-25 ℃ 525 milliliters the titanium tetrachloride.2.5 be warming up to 135 ℃ in hour, when being warming up to 40 ℃, add 2-fluorenyl trihydroxybutane three methyl ether 5.6g.135 ℃ were reacted 3 hours, and in 65 ℃ of washings five times, the 60ml hexane wash is 1 time under the room temperature with 65 milliliters of hexanes.Behind the suction filtration, vacuum-drying gets solid catalyst 14.3g gram, and titanium content is 3.18%.Olefinic polymerization: the method for propylene polymerization is with embodiment 1, but the polymeric solvent is a toluene, makes promotor (3.6mmol/ml) with triisobutyl aluminium, and operational condition and polymer property are listed in table 1.
Synthetic and the olefine polymerizing process of the catalyzer of embodiment 4～5. is with embodiment 3, but the ether that embodiment 4～5 is adopted is respectively 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diamyl-1,3-Propanal dimethyl acetal.Operational condition and polymer property are listed in table 1.Embodiment 6 catalyzer are synthetic: with adding Magnesium Chloride Anhydrous 3l gram, kerosene 330ml and isooctyl alcohol 70ml in the abundant metathetical reactor of nitrogen successively.Be heated to 125 ℃ of reactions 2.5 hours under stirring, after the solid dissolving, add 2,2-dibenzyl-1,3-methoxy propane 4.2g reacted 30 minutes again.Be cooled to 25 ℃, in 2.5 hours, splash in-22 ℃ 985 milliliters the titanium tetrachloride.2.5 be warming up to 120 ℃ in hour, when being warming up to 60 ℃, add 2,2-dibenzyl-1,3-Propanal dimethyl acetal 9.3g, 120 ℃ were reacted 2 hours.Behind the suction filtration, add TiCl
4950 milliliters, 120 ℃ were reacted 2 hours.Behind the suction filtration, in 55 ℃ of washings five times, the 150ml hexane wash is 1 time under the room temperature with the 150ml hexane.Behind the suction filtration, vacuum-drying gets solid catalyst 36.8g gram, and titanium content is 3.77%.Olefinic polymerization: the method for propylene polymerization is with embodiment 1, and operational condition and polymer property are listed in table 1.
Embodiment 7 catalyzer are synthetic: get MgCl
2.2.5C
2H
5OH shaping carrier 14.5g slowly joins in-22 ℃ 385 milliliters the titanium tetrachloride.2.5 be warming up to 120 ℃ in hour, when being warming up to 60 ℃, add tetramethylolmethane tetramethyl ether 1.8g, 120 ℃ were reacted 2.5 hours.Behind the suction filtration, add TiCl
4350 milliliters, 115 ℃ were reacted 2 hours.Behind the suction filtration, in 65 ℃ of washings five times, the 50ml hexane wash is 1 time under the room temperature with the 50ml hexane.Behind the suction filtration, vacuum-drying gets solid catalyst 7.8g gram, and titanium content is 2.77%.Olefinic polymerization: the method for propylene polymerization is with embodiment 2, and operational condition and polymer property are listed in table 1.
Embodiment 8 catalyzer are synthetic: get MgCl
2.2.1C
2H
5OH shaping carrier 16.7g slowly joins in 0 ℃ 415 milliliters the titanium tetrachloride.Be warming up to 100 ℃ in 2 hours, when being warming up to 40 ℃, add 2-benzyl trihydroxybutane three methyl ether 2.8g, 100 ℃ were reacted 2 hours.After filtering, add TiCl
4410 milliliters, temperature rose to 100 ℃ and adds 2-benzyl trihydroxybutane three methyl ether 4.2g, in 120 ℃ of reactions 2 hours.Behind the suction filtration, in 60 ℃ of washings five times, the 55ml hexane wash is 1 time under the room temperature with the 55ml hexane.Behind the suction filtration, vacuum-drying gets solid catalyst 9.7g gram, and titanium content is 3.22%.Olefinic polymerization: the method for propylene polymerization is with embodiment 2, and operational condition and polymer property are listed in table 1.
The polymerizing condition of table 1. embodiment 1～8 and polymerization result
Polymerizing condition: 70 ℃, 60 minutes, AlR
3Concentration 3.6mmol/ml, M
w* 10
4, solvent is heptane or toluene
| Sequence number titanium content catalytic amount AlR 3Active M wFusing point degree of isotacticity (%) (g) (ml) (gPP/gCat.) (℃) (%) |
| Example 1 3.06 0.1220 2.2 187.3 30.33 160.2 94.7 examples 2 2.33 0.1087 3.0 276.7 12.16 163.7 97.6 |
| Example 3 3.18 0.1479 4.1 264.4 16.58 161.5 95.8 examples 4 3.02 0.1316 1.2 220.2 35.66 162.4 96.2 examples 5 3.32 0.1268 3.7 234.6 22.79 162.9 96.0 examples 6 3.77 0.1388 3.1 271.8 18.64 164.2 97.3 examples 7 2.77 0.1306 4.2 215.3 10.03 161.6 96.1 examples 8 3.22 0.1472 2.8 258.4 27.35 163.8 97.2 |
Synthetic and the olefine polymerizing process of embodiment 9～14 catalyzer is with embodiment 2, but the ether that is adopted from embodiment 9～14 is respectively 2,2-diethyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1, the 3-Propanal dimethyl acetal, 2,2-phenylbenzene-1,3-Propanal dimethyl acetal, 2-isobutyl-trihydroxybutane three methyl ethers, 2-indenyl trihydroxybutane three methyl ethers.Operational condition and polymer property are listed in table 2
The polymerizing condition of table 2. embodiment 9～14 and polymerization result
Polymerizing condition: 70 ℃, 60 minutes, AlEt
3Concentration 3.6mmol/ml, M
w* 10
4, solvent is a toluene
| The active M of sequence number titanium content catalytic amount AlEt3 wFusing point degree of isotacticity (%) (g) (ml) (gPP/gCat.) (℃) (%) |
| Example 9 3.17 0.0849 1.5 203.4 34.66 159.7 95.0 examples 10 2.43 0.0759 1.6 325.7 18.93 164.1 97.3 examples 11 4.62 0.1005 1.4 311.6 36.75 162.6 95.2 examples 12 2.86 0.08631 2.9 286.6 12.66 162.2 96.0 examples 13 3.20 0.0775 1.5 291.2 29.87 162.3 95.9 examples 14 3.04 0.0995 1.8 306.8 26.36 163.4 96.8 |
Synthetic and the olefine polymerizing process of embodiment 15～18 catalyzer is with embodiment 6, but ether difference 2-benzyloxymethyl trihydroxybutane three methyl ethers from embodiment 15～18 employings, 2,2-benzyloxy methyl isophthalic acid, the 3-Propanal dimethyl acetal, tetramethylolmethane tetrem ether, 2,2-diisopropoxy methyl isophthalic acid, the 3-Propanal dimethyl acetal.Operational condition and polymer property are listed in table 3
The polymerizing condition of table 3. embodiment 15～18 and polymerization result
Polymerizing condition: 70 ℃, 60 minutes, AlEt
3Concentration 3.6mmol/ml, M
w* 10
4, solvent is a heptane
| The active M of sequence number titanium content catalytic amount AlEt3 wFusing point degree of isotacticity (%) (g) (ml) (gPP/gCat.) (℃) (%) |
| Example 15 3.27 0.1442 2.8 236.5 18.62 161.4 95.6 examples 16 2.83 0.1052 1.7 241.6 14.35 161.1 96.0 examples 17 3.46 0.1270 3.8 263.3 9.47 162.0 95.1 examples 18 3.09 0.1357 2.5 254.8 12.69 164.5 97.3 |
Synthesizing of embodiment 19～23 catalyzer with embodiment 2, but distinguish 2,2-dibutyl-1 from the ether that embodiment 19～23 adopts, the 3-Propanal dimethyl acetal, 2,2-diamyl-1,3-Propanal dimethyl acetal, 2-benzyl trihydroxybutane three methyl ethers, 2,2-benzyloxy methyl isophthalic acid, 3-Propanal dimethyl acetal and 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal.Olefinic polymerization: 2 raise presses in the reactor, uses nitrogen replacement three times after thorough drying, after propylene is fully replaced, adds 0.5 liter propylene again, adds the n-heptane solution (0.9mmol/ml) of triethyl aluminum.Add 0.5 liter of propylene again, temperature is elevated to 70 ℃ rapidly, polymerization is 2 hours under this temperature, emits unreacted propylene, obtains polymkeric substance.Operational condition and polymer property are listed in table 4.
The polymerizing condition of table 4. embodiment 19～23 and polymerization result
Polymerizing condition: 70 ℃, 2 hours, AlEt
3Concentration 0.9mmol/ml, active * 10
4, M
w* 10
4
| The active M of sequence number titanium content catalytic amount AlEt3 wFusing point degree of isotacticity (%) (g) (ml) (gPP/gCat.) (℃) (%) |
| Example 19 3.42 0.0052 0.7 7.36 14.32 163.6 96.7 examples 20 2.98 0.0047 0.5 6.95 15.86 162.5 96.2 examples 21 4.46 0.0049 1.0 8.72 8.67 164.0 97.4 examples 22 4.19 0.0038 0.8 9.46 10.32 163.7 98.2 examples 23 4.05 0.0044 0.9 12.8 11.87 164.2 98.6 |
Claims (11)
1. catalyst system for ether-type olefine polymerization, contain Primary Catalysts and promotor, it is characterized in that a kind of solid catalyst that described Primary Catalysts is made up of magnesium chloride support load titanium tetrachloride and ether compound, wherein the mole proportioning of magnesium chloride and ether compound is 50: 1～1: 1, promotor is triethyl aluminum and triisobutyl aluminium, and the structural formula of above-mentioned ether compound is:
X
1, X
2, X
3And X
4Be-oxyl or alkyl.
2. a kind of catalyst system for ether-type olefine polymerization according to claim 1 is characterized in that described ether compound is a diether compounds, three ether compounds or tetraether compound.
3. ether compound according to claim 2 is characterized in that the substituent X of described diether compounds
1=X
2Be methoxyl group, X
3And X
4Be alkyl, diether compounds is: 2, and 2-diethyl-1,3-Propanal dimethyl acetal, 2,2-dipropyl-1,3-Propanal dimethyl acetal, 2,2-dibutyl-1,3-Propanal dimethyl acetal, 2,2-diisobutyl-1,3-Propanal dimethyl acetal, 2,2-diamyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1,3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal, 2,2-dibenzyl-1,3-Propanal dimethyl acetal or 2,2-phenylbenzene-1,3-Propanal dimethyl acetal.
4. ether compound according to claim 2 is characterized in that the substituent X of described three ether compounds
1=X
2=X
3Be methoxyl group, X
4Be alkyl, three ether compounds are: 2-benzyl trihydroxybutane three methyl ethers, 2-isobutyl-trihydroxybutane three methyl ethers, 2-indenyl trihydroxybutane three methyl ethers or 2-fluorenyl trihydroxybutane three methyl ethers.
5. ether compound according to claim 2 is characterized in that the substituent X of described tetraether compound
1, X
2, X
3And X
4Be-oxyl, the tetraether compound is: tetramethylolmethane tetramethyl ether, tetramethylolmethane tetrem ether, 2,2-diisopropoxy methyl isophthalic acid, 3-Propanal dimethyl acetal, 2,2-benzyloxy methyl isophthalic acid, 3-Propanal dimethyl acetal or 2-benzyloxy trihydroxybutane three methyl ethers.
6. the preparation method of a kind of catalyst system for ether-type olefine polymerization according to claim 1, it is characterized in that carrying out in the following order: (1) is with magnesium chloride, inertia dispersion agent decane or kerosene and alcohol mix, heated and stirred, in 80～150 ℃ of reactions 1～8 hour, be cooled to 20～80 ℃ and add ether compound, be cooled to 25 ℃, obtain the magnesium chloride alcoholic solution, alcohol is 1～10 with the mol ratio of magnesium chloride, magnesium chloride and ether compound mol ratio are 50～0, the concentration of magnesium chloride in dispersion agent is 5-30g/l, and (2) with above-mentioned magnesium chloride alcoholic solution, joins in-25～0 ℃ the titanium tetrachloride solution, stirred 1～3 hour, add ether compound at 40～100 ℃, the mol ratio of magnesium chloride and ether compound 20: 1～2: 1 is warming up to 100～135 ℃ of reactions 1～4 hour, solid after filtering was handled 1～4 hour in 100～135 ℃ with titanium tetrachloride again, filter washing, the dry solid catalyst that gets.
7. the preparation method of a kind of catalyst system for ether-type olefine polymerization according to claim 1, it is characterized in that magnesium chloride alcohol adduct shaping carrier, join in-25～0 ℃ the titanium tetrachloride, in the time of 40-100 ℃, add ether compound, the mol ratio of magnesium chloride and ether compound 20: 1～2: 1 100～135 ℃ of reactions 2 hours, adds TiCl in the solid after overanxious
4,, filter washing, the dry solid catalyst that gets 100～135 ℃ of reactions 2 hours.
8. the preparation method of a kind of catalyst system for ether-type olefine polymerization according to claim 6, the mol ratio that it is characterized in that above-mentioned alcohol and magnesium chloride is 2～5.
9. according to the preparation method of claim 6 or 7 described a kind of catalyst system for ether-type olefine polymerization, it is characterized in that described diether compounds is: 2,2-dibutyl-1, the 3-Propanal dimethyl acetal, 2,2-diisobutyl-1, the 3-Propanal dimethyl acetal, 2,2-two cyclopentyl-1, the 3-Propanal dimethyl acetal, 2,2-dicyclohexyl-1,3-Propanal dimethyl acetal or 2,2-dibenzyl-1, the 3-Propanal dimethyl acetal.
10. according to the preparation method of claim 6 or 7 described a kind of catalyst system for ether-type olefine polymerization, it is characterized in that described three ether compounds are: 2-benzyl trihydroxybutane three methyl ethers, 2-isobutyl-trihydroxybutane three methyl ethers, 2-indenyl trihydroxybutane three methyl ethers or 2-fluorenyl trihydroxybutane three methyl ethers.
11. preparation method according to claim 6 or 7 described a kind of catalyst system for ether-type olefine polymerization, it is characterized in that described tetraether compound is: tetramethylolmethane tetramethyl ether, tetramethylolmethane tetrem ether, 2,2-diisopropoxy methyl isophthalic acid, 3-Propanal dimethyl acetal, 2,2-benzyloxy methyl isophthalic acid, 3-Propanal dimethyl acetal or 2-benzyloxy trihydroxybutane three methyl ethers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297574C (en) * | 2003-08-20 | 2007-01-31 | 中国石油化工股份有限公司 | Catalyst component for olefine polymerization and catalyst thereof |
| CN104591979A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Compound, catalyst solid component containing compound, and catalyst |
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2000
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297574C (en) * | 2003-08-20 | 2007-01-31 | 中国石油化工股份有限公司 | Catalyst component for olefine polymerization and catalyst thereof |
| CN104591979A (en) * | 2013-11-01 | 2015-05-06 | 中国石油化工股份有限公司 | Compound, catalyst solid component containing compound, and catalyst |
| CN104591979B (en) * | 2013-11-01 | 2016-09-21 | 中国石油化工股份有限公司 | A kind of compound, catalyst solid constituent containing described compound and catalyst |
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