CN1132860C - Process for preparing high-density syndiotactic polypropylene by liquid-phase bulk polymerization - Google Patents
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- CN1132860C CN1132860C CN 01119815 CN01119815A CN1132860C CN 1132860 C CN1132860 C CN 1132860C CN 01119815 CN01119815 CN 01119815 CN 01119815 A CN01119815 A CN 01119815A CN 1132860 C CN1132860 C CN 1132860C
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Abstract
The present invention relates to a method of preparing high-density syndiotactic polypropylene by adopting liquid-phase bulk polymerization. The method comprises that a carried metallocene catalyst is added in a polymerizing and stirring reaction still; the prepolymerization is firstly carried out under the condition of temperature below polymerization temperature; and then, propene is polymerized at 50 to 100 DEG C and at the pressure of 2.0 to 4.0MPa. The reaction still is provided with a spiral stirring paddle. Syndiotactic polypropylene with the density of 0.35 to 0.48 g/cm<3> can be prepared by adopting the method.
Description
The present invention is a kind of preparation method of high-bulk-density syndiotactic polyolefins, specifically, is a kind of method that adopts liquid-phase bulk polymerization to prepare the high-bulk-density syndiotactic polypropylene.
Syndiotactic polypropylene sPP is known very early, but up to J.A.Ewen adopt have asymmetrical metallocene catalyst system just obtain normal polypropylene between height (J.Am.Chem.Soc., 1988,110,6255-6256).But, the sPP that uses the homogeneous phase metallocene catalyst to prepare in slurry or mass polymerization is normally fluffy, and tap density is low, only is 0.1～0.2 gram per centimeter
3, particle is tiny, broad particle distribution.The polymkeric substance of this fluffy form is restricted its application because of being difficult to processing.For addressing this problem, people are from improving the metallocene catalysts method and improving polymerization technique two aspects and carried out multiple trial.
Te Kaiping 4-224808, spy open that flat 5-125112, spy open flat 5-155925, the spy opens patents such as flat 3-263410 and the flat 4-31403 of Te Kai, provide by improving supported catalyst to prepare the polyolefinic method of high-density syndiotactic.Wherein, the spy opens flat 3-263410 and adopts porous inorganic oxide,, will have the metallocene of bridging unsymmetric ligand and methylaluminoxane MAO and be carried in the presence of organic solvent and make catalyzer on the carrier as carrier as silicon-dioxide, aluminum oxide etc.Carry out the mass polymerization of propylene gas phase with it, can obtain bulk density is 0.37g/cm
3, a normality is 0.915 sPP.
EP0354893 provides a kind of method that adopts liquid-phase bulk polymerization to prepare high bulk density, macrobead sPP.It is by being starkly lower than polymerization temperature, preferably is lower than under 40 ℃ the condition, makes olefinic monomer carry out pre-polymerization earlier in the presence of homogeneous metallocene and methylaluminoxane, and the number of times of pre-polymerization is preferably twice.And then make alkene carry out polyreaction under 85 ℃ being lower than.This method its objective is and will avoid producing number of polymers to obtain highdensity polymkeric substance when being lower than polymerization temperature by the sPP of low temperature pre-polymerization, intensification pre-polymerization and polyreaction three phases production high-bulk-density.It is to carry out under 1200 rev/mins of high rotating speeds at rotating speed that common stirring rake is adopted in polymerization.
Produce in the isotatic polypropylene reaction in the gas phase mass polymerization, for enhance heat, USP6,114,478 disclose a kind of method that adopts the ribbon stirring rake to prepare powdered polypropylene.This method is introduced reactive system with propylene feedstocks and catalyzer by reactor head and one or two perpendicular tubule, and described inlet tube is positioned at the gas-phase space of reactor, and its end is in the upper end of stirring reaction bed.This fresh propylene enters the method for reactor than introducing the method for propylene from side line from the top, owing to catalyzer is sneaked in the propylene before entering reactor, therefore shortened mixing time, and reaction temperature profile is more even, thereby polymerization yield rate is increased.
The purpose of this invention is to provide a kind of liquid-phase bulk polymerization and produce the method for the syndiotactic polypropylene of high-bulk-density.The syndiotactic polypropylene smalls that this method is produced is few, but caking in the basically eliminate polymerization process and sticking still phenomenon.
We find, when being equipped with syndiotactic polypropylene with the liquid-phase bulk polymerization legal system, adopt the ribbon stirring rake, can not only strengthen the polyreaction thermodiffusion under low mixing speed, make reaction more even, also can reduce the generation of fine particle, prevent sticking still.Before polymerization, adopt the low temperature prepolymerization method simultaneously, can make the syndiotactic polypropylene of high-bulk-density.
Specifically, method of the present invention is included in the polymerization stirred autoclave and adds carried metallocene catalyst, earlier carry out prepolymerization under the polymerization temperature being lower than, and then make propylene carry out polyreaction at 50～100 ℃, 3.0～4.0MPa, described reactor has the ribbon stirring rake.
Described ribbon stirring rake can be single ribbon stirring rake or two ribbon stirring rake.Polymerization reaction kettle is vertical stirring tank or horizontal stirring tank, and the structure of described single ribbon stirring rake and two ribbon stirring rakes as shown in Figure 1.The pitch h of ribbon stirring rake equates among Fig. 1, should be 0.70～1.00 times of still diameter, and ribbon radius d is 0.90～0.99 times of still radius, and ribbon width of blade c is 0.09～0.12 times of still diameter.If adopt two ribbon stirring rakes, its two ribbons should be the axle center symmetric offset spread, shown in Fig. 1 (b).
Method of the present invention needs to carry out prepolymerization at low temperatures earlier, and then carries out polyreaction.The temperature of reaction of pre-polymerization is 10～40 ℃, and preferred 15～40 ℃, the time is preferably 0.1～2.0 hour, preferred 10～40 minutes.Prepolymer can be selected propylene or ethene, is preferably propylene.The ribbon stirring rake stirs under lower rotating speed during prepolymerization, and its rotating speed is 10～100 rev/mins, preferred 20～70 rev/mins.
After prepolymerization, add propylene liquid and carry out polyreaction, polyreaction preferably is controlled at 60～80C, preferred 60～75 ℃.The reaction heat-up rate is unrestricted, and pressure should be controlled at proper range in the polyreaction, so that propylene is in a liquid state, polymeric improves the rotating speed of ribbon stirring rake simultaneously, and the polymerization stage appropriate rotating speed is 100～800 rev/mins, preferred 200～500 rev/mins.
It is 0.35～0.48 gram per centimeter that the inventive method can be prepared bulk density
3Syndiotactic polypropylene, its size distribution is even, fine powder is few.
The used catalyzer of the present invention is the metallocene catalyst with unsymmetric ligand structure of load, specifically comprises following component:
A) the following A of expression formula
2C[CpR
1] [FluR
2] MeQ
2The metallocene active ingredient,
B) alkylaluminoxane and
C) carrier silicon-dioxide,
Wherein in the metallocene expression formula A for replacing or unsubstituted aryl, C
1～C
6Alkyl or silylation; Cp is a cyclopentadienyl, and Flu is a fluorenyl, R
1, R
2Be selected from hydrogen, C respectively
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy and hydroxyl or halogen; Me is a kind of element of IVB family in the periodic table of elements; Q is a halogen.
The preferred phenyl of A, naphthyl, pyridyl or C in the above-mentioned metallocene expression formula
1～C
3Alkyl, as methyl, ethyl, propyl group, R
1, R
2Preferred hydrogen or C
1～C
3Alkyl, the preferred zirconium of Me, the preferred chlorine of Q.
Described b) the component alkylaluminoxane is a promotor, and its structure can be linear or the cyclic polymkeric substance, and preferred promotor is a methylaluminoxane.
The surface-area of described carrier silicon-dioxide is 150～500 meters
2/ gram, preferred 200～400 meters
2/ gram, pore volume are 1.0～5.0 milliliters/gram, preferred 2.0～4.0 milliliters/gram.
The preparation method of above-mentioned loaded catalyst comprises a) described metallocene active ingredient and partially dehydroxylated SiO
2Handle with the toluene solution of alkylaluminoxane respectively and form suspension, and then two kinds of suspension are mixed 30～95 ℃ of abundant contacts, the solid that removes the gained that desolvates makes with alkane washing after drying.Preparation process comprises particularly:
(1) SiO
2Dehydroxylation: 200～600 ℃ of following calcinations, the time is preferably 4～8 hours with silica gel, makes its The adsorbed hydroxyl content be not more than 0.6 mmole/gram SiO
2
(2) SiO
2Processing: with the SiO of dehydroxylation
2With alkylaluminoxane according to 1: 0.2～5.0 weight ratio stirring at room 0.1～10 hour in the presence of the toluene medium, preferred 1～4 hour.
(3) processing of metallocene: with above-mentioned expression formula is A
2C[CpR
1] [FluR
2] MeQ
2Metallocene active ingredient and alkylaluminoxane were according to 1: 0.5～50 weight ratio stirring at room 0.1～10 hour in the toluene medium, preferred 1～4 hour.
(4) load of metallocene active ingredient: two kinds of solution that make in (2) and (3) are mixed, at 30～95 ℃, stirred 0.1～10 hour preferred 1～4 hour under preferred 35～55 ℃ of conditions.Remove the solvent in the reactant then, resistates is used hexane wash, is filtered after drying at 30～80 ℃ under preferred 35～45 ℃ condition.
The reactant of (4) step gained removes to desolvate and concentrates in the above-mentioned preparation process, the residuum hexane wash, and the dosage of hexane should be 1～3 times of residuum volume, washing times can be 1～4 time, washing after-filtration, drying, drying temperature is 30～80 ℃, the time is 1～5 hour.
In the described carried metallocene catalyst preparation, the metallocene active ingredient a) can adopt the metallocene ether inorganic salt adducts with following general expression
A
2C[CpR
1] [FluR
2] MeQ
2RXR ' nMe ' Q
2/nIn the formula, A is for replacing or unsubstituted aryl; Cp is a cyclopentadienyl, and Flu is a fluorenyl, R
1, R
2Be selected from hydrogen, C respectively
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy and hydroxyl or halogen;
Me is a kind of element of IVB family in the periodic table of elements; Q is a halogen, and R and R ' are identical or different, are selected from C
1～C
6Alkyl; X is oxygen or sulphur; Me ' is basic metal or alkaline-earth metal; The value of n is 1 or 2.
The preferred phenyl of A, naphthyl or pyridyl in the described metallocene ether inorganic salt adducts expression formula; R
1, R
2Preferred hydrogen of difference or C
1～C
3Alkyl; The preferred zirconium of Me, the preferred chlorine of Q, the preferred ether of RXR ', Me ' preferred lithium, n value are 2.
So-called adducts be a certain material when forming crystal, another kind of material joins in an orderly manner in the crystal defect of this material and forms, a material combines with Intermolecular Forces with another material.Metallocene adduct described in the present invention similarly, the reactive force between each component of adducts can improve the stability of metallocene adduct, the component beyond the metallocene has no adverse effect to olefinic polyreaction except that stablizing metallocene.So the adducts that makes can be without the recrystallization metallocene of purifying, thereby has simplified preparation process.The concrete preparation method of metallocene adduct of the present invention sees CN1140720A for details.
The promotor that contains in the loaded catalyst of the present invention's preparation is 50～500: 1 with the ratio of metallocene with Al/ transition metal molar ratio computing, preferred 50～300: 1, and the content of transition metal is 0.1～2.0 heavy % in the catalyzer.
The present invention adopts the liquid-phase bulk polymerization method to prepare syndiotactic polypropylene, is divided into two steps of prepolymerization and polymerization, and polymerization process does not need to add promotor again, reaction adopts the ribbon stirring rake to stir, can increase mass-transfer efficiency, reduce sticking still, make the sPP of high-bulk-density.
Further specify the present invention below by example, but the present invention is not limited to this.
Example 1
Prepare loaded catalyst with metallocene adduct.
A) prepare different hydrocinnamyl-(fluorenyl)-(cyclopentadienyl) zirconium dichloride ether lithium chloride adducts Ph
2C-(9-Flu)-(Cp) ZrCl
2Et
2O2LiCl
In 250 milliliters of Schlenk reaction flasks, add 5.10 gram (30.7 mmole) fluorenes, after 60 milliliters of anhydrous tetrahydro furans (THF) dissolving, under room temperature, add the phenyl lithium diethyl ether solution of 38.4 milliliters of (30.7 mmole) 0.8 mol by constant pressure funnel, at room temperature reacted 2 hours.Add 7.07 gram (30.7 mmole) phenylbenzene fulvene then, at room temperature continue reaction after 12 hours, add the suitable quantity of water hydrolysis.Tell organic phase, with the mixed solution recrystallization of methyl alcohol and chloroform, obtain the different hydrocinnamyl of white powder two cyclopentadienyl ligands-(fluorenyl) cyclopentadiene Ph of 6.2 grams behind the vacuum concentration
2C-(9-Flu)-Cp, productive rate are 51%.
2.0 gram (5.0 mmole) above-mentioned parts that obtain are dissolved in 20 milliliters of ether, at 0 ℃ of 6.4 milliliters of n-buli hexane solution (10 mmole) that add 1.6 mol down, after at room temperature reacting 15 hours, gained suspension is cooled to-50 ℃, adds 1.16 gram (5.0 mmole) ZrCl
4, under agitation make mixture slowly rise to room temperature, filter and, obtain 3.1 after the drying and restrain solid powdery adducts Ph with a small amount of ether washing leaching cake
2C-(9-Flu)-(Cp) ZrCl
2Et
2O2LiCl, its zirconium content are 11.0 heavy %, and yield is counted 85 heavy % with zirconium.
B) silica gel dehydroxylation
Getting trade names is the silica gel of Davison 955 (U.S., Grace company), at N
2Under the protection, 200 ℃ activate 2 hours in fluidized-bed, and 600 ℃ activate 4 hours, take out while hot, put in the vacuum drier, vacuumize and are cooled to room temperature, and inflated with nitrogen is preserved.
C) preparation supported catalyst
Get the SiO of 352 milligrams of dehydroxylations
2, 7.5 milliliters of the MAO toluene solutions (U.S. Albemarle company) of adding concentration 10% add 10 milliliters of toluene again, and room temperature reaction 1 hour gets mixed liquor A.
Get 22 milligrams of the metallocene adducts that a) step makes, add 7.5 milliliters of the MAO solution of same concentration, add 10 milliliters of toluene again, room temperature reaction 1 hour, mixed liquid B.
Mixed liquid B is added in the mixed liquor A, and 55 ℃ of reactions 1 hour vacuumize to remove under same temperature then and desolvate, and resistates with 20 milliliters of hexane wash three times, vacuumized 2 hours under room temperature, and 40 ℃ of dryings 2 hours must loaded catalyst M.Zr content 0.17 heavy % in the catalyzer, Al content 14.67 heavy %.
Example 2
This example adopts the metallocene-prepared loaded catalyst.
Method according to example 1 prepares catalyzer, and different is to replace metallocene adduct with 11 milligrams of sec.-propyls-(fluorenyl)-(cyclopentadienyl) zirconium dichloride, obtains catalyst n, and its Zr content is 0.15 heavy %, and Al content is 15.87 heavy %.
Example 3
Adopt liquid-phase bulk polymerization to prepare syndiotactic polypropylene.
(1) system handles
The diameter that will have single ribbon stirring rake shown in Fig. 1 (a) is 5 liters of vertical polymeric kettles of 143 millimeters under 80～90 ℃ of vacuum dry 3～5 hours, reduce to normal temperature, the pitch h of described ribbon stirring rake is 105 millimeters, and ribbon radius d is 70 millimeters, and the wide c of ribbon blade is 15 millimeters.Polymeric kettle with refining propylene displacement 3 times, makes polymeric kettle be in propylene atmosphere with high pure nitrogen displacement 3 times again.20 milliliters of triisobutyl aluminium hexane solutions that add 0.74 mol guarantee system's anhydrous and oxygen-free.Speed stirring with 20 rev/mins was carried out pre-polymerization after 20 minutes.
(2) prepolymerization
Bring 4.46 gram supported catalyst M into polymeric kettle with 1.2 liters of refining propylene, mixing speed increases to 50 rev/mins, feeds liquid propene, and prepolymerization is 40 minutes under 40 ℃, the condition of 1.9MPa.
(3) polyreaction
Feed 2.1 liters of refining propylene in polymeric kettle, and mixing speed is increased to 250 rev/mins, temperature is warming up to 70 ℃ after 5 minutes, and pressure is 2.9MPa, polymerization 2 hours.The unreacted propylene of decompression emptying, termination reaction obtains 816 gram class globular polymer particles.Catalyst activity 4.95 * 10
6During gram/mole Zr, particulate polymers tap density 0.48 gram per centimeter
3, polymer property sees Table 1.The electron microscope photo scanning of polymer beads as shown in Figure 2, as shown in Figure 2, polymkeric substance has good particle form, the surface closely knit.
Example 4
Method according to example 3 prepares syndiotactic polypropylene, and different is that pre-polymerization process adds 2.32 gram catalyzer M, 30 ℃ of prepolymerization temperature, 25 minutes time.Add 1.76 liters of refining propylene during polymerization, mixing speed is 250 rev/mins, and the post polymerization temperature rose to 75 ℃ in 10 minutes, and pressure is 2.9MPa.Polymerization is 2 hours with this understanding, the unreacted propylene of decompression emptying, reaction terminating.Obtain 730 gram class globular polymer particles, catalyst activity 5.68 * 10
6During gram/mole Zr, particulate polymers tap density 0.46 gram per centimeter
3, polymer property sees Table 1.The electron microscope photo scanning of polymer beads as shown in Figure 3, as shown in Figure 3, the polymer beads form is better.
Example 5
Method by example 3 is carried out polyreaction, and the stirring rake that different is in the vertical retort is the two ribbon stirring rakes shown in Fig. 1 (b).
Pre-polymerization process adds 2.84 gram catalyzer M, 30 ℃ of prepolymerization temperature, 20 minutes time, 200 rev/mins of mixing speed.
After prepolymerization finishes, add 1.50 liters of refining propylene to reactor, mixing speed is increased to 450 rev/mins simultaneously, after 10 minutes, the polymeric kettle temperature rises to 70 ℃, and pressure is 2.9MPa.Polyreaction is 2 hours with this understanding, the unreacted propylene of decompression emptying, reaction terminating.Obtain 334 gram class spherical polymer particles, catalyst activity 3.18 * 10
6During gram/mole Zr, particulate polymers tap density 0.40 gram per centimeter
3, polymer property sees Table 1.The electron microscope photo scanning of polymer beads as shown in Figure 4, as shown in Figure 4, the polymer beads form is better.
Example 6
Method by example 3 is carried out the liquid propylene polymerization, and different is that the catalyst n that adds 3.1 grams replaces catalyzer M, obtains 143 gram class spherical polymer particles, catalyst activity 2.8 * 10
6During gram/mole Zr, particulate polymers tap density 0.38 gram per centimeter
3
Comparative Examples
Press example 3 polymerization processs, adopt the vertical response still that has anchor formula stirring rake to carry out the liquid propylene polymerization, different is that (2) step pre-polymerization process adds 2.5 gram catalyzer M, 30 ℃ of prepolymerization temperature.Prepolymerization is added 1.76 liters of refining propylene after finishing in reactor, carry out polyreaction.At 70 ℃, 2.9MPa, mixing speed polymerization 2 hours under 250 rev/mins the condition, the unreacted propylene of emptying that reduces pressure then, reaction terminating.Obtain 245 gram class spherical polymer particles, catalyst activity 2.2 * 10
6During gram/mole Zr, particulate polymers tap density 0.21 gram per centimeter
3, polymer property sees Table 1.The electron microscope photo scanning of polymer beads as shown in Figure 5, Fig. 5 shows that the polymer beads surface is fluffy, and is closely knit inadequately, so the bulk density of product is lower.
Table 1
| Instance number | Tap density, gram per centimeter 3 | Between normality, rrrr% | Molecular weight Mw * 10 4， | Particle diameter (diameter) distributes, heavy % | ||
| ＜0.4 millimeter | 0.4～2.8 millimeters | ＞2.8 millimeters | ||||
| Example 3 examples 4 examples 5 examples 6 Comparative Examples | 0.48 0.46 0.40 0.38 0.21 | 78.94 78.37 78.41 81.11 78.37 | 31.7 33.8 30.6 20.6 37.5 | 0.98 1.92 ＜0.3 0.85 11.4 | 94.4 89.6 95.2 91.3 86.3 | 4.66 8.49 3.59 7.85 2.30 |
Claims (11)
1, a kind of method that adopts liquid-phase bulk polymerization to prepare high-density syndiotactic polypropylene, be included in the polymerization stirred autoclave and add carried metallocene catalyst, earlier carry out prepolymerization under the polymerization temperature being lower than, and then make propylene carry out polyreaction at 50～100 ℃, 2.0～4.0MPa, described reactor has the ribbon stirring rake, and carried metallocene catalyst contains a) the following A of expression formula
2C[CpR
1] [FluR
2] MeQ
2Metallocene active ingredient, b) alkylaluminoxane and c) carrier silicon-dioxide, wherein in the metallocene expression formula A for replacing or unsubstituted aryl, C
1～C
6Alkyl, silylation; Cp is a cyclopentadienyl, and Flu is a fluorenyl, R
1, R
2Be selected from hydrogen, C respectively
1～C
12Alkyl, alkoxyl group, aryl, aralkoxy and hydroxyl or halogen; Me is a kind of element of IVB family in the periodic table of elements; Q is a halogen.
2, in accordance with the method for claim 1, it is characterized in that described stirring rake is single ribbon stirring rake or two ribbon stirring rake.
3, according to claim 1 or 2 described methods, the rotating speed of ribbon stirring rake is 10～200 rev/mins when it is characterized in that prepolymerization, and the rotating speed of ribbon stirring rake is 100～800 rev/mins during polyreaction.
4, according to claim 1 or 2 described methods, it is characterized in that described prepolymerization temperature of reaction is 10～40 ℃, the time is 20～60 minutes.
5,, it is characterized in that described prepolymer is propylene or ethene according to claim 1 or 2 described methods.
6, according to claim 1 or 2 described methods, the density that it is characterized in that described syndiotactic polypropylene is 0.35～0.48 gram per centimeter
3
7, in accordance with the method for claim 1, it is characterized in that a) A is phenyl, C in the described metallocene expression formula
1～C
3Alkyl, R
1, R
2Be respectively hydrogen or C
1～C
3Alkyl, Me is a zirconium, Q is a chlorine, b) described alkylaluminoxane is a methylaluminoxane, the mol ratio of zirconium and aluminium is 50～300: 1 in the catalyzer.
8, in accordance with the method for claim 1, the preparation method who it is characterized in that described carried metallocene catalyst comprises metallocene active ingredient shown in a) and partially dehydroxylated SiO
2Handle with the toluene solution of alkylaluminoxane respectively and form suspension, and then two kinds of suspension are mixed 30～95 ℃ of abundant contacts, remove and desolvate, the solid of gained washs after drying with alkane.
9, in accordance with the method for claim 1, the preparation method who it is characterized in that described carried metallocene catalyst comprises and will have the metallocene ether inorganic salt adducts and the partially dehydroxylated SiO of following general expression
2Handle with the toluene solution of alkylaluminoxane respectively and form suspension, and then two kinds of suspension are mixed 30～95 ℃ of abundant contacts, remove and desolvate, the solid of gained washs after drying with alkane,
A
2C[CpR
1] [FluR
2] MeQ
2RXR ' nMe ' Q
2/nA is for replacing or unsubstituted aryl in the described adducts expression formula; Cp is a cyclopentadienyl, and Flu is a fluorenyl, R
1, R
2Be selected from hydrogen, C respectively
1～C
12Alkyl, alkoxyl group, aryl, aralkoxy and hydroxyl or halogen;
Me is a kind of element of IVB family in the periodic table of elements; Q is a halogen, and R and R ' are identical or different, are selected from C
1～C
6Alkyl; X is oxygen or sulphur; Me ' is basic metal or alkaline-earth metal; The value of n is 1 or 2.
10, in accordance with the method for claim 9, it is characterized in that A is phenyl, naphthyl or pyridyl in the described metallocene adduct expression formula; R
1, R
2Be respectively hydrogen or C
1～C
3Alkyl; Me is a zirconium, and Q is a chlorine, and RXR ' is an ether, and Me ' is a lithium, and the n value is 2.
11, according to claim 8 or 9 described methods, used alkylaluminoxane is a methylaluminoxane when it is characterized in that preparing carried metallocene catalyst, and two kinds of solution mix except that the back gained solid hexane wash of desolvating.
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Granted publication date: 20031231 |
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| CX01 | Expiry of patent term |