CN101205263B - Olefin polymerization solid catalyst carrier and preparation thereof - Google Patents
Olefin polymerization solid catalyst carrier and preparation thereof Download PDFInfo
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- CN101205263B CN101205263B CN2006101695060A CN200610169506A CN101205263B CN 101205263 B CN101205263 B CN 101205263B CN 2006101695060 A CN2006101695060 A CN 2006101695060A CN 200610169506 A CN200610169506 A CN 200610169506A CN 101205263 B CN101205263 B CN 101205263B
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Abstract
An olefin polymerization solid catalyst vector has the following general expression formula: (MgCl2)(R1MgCl)pMgq[Ti(OR<2>)<4>]x [Si(OR3)4]y; in the formula, R1 and R2 are respectivley selected from alkyls with carbon atoms ranging from C2 to C4 and R3 is selected from the alkyl with carbon atoms ranging from C1; p value ranges from 0.4 to 0.8, q value ranges from 0.02 to 0.15, x value ranges from0.03 to 0.09 and y value ranges from 0.1 to 0.3. The solid catalysts obtained through the supported metallocene or non-metallocene after the vector is activated by alcohols and treated by the alkylaluminium are used for the olefin polymerization with higher catalytic activity and the prepared polymer particles have better morphology and higher bulk density.
Description
Technical field
The present invention is a kind of olefin polymerization solid catalyst carrier and preparation method, specifically, is a kind of carrier and preparation method who contains magnesium chloride.
Background technology
The efficient polyolefin catalyst of loading type is many to be carrier with the solid inorganic thing, and the carrying transition metal compound is made, and particularly metallocene and non-metallocene catalyst all need carry out loadization earlier in application usually.Loadization is in order to satisfy more polymerization technique process, as the needs of vapour phase polymerization, slurry polymerization, improve the catalytic efficiency of active ingredient, increase the stability in active centre, and improve the form of polymkeric substance, improve the apparent density of polymkeric substance and reduce the consumption of promotor.Therefore the character of carrier is most important to the loaded catalyst Effect on Performance.
Comparatively commonly used and effective supported catalyst agent carrier is for being magnesium chloride.This is because magnesium chloride not only can play the physics dissemination, and the active centre number is increased, and can also reduce the activation energy of polyreaction by increasing the cloud density in active centre with the Chemical bond in active centre, improves vinyl polymerization speed.People such as K.Soga are at J.Polyrn.Sci., Polym.Chem.Ed.35, the polymerization that the cyclopentadiene titanous chloride is carried on the catalyzer that makes on the magnesium chloride support discussed in the article that 291-297 delivers, this catalyzer and triisobutyl aluminum cocatalyst are used and can prepare polypropylene, and have high polymerization activity.
Prepare active MgCl
2The method of carrier is used polishing in early days, is about to each component of catalyzer and grinds altogether in ball mill with certain proportioning.The main effect of grinding is to destroy MgCl
2Crystalline structure that it is become is unordered, MgCl
2Crystal diminishes, and specific surface area increases, and active ingredient embeds MgCl
2Disperseed fully in the lattice defect.This method technology is simple, but the catalyst activity that makes is not high, and form is bad.
Anhydrous MgCl
2The chemical activation method be that it is dissolved in as in the electron donor compounds such as alcohol, ester or ethers, form adduct solution, the method with thermal treatment and evaporation removes the electron donor compound then, makes MgCl
2Recrystallization, or make MgCl with technology such as condensation and muriate precipitations
2From solution, separate out again.CN1085569A discloses a kind of method for preparing titanium catalyst, and the pure and mild hydrocarbon solvent of six carbon atom forms magnesium solution to this method with containing at least with magnesium halide, and then makes solid mangnesium-aluminium complex with the organo-aluminium compound reaction.This solid magnesium aluminum compound is suspended in the hydrocarbon solvent, adds the solid titanium catalyst that tetravalent titanium compound promptly obtains being applicable to vinyl polymerization.
With Mg (OR)
2, compound such as Grignard reagent and dialkyl magnesium and chlorine-containing compound reaction can prepare the active MgCl of polymolecularity
2Carrier; The MgCl that contains 6 crystal water
26H
2O also can be used as starting raw material, through obtaining active MgCl after the dehydration
2Carrier; Metal magnesium powder also is the magnesium source of using always, with the alkyl chloride reaction, can obtain the MgCl of nascent state in the presence of ethers or alkane solvent
2
CN1054776A discloses a kind of olefin polymerization catalysis, and its carrier magnesium chloride is to make by tertiary butyl chloride and dibutylmagnesium are reacted, and adds electron donor compound isoamyl oxide in the preparing carriers process, obtains ball type carrier.Then this carrier is activated with a small amount of propyl carbinol in the presence of normal hexane, after the normal hexane washing, be suspended in the normal hexane, the toluene solution reaction with containing two (cyclopentadienyl) zirconium dichloride makes solid catalyst.Need add promotor MAO during polymerization, and to make the Al/Zr mol ratio be 2500.
EP0878483 and EP0878484 react in the presence of electron donor with magnesium powder and two enparas, and the nascent state magnesium chloride of generation is a carrier, make catalyzer with the metallocene compound impregnated carrier then in this electron donor solvent.The toluene solution that need add promotor MAO during polymerization, its add-on is 5000 for the Al/Zr mol ratio.
It is the loaded catalyst of catalyst activity component with the semi-metallocene that contains the beta-diketo derivative part that CN00124667.4 discloses a kind of, its preparation method is that the butter solution that will be dissolved in tetrahydrofuran (THF) fully contacts with the semi-metallocene solution that is dissolved in polar organic solvent, in mixing solutions, add non-polar organic solvent then, being placed to precipitation fully separates out, filter drying then.Bad with the granules of catalyst form that this method makes, and the charge capacity of active ingredient is limited, it is lower that catalyzer carries the titanium amount, so the polymerization efficiency of unit mass catalyzer is not high, and the resulting polymers bulk density is low, and form is not good.
Summary of the invention
The purpose of this invention is to provide a kind of carrier for olefin polymerization catalyst and preparation method, this carrier granule form is good and be evenly distributed, and supported solid catalyzer prepared therefrom has advantages of high catalytic activity.
Olefin polymerization solid catalyst carrier provided by the invention has following general expression:
(MgCl
2)(R
1MgCl)
pMg
q[Ti(OR
2)
4]
x[Si(OR
3)
4]
y
R in the formula
1And R
2Be selected from C respectively
2～C
4Alkyl, R
3Be selected from C
1～C
3Alkyl, the p value is 0.4～0.8, the q value is that 0.02～0z15, x value are 0.03～0.09, the y value is 0.1～0.3.
The present invention is a raw material with the magnesium powder, by the prepared in reaction active carrier of magnesium powder and halogenated alkane, add the electron donor compound in the preparing carriers process, carrier is again after alcohol activation loaded metal active ingredient, it is higher that the olefin polymerization catalysis that makes carries the titanium amount, and have good mobility and intensity.This catalyzer is used for ethylene polymerization, has catalytic activity preferably, and the resulting polymers particle form is good, has higher bulk density.
Description of drawings
Fig. 1 is the infrared spectrogram of the carrier of the present invention's preparation.
Fig. 2 is the sem photograph of the carrier of the present invention's preparation.
Embodiment
The inventive method joins magnesium powder and varsol in the reactor earlier, adds electron donor, can add a small amount of iodine as catalyzer simultaneously, adds halogenated alkane then and reacts, and makes the carrier that contains active magnesium chloride of nascent state.With the active magnesium chloride C of this nascent state
2～C
8Fatty Alcohol(C12-C14 and C12-C18) further after the activation, can directly prepare the solid ingredient of Ziegler-Natta type catalyzer, the carrier after the described alcohol activation is handled with aluminum alkyls, but load is luxuriant or the Nonmetallocene active ingredient is made solid catalyst.Carrier provided by the invention is compared with common Magnesium Chloride Anhydrous, has bigger specific surface area and pore volume, and magnesium chloride wherein is typical δ-MgCl
2Structure, avtive spot is more on the carrier, thereby the supported catalyst that makes carries titanium amount height, makes the unit mass activity of such catalysts obviously improve.In addition, adopt a small amount of alcohol in the inventive method, can further improve the carrier avtive spot, thereby increase the catalytic activity of catalyzer active magnesium chloride reactivate.Because the alcohol amount that carrier alcohol activation is adopted is less, not fusion of carrier in the treating processes is in solid-stately all the time, therefore can make activation back carrier have good form, and the supported catalyst that makes also has particle form preferably.
Carrier of the present invention comprises magnesium chloride and alkylmagnesium chloride, R in its general formula
1Be the alkyl in the alkyl magnesium chloride, preferred butyl, described R
2Be the alkyl in the titan-alkoxide that adds in the preparation carrier, R
2Preferred propyl group or butyl, R
3Be the alkyl in the siloxanes that adds in the carrier, each alkyl in the siloxanes can be identical or different, but 4 R in the preferred siloxanes
3Be the siloxanes of ethyl or propyl group, as tetramethoxy-silicane, tetraethoxysilane, tetrapropoxysilane or tetraisopropoxysilan.
The preparation method of carrier of the present invention is included in adding magnesium powder in the varsol, and the back that stirs adds the electron donor compound, and adding and magnesium powder mol ratio are 2.0～8.0: 1 C then
2～C
5Halogenated alkane fully react, filter, collect solids washing and dry, described electron donor compound is general formula Si (OR
3)
4Siloxanes and Ti (OR
2)
4Mixture.
In the above-mentioned preparing carriers process, mainly be to make magnesium powder and halogenated alkane reaction generate active magnesium chloride, the while is with the generation of alkyl magnesium chloride.The preferred C of described halohydrocarbon
2～C
5A chloroparaffin, as chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane, tert-butyl chloride, chloro iso-pentane or chloro-n-pentane.Add the mol ratio preferred 2.5～5.0: 1 of halohydrocarbon and magnesium powder, described halogenated alkane can once join and react in the magnesium powder, also can join in the magnesium in batches and react.Described temperature of reaction is 20～100 ℃, preferred 40～85 ℃.Reaction times is 0.5～8.0 hour, preferred 1～6 hour.Can add iodine as magnesium powder and halogenated alkane catalyst for reaction for adding fast response.
The required preferred C of varsol in the preparing carriers
5～C
8Alkane or C
6～C
8Aromatic hydrocarbons, more preferably hexane, decane, heptane, octane, benzene or toluene.The suitable mass ratio of varsol and magnesium powder is 5～100, preferred 5～50.
Also need add siloxanes and titan-alkoxide in the described reaction, the Si (OR of adding
3)
4With the mol ratio of magnesium powder be 0.05～0.5, preferred 0.09～0.2.Titan-alkoxide Ti (OR
2)
4With the mol ratio of magnesium powder be 0.01～0.05, preferred 0.015～0.04.
Carrier of the present invention preferably carries out reactivate before load active component handles, and process for reactivation comprises described carrier is suspended in the unreactive hydrocarbons solvent, adds titan-alkoxide and C
2～C
8Fatty Alcohol(C12-C14 and C12-C18), in 30～200 ℃ of fully reactions, collect solid and dry, the mol ratio of magnesium chloride is 0.01～0.2 in described titan-alkoxide and the carrier, the mol ratio of magnesium chloride is 0.1～1.0 in Fatty Alcohol(C12-C14 and C12-C18) and the carrier.
Alkyl in the titan-alkoxide that adds in the described reaction is selected from C
2～C
7Alkyl, preferred C
2～C
4Alkyl, the preferred ethanolato-titanium of described titan-alkoxide, titanium propanolate or titanium butoxide, the mol ratio of magnesium chloride preferred 0.01～0.1 in described titan-alkoxide and the carrier.Described Fatty Alcohol(C12-C14 and C12-C18) preferred alcohol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, octanol or isooctyl alcohol.The mol ratio of magnesium chloride preferred 0.1～0.8 in Fatty Alcohol(C12-C14 and C12-C18) and the carrier.Preferred 40～80 ℃ of described pure activatory temperature of reaction.
Described unreactive hydrocarbons solvent is C
5～C
10Alkane, preferred hexane, decane, heptane or octane.The suitable mass ratio of unreactive hydrocarbons solvent and carrier is 5～100, preferred 5～20.
Carrier after the above-mentioned alcohol activation is applicable to the solid ingredient of preparation Ziegler-Natta type catalyzer, and the preparation method is: with being suspended in the unreactive hydrocarbons solvent after the carrier drying after the alcohol activation, add halogenated titanium, preferred TiCl
4It is 1: 1～30 that the add-on of halogenated titanium should be controlled at magnesium/titanium mol ratio, preferred 1: 1～10, and then at 30～200 ℃, preferred 40～150 ℃ of fully reactions, preferred 0.5～5.0 hour of reaction times.The solid that obtains after the reaction washs with unreactive hydrocarbons, removes the free halogenated titanium, and drying promptly gets solid catalyst particle, preferred 0.2～10 quality % of titanium content in the solid catalyst.
Carrier after the above-mentioned alcohol activation is wanted load metallocene or Nonmetallocene compound, carrier after the drying should be handled with aluminum alkyls, treatment temp is-20～20 ℃, preferred-10～10 ℃, the mol ratio of magnesium chloride is 0.1～10 in described aluminum alkyls and the carrier, preferred 0.1～5.0.The preferred triethyl aluminum of described aluminum alkyls, tri-propyl aluminum, three n-butylaluminum or triisobutyl aluminium.
The method of handling carrier loaded metallocene in back or Nonmetallocene compound with aluminum alkyls is: with described carrier be dissolved in the luxuriant of polar organic solvent or the Nonmetallocene compound fully contacts, 30～200 ℃, preferred 50～100 ℃ of reactions 10～500 minutes, preferred 20～200 minutes.The gained solid is through washing, be drying to obtain the solid catalyst of load metallocene or Nonmetallocene.In the reaction process in the carrier mol ratio of magnesium chloride and active ingredient be 1～50, preferred 1～10.Described polar organic solvent is selected from chloroparaffin, as methylene dichloride, trichloromethane or 1,2-ethylene dichloride.
With the solid catalyst that carrier of the present invention makes, be applicable to the copolymerization of vinyl polymerization and ethene and alpha-olefin, also needing to add aikyiaiurnirsoxan beta or aluminum alkyls during polymerization is promotor, polymerization temperature is 10～100 ℃, preferred 30～80 ℃.Polymerization can adopt body, slurry or technology such as gas-phase fluidized-bed to carry out.The mol ratio of titanium in aluminium and the Primary Catalysts in promotor during polyreaction, promptly the Al/Ti mol ratio is 25～2000, preferred 100～1000.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare carrier of the present invention.
In the 250mL flask, add 0.2mol magnesium powder, 150ml hexane, 6mmol tetrabutyl titanate, 36mmol tetraethoxy and 0.02g iodine successively, be heated to 75 ℃ of stir-activatings 2 hours, drip 1mol exsiccant n-propylcarbinyl chloride, can be observed tangible reaction, continue reaction 3 hours, filter, gained solid hexane wash after drying, obtain active carrier a, its composition formula is as follows:
(MgCl
2)(BuMgCl)
0.58Mg
0.08[Ti(OC
4H
9)
4)]
0.07[Si(OC
2H
5)
4]
0.23
The infrared spectrum of active carrier a is seen Fig. 1, amplifies 400 times sem photograph and sees Fig. 2.
As seen from Figure 1: in wave number is 1083.8cm
-1And 1047.2cm
-1Two peaks that intensity is suitable appear in the place, belong to Si-OC
2H
5The antisymmetric stretching vibration absorption peak of key, 945.8cm
-1Locating also corresponding the appearance belongs to Si-OC in the peak
2H
5The symmetrical stretching vibration absorption peak of key; In wave number is 883.8cm
-1The peak at place is the distinctive stretching vibration peak of Ti-OR key, at 2960～2850cm
-1Between a series of peaks of occurring be the stretching vibration absorption peak of the c h bond of methyl and methylene radical.These data show that the tetraethoxy and the tetrabutyl titanate that add all have distribution on active carrier in preparation carrier process, and and MgCl
2Form surface complex.
At 3650～3100cm
-1Between the last one arranged and wide peak, this mainly be since carrier surface contain BuMgCl, in the compressing tablet process, absorbed airborne moisture and generated due to the pure association body; In wave number is 3679cm
-1There is a little spike at the place, is the stretching vibration absorption peak of free-OH group of alcohol, and this is because the Mg-R key on airborne moisture and the carrier is had an effect and generated pure the generation and vacillate-the stretching vibration absorption peak of OH group.
At 700～600cm
-1Between MgCl has appearred
2Distinctive Cl-Mg-Cl stretching vibration peak shows in the prepared carrier and contains MgCl
2
As shown in Figure 2, the active carrier that the inventive method makes has the particle shape of good dispersiveness and rule, mostly is the class sphere, and particle size distribution is even and crystal grain is very little.In addition, can see that also there are many folds on the carrier particle surface, show that active carrier has certain microvoid structure.
Example 2
Method by example 1 prepares carrier, and the add-on of different is tetrabutyl titanate is 3mmol, and the add-on of tetraethoxy is 18mmol, obtains active carrier b after the drying, and its composition formula is as follows:
(MgCl
2)(BuMgCl)
0.58Mg
0.04[Ti(OC
4H
9)
4]
0.04[Si(OC
2H
5)
4]
0.12
Example 3
Method by example 1 prepares carrier, and the add-on of different is tetrabutyl titanate is 3mmol, and the add-on of tetraethoxy is 36mmol, obtains active carrier c after the drying, and its composition formula is as follows:
(MgCl
2)(BuMgCl)
0.58Mg
0.06[Ti(OC
4H
9)
4]
0.04[Si(OC
2H
5)
4]
0.24
Example 4
Method by example 1 prepares carrier, and the add-on of different is n-propylcarbinyl chloride is 0.5mol, obtains active carrier d after the drying, and its composition formula is as follows:
(MgCl
2)(BuMgCl)
0.75Mg
0.13[Ti(OC
4H
9)
4)]
0.07[Si(OC
2H
5)
4]
0.23
Example 5
Following example carries out reactivate to the active carrier that the present invention makes.
(1) prepares active magnesium chloride-alcohol carrier
Get 40 milliliters of exsiccant hexanes, the there-necked flask that places nitrogen purging to cross stirs 0.30 milliliter (8.8 * 10 of adding down
-4Mol) titanium n-butoxide adds active carrier a2 gram then and (contains magnesium chloride 2.1 * 10
-2Mol), it is suspended in the hexane, is heated to 70 ℃, under this temperature, stirred 30 minutes, drip propyl carbinol again 0.8 milliliter (8.7 * 10
-3Mol), stirred suspension 30 minutes filters, and solid is with 30 milliliters of hexane wash three times, and 30 ℃ of dryings 2 hours must mobile good white powder carrier, is active magnesium chloride-alcohol carrier.
(2) handle carrier with aluminum alkyls
The there-necked flask that active magnesium chloride-alcohol carrier that (1) step is obtained places nitrogen purging to cross, add 40 milliliters of exsiccant hexanes, stirring down, adding 6.4 ml concns are the hexane solution of the triethyl aluminum of 1 mol, 0 ℃ was reacted 2 hours, filter, solid is with 30 milliliters of hexane wash three times, and 30 ℃ of dryings 2 hours obtain the carrier a that triethyl aluminum is handled
1
Example 6
Method by example 5 prepares active magnesium chloride-alcohol carrier, and different is (1) step to add active carrier b, and the active magnesium chloride-alcohol carrier that obtains is handled with triethyl aluminum by the method in (2) step again, obtains the carrier b that aluminum alkyls is handled
1
Example 7
Method by example 5 prepares active magnesium chloride-alcohol carrier, and different is (1) step to add active carrier c, and the active magnesium chloride-alcohol carrier that obtains is handled with triethyl aluminum by the method in (2) step again, obtains the carrier c that triethyl aluminum is handled
1
Example 8
Method by example 5 prepares active magnesium chloride-alcohol carrier, and different is (1) step to add active carrier d, obtains active magnesium chloride-alcohol carrier and handles with triethyl aluminum by the method in (2) step, obtains the carrier d that triethyl aluminum is handled
1
Example 9
Following examples preparation supported solid catalyzer.
(1) preparation active ingredient
With concentration is the TiCl of 4.74 quality %
4Diethyl ether solution, the diethyl ether solution of the diphenylpropane-1,3-dione(DPPO) of 56.06 quality % (production of Shanghai chemical reagent work) adds in the encloses container, and makes TiCl
4With the mol ratio of diphenylpropane-1,3-dione(DPPO) be 1: 1, be heated with stirring to reflux temperature, reacted 1 hour, filter, solid makes (diphenylpropane-1,3-dione(DPPO)) titanous chloride with ether washing 3 times.
Get 5.5 milliliters of cyclopentadiene and be dissolved in 25 milliliters of tetrahydrofuran (THF)s ,-10 ℃ add 1.4 gram sodium Metal 99.5 reactions 2 hours, and removal of solvent under reduced pressure obtains 4.67 gram cyclopentadiene sodium.
(diphenylpropane-1,3-dione(DPPO)) titanous chloride is dissolved in the solution that toluene is made into 94.35 quality %, adding concentration at-10 ℃ then is the toluene solution of the cyclopentadiene sodium of 22.02 quality %, and the mol ratio that makes (diphenylpropane-1,3-dione(DPPO)) titanous chloride and cyclopentadiene sodium is 1: 1,20 ℃ of stirring reactions 5 hours, filter, wash 3 times with ether, 50 ℃ of dryings 24 hours make cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride.
(2) preparation catalyzer
With 2.13 gram carrier a
1The there-necked flask that places nitrogen purging to cross adds 40 milliliters of exsiccant hexanes, will contain 3.0 grams (6.88 * 10
-3Mol) dichloromethane solution of cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride splashes into wherein for 30 milliliters, be heated to 70 ℃ of stirring reactions 1 hour, and filtered, solid is with 30 milliliters of hexane wash three times, 30 ℃ of dryings 2 hours obtain mobile well deep yellow powder catalyst A.The titanium content that plasma emission spectrum (ICP) method records catalyst A is 6.23 quality %, and Mg content is 10.26 quality %, and aluminium content is 1.12 quality %.
Example 10
Press the method activated carrier a of example 5, different is that the propyl carbinol amount that adds in (1) step is 1.2 milliliter (1.3 * 10
-2Mol), adding 8.7 ml concns in (2) step is the hexane solution of the triethyl aluminum of 1 mol, obtains the carrier a that triethyl aluminum is handled
2
Get 2.15 gram carrier a
2, preparing catalyst B by the method for example 9, its titanium content is 6.56 quality %, and Mg content is 10.09 quality %, and aluminium content is 1.39 quality %.
Example 11
Method by example 9 prepares catalyzer, and the different carriers that is to use is b
1, the titanium content of the catalyzer C that obtains is 5.98 quality %, and Mg content is 11.26 quality %, and aluminium content is 1.09 quality %.
Example 12
Method by example 9 prepares catalyzer, and the different carriers that is to use is c
1, the titanium content of the catalyzer D that obtains is 6.02 quality %, and Mg content is 10.78 quality %, and aluminium content is 1.16 quality %.
Example 13
Method by example 9 prepares catalyzer, and the different carriers that is to use is d
1, the titanium content of the catalyzer E that obtains is 6.16 quality %, and Mg content is 10.63 quality %, and aluminium content is 1.11 quality %.
Example 14
Get 2.16 gram carrier a
1, prepare catalyzer by the method in 9 (2) steps of example, different is to contain 0.5 gram (1.4 * 10
-3Mol) toluene solution of two (butyl cyclopentadienyl) titanium dichloride splashes in the exsiccant hexane for 10 milliliters, be heated to 70 ℃ of stirring reactions 1 hour, filter, solid is with 30 milliliters of hexane wash three times, 30 ℃ of dryings 2 hours, titanium content is 2.18 quality % among the catalyzer F that obtains, and Mg content is 14.08 quality %, and aluminium content is 1.69 quality %.
Example 15
Get 2.0 gram carrier a, the method that goes on foot by example 5 (1) further activates with propyl carbinol.Carrier after then alcohol being activated is at N
2Protection joins in the there-necked flask that the 50mL hexane is housed down, stirs.Add 1.0mL (9 * 10 at 50 ℃
-3Mol) titanium tetrachloride reaction is 4 hours, and solids is used the 50mL hexane wash respectively three times, and decompression dry 2 hours down gets catalyzer G, and wherein titanium content is 8.12 quality %, and Mg content is 9.54 quality %.
Comparative Examples 1
Get 2.0 gram Magnesium Chloride Anhydrouss and carry out activation treatment by the method for example 5, the method by 9 (2) steps of example prepares catalyzer again, and the titanium content of gained catalyzer H is 5.34 quality %, and Mg content is 10.84 quality %, and aluminium content is 1.23 quality %.
Comparative Examples 2
Method according to CN00124667.4 prepares catalyzer.Get water content and put into reaction flask less than dry magnesium chloride (production of Jinzhou aluminium manufacturer) 1.2 grams of 1.0 quality %, add 60 milliliters of exsiccant tetrahydrofuran (THF)s, 55 ℃ of reactions formed adduct solution in 1 hour.Slowly splash into 15 milliliters of dichloromethane solutions that are dissolved with 0.51 gram cyclopentadiene-(diphenylpropane-1,3-dione(DPPO)) titanium dichloride in the reaction flask, 20 ℃ of stirring reactions 1 hour, stop to stir, add 100 milliliters of hexane solutions, staticly settled 2 hours, and filtered, solid was obtained 1.01 gram pink colour catalyst I in 6 hours 20 ℃ of dryings, wherein titanium content is 1.11 quality %, and Mg content is 13.36 quality %.
Comparative Examples 3
Get Magnesium Chloride Anhydrous 2.0 grams, add hexane 60mL, be warming up to 60 ℃ of temperature, added 0.6mL tetrabutyl titanate (1.76mmol) stirring reaction 1 hour, drip 1.2mL (20mmol) ethanol then, continue reaction 1 hour, stir and drip 4.6mLTiCl down
4Reacted 0.5 hour, and got catalyzer J, wherein titanium content is 7.46 quality %, and Mg content is 10.24 quality %.
Example 16～25
Following example carries out the reaction of normal pressure ethylene homo.
250 milliliters of round-bottomed flasks are vacuumized back nitrogen purging three times, feed ethene behind the emptying nitrogen, keep-up pressure and be 0.1MPa, add toluene solution, the 50 milliliters of exsiccant hexanes of the methylaluminoxane that 9.6 ml concns are 10 quality % (MAO) and contain the catalyzer of 0.03mmolTi, making the Al/Ti mol ratio is 500.40 ℃ of polyreactions 0.5 hour are used the HCl termination reaction.The bulk density of each example catalyst system therefor, catalytic activity and polymkeric substance sees Table 1.
Example 26～35
Following example carries out the high-pressure ethylene homopolymerization.
2 liters of stainless steel autoclaves are vacuumized back nitrogen purging three times, feed ethene behind the emptying nitrogen, keep-uping pressure is 0.8MPa, adds hexane solution, the 1 liter of exsiccant hexane that 20 ml concns are the triethyl aluminum of 10 quality % and contains the catalyzer of 0.1mmolTi, and making the Al/Ti mol ratio is 200.80 ℃ of polyreactions 2 hours are used the HCl termination reaction.The bulk density of each example catalyst system therefor, catalytic activity and polymkeric substance sees Table 2, and the polyethylene size distribution of gained sees Table 3.
Table 1
Table 2
Table 3
Claims (12)
1. olefin polymerization solid catalyst carrier has following general expression:
(MgCl
2)(R
1MgCl)
pMg
q[Ti(OR
2)
4]
x[Si(OR
3)
4]
y
R in the formula
1And R
2Be selected from C respectively
2～C
4Alkyl, R
3Be selected from C
1～C
3Alkyl, the p value is 0.4～0.8, the q value is 0.02～0.15, the x value is 0.03～0.09, the y value is 0.1～0.3.
2. according to the described carrier of claim 1, it is characterized in that R in the described general formula
1Be butyl, R
2Be propyl group or butyl, R
3Be ethyl or propyl group.
3. the preparation method of the described carrier of claim 1 is included in adding magnesium powder in the varsol, and the back that stirs adds the electron donor compound, and adding and magnesium powder mol ratio are 2.0～8.0: 1 C then
2～C
4A chloroparaffin fully react, filter, collect solids washing and dry, described electron donor compound is general formula Si (OR
3)
4Siloxanes and Ti (OR
2)
4Mixture, described Si (OR
3)
4With the mol ratio of magnesium powder be 0.09～0.2, Ti (OR
2)
4With the mol ratio of magnesium powder be 0.015～0.04.
4. in accordance with the method for claim 3, it is characterized in that a described chloroparaffin is chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane or tert-butyl chloride.
5. in accordance with the method for claim 3, the temperature of reaction that it is characterized in that described magnesium powder and chloroparaffin is 20～100 ℃.
6. in accordance with the method for claim 3, it is characterized in that described varsol is selected from C
5～C
8Alkane or C
6～C
8Aromatic hydrocarbons.
7. the process for reactivation of the described carrier of claim 1 comprises the described carrier of claim 1 is suspended in the unreactive hydrocarbons solvent, adds titan-alkoxide and C
2～C
8Fatty Alcohol(C12-C14 and C12-C18), in 30～120 ℃ of fully reactions, collect solid and dry, the mol ratio of magnesium chloride is 0.01～0.2 in described titan-alkoxide and the carrier, the mol ratio of magnesium chloride is 0.1～1.0 in Fatty Alcohol(C12-C14 and C12-C18) and the carrier.
8. in accordance with the method for claim 7, it is characterized in that temperature of reaction is 40～80 ℃.
9. in accordance with the method for claim 7, it is characterized in that the alkyl in the described titan-alkoxide is selected from C
2～C
7Alkyl, the mol ratio of magnesium chloride is 0.01～0.1 in titan-alkoxide and the carrier.
10. in accordance with the method for claim 7, it is characterized in that described unreactive hydrocarbons solvent is C
5～C
10Alkane, described Fatty Alcohol(C12-C14 and C12-C18) is ethanol, propyl alcohol, Virahol, butanols, isopropylcarbinol, amylalcohol, hexanol, enanthol, octanol or isooctyl alcohol.
11. in accordance with the method for claim 7, it is characterized in that carrier after the drying is handled with aluminum alkyls, treatment temp is-10～10 ℃, and the mol ratio of magnesium chloride is 0.1～10 in described aluminum alkyls and the carrier.
12. in accordance with the method for claim 11, it is characterized in that described aluminum alkyls is selected from triethyl aluminum, tri-propyl aluminum, three n-butylaluminum or triisobutyl aluminium.
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| CN111499777B (en) * | 2020-04-29 | 2023-02-17 | 江苏扬农化工集团有限公司 | Ultrahigh molecular weight polyethylene catalyst, and preparation method and application thereof |
| CN113801253A (en) * | 2020-06-17 | 2021-12-17 | 中化学科学技术研究有限公司 | Catalyst component, solid titanium catalyst, ethylene polymerization catalyst and application thereof, and polyethylene product |
| CN113943386A (en) * | 2021-10-21 | 2022-01-18 | 中化学科学技术研究有限公司 | Method for regulating and controlling particle size and particle size distribution of ultrahigh molecular weight polyethylene |
| CN113943384A (en) * | 2021-11-04 | 2022-01-18 | 中化学科学技术研究有限公司 | Catalyst, catalyst system, polyethylene and preparation method |
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| CN1264713A (en) * | 1999-02-26 | 2000-08-30 | 中国石油化工集团公司 | Process for preparing catalyst carrier for olefin polymerization |
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