CN100569808C - A kind of load type non-metallocene catalyst and preparation method thereof - Google Patents
A kind of load type non-metallocene catalyst and preparation method thereof Download PDFInfo
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- CN100569808C CN100569808C CNB2005100597719A CN200510059771A CN100569808C CN 100569808 C CN100569808 C CN 100569808C CN B2005100597719 A CNB2005100597719 A CN B2005100597719A CN 200510059771 A CN200510059771 A CN 200510059771A CN 100569808 C CN100569808 C CN 100569808C
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Abstract
A kind of load type non-metallocene catalyst comprises that the expression formula that loads on the magnesium halide carrier is L
nMX
4-nThe Nonmetallocene active ingredient, M is selected from titanium or zirconium in the formula, X is a halogen, n is 1 or 2, L removes the group that forms behind the H proton for the part with formula (I) structure, the number of the substituent R in the formula (I) on the pyrrole ring is 1 to 3, and adjacent substituting group can be connected with each other and pyrrole ring forms condensed ring, and R is selected from hydrogen or C
1～C
12Alkyl, the substituent R on the phenyl ring
1Number be 1 to 5, R
1Be selected from hydrogen or C
1～C
12Alkyl, C
6～C
9Alkaryl, nitro or halogen, R
2Be selected from hydrogen or C
1～C
3Alkyl.This method for preparing catalyst is simple, and has advantages of high catalytic activity.
Description
Technical field
The present invention is a kind of carry type non-metallocene calalyst for polymerization of olefine and preparation method thereof.Specifically, be a kind of be carrier with the magnesium halide, be olefin polymerization catalysis of active ingredient and preparation method thereof with the Nonmetallocene that contains Schiff base ligand.
Background technology
After metallocene catalyst, the Nonmetallocene compound that contains coordination heteroatom ligands such as aerobic, nitrogen in the another kind of conjugated system more and more causes people's attention and concern in the application aspect polyolefine, the especially polyethylene catalysts.Metallocene and non-metallocene catalyst are wanted loadization in using usually, to satisfy more polymerization technique process, as the service requirements of vapour phase polymerization, slurry polymerization.Carried catalyst can also improve the catalytic efficiency of active ingredient, increases the stability in active centre, improves the form of polymkeric substance, improves the apparent density of polymkeric substance, and reduces the consumption of promotor significantly, reduces catalyst production cost.
Usually the load of metallocene or non-metallocene olefin polymerization catalyst is all adopted first composite reactive component, and then metallocene or Nonmetallocene active constituent loading are made loaded catalyst on carrier.Disclosing a kind of as USP5869417 is active ingredient with the metallocene, is the preparation method of the loaded catalyst of carrier with the molecular sieve, and wherein said molecular sieve is for having 7～15
The large pore molecular sieve in aperture is as faujusite, SAPO-37 etc.This catalyzer can be used for ethene, propylene or cinnamic polymerization.
CN1461756A discloses a kind of non-metallocene catalyst and loaded catalyst thereof; the part of this catalyzer is the acyl-naphthaline phenolic compound; the Nonmetallocene active ingredient is reacted at a lower temperature with an alkali metal salt of acyl group naphthols and transition metal halide and is made; loaded catalyst is dispersed in the Nonmetallocene active ingredient that makes in the solvent, makes with the carrier reaction again.
CN1418227A discloses a kind of preceding body catalyst that comprises bidentate ligand that contains, and described preceding body catalyst is ML
xX
4-x, wherein L is the single anion bidentate ligand, and it is attached on the M by two atoms that are selected from oxygen, sulphur, selenium, tellurium, nitrogen, phosphorus, arsenic, antimony and bismuth, and X is a halogen.The preparation method of its loaded catalyst will make catalyzer with the carrier reaction after catalyst precursor and the aluminum alkyls effect earlier again.
Aforesaid method all exists Preparation of Catalyst cost height, complicated operation, and the polymer stacks density that produces is little, defectives such as poor morphology.
CN1128820C discloses polyolefin catalyst and the preparation method who contains pyrrole ring in a kind of part, the part of this catalyzer is the condenses of carbonyl pyrrolidine derivative and anils, the Preparation of catalysts method is earlier ligand compound to be made sodium salt, and the tetrahalide reaction with its sodium salt and transition metal makes again.But do not put down in writing the loaded catalyst of this active ingredient of load in the literary composition.
Summary of the invention
The purpose of this invention is to provide a kind of load type non-metallocene catalyst and preparation method thereof, this catalyzer adopts in-situ synthesis to prepare loaded catalyst, and the preparation method is simple, cost is low, and the catalyzer that makes has high polymerization activity.
Load type non-metallocene catalysis profit provided by the invention comprises that the expression formula that loads on the magnesium halide carrier is L
nMX
4-nThe Nonmetallocene active ingredient, M is selected from IVB family metal in the formula, X is a halogen, n is 1 or 2, and L removes the group that forms behind the H proton for the part with formula (I) structure, and the content of IVB family metal is 1.0～8.0 quality % in the described catalyzer, Mg content is 5～25 quality %
In the formula (I), the number of the substituent R on the pyrrole ring is 1 to 3, and adjacent substituting group can be connected with each other and pyrrole ring forms condensed ring, and R is selected from hydrogen or C
1～C
12Alkyl, the substituent R on the phenyl ring
1Number be 1 to 5, R
1Be selected from hydrogen or C
1～C
12Alkyl, C
6～C
9Alkaryl, nitro or halogen, R
2Be selected from hydrogen or C
1～C
3Alkyl.
It is carrier that catalyzer of the present invention adopts the nascent state magnesium halide, the synthetic non-metallocene catalyst of original position on carrier, and the method preparation that the Nonmetallocene after will synthesizing loads on the carrier is more simple, and the catalyzer that makes has higher activity.Thereby can effectively reduce the Preparation of catalysts cost.
Embodiment
The present invention's magnesium halide of magnesium powder and halogenated alkane prepared in reaction nascent state, the ligand compound that will contain western Buddhist alkali again loads on the magnesium halide carrier, add the halogenide and the ligand compound reaction of transition metal, original position generates the Nonmetallocene compound on carrier, makes loaded catalyst.
IVB family metal described in the catalyzer of the present invention is selected from titanium or zirconium, and X is a chlorine, the preferred magnesium chloride of magnesium halide.
In the formula (I), the substituent R on the pyrrole ring can be at an arbitrary position, and two adjacent substituting groups can be interconnected to form condensed ring, as indoles, and preferred hydrogen of R or C
1～C
4Alkyl.Substituent R on the phenyl ring
1Also can be in any replacement position, R
1Preferred hydrogen, C
1～C
4Alkyl, phenyl, nitro or fluorine.R is got in replacement on the Buddhist alkali carbon atom of west
2Preferred hydrogen or methyl.
Described magnesium halide is the nascent state magnesium halide that raw material is made with the magnesium powder preferably.
In the described catalyzer, preferred 1.0～6.0 quality % of the content of IVB family metal, preferred 10～20 quality % of Mg content.Also contain C in the catalyzer
4～C
8Fatty Alcohol(C12-C14 and C12-C18), preferred alcohol, propyl alcohol, butanols, amylalcohol, hexanol, enanthol, octanol, described alcohol comprise its various isomeric forms, as isopropylcarbinol, isooctyl alcohol.
Also contain the electron donor compound in the described catalyzer, its content is 2～20 quality %, and described electron donor compound is selected from organoalkoxysilane or phosphoric acid ester.The preferred C of alkoxyl group in the described organoalkoxysilane
2～C
4Alkoxyl group, described phosphoric acid ester preferably phosphoric acid tri-n-butyl.
Preparation of catalysts method of the present invention comprises the steps:
(1) in saturated hydrocarbon solvent, add magnesium powder and halogenated alkane and fully react the suspension that generation contains the nascent state magnesium halide, the mol ratio of described halogenated alkane and magnesium powder is 1～10: 1,
(2) in nascent state magnesium halide suspension, the described part of adding formula (I) fully reacts,
(3) the cooling back adds MX
4Compound and formula (I) part fully reacts, and filters, with solids washing and dry, described MX
4In, M is selected from IVB family metal, and X is a halogen.
(1) step is the magnesium halide of preparation nascent state, preferred nascent state magnesium chloride, the preferred C of wherein said saturated hydrocarbon solvent in the described method
5～C
7Alkane, as pentane, hexane or heptane, the consumption of saturated hydrocarbon solvent is 10～200 times of magnesium powder.The preferred C of described halogenated alkane
4～C
7Chloroparaffin, as n-propylcarbinyl chloride, chloro-n-pentane.For making magnesium powder and halogenated alkane accelerated reaction, should in reactant, add a small amount of iodine as catalyzer.React the mol ratio preferred 1.5～6.0: 1 of used magnesium powder and halogenated alkane, suitable temperature of reaction is 10～100 ℃, preferred 20～85 ℃; Reaction times is 0.5～8 hour, preferred 1～6 hour.
Described method (2) step is that the described Schiff base ligand of formula (I) is loaded on the nascent state magnesium halide, and the part of adding and the mol ratio of magnesium halide are 0.03～1.0, preferred 0.1～0.7: 1.The temperature of reaction of load type on the nascent state magnesium halide (I) part is 0～100 ℃, preferred 0～80 ℃.
Described method (3) step is to make MX
4React the synthetic Nonmetallocene compound of original position on carrier with formula (I) part that loads on the magnesium halide carrier.MX in this step
4With formula (I) part mol ratio be 0.5～10: 1, preferred 0.5～8: 1.Add MX
4The temperature of reacting with formula (I) part is-30～30 ℃, preferred-10～10 ℃.
For improving catalyst activity, can neutralization in nascent state magnesium halide suspension, add C in (2) step
4～C
10Fatty Alcohol(C12-C14 and C12-C18) activated carrier 0.1～5.0 hour, and then the described part reaction of adding formula (I), add Fatty Alcohol(C12-C14 and C12-C18) and magnesium halide mol ratio be 0.3～2.0: 1.The preferred C of described alcohol
2～C
12, more preferably C
2～C
8Fatty Alcohol(C12-C14 and C12-C18), as ethanol, propyl alcohol, propyl carbinol, 2-methyl amyl alcohol or isooctyl alcohol.The optimal temperature that adds pure activated carrier is 20～80 ℃.
Except that adding pure activated carrier, also can in (3) step, add the electron donor compound, described electron donor compound is selected from organoalkoxysilane or phosphoric acid ester, and the mol ratio of electron donor and formula (I) part is 0.2～10: 1, preferred 0.5～5.0: 1.The alkoxyl group number of described organoalkoxysilane is 1～4, and alkyl wherein is C
1～C
12Alkyl or C
6～C
10Alkaryl, preferred tetraethoxysilane, tetrapropoxysilane, four butoxy silanes or dimethoxydiphenylsilane.Electron donor should add MX
4Join in the reaction system, the temperature of load electron donor compound is 0～80 ℃ before.
The another kind of method that increases catalyst activity is in (3) step, MX
4After compound and formula (I) part fully reacts, continue to add halogenated alkane reaction 0.5～3 hour, suitable temperature of reaction is 0～80 ℃.Described halogenated alkane is selected from C
3～C
6One chloro thing of alkane is as chloro-propane, n-propylcarbinyl chloride, chloro-iso-butane, tert-butyl chloride, chloro iso-pentane or chloro-n-pentane.The haloalkane and the MX that add
4Mol ratio be 1～8: 1.
Above-mentioned three kinds of methods of improving catalyst performances can be used separately in catalyst preparation process, also can any two kinds of combinations or three kinds of methods use simultaneously.
The synthetic method of the Schiff base ligand of formula of the present invention (I) structure is: anils and the mol ratio of the carbonyl pyrrolidine derivative with formula (II) structure by 1: 1 are joined in the appropriate amount of organic, stirring and dissolving, add a small amount of organic acid as catalyzer, being heated to reflux temperature fully reacts, crystallisation by cooling then, filter, with the solids washing for several times, drying under reduced pressure gets final product.
In the formula (II), the number of the substituent R on the pyrrole ring is 1 to 3, and adjacent substituting group can be connected with each other and pyrrole ring forms condensed ring, and R is selected from hydrogen or C
1～C
12Alkyl, R
2Be selected from hydrogen or C
1～C
3Alkyl.
In the reaction of above-mentioned preparation part, organic solvent is selected from C
1～C
10Fatty Alcohol(C12-C14 and C12-C18), C
5～C
10Alkane or C
6～C
12Aromatic hydrocarbons, preferred alcohol, propyl alcohol, butanols, benzene, toluene or dimethylbenzene.Organic acid is selected from C
1～C
10Aliphatic carboxylic acid, preferable formic acid or acetate.
Catalyzer of the present invention is applicable to ethylene polymerization, is Primary Catalysts with catalyzer provided by the invention during polymerization, is promotor with the alkylaluminoxane, makes vinyl polymerization at 10～100 ℃, the condition of 0.1～1.0MPa.
Described alkylaluminoxane is selected from methylaluminoxane, and the mol ratio of IV B family metal is 20～500: 1 in Al during polyreaction in the promotor and the Primary Catalysts.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare catalyzer of the present invention.
(1) preparation pyrrole aldehyde anil
Getting the 31.5mmol pyrrole aldehyde joins in the there-necked flask of being with return line, add the 4ml propyl carbinol, be warming up to 70 ℃, add 31.5mmol aniline, splash into several Glacial acetic acid reactions 2 hours, being cooled to-10 ℃ promptly has a large amount of crystal to produce, filter, solids hexane wash 3 times obtain 4.18 gram pyrrole aldehyde anils, and yield is 78 quality %.Results of elemental analyses following (in the bracket is calculated value, is mass percent):
C：77.61(77.62)；N：16.36(16.46)；H：5.90(5.92)
(2) preparation nascent state magnesium chloride
Get 12.4mmol magnesium powder and place the there-necked flask through the 250ml of nitrogen replacement, add 25ml heptane and 0.02g iodine, 75 ℃ of stir-activatings 2 hours drip the 62mmol n-propylcarbinyl chloride, react 3 hours, obtain the suspension of nascent state magnesium chloride.
(3) the original position load prepares catalyzer
Nascent state magnesium chloride suspension is reduced to 25 ℃, dropping is dissolved with the 20ml normal hexane of 3.8mmol pyrrole aldehyde anil and the mixing solutions of 10ml toluene, it is red that the system color gradually becomes, react after 1 hour cooling, slowly drip the 18.2mmol titanium tetrachloride while stirring under 0 ℃, be warming up to 50 ℃ and continue reaction 3 hours, filter, solid is drained solvent with normal hexane washing three times, obtains being loaded with on the 1.31g magnesium chloride brown solid catalyst A of (pyrrole aldehyde anil) titanous chloride.The Ti content that records catalyst A with the plasma emission spectroscopy method is that 4.55 quality %, Mg content are 13.05 quality % (down together).Its diffuse reflectance infrared spectroscopy peak sees Table 1.As shown in Table 1, the C=N characteristic peak of supported catalyst A is offset to some extent than the C=N characteristic peak positions of Schiff base ligand, show that the N on Ti and the western Buddhist alkali C=N has interaction, and the Mg-Cl characteristic peak of supported catalyst is compared with pure nascent state magnesium chloride, also skew to some extent shows that the non-luxuriant active ingredient of generation loads on the magnesium chloride support.
Example 2
Method by example 1 prepares catalyst B, different is that the add-on of n-propylcarbinyl chloride was 22.3mmol during (2) went on foot, get the catalyst B that is loaded with (pyrrole aldehyde anil) titanous chloride on the 1.34g magnesium chloride, its Ti content is 3.25 quality %, Mg content is 14.01 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 3
Method by example 1 prepares catalyzer C, different is in (3) step, the add-on of pyrrole aldehyde anil is 6.3mmol, the add-on of titanium tetrachloride is 6.4mmol, dripping the post-reacted temperature of titanium tetrachloride is 80 ℃, gets the catalyzer C that is loaded with (pyrrole aldehyde anil) titanous chloride on the 1.92g magnesium chloride, and its Ti content is 4.27 quality %, Mg content is 11.47 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 4
Method by example 1 prepares catalyzer D, and different is that the add-on of titanium tetrachloride was 1.9mmol during (3) went on foot.Get the catalyzer D that is loaded with two (pyrrole aldehyde anil) titanium dichloride on the 1.23g magnesium chloride, its Ti is 2.19 quality %, and Mg content is 13.22 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 5
Method by example 1 prepares catalyzer E, different is in the step (3), after dripping titanium tetrachloride reaction, add the 6ml chlorocyclohexane, and, getting the catalyzer E that is loaded with (pyrrole aldehyde anil) titanous chloride on the 1.32g magnesium chloride 50 ℃ of continuation reactions 1 hour, its Ti content is 4.61 quality %, Mg content is 15.10 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 6
Method by example 1 prepares catalyzer F, different is in step (3), after dripping titanium tetrachloride reaction, the n-propylcarbinyl chloride that adds 12.4mmol, and, getting the catalyzer F that is loaded with (pyrrole aldehyde anil) titanous chloride on the 1.33g magnesium chloride 50 ℃ of continuation reactions 1 hour, its Ti content is 3.85 quality %, Mg content is 15.10 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 7
(1) preparation pyrrole aldehyde 2,4 xylidines that contract
Get the 15.8mmol pyrrole aldehyde and join in the there-necked flask of being with return line, add the 2.5ml propyl carbinol, be warming up to 70 ℃, add 2,4-xylidine 15.8mmol splashes into several Glacial acetic acid reactions 2 hours, being cooled to-10 ℃ promptly has a large amount of crystal to produce, filter, solids hexane wash 3 times obtain 2.34 gram pyrrole aldehydes and contract 2, the 4-xylidine, yield is 75 quality %, results of elemental analyses following (in the bracket is calculated value, is mass percent):
C：78.70(78.75)；N：14.05(14.13)；H：7.10(7.12)。
(2) preparation loading type non cyclopentadienyl catalyst
Method by 1 (2) step of example prepares the nascent state magnesium chloride, prepare catalyzer G by (3) one step process then, different is that the part that adds is that pyrrole aldehyde contracts 2, the 4-xylidine, add-on is 3.8mmol, and after adding titanium tetrachloride reaction, add the 6ml chlorocyclohexane, 50 ℃ were reacted 1 hour.Get the catalyzer G that is loaded with (pyrrole aldehyde contracts 2, the 4-xylidine) titanous chloride on the 1.35g magnesium chloride, its Ti content is 4.35 quality %, and Mg content is 15.41 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 8
(1) the preparation pyrrole aldehyde contracts 2, the 6-diisopropyl aniline
Getting the 15.8mmol pyrrole aldehyde joins in the there-necked flask of being with return line, add the 2.5ml propyl carbinol, be warming up to 70 ℃, add 2,6-diisopropyl aniline 15.8mmol, splash into several Glacial acetic acid reactions 2 hours, being cooled to-10 ℃ promptly has a large amount of crystal to produce, and filters, solids hexane wash 3 times, obtain the 2.21g pyrrole aldehyde and contract 2,6-diisopropyl aniline, yield are 55 quality %.Results of elemental analyses following (in the bracket is calculated value, is mass percent):
C：79.96(80.27)；N：10.97(11.02)；H：8.62(8.72)。
(2) loading type non cyclopentadienyl catalyst
Method by 1 (2) step of example prepares the nascent state magnesium chloride, prepare catalyzer G by (3) one step process then, different is that the part that adds is that pyrrole aldehyde contracts 2, the 6-diisopropyl aniline, the add-on of part is 3.8mmol, and after adding titanium tetrachloride reaction, add the 6ml chlorocyclohexane, 50 ℃ were reacted 1 hour.Get the catalyzer H that is loaded with (pyrrole aldehyde contracts 2, the 6-diisopropyl aniline) titanous chloride on the 1.29g magnesium chloride, its Ti content is 3.49 quality %, and Mg content is 13.40 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 9
Method by example 1 prepares catalyzer, different is that adding pyrrole aldehyde anil is 2.1mmol reaction 1 hour in (3) step, be warming up to 60 ℃, add 4.2mmol tetraethoxysilane reaction 1 hour, be cooled to 0 ℃ then, slowly drip the 18.2mmol titanium tetrachloride while stirring, after dropwising, be warming up to 50 ℃ of reactions 2 hours, add the 6ml chlorocyclohexane and under this temperature, continue reaction 1 hour, filter, solid hexane wash three times, drain solvent, obtain being loaded with on the 1.31g magnesium chloride brown solid catalyst I of (pyrrole aldehyde anil) titanous chloride and tetraethoxysilane, its Ti content is 4.31 quality %, and Mg content is 16.80 quality %, silicone content is 1.12 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 10
Method by example 9 prepares catalyzer, different is to replace tetraethoxysilane to react with the 4.2mmol tributyl phosphate in (3) step, obtain being loaded with on the 1.05g magnesium chloride catalyzer J of (pyrrole aldehyde anil) titanous chloride and tributyl phosphate, its Ti content is 2.99 quality %, Mg content is 16.12 quality %, phosphorus content is 1.01 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 11
Method by example 1 prepares catalyzer, when different is (3) step preparation loaded catalyst, after nascent state magnesium chloride suspension is cooled to 25 ℃, to wherein dripping 13.1mmol propyl carbinol reaction 1 hour, drip the 10ml toluene and the 20ml hexane solution of 1.8mmol pyrrole aldehyde anil again, along with the carrying out that drips, the reaction solution color gradually becomes light yellow look, dropwised afterreaction 1 hour, and moved into ice-water bath, beginning slowly drips 18.2mmolTiCl under ice-water bath
4Become pale brown look, be warming up to 50 ℃ after dropwising gradually, reacted 2 hours, add the 6ml chlorocyclohexane and continue reaction 1 hour, filter, solid hexane wash 3 times are drained, obtain being loaded with on the 1.32g magnesium chloride catalyzer K of (pyrrole aldehyde anil) titanous chloride and propyl carbinol, its Ti content is 3.56 quality %, and Mg content is 14.68 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 12
Method by example 11 prepares catalyzer, different is to replace propyl carbinol to react with the 13.1mmol isooctyl alcohol, obtain being loaded with on the 1.38g magnesium chloride catalyzer L of (pyrrole aldehyde anil) titanous chloride and isooctyl alcohol, wherein Ti content is 3.55 quality %, Mg content is 14.31 quality %, and the diffuse reflectance infrared spectroscopy peak sees Table 1.
Example 13～24
Following example carries out the reaction of normal pressure ethylene homo with catalyzer of the present invention.
The 250ml there-necked flask is replaced three times with twice of nitrogen replacement, ethene, and feeding ethene to pressure is 0.1MPa, adds 40ml hexane and an amount of methylaluminoxane, 40 ℃ of adding catalyzer, and making the Al/Ti mol ratio is 500: 1, and reacts 30 minutes under this temperature.Stop to feed ethene, adding 20ml ethanol and 5ml concentration is the hydrochloric acid termination reaction of 98 quality %.Each example catalyst system therefor activity sees Table 2.
Example 25～36
Below carry out the high-pressure ethylene homopolymerization with catalyzer of the present invention.
In 2 liters of stainless steel autoclaves that nitrogen replacement is crossed, feed 2kg hydrogen, feed ethene again, the maintenance total pressure is 0.8MPa, the hydrogen dividing potential drop is 0.2MPa, adds 1000ml hexane and an amount of triethyl aluminum, and 70 ℃ add catalyzer, making the Al/Ti mol ratio is 200: 1,70 ℃ of polyreactions 1 hour stop to feed ethene, obtain polymkeric substance.Each example catalyst system therefor activity and the poly bulk density of gained see Table 3.
Table 1
Table 2
| Instance number | The catalyzer numbering | Catalytic activity * 10 -5，gPE/molTi·hr |
| 13 | A | 1.34 |
| 14 | B | 1.24 |
| 15 | C | 1.70 |
| 16 | D | 1.54 |
| 17 | E | 1.72 |
| 18 | F | 1.69 |
| 19 | G | 1.33 |
| 20 | H | 0.78 |
| 21 | I | 1.53 |
| 22 | J | 2.35 |
| 23 | K | 3.70 |
| 24 | L | 5.02 |
Table 3
| Instance number | The catalyzer numbering | Catalytic activity * 10 -6， gPE/molTi·hr | The polyethylene bulk density, g/cm 3 |
| 25 | A | 2.78 | 0.210 |
| 26 | B | 2.56 | 0.180 |
| 27 | C | 3.66 | 0.187 |
| 28 | D | 2.74 | 0.250 |
| 29 | E | 3.54 | 0.210 |
| 30 | F | 3.43 | 0.210 |
| 31 | G | 2.83 | 0.235 |
| 32 | H | 1.04 | 0.125 |
| 33 | I | 3.17 | 0.245 |
| 34 | J | 3.75 | 0.250 |
| 35 | K | 8.33 | 0.260 |
| 36 | L | 10.5 | 0.310 |
Claims (20)
1, a kind of load type non-metallocene catalyst comprises that the expression formula that loads on the magnesium halide carrier is L
nMX
4-nThe Nonmetallocene active ingredient, M is selected from IVB family metal in the formula, X is a halogen, n is 1 or 2, L removes the group that forms behind the H proton for the part with formula (I) structure, and the content of IVB family metal is 1.0～8.0 quality % in the described catalyzer, and Mg content is 5～25 quality %, described magnesium halide is the nascent state magnesium halide with magnesium powder and halogenated alkane prepared in reaction
In the formula (I), the number of the substituent R on the pyrrole ring is 1 to 3, and adjacent substituting group can be connected with each other and pyrrole ring forms condensed ring, and R is selected from hydrogen or C
1～C
12Alkyl, the substituent R on the phenyl ring
1Number be 1 to 5, R
1Be selected from hydrogen or C
1～C
12Alkyl, phenyl, remove C
6Outside C
6～C
9Alkaryl, nitro or halogen, R
2Be selected from hydrogen or C
1～C
3Alkyl.
2, according to the described catalyzer of claim 1, it is characterized in that described IVB family metal is selected from titanium or zirconium, X is a chlorine, magnesium halide is a magnesium chloride.
3,, it is characterized in that R is selected from hydrogen or C in the formula (I) according to the described catalyzer of claim 1
1～C
4Alkyl, R
1Be selected from hydrogen, C
1～C
4Alkyl, nitro or fluorine, R
2Be selected from hydrogen or methyl.
4, according to the described catalyzer of claim 1, the content that it is characterized in that IVB family metal in the catalyzer is 1.0～6.0 quality %, and Mg content is 10～20 quality %.
5,, it is characterized in that also containing in the described catalyzer C according to the described catalyzer of claim 1
4～C
8Fatty Alcohol(C12-C14 and C12-C18).
6, according to claim 1 or 5 described catalyzer, it is characterized in that containing in the described catalyzer electron donor compound, its content is 2～20 quality %.
7,, it is characterized in that described electron donor compound is selected from organoalkoxysilane or phosphoric acid ester according to the described catalyzer of claim 6.
8,, it is characterized in that the alkoxyl group in the described organoalkoxysilane is C according to the described catalyzer of claim 7
2～C
4Alkoxyl group, described phosphoric acid ester is a tributyl phosphate.
9, the described Preparation of catalysts method of a kind of claim 1 comprises the steps:
(1) in saturated hydrocarbon solvent, add magnesium powder and halogenated alkane and fully react the suspension that generation contains the nascent state magnesium halide, the mol ratio of described halogenated alkane and magnesium powder is 1～10: 1,
(2) in nascent state magnesium halide suspension, the described part of adding formula (I) fully reacts,
(3) the cooling back adds MX
4Compound and formula (I) part fully reacts, and filters, with solids washing and dry, described MX
4In, M is selected from IVB family metal, and X is a halogen.
10, in accordance with the method for claim 9, it is characterized in that described magnesium halide of (1) step is a magnesium chloride, saturated hydrocarbon solvent is selected from C
5～C
7Alkane, halogenated alkane is selected from C
4～C
7Chloroparaffin, the part that (2) step adds is 0.03～1.0: 1 with the mol ratio of magnesium halide, MX during (3) go on foot
4With the mol ratio of formula (I) part be 0.5～10: 1.
11, in accordance with the method for claim 9, it is characterized in that the temperature of reaction of magnesium powder and halogenated alkane in (1) step is 10～100 ℃, in (2) step on the nascent state magnesium halide temperature of reaction of load type (I) part be 0～100 ℃, (3) step adds MX
4The temperature of reacting with formula (I) part is-30～10 ℃.
12, in accordance with the method for claim 11, it is characterized in that the temperature of reaction of magnesium powder and halogenated alkane in (1) step is 20～85 ℃, in (2) step on the nascent state magnesium halide temperature of reaction of load type (I) part be 0～80 ℃, (3) step adds MX
4The temperature of reacting with formula (I) part is-10～10 ℃.
13, in accordance with the method for claim 9, it is characterized in that in nascent state magnesium halide suspension, adding C in (2) step
2～C
12Fatty Alcohol(C12-C14 and C12-C18) activation 0.1～5.0 hour, add the described part reaction of formula (I) again, the mol ratio of described Fatty Alcohol(C12-C14 and C12-C18) and magnesium halide is 0.3～2.0: 1.
14, in accordance with the method for claim 13, it is characterized in that described alcohol is C
2～C
8Fatty Alcohol(C12-C14 and C12-C18).
15, according to described any one method of claim 9～14, it is characterized in that in (3) step, adding the electron donor compound, described electron donor compound is selected from organoalkoxysilane or phosphoric acid ester, and the mol ratio of electron donor and formula (I) part is 0.5～5.0: 1.
16, in accordance with the method for claim 9, it is characterized in that MX in (3) step
4After compound and formula (I) part fully reacts, continue to add halogenated alkane reaction 0.5～8 hour.
17, in accordance with the method for claim 15, it is characterized in that MX in (3) step
4After compound and formula (I) part fully reacts, continue to add halogenated alkane reaction 0.5～8 hour.
18,, it is characterized in that the halogenated alkane that described continuation adds is selected from C according to claim 16 or 17 described methods
3～C
6One chloro thing of alkane.
19, a kind of ethene polymerization method comprises that with the described catalyzer of claim 1 be Primary Catalysts, is promotor with alkylaluminoxane or aluminum alkyls, makes vinyl polymerization at 10～100 ℃, the condition of 0.1～1.0MPa.
20, in accordance with the method for claim 19, it is characterized in that described alkylaluminoxane is selected from methylaluminoxane, aluminum alkyls is selected from triethyl aluminum, and the mol ratio of IVB family metal is 50～1000: 1 in A1 during polyreaction in the promotor and the Primary Catalysts.
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| WO2009052700A1 (en) | 2007-10-16 | 2009-04-30 | Sinopec Yangzi Petrochemical Company Ltd. | Supported non-metallocene catalyst and its preparation method |
| US8716416B2 (en) | 2007-10-16 | 2014-05-06 | Sinopec Yangzi Petrochemical Company Ltd. | Magnesium-compound supported nonmetallocene catalyst and preparation thereof |
| CN104001546A (en) * | 2014-06-09 | 2014-08-27 | 浙江科技学院 | Supported catalyst for preparing hexa-olefin by dimerization of propylene and preparation method of supported catalyst |
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Non-Patent Citations (4)
| Title |
|---|
| "New Titanium Complexes Having Two Pyrrolide-ImineChelate Ligangs：Syntheses，Structures，and EthylenePolymerization Behavior". Yasunori Yoshida等.Organometallics,Vol.20卷 . 2001 |
| "New Titanium Complexes Having Two Pyrrolide-ImineChelate Ligangs：Syntheses，Structures，and EthylenePolymerization Behavior". Yasunori Yoshida等.Organometallics,Vol.20卷 . 2001 * |
| "新型Schiff碱钛配合物[N,N]TiCl3的合成、负载及催化乙烯聚合". 张东平等.《石油化工》，第32卷第6期. 2003 |
| "新型Schiff碱钛配合物[N,N]TiCl3的合成、负载及催化乙烯聚合". 张东平等.《石油化工》，第32卷第6期. 2003 * |
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