CN1090638C - Catalyst for olefine polymer and copolymer and its preparing method - Google Patents
Catalyst for olefine polymer and copolymer and its preparing method Download PDFInfo
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- CN1090638C CN1090638C CN96109129A CN96109129A CN1090638C CN 1090638 C CN1090638 C CN 1090638C CN 96109129 A CN96109129 A CN 96109129A CN 96109129 A CN96109129 A CN 96109129A CN 1090638 C CN1090638 C CN 1090638C
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Abstract
The present invention relates to a homogeneous phase metallocene catalyst for olefinic polymerization and copolymerization and a preparing method thereof. A plurality of aluminum alkyl compounds are adopted. The molecular weight distribution of an olefin polymer prepared from the catalyst is adjustable, and the olefin polymer can also have wide molecular weight distribution, so that the processing and the application of the polymer become favorable.
Description
The present invention relates to a kind of olefinic polymerization polymeric catalyzer and method for making thereof together of being used for, more particularly, relate to a kind of olefinic polymerization polymeric homogeneous phase metallocene catalyst and method for making thereof together of being used for.
As everyone knows, with the various metallocene compounds that are positioned at period of element IVB group 4 transition metal such as zirconium, hafnium, titanium etc. is Primary Catalysts, aikyiaiurnirsoxan beta (MAO) is the homogeneous catalysis system that promotor forms, and has obtained extensive studies and application in the polymerization of alkene and copolymerization.On this basis, further developed the technology for preparing homogeneous catalyst with transition metal metallocene, aluminum alkyls and water again, for example patent WO 89/02448 discloses a kind of method for preparing the homogeneous phase metallocene catalyst in polymerization process on the spot, wherein the promotor aikyiaiurnirsoxan beta is generated by aluminum alkyls and water situ reaction, water adds polymerization system with polymerization single polymerization monomer, the content of water is 100～10000ppm in the monomer, and the mol ratio of water and aluminum alkyls is 1: 1～1: 2.
European patent EP 575 875A disclose a kind of catalyst for olefines polymerizing, it is made by following substance reaction: the list of (1) metal Ti, Zr or Hf or the compound of dicyclopentadiene, (2) a kind of alkylaluminium cpd, wherein having an alkyl at least is non-straight chained alkyl, (3) water, Al/H in the reaction system
2The ratio of O is 1: 1～100: 1.
In the above-mentioned prior art, the employed alkylaluminium cpd kind of promotor is single, and the polyolefinic molecular weight distribution that is generated is narrower, and MWD is 2～3, and the processing characteristics of polymkeric substance is relatively poor.
The objective of the invention is to overcome the defective of the narrow molecular weight distribution that exists in the above-mentioned prior art, a kind of olefinic polymerization polymeric high activated catalyst together that is used for is provided, adopted multiple alkylaluminium cpd, use the molecular weight distribution of olefin polymer of this catalyzer gained adjustable and can have wider molecular weight distribution, thereby help the processed and applied of polymkeric substance.
Second purpose of the present invention provides a kind of described Preparation of catalysts method.
The 3rd purpose of the present invention provides a kind of olefinic polymerization and process for copolymerization that uses described catalyzer.
To describe described catalyzer and its method for making and purposes below in detail.
Catalyzer of the present invention is contacted by following component and makes:
(first) has the Metallocenic compound of general formula for (I)
(C
5R
1 X-mH
5-x) R
m 2(C
2R
1 Y-mH
5-y) M
nQ
3-n(I) metal M is Ti, Zr or Hf in the formula;
Q is Cl or methyl;
C
5R
1 X-mH
5-xAnd C
5R
1 Y-mH
5-yBe to contain identical or different substituent cyclopentadienyl, wherein substituent R
1Be the aromatic base that the alkyl that contains 1～20 carbon atom, alkenyl, aromatic base, alkyl replace, substituting group is identical or different each other, and these substituting groups can contain Si or Ge atom or Si (CH
3)
3, and two or four substituent R of same cyclopentadienyl
1Can constitute one or two ring of 4～6 carbon atoms;
R
2Be the bridged group of two cyclopentadiene parts of connection of one two valency, can be selected from one of following radicals: CR
3 2, C
2R
3 4, SiR
3 2, Si
2R
3 4, GeR
3 2, Ge
2R
3 4, substituent R wherein
3Be R
1Or H, each other can be identical or different, and 2 or 4 s' substituent R
3Can form one or two ring that contains 3～6 carbon atoms;
M=0,1, n=0,1, and during m=1, n=1;
X is one and is not less than m and is not more than 5 integer, and y is one and is not less than m and is not more than 5 integer;
(second) molecular formula is AlR
3-ZH
ZThe compound that two or more is arranged in organo-aluminium compound, R are alkyl, alkenyl or the alky-substituted aromatic base that contains 1～10 carbon atom, each other can be identical can be different, Z is 0 or 1;
(the third) free-water or be loaded with the material of certain water gaging or for containing the organism of two or more oh groups with arbitrary form;
Wherein the mol ratio of the middle Al of metal M and (second) is 1: 100～1: 10000 in (first), is preferably 1: 500～1: 5000, and the best is 1: 1000～1: 2000; The weight ratio of (second) and (third) is with Al/H
2The mol ratio of O is 0.3: 1～100: 1, is preferably 0.3: 1～1: 1, and the best is 0.5: 1.
Above-mentioned Metallocenic compound is selected from dicyclopentenyl zirconium dichloride Cp
2ZrCl
2, ethylidene bridging two indenyl zirconium dichloride En (Ind)
2ZrCl
2, En (IndH
4) ZrCl
2, Me
2Si (Ind)
2ZrCl
2, rac-En (4,7-Me-l-Ind)
2ZrCl, Cp
2HfCl
2.
The organoaluminum compound is selected from trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, triisobutyl aluminium, tri-butyl aluminum in above-mentioned (second) component.
The preferred of two kinds of organo-aluminium compounds is trimethyl aluminium and triisobutyl aluminium, trimethyl aluminium and triethyl aluminum or triethyl aluminum and triisobutyl aluminium in the component (second), and its mol ratio is 1: 99～99: 1, is preferably 1: 10～10: 1.
By changing the kind and the ratio of two or more organo-aluminium compound, the molecular-weight average of resulting polymers and molecular weight distribution can be regulated within the specific limits in the present invention.Owing to formed multiple Organoaluminoxy compound after multiple organo-aluminium compound and the water reaction, form the various active center with Primary Catalysts metallocene reaction back again, this various active center and the catalyst system of depositing can be widened the molecular weight distribution of polymkeric substance with respect to prior art.
Above-mentioned (third) component can be free-water, also can be with arbitrary form and is loaded with the material of certain water gaging or for containing the organism of two or more oh groups; Salt hydrate or adsorb the inert support of certain water gaging: SiO for example
2, Al
2O
3, polymer support such as polyethylene, styrene diethylene benzene copoly mer etc.
Can carry out contact reacts by following several modes between each component of catalyzer of the present invention:
(1) (second) is contacted with (third) component reacts with (first) component again after reacting; Wherein the multiple organo-aluminium compound in (second) component can contact with (third) component simultaneously, also can contact with (third) component respectively.
(2) (first) component is contacted with (second) component react with (third) component again after reacting; Wherein the multiple organo-aluminium compound in (second) component can contact with (first) component simultaneously, also can contact with (first) component respectively.
(3) under polymerizing condition, each component of catalyzer is with polymerization single polymerization monomer contact reacts on the spot.
Wherein (1) kind is the best preparation method of catalyzer of the present invention.
Catalyzer of the present invention can be used for the equal polymerization reaction of ethene or alpha-olefin, also can be used for the copolymerization of ethene and other alkene, and the molecular formula of its comonomer is CH
2=CHR, R is straight chain, branching or the annular alkyl diradical that contains 1～20 carbon atom here.As: propylene, butene-1, amylene-1, hexene-1,4-methylpentene-1, octene-1, decylene-1 etc.
Catalyzer of the present invention can be used for liquid-phase polymerization, and the solvent of employing has: aromatic hydrocarbon solvent, and as toluene, dimethylbenzene, or aliphatic solvents, as: hexane, heptane, Trimethylmethane, hexanaphthene.
Polymerization temperature is 0～250 ℃, is preferably 20～100 ℃.
Each component in catalyzer back that can contact before polymerization adds in the polymerization system, also can be in polymerization system with polymerization single polymerization monomer contact reacts on the spot.
The maximum characteristics of catalyzer of the present invention are by changing the kind and the ratio of two or more organo-aluminium compounds in the catalyzer, the molecular weight distribution of resulting polymers can being regulated in 1.5～10 scopes.
And the homogeneous phase metallocene catalyst is under the situation that does not adopt other measure in the prior art, and its molecular weight distribution generally only limits to 1.5～2.5.Be beneficial to post-treatment production if will widen the molecular weight distribution of polymkeric substance, generally be by adopting a plurality of metallocene compounds or adopting the multi-stage polymeric mode, adopt the different polymerization temperatures and the molecular weight regulator of different concns at each section, therefore need bigger facility investment and more loaded down with trivial details technical process.Catalyzer of the present invention is then comparatively simple for the control and the adjusting of polymericular weight and molecular weight distribution.
Each component that another characteristics of catalyzer of the present invention are catalyzer can be in polymerization system with polymerization single polymerization monomer contact reacts on the spot, avoided the treating process of aikyiaiurnirsoxan beta in the ordinary method, thereby reduced the loss of Al and can obtain advantages of high catalytic activity.
In addition, in catalyst system of the present invention, Al/H
2The mol ratio of O is 0.3: 1～100: 1, is preferably 0.3: 1～1: 1, and the best is 0.5: 1, and at lower Al/H
2The O ratio has obtained high polymerization activity down.For example: Al/H
2O=1: 1 o'clock, active=3.71 * 10
6PEg/molZrh, Al/H
2O=0.5: 1 o'clock, active=6.09 * 10
6PEg/molZrh.And the Al/H of prior art
2Therefore O was at least 1: 1, and under the identical situation of activity, in the catalyst system of the present invention, the add-on of water can suitably increase and the add-on of aluminum alkyls can reduce relatively, therefore can reduce catalyst production cost widely.
Embodiment
Example 1 under the nitrogen protection, adds the 100ml toluene solvant in the reaction flask of a 500ml, stir to add trimethyl aluminium toluene solution 1.5ml (concentration 1.0M) and triisobutylaluminum toluene solution 0.1ml (concentration 1.0M), H down
2O 0.04ml, saturated with ethene, under 40 ℃ and normal pressure, add Cp
2ZrCl
2Toluene solution 1.0ml (concentration 1.5mM), reaction 10min ends with HCl methyl alcohol, can obtain polyethylene powders 5.75g, catalytic activity 2.3 * 10
7GPE/molZrhr, its number-average molecular weight is 290,000, molecular weight distribution is 2.6 (GPC testing method).
Comparative Examples 1 reaction conditions only adopts a kind of organo-aluminium compound with example 1, and it the results are shown in Table 1.
Example 2 reaction conditionss are only changed into the ratio of two kinds of organo-aluminium compounds with example 1, trimethyl aluminium toluene solution 1.0ml (concentration 1.0M) and triisobutylaluminum toluene solution 0.5ml (concentration 1.0M), and it the results are shown in Table 1.
Example 3 reaction conditionss are only changed into the ratio of two kinds of organo-aluminium compounds trimethyl aluminium toluene solution 0.75ml (concentration 1.0M) and triisobutylaluminum toluene solution 0.75ml (concentration 1.0M) with example 1, and it the results are shown in Table 1.
Table 1
| Embodiment | Trimethyl aluminium (ml) | Triisobutyl aluminium (ml) | Water (ul) | Polymerization temperature (℃) | Metallocene 1.5mM | Polymkeric substance (g) | Polymerization activity * | Mn (×10 4) | MWD |
| Example 1 example 2 | 1.5 1.0 | 0.1 0.5 | 30 30 | 40 40 | Cp 2ZrCl 2 Cp 2ZrCl 2 | 5.75 15.8 | 23 63 | 27 30 | 2.6 3.5 |
| Example 3 | 0.75 | 0.75 | 30 | 40 | Cp 2ZrCl 2 | 3.5 | 14 | 50 | 7.2 |
| Contrast 1 | 1.6 | 30 | 40 | Cp 2ZrCl 2 | 6.25 | 25 | 26 | 1.8 |
Polymerization activity unit: 10
6G polymkeric substance/molcathr
Example 4～example 6: reaction conditions is with example 1, and only the ratio with two kinds of organo-aluminium compounds changes and the kind change, and polymerization time is 30min, obtains Alathon, and it the results are shown in Table 2
Table 2
| Embodiment | Aluminum alkyls 1 (1.5ml) | Aluminum alkyls 2 (0.1ml) | Water (ul) | Polymerization temperature (℃) | Metallocene 1.5mM | Polymkeric substance (g) | Polymerization activity * | Mn (×10 4 ) | MWD |
| Example 4 examples 5 examples 6 | Trimethyl aluminium trimethyl aluminium triethyl aluminum | Triisobutyl aluminium triethyl aluminum triisobutyl aluminium | 30 30 30 | 40 40 40 | Cp 2ZrCl 2 Cp 2ZrCl 2 Cp 2ZrCl 2 | 17.3 12.0 2.55 | 23 16 3.4 | 27 | 2.6 2.7 2.3 |
Example 7 under the nitrogen protection, adds the 100ml toluene solvant in the reaction flask of a 500ml, stir to add trimethyl aluminium toluene solution 2.9ml (concentration 1.0M) and triisobutylaluminum toluene solution 0.1ml (concentration 1.0M), H down
2O 0.108ml, saturated with propylene, under 40 ℃ and normal pressure, add En[Ind]
2ZrCl
2Toluene solution 1.0ml (concentration 2.0mM), reaction 30min ends with HCl methyl alcohol, can obtain polypropylene powder 4.30g, catalytic activity 4.3 * 10
7GPE/molZrhr, its number-average molecular weight is 1.3 ten thousand, molecular weight distribution is 3.2 (GPC testing method).
Example 8～10 reaction conditionss are with example 5, only the gas mixture of ethene and propylene are replaced ethene (ethene: propylene=1: 1), and change the ratio and the Cp of two kinds of aluminum alkylss
2ZrCl
2The concentration of toluene solution is 4.3mM, can obtain ethylene-propylene copolymer, the results are shown in Table 3.
Table 3
| Embodiment | Trimethyl aluminium (ml) | Triisobutyl aluminium (ml) | Water (ul) | Polymerization temperature (℃) | Metallocene 4.3mM | Polymkeric substance (g) | Polymerization activity * | Mn (×10 4) | MWD |
| Example 8 examples 9 examples 10 | 2.9 2.7 2.0 | 0.1 0.3 1.0 | 40 40 40 | 40 40 40 | Cp 2ZrCl 2 Cp 2ZrCl 2 Cp 2ZrCl 2 | 4.30 3.22 1.72 | 2.0 1.5 0.80 | 0.30 0.26 1.2 | 2.6 3.7 8.0 |
Example 11～14 reaction conditionss change the kind of metallocene and the consumption of consumption and aluminum alkyls with example 8, obtain ethylene-propylene copolymer, and it the results are shown in Table 4.
Table 4
| Embodiment | Trimethyl aluminium (ml) | Triisobutyl aluminium (ml) | Water (ul) | Polymerization temperature (℃) | Metallocene 1ml | Polymkeric substance (g) | Polymerization activity * | Mn (×10 4) | MWD |
| Example 11 | 0.95 | 0.05 | 16 | 40 | Cp 2TiCl 2 1.0mM | 0.16 | 0.31 | 2.3 | |
| Example 12 | 1.5 | 0.1 | 29 | 40 | Cp 2HfCl 2 1.1mM | 0.22 | 0.40 | 1.4 | 2.2 |
| Example 13 | 1.5 | 0.1 | 30 | 40 | Me 2Si[Ind] 2ZrCl 2 0.90mM | 22.5 | 50 | 3.1 | |
| Example 14 | 0.68 | 0.02 | 25 | 40 | En[Ind] 2ZrCl 2 0.50mM | 5.25 | 21 | 2.8 | 2.1 |
Claims (11)
1, a kind of catalyzer that can be used for olefinic polymerization and copolymerization is characterized in that, being contacted by following component makes:
(first) has the Metallocenic compound of general formula for (I)
(C
5R
1 X-mH
5-x) R
m 2(C
5R
1 Y-mH
5-y)
nMQ
3-n(I) metal M is Ti, Zr or Hf in the formula;
Q is Cl or methyl;
C
5R
1 X-mH
5-xAnd C
5R
1 Y-mH
5-yBe to contain identical or different substituent cyclopentadienyl, wherein substituent R
1Be the aromatic base that the alkyl that contains 1～20 carbon atom, alkenyl, aromatic base, alkyl replace, substituting group is identical or different each other, and these substituting groups can contain Si or Ge atom or Si (CH
3)
3, and two or four substituent R of same cyclopentadienyl
1Can constitute one or two ring of 4～6 carbon atoms;
R
2Be the bridged group of two cyclopentadiene parts of connection of one two valency, be selected from one of following radicals: CR
3 2, C
2R
3 4, SiR
3 2, Si
2R
3 4, GeR
3 2, Ge
2R
3 4, substituent R wherein
3The same R of definition
1Or H, each other can be identical or different, and 2 or 4 s' substituent R
3Can form one or two ring that contains 3～6 carbon atoms;
M=0,1, n=0,1, and during m=1, n=1;
X is one and is not less than m and is not more than 5 integer, and y is one and is not less than m and is not more than 5 integer;
(second) molecular formula is AlR
3-ZH
ZTwo or more compound in the organo-aluminium compound, R are alkyl, alkenyl or the alky-substituted aromatic base that contains 1～10 carbon atom, each other can be identical can be different, Z is 0 or 1;
(the third) free-water or be loaded with the material of certain water gaging or for containing the organism of two or more oh groups with arbitrary form;
Wherein the mol ratio of metal M and (second) is 1: 100～1: 10000 in (first), and the amount ratio of (second) and (third) is with Al/H
2The molar ratio computing of O is 0.3: 1～100: 1.
2, catalyzer according to claim 1 is characterized in that, component (first) is dicyclopentadienyl zirconium dichloride, ethylidene bridging two indenyl zirconium dichlorides or dimethyl-silicon bridging two indenyl zirconium dichlorides.
3, catalyzer according to claim 1 is characterized in that, component (second) is trimethyl aluminium and triisobutyl aluminium, trimethyl aluminium and triethyl aluminum or triethyl aluminum and triisobutyl aluminium.
4, catalyzer according to claim 1 is characterized in that, wherein a kind of in the component (second) is trimethyl aluminium.
According to claim 1 or 3 described catalyzer, it is characterized in that 5, the mol ratio of two kinds of organo-aluminium compounds is 1: 99～99: 1 in the component (second).
According to claim 1 or 3 described catalyzer, it is characterized in that 6, the mol ratio of two kinds of organo-aluminium compounds is 1: 10～10: 1 in the component (second).
7, catalyzer according to claim 1 is characterized in that, the amount ratio of component (second) and (third) is with Al/H
2The molar ratio computing of O is 0.3: 1～1: 1.
8, catalyzer according to claim 1 is characterized in that, the amount ratio of component (second) and (third) is with Al/H
2The molar ratio computing of O is 0.5: 1.
9, the described Preparation of catalysts method of claim 1 is characterized in that: a kind of mode during each component of described catalyzer is can be following several is reacted:
(1) (second) is contacted with (third) component reacts with (first) component again after reacting; Wherein the multiple organo-aluminium compound in (second) component can contact with (third) component simultaneously, also can contact with (third) component respectively;
(2) (first) component is contacted with (second) component react with (third) component again after reacting;
(3) under polymerizing condition, each component of catalyzer is with polymerization single polymerization monomer contact reacts on the spot.
10, the application of the described catalyzer of one of claim 1 to 8 in the copolymerization of the equal polymerization reaction of ethene, alpha-olefin or ethene and alpha-olefin, it is characterized in that: the back that contacted before polymerization of each component in the catalyzer adds in the polymerization system, or in polymerization system with polymerization single polymerization monomer contact reacts on the spot.
11, purposes according to claim 10 is characterized in that, described equal polymerization reaction or copolymerization are liquid-phase polymerizations.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109129A CN1090638C (en) | 1996-07-26 | 1996-07-26 | Catalyst for olefine polymer and copolymer and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109129A CN1090638C (en) | 1996-07-26 | 1996-07-26 | Catalyst for olefine polymer and copolymer and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1172118A CN1172118A (en) | 1998-02-04 |
| CN1090638C true CN1090638C (en) | 2002-09-11 |
Family
ID=5120242
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96109129A Expired - Lifetime CN1090638C (en) | 1996-07-26 | 1996-07-26 | Catalyst for olefine polymer and copolymer and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1090638C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051684A (en) * | 1989-10-10 | 1991-05-29 | 弗纳技术股份有限公司 | The metalloscene catalyst that contains Lewis acid and aluminum alkyls |
| EP0575875A2 (en) * | 1992-06-18 | 1993-12-29 | Montell Technology Company bv | Catalysts for the polymerization of olefins |
-
1996
- 1996-07-26 CN CN96109129A patent/CN1090638C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051684A (en) * | 1989-10-10 | 1991-05-29 | 弗纳技术股份有限公司 | The metalloscene catalyst that contains Lewis acid and aluminum alkyls |
| EP0575875A2 (en) * | 1992-06-18 | 1993-12-29 | Montell Technology Company bv | Catalysts for the polymerization of olefins |
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| Publication number | Publication date |
|---|---|
| CN1172118A (en) | 1998-02-04 |
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