CN1163526C - Bifunational catalysis system for preparing ultralow-density polyethyleen (ULDPE) by ethylene polymerization - Google Patents
Bifunational catalysis system for preparing ultralow-density polyethyleen (ULDPE) by ethylene polymerization Download PDFInfo
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- CN1163526C CN1163526C CNB001057960A CN00105796A CN1163526C CN 1163526 C CN1163526 C CN 1163526C CN B001057960 A CNB001057960 A CN B001057960A CN 00105796 A CN00105796 A CN 00105796A CN 1163526 C CN1163526 C CN 1163526C
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- alkylaluminoxane
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- density polyethylene
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Abstract
The present invention relates to a double-function catalyst system used for preparing ultra-low-density polyethylene by ethylene polymerization, which is composed of a dimerization catalyst (Ti(OR)4) and a copolymerization catalyst (EtInd2ZrCl2, Me2SiInd2ZrCl2, C5Me4Me3SiIndt-BuNiCl2 or Cp2Zrcl2). The polymerization system has high catalytic activity which is two to three times of the vinyl homopolymerization activity of metallocene compounds.
Description
The invention relates to polymerization new LDPE (film grade) (ULDPE), particularly a kind of ultralow close poly bifunctional catalyst system.
LLDPE (USP, 4 542 199) adopts catalyst for copolymerization catalyzed ethylene and alpha-olefin such as butylene more, and monomer copolymerizations such as hexene form, and it requires high to polymerization single polymerization monomer, polymerization technique complexity, shortcoming such as molecular chain structure is wayward.
(J.Polym.Chem.Ed., 22,3027,1984 in the document; J.Polym.Sci.A, Polym Chem., 24,1069,1984), adopt bifunctional catalyst system to be prepared LLDPE, provide an extraordinary method for simplifying production technique, it adopts Ti (OR)
4Be dimerization catalyst, adopt TiCl
4/ PE-MgCl
2The Z-N catalyzer be that catalyst for copolymerization is at promotor AlR
3Effect under, adopting ethene is that unique polymerization single polymerization monomer in-situ polymerization gets.Because adopting the Z-N catalyzer is catalyst for copolymerization, its activity is low, and comonomer butylene insertion rate is low, and molecular weight distribution is wide, shortcomings such as density height, the regularity of more uncontrollable molecular chain.
Chemistry institute of Chinese Academy of Sciences application number is that the bifunctional catalysis system of 991196652.X prepares LLDPE, although used metallocene as catalyst for copolymerization, is adopted as dimerization catalyst and is prepared LLDPE, because the promotor of beta-diketon zirconium dichloride is AlEt
2Cl, and the promotor of metallocene is MAO, wherein if adopt difunctional system to carry out polymerization, must use the blended alkyl aluminum system, and studies show that in a large number aluminum alkyls is non-coagent for metallocene catalyst, the inevitable metallocene catalysis performance that influences greatly, caused polymerization activity obviously to descend, copolymerization performance descends, and monomer insertion rate is low altogether.The another one deadly defect is exactly the dimerization catalyst content height that uses in the bifunctional catalysis system, is generally about 10-20 times of catalyst for copolymerization.
The present invention seeks to overcome above-mentioned two kinds of mutual interference of promotor, polymerization activity is risen, copolymerization performance is good, be total to monomer insertion rate height, shortcomings such as dimerization catalyst content is low, and molecular weight distribution is low, and density is low, proposed that a kind of to be used for adopting metallocene by ethene be difunctional polymeric catalyst for copolymerization, Ti (OR)
4Be dimerization catalyst, the ultralow close poly bifunctional catalysis system of polymerization.
A kind of bifunctional catalysis system that is used for vinyl polymerization ultra-low density polyethylene (ULDPE) of the present invention comprises dimerization catalyst and copolymerization catalyst system.Wherein said dimerization catalyst refers to comprise that the dimerization Primary Catalysts is alkoxy titanium compound (Ti (OR)
4) (wherein R is C
1-C
6Alkyl or aryl) and promotor alkylaluminium cpd AlR '
3(wherein R ' is C
1-C
6Alkyl) form.
Catalyst for copolymerization of the present invention is by the Primary Catalysts metallocene compound, and its general molecular formula has following structure;
C
P IMR
1R
2R
3(I) C
PI-A-R
1MR
2R
3 (II)
C
P IC
P IIMR
1R
2(III) C
P I-A-C
P IIMR
1R
2(IV)
Form with promoter aluminium alkyl oxygen alkane.
Wherein M is Ti, Zr, Hf; C
P IAnd C
P IIBe the cyclopentadiene of cyclopentadiene or replacement, indenyl, the monocycle of band such as fluorenyl conjugated pi electron or the ligand of polynuclear plane all can have substituting group.R
1, R
2, R
3, be H, alkyl, halogen, silane, alkoxyl group, amido, phosphino-s etc. contain O, Si, N, P ligand compound.A is meant bridged group, refers to-(OY
2) n-,-(SiY2) n-,-(GeY2) n-, wherein, Y is an alkyl, halogen, alkoxyl group, silylation, amido, phosphino-.N=1-4, A also can be the ring texture group; Abutment can be doube bridge, single bridge, many bridge constructions.Concrete metallocene compound is Cp
2ZrCl
2, EtInd
2ZrCl
2, Me
2SiInd
2ZrCl
2, C
5Me
4Me
2SiInd
tBuNTiCl
2
Alkylaluminoxane has following structure: linear structure R-(AlR-O) n-AlR
2The m of ring texture-(AlR-O), n=1-40 wherein, the best is 20, m=3-40, the best is 3-20, R is a kind of C
1-C
8Alkyl, be preferably methyl.As MMAO, MAO, BAO, EAO.
The method for making of bifunctional catalysis system of the present invention follows these steps to carry out:
1) alkylaluminoxane and toluene are formulated as 1.0-3.0mol/L, optimum concn is the toluene solution of 1.4-2.5mol/L.
2) with metallocene and alkylaluminoxane toluene solution, be 1 in molar ratio: 100-1: 5000 ratio, the best are 1: 500-1: 2000 are made into mixing solutions, at Ar or (N
2) protect down, 25 ℃ were stirred 0.2-4 hour down, obtain the mixing solutions of metallocene and alkylaluminoxane.
3) feed ethene in the reactor that nitrogen and ethene were replaced, add toluene through the deoxidation of sodium Metal 99.5 reflux dewatering.Under agitation keep pressure 1.02MPa in the bottle, temperature of reaction 0-100 ℃, best 30-70 ℃.
4) add 1. AlR successively
3(R is Et, CH
3, isobutyl-), wherein with AlEt
3, AlMe
3, Al (
I-Bu)
32. Ti (OR)
4, R is C
1-C
6Alkyl or aryl, best Ti (OBu)
4Toluene solution.Dimerization promotor/Ti (OBu) wherein
4Mol ratio is 5: 1000, and optimum mole ratio is 5: 100.Carry out pre-polymerization 0-20min.
5) mixing solutions with metallocene and alkylaluminoxane adds in the reactor, and its dimerization catalyst/metallocene mol ratio is 0.1-20, and optimum mole ratio is 0.25-10.
6) reaction 30-120min adds acidifying ethanol termination reaction, and washing, vacuum-drying obtain theoretical density ethene, wherein can obtain ULDPE.
The catalyst system of preparation method's gained of the present invention has following feature:
1) the present invention at first carries out alkylating reaction with alkylaluminoxane with metallocene, has avoided itself and AlR
3Generate the nonreactive activity species.The alkylaluminoxane that uses comprises methylaluminoxane MAO, and ethyl aikyiaiurnirsoxan beta EAO etc. wherein are best with MAO, and consumption is the 1/2-2/3 that the metallocene catalyst ethylene homo closes.
2) this difunctional polymerization system has advantages of high catalytic activity, and its activity is the active 2-3 of metallocene ethylene homo times.
3) polymkeric substance that is obtained after this difunctional polymerization system polymerization is not the full density polythene of 0.8g-0.96g not reach enterprise's density by the content of adjusting dimerization catalyst, and wherein least density reaches the ULDPE scope.
4) use difunctional polymerization system, available ultra-low molecular amount is to the polyethylene kind of ultra-high molecular weight, and it can reach by adjusting dimerization/copolymerization ratio.
5) this catalyst system good reproducibility, monomer insertion rate is 15-5% (mol%) altogether.Altogether monomer is distributed as line style in Polyethylene Chain, and it is had than low melting point, and melting range 70-133 ℃, its degree of crystallinity is 5-90%.The narrow molecular weight distribution of the polymkeric substance that obtains, Mn/Mw=1.5-3.0.
6) pass through
13This polymkeric substance of CNMR is an ethylene-butene copolymer, and its peak is σ 3..75,33.14,29.65,29.17,26.44,25.84,24.16,10.34, and show by calculating and not have block structure in its sequential structure that its number average chain length is n
E=10-20.
Embodiment
Embodiment 1.
All under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
With Ti (OBu-n)
4(I), be the dimerization Primary Catalysts, and AlEt
3(II) be the dimerization promotor, copolyreaction Primary Catalysts and promotor are respectively Et (Ind)
2ZrCl
2(IV) and MAO (V).
Mix reaction by a certain percentage with (IV) with (V), obtain mixing solutions.
The toluene that adds 100ml in the there-necked flask of a 250ml stirs and adds a certain proportion of (II) and (I) down, carry out pre-dimerization reaction at a certain temperature, then (V) and mixing solutions (IV) are added in the reactor, pressure at ethene is under the condition of 770mmHg, through polyreaction, carry out termination reaction, drying by adding acidifying ethanol, washing obtains polymkeric substance.Its operational condition and polymer property are listed in the table 1.
Embodiment 2.
All under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
With Ti (OBu-n)
4(I), be the dimerization Primary Catalysts, and AlEt
3(II) be the dimerization promotor, copolyreaction Primary Catalysts and promotor are respectively Me
2Si (Ind)
2ZrCl
2(IV) and BAO (V).
Mix reaction by a certain percentage with (IV) with (V), obtain mixing solutions.
The toluene that adds 100ml in the there-necked flask of a 250ml stirs and adds a certain proportion of (II) and (I) down, carry out pre-dimerization reaction at a certain temperature, then (V) and mixing solutions (IV) are added in the reactor, pressure at ethene is under the condition of 770mmHg, carry out polyreaction, and carry out termination reaction by adding acidifying ethanol.Its operational condition and polymer property are listed in the table 1.
Embodiment 3.
All under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
With Ti (OBu-n)
4(I), be the dimerization Primary Catalysts, and AlEt
3(II) be the dimerization promotor, copolyreaction Primary Catalysts and promotor are respectively Me
2SiInd
T-BuNTiCl
2(IV) and MAO (V).
Mix reaction by a certain percentage with (IV) with (V), obtain mixing solutions.
The toluene that adds 100ml in the there-necked flask of a 250ml stirs and adds a certain proportion of (II) and (I) down, carry out pre-dimerization reaction at a certain temperature, then (V) and mixing solutions (IV) are added in the reactor, pressure at ethene is under the condition of 770mmHg, carry out polyreaction, and carry out termination reaction by adding acidifying ethanol.Its operational condition and polymer property are listed in the table 1.
Embodiment 4.
All under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
With Ti (OBu-n)
4(I), be the dimerization Primary Catalysts, and AlEt
3(II) be the dimerization promotor, copolyreaction Primary Catalysts and promotor are respectively Cp
2ZrCl
2(IV) and MMAO (V).
Mix reaction by a certain percentage with (IV) with (V), obtain mixing solutions.
The toluene that adds 100ml in the there-necked flask of a 250ml stirs and adds a certain proportion of (II) and (I) down, carry out pre-dimerization reaction at a certain temperature, then (V) and mixing solutions (IV) are added in the reactor, pressure at ethene is under the condition of 770mmHg, carry out polyreaction, and carry out termination reaction by adding acidifying ethanol.Its operational condition and polymer property are listed in the table 1.
The polymerizing condition of table 1 embodiment and polymeric material parameter
The dimerization catalyst catalyst for copolymerization
Mn A Tm
Sequence number
Ti(OR)
4 Al/Ti Zr MAO/Zr 10
4 ℃ d
25
μmol (mol) μmol (mol)
Embodiment 1984 1000＞100 2.6＜40＜0.850
91.93
Embodiment 1384 1,500 4.89 3.15 0.901
97.58
Embodiment 1384 800 10.13 4.61 92.21 0.905
Embodiment 1384 500 4.5 3.31 115.9 0.889
Embodiment 1384 1,000 4.21 5.14 109.2 0.918
Embodiment 2684 1,000 1.1 1.37＜50＜0.850
Embodiment 2184 1,000 5.3 5.57 1.16.9 0.929
Embodiment 2 1.5 84 1,000 4.5 3.64 96.86 0.906
Embodiment 2 4.5 84 1,000 3.24 1.90 118.7 0.906
88.89
Embodiment 2984 1000＞100 1.02＜0.850
118.38
99.99
Embodiment 3384 1000＞100 4.27 0.9015
93.23
Embodiment 3 1.5 84 1000＞100 4.10 108 0.9240
81.9
Embodiment 3684 1000＞100 4.45 0.900
72.0
2.51 82.5
Embodiment 4384 700＞100 0.9075
98.39
Embodiment 4384 1500＞100 4.70 110.67 0.9250
Embodiment 4 2.25 83 2000＞100 1.43 115.78 0.9350
A: polymerization activity 10
6GPE/molZr.h, Tm: fusing point, d
25: density g/cm
3, 50 ℃ of temperature, Mn: viscosity-average molecular weight, pre-polymerization time 5min, polyase 13 0min
Claims (7)
1. a bifunctional catalysis system that is used for the vinyl polymerization ultra-low density polyethylene is made up of Primary Catalysts and promotor, it is characterized in that described Primary Catalysts is dimerization catalyst and catalyst for copolymerization,
Above-mentioned dimerization catalyst is by alkoxy titanium compound Ti (OR)
4R is C in the formula
1-C
6The dimerization Primary Catalysts of alkyl or aryl and alkylaluminium cpd AlR ＇
3, R ' is C in the formula
1-C
6The promotor of the dimerization catalyst of alkyl is formed,
Above-mentioned catalyst for copolymerization is by EtInd
2ZrCl
2, Me
2SiInd
2ZrCl
2, C
5Me
4Me
2SiInd
tBuNTiCl
2Or Cp
2ZrCl
2And have linear structure MMAO, the alkylaluminoxane of MAO or BAO is formed.
2. according to a kind of method for making that is used for the bifunctional catalysis system of vinyl polymerization ultra-low density polyethylene, it is characterized in that step is carried out in the following order:
1) alkylaluminoxane and toluene are formulated as the 1.0-3.0mol/L toluene solution,
2) with Cp
2ZrCl
2, EtInd
2ZrCl
2, Me
2SiInd
2ZrCl
2Or C
5Me
4Me
2SiInd
tBuNTiCl
2With the alkylaluminoxane toluene solution, be 1 in molar ratio: 100-1: 5000, at Ar or N
2Under the protection, 25 ℃ were stirred 0.2-4 hour down, obtained the mixing solutions of metallocene compound and alkylaluminoxane,
3) in the reactor that nitrogen and ethene were replaced, feed ethene, add toluene, under agitation keep pressure 1.02MPa in the bottle through the deoxidation of sodium Metal 99.5 reflux dewatering, temperature of reaction 0-100 ℃,
4) add AlEt
3, AlMe
3Or Al (Bu)
2And Ti (OR)
4, R is C
1-C
6Alkyl or aryl, toluene solution, Ti wherein: the Al mol ratio is 5: 1000, carries out pre-polymerization 0-20min,
5) with Cp
2ZrCl
2, EtInd
2ZrCl
2, Me
2SiInd
2ZrCl
2Or C
5Me
4Me
2SiInd
tBuNTiCl
2The mixing solutions of metallocene compound and alkylaluminoxane adds in the reactor, and the mol ratio of its dimerization catalyst/metallocene compound is 0.1-20,
6) reaction 30-120min adds acidifying ethanol termination reaction, and washing, vacuum-drying obtain theoretical density ethene, wherein can obtain ultralow close polyethylene.
3. a kind of method for making that is used for the bifunctional catalysis system of vinyl polymerization ultra-low density polyethylene according to claim 2, the strength of solution that it is characterized in that described alkylaluminoxane and toluene is 1.4-2.5mol/L.
4. a kind of method for making that is used for the bifunctional catalysis system of vinyl polymerization ultra-low density polyethylene according to claim 2 is characterized in that described metallocene and alkylaluminoxane mol ratio are 1: 500-1: 2000.
5. a kind of method for making that is used for the bifunctional catalysis system of vinyl polymerization ultra-low density polyethylene according to claim 2 is characterized in that described temperature of reaction is 30-70 ℃.
6. a kind of method for making that is used for the bifunctional catalysis system of vinyl polymerization ultra-low density polyethylene according to claim 2 is characterized in that described dimerization catalyst/metallocene mol ratio is 0.25-10.
7. a kind of method for making that is used for the bifunctional catalysis system of vinyl polymerization ultra-low density polyethylene according to claim 2 is characterized in that described dimerization catalyst is Ti (O
N-Bu)
4The time Ti/Al mol ratio be 5: 100.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001057960A CN1163526C (en) | 2000-04-11 | 2000-04-11 | Bifunational catalysis system for preparing ultralow-density polyethyleen (ULDPE) by ethylene polymerization |
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|---|---|---|---|
| CNB001057960A CN1163526C (en) | 2000-04-11 | 2000-04-11 | Bifunational catalysis system for preparing ultralow-density polyethyleen (ULDPE) by ethylene polymerization |
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| CN1163526C true CN1163526C (en) | 2004-08-25 |
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| US8722821B1 (en) | 2013-03-18 | 2014-05-13 | King Fahd University Of Petroleum And Minerals | Method of making polyolefin with a silicon nitride nano-filler |
| CN106699948B (en) * | 2015-11-13 | 2020-05-12 | 中国石油化工股份有限公司 | Preparation method of ultra-low density polyethylene |
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