CN1421467A - In-situ copolymerization catalyst system for preparing linear low-density polyethylene - Google Patents

In-situ copolymerization catalyst system for preparing linear low-density polyethylene Download PDF

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CN1421467A
CN1421467A CN 01139773 CN01139773A CN1421467A CN 1421467 A CN1421467 A CN 1421467A CN 01139773 CN01139773 CN 01139773 CN 01139773 A CN01139773 A CN 01139773A CN 1421467 A CN1421467 A CN 1421467A
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oligomerization
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CN1167716C (en
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胡友良
王航
马志
邹军锋
张明革
柯毓才
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Abstract

The in-situ copolymerization catalyst system for preparing linear low-density polyethylene consists of oligomerizing catalyst, copolymerizing catalyst and cocatalyst. The oligomerizing catalyst is homogeneous or carried alpha-diimino pyridine iron compound, the copolymerizing catalyst is the cyclopentadienyl compound with Ti, Zr, or Hf as central atom or its carried catalyst, and the cocatalyst is alkyl aluminoxane. The catalyst system of the present invention has high catalytic activity, and the product has relatively low smelting point, 106.2-123.9 deg.c, relatively low crystallization degree, 16.7-65.8%, and density of 0.920-0.945 g/cu.cm.

Description

A kind of in-situ copolymerization catalyst system for preparing linear low density polyethylene
Technical field
The present invention relates to the in-situ copolymerization catalyst system of a kind of preparation linear low density polyethylene (LLDPE).
Background technology
Realize that with metallocene catalyst or constrained geometry catalyst the copolymerization LLDPE of ethene and alpha-olefin is a research focus in the last few years, required is generated by ethylene oligomerization usually, obtains hexene, octene, decene etc. through rectifying then.If can adopt a kind of in-situ copolymerization catalyst system, promptly in reaction system with catalyst for oligomerization by ethene at first oligomerisation be that alpha-olefin adds catalyst for copolymerization then, generate LLDPE with in-situ copolymerization then.This will simplify production technique, has solved the problem of the main dependence on import of domestic alpha-olefin simultaneously, greatly reduces production cost.J.Polym.Sci, Polym.Chem.Ed.22,3027 (1984); 24,1069 (1986), petrochemical complex, 23.491 (1994).
Traditional Ziegler-Natta catalyst is applied to ethene and the fashionable LLDPE that can not obtain high insertion rate of alpha-olefin copolymer, and is poorer for its copolymerization performance of high carbon number alpha-olefin.And the methylaluminoxane of finding at the eighties Kaminsky (MAO) can improve catalytic activity and polymeric copolymerization performance (Angew.Chem.Int.Ed.Engl.19,396 (1980)) thereof as the promotor of metallocene.At present, the multipolymer by metallocene catalysts ethene and propylene, high carbon number alpha-olefin is the research focus of polyolefine material.In recent years, emerging constrained geometry catalyst then is present ideal copolymerization catalyst for ethylene.Bazan [J.Am.Chem.Soc.120,7143 (1998)] design synthetic (C 6H 5B-OEt) 2ZrCl 2Can under the effect of MAO, the catalyzed ethylene oligomerisation close, obtain ethylene oligomer, and then utilize constrained geometry catalyst and in-situ copolymerization, successfully obtain LLDPE.But, its maximum shortcoming is the alpha-olefin poor selectivity of its ethylene oligomerization catalyst instability that adopts and catalyzer, selectivity is 40-90%, its oligomerization product is the 1-alkene, 2-alkyl-1-alkene and 2-alkene, wherein, 2-alkyl-1-alkene and 2-alkene can not form copolymerization product with ethene.
Summary of the invention
The present invention is based on above-mentioned technical background, the in-situ copolymerization catalyst system of a kind of preparation linear low density polyethylene (LLDPE) is provided, it is that the novel alpha-diimine pyridine iron with homogeneous phase with high reactivity, highly selective or loading type is that title complex is that (alpha-olefin selection rate＞99%, carbon number distribution are C to catalyst for oligomerization 4～C 30, be mainly C 8～C 14), homogeneous phase or loaded metallocene title complex are that catalyst for copolymerization is formed jointly, with ethene is unique raw material, alkylaluminoxane is unique promotor, elder generation's original position generates alpha-olefin, the in-situ copolymerization prepared in reaction of finishing then with ethene goes out linear low density polyethylene (LLDPE), solves the deficiency in the above-mentioned research, has reached and can carry out the effect that molecule is cut out to polymkeric substance.
A kind of in-situ copolymerization catalyst system for preparing linear low density polyethylene of the present invention is made up of catalyst for oligomerization, catalyst for copolymerization and promotor.
Described catalyst for oligomerization is that the novel alpha-diimine pyridine iron of homogeneous phase or loading type is title complex (presses document J.Am.Chem.Soc., 1998,120:7143-7144 is synthetic), and the alpha-diimine pyridine iron is that the molecular structural formula of title complex is as follows: R 1=-H ,-CH 3X=Br, ClR 2=-CH 3,-CH 2CH 3,-CH (CH 3) 2,-OCH 3R 3=-CH 3,-CH 2CH 3,-CH (CH 3) 2,-OCH 3,-Br ,-Cl ,-FX=-Br ,-Cl
Described catalyst for copolymerization is for being the cyclopentadienyl compound of central atom or their supported catalyst with Ti, Zr, Hf.The cyclopentadienyl compound can be single bridging, and doube bridge connection or non-bridge crosslinking structure are that the central atom metallocene is best with the Zr of bridging, and these compounds are streat drug Et (Ind) 2ZrCl 2, Me 2Si (Ind) 2ZrCl 2, Et (Ind) 2ZrMe 2, Me 2Si (Ind) 2ZrMe 2, Cp *SiMe 2NBu tZrCl 2, Cp *SiMe 2NBu tTiCl 2, IndSiMe 2NBu tZrCl 2Deng.
The raw material carrier of described loading type oligomerisation, catalyst for copolymerization is organic carrier or inorganic carrier, generally mostly is porous carrier.The example of non-limiting scope is as SiO 2, MgCl 2, Al 2O 3, talcum, zeolite, polynite, polyethylene, polystyrene etc.The granular size of carrier is 0.1-1000 μ m, and specific surface area is 60-500m 2/ g, pore volume are 0.1-7.0cc/g, and the aperture is 30-700 .
Described promotor is an alkylaluminoxane, as methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta (EAO), isobutyl aluminium alkoxide (iBAO) etc.
The in-situ copolymerization catalyst system of a kind of preparation linear low density polyethylene of the present invention (LLDPE) has following feature:
1. the catalyst for oligomerization of the present invention's employing is that homogeneous phase or loading type alpha-diimine pyridine iron are title complex, and its chemical molecular structural formula is as follows: R 1=-H ,-CH 3X=Br, ClR 2=-CH 3,-CH 2CH 3,-CH (CH 3) 2,-OCH 3R 3=-CH 3,-CH 2CH 3,-CH (CH 3) 2,-OCH 3,-Br ,-Cl ,-FX=-Br ,-Cl
2. the homogeneous phase or the loading type catalyst for oligomerization of the present invention's employing are copolymer at copolymerization catalyst system
Concentration in the system is 5 * 10 -6Mol/L～400 * 10 -6Mol/L, the best is 10 * 10 -6Mol/L～200 * 10 -6Mol/L.
3. the catalyst for copolymerization of the present invention's employing is that homogeneous phase or carried metallocene catalyst: Ti, Zr, Hf are the cyclopentadienyl compound of central atom.The cyclopentadienyl compound can be single bridging, and doube bridge connection or non-bridge crosslinking structure are that the central atom metallocene is best with the Zr of bridging, and these compounds are
Et(Ind) 2ZrCl 2、Me 2Si(Ind) 2ZrCl 2、Et(Ind) 2ZrMe 2、Me 2Si(Ind) 2ZrMe 2、
Cp *SiMe 2NBu tZrCl 2, Cp *SiMe 2NBu tTiCl 2, IndSiMe 2NBu tZrCl 2Deng.
4. the homogeneous phase that adopts of the present invention or carried metallocene catalyst are that concentration in the copolymerization system is 5 * 10 at copolymerization catalyst system -6Mol/L～100 * 10 -6Mol/L, the best is 10 * 10 -6Mol/L～60 * 10 -6Mol/L.
5. the catalyst for oligomerization of the present invention's employing and the mol ratio of catalyst for copolymerization are 1: 4～50: 1, and the best is 1: 1～20: 1.
6. the loading type catalyst for oligomerization and the employed carrier of catalyst for copolymerization of the present invention's employing are organic carrier or inorganic carrier, as SiO 2, MgCl 2, Al 2O 3, talcum, zeolite, polynite, polyethylene, polystyrene etc. are preferably SiO 2
7. the promotor of the present invention's employing is an alkylaluminoxane, as methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta (EAO), isobutyl aluminium alkoxide (iBAO) etc., wherein is best with MAO.Keep Al/ (Fe+Zr or Ti) mol ratio=500: 1～5000: 1, the best is 1000: 1～3000: 1.
8. polymerization system of the present invention has advantages of high catalytic activity, and product has than low melting point and lower degree of crystallinity, and its melting range is 106.2 ℃～123.9 ℃, and its degree of crystallinity scope is 16.7%～65.8%, and density range is at 0.920～0.945g/cm 3
Embodiment
In following examples, adopt bifunctional catalyst system, follow these steps to carry out directly by the preparation method of the synthetic LLDPE of ethene:
1. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL adding through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 30 ℃～80 ℃, stir adding alkylaluminoxane promotor down, stir after 2 minutes, add the catalyst for oligomerization of a certain amount of homogeneous or load, reacted 0 minute～20 minutes
2. the co-catalyst that adds homogeneous or load, keeping ethylene pressure in the bottle is 770mmHg polymerase 10 .5 hour～1 hour,
3. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.
Embodiment 1
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
B: catalyst for copolymerization Et (Ind) 2ZrCl 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 50 ℃, add MAO[Al/ (Fe+Zr)=2000: 1 (mol ratio) under stirring], stir after 2 minutes adding 1 * 10 -6Mol catalyst for oligomerization A reacted 5 minutes;
4. add 1 * 10 -6Mol co-catalyst B, the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerase 10 .5 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 2
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
B: catalyst for copolymerization, SiO 2Loading type Et (Ind) 2ZrCl 2
With 1gSiO 2400 ℃ of following roastings 6 hours, then under vacuum 200 ℃ handled 2 hours.Be cooled to room temperature, add 10mLMAO (1.4mol/L toluene solution) and 10mL toluene, 50 ℃ were reacted 12 hours down.With toluene wash for several times, vacuum is drained, and preserves standby under noble gas.With 0.05g catalyzer Et (Ind) 2ZrCl 2Join in the above-mentioned system, add 20mL toluene again, stirred 12 hours down at 60 ℃.With toluene wash for several times, till supernatant liquid becomes colorless.Vacuum is drained, and preserves standby under noble gas.
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 60 ℃, add MAO[Al/ (Fe+Zr)=1000: 1 (mol ratio) under stirring], stir after 2 minutes adding 1 * 10 -6Mol catalyst for oligomerization A reacted 10 minutes;
4. add 0.0182g (1 * 10 -6Mol) co-catalyst B (Zr content 0.0050gZr/g supported catalyst), the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerase 10 .5 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 3
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
B: catalyst for copolymerization Et (Ind) 2ZrCl 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 50 ℃, add MAO[Al/ (Fe+Zr)=2000: 1 (mol ratio) under stirring], stir after 2 minutes adding 1 * 10 -6Mol catalyst for oligomerization A reacted 5 minutes;
4. add 2 * 10 -6Mol co-catalyst B, the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerase 10 .5 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 4
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
Figure A0113977300101
B: catalyst for copolymerization Et (Ind) 2ZrCl 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 50 ℃, add MAO[Al/ (Fe+Zr)=2000: 1 (mol ratio) under stirring], stir after 2 minutes adding 2 * 10 -6Mol catalyst for oligomerization A reacted 2 minutes;
4. add 1 * 10 -6Mol co-catalyst B, the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerase 10 .5 hour; Add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 5
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
Figure A0113977300102
B: catalyst for copolymerization Et (Ind) 2ZrCl 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 50 ℃, add MAO[Al/ (Fe+Zr)=2000: 1 (mol ratio) under stirring], stir after 2 minutes adding 8 * 10 -6Mol catalyst for oligomerization A reacted 2 minutes;
4. add 2 * 10 -6Mol co-catalyst B, the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerization 1 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 6
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
B: catalyst for copolymerization Et (Ind) 2ZrCl 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 50 ℃, add MAO[Al/ (Fe+Zr)=3000: 1 (mol ratio) under stirring], stir after 2 minutes adding 4 * 10 -6Mol catalyst for oligomerization A reacted 10 minutes;
4. add 8 * 10 -6Mol co-catalyst B, the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerization 1 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 7
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
B: catalyst for copolymerization Me 2Si (Ind) 2ZrCl 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 50 ℃, add MAO[Al/ (Fe+Zr)=2000: 1 (mol ratio) under stirring], stir after 2 minutes adding 2 * 10 -6Mol catalyst for oligomerization A reacted 5 minutes;
4. add 2 * 10 -6Mol co-catalyst B, the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerization 1 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 8
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
Figure A0113977300122
B: catalyst for copolymerization Cp *SiMe 2NBu tZrCl 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 70 ℃, add MAO[Al/ (Fe+Zr)=2000: 1 (mol ratio) under stirring], stir after 2 minutes adding 4 * 10 -6Mol catalyst for oligomerization A reacted 10 minutes;
4. add 2 * 10 -6Mol co-catalyst B, the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerase 10 .5 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.
Embodiment 9
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: catalyst for oligomerization
Figure A0113977300131
B: catalyst for copolymerization, SiO 2Supported catalyst Cp *SiMe 2NBu tTiCl 2
With 1gSiO 2400 ℃ of following roastings 6 hours, then under vacuum 200 ℃ handled 2 hours.Be cooled to room temperature, add 15mLMAO (1.4mol/L toluene solution) and 15mL toluene, 60 ℃ were reacted 12 hours down.With toluene wash for several times, vacuum is drained, and preserves standby under noble gas.With 0.052g catalyzer Cp *SiMe 2NBu tTiCl 2Join in the above-mentioned system, add 20mL toluene again, stirred 12 hours down at 60 ℃.With toluene wash for several times, till supernatant liquid becomes colorless.Vacuum is drained, and preserves standby under noble gas.
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feeds ethene then, add 100mL toluene, be warming up to 60 ℃, add MAO[Al/ (Fe+Ti)=1000: 1 (mol ratio) under stirring], stir after 2 minutes adding 4 * 10 -6Mol catalyst for oligomerization A reacted 10 minutes;
4. add 0.0106g (1 * 10 -6Mol) co-catalyst B (Ti content 0.0045g/g supported catalyst), the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerization 1 hour; 5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymer property are listed in the table 1.Embodiment 10
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A:SiO 2The load catalyst for oligomerization
With 1gSiO 2300 ℃ of following roastings 6 hours, then under vacuum 200 ℃ handled 4 hours.Be cooled to room temperature, add 10mLMAO (1.4mol/L toluene solution) and 10mL toluene, 50 ℃ were reacted 12 hours down.With toluene wash for several times, vacuum is drained, and preserves standby under noble gas.The 0.05g catalyzer is joined in the above-mentioned system 40 ℃ of following stirrings 10 hours.With toluene wash for several times, till supernatant liquid becomes colorless.Vacuum is drained, and preserves standby under noble gas.
B: catalyst for copolymerization, SiO 2Supported catalyst Et (Ind) 2ZrCl 2
Method for making is with embodiment 2
C: promotor MAO
3. a 250mL there-necked flask that agitator is housed is replaced with nitrogen and ethene respectively, feed ethene then, add 100mL toluene, be warming up to 50 ℃, stir and add MAO[Al/ (Fe+Zr)=1000: 1 (mol ratio) down], stir after 2 minutes, add 0.0279g (2 * 10 -6Mol) catalyst for oligomerization A (Fe content 0.0040g/g supported catalyst) reacted 20 minutes;
4. add 0.0182g (1 * 10 -6Mol) co-catalyst B (Zr content 0.0050gZr/g supported catalyst), the ethylene pressure in keeping bottle is under the condition of 770mmHg, polymerization 1 hour;
5. add the ethanol solution hydrochloride termination reaction of 10% (volume ratio), obtain the LLDPE product through washing with alcohol, vacuum-drying.Its operational condition and polymerization property thing are listed in the table 1.
Polymerizing condition among table 1. embodiment and aggregated data
Embodiment Catalyst for oligomerization (μ mol) Catalyst for copolymerization (μ mol) Promotor/catalyzer (mol/mol) Catalyst activity a Fusing point (℃) Degree of crystallinity (%) Density (g/cm 3)
????1 ????1 ????1 ????2000 ????8.94 ??110.8 ????25.0 ????0.920
????2 ????1 ????1 ????1000 ????0.85 ??119.0 ????30.6 ????0.925
????3 ????1 ????2 ????2000 ????7.27 ??117.6 ????28.1 ????0.923
????4 ????2 ????1 ????2000 ????7.62 ??115.1 ????16.7 ????0.921
????5 ????8 ????2 ????2000 ????3.08 ??121.4 ????39.8 ????0.935
????6 ????4 ????8 ????2000 ????6.88 ??126.1 ????65.8 ????0.945
????7 ????2 ????2 ????2000 ????6.53 ??122.3 ????43.6 ????0.931
????8 ????4 ????2 ????2000 ????9.42 ??106.2 ????23.0 ????0.920
????9 ????4 ????1 ????1000 ????0.74 ??120.6 ????24.3 ????0.929
????10 ????2 ????1 ????1000 ????0.51 ??123.9 ????19.6 ????0.936
aCatalyst activity: 10 6GPEmol -1(Fe+Zr or Ti) h -1Atm -1

Claims (6)

1. an in-situ copolymerization catalyst system for preparing linear low density polyethylene is made up of catalyst for oligomerization, catalyst for copolymerization and promotor;
Described catalyst for oligomerization is that homogeneous phase or loading type alpha-diimine pyridine iron are title complex, and its concentration in copolymerization catalyst system is 5 * 10 -6Mol/L～400 * 10 -6Mol/L, its molecular structural formula is as follows: R 1=-H ,-CH 3X=Br, ClR 2=-CH 3,-CH 2CH 3,-CH (CH 3) 2,-OCH 3R 3=-CH 3,-CH 2CH 3,-CH (CH 3) 2,-OCH 3,-Br ,-Cl ,-FX=-Br ,-Cl
Described catalyst for copolymerization is for being the cyclopentadienyl compound of central atom or their supported catalyst with Ti, Zr, Hf, and its concentration in copolymerization catalyst system is 5 * 10 -6Mol/L～100 * 10 -6Mol/L;
The mol ratio of described catalyst for oligomerization and catalyst for copolymerization is 1: 4～50: l;
The raw material carrier of described loading type oligomerisation, catalyst for copolymerization is organic carrier or inorganic carrier, and the granular size of carrier is 0.1-1000 μ m, and specific surface area is 60-500m 2/ g, pore volume are 0.1-7.0cc/g, and the aperture is 30-700 ;
Described promotor is an alkylaluminoxane, Al/ (Fe+Zr or Ti) mol ratio=500: 1～5000: 1.
2. according to a kind of in-situ copolymerization catalyst system for preparing linear low density polyethylene of claim 1, it is characterized in that: the concentration of described catalyst for oligomerization catalyst for oligomerization in copolymerization catalyst system is 10 * 10 -6Mol/L～200 * 10 -6Mol/L, the concentration of described catalyst for copolymerization in copolymerization catalyst system is 10 * 10 -6Mol/L～60 * 10 -6Mol/L, the mol ratio of described catalyst for oligomerization and catalyst for copolymerization is 1: 1～20: 1.
3. according to a kind of in-situ copolymerization catalyst system for preparing linear low density polyethylene of claim 1 or 2, it is characterized in that: described Al/ (Fe+Zr or Ti) mol ratio=1000: 1～3000: 1.
4. according to a kind of in-situ copolymerization catalyst system for preparing linear low density polyethylene of claim 1 or 2, it is characterized in that: described cyclopentadienyl compound is Et (Ind) 2ZrCl 2, Me 2Si (Ind) 2ZrCl 2, Et (Ind) 2ZrMe 2, Me 2Si (Ind) 2ZrMe 2, Cp *SiMe 2NBu tZrCl 2, Cp *SiMe 2NBu tTiCl 2, IndSiMe 2NBu tZrCl 2
5. according to a kind of in-situ copolymerization catalyst system for preparing linear low density polyethylene of claim 1 or 2, it is characterized in that: described raw material carrier is SiO 2, MgCl 2, Al 2O 3, talcum, zeolite, polynite, polyethylene, polystyrene.
6. according to a kind of in-situ copolymerization catalyst system for preparing linear low density polyethylene of claim 1 or 2, it is characterized in that: described promotor is methylaluminoxane, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide.
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