CN1727367A - Catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density - Google Patents
Catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density Download PDFInfo
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Abstract
A catalyst system for preparing linear low-density polyethene (LLDPE) from ethene by in-situ copolymerizing is a bifunctional one composed of the oligomerizing catalyst prepared from biphosphocrumium catalyst and alkylaluminoxane cocatalyst and the copolymerizing catalyst prepared from metallocene catalyst and alkylaluminoxane cocatalyst. Said LLDPE is prepared from ethene through oligomerizing and copolymerizing.
Description
The present invention relates to the catalyst system of a kind of ethane copolymerization in situ for producing linear polyethylene in low density (LLDPE).
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.Since Kaminsky has found (Angew.Chem.Int.Ed.Engl.19 since methylaluminoxane (MAO) can improve catalytic activity and polymeric copolymerization performance thereof as the promotor of metallocene, 396 (1980)), the multipolymer by metallocene catalysts ethene and propylene, high carbon number alpha-olefin becomes the research focus of polyolefine material.In recent years, emerging constrained geometry catalyst then is the present ideal ethene and the catalyzer of alpha-olefin copolymer.Metallocene catalyst and constrained geometry catalyst have not only overcome in the past low, the low shortcoming of monomer insertion amount altogether of Ziegler-Natta catalyst activity, but also have characteristics such as narrow molecular weight distribution, side chain are evenly distributed.Wherein with the 1-octene be comonomer make poly mechanical property and optical property fine, its tearing toughness and resistance to impact shock are to be 2 times of comonomer with the 1-butylene, are to be 1.5 times of comonomer with the 1-hexene.Alpha-olefin as the polyethylene comonomer is generated by ethylene oligomerization usually, obtains 1-hexene, 1-octene, 1-decene etc. through rectifying then.Adopt a kind of bifunctional catalyst system in polymerization reactor, to realize the oligomerisation and the in-situ copolymerization of ethene, promptly in reaction system, synthesize linear alpha-alkenes such as 1-octene, 1-hexene by at first oligomerisation highly selective of ethene with catalyst for oligomerization, the alpha-olefin that is generated generates LLDPE with in-situ copolymerization more then, this will simplify production technique, solve the problem of the main dependence on import of domestic alpha-olefin simultaneously, greatly reduced production cost.Adopt a kind of bifunctional catalyst system in polymerization reactor, to realize the oligomerisation and the in-situ copolymerization of ethene, a lot of research papers and patent report have been arranged, as J.Polym.Sci, Polym.Chem.Ed.22,3027 (1984); J.Polym.Sci, Polym.Chem.Ed.24,1069 (1986); Petrochemical complex, 23:491 (1994); CN1163525, CN1317503A, CN1275580A, CN1289785A, CN1417235A, CN1493404A, CN1167716C, CN1493404A, CN1163525.The in-situ copolymerization catalyst system of being reported in these documents, its shortcoming mainly is used catalyst for oligomerization, or is the ethylene dimerization catalyzer, the linear low density polyethylene that obtains has short side chain; Catalyst for oligomerization is a rear transition metal iron complex catalyzer, be characterized in oligomerization product carbon number distribution broad (C4～C30), the result makes the alpha-olefin of oligomerization product medium high carbon part be not easy to be inserted in the Polyethylene Chain, remains in the quality that has influence on linear low density polyethylene in the polymerization solvent.
The objective of the invention is to overcome the deficiency of catalyst for oligomerization in the above-mentioned in-situ copolymerization catalyst system, a kind of catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density is provided; This catalyst system is by to have high reactivity, the diphosphorus chromium series catalysts system of the homogeneous phase of highly selective or loading type is catalyst for oligomerization (alpha-olefin purity＞98% in the oligomerization product, selectivity＞85% of 1-octene+1-hexene), homogeneous phase or loaded metallocene title complex are that catalyst for copolymerization and promotor are formed jointly, with ethene is unique raw material, elder generation's original position highly selective generates 1-octene and 1-hexene, the in-situ copolymerization prepared in reaction of finishing then with ethene goes out linear low density polyethylene (LLDPE), solved the deficiency in the existing research, reached and to have carried out the effect that molecule is cut out to polymkeric substance.
The present invention is achieved by the following technical programs: the catalyst system of ethane copolymerization in situ for producing linear polyethylene in low density is made of jointly catalyst for oligomerization, catalyst for copolymerization, promotor; With ethene is unique raw material, and first original position highly selective generates 1-octene and 1-hexene, and the in-situ copolymerization prepared in reaction of finishing then with ethene goes out linear low density polyethylene (LLDPE); Catalyst for oligomerization wherein is the diphosphorus chromium series catalysts system with homogeneous phase or loading type of high reactivity, highly selective.
Described catalyst for oligomerization system is that the novel diphosphorus chromium series catalysts system title complex of homogeneous phase or loading type (is pressed document J.AM.CHEM.SOC.2004,126,14712-14713 is synthetic), diphosphorus chromium is that the central metal atom of ethylene oligomerization system is a chromium, the molecular structural formula of its part is as follows:
Wherein, group A and D, identical or different, can be selected from the group that contains phosphorus, nitrogen, sulphur atom; B is a linking group or single atom, can be selected from C, N, P atom, also can be selected from alkyl and derivative thereof, aryl and derivative thereof; R5 can be selected from alkyl, the cycloalkyl of hydrogen, straight or branched, also can be selected from monocycle and polyaromatic and derivative thereof; R1, R2, R3, R4 can be selected from phenyl, substituted-phenyl and derivative thereof;
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.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
2Deng.
The mol ratio of described catalyst for oligomerization and catalyst for copolymerization is 1: 100～1000: 1, is preferably 1: 10～100: 1.
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, hydrotalcite, zeolite, polynite, polyethylene or 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 0.1～7.0ml/g, and the aperture is 3～100nm.
The weight ratio of described carrier and catalyst for oligomerization system, catalyst for copolymerization total amount (carrier/catalyst for oligomerization and catalyst for copolymerization total amount) is 5: 1～100: 1, and the best is 10: 1～50: 1.
Described promotor is an alkylaluminoxane, as methylaluminoxane (MAO), ethyl aikyiaiurnirsoxan beta (EAO), isobutyl aluminium alkoxide (i-BuAO) etc., wherein be best with MAO, keep Al/ (Cr+Zr or Ti) mol ratio=1: 1～5000: 1, the best is 10: 1～3000: 1.
The present invention has the following advantages and positively effect: the present invention has higher selectivity (selectivity＞85% of 1-hexene+1-octene in the oligomerization product) to 1-hexene and 1-octene.
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. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir adding alkylaluminoxane promotor down, stir after 2 minutes, add the catalyst for oligomerization of a certain amount of homogeneous or load.
2. add the catalyst for copolymerization of homogeneous or load, keeping the pressure of ethene in the reactor is 3.0MPa, polymerase 10 .5 hour.
3. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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.
1. all under the condition of anhydrous and oxygen-free, all solvents all require dehydration and deoxidation to handle to all operations.
2.A: the catalyst for oligomerization system
The part of catalyst for oligomerization (press document J.AM.CHEM.SOC.2004,126,14712-14713 is synthetic) as shown below, chromium cpd is
CrCl
3(THF)
3。
B: catalyst for copolymerization Et (Ind)
2ZrCl
2,
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=200: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.0016mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is CrCl
3(THF)
3
B:SiO
2Loading type catalyst for copolymerization Et (Ind)
2ZrCl
2
With 1g SiO
2400 ℃ of following roastings 6 hours, then under vacuum 200 ℃ handled 2 hours.Be cooled to room temperature, add 10mL MAO (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 inert atmosphere.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 inert atmosphere.
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=200: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and 0.0016mmol catalyst for copolymerization B (Zr content 0.005gZr/g supported catalyst), the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is CrCl
3(THF)
3
B: catalyst for copolymerization Et (Ind)
2ZrCl
2
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=200: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.0032mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is a chromium acetylacetonate.
B: catalyst for copolymerization Et (Ind)
2ZrCl
2
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=200: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.016mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is CrCl
3(THF)
3
B: catalyst for copolymerization Et (Ind)
2ZrCl
2
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=300: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.0008mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is CrCl
3(THF)
3
B: catalyst for copolymerization Et (Ind)
2ZrCl
2
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=200: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.0032mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is CrCl
3(THF)
3
B: catalyst for copolymerization Me
2Si (Ind)
2ZrCl
2
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=400: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.0032mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. release, the ethanol solution hydrochloride termination reaction of adding 10% (volume ratio) obtains 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is CrCl
3(THF)
3
B: catalyst for copolymerization Cp
*SiMe
2NBu
tZrCl
2
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=200: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.0008mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. 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: the catalyst for oligomerization system
The part of catalyst for oligomerization is as shown below, and chromium cpd is CrCl
3(THF)
3
B: catalyst for copolymerization is SiO2 supported catalyst Cp
*SiMe
2NBu
tTiCl
2
C: promotor MAO
3. the autoclave of 250mL is replaced with nitrogen and ethene respectively, feed ethene then, add the toluene of 100mL through the deoxidation of sodium Metal 99.5 reflux dewatering, be warming up to 60 ℃, stir and add MAO[Al/ (Cr+Zr)=200: 1 (mol ratio) down], stir after 2 minutes, add above-mentioned part 0.032mmol, CrCl
3(THF)
3Complex compound 0.016mmol and catalyst for copolymerization B0.0032mmol, the maintenance ethylene pressure is 3.0MPa, polymerase 10 .5 hour.
4. 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.
Polymerizing condition among table 1 embodiment and polymerization result
| Embodiment | Catalyst for oligomerization (mmol) | Catalyst for copolymerization (mmol) | Promotor/catalyzer (mol/mol) | Catalyst activity a | Mn | Mw | MWD | Fusing point/(℃) | Degree of crystallinity/(%) | The degree of branching |
| 1 2 3 4 5 6 7 8 9 | 0.016 0.016 0.016 0.016 0.016 0.016 0.016 0.016 0.016 | 0.0016 0.0016 0.0032 0.0016 0.0008 0.0032 0.0032 0.0008 0.0032 | 200 200 200 200 300 200 400 200 200 | 1.81 1.35 1.98 3.48 2.64 3.42 2.86 3.08 2.86 | 26483 32500 22181 25483 29931 31014 30005 38289 32135 | 77455 73806 73221 79769 146217 94575 188579 102757 79663 | 2.92 2.27 3.30 3.13 4.89 3.05 6.28 2.68 2.48 | 133.7 133.7 131.7 132.7 134.03 134.03 135.03 133.87 133.03 | 60 59.98 54,23 55.32 51.25 65.40 52.77 63.68 59.32 | 3.8 2.7 4.8 3.1 6.9 2.7 6.0 3.3 5.6 |
aCatalyst activity: 10
6GPEmol
-1(Fe+Zr or Ti) h
-1Reaction pressure: 3.0MPa; Temperature of reaction: 60 ℃.
Claims (6)
1. the catalyst system of an ethane copolymerization in situ for producing linear polyethylene in low density is made up of catalyst for oligomerization, catalyst for copolymerization and promotor; Described catalyst for oligomerization is the diphosphorus chromium class catalyst system for ethylene oligomerization of homogeneous phase or loading type, and the molecular structural formula of its phosphorus-containing ligand is as follows:
Wherein, group A and D, identical or different, be selected from the group that contains phosphorus, nitrogen, sulphur atom; B is a linking group or single atom, can be selected from C, N, P atom, also can be selected from alkyl and derivative thereof, aryl and derivative thereof; R5 can be selected from alkyl, the cycloalkyl of hydrogen, straight or branched, also can be selected from monocycle and polyaromatic and derivative thereof; R1, R2, R3, R4 can be selected from phenyl, substituted-phenyl and derivative thereof; Another component of catalyst for oligomerization is chromium cpd or complex compound, can be selected from CrCl
3(THF)
3, chromium acetylacetonate, isocaprylic acid chromium etc.;
Described catalyst for copolymerization is for being the cyclopentadienyl compound of central atom or their supported catalyst with Ti, Zr, Hf;
The mol ratio of described catalyst for oligomerization and catalyst for copolymerization is 1: 10～100: 1; 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 μ m～1000 μ m, and specific surface area is 60～500m
2/ g, pore volume are 0.1～7.0ml/g, and the aperture is 3～100nm; Described promotor is an alkylaluminoxane.
2. according to the catalyst system of a kind of ethane copolymerization in situ for producing linear polyethylene in low density of claim 1, 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
3. according to the catalyst system of a kind of ethane copolymerization in situ for producing linear polyethylene in low density of claim 1 or 2, it is characterized in that: described Al/ (Cr+Zr or Ti) mol ratio=10: 1～3000: 1.
4. according to the catalyst system of a kind of ethane copolymerization in situ for producing linear polyethylene in low density of claim 1 or 2, it is characterized in that: the raw material carrier of described loading type oligomerisation, catalyst for copolymerization is SiO
2, MgCl
2, Al
2O
3, hydrotalcite, zeolite, polynite, polyethylene or polystyrene.
5. according to the catalyst system of a kind of ethane copolymerization in situ for producing linear polyethylene in low density of claim 1 or 2, it is characterized in that: in position in the polymerization process, described catalyst for oligomerization system can original position be synthesized in polymerization reactor, also can synthesize in advance; The catalyst for oligomerization system can together add with metallocene catalyst, also can join in the reactor earlier.
6. according to the catalyst system of a kind of ethane copolymerization in situ for producing linear polyethylene in low density of claim 1 or 2, it is characterized in that: described promotor is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide.
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