CN101029108A - Copolymerization of ethene and norbornene - Google Patents
Copolymerization of ethene and norbornene Download PDFInfo
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- CN101029108A CN101029108A CN 200610008073 CN200610008073A CN101029108A CN 101029108 A CN101029108 A CN 101029108A CN 200610008073 CN200610008073 CN 200610008073 CN 200610008073 A CN200610008073 A CN 200610008073A CN 101029108 A CN101029108 A CN 101029108A
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Abstract
A method for copolymerizing ethane and norbornene is carried out by polymerizing ethane with norbornene under existence of cyclopentadienyl metal additive compound catalyst and alundumne catalytic auxiliaries in proportion of 3000-200mol. In general formula Ar2C(CpR1)(FluR2)MeQ2.RXR'nMe'Q2/n, Ar is substituted or unsubstituted aryl group; Cp is cyclopentadiene, Flu is fluoryl, R1 and R2 are hydrogen, C1-C12 alkyl, alkoxy, silane, aryl, aralkyl, hydroxyl or halogen separately; Me comes from any kind of IVB family; Q is halogen, alkyl, alkoxy, aromatic condensed ring or heterocyclic radical; R and R' are selected from C1-C6 alkyl, X is oxygen or sulfur; Me' is alkali metal or alkaline earth metal, and n value is 1 or 2. It has high conversion temperature and impact resistance.
Description
Technical field
The present invention is the copolymerization process of a kind of ethene and norbornylene.Specifically, be a kind of be Primary Catalysts with the metallocene, be the ethene of promotor and the process for copolymerization of norbornylene with the alkylaluminoxane.
Background technology
Metallocene catalyst is the efficient olefin polymerization catalysis of developing in recent years, and it can make alkene carry out the stereoselective polymerization, all right catalysis cyclic olefin polymerization and cycloolefin and ethylene copolymerization, thus obtain the novel thermoplastics of a class.The multipolymer of ethene and cycloolefin has characteristics such as the good optical transparency, low-birefringence, low water absorbable, high glass-transition temperature (Tg), high strength, moisture resistance, high temperature resistant, low density, splendid dielectric strength and biocompatibility.High-density CD-ROM coils, optics is with a wide range of applications with high-tech sectors such as lens, optical fiber, capacitor film, medical devices making.
Cyclic olefine copolymer generally prepares with the method for metathesis ring-opening polymerization or addition polymerization.The ring-opening polymerization resulting polymers contains two keys, and easy oxidation during forming process variable color takes place makes the product property variation.Addition polymerization then obtains saturated polymkeric substance fully, stable in properties.Kaminskay finds that at first metallocene/methylaluminoxane (MAO) catalyst system can realize the addition polymerization of cycloolefin, and the polymkeric substance that obtains has high-crystallinity and high-melting-point, but polymkeric substance at high temperature not fusion just decompose, and be insoluble to organic solvent.
Michael[Macromol.Chem.Phys.199,1221-1232 (1998)] studied Me in great detail
2C (3-BuCp) is ZrCl (Flu)
2The catalyzed reaction rule that is used for norbornylene and ethylene copolymer, its used promotor is a methylaluminoxane.Used promotor is more during polymerization, could obtain high catalytic activity in the Al/Zr mol ratio under greater than 4000 situation, and the Al/Zr mol ratio is at 1600 o'clock, and activity of such catalysts is lower.In addition, the utilization ratio of norbornylene is low during this catalyzer copolymerization, and the norbornylene amount that promptly participates in copolyreaction in the raw material is few, and the second-order transition temperature of the ethylene-norbornene copolymer that makes only is 72.5～76.2 ℃ far below 100 ℃.
CN1113908C discloses a kind of ethylene polymer composition with norbornene comonomer.Adopting the silicon-dioxide of load metallocene and methylaluminoxane when said composition prepares is catalyzer, adds triethyl aluminium solution during polymerization, can make ethene/norbornylene or ethene/norbornylene/alpha-olefin ter-polymer resin.This resin is mainly used in toughness and the processibility of improving film.
CN1183789A discloses the cyclic olefin monomers multipolymer of a kind of amorphous olefin and aryl replacement, its used cyclic olefin monomers is phenyl or 2, the norbornylene that the 3-indanyl replaces, adopting the dichloride of ethene two (indenyl) zirconium dichloride or dimethylsilyl two (indenes) zirconium is Primary Catalysts, in the presence of the promotor methylaluminoxane, cause the copolymerization of the norbornylene of ethene and replacement, obtain the polymkeric substance of a series of different glass transition temperatures and Shore hardness.The Al/Zr mol ratio is 3000～6000 during polymerization, and polymerization temperature is 30～50 ℃, though cyclic olefin monomers content is high in its polymers that makes, second-order transition temperature is generally lower, have in addition be the oily oligopolymer.
CN1140720A discloses a kind of syndiotactic selective compound metallocene catalyst, is metallocene-ether-inorganic salt three component adductss, and its preparation method is simple, need not to purify.This catalyzer is used to prepare syndiotactic polypropylene.
Summary of the invention
The purpose of this invention is to provide a kind of is the ethene of Primary Catalysts and the copolymerization process of norbornylene with the metallocene, and promotor used during this method polymerization is few, and catalytic activity is higher.
The method of ethene provided by the invention and norbornylene copolymerization, comprise ethene and norbornylene are carried out polyreaction in the presence of metallocene adduct catalyzer with following general expression and alkylaluminoxane promotor, during polymerization in the promotor in aluminium and the metallocene adduct mol ratio of Me be 200～3000
Ar
2C[CpR
1][FluR
2]MeQ
2·RXR′·nMe′Q
2/n
In the formula, Ar is for replacing or unsubstituted aryl; Cp is a cyclopentadienyl, and Flu is a fluorenyl, R
1And R
2Be respectively hydrogen, C
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy, hydroxyl or halogen; Me is a kind of in the IVB family element; Q is halogen, alkyl, alkoxyl group, aromatic cluste or heterocyclic radical; R and R ' are selected from C respectively
1-C
6Alkyl, X is oxygen or sulphur; Me ' is basic metal or alkaline-earth metal, and the n value is 1 or 2.
The present invention uses metallocene ether inorganic salt adducts to be Primary Catalysts, can under lower promotor consumption, make ethene and norbornene polymerization, and the percent polymerization height of norbornylene during polymerization, can utilize the norbornylene in the raw material more fully, reduce the multipolymer production cost.The ethene that the inventive method makes and the second-order transition temperature of norbornene copolymer all are higher than 100 ℃, and have the good impact resistance and the transparency.
Embodiment
The inventive method is a Primary Catalysts with metallocene ether inorganic salt adducts, with the alkylaluminoxane is that promotor makes ethene and norbornylene carry out copolyreaction under polymerizing condition, the promotor consumption is few during reaction, the catalyst activity height, the multipolymer good physical performance that makes, and the norbornylene in the raw material can participate in copolyreaction, percent polymerization height more.In addition, add aluminum alkyls during polymerization, can reduce the consumption of promoter aluminium alkyl oxygen alkane, and catalyst activity is unaffected, the multipolymer character that obtains is constant substantially.
Metallocene adduct of the present invention is made up of metallocene, ether and inorganic salt.So-called adducts be a certain material when forming crystal, another kind of material joins in an orderly manner in the crystal defect of this material and forms, a material combines with Intermolecular Forces with another material.Metallocene adduct described in the present invention similarly, reactive force between each component of adducts can improve the stability of metallocene adduct, component beyond the metallocene is except that stablizing metallocene, olefinic polyreaction is had no adverse effect, so the adducts that makes can be without the recrystallization metallocene of purifying.
The preferred phenyl of Ar in the described metallocene adduct, R
1And R
2Preferred hydrogen of difference or C
1～C
3Alkyl, the preferred zirconium of Me, the preferred halogen of Q, preferred ether of RXR ' or tetrahydrofuran (THF), when Me ' was basic metal, n was 2, when Me ' was alkaline-earth metal, n was 1.Me ' preferred lithium.
The preparation method of described metallocenes ether inorganic salt adducts has a detailed description in CN1140720A.This method comprises:
(1) in ether solvent, make to replace or unsubstituted fluorenes and highly basic reaction, fluorenes negative ion that again reaction is obtained and substitution in ring or unsubstituted diaryl fulvene at room temperature react, and obtain ligand compound;
(2) in inert solvent, make the reaction of ligand compound and alkaline reagents, the part pairs of anion and the chemical formula that will react gained again are MeQ
4Metallic compound reaction, wherein, Me is selected from a kind of metal in the IVB family in the periodic table of elements, Q is selected from halogen, alkyl, alkoxyl group, aromatic cluste or heterocyclic radical.
The described promoter aluminium alkyl oxygen alkane preferable methyl of the inventive method aikyiaiurnirsoxan beta, the mol ratio of Me preferred 500～2000 in aluminium and the metallocene adduct in the promotor.For reducing the consumption of alkylaluminoxane, also contain aluminum alkyls in the polymerization system, just when adding promotor, add aluminum alkyls.The mol ratio of Me preferred 500～1800 in aluminium in the described aluminum alkyls and the Primary Catalysts.Preferred triethyl aluminum of described aluminum alkyls or triisobutyl aluminium.
The copolyreaction of ethene of the present invention and norbornylene is preferably carried out in the presence of polar organic solvent, the preferred toluene of described solvent.
When adopting the inventive method to carry out ethene and norbornylene copolymerization, suitable polymerization temperature is 10～100 ℃, preferred 30～80 ℃.The mol ratio of norbornylene and ethene is 0.5～6.0 during polymerization, preferred 0.5～4.0.
Below by example in detail the present invention, but the present invention is not limited to this.
Example 1
Prepare metallocene adduct of the present invention.
In 250 milliliters of Schlenk reaction flasks, add 5.10 gram (30.7 mmole) fluorenes, after 60 milliliters of anhydrous tetrahydro furans (THF) dissolving, 25 ℃ of phenyl lithium diethyl ether solutions by 38.4 milliliters of (30.7 mmole) 0.8 mol of constant pressure funnel adding, and under this temperature, reacted 2 hours.Add 7.07 gram (30.7 mmole) phenylbenzene fulvene then, continue reaction 12 hours, add the suitable quantity of water hydrolysis.Tell organic phase, with the mixed solution recrystallization of methyl alcohol and chloroform, obtain the different hydrocinnamyl of white powder ligand compound (fluorenes) cyclopentadiene [Ph of 6.2 grams behind the vacuum concentration
2C (9-Flu) Cp], productive rate is 51 quality %.
2.0 gram (5.0 mmole) above-mentioned parts that obtain are dissolved in 20 milliliters of ether, 0 ℃ of 6.4 milliliters of n-buli hexane solution (10 mmole) that add 1.6 mol, 25 ℃ were reacted 15 hours, and gained suspension is cooled to-50 ℃, added 1.16 gram (5.0 mmole) ZrCl
4, under agitation make mixture slowly rise to 25 ℃, filter and, obtain 3.1 after the drying and restrain the solid powdery adductss with a small amount of ether washing leaching cake, be different hydrocinnamyl-(fluorenyl)-(cyclopentadienyl) zirconium dichloride ether lithium chloride adducts [Ph
2C (9-Flu) is ZrCl (Cp)
2Et
2O2LiCl], its zirconium content is 11.0 quality %, yield is counted 85 quality % with zirconium.
Example 2～7
Following example carries out the normal pressure copolymerization of ethene and norbornylene.
In 250 milliliters of Schlenk reaction flasks, add the toluene solution of methylaluminoxane (MAO) and the toluene solution of norbornylene, adding toluene toluene total amount to the reaction flask again is 100 milliliters.Adding ethene, to make its vapour pressure be 0.1MPa, adds the metallocene adduct catalyzer that the example 1 of metering makes then and carry out polyreaction, and the dosage of metallocene adduct should make the Al/Zr mol ratio reach prescribed value.Under different temperature, reacted 1 hour then, stop ethylene feed, finish reaction.Reactant is with ethanol-hydrochloric acid soln sedimentation, filters back 80 ℃ of dryings 5 hours in vacuum drying oven.Each example reaction conditions, catalyst activity and multipolymer character see Table 1.
Comparative Examples 1
Carry out the polyreaction of norbornylene according to the method for example 2, the Al/Zr mol ratio was 1500 when different was reaction, and it the results are shown in Table 1.
As shown in Table 1, the inventive method catalyst system therefor has higher copolymerization activity, the Al/Zr mol ratio is lower during polymerization, and the norbornylene major part that feeds intake used is reacted, and the second-order transition temperature of gained multipolymer (Tg) is basic suitable with polynorbornene.
Example 8～11
In 250 milliliters of Schlenk reaction flasks, add toluene solution, the toluene solution of triethyl aluminum and the toluene solution of norbornylene of methylaluminoxane (MAO), adding toluene toluene total amount to the reaction flask again is 100 milliliters.Adding ethene, to make its vapour pressure be 0.1MPa, adds the metallocene adduct catalyzer that the example 1 of metering makes then and carry out polyreaction, and the dosage of metallocene adduct should make the Al/Zr mol ratio reach prescribed value.60 ℃ were reacted 1 hour, stopped ethylene feed, finished reaction.Reactant is with ethanol-hydrochloric acid soln sedimentation, filters back 80 ℃ of dryings 5 hours in vacuum drying oven.The dosage of reaction conditions and MAO and triethyl aluminum, catalyst activity and multipolymer character see Table 2 in each example.
Table 2 data show, add triethyl aluminum and can significantly reduce the consumption of MAO when reaction, and make catalyzer still keep advantages of high catalytic activity.
Example 12～15
Following example carries out the high pressure copolymerization of ethene and norbornylene.
In 2000 milliliters of autoclaves, add the toluene solution of an amount of methylaluminoxane and the toluene solution of norbornylene, add toluene and make that toluene level is 1000 milliliters in the autoclave, add the catalyzer that the example 1 of metering makes, the Al/Zr mol ratio reaches prescribed value when making reaction.It is 0.8MPa that feeding ethene makes the still internal pressure, and reaction is 1 hour under the temperature of reaction of regulation, stops ethylene feed, finishes reaction.Reactant is with ethanol-hydrochloric acid soln sedimentation, filters the back 80 ℃ of dryings of vacuum drying oven 3～5 hours, and taking-up is weighed.Each example polymeric reaction condition and the results are shown in Table 3, the performance of copolymer test data that makes sees Table 4.
Ethene/norbornene copolymer that table 4 data presentation, the inventive method make has stronger shock resistance and transmittance preferably, and second-order transition temperature is higher.
Table 1
| Instance number | Reaction conditions | Catalytic activity * 10 -6， g/molZr·hr | Multipolymer character | ||||
| The Al/Zr mol ratio | The N dosage, gram | The N/E mol ratio | Temperature, ℃ | N content, mol% | Tg， ℃ | ||
| 2 | 1300 | 6.2 | 1.83 | 60 | 2.34 | 40.46 | 124.6 |
| 3 | 1800 | 3.1 | 0.916 | 60 | 3.60 | 22.96 | 123.7 |
| 4 | 1300 | 12.4 | 3.66 | 60 | 2.10 | 53.32 | 128.2 |
| 5 | 3000 | 6.2 | 1.83 | 30 | 1.36 | 34.54 | 128.0 |
| 6 | 1700 | 3.1 | 0.916 | 40 | 1.81 | 19.01 | 124.0 |
| 7 | 1700 | 3.1 | 0.916 | 50 | 1.31 | 19.40 | 125.8 |
| Comparative Examples 1 | 1500 | 12.4 | - | 60 | 0.13 | 100 | 128.1 |
*MAO-methylaluminoxane in the table 1, N-norbornylene, E-ethene
Table 2
| Instance number | Reaction conditions | Catalytic activity * 10 -6， g/molZr·hr | Multipolymer character | ||||
| Al/Zr mol ratio (MAO) | Al/Zr mol ratio (Et 3Al) | The N dosage, gram | The N/E mol ratio | N content, mol% | Tg， ℃ | ||
| 8 | 1000 | 1000 | 6.2 | 1.83 | 2.31 | 39.45 | 125.3 |
| 9 | 1000 | 1400 | 3.1 | 0.916 | 3.15 | 19.36 | 123.5 |
| 10 | 500 | 1400 | 3.1 | 0.916 | 1.98 | 15.80 | 122.3 |
| 11 | 300 | 1400 | 3.1 | 0.916 | 1.87 | 15.67 | 123.1 |
Et in the table 2
3The Al-triethyl aluminum, N-norbornylene, E-ethene
Table 3
| Instance number | The Al/Zr mol ratio | The N dosage, gram | The N/E mol ratio | Temperature, ℃ | Catalytic activity * 10 -6， g/molZr·hr |
| 12 | 1000 | 30 | 0.56 | 65 | 1.80 |
| 13 | 1200 | 30 | 0.56 | 70 | 3.03 |
| 14 | 1200 | 100 | 1.87 | 76 | 3.33 |
| 15 | 1000 | 67 | 1.19 | 80 | 1.93 |
N-norbornylene in the table 3, E-ethene
Table 4
| Instance number | N content, mol% | Density, gcm -3 | Tg，℃ | Tensile strength, MPa | Elongation at break, % | Transmittance, % |
| 12 | 7.01 | 0.97 | 120.2 | 43 | 3.0 | 91 |
| 13 | 4.56 | 0.98 | 135.2 | 52 | 3.1 | 92 |
| 14 | 28.98 | 0.98 | 153.3 | 63.2 | 6.5 | 92 |
| 15 | 10.76 | 0.99 | 131.6 | 60.1 | 3.5 | 91 |
N-norbornylene in the table 4.
Claims (10)
1, the copolymerization process of a kind of ethene and norbornylene, comprise ethene and norbornylene are carried out polyreaction in the presence of metallocene adduct catalyzer with following general expression and alkylaluminoxane promotor, during polymerization in the promotor in aluminium and the metallocene adduct mol ratio of Me be 200～3000
Ar
2C[CpR
1][FluR
2]MeQ
2·RXR′·nMe′Q
2/n
In the formula, Ar is for replacing or unsubstituted aryl; Cp is a cyclopentadienyl, and Flu is a fluorenyl, R
1And R
2Be respectively hydrogen, C
1～C
12Alkyl, alkoxyl group, silylation, aryl, aralkoxy, hydroxyl or halogen; Me is a kind of in the IVB family element; Q is halogen, alkyl, alkoxyl group, aromatic cluste or heterocyclic radical; R and R ' are selected from C respectively
1～C
6Alkyl, X is oxygen or sulphur; Me ' is basic metal or alkaline-earth metal, and the n value is 1 or 2.
2, in accordance with the method for claim 1, it is characterized in that Ar is a phenyl in the described metallocene adduct, R
1And R
2Be respectively hydrogen or C
1～C
3Alkyl, Me is a zirconium, Q is a halogen, RXR ' is an ether, Me ' is a basic metal, n is 2.
3, in accordance with the method for claim 1, it is characterized in that Ar is a phenyl in the described metallocene adduct, R
1And R
2Be respectively hydrogen or C
1～C
3Alkyl, Me is a zirconium, Q is a chlorine, RXR ' is an ether, Me ' is a lithium, n is 2.
4, in accordance with the method for claim 1, when it is characterized in that polymerization in the promotor in aluminium and the metallocene adduct mol ratio of Me be 500～2000.
5,, it is characterized in that also containing in the polymerization system aluminum alkyls according to claim 1 or 4 described methods.
6, in accordance with the method for claim 5, it is characterized in that the mol ratio of Me in aluminium in the described aluminum alkyls and the Primary Catalysts is 500～1800, described aluminum alkyls is triethyl aluminum or triisobutyl aluminium.
7, in accordance with the method for claim 1, it is characterized in that described polyreaction carries out in the presence of polar organic solvent.
8, in accordance with the method for claim 7, it is characterized in that described solvent is a toluene.
9, in accordance with the method for claim 1, the mol ratio of norbornylene and ethene is 0.5～4.0 when it is characterized in that polymerization.
10, in accordance with the method for claim 1, it is characterized in that described polymerization temperature is 10～100 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884971A (en) * | 2014-09-05 | 2016-08-24 | 中国石油化工股份有限公司 | Chain olefin-cycloolefin copolymer |
| CN111825726A (en) * | 2020-08-03 | 2020-10-27 | 柴肖芳 | Benzimidazole catalyst and preparation method thereof |
| CN112225852A (en) * | 2020-09-28 | 2021-01-15 | 浙江大学 | Polysiloxane functionalized ethylene-norbornene copolymer and preparation method thereof |
| CN113372478A (en) * | 2021-06-24 | 2021-09-10 | 万华化学集团股份有限公司 | Aldehyde group functionalized cycloolefin-ethylene copolymer and preparation method thereof |
-
2006
- 2006-02-28 CN CNB2006100080730A patent/CN100549046C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105884971A (en) * | 2014-09-05 | 2016-08-24 | 中国石油化工股份有限公司 | Chain olefin-cycloolefin copolymer |
| CN105884971B (en) * | 2014-09-05 | 2019-03-15 | 中国石油化工股份有限公司 | A kind of olefine-cyclic olefine copolymer |
| CN111825726A (en) * | 2020-08-03 | 2020-10-27 | 柴肖芳 | Benzimidazole catalyst and preparation method thereof |
| CN112225852A (en) * | 2020-09-28 | 2021-01-15 | 浙江大学 | Polysiloxane functionalized ethylene-norbornene copolymer and preparation method thereof |
| CN112225852B (en) * | 2020-09-28 | 2021-10-08 | 浙江大学 | Polysiloxane functionalized ethylene-norbornene copolymer and preparation method thereof |
| CN113372478A (en) * | 2021-06-24 | 2021-09-10 | 万华化学集团股份有限公司 | Aldehyde group functionalized cycloolefin-ethylene copolymer and preparation method thereof |
| CN113372478B (en) * | 2021-06-24 | 2022-07-15 | 万华化学集团股份有限公司 | Aldehyde group functionalized cycloolefin-ethylene copolymer and preparation method thereof |
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