CN103030722B - A kind of polymerisation process of cycloolefin - Google Patents
A kind of polymerisation process of cycloolefin Download PDFInfo
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- CN103030722B CN103030722B CN201110291490.1A CN201110291490A CN103030722B CN 103030722 B CN103030722 B CN 103030722B CN 201110291490 A CN201110291490 A CN 201110291490A CN 103030722 B CN103030722 B CN 103030722B
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Abstract
The invention provides a kind of polymerisation process of cycloolefin, this reaction such as formula shown in I with the mono-metallocene compound Primary Catalysts of sulfur-containing ligand and the catalysis of methyl alumoxane cocatalyst under carry out, in formula I, X is alkyl or-oxyl; Cp ' is for using the substituted or unsubstituted cyclopentadienyl of alkyl, indenyl or fluorenyl.This catalyst catalyzes cyclic olefin polymerization obtains polycyclic alkene, in particular for the addition polymerization of norbornylene.
Description
Technical field
The invention belongs to catalysis and field of olefin polymerisation, relate to a kind of polymerization process of cycloolefin, specifically, is a kind ofly be Primary Catalysts with the Binary catalysts with sulfur-containing ligand, take methylaluminoxane as the cyclic olefin polymerization method of promotor catalysis.
Background technology
The metallocene catalyst of for olefines polymerization is the study hotspot of Organometallic Chemistry, catalysis, polymer chemistry and materialogy in nearly decades always.The metallocene catalyst of broad sense comprises metallocene catalyst (dual metallocene catalysts) and single metallocene catalyst.And from another angle, metallocene catalyst is divided into again bridging and non-bridging two kinds.Use broad sense metallocene catalyst, both can obtain molecular weight distribution and all well-proportioned olefin polymer of chemical constitution distribution; Simultaneously by adjustment catalyst structure make the molecular structure of polymkeric substance and molecular weight height controlled.In addition, by using metallocene catalyst, the not getable olefin polymer of traditional Z iegler-Natta catalyzer can also be obtained.
Constrained geometry catalyst (CGC) has Cp-Ti-N structure, and it is a kind of single metallocene catalyst of bridging.CGC catalyzer demonstrates very superior polymerization property, the olefin polymer superior performance obtained.In recent years, in the research of olefin polymerization catalysis, with more and more coming into one's own to the single metallocene catalyst of electron donor ligand, because this kind of catalyzer and CGC catalyzer have similar structure, and easilier than CGC catalyzer to synthesize.The many this kind of catalyzer with special performance of bibliographical information.
Patent US5064802 as Dow Chemical in 1991 reports compound as described in chemical formula 1 and [HNEt
3]
+[B (C
6f
5)
4]
-the catalyst system of composition, at room temperature catalyzed ethylene (1atm) polymerization, activity is 12.3kg-PE/mol.-Ti/hr.
Mono-metallocene Cp ' Ti (OAr) Cl with aryloxy as shown in chemical formula 2
2(Organometallics 1998,17,2152), has not only showed catalyzed ethylene (Organometallics 1998,17,2152; Macromolecules 1998,31,7588), the high reactivity that is all polymerized of vinylbenzene (Macromolecules 2004,37,5520), non-conjugated diene (Macromolecules 2004,37,1693); And to catalysis alpha-olefin (Organometallics 1998,17,2152), cycloolefin (Macromolecules 2003,36,3797; Adv.Synth.Catal.2005,347,433) etc. with the copolymerization of ethene, there is very high activity and outstanding copolymerized ability; The monomer that simultaneously general single-site catalysts can also be made not to be polymerized, as tetrahydrobenzene (J.Am.Chem.Soc.2005,127,4582), 2-Methyl-1-pentene (Macromolecules 2005,38,2053) etc. participate in ethylene copolymer.
With mono-metallocene Cp ' Ti (OAr) Cl of aryloxy
2be used for vinyl polymerization as olefin polymerization catalysis, during with modified methylaluminoxane (MMAO) for promotor, activity can reach 9290kg-PE/mol-Ti/hr, and resulting polymers has high molecular and narrow molecular weight distribution.Its polymerization activity and catalyst structure closely related, the substituting group on Cp ' part and aryloxy affects polymerization behavior all strongly.If mono-metallocene Cp ' Ti (OAr) Cl
2on a chlorine atom replaced by an aryloxy further, ethylene polymerization activity also can higher (J.Organomet.Chem.1999,591,185).
And with the bridging biphenol such as shown in chemical formula 3 for bidentate ligand, when synthesis Binary catalysts is used for catalyzed ethylene polymerization, catalytic activity lower (Organometallics 2006,25,4358).
With the such as trolamine shown in chemical formula 4 for tetradentate ligands, the Monodentate compound of synthesis Ti, Zr, Hf, and for vinyl polymerization.Under same reaction conditions, the catalyzed polymerization activity of titanium compound is the highest; The molecular weight of polyethylene that zirconium compounds catalysis obtains is the highest; And the catalytic activity of hafnium compound is minimum, the molecular weight of resulting polymers also minimum (J.Organomet.Chem.2006,691,1121).
Norbornylene, i.e. two rings [2,2,1] hept-2-ene", its polymerization methods has multiple, and the polymer architecture that different polymerization methods obtains is also different.Usually it can obtain the polymkeric substance of different structure by three kinds of polymerization methodses in following formula.The first is for obtain product IV by approach A ring-opening metathesis polymerization, the second is for obtain product V by approach B addition polymerization, the third obtains product VI (Coord.Chem.Rev.2009,253,827) by approach C ionic polymerization or radical polymerization.
Norbornylene is use transistion metal compound to be catalyzer by the addition polymerization of approach B, is realized by polycoordination mechanism.The institute polymerisate V that obtains is to chemical reagent and solvent performance inertia; And due to its second-order transition temperature higher, polymkeric substance V has good thermostability and optical transparence; It has outstanding mechanical property simultaneously; Coating and the protective layer of electrical part and optical goods can be widely used in.
First the people such as Kaminsky use metallocene catalyst to achieve the addition polymerization of norbornylene, and resulting polymers fusing point is (J.Mol.Catal.1992,74,10 more than 400 DEG C; Macromol.Chem.Phys.1996,197,3907).In a lot of researchs afterwards, the single-site catalysts of number of different types all obtains application in the polymerization of norbornylene with other cycloolefins, and involved cycloolefin not only has norbornylene and its various derivatives, also comprises various cycloolefin.
As can be seen from existing document, about a lot of with the polymerization studies of being used for cycloolefin to the luxuriant transition-metal catalyst of list of electron donor ligand, this kind of catalyzer shows the feature different from traditional metallocene, so research and develop new part to prepare the polymerization of the luxuriant transition-metal catalyst of new list for cycloolefin, remain an important problem.
Summary of the invention
The invention provides a kind of polymerisation process of cycloolefin, this reaction is carried out under the catalysis such as formula the Primary Catalysts mono-metallocene compound shown in I and promotor methylaluminoxane,
In formula I, X is alkyl or-oxyl; Cp ' is for using the substituted or unsubstituted cyclopentadienyl of alkyl, indenyl or fluorenyl.
Preferably described X is methyl, alkoxyl group or phenoxy group; Wherein said alkoxyl group is more preferably methoxyl group, isopropoxy or butoxy.
Preferred Cp ' of the present invention is cyclopentadienyl, pentamethylcyclopentadiene base or indenyl.
In preferred mono-metallocene compound of the present invention, in Ti and methylaluminoxane, the mol ratio of Al is 1: 50 to 1: 20000, is more preferably 1: 200 to 1: 10000, most preferably is 1: 500 to 1: 3000.
The structure of methylaluminoxane of the present invention is for shown in formula II or III:
In formula II and III, R represents methyl; N represents the integer of 4-30, is preferably the integer of 10-30.
During preferred mono-metallocene compound catalysis cyclic olefin polymerization of the present invention, concentration is in the solution 1 × 10
-8mol/L to 1 × 10
-2mol/L, is preferably 1 × 10
-7mol/L to 1 × 10
-3mol/L.During olefinic polymerization, described promotor and mono-metallocene compound together or respectively add polymerization reactor and use.Polyreaction of the present invention is carried out in organic solvent toluene, and polymerization temperature is-50 DEG C to 200 DEG C, is preferably-20 DEG C to 150 DEG C.
Preferred cycloolefin of the present invention is norbornylene.
Embodiment
The present invention is further illustrated by the following examples, but should not be construed as limitation of the invention.
MAO solution used in embodiment is the toluene solution of methylaluminoxane, and every ml soln is 1.67mmol containing MAO; Catalyst solution used is the toluene solution of mono-metallocene compound, and every ml soln comprises mono-metallocene compound 1 × 10
-5mol.
Embodiment 1
The synthesis of pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium:
Magneton is put into 250 milliliters of dry there-necked flasks, bottle is placed in the magnetic stirring apparatus of oil bath temperature control; There-necked flask is vacuumized rear nitrogen and repeatedly rinse three times.And adding pentamethylcyclopentadiene base-trimethoxy titanium 1.8g, toluene 50mL in a nitrogen atmosphere, penta fluoro benzene thiophenol 1.35g, stirring at room temperature reaction is spent the night.Obtain yellow powder 2.1g after solvent removed in vacuo, the product pentamethylcyclopentadiene base namely in the present invention-penta fluoro benzene sulfenyl-dimethoxy titanium, its molar yield is 72%.
The yellow powder that takes a morsel adds a small amount of toluene and dissolves, and freezing and crystallizing, obtains yellow prismatic crystal.Its characterization result is as follows, nucleus magnetic resonance:
1h-NMR (CDCl
3, 25C): δ=2.12 (15H), 3.96 (6H).Ultimate analysis calculated value is C, 48.66; H, 4.76.Experimental value is C, 48.73; H, 4.38.
With pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium for Primary Catalysts catalysis norbornene polymerization:
Add 2.0 grams of norbornylenes in dry polymerization bottle, vacuumize rear nitrogen and repeatedly rinse three times; At polymerization temperature 25 DEG C, add catalyzer toluene solution 1 milliliter prepared by 12.0 milliliters of MAO toluene solutions (MAO is 20.0mmol) and above-mentioned yellow powder successively, start timing.Polymerization time, after 30 minutes, carefully pours reaction solution into beaker, adds acidic ethanol, stirs to filter after 6 hours to obtain polymkeric substance, filter cake vacuum-drying 24 hours at 60 DEG C.Weigh and obtain 0.85 gram, polymkeric substance, active 1.7 × 10
5g/mol-cat/hr.Detect through gel permeation chromatography (GPC), polymericular weight M
w=2.76x10
5, molecular weight distribution is MWD=2.75.
Claims (8)
1. the polymerisation process of a norbornylene, this reaction is carried out under the catalysis such as formula the Primary Catalysts mono-metallocene compound shown in I and promotor methylaluminoxane, and in described mono-metallocene compound, in Ti and methylaluminoxane, the mol ratio of Al is 1:2000;
In formula I, X is alkyl or-oxyl; Cp ' is for using the substituted or unsubstituted cyclopentadienyl of alkyl, indenyl or fluorenyl.
2. method according to claim 1, is characterized in that, described X is methyl, alkoxyl group or phenoxy group.
3. method according to claim 2, is characterized in that, described alkoxyl group is methoxyl group, isopropoxy or butoxy.
4. method according to claim 1, is characterized in that, described Cp ' is cyclopentadienyl, pentamethylcyclopentadiene base or indenyl.
5. method according to claim 1, is characterized in that, during described mono-metallocene compound catalysis norbornene polymerization, concentration is in the solution 1 × 10
-8mol/L to 1 × 10
-2mol/L.
6. method according to claim 5, is characterized in that, during described mono-metallocene compound catalysis norbornene polymerization, concentration is in the solution for being 1 × 10
-7mol/L to 1 × 10
-3mol/L.
7. method according to claim 1, is characterized in that, described polyreaction is carried out in organic solvent toluene, and polymerization temperature is-50 DEG C to 200 DEG C.
8. method according to claim 7, is characterized in that, polymerization temperature is-20 DEG C to 150 DEG C.
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