CN1769314A - Copolymer of olefin and omega-tolyl-alpha-olefin and its preparation method - Google Patents
Copolymer of olefin and omega-tolyl-alpha-olefin and its preparation method Download PDFInfo
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- CN1769314A CN1769314A CN 200410088512 CN200410088512A CN1769314A CN 1769314 A CN1769314 A CN 1769314A CN 200410088512 CN200410088512 CN 200410088512 CN 200410088512 A CN200410088512 A CN 200410088512A CN 1769314 A CN1769314 A CN 1769314A
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Abstract
The invention relates the copolymer of alkene and omega- cresyl-alpha-alkene and the method for preparation of the copolymer, which is making the alkene and omega- cresyl-alpha-alkene polymerize with the method of alkene coordination and polymerization. The catalytic system comprises Ziegler-Natta catalyst, metallocene catalyst, limited geometric configuration catalyst, 2, 6-bis (imino) pyridine transient metal catalyst and nitrogen-oxygen transient metal catalyst.
Description
Technical field
The present invention relates to a kind of alkene and omega-tolyl-alpha-olefin multipolymer.
The invention still further relates to the preparation method of above-mentioned multipolymer.
Technical background
Polyolefine material, comprise polyethylene (PE), polypropylene (PP), poly-1-butylene, poly(4-methyl-1-pentene), ethylene-propylene rubber(EPR) (EPR), EPDR (EPDM) etc., have ratio of performance to price height, mechanical property is good and thermal characteristics is stable and characteristics such as crystallinity modulation scope is big, processing characteristics is good, security and stability good, utilization more capable of circulation, is widely used in every field such as industrial or agricultural, health care, scientific research, military affairs and daily life.The monomer that is used for producing polyolefine material is cheap, and activity of such catalysts is very high, makes polyolefine become the low-cost and high-performance polymkeric substance.Most of polyolefine material can by extrude, methods such as injection molding, pressing mold, injection blow molding, be processed into the goods such as film, plate, pipe and fiber of different shapes and size.But the polyolefine macromolecular chain is made up of nonpolar hydrocarbon atom, causes polyolefinic printing and dyeing performance and adhesiveproperties poor, and is poor with the inorganics consistency, poor with other superpolymer consistency.In order to improve polyolefinic these shortcomings, with application extension to a brand-new field of polyolefin products, require on the polyolefine macromolecular chain, to introduce polar group or other kind macromolecular chain, promptly polyolefine is carried out functional modification.
As far back as the fifties, Natta etc. just begin to introduce heteroatoms in olefinic polymerization, but the result is unsatisfactory.Now, the polyolefin functional method that grows up has three kinds:
First kind is the direct polymerization method, and with alpha-olefin and function monomer direct copolymerization, function monomer generally only contains heteroatomic polar monomer; Second kind is the back functional method, by chemistry or physical method modified polyolefin; The 3rd is the reactive group functional method, introduces reactive comonomer in polymkeric substance, changes reactive group into functional group efficiently after obtaining polymkeric substance.
The polymerizing catalyst of alkene generally is a polycoordination mechanism, easily and the nucleophilic reagent coordination, but function monomer generally all has the nucleophilic heteroatoms, as nitrogen, oxygen, sulphur, phosphorus atom, be easy to active centre with the polymerizing catalyst of alkene, metallic ion coordination sharply descends activity of such catalysts, and molecular weight also reduces greatly.
Reaction extrudes that modification is a functional method after two kinds that use always with surfaces of polymeric articles.The maleic anhydride inoculated polypropylene that preparation is extruded in polypropylene, radical initiator and maleic anhydride reaction is to use maximum functional polyolefin materials, is usually used in the compatilizer of polypropylene and nylon blending and the preparation of aluminum-plastic laminated tube.The common practices of polymer surface modification is with gamma-rays or plasma radiation polymer surfaces, produces free radical, reacts with polar monomer again.Produce a large amount of free radicals during back functionalization and can cause the chain rupture of polyolefine macromolecular chain and crosslinked, this is undesirable, and the distribution of functional group on high molecular is not very even.
Direct function method and back functional method all have certain limitation, comparatively speaking, the reactive group functional method is near the situation of industrialization actual production, and this kind method is controlling polymers molecular structure and molecular weight distribution effectively, the diversified polyolefine of complex functionality group.The advantage that the reactive group functional method combines the former two has overcome their shortcoming again.Reaction is divided into two steps: the direct and olefin-copolymerization of reactive comonomer, do not influence activity of such catalysts, and in existing industrial building-up process, can realize fully; Second goes on foot, and obtains containing the polymkeric substance of reactive group, as the intermediate medium of reaction kinetic, can change required functional group selectively into, and this step can carry out in fusion or solution state.This method is mainly grown up by people such as MikeChung.The alpha-olefin and the alpha-olefinic copolymerization that will contain borine, borine are very active reactive groups, can efficiently be converted into other polar groups fast, as hydroxyl, and amido, halogen etc.; Obtain the carbon oxyradical behind borine and the oxygen reaction, the carbon oxyradical can cause multiple monomer and carry out radical polymerization, vinylbenzene for example, and phenylethylene/maleic anhydride, methymethacrylates etc. are prepared polyolefinic graft copolymer.Also p-methylstyrene and alpha-olefin copolymer can be closed, methyl on the phenyl ring is more active, multiple reaction can take place, and produces carboxyl and has a few lithium reactions to produce the benzyl negatively charged ion such as oxidizing reaction, further and carbonic acid gas, bromine, halohydrocarbon and halogenated silanes reaction also can be used benzyl anionic initiation monomer polymerization, such as vinylbenzene, prepare polyolefin graft copolymer.
The monomer and the polyolefine copolymerization performance that contain borine are fine, and activity of such catalysts is not had big influence yet, but the boron monomer is very expensive, are not suitable for the big production of industry.The copolymerization performance of p-methylstyrene and ethene is fine, and the copolymerization of propylene comparatively difficult; In when polymerization, also can produce the homopolymer of p-methylstyrene under some condition.The present invention uses omega-tolyl-alpha-olefin and alkene to have good copolymerization performance, but and has kept the functionalization feature of tolyl.In the method for reactive monomer method functional polyolefin, the multipolymer of omega-tolyl-alpha-olefin and alkene can the most a kind of good intermediate.
Summary of the invention
The object of the present invention is to provide the multipolymer of a kind of alkene and omega-tolyl-alpha-olefin.
Another purpose of the present invention is to provide a kind of method for preparing above-mentioned multipolymer.
For achieving the above object, the multipolymer of alkene provided by the invention and omega-tolyl-alpha-olefin has structure as shown in Equation 1:
Formula 1
In the formula 1: R
1Group is: H, CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2(CH
3)
2, CH
2CH
2(CH
3)
2, (CH
2)
3CH
3, (CH
2)
4CH
3, (CH
2)
5CH
3, phenyl (Ph), C
6H
4CH
3, or C
6H
4CHCH
2
R
2Group refers to contain straight chain, side chain or the cyclic alkyl of 1-8 carbon, for example-and (CH
2)
n-, n=1～9;-CH
2-C
6H
4-(CH
2)
n-n=1～9;-(CH
2)
m-CHR
3-(CH
2)
n-, m=1～7, n=8-m.Methyl on the phenyl can be positioned at R
2The ortho position of group, a position or contraposition.
The molar content that is less than the alkene of 10 carbon in this multipolymer is 60-99.9%, and the molar content of omega-tolyl-alpha-olefin is 0.1-40%.
The number-average molecular weight that gel chromatography (GPC) is measured is 1000-300000, and molecular weight distribution is 1.0-20.
Described alkene refers to the straight chain that contains 2-10 carbon, side chain hydro carbons or vinylbenzene and the derivative thereof that the end has two keys, for example ethene, propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, vinylbenzene, p-methylstyrene, to one or several the combination in the Vinylstyrene etc.
Described omega-tolyl-alpha-olefin has structure as shown in Equation 2:
In the formula 2: R
2Group refers to contain straight chain, side chain or the cyclic alkyl of 1-8 carbon, for example-and (CH
2)
n-, n=1～9;-CH
2-C
6H
4-(CH
2)
n-n=1～9;-(CH
2)
m-CHR
3-(CH
2)
n-, m=1～7, n=8-m, wherein R
3Can be-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH (CH
3)
2Methyl on the phenyl can be positioned at R
2The ortho position of group, a position or contraposition.
The above-mentioned multipolymer method of preparation provided by the invention, its principle is copolymerization omega-tolyl-alpha-olefin and alkene, prepares multipolymer.
The key step of its preparation is as described below:
The 600mL stainless steel Parr reactor that mechanical stirrer is housed is heated to 80-100 ℃ vacuumizes, remove oxygen and steam in the still.Adding alkene (if alkene is gas, then directly charges into, if alkene is liquid, then earlier charges into nitrogen in still, add alkene under nitrogen gas stream.), solvent and omega-tolyl-alpha-olefin, catalyzer and promotor, sealed reactor starts stirring, and the temperature of polyreaction is preferably between 40 ℃ to 100 ℃ from 20 ℃ to 100 ℃.Reaction times generally is less than 10 hours, is preferably 0.5-2 hour.Polymerization monomer altogether can disposablely add, and also can add in batches.With acidifying ethanol termination reaction, go out polymkeric substance with ethanol sedimentation, and wash three times, last vacuum-drying polymkeric substance.
This preparation process has following feature:
The method of the olefin coordination polymerization that the present invention adopts is meant uses the olefin coordination polymerization catalyzer, catalyzed polymerization alpha-olefin and omega-tolyl-alpha-olefin copolymerization, operable catalyzer is a Ziegler-Natta catalyst, metallocene catalyst, constrained geometry catalyst, pyridine diimine class coordinate transition-metal catalyst and nitrogen oxygen coordinate transition-metal catalyst.
The main component of the Ziegler-Natta catalyst that the present invention adopts is MgCl
2The TiCl of load
4, contain lipid or two ethers internal electron donors.The promotor that such catalyzer uses is AlR
3, AlR
2X or AlRX
2, perhaps several mixtures, wherein R is methyl, hexyl, sec.-propyl, the tertiary butyl or phenyl; X is chlorine, bromine atoms.If do not contain two ethers internal electron donors in the Ziegler-Natt catalyzer, then can add two ethers external electron donor, for example dimethoxydiphenylsilanes during polymerization.
The metallocene catalyst that the present invention adopts has following structure: (Cp
*)
nMA
mB
pCp wherein
*Refer to cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl or replace fluorenyl, substituting group can contain the aliphatics or the cyclic alkyl of 1-12 carbon, preferably 1-6 carbon.Cp
*Between polymethylene or dialkyl group silicon can be arranged to connection, for example-CR
1R
2-,-CR
1R
2-CR
1R
2-,-SiR
1R
2-, R
1And R
2Be the aliphatics or the cycloalkyl of a hydrogen or 1-8 carbon.A, B are if halogen then is fluorine, chlorine, bromine or iodine, if alkyl then is that straight chain, side chain or cyclic contain 1-8 carbon alkyl, such as methyl, hexyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl and/or n-hexyl.M refers to the metal essence of IVB or VB, such as titanium, zirconium, hafnium or vanadium.N=1,2; M=0-3; P=0-3; N, m, p sum equal the valence state of metal.
The catalyzer that for example can adopt but be not limited to has following kind:
The cyclopentadienyl titanous chloride, the bicyclic pentadiene zirconium dichloride, dicyclic pentylene titanium dichloride, the bicyclic pentadiene hafnium dichloride, two methyl cyclopentadienyl titanium dichloride, two methyl cyclopentadienyl zirconium dichlorides, two methyl cyclopentadienyl hafnium dichloride, bicyclic pentadiene dimethyl titanium, the bicyclic pentadiene zirconium dimethyl, bicyclic pentadiene dimethyl hafnium, two methyl cyclopentadienyl dimethyl titaniums, two methyl cyclopentadienyl zirconium dimethyls, two methyl cyclopentadienyl dimethyl hafniums, two (1,3-dimethyl cyclopentadienyl) zirconium dichloride, two (1,3-dimethyl cyclopentadienyl) hafnium dichloride, two (trimethylammonium cyclopentadienyl) zirconium dichloride, two (trimethylammonium cyclopentadienyl) titanium dichloride, two indenyl zirconium dichlorides, two indenyl zirconium dimethyls, two indenyl hafnium dichloride, two indenyl dimethyl hafniums, two fluorenyl zirconium dichlorides, two (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride, hexyl abutment two indenes zirconium dichlorides, hexyl abutment two indenes zirconium dimethyls, hexyl abutment two indenes phenylbenzene zirconiums, dimethyl-silicon abutment two indenes zirconium dichlorides, dimethyl-silicon abutment two indenes zirconium dimethyls, phenylbenzene silicon bridge base two indenes zirconium dichlorides, dimethyl-silicon abutment-9-fluorenyl-cyclopentadienyl zirconium dichloride, similar compounds such as methyl abutment-9-fluorenyl-cyclopentadienyl zirconium dichloride and dimethyl-silicon abutment (2-methyl-4-naphthyl-indenyl) zirconium dichloride.
The constrained geometry catalyst that the present invention adopts has following structure: ZLMX
pX '
qM is the metal of IVB, has 2
+, 3
+Perhaps 4
+Valency, and and ligand L close with 5 η bonds.L is cyclopentadienyl, indenyl, fluorenyl, tetrahydro indenyl or the tetrahydrofluorenyl that Z replaces.L can have 1-8 substituting group, and these substituting groups can be alkyl, halogen, dialkylamine, haloalkane, dialkyl phosphine or silane, and the non-hydrogen atom number is less than 20 in the substituting group.L is a bivalent atom, perhaps have a σ key and a pair of can with the neutral electronics of M coordinate.Z can be the essence of IVA in boron, nitrogen, phosphine, sulphur, oxygen or the periodictable.X is the anion ligand that is less than 60 atoms, does not comprise ring-type and the group with delocalized structure.X ' is the neutral ligand that is less than 20 atoms.Q=0,1 or 2; P=0,1 or 2, and lack 2 than the valence state of M.
The pyridine diimine class coordinate transition-metal catalyst that the present invention adopts have suc as formula 3 or formula 4 shown in structure:
Formula 3 or
Formula 4
In formula 3 or the formula 4: R
1-R
6Be H, alkyl or aromatic base; X
1, X
2Be alkyl, halogen or H.Detailed description can be consulted U.S. Pat 5880323.
The nitrogen oxygen coordinate transition-metal catalyst that the present invention adopts has structure as shown in Equation 5:
In the formula 5: M is the metal essence of IIIB-IB, R
1-R
5Be H, alkyl or aromatic base, m=1-6, X are halogen, and n makes metal valence state balance, and its detailed description can be consulted U.S. Pat 6309997 or European patent EP 0874005.
The olefin coordination polymerization method that the present invention adopts mainly refers to the method for slurry polymerization, and used solvent is alkanes or aromatic hydrocarbons, as: pentane, hexane, heptane, decane, sherwood oil, hexanaphthene, benzene, toluene and/or dimethylbenzene.The solvent for use deoxygenation that need dewater.All polymerization single polymerization monomers that polymerization is used need the deoxygenation that dewaters too.
In the polymerization process described in the present invention, when used alkene was gas, alkene added continuously, and pressure is the 1-10 normal atmosphere; When used alkene was liquid, alkene added in batches, and concentration is the 1-5 mol.The concentration of omega-tolyl-alpha-olefin is the 0.05-5 mol.Catalyst concentration is the 1-100 micromoles per liter.
In the polymerization process described in the present invention, when used catalyzer was Ziegler-Natta catalyst, employed promotor was AlR
3, AlR
2X and/or AlRX
2, wherein R is methyl, hexyl, sec.-propyl, the tertiary butyl or phenyl; X is chlorine, bromine atoms.The ratio of the amount of substance of used promotor and the amount of substance of catalyzer is 10-500.When used catalyzer is metallocene catalyst, constrained geometry catalyst, pyridine diimine class coordinate transition-metal catalyst and nitrogen oxygen coordinate transition-metal catalyst, used promotor is a methylaluminoxane, the ethyl aikyiaiurnirsoxan beta, tertiary butyl aikyiaiurnirsoxan beta or this three's mixture, the ratio of the amount of substance of used promotor and the amount of substance of catalyzer is 100-5000.Used promotor also can be the tri-substituted phenyl boron compound, as three (pentafluorophenyl group) boron, and three [3,5-two (trifluoromethyl) phenyl] boron, promotor and molecular proportion of catalyst are 1-3.
Embodiment
Embodiment 1-6
To have churned mechanically Parr reactor and be heated to 100 ℃ and vacuumized 1 hour, remove wherein steam and oxygen.Cooling, charge into ethylene gas, add 100 milliliters of toluene more successively, comonomer is to allyl group toluene (p-AT), 1 milliliter of promotor methylaluminoxane (MAO, toluene solution, 10% weight content) and 1 micromole's catalyzer hexyl abutment, two indenes zirconium dichlorides, catalyst concn is 10 micromoles per liter, Al/Zr=1400.60 ℃ of polymerization temperatures, ethylene pressure 1 normal atmosphere, polymerization time 30 minutes, polymerization is used the acidic alcohol termination reaction after finishing, and uses washing with alcohol polymkeric substance three times, and polymkeric substance was 60 ℃ of vacuum-dryings 8 hours.Used toluene refluxes to remove through sodium Metal 99.5 and anhydrates, and bubbling is 1 hour under nitrogen, removes deoxidation.Comonomer hydrolith drying, underpressure distillation goes out.Ethene is polymerization-grade.Experimental result is listed in table 1.Common monomer content in the multipolymer by
1HNMR measures.Molecular weight is measured with GPC.
Table 1 ethene and to allyl group toluene copolymerization result
| Numbering | P-AT add-on mol | Catalyst activity 10 6Gram/mole Zr hour | The content mole % of p-AT in multipolymer | Number-average molecular weight | Molecular weight distribution |
| PEAT-1 PEAT-2 PEAT-3 PEAT-4 PEAT-5 PEAT-6 | 0 0.05 0.2 0.6 1.0 2.0 | 6.8 7.4 4.0 4.0 4.4 5.0 | 0 1.4 6.4 8.4 12.4 20.2 | 109500 80700 51000 43900 21300 8100 | 5.2 3.7 2.9 2.7 2.3 2.2 |
Embodiment 7
Polymerizing condition is: the concentration to allyl group toluene is 1.5mol/L, and polymerization temperature is 80 ℃, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 29.8%.
Embodiment 8
Polymerizing condition is: the concentration to allyl group toluene is 1.5mol/L, and polymerization temperature is 100 ℃, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 35.1%.
Embodiment 9
Polymerizing condition is: the concentration to allyl group toluene is 2.0mol/L, and polymerization temperature is 100 ℃, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 39.8%, and weight-average molecular weight is 2100.
Embodiment 10
Polymerizing condition is: the concentration to allyl group toluene is 0.05mol/L, and polymerization temperature is 80 ℃, and ethylene pressure is 4.5 normal atmosphere, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 0.45%.
Embodiment 11
Polymerizing condition is: ethylene pressure is 10 normal atmosphere, and other is with embodiment 10.Molar content to allyl group toluene in the multipolymer is 0.11%.
Embodiment 12
Polymerizing condition is: catalyzer is the dicyclopentadienyl zirconium dichloride, and concentration is 10 micromoles per liter, and the mol ratio of methylaluminoxane and catalyzer is 3000, is 0.2 mol to the allyl group toluene concentration, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 3.2%.
Embodiment 13
Polymerizing condition is: catalyzer is two (pentamethyl-cyclopentadienyl) zirconium dichloride, and concentration is 100 micromoles per liter, and the mol ratio of methylaluminoxane and catalyzer is 100, is 0.2 mol to the allyl group toluene concentration, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 0.4%.
Embodiment 14
Polymerizing condition is: solvent is a hexane, catalyzer is a constrained geometry catalyst, the amino titanium dichloride of the dimethyl-silicon abutment tetramethyl-ring pentadienyl tertiary butyl, concentration is 100 micromoles per liter, is 0.5 mol to the allyl group toluene concentration, and polymer concentration is 30 ℃, ethylene pressure is 3 normal atmosphere, polymerization time is 1 hour, and the mol ratio of methylaluminoxane and catalyzer is 1500, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 16.5%.
Embodiment 15
Polymerizing condition is: catalyzer is a pyridine diimine class coordinate transition-metal catalyst, structure is suc as formula 6, concentration is 100 micromoles per liter, the mol ratio of promotor and catalyzer is 5000, to the allyl group toluene concentration is 0.5 mol, and polymer concentration is 20 ℃, and ethylene pressure is 1 normal atmosphere, polymerization time is 2 hours, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 3.2%.
Embodiment 16
Polymerizing condition is: catalyzer is a nitrogen oxygen coordinate transition-metal catalyst, structure is suc as formula 7, concentration is 1 micromoles per liter, the mol ratio of promotor and catalyzer is 2000, to the allyl group toluene concentration is 1.0 mol, and polymer concentration is 20 ℃, and ethylene pressure is 1 normal atmosphere, polymerization time is 0.5 hour, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 3.6%.
Embodiment 17
Polymerizing condition is: catalyzer is ethyl abutment two indenes zirconium dimethyls, concentration is 10 micromoles per liter, promotor is three (pentafluorophenyl group) boron, the mol ratio of promotor and catalyzer is 1, to the allyl group toluene concentration is 1.0 mol, and polymer concentration is 20 ℃, and ethylene pressure is 1 normal atmosphere, polymerization time is 0.5 hour, and other is with embodiment 1.Molar content to allyl group toluene in the multipolymer is 10.3%.
Embodiment 18
Polymerizing condition is: monomer is 4-tolyl-1-butylene altogether, and concentration is 0.2 mol, and other is with embodiment 1.The molar content of 4-tolyl-1-butylene is 4.1% in the multipolymer.
Embodiment 19
Polymerizing condition is: monomer is 4-tolyl-1-butylene altogether, and concentration is 0.2 mol, and other is with embodiment 1.The molar content of 4-tolyl-1-butylene is 4.1% in the multipolymer.
Embodiment 20
Polymerizing condition is: comonomer is 6-tolyl-1-hexene, and concentration is 0.2 mol, and other is with embodiment 1.The molar content of 6-tolyl-1-butylene is 1.6% in the multipolymer.
Embodiment 21
Polymerizing condition is: comonomer be between allyl group toluene, concentration is 0.2 mol, other is with embodiment 1.The molar content of allyl group toluene is 5.4% in the middle of the multipolymer.
Embodiment 22
To have churned mechanically Parr reactor and be heated to 100 ℃ and vacuumized 1 hour, remove wherein steam and oxygen.Cooling charges into argon gas, adds 100 milliliters of toluene successively, 1-hexene, concentration are 3 mol, to allyl group toluene, concentration is 0.5 mol, the amino titanium dichloride catalyzer of the methylaluminoxane and the dimethyl-silicon abutment tetramethyl-ring pentadienyl tertiary butyl, Al/Ti=3000.40 ℃ of polymerization temperatures, polymerization time 10 hours, polymerization is used the acidic alcohol termination reaction after finishing, and uses washing with alcohol polymkeric substance three times, and polymkeric substance was 60 ℃ of vacuum-dryings 8 hours.Polymkeric substance in be 5.6% to the molar content of allyl group toluene.
Embodiment 23
To have churned mechanically Parr reactor and be heated to 100 ℃ and vacuumized 1 hour, remove wherein steam and oxygen.Cooling charges into argon gas, adds 100 milliliters of toluene successively, vinylbenzene, and concentration is 5 mol, to allyl group toluene, concentration is 0.5 mol, methylaluminoxane and cyclopentadienyl titanium trichloride catalyst, Al/Ti=2000.60 ℃ of polymerization temperatures, polymerization time 5 hours, polymerization is used the acidic alcohol termination reaction after finishing, and uses washing with alcohol polymkeric substance three times, and polymkeric substance was 60 ℃ of vacuum-dryings 8 hours.Polymkeric substance in be 1.5% to the molar content of allyl group toluene.
Embodiment 24
To have churned mechanically Parr reactor and be heated to 100 ℃ and vacuumized 1 hour, remove wherein steam and oxygen.Cooling charges into propylene gas, adds 100 milliliters of heptane successively, and to allyl group toluene, concentration is 0.5 mol, 3.6 mmole triethyl aluminums and the Ziegler-Natta catalyst that contains 0.036 mmole titanium, Al/Ti=100.40 ℃ of polymerization temperatures, propylene pressure 1 normal atmosphere, polymerization time 2 hours, polymerization is used the acidic alcohol termination reaction after finishing, and uses washing with alcohol polymkeric substance three times, and polymkeric substance was 60 ℃ of vacuum-dryings 8 hours.Propylene is a polymerization-grade.Polymkeric substance in be 0.7% to the molar content of allyl group toluene, weight-average molecular weight is 298900.
Embodiment 25
Polymerizing condition is: to the allyl group toluene concentration is 5.0 mol, and other is with embodiment 24.Molar content to allyl group toluene in the multipolymer is 6.5%.
Claims (15)
1. the multipolymer of alkene and omega-tolyl-alpha-olefin, the structural formula of this multipolymer as shown in Equation 1
Formula 1
In the formula 1: R
1Group is: H, CH
3, CH
2CH
3, CH
2CH
2CH
3, CH
2(CH
3)
2, CH
2CH
2(CH
3)
2, (CH
2)
3CH
3, (CH
2)
4CH
3, (CH
2)
5CH
3, phenyl (Ph), C
6H
4CH
3Or C
6H
4CHCH
2
R
2Group refers to contain straight chain, side chain or the cyclic alkyl of 1-8 carbon;
Methyl on the phenyl is positioned at R
2The ortho position of group, a position or contraposition;
The molar content that is less than the alkene of 10 carbon in this multipolymer is 60-99.9%, and the molar content of omega-tolyl-alpha-olefin is 0.1-40%;
The weight-average molecular weight that gel chromatography is measured is 1000-300000, and molecular weight distribution is 1.0-20;
Alkene is the straight chain that contains 2-10 carbon, side chain hydro carbons or vinylbenzene and the derivative thereof that the end has two keys;
Omega-tolyl-alpha-olefin has structure as shown in Equation 2:
R in the formula 2
2Group refers to contain straight chain, side chain or the cyclic alkyl of 1-8 carbon; Methyl on the phenyl is positioned at R
2The ortho position of group, a position or contraposition.
2. multipolymer as claimed in claim 1, it is characterized in that alkene is ethene, propylene, 1-butylene, 1-amylene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, vinylbenzene, p-methylstyrene, to one or several the combination in the Vinylstyrene.
3. multipolymer as claimed in claim 1 is characterized in that, the R in the omega-tolyl-alpha-olefin
2Group is :-(CH
2)
n-, n=1～9;-CH
2-C
6H
4-(CH
2)
n-, n=1～9;-(CH
2)
m-CHR
3-(CH
2)
n-, m=1～7, n=8-m, wherein R
3For-CH
3,-CH
2CH
3,-CH
2CH
2CH
3Or-CH (CH
3)
2
4. prepare the method for multipolymer according to claim 1, use olefin coordination polymerization catalyst olefin polymerization and omega-tolyl-alpha-olefin copolymerization, key step is:
Reactor is heated to 80-100 ℃ and vacuumizes, remove oxygen and steam, add alkanes or aromatic hydrocarbon solvent, alkene, omega-tolyl-alpha-olefin, catalyzer and promotor are added in the reactor, sealed reactor, in 20 ℃ to 100 ℃ following stirring reactions 0.5 to 10 hour, acidifying ethanol termination reaction, be settled out polymkeric substance, vacuum-drying;
The deoxygenation that need dewater of the alkene that used solvent and polymerization are used, omega-tolyl-alpha-olefin;
Used catalyzer is Ziegler-Natta catalyst, metallocene catalyst, constrained geometry catalyst, pyridine diimine class coordinate transition-metal catalyst and nitrogen oxygen coordinate transition-metal catalyst.
When used alkene was gas, alkene added continuously, and pressure is the 1-10 normal atmosphere; When used alkene was liquid, alkene added in batches, and concentration is the 0.1-5 mol; The concentration of omega-tolyl-alpha-olefin is the 0.05-5 mol; Catalyst concentration is the 1-100 micromoles per liter;
When catalyzer was Ziegler-Natta catalyst, promotor was AlR
3, AlR
2X and/or AlRX
2, wherein R is methyl, hexyl, sec.-propyl, the tertiary butyl or phenyl; X is chlorine, bromine atoms; The ratio of the amount of substance of promotor and the amount of substance of catalyzer is 10-500;
When catalyzer was metallocene catalyst, constrained geometry catalyst, pyridine diimine class coordinate transition-metal catalyst and nitrogen oxygen coordinate transition-metal catalyst, promotor was methylaluminoxane, ethyl aikyiaiurnirsoxan beta and/or tertiary butyl aikyiaiurnirsoxan beta; The ratio of the amount of substance of promotor and the amount of substance of catalyzer is 100-5000;
When used promotor was three (pentafluorophenyl group) boron or three [3,5-two (trifluoromethyl) phenyl] boron, promotor and molecular proportion of catalyst were 1-3.
5. method as claimed in claim 4 is characterized in that, the composition of Ziegler-Natta catalyst is MgCl
2The TiCl of load
4, contain lipid or two ethers internal electron donors.
6. method as claimed in claim 4 is characterized in that metallocene catalyst has following structure: (Cp
*)
nMA
mB
p
Cp wherein
*Refer to cyclopentadienyl, substituted cyclopentadienyl, indenyl, substituted indenyl, fluorenyl or replace fluorenyl, substituting group can contain the aliphatics or the cyclic alkyl of 1-12 carbon; Cp
*Between polymethylene or dialkyl group silicon can be arranged to connection;
A, B are that halogen or straight chain, side chain or cyclic contain 1-8 carbon alkyl;
M is the metallic element of IVB or VB family;
N=1-2; M=0-3; P=0-3; N, m, p sum equal the valence state of metal.
7. method as claimed in claim 6 is characterized in that, described polymethylene or dialkyl group silicon to connection are :-CR
1R
2-,-CR
1R
2-CR
1R
2-or-SiR
1R
2-; R wherein
1And R
2Be the aliphatics or the cycloalkyl of a hydrogen or 1-8 carbon.
8. method as claimed in claim 6 is characterized in that, described carbon alkyl is: methyl, hexyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, n-pentyl or n-hexyl.
9. method as claimed in claim 6 is characterized in that, the metallic element of described M representative is titanium, zirconium, hafnium or vanadium.
10. method as claimed in claim 6 is characterized in that, used metallocene catalyst is:
The cyclopentadienyl titanous chloride, the bicyclic pentadiene zirconium dichloride, dicyclic pentylene titanium dichloride, the bicyclic pentadiene hafnium dichloride, two methyl cyclopentadienyl titanium dichloride, two methyl cyclopentadienyl zirconium dichlorides, two methyl cyclopentadienyl hafnium dichloride, bicyclic pentadiene dimethyl titanium, the bicyclic pentadiene zirconium dimethyl, bicyclic pentadiene dimethyl hafnium, two methyl cyclopentadienyl dimethyl titaniums, two methyl cyclopentadienyl zirconium dimethyls, two methyl cyclopentadienyl dimethyl hafniums, two (1,3-dimethyl cyclopentadienyl) zirconium dichloride, two (1,3-dimethyl cyclopentadienyl) hafnium dichloride, two (trimethylammonium cyclopentadienyl) zirconium dichloride, two (trimethylammonium cyclopentadienyl) titanium dichloride, two indenyl zirconium dichlorides, two indenyl zirconium dimethyls, two indenyl hafnium dichloride, two indenyl dimethyl hafniums, two fluorenyl zirconium dichlorides, two (4,5,6,7-tetrahydrochysene-1-indenyl) zirconium dichloride, hexyl abutment two indenes zirconium dichlorides, hexyl abutment two indenes zirconium dimethyls, hexyl abutment two indenes phenylbenzene zirconiums, dimethyl-silicon abutment two indenes zirconium dichlorides, dimethyl-silicon abutment two indenes zirconium dimethyls, phenylbenzene silicon bridge base two indenes zirconium dichlorides, dimethyl-silicon abutment-9-fluorenyl-cyclopentadienyl zirconium dichloride, methyl abutment-9-fluorenyl-cyclopentadienyl zirconium dichloride or dimethyl-silicon abutment (2-methyl-4-naphthyl-indenyl) zirconium dichloride.
11. method as claimed in claim 4 is characterized in that, constrained geometry catalyst has following structure: ZLMX
pX '
q
M is the metal of 1VB, has 2
+, 3
+Perhaps 4
+Valency, and and ligand L close with 5 η bonds;
L is cyclopentadienyl, indenyl, fluorenyl, tetrahydro indenyl or the tetrahydrofluorenyl that Z replaces; L has 1-8 substituting group, and these substituting groups are alkyl, halogen, dialkylamine, haloalkane, dialkyl phosphine or silane, and the non-hydrogen atom number is less than 20 in the substituting group; L is a bivalent atom, perhaps have a σ key and a pair of can with the neutral electronics of M coordinate;
Z is the element of IVA in boron, nitrogen, phosphine, sulphur, oxygen or the periodictable;
X is the anion ligand that is less than 60 atoms, does not comprise ring-type and the group with delocalized structure;
X ' is the neutral ligand that is less than 20 atoms;
Q=0,1 or 2; P=0,1 or 2, and lack 2 than the valence state of M.
12. method as claimed in claim 4 is characterized in that, pyridine diimine class coordinate transition-metal catalyst have suc as formula 3 or formula 4 shown in structure:
In the formula: R
1-R
6Be H, alkyl or aromatic base;
X
1, X
2Be alkyl, halogen or H.
13. method as claimed in claim 4 is characterized in that, nitrogen oxygen coordinate transition-metal catalyst has structure as shown in Equation 5:
In the formula: M is the metallic element of IIIB-IB, R
1-R
6Be H, alkyl or aromatic base, m=1-6, X are halogen, and n makes metal valence state balance.
14. method as claimed in claim 4 is characterized in that, used alkanes or aromatic hydrocarbon solvent are: pentane, hexane, heptane, decane, sherwood oil, hexanaphthene, benzene, toluene and/or dimethylbenzene.
15. method as claimed in claim 4 is characterized in that, alkene, omega-tolyl-alpha-olefin are for add in batches.
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| CN105482007A (en) * | 2016-01-08 | 2016-04-13 | 山西大学 | Bis-diimine silicon-bridged zirconium catalyst and preparation method thereof |
| CN106397259A (en) * | 2015-07-31 | 2017-02-15 | 中国石油化工股份有限公司 | Diimine ligand, and diimine-nickel complex and application thereof |
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| CN106397260A (en) * | 2015-07-31 | 2017-02-15 | 中国石油化工股份有限公司 | Diimine ligand compound, and nickel complex and application thereof |
| CN106397263A (en) * | 2015-07-31 | 2017-02-15 | 中国石油化工股份有限公司 | Ligand compound and preparation thereof, and complex containing ligand compound |
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| CN106397259A (en) * | 2015-07-31 | 2017-02-15 | 中国石油化工股份有限公司 | Diimine ligand, and diimine-nickel complex and application thereof |
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| CN106397263A (en) * | 2015-07-31 | 2017-02-15 | 中国石油化工股份有限公司 | Ligand compound and preparation thereof, and complex containing ligand compound |
| CN106397262B (en) * | 2015-07-31 | 2018-06-12 | 中国石油化工股份有限公司 | Diimide ligand, preparation method and application |
| CN106397264B (en) * | 2015-07-31 | 2018-07-20 | 中国石油化工股份有限公司 | A kind of diimide ligand compound, complex and application |
| CN106397263B (en) * | 2015-07-31 | 2018-07-20 | 中国石油化工股份有限公司 | Ligand compound, it is prepared and the complex containing the ligand compound |
| CN105482007A (en) * | 2016-01-08 | 2016-04-13 | 山西大学 | Bis-diimine silicon-bridged zirconium catalyst and preparation method thereof |
| CN115572341A (en) * | 2022-11-04 | 2023-01-06 | 大连万慷工业科技有限公司 | Functionalized polyolefin elastomer and preparation method thereof |
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