CN103030724A - Copolymerization method of alpha-olefin and polar group-containing olefin - Google Patents
Copolymerization method of alpha-olefin and polar group-containing olefin Download PDFInfo
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Abstract
The invention provides a copolymerization method of alpha-olefin and polar group-containing olefin. The reaction is carried out under the catalysis of a sulfur-containing ligand equipped half-metallocene main catalyst shown as formula I and a methylaluminoxane cocatalyst. In formula I, X is alkyl or hydrocarbyloxy; and Cp' is alkyl substituted or unsubstituted cyclopentadienyl, indenyl or fluorenyl. Under the circumstance of maintaining catalyst polymerization activity, a polyolefin material with a high polar monomer content can also be obtained at the same time by the method provided in the invention.
Description
Technical field
The invention belongs to catalysis and field of olefin polymerisation, be specifically related to a kind of alpha-olefin and copolyreaction method with the alkene of polar group.The Primary Catalysts of reaction is the luxuriant transistion metal compound of a kind of list with sulfur-containing ligand, and promotor is methylaluminoxane; This catalyst alpha-olefin with the olefin-copolymerization of polar substituent, obtain containing the polyolefine material of polar group.
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 two kinds of bridging and non-bridgings.Use the broad sense metallocene catalyst, both can obtain all well-proportioned olefin polymers of molecular weight distribution and chemical constitution distribution; Simultaneously can be by adjusting catalyst structure so that the molecular structure of polymkeric substance and molecular weight height are controlled; In addition, by using metallocene catalyst, can also obtain the olefin polymer that traditional Z iegler-Natta catalyzer can not obtain.
Polyolefine has good mechanical property, electric property, chemical property and processing characteristics, and cheap, is widely used in the fields such as daily life, industrial and agricultural production.That polyolefin chain presents is nonpolar, surface energy is low, and molecule is unreactiveness, and these characteristics greatly affect its application in many aspects, makes it be difficult to satisfy the growing demand of society.Polyolefine is being carried out in all multi-methods of functional modification, polar monomer is being introduced the great attention that always just is subject to people in the polyolefin chain by copolymerization process.Introduce polar group, not only can effectively control polyolefinic many critical natures, such as binding property, dyeability, printing, solvent resistance, consistency and rheological etc., and can keep well the original characteristic of polyolefine.
But after polar group is introduced polymerization system, can coordination, the growth of polymerization process be produced and have a strong impact on, thereby it is active to reduce polymerization catalyst, can cause catalyst deactivation when serious.Because it is little a lot of that polar group will be compared the Former transition metal catalyst impact to late transition metal catalyst impact, thus most of about the research of polar monomer copolymerization all use late transition metal catalyst (Science 2000,287,460; Chem.Rev.2000,100,1479; Chem.Rev.2000,100,1169) particularly the research of IVB metal catalyst (such as titanium, zirconium) is relatively less, to use early transition metal.
Use the Ziegler-Natta catalyst system, homopolymerization that can catalysis straight chain ω-alkene ester.Generally use first R
2AlCl is (such as Et
2AlCl) process ω-allyl ester monomer, sterically hindered larger ω-alkene ester has higher transformation efficiency (J.Polym.Sci.Polym.Chem.1988,26,677).Use same catalyst system, can realize comprising the copolymerization (J.Polym.Sci.Polym.Chem.1989,27,2051) of a series of alpha-olefins such as ethene and ω-alkene ester.
Use metallocene catalysis system can realize that ω-allyl ester monomer is with ethene and copolymerization of propylene.When using (n-BuCp)
2ZrCl
2/ MAO is catalyst ethene and 9-ten alkene methyl ester copolymerization and with Et (Ind)
2ZrCl
2When/MAO catalyzing propone and 9-ten alkene methyl ester, the copolymerization of 10-hendecene isobutyl, can observe remarkable reduction (Eur Polym.J.1997,33,1187 with ethylene homo phase specific activity; 1998,34,1093).In addition, use means of special bridged metallocene catalysts can prepare the terpolymer (Macromol.Chem.Phys.1997,198,291) of the random copolymers of 11-chloro-1-hendecene and 1-heptene and 1-chloro-1-hendecene and ethene, propylene.M ü lhaupt uses zirconocene catalyst can realize N, the copolymerization (Polymer, 1997,38,2455) of N-two (trimethylsilyl)-1-amido-10-hendecene and ethene.Novak non-bridged combined metal catalyzer makes ethene and acrylate monomer carry out copolymerization (Polym.Mater.Sci.Eng.1999,80,45).
Use non-luxuriant zirconium-based catalyst catalyzed ethylene and undecylenyl alcohol to carry out copolymerization, its catalytic activity is basic and its catalyzed ethylene homopolymerization is quite active, polar monomer molar fraction in polymkeric substance surpasses 8% (J.Polym.Sci.Polym.Chem.2005,43,5944)." the FI catalyzer " of Mitsui also can be used for the copolymerization of ethene and polar monomer; Use this class catalyzer, successfully make 5-hexenyl-1-acetic ester and ethene carry out copolymerization, along with the increase of common monomer consumption, polar monomer content in polymkeric substance increases, and reaches as high as 3.2%; But simultaneously all obviously decline (J.Am.Chem.Soc.2008,130,17636) of polymerization activity and polymericular weight.
Patent CN1769313 discloses the titanium catalyst that uses the coordination of Schiff alkali, but catalysis alpha-olefin and polar monomer copolymerization.CN1887924 uses the titanium catalyst of tridentate ligand coordination to carry out the copolymerization of ethene and polar monomer, and its polar monomer scope of application is extensive, and activity is higher, and monomer insertion rate can surpass 8% altogether.
Alpha-olefin and polar monomer copolymerization are very important research directions.Can find out from document, mainly have at present following several problem.First, since the nearer polar group of the two keys of distance very easily with the active centre coordination, and cause catalyst deactivation, so in most research and development, all use long-chain to be total to monomer and be the common monomer with polar group, the carbon atom that is interval between olefinic double bonds and the polar group is more, can not bring too much the catalyst activity loss to guarantee polar group.The second, although be the polar monomer that adopts than long-chain, generally speaking, the effect of its polar group and catalyst active center is still inevitable, thereby compares with the homopolymerization of alpha-olefin, and the activity of alpha-olefin and polar monomer copolymerization is much lower.The 3rd, to compare with the homopolymerization of alpha-olefin, the polymericular weight that alpha-olefin and polar monomer copolymerization obtain is also much lower.So research and develop new polymerization catalyst system, guarantee good polymerization behavior and polymer architecture performance, thereby obtain novel polyolefine material, remain an important problem.
Summary of the invention
The invention provides a kind of alpha-olefin and copolyreaction method with the alkene of polar group, this reaction is carried out under the catalysis suc as formula the Primary Catalysts mono-metallocene compound shown in the I and promotor methylaluminoxane,
Among the formula I, X is alkyl or-oxyl; Cp ' replaces or unsubstituted cyclopentadienyl, indenyl or fluorenyl with alkyl.
Preferred X of the present invention is methyl, alkoxyl group or phenoxy group.Wherein said alkoxyl group is methoxyl group, isopropoxy or butoxy more preferably.
Preferred Cp ' of the present invention is cyclopentadienyl, pentamethyl-cyclopentadienyl or indenyl.
In the preferred mono-metallocene compound of the present invention in Ti and the methylaluminoxane mol ratio of Al be 1: 50 to 1: 20000, more preferably 1: 200 to 1: 10000, most preferably be 1: 500 to 1: 3000.
The structure of methylaluminoxane of the present invention is shown in formula II or the III:
R represents methyl among formula II and the III; N represents the integer of 4-30, is preferably the integer of 10-30.
Concentration during preferred mono-metallocene compound catalyzed copolymerization reaction of the present invention in solution is 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 to be used.Polyreaction of the present invention is carried out in organic solvent toluene, and polymerization temperature is-50 ℃ to 200 ℃, is preferably-20 ℃ to 150 ℃.
In the present invention, described alpha-olefin is the alpha-olefin that ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene or 4-methyl-1-pentene etc. contain 2-30 carbon atom; Preferred described alpha-olefin is ethene.
Preferred described alkene Semi-polarity group with polar group is hydroxyl, carboxyl, amido, sulfydryl or phosphino-; Wherein, hydroxyl most preferably.
Embodiment
The analysis that is total to monomer (with the monomer of polar group) content in the polymkeric substance is passed through
1H-NMR measures; Method of calculation behind its assay are as described below.Wherein, the chemical structural formula of polymkeric substance is as follows.
In the said structure formula, the hydrogen atom on the main polymer chain derives from ethene (e, f in the formula) and is total to two keys position (d in the formula) of monomer 4-amylene-1-ol, and wherein f is terminal hydrogen, because its content is seldom,
1Only to see faint signal, when calculating, can ignore on the H-NMR spectrogram.
In the said structure formula, polymkeric substance side chain hydrogen is for being total to the two keys of monomer 4-amylene-1-ol hydrogen in addition, i.e. a in the formula, b, c and hydroxyl hydrogen.Wherein, hydroxyl hydrogen exists
1The upper general signal of H-NMR is very faint, can ignore when calculating.
In above-mentioned these signals, a is presented near the 3.46ppm, and all the other signals (comprising b-e) are all between 1.3～1.5.With the integration height of I expression signal, represent ethene and the mole number that is total to monomer in the polymkeric substance with m and n respectively, can obtain following formula:
I
a＝2n
I
b-e＝4m+3n+2n+2n
The content (mol%) that the conversion of process equation obtains common monomer is:
1H-NMR calculates m and n value after detecting, and can learn the together molar content of monomer of ethene.
The present invention is further illustrated by the following examples, but should not be construed as limitation of the invention.
Used MAO solution is the toluene solution of methylaluminoxane among the embodiment, and it is 1.67mmol that every ml soln contains MAO; Used catalyst solution is the toluene solution of mono-metallocene compound, and every ml soln comprises mono-metallocene compound 1 * 10
-5Mol; Used triisobutyl aluminum solutions is the toluene solution of triisobutyl aluminium, and every ml soln comprises triisobutyl aluminium 0.625mmol.
Embodiment 1
Synthesizing of pentamethyl-cyclopentadienyl-penta fluoro benzene sulfenyl-dimethoxy titanium:
Magneton is put into 250 milliliters of dry there-necked flasks, bottle is placed the magnetic stirring apparatus of oil bath temperature control; There-necked flask vacuumized repeatedly wash three times with nitrogen afterwards.And under nitrogen atmosphere, add pentamethyl-cyclopentadienyl-trimethoxy titanium 1.8g, and toluene 50mL, penta fluoro benzene thiophenol 1.35g, the stirring at room reaction is spent the night.Obtain yellow powder 2.1g after the solvent removed in vacuo, i.e. product pentamethyl-cyclopentadienyl among 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 dissolving, and freezing and crystallizing obtains yellow rib shape crystal.Its characterization result is as follows, nucleus magnetic resonance:
1H-NMR (CDCl
3, 25C): δ=2.12 (15H), 3.96 (6H).The ultimate analysis calculated value is C, 48.66; H, 4.76.Experimental value is C, 48.73; H, 4.38.
Take pentamethyl-cyclopentadienyl-penta fluoro benzene sulfenyl-dimethoxy titanium as the Primary Catalysts catalyzed ethylene and the copolymerization of 4-amylene-1-ol:
The polymerization bottle of drying vacuumized repeatedly wash three times with nitrogen afterwards, vacuumize again; Be filled with ethene under solenoid control, keeping ethylene pressure is normal pressure.Under 30 ℃ of oil bath temperature controls, add successively toluene 7.5mL, 4-amylene-1-ol 4.8mmol and triisobutylaluminum toluene solution 8mL, stir after 10 minutes, add the catalyzer toluene solution 1mL of MAO toluene solution 3mL and above-mentioned yellow powder preparation, the beginning timing.Behind the polymerization time 20 minutes, close ethene, pour reaction solution into beaker, add acidifying ethanol, stir more than 6 hours, filter and obtain polymkeric substance, filter cake was 60 ℃ of lower vacuum-dryings 24 hours, and weighing obtains polymkeric substance 0.72g, and activity is 2.16x10
5G-polymkeric substance/mol-Ti/hr.GPC determining molecular weight M
w=4.53x10
4, molecular weight distribution MWD=2.26.
1Containing 4-amylene-1-ol unit (with the alkene of polar group) mole fraction in the H-NMR mensuration polymkeric substance is 8.6%.
By above-described embodiment explanation, in the present invention, even use is the short carbon chain polar comonomers, also can when guaranteeing the catalyzer high polymerization activity, obtain having the polyolefine material of high polarity group content.Explanation is with the catalyst system of Primary Catalysts mono-metallocene compound of the present invention and promotor methylaluminoxane, is suitable for catalysis alpha-olefin and copolyreaction with the alkene of polar group.
Claims (12)
1. an alpha-olefin and copolyreaction method with the alkene of polar group, this reaction is carried out under the catalysis suc as formula the Primary Catalysts mono-metallocene compound shown in the I and promotor methylaluminoxane,
Among the formula I, X is alkyl or-oxyl; Cp ' replaces or unsubstituted cyclopentadienyl, indenyl or fluorenyl with alkyl.
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, pentamethyl-cyclopentadienyl or indenyl.
5. method according to claim 1 is characterized in that, in the described mono-metallocene compound in Ti and the methylaluminoxane mol ratio of Al be 1: 50 to 1: 20000.
6. method according to claim 5 is characterized in that, in the described mono-metallocene compound in Ti and the methylaluminoxane mol ratio of Al be 1: 200 to 1: 10000.
7. method according to claim 6 is characterized in that, in the described mono-metallocene compound in Ti and the methylaluminoxane mol ratio of Al be 1: 500 to 1: 3000.
8. method according to claim 1 is characterized in that, the concentration during described mono-metallocene compound catalyzed copolymerization reaction in solution is 1 * 10
-8Mol/L to 1 * 10
-2Mol/L is preferably 1 * 10
-7Mol/L to 1 * 10
-3Mol/L.
9. method according to claim 1 is characterized in that, described polyreaction is carried out in organic solvent toluene, and polymerization temperature is-50 ℃ to 200 ℃, is preferably-20 ℃ to 150 ℃.
10. the described method of any one in 9 according to claim 1 is characterized in that described alpha-olefin is ethene.
11. the described method of any one in 9 is characterized in that described alkene Semi-polarity group with polar group is hydroxyl, carboxyl, amido, sulfydryl or phosphino-according to claim 1.
12. method according to claim 11 is characterized in that, described polar group is hydroxyl.
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