CN103030724B - Copolymerization method of alpha-olefin and polar group-containing olefin - Google Patents

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

A kind of alpha-olefin and the copolyreaction method with the alkene of polar group

Technical field

The invention belongs to catalysis and field of olefin polymerisation, be specifically related to a kind of alpha-olefin and the 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 and the olefin-copolymerization with polar substituent, obtain the polyolefine material containing 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 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.

Polyolefine has good mechanical property, electric property, chemical property and processing characteristics, and cheap, is widely used in the field such as daily life, industrial and agricultural production.Polyolefin chain present nonpolar, surface energy is low, molecule is unreactiveness, and these characteristics greatly affect its application in many aspects, makes it be difficult to meet the growing demand of society.Carrying out in all multi-methods of functional modification to polyolefine, polar monomer is being introduced the great attention being always just subject to people in polyolefin chain by copolymerization process.Introduce polar group, not only effectively can control polyolefinic many critical natures, as binding property, dyeability, printing, solvent resistance, consistency and rheological etc., and the original characteristic of polyolefine can be kept well.

But after polar group introduces polymerization system, can have a strong impact on the coordination of polymerization process, growth generation, thus it is active to reduce polymerization catalyst, can cause catalyst deactivation time serious.Because polar group wants the impact of comparison Former transition metal catalyst much little, so major part all uses late transition metal catalyst (Science 2000,287,460 about the research of polar monomer copolymerization on late transition metal catalyst impact; Chem.Rev.2000,100,1479; Chem.Rev.2000,100,1169), use the research of early transition metal particularly IVB metal catalyst (as titanium, zirconium) relatively less.

Use Ziegler-Natta catalyst system, can the homopolymerization of catalysis straight chain ω-alkene ester.Generally first use R ₂alCl is (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, the copolymerization (J.Polym.Sci.Polym.Chem.1989,27,2051) comprising a series of alpha-olefins such as ethene and ω-alkene ester can be realized.

Use metallocene catalysis system can realize ω-allyl ester monomer with ethene and copolymerization of propylene.When use (n-BuCp) ₂zrCl ₂/ MAO is catalyst ethene and the methyl ester copolymerization of 9-ten alkene and with Et (Ind) ₂zrCl ₂when/MAO catalyzing propone and 9-ten alkene methyl ester, the isobutyl copolymerization of 10-hendecene, remarkable reduction (Eur Polym.J.1997,33,1187 with ethylene homo phase specific activity can be observed; 1998,34,1093).In addition, means of special bridged metallocene catalysts is used can to prepare the terpolymer (Macromol.Chem.Phys.1997,198,291) of the random copolymers of 11-chloro-1-hendecene and 1-heptene and the chloro-1-hendecene of 1-and ethene, propylene.M ü lhaupt uses zirconocene catalyst can realize N, the copolymerization (Polymer, 1997,38,2455) of N-bis-(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).

Non-luxuriant zirconium-based catalyst catalyzed ethylene and undecylenyl alcohol is used to carry out copolymerization, its catalytic activity is basic and its catalyzed ethylene homopolymerization is quite active, polar monomer in the polymer molar fraction more than 8% (J.Polym.Sci.Polym.Chem.2005,43,5944)." the FI catalyzer " of Mitsui also may be used for the copolymerization of ethene and polar monomer; Use this kind of catalyzer, successfully make 5-hexenyl-1-acetic ester and ethene carry out copolymerization, along with the increase of common monomer consumption, polar monomer in the polymer content increases, and reaches as high as 3.2%; But polymerization activity and polymericular weight all obviously decline (J.Am.Chem.Soc.2008,130,17636) simultaneously.

Patent CN1769313 discloses the titanium catalyst using Schiff coordination, can 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 is applied widely, and activity is higher, and monomer insertion rate can more than 8% altogether.

Alpha-olefin and polar monomer copolymerization are very important research directions.As can be seen from document, mainly there is following Railway Project at present.First, due to the nearer polar group of distance double bond very easily with active centre coordination, and cause catalyst deactivation, so in most research and development, all the common monomer of use long-chain is the common monomer with polar group, namely between olefinic double bonds and polar group, the carbon atom at interval is more, to ensure that polar group can not bring loss of catalyst activity too much.The second, although be adopt the polar monomer compared with long-chain, generally, the effect of its polar group and catalyst active center is still inevitable, and thus compared with the homopolymerization of alpha-olefin, the activity of alpha-olefin and polar monomer copolymerization is much lower.3rd, compared 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, thus obtain novel polyolefine material, remain an important problem.

Summary of the invention

The invention provides a kind of alpha-olefin and the copolyreaction method with the alkene of polar group, 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.

Preferred X of the present invention 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 catalyzed copolymerization of the present invention reaction, 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.

In the present invention, described alpha-olefin is the alpha-olefin containing 2-30 carbon atom such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene, 1-octene or 4-methyl-1-pentene; Preferably described alpha-olefin is ethene.

The preferably described alkene polar groups with polar group is hydroxyl, carboxyl, amido, sulfydryl or phosphino-; Wherein, most preferably hydroxyl.

Embodiment

In polymkeric substance, monomer (monomer with polar group) passes through containing quantitative analysis altogether ¹h-NMR measures; Method of calculation after its assay are as described below.Wherein, the chemical structural formula of polymkeric substance is as follows.

In structure above, the hydrogen atom on main polymer chain derive from ethene (the double bond position of e in formula, f) and altogether monomer 4-amylene-1-ol (and in formula d), wherein f is terminal hydrogen, because its content is little, ¹only to see faint signal on H-NMR spectrogram, negligible when calculating.

In structure above, polymkeric substance side chain hydrogen is the hydrogen beyond common monomer 4-amylene-1-ol double bond, a, b, c namely in formula and hydroxyl hydrogen.Wherein, hydroxyl hydrogen exists ¹the upper general signal of H-NMR is very faint, negligible when calculating.

In these signals above-mentioned, a is presented near 3.46ppm, and all the other signals (comprising b-e) are all between 1.3 ~ 1.5.With the integrated height of I expression signal, represent ethene and the mole number being total to monomer in polymkeric substance with m and n respectively, can following formula be obtained:

I _a＝2n

I _b-e＝4m+3n+2n+2n

The content (mol%) obtaining common monomer through equation conversion is: $\frac{100n}{m+n}=\frac{4I_a}{2I_{b-e}-3I_a}\×100.$

¹h-NMR calculates m and n value after detecting, and can learn the molar content of ethene monomer together.

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; Triisobutyl aluminum solutions used is the toluene solution of triisobutyl aluminium, and every ml soln comprises triisobutyl aluminium 0.625mmol.

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 catalyzed ethylene and the copolymerization of 4-amylene-1-ol:

The polymerization bottle of drying is vacuumized rear nitrogen and repeatedly rinses three times, then vacuumize; Under solenoid control, be filled with ethene, maintenance ethylene pressure is normal pressure.At oil bath temperature control 30 DEG C, add toluene 7.5mL, 4-amylene-1-ol 4.8mmol and triisobutylaluminum toluene solution 8mL successively, stir after 10 minutes, add catalyzer toluene solution 1mL prepared by MAO toluene solution 3mL and above-mentioned yellow powder, start timing.Polymerization time is after 20 minutes, closes ethene, pours reaction solution into beaker, add acidic ethanol, stirs more than 6 hours, and filtration obtains polymkeric substance, and filter cake vacuum-drying 24 hours at 60 DEG C, weigh and obtain polymkeric substance 0.72g, 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 (alkene with polar group) mole fraction in H-NMR mensuration polymkeric substance is 8.6%.

Illustrated by above-described embodiment, in the present invention, even if use short carbon chain polar comonomers, also while guarantee catalyzer high polymerization activity, the polyolefine material with high polarity group content can be obtained.Catalyst system with Primary Catalysts mono-metallocene compound of the present invention and promotor methylaluminoxane is described, is suitable for catalysis alpha-olefin and the copolyreaction with the alkene of polar group.

Claims (8)

1. a copolyreaction method for ethene and 4-amylene-1-ol, this reaction is carried out under the catalysis of Primary Catalysts pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium and promotor methylaluminoxane.

2. method according to claim 1, is characterized in that, in pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium, in Ti and methylaluminoxane, the mol ratio of Al is 1:50 to 1:20000.

3. method according to claim 2, is characterized in that, in pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium, in Ti and methylaluminoxane, the mol ratio of Al is 1:200 to 1:10000.

4. method according to claim 3, is characterized in that, in pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium, in Ti and methylaluminoxane, the mol ratio of Al is 1:500 to 1:3000.

5. method according to claim 1, is characterized in that, during the reaction of pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium catalyzed copolymerization, concentration is in the solution 1 × 10 ^-8mol/L to 1 × 10 ^-2mol/L.

6. 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.

7. method according to claim 5, is characterized in that, during the reaction of pentamethylcyclopentadiene base-penta fluoro benzene sulfenyl-dimethoxy titanium catalyzed copolymerization, concentration is in the solution 1 × 10 ^-7mol/L to 1 × 10 ^-3mol/L.

8. method according to claim 6, is characterized in that, described polymerization temperature is-20 DEG C to 150 DEG C.