CN1067086C - Propylene copolymer - Google Patents

Abstract

A substantially syndiotactic propylene copolymer comprising propylene and at least one C6 to C25 cyclic diolefin or C6 to C25 alkadiene having at least one terminal double bond, wherein the peak intensity observed at about 20.2 ppm in the <13>C-NMR spectrum measured in solution in 1,2,4-trichlorobenzene with tetramethylsilane as the internal reference is at least 0.5 of all the peak intensities assignable to the propylene methyl group, the content of the cyclic diolefin or alkadiene is 0.01 to 20 mole %, and the limiting viscosity [ eta ] as measured at 135 DEG C in tetralin is 0.1 to 10 dl/g. This copolymer may further contain an alpha -olefin other than propylene, particularly ethylene.

Description

The preparation method of propylene copolymer

The invention relates to a kind of preparation method of propylene copolymer, more particularly, be to contain propylene and a kind of specific cyclic diolefine or the multipolymer of alkadiene about a kind of, and the structure of this multipolymer is syndiotactic structure basically.

For a long time, the polyacrylic method of preparation syndiotactic structure known to the people is in the presence of low temperature and vanadium-containing compound and organo aluminum catalyst, makes propylene polymerization.But with the prepared polymkeric substance of this traditional method, rule property is poor therebetween, thereby people think that hardly the polymkeric substance that makes thus can have the polyacrylic natural characteristics of syndiotactic structure.

People such as J.A.Ewen disclose a kind of high normal polypropylene and preparation method thereof on special the 110th volume 6255-6256 (1988) of the Hui Chi of U.S. state Chemical Society.But the syndiotactic polypropylene described in the document is being made aspect the moulded product, though good physical performance, cohesiveness and dyeability are poor, and mouldability is also poor.

The objective of the invention is to provide a kind of propylene copolymer of novelty.

Another object of the present invention is that will to provide a kind of be that syndiotactic structure and physicals are suitable for the propylene copolymer that moulded product is produced basically.

Further purpose of the present invention provides a kind of method for preparing the aforesaid propylene multipolymer.

Some other purpose of the present invention will obviously be found out from following explanation.

Basically be the propylene copolymer of the present invention of syndiotactic structure, be a kind of multipolymer that contains propylene repeating unit and at least a diene repeat units, this diene is selected from the cyclic diolefine of 6 to 25 carbon atoms and has 6 to 25 carbon atoms and alkadiene that have a terminal double bond at least; The content of diene repeat units is 0.01-20 mole %; This multipolymer is 1,2, and in the 4-trichlorobenzene solution in the determined 13C nucleus magnetic resonance spectral line (NMR), with reference to the tetramethylsilane of 0.0ppm, the peak strength on about 20.2ppm is more than 0.5 or 0.5 of total peak strength that methyl characterized in the propylene; This multipolymer 135 ℃ of limiting viscosities of measuring down in 1,2,3,4-tetralin solution are 0.1～10dl/g.

Propylene copolymer with syndiotactic structure can obtain by propylene and from carrying out copolymerization as at least a diene of selecting next group diene, this group diene is by the cyclic diolefine and 6-25 the carbon atom of 6-25 carbon atom and have at least the alkadiene of a terminal double bond to form, and copolyreaction at general formula is: A kind of transistion metal compound and a kind of co-catalyst carry out that (A and B are mutually different ring unsaturated alkyls in the formula under existing, R connects A and the alkyl that 1-20 carbon atom arranged of B or a group of siliceous or germanium, X is halogen atom or the alkyl that 1-20 carbon atom arranged, and M is an atoms metal that is selected from titanium, zirconium and hafnium).

Fig. 1 is the infrared absorption spectrum of the thick multipolymer sheet of 0.5mm that obtains in the example 1.

Fig. 2 is that the multipolymer that obtains in the example 1 is at benzene-d ₆Measure in the solution ¹The H-NMR spectral line.

Fig. 3 is the infrared absorption spectrum of the thick multipolymer sheet of 0.5mm that obtains in the example 2.

Fig. 4 is that the multipolymer that obtains in the example 2 is at benzene-d ₆Measure in the solution ¹The H-NMR spectral line.

Fig. 5 is the infrared absorption spectrum of the thick multipolymer sheet of 0.5mm that obtains in the example 3.

Fig. 6 is that multipolymer in the example 3 is at benzene-d ₆Measure in the solution ¹The H-NMR spectral line.

Fig. 7 is the infrared absorption spectrum of the thick polymer sheet of the 0.5mm in the comparative example 1.

Fig. 8 is the infrared absorption spectrum of the thick multipolymer sheet of the 0.7mm in the example 7.

Fig. 9 is the infrared absorption spectrum of the thick polymer sheet of the 0.7mm in the comparative example 2.

Figure 10 is that multipolymer in the example 7 is at benzene-d ₆Measure in the solution ¹The H-NMR spectral line.

Figure 11 is the graph of a relation of the melt viscosity of example 5 multipolymers under differing temps to frequency.

Figure 12 is the melt viscosity of polymkeric substance under differing temps and the graph of a relation of frequency of comparative example 2.

Figure 13 be the multipolymer of example 5 under differing temps the energy storage Young's modulus and the graph of a relation of frequency.

Figure 14 be the polymkeric substance of comparative example 2 under differing temps the energy storage Young's modulus and the graph of a relation of frequency.

In the present invention, in the propylene copolymer that basically is syndiotactic structure, consist of two The diene of alkene unit is ring 2 6～25 carbon atoms, that be preferably 7～20 carbon atoms Alkene, or 6～25 carbon atoms, be preferably 6～20 carbon atoms and have one at least The alkadiene of terminal double bond.

Cyclic diolefine has a ring structure and two two keys at least, and the example of cyclic diolefine comprises: Norbornadiene, 5-methylene-2-ENB, 4-vinyl-1-hexamethylene Alkene, 5-ethylidene-2-ENB, 5-vinyl-2-ENB, two rings The dimer of pentadiene, methyl cyclopentadiene and 1,5-cyclo-octadiene.

Have at least the alkadiene of a terminal double bond to comprise: each has a terminal double bond Alkadiene, Isosorbide-5-Nitrae-hexadiene, 1 for example, 5-octadiene, 1,8-decadinene, 1,7-12 carbon diene and 1,12-, 14 carbon diene, and each has the chain of two terminal double bonds Diene, for example 1, the 5-hexadiene, 1,7-octadiene, 1,9-decadinene, 1,11-ten Two carbon diene, 1,13-14 carbon diene and 1,17-, 18 carbon diene.

The content of diene repeat units is 0.01～20mol%, preferably 0.01～10mol%. The repetitive content that each has the diene of two terminal double bonds is preferably 0.01～5mol%. When repetitive content during less than 0.01mol%, order of the present invention Can not reach, and when it surpasses 5mol%, will contain high branching in the copolymer The gel component of structure, thus this polymer have the part be insoluble to solvent, and have the part not Can melting (even when heating).

In above-mentioned diene, cyclic diolefine also has the molecular weight of control syndiotactic polypropylene Effect. Even in making syndiotactic polypropylene, come the Molecular regulator amount with hydrogen, can not be complete Entirely reach the purpose of control molecular weight, but adopt cyclic diolefine can make molecular weight control to institute The value that needs.

In addition, in copolymer, the weight that consists of when the alkadiene that contains by two terminal double bonds During multiple unit, compare with the homopolymers of syndiotactic polypropylene, this copolymer has melting and refers to Number low (melt viscosity height), die swelling is big, melt strength height, the smooth rate of melt viscosity Dependence is big, and the big advantage of the elastic modelling quantity of molten condition.

Also have, when such alkadiene and copolymerization of propylene, one and copolymerization of propylene in two terminal double bonds obtain a kind of multipolymer that branched structure is arranged, if and the conditioned reaction condition make another terminal double bond also with copolymerization of propylene, then can obtain having the multipolymer of long chain branched.

Multipolymer of the present invention can contain the alpha-olefin repeating unit of 2～20 carbon atoms except that propylene, especially can contain the repeating unit of ethene, if the structure of rule between this multipolymer being had be basically, as long as just make it 1,2, surveyed in the 4-trichlorobenzene solution ¹³In the C-NMR spectral line, the observed peak strength that is produced by the propylene chain with syndiotactic structure is more than 0.5 or 0.5 of total peak strength that methyl characterized in the propylene on about 20.2ppm.The content of this ethylene unit, preferably 0～60% (weight) or few slightly is more preferably 0～50% (weight), especially preferably 0～40% (weight).

The existence of ethene has improved the copolymerization of diene and propylene.And, containing the multipolymer of propylene units, diene units and ethylene unit, can vulcanize as ethylene-propylene rubber(EPR), therefore, this analog copolymer also can use as rubber.

The characteristic of multipolymer of the present invention is, to its 1,2,4-trichlorobenzene solution is measured ¹³In the C-NMR spectral line, serve as with reference to being more than 0.5 or 0.5 of total peak strength about observing peak strength (this is the caused resonance peak of methyl by the propylene chain of five yuan of chains of rule between having) on the 20.2ppm with tetramethylsilane 0.0ppm greatly.And this multipolymer limiting viscosity under 135 ℃ in 1,2,3,4-tetralin solution is 0.1～10dl/g.When this limiting viscosity of multipolymer surpassed 10, melt viscosity was too high, the molding difficulty.Otherwise, when it less than 0.1 the time, multipolymer is soft and be the wax shape, is difficult to separately this multipolymer be carried out molding.

Multipolymer of the present invention can be by propylene, above-mentioned diene, when needing and alpha-olefin (as ethene), carries out copolymerization and obtain in the presence of catalyzer.This catalyzer when being used in the independent polymerization of propylene, can make polypropylene have more than 0.7 or 0.7 between rule five yuan of ratios.The preferred catalyzer that uses is the combination catalyst of a kind of transistion metal compound and a kind of co-catalyst, and the general formula of this transistion metal compound is:

A and B are mutually different ring unsaturated alkyls in the formula, and R is used for connecting the alkyl that 1～20 carbon atom is arranged of A and B or a group of siliceous or germanium.X is that halogen atom or alkyl, the M that 1～20 carbon atom is arranged are atoms metals that is selected from titanium, zirconium or hafnium.

The exemplary of above-mentioned transistion metal compound, be included in isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride and isopropylidene (cyclopentadienyl fluorenyl) hafnium dichloride described in people's such as aforementioned J.A.Ewen the document, and at aminomethyl phenyl methylene radical (cyclopentadienyl fluorenyl) the zirconium dichloride described in open № .2-274703 of Japan's special permission and the 2-274704, aminomethyl phenyl methylene radical (cyclopentadienyl fluorenyl) hafnium dichloride, phenylbenzene methylene radical (cyclopentadienyl fluorenyl) zirconium dichloride and phenylbenzene methylene radical (cyclopentadienyl fluorenyl) hafnium dichloride.

As urging altogether than agent, what preferably use is aikyiaiurnirsoxan beta, but also can use at the ionic compound described in open № 2-501950 of Japan's special permission and the 2-502036.

The preferred example of aikyiaiurnirsoxan beta comprises the compound of following general formula (R in the formula ¹Be the alkyl that 1-3 carbon atom arranged, m is the integer of 1-50) particularly use R ¹For methyl, M are 5 or proper greater than this aikyiaiurnirsoxan beta of 5 integer.

For example doing with aikyiaiurnirsoxan beta under the situation of co-catalyst, the consumption of aikyiaiurnirsoxan beta is 10～100000mol a times of transistion metal compound, normally 50～10000mol doubly, and make the situation of co-catalyst with ionic compound, the consumption of ionic compound is 0.1～100000mol a times of transistion metal compound, is generally 0.5～5000mol doubly.

On polymerization technique and polymerizing condition, do not have special restriction, can adopt the known technology that is used for alpha-olefine polymerizing, for example use the solvent polymeric of unreactive hydrocarbons medium, do not have the mass polymerization or the vapour phase polymerization of unreactive hydrocarbons medium basically.Usually, polymerization temperature is-100～200 ℃, and polymerization pressure is that atmosphere is pressed onto 100kg/cm ²Preferred polymerization temperature is that atmosphere is pressed onto 50kg/cm for-50 ° of-100 ℃ of polymerization pressures ²

The example of the hydrocarbon medium of using in polyreaction comprises stable hydrocarbon, and for example butane, pentane, hexane, heptane, octane, nonane, decane, pentamethylene and hexanaphthene also comprise aromatic hydrocarbons, for example benzene, toluene and dimethylbenzene.

For further improving by normality between the multipolymer of above-mentioned copolymerization process gained, effectively way is with the catalyzer that contains high purity (90% or higher) transistion metal compound, and under 100 ℃ or lower temperature, carry out polymerization, in addition, number is also comparatively arranged with hydrocarbon solvent washing multipolymer.

Varsol is the compound that 3-20 carbon atom arranged, its example comprises propylene, stable hydrocarbon (for example propane, butane, pentane, hexane, heptane, octane and nonane), aromatic hydroxy compound (for example benzene,toluene,xylene and ethylbenzene), and their part or all of hydrogen atom is by the similar compound of fluorine, chlorine, bromine or iodine replacement.Ether or ester that other available examples of solvents includes the alcohols of 1～20 carbon atom and 2～20 carbon atoms are arranged, these solvents all can dissolve or disperse low molecular random component.On washing methods, do not have special restriction, but under 0 ℃～100 ℃, wash usually.

In multipolymer of the present invention, the diene that the unitary multipolymer of cyclodiene is arranged or a terminal double bond arranged is as the unitary multipolymer of alkene, because two keys are arranged, thereby can react and modification with various compound, for example can obtain useful resin [S.Kitagawa etc., polymkeric substance circular, 10 with the currently known methods modification of being adopted in the isotatic polypropylene field, 196～200 (1983), open № 61-85404 of Japan's special permission and 61-85405].

To quote embodiment and comparative example below and describe the present invention in detail, still, these examples only are for the present invention is described, and should not be interpreted as restriction the present invention to them.

Example 1

[preparation of catalyst solution]

Document synthetic isopropylidene (cyclopentadienyl fluorenyl) the zirconium dichloride by people such as above-mentioned J.A.Ewen of 10mg is dissolved in the 20ml toluene, in this solution of gained, add 2.6g by the methylaluminoxane (polymerization degree 17.7) that Toso Akzo company limited produces, make the catalyst solution of purple.

[polymerization process]

In the autoclave of one 2 liter, behind nitrogen replacement air wherein, pack into 1 liter pentane and 3.0 gram 5-methylene-2-norbornene.Change protective atmosphere in this autoclave with propylene, then above-mentioned catalyst solution is added wherein, add-on counts 9.2 * 10 with zirconium atom ^-3Mmole.In addition, add propylene, 40 ℃ of following polymerizations 1 hour, simultaneously the pressure in the autoclave is remained on 9kg/cm then ²(gauge pressure).After polyreaction finishes, this product slurry is taken out from autoclave, add 1 these slurries of liter heptane wash, then filter and drying, obtain 29.4 gram copolymer powders thus.

In addition, underpressure distillation filtrate is removed solvent wherein, thereby obtains the component that 5.2 grams dissolve in this solvent.

According to the mensuration in 135 ℃ of following 1,2,3,4-tetralin solution, the limiting viscosity of this copolymer powder (after this being called for short " [η] ") is 0.62 (deciliter/gram), and according to usefulness ¹³The mensuration of C-NMR is calculated by the peak strength of about 20.2ppm, and five yuan of ratios of rule are 0.82 between this powder.And, at benzene-d ₆This multipolymer of measured in solution ¹In the H-NMR spectral line (Fig. 2), observe by in the 5-methylene-2-norbornene with the caused resonance peak of methene proton of two key adjacency.

The infrared absorption spectrum (Fig. 1) of the thick print of 0.5mm that makes according to above-mentioned multipolymer is from about 1640cm ^-1The peak value that the place is caused by two keys, the content that can draw 5-methylene-2-norbornene are 2.3% (weight).In addition, according to differential scanning calorimetric analysis method (DSC), measure under 10 ℃/minute heat-up rate, the fusing point of this multipolymer is 143.4 ℃.Measure according to gel permeation chromatography (GPC), the molecular weight distribution of this multipolymer (Mw/Mn) is 4.9.

Example 2

The polymeric processing step is identical with the previous section [polymerization process] of example 1, replaces the 5-methylene-2-norbornene except fall ice method alkene with 3.0g5-ethylidene-2-.Obtain the 32.7g copolymer powder, heptane soluble constituent 4.8g.

[η] of this powder is 0.54, and Mw/Mn is 3.6, and five yuan of ratios of rule are 0.83.

Benzene-d at the multipolymer of gained ₆Surveyed in the solution ¹In the H-NMR spectral line (Fig. 4), observe in the 5-ethylidene-2-norbornene and the caused peak of methene proton of two key adjacency.The infrared absorption spectrum (Fig. 3) of the thick print of 0.5mm that makes according to above-mentioned multipolymer, the content of 5-ethylidene-2-norbornene is 2.3% (weight).According to the mensuration of DSC, the fusing point of this multipolymer is 144.5 ℃.

Example 3

The polymeric processing step is identical with the previous section [polymerization process] of example 1, and except using 1 of 3.0g, the 7-octadiene replaces outside the 5-methylene-2-norbornene.Obtain the component that 127g copolymer powder and 0.2g dissolve in heptane.

[η] of this multipolymer and five yuan of ratios of rule are respectively 2.68 and 0.84.

Benzene-d at the gained multipolymer ₆Measure in the solution ¹In the H-NMR spectral line (Fig. 6), observe the peak of about 6.0ppm vinyl proton, according to calculating, its content is 0.5mol%.In the infrared absorption spectrum of surveying by the thick print of this multipolymer 0.5mm (Fig. 5), at about 1640cm ^-1The vinyl absorption peak appears in the place, has confirmed 1, the copolymerization of 7-octadiene.

Comparative example 1

The polymeric processing step is identical with the previous section [polymerization process] of example 1, except without the 5-methylene-2-norbornene, obtains the component that 140g copolymer powder and 0.1g are not fused to heptane.

[η] of this multipolymer and five yuan of ratios of rule are respectively 1.40 and 0.86.The infrared absorption spectrum of the thick print of this multipolymer 0.5mm is shown in Fig. 7.

Example 4

In the autoclave of one 5 liter, used identical aikyiaiurnirsoxan beta in used identical transistion metal compound and 1.36g and the example 1 in 10mg and the example 1 of packing into, add 1.5kg propylene and 6g5-ethylidene-2-norbornylene and ethene again, the dividing potential drop of ethene just may be 10kg/cm like this ²(gauge pressure).Then, 50 ℃ of following polymerizations 1 hour, obtain the 116.7g polymkeric substance.The ethylene content of this polymkeric substance and 5-ethylidene-2-norbornene content are respectively 29% (weight) and 1% (weight).According to ¹³C-NMR measures, and the ratio of the peak strength that the peak strength that occurs in about 20.2ppm place and the methyl group of propylene are total is 0.72.

Example 5

[preparation of catalyst solution]

In 35ml toluene, the toluene solution of 20% methylaluminoxane of dissolving 20mg sec.-propyl (its fluorenyl of cyclopentadiene) zirconium dichloride and 14.4ml (this methylaluminoxane is that Toso Akzo company limited makes) makes catalyst solution thus.

[polymerization process]

Atmosphere in 3 liter autoclaves adds 1 liter pentane and 0.60g7-octadiene after replacing with nitrogen in still.Change atmosphere in this system with propylene.

To be 9.2 * 10 with the zirconium atom metering ^-3The above-mentioned catalyst solution of mmole adds this system, adds propylene then.Copolyreaction was carried out under 40 ℃ 1 hour, kept the still internal pressure at 9kg/cm simultaneously ²(gauge pressure) adds the 15ml Virahol then and makes reaction terminating.The slurries of reaction gained are taken out in the cooling back from still, add 1 liter heptane, then filter.With 1 liter heptane wash filter cake, drying obtains the 149g polymer powder then.After twice solvent merging, evaporated in vacuo obtains the component that 12.02g dissolves in heptane.

The polymkeric substance that obtains thus is dissolved in 1 of heat with it, 2,3, in the 4-tetraline, [η] of this polymkeric substance is 1.48, and five yuan of ratios of rule are 0.87, and melting index is 1.6 (restraining/10 minutes), die swelling is 1.60 (-), and melt strength (recording at 220 ℃) is 2.2 (g) (drawing 150 meters/minute of speed).

In addition, the measuring method of relevant these physicalies is as follows:

Melting index is according to ASTM D-1238, and with a 2.19mm diameter, the nozzle that 8mm is long is measured under the load of 230 ℃ of 2.16kg.

Die swelling is determined by above-mentioned resin diameter and nozzle diameter ratio when extruding in measuring melting index.

Melt strength is to measure with a determinator surveying melting index, is equipped with to survey tensile Resin Wound machine and load transducer in this device.

Between five yuan of ratios of rule measure according to the method described in the open № .2-41303 of Japan's special permission.

¹H-NMR is the spectroscope with 270 megahertzes, with benzene-d ₆Measure as solvent.

Example 6

Imitate the method identical, but 1, the consumption of 7-octadiene changes 0.40g into, obtains the 152g polymer powder thus with example 5.

It is 1.40 that the polymer powder that obtains is like this recorded [η], and five yuan of ratios of rule are 0.28, and melting index is 3.0, and die swelling is 1.43, and melt strength (220 ℃ of mensuration) is 1.8.

Comparative example 2

Imitate the method identical with example 5, but need not 1, the 7-octadiene obtains the component that 140g polymer powder and 0.1g dissolve in solvent thus.[η] that this powder is measured is 1.40, and five yuan of ratios of rule are 0.86, and melting index is 3.6, and expanding from the mould mould is 1.09, and melt strength (220 ℃ of mensuration) is 1.78.

Example 7

Except with 1 of 3.0g, outside the 7-octadiene, other all imitates the processing step of example 5, thereby obtains the component that 127g polymer powder and 0.2g dissolve in solvent.

The powder that obtains thus at 135 ℃, is dissolved in the 1,2,3,4-tetralin fully, and [η] that record for this polymkeric substance is 2.68, and five yuan of ratios of rule are 0.84, and melting index is 0.08 (decilitre/10 minutes).

With above-mentioned multipolymer and stablizer blend, then at 230 ℃ and 120kg/cm ²Under keep making in 3 minutes compressing tablet.This compressing tablet is transparent, and some is inhomogeneous but transparency seems, therefore can judge this compressing tablet that obtains under the above-mentioned condition has begun to form gel.

Fig. 8 represents the infrared absorption spectrum of the thick compressing tablet of above-mentioned 0.7mm, and Fig. 9 is the infrared absorption spectrum of the similar compressing tablet of comparative example 2 resulting polymers.

Multipolymer with regard to example 7 is measured, 1640 ^-1The absorption peak of vinyl appears in the place, find out 1 significantly, and the 7-octadiene is by copolymerization.

Again by measuring ¹The H-NMR spectral line carries out quantitative analysis to vinyl.The mensuration of this nucleus magnetic resonance spectral line is the spectroscope with 270 megahertzes, with benzene-d ₆For solvent carries out at 140 ℃.The diene that joins in the polymkeric substance is done quantitative analysis, employing be described in the open № .2-64111 of Japan special permission technology as a reference.As shown in figure 10, the absorption peak based on the vinyl atom occurring when about 6.0ppm, is 0.5mol% according to its content of calculating (survey vinyl).

The gelation theory of polymkeric substance points out, as 50% or more vinyl when being reacted, gel can occur, and therefore on this time point, the amount of vinyl also is 0.5mol%.Estimate in this propylene copolymer 1 at last, the content of 7-octadiene is 1.0mol%.

1, the inlet amount of 7-octadiene is 3.0g, and obtaining polymkeric substance is 127g, judges from this fact, react 1, the weight of 7-octadiene is quantitative substantially.

Reference example

Figure 11 and Figure 12 represent the dependence of example 4 multipolymer melt viscosities and comparative example 2 syndiotactic polypropylene homopolymer melt viscosities and frequency.

The viscosity of this homopolymer is subjected to the influence of frequency change hardly, so the performance of this multipolymer is just as Newtonian viscosity.And on the other hand, the viscosity-frequency dependence of example 4 multipolymers is big, and non-Newtonian viscosity shows obviously in this multipolymer.

Figure 13 and Figure 14 are that above-mentioned multipolymer and the energy storage Young's modulus of homopolymer (G ＇) are mapped to frequency.From the polymkeric substance inference of long chain branched, the sample of example 4 has big energy storage Young's modulus.

In these multipolymers of the present invention, there is the multipolymer that two keys exist can modification and improve its performance in the polymeric chain.

In addition, under with the situation of cyclic diolefine as comonomer, the molecular weight that can control multipolymer in polymerization process makes it reach desired numerical value.

In addition, contain the multidimensional multipolymer of ethene etc. and contain with the alkadiene of two terminal double bonds and all have above-mentioned characteristic as the multipolymer of diene units.

As mentioned above, visible co-polymer of the present invention industrial be of great value.

Claims (11)

1. the preparation method of a propylene copolymer, described method comprises, the step that makes propylene and at least a diene carry out copolymerization,

Described diene is selected from the cyclodiene of 6-25 carbon atom, and, the alkadiene of 6-25 carbon atom and at least one terminal double link is arranged,

Described copolymerization is that temperature, normal atmosphere at-100 °-200 ℃ is to 100kg/cm ²Pressure, and in the presence of a kind of transistion metal compound and a kind of co-catalyst, carry out,

The general formula of described transistion metal compound is

In the formula,

A and B are mutually different ring unsaturated groups,

R is the alkyl that connects 1-20 the carbon atom of A and B, or the group of siliceous or germanium,

X is the alkyl of a halogen atom or 1-20 carbon atom,

M is a kind of atoms metal, and it is selected from titanium, zirconium and hafnium,

The consumption of described co-catalyst be the described 10-100000 mole of crossing the metallizing compound doubly, when described catalyzer adopted ionic compound, the consumption of ionic compound was the 0.1-100 of metallizing compound, 000 mole doubly.

Described propylene copolymer is essentially syndiotactic structure, and this propylene copolymer comprises propylene repeating unit and at least a diene repeat units,

Described diene is selected from the cyclodiene of 6-25 carbon atom and the alkadiene of 6-25 carbon atom and at least one terminal double link;

The content of described diene repeat units is 0.01-20 mole %;

Described multipolymer is measured 1,2, in the 4-trichlorobenzene liquation ¹³In the C-NMR nuclear magnetic resonance spectrum, be 0.0ppm with the described spectral line of tetramethylsilane, as reference, described multipolymer is more than 0.5 or 0.5 of total peak intensity that belongs to methyl in the propylene in the observed peak intensity of 20.2ppm;

Described multipolymer is 0.1-10dl/g in 135 ℃ of limiting viscosities that record in 1,2,3,4-tetralin solution.

2. preparation method according to claim 1, wherein, the content range of described diene repeat units is 0.01 to 10mol%.

3. preparation method according to claim 1, wherein, described cyclodiene has at least one ring structure, two two keys and 7 to 20 carbon atoms.

4. preparation method according to claim 3, wherein, described cyclodiene is norbornadiene, 5-methylene-2-norbornene, 4-vinyl-1-tetrahydrobenzene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornylene, Dicyclopentadiene (DCPD), methylcyclopentadiene dimer or 1, the 2-cyclooctadiene.

5. preparation method according to claim 1, wherein, described alkadiene has a terminal double link and 6 to 20 carbon atoms.

6. preparation method according to claim 5, wherein, described alkadiene is 1,4-hexadiene, 1,5-octadiene, 1,8-decadiene, 1,7-12 carbon diene or 1,12-14 carbon diene.

7. preparation method according to claim 1, wherein, described alkadiene has two terminal double links and 6-20 carbon atom.

8. preparation method according to claim 7, wherein, described alkadiene is 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, 1,11-12 carbon diene, 1,13-14 carbon diene or 1,17-18 carbon diene.

9. preparation method according to claim 1, wherein, described propylene copolymer also contains the repeating unit of the propylene copolymer alpha-olefin in addition of 2-20 carbon atom.

10. preparation method according to claim 9, wherein, the content of described alpha-olefin repeating unit is 40 weight % or less than 40 weight %.

11. preparation method according to claim 1 wherein, makes described propylene, described diene and a kind of 2-20 carbon atom, the alpha-olefin except that propylene carries out copolymerization.

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