TW200403256A - Highly stereoregular polypropylene with improved properties - Google Patents

Abstract

Propylene polymers having a content of isotactic pentads (mmmm) higher than 97%, molecular weight distribution, expressed by the Mw/Mn ratio, equal to or higher than 6 and a value of Mz/Mw ratio equal to or lower than 5.5. The said polymers are prepared in the presence of a particular combination of Ziegler-Natta solid catalyst components and highly stereoregulating electron-donor compounds. Laminated articles, in particular bi-axially oriented films and sheets can be prepared with the said polymers.

Description

200403256 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to a crystalline propylene polymer having a high level of three-dimensional regularity of segments, especially a high content of isotactic pentads, which has improved properties. Processability in the molten state, and its manufacturing method. [Prior art] We are known to be able to obtain highly crystalline propylene polymerization with high mechanical properties due to the high stereospecificity contribution achieved by the Ziegler-Natta catalyst. Therefore, they are suitable for manufacturing products having excellent stiffness and mechanical resistance, even if they are small and thin. Commonly used propylene polymers exhibit a sufficiently high level of melt strength, that is, viscoelasticity in the molten state. We know that if the melt strength of the propylene polymer is not high enough, it will cause irregular deformation of the molten material, and there will be subsequent difficulties related to processability during the conversion process. European Patent No. 5 7 3,8 62 discloses that the melt strength can be significantly improved by expanding the molecular weight distribution of the polymer. According to this patent, the molecular weight distribution is at least 20. Therefore, the processability of the highly crystalline propylene polymer is improved. However, the thickness distribution and consistency of the alignment film obtained from the propylene polymer are still not completely satisfactory. [Summary of the Invention] Summary of the Invention We have now found that in the polymerization reaction, under appropriate conditions, by using a Ziegler-Natta catalyst component and a high stereoregularity of 200403256 electron donor compounds (external administration Specific composition), which can obtain a propylene polymer that still has the high stiffness and other mechanical properties characteristic of a typical highly crystalline propylene polymer, but it can also have Improved processability. In particular, the advantage is that this propylene polymer can be processed over a wide temperature range and is easier to process. A further specific example of the present invention relates to a biaxially oriented film or sheet comprising the propylene polymer. The advantages of the laminated products of the present invention, especially films and sheets, are that they have a uniform thickness, and also have a high degree of elongation and tensile stress at break. Especially for packaging (such as cigarette packages), and food packaging. Therefore, the present invention provides a propylene polymer, preferably a homopolymer, having the following characteristics: 1) The content of five elements in the same row is higher than 97%, preferably higher than 9 7.5%, and more preferably Above 98 ° /. (It is measured by nuclear magnetic resonance (NMR)) 2) The molecular weight distribution (Swmn) represented by the ratio of weight average molecular weight to number average molecular weight is equal to or higher than 6, preferably from 6 to 1 1; And 3) The ratio (zd / Mw) of z average molecular weight to weight average molecular weight is equal to or lower than 5 · 5 ', preferably equal to or lower than 5, and more preferably equal to 4.8. If necessary, the propylene polymer may contain a small amount of comonomers, such as 200403256 such as ethylene or C4-C1Q α-olefins (examples of which are 1-butene, 1-hexene, 3-methyl- 1-pentene). In general, when these comonomers are contained, based on the total weight of the polymer, it is not more than 5% by weight (in the case of ethylene, preferably not more than 2% by weight). Other preferred features of the polymers of the present invention are:-The stereoblock content up to 98 ° C is 10% or less, as measured by a temperature-raised fractionation (TREF) method;-The polydispersity index (P · Ι ·) is 6 or less, more preferably 5.5 or less, and particularly preferably less than 5;

-The main elution peak temperature 値 (measured according to TREF) is higher than 114 ° C 9-The elution fraction 直到 up to 94 ° C is equal to or lower than 5%;-MFRL 値 is from 0 · 1 to 50 G / 10 minutes, more preferably from 1 to 30 g / 10 minutes; the melting temperature of the preferred polymer according to the invention is 164. C or higher, more preferably 165 Υ or higher, such as from 165 to 168. (:. The propylene polymer of the present invention can be obtained directly in the polymerization reaction, and it uses a Ziegler-Natta catalyst comprising:-a solid catalyst component 'comprising magnesium (Mg), titanium (Ti), Halogen and at least two electron donor compounds, the catalyst component is characterized in that at least one electron donor compound is based on the total amount of the electron donor compound, and its content is from 15 to 50 mol%, which is selected From esters of succinic acids and which cannot be extracted at least 20 mole% under the following conditions, and at least another electron donor compound and which can be extracted at more than 30 mole% under the same conditions 200403256 (ie, can be Extracted electron donor compounds);-~ organometallic compounds;-~ highly stereoregular electron donor compounds (external donors). The catalyst component is disclosed in World Patent No. 02/30998. As explained above In addition to the above-mentioned electron donor compound, the solid catalyst component contains titanium (Ti), magnesium (Mg) and halogen. In particular, the catalyst component contains a titanium compound having at least one titanium- Prime bond, and the above electron donor compound is supported on magnesium halide. Magnesium halide is preferably MgCl2 in active form, which is widely known from the patent literature as a carrier for Ziegler-Natta catalysts. US Patent No. 4,298,718 No. 4 and No. 4,495,338 are the first to disclose the use of these compounds in Ziegler-Natta catalysts. From these patents, it is known that magnesium dihalides in active form are used as catalyst components in olefin polymerization reactions. As a carrier or co-carrier, it is qualitatively determined by the X-ray spectrum, in which the intensity of the strongest ray that appears in the spectrum of the inactive halide is reduced and replaced by a halo, where the maximum intensity is The displacement is oriented at a lower angle relative to the stronger line. The preferred titanium compounds are TiCl4 and TiCl3; in addition, titanium-haloalcoholates of the formula Ti (OR) n_yXy can also be used, where η is the valence of titanium , Y is a number between 1 and n-1, X is a halogen, and R is a hydrocarbon group having 1 to 10 carbon atoms. The preparation of solid catalyst components can be implemented according to several methods. Known in the arts and uncovered According to a preferred method, the solid catalyst component is obtained by formulating a formula such as 200403256

Ti (OR) n_yXy titanium compound (where η is the valence of titanium, y is a number between 1 and η, and is preferably TiCl4) and a magnesium chloride derived from an adduct of the formula MgCl2 · ROH ( Wherein P is between 0.1 and 6, preferably from 2 to 3.5, and R is a hydrocarbon group having from 1 to 18 carbon atoms). The adduct can be appropriately mixed by mixing alcohol and magnesium chloride in the presence of inert hydrocarbons which are incompatible with the adduct-under the stirring conditions of the melting temperature of the adduct (100 ~ 130 ° C) Operate to obtain a spherical shape. Then, the emulsion was rapidly quenched, thereby causing the adduct to solidify and take a spherical shape. Φ Examples of spherical adducts prepared according to this step are disclosed in U.S. Patent No. 4,3,9,054 and U.S. Patent No. 4,469,648. The adduct thus obtained can be reacted directly with the titanium compound, or it can be subjected to a thermally controlled dealcoholization reaction (80 ~ 1 30 ° C), so an adduct is obtained in which the molar number of the alcohol is usually low At 3, preferably between 0.1 and 2.5. The reaction with titanium compounds can be carried out by suspending the adduct (dealcoholized or used as it is) in cold (usually 0 ° C) TiCl4; heating the mixture up to 80 ~ 130 C, and maintained at this temperature for a period of 0.5 to 2 hours. The treatment with TiC 14 can be performed one or more times. The electron donor compound can be added during the treatment with TiCl4. They can be added together in the same treatment with TiCl4, or separately in two or more treatments. Regardless of the preparation method used, the final amount of the two or more electron-donor compounds is such that the molar ratio with respect to M g C12 is from 0. 001 to 1, preferably from 0.05 to 0.5. Among the non-extractable vinegar acids as described above, particularly preferred are succinates represented by the following formula (j) -10-200403256:

Among them, the group center and each other may be the same or different) is Ci_C2. Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl, or alkaryl groups, which may contain heteroatoms as required; and groups R3 and R4 (which may be the same or different from each other) -Cm's radical, cycloalkyl, aryl, aralkyl or alkaryl group 'may optionally contain heteroatoms, with the limitation that at least one of them is a branched radical; in the formula ( I) Two asymmetric carbon atoms identified in the structure. These compounds are stereoisomers of the type (S, R) or (R, S) in pure form or in mixture.

Ri and R2 are preferably alkyl, cycloalkyl, aryl, aralkyl and alkaryl. Particularly preferred compounds are those in which I and R2 are selected from the primary alkyl groups, and especially branched primary alkyl groups. Examples of suitable I and R2 groups are methyl, ethyl, n-propyl, n-butyl, neopentyl, 2-ethylhexyl. Particularly preferred are ethyl, isobutyl and neopentyl. Particularly preferred compounds are those in which R3 and / or R4 are secondary alkyl groups such as isopropyl, second-butyl, 2-pentyl, 3-pentyl, or cycloalkyl groups such as cyclohexyl, cyclo Amyl and cyclohexylmethyl. Examples of the above compounds are diethyl 2,3-bis (trimethylsilyl) succinate in the form of (S, R) (R, S) in pure form or in a mixture of 200403256, if necessary, in racemic form. , 2,3-bis (2-ethylbutyl) diethyl succinate, diethyl 2,3-diphenylmethyl succinate, diethyl 2,3-diisopropyl succinate, 2, Diisobutyl 3-diisopropylsuccinate, Diethyl 2,3-bis (cyclohexylmethyl) succinate, Diethyl 2,3-diisobutylsuccinate, 2,3-Dixin Diethyl pentylsuccinate, diethyl 2,3-dicyclopentylsuccinate, and diethyl 2,3-dicyclohexylsuccinate. Among the extractable electron donor compounds, organic mono- or dicarboxylic acid esters are particularly preferred, such as benzoates' malonates and succinates. Esters of aromatic carboxylic acids are preferred. Among the malonates, particularly preferred is the one represented by the following formula (II): 0

Where 'Ri is hydrogen, or a kind of eve' linear or branched radical, flammable radical 0, cycloalkyl, aryl, aralkyl or alkaryl radical; r2 is a Ci_c2. Linear or branched Yuan, Ji, Jiu, Yuan, Ai, Ai, or Ai; and groups R3 and R4 (which may be the same or different from each other) are linear or branched alkyl groups of Ci_c2 () Or C3-C2Q cycloalkyl group. R3 and R4 are preferably first-order, linear or branched cvC2 () courtyard bases, and they are more preferably first-order branched cvc: 2. alkyl groups , Such as isobutyl. Group or neopentyl group. -12- 200403256 Especially when R is hydrogen, preferably a linear or branched alkyl, cycloalkyl, or aralkyl group; R2 is more It is preferably a kind of C3-C2. The second alkyl group, cycloalkyl group, or aralkyl group. The esters of the more aromatic carboxylic acids are selected from the group consisting of benzoic acid and phthalic acid. Square-based esters, if possible, substituted. Alkyl esters of these acids are preferred. Particularly preferred are C1-C6 linear or branched alkyl esters. Specific examples are ethyl benzoate, benzoic acid N-butyl ester, para-methoxy ethyl benzoate , Ethyl p-ethoxylate, iso-butyl benzoate, ethyl p-toluate, diethyl p-formate, di-n-propyl phthalate, di-n-butyl phthalate, benzene dibenzoate Di-n-pentyl formate, diiso-pentyl phthalate, bis (2-ethylhexyl) phthalate, ethyl-isobutyl phthalate, ethyl-n-butyl phthalate, Di-n-hexyl phthalate and di-isobutyl phthalate. The aforementioned organometallic compounds are preferably selected from alkyl-aluminum compounds, and especially from trialkylaluminum compounds, such as triethyl Aluminium, triisobutylaluminum, tri-n-butylaluminum, tri-n-hexylaluminum and tri-n-octylaluminum. It is also possible to use alkylaluminum halides, alkylaluminum hydrides, or alkanes Aluminium sesquichloride, such as AlEt2Cl and Al2Et3Cl3, may be in the form of a mixture with the trialkylaluminums cited above. Suitable external electron donor compounds include: certain silanes, ethers, esters, amines, heterocycles Compounds and ketones. In particular, 'appropriate highly stereoregular silanes are contained in the formula Ra5R / Si (OR7). Where a and b are integers from 0 to 2, c is an integer from 1 to 4 'and the sum (a + b + c) is 4; R5, R6, and R7 are alkyl, alkyl, cyclofluorenyl, or -13- 200403256 Aryl has 1 to 18 carbon atoms and contains heteroatoms as needed. Particularly preferred silicone compounds are those in which at least one of R5 and R6 is selected from a branch having 3 to 10 carbon atoms Type alkyl and cycloalkyl groups, and ... are alkyl groups, especially methyl groups. Specific examples of preferred silanes are dicyclopentyldimethoxysilane, third-hexyltrimethoxysilane, and dialkyl. Isopropyl dimethoxy sand courtyard. Particularly preferred is dicyclopentyl dimethoxy radical courtyard. The external donor is used in an amount such that the molar ratio of the organoaluminum compound to the external electron donor compound is from 1 to 500, preferably from 1 to 300, and more preferably from 3 to 100. The polymerization method can be carried out according to a conventional technique, such as a slurry polymerization reaction using an inert hydrocarbon solvent as a diluent, or an overall polymerization reaction using a liquid monomer (such as propylene) as a reaction medium. In addition, the polymerization can also be carried out in a gas phase in one or more fluidized bed or mechanical stirred bed reactors. The polymerization reaction is usually carried out at a temperature of from 20 to 120 ° C, preferably from 40 to 80 ° C. When the polymerization reaction is carried out in the gas phase, the operating pressure is usually between 0.5 and 10 MPa, preferably between 1 and 6 MPa. In the overall polymerization reaction, the operating pressure is usually between 1 and 8 MPa, preferably between 1.5 and 5 MPa. It should be noted that the broad molecular weight distribution is obtained in a single polymerization reaction stage, that is, it has a substantially unimodal mode distribution, which can avoid any problems due to the heterogeneity of the polymer product. According to a preferred polymerization method, the polymer of the present invention can be prepared by a gas phase polymerization method -14-200403256 in at least two interconnected polymerization reaction zones. This type of method is exemplified in European Patent Application No. 7 8 2,5 87. In detail, the above method includes feeding one or more monomers into the polymerization reaction zone containing a catalyst under reaction conditions, and collecting a polymer product from the polymerization reaction zone. In this method, growing polymer particles flow up through one of the polymerization reaction zones (the first zone) (riser) under rapid fluidization, leave the riser and enter the other (section 2) Polymerization reaction zone (downcomer), through which they flow downward under the action of gravity to form a compacted form, leave the downcomer and lead into the riser, so the polymer is established in the riser Circulation system with downcomer. In the downcomer, the density of solids reaches a high density, which is close to the overall density of the polymer. Therefore, a positive increase in pressure along the direction of flow can be achieved, making it possible to introduce the polymer into the riser without the assistance of special mechanical devices. In this way, a "ring" cycle is set, which is defined by the pressure balance between the two polymerization reaction zones and the head loss induced by the intervention system. Generally, the conditions for rapid fluidization in a riser are established by feeding a gas mixture containing the relevant monomers into the riser. It is preferred that the feeding of the gas mixture is performed below the point at which the polymer re-introduction intervenes in the riser, by using a suitable gas distribution device. The speed of conveying gas into the riser is higher than the conveying speed under operating conditions, preferably from 2 to 15 m / s. Generally speaking, the polymer and gas mixture exiting the riser is transported to a solid / gas separation zone. The solid / gas separation can be effectively performed by a conventional separation device used in 200403256. From the separation zone, the polymer enters the downcomer. The gas mixture leaving the separation zone is compressed, cooled and transferred to a riser, which may include the addition of supplemental monomers and / or molecular weight regulators, if appropriate. The transfer can be effectively carried out by means for a recirculation line of the gas mixture. The control of the polymer cycle between two polymerization reaction zones can be effectively implemented by using a device (such as a mechanical valve) suitable for controlling the flow of solids to meter the amount of polymer leaving the downcomer. Operating parameters (such as temperature) are those commonly used in gas-phase olefin polymerization processes, such as temperatures between 50 and 120 ° C. The process can be carried out at an operating pressure between 0.5 and 10 MPa, preferably between 1.5 and 6 MPa. It is advantageous to maintain one or more inert gases in the polymerization reaction zone in an amount such that the sum of the partial pressures of the inert gases is preferably between 5 and 80% of the total pressure of the gases. The inert gas may be, for example, nitrogen or C-house. Various catalysts can be fed into the riser at any point in the riser. However, they can also be fed at any point in the downcomer. The catalyst can be in any physical state, so the catalyst can be used in a solid or liquid state, either. Conventional additives such as stabilizers and pigments can also be added to the polymers and compositions of the present invention. As mentioned above, the propylene polymer according to the present invention is particularly suitable for preparing films and sheets, especially biaxially oriented films and sheets. A further specific example of the present invention is to provide laminated products, especially thin -16-200403256 laminated products of films and sheets, which have improved extensibility and shielding properties, especially moisture resistance. These products are made of a polymer composition containing the above-mentioned polymers and a hard resin such as a polymer of coke oven gas, cracked light oil, gas oil, terpene oil, and a masking resin. A blocking compound is preferred. The content of the hard resin is usually from 0.5 to 20% by weight, preferably from 0.5 to 15% by weight, based on the entire composition. The laminated article (i.e., film and sheet) of the present invention may be multi-layered, and at least one layer contains the above-mentioned propylene polymer or composition. The laminated articles (i.e., films and sheets) of the present invention are compositions obtained from the above-mentioned propylene polymers and by using a well-known method for manufacturing polyolefin films / sheets. [Embodiments] The following examples are provided as examples, but they do not limit the present invention. Qualitative analysis for extractables test of electron donor (ED) compounds A) Preparation of solid catalyst components Add 250 ml 1 ^ (: 14 at 0 ° C to a 500 ml four-necked circle washed with nitrogen 10.0 g of microspherical MgCl2 · 2.8C2H5OH (prepared according to the method disclosed in Example 2 of U.S. Patent No. 4,3 99,054, but operated at 3,000 rpm instead of 1 with stirring. 〇 ， 〇〇〇〇〇〇〇RPn] i). Also added to the selected electron donor compound 4.4 millimolar. The temperature was increased to 100 ° C, and maintained at this temperature for 120 minutes. 200403256 Then, the stirring was interrupted, the solid product was allowed to settle and the supernatant liquid was siphoned out. 250 ml of fresh T i C 14 was added. The mixture was allowed to react at 120 ° C for 60 minutes with stirring, and then The supernatant liquid was siphoned out. The solid (A) was washed six times with anhydrous hexane (100 ml each time) at 60 ° C, under vacuum-dried and analyzed to quantitatively determine magnesium (Mg) and electron donor compounds -. Therefore, the molar ratio of the electron donor compound to magnesium can be determined Rate A) ° B) Treatment of solid A in a nitrogen atmosphere, 190 ml of anhydrous n-hexane, 19 mmol of β AlEt3, and 2 g of the catalyst component prepared according to the method disclosed in A) Add to a 250 ml jacketed glass reactor equipped with a mechanical stirrer and filter membrane. The mixture was heated (at a stirring rate of 400 rpm) at 60 ° C for 1 hour. After this time, the mixture was filtered, rinsed four times with n-hexane at 60 ° C, and finally under vacuum at 30. (: It is dried for 4 hours. Then the solid is analyzed to quantitatively determine magnesium (Mg) and the electron donor compound. Therefore, the Mohr ratio (ratio B) of the electron donor compound to magnesium can be determined. Φ Electron donation The extractability of the bulk compound is calculated according to the following formula: The percentage of the extracted electron donor compound = (ratio A-ratio B) / (ratio A). The microstructure analysis of the polymer will be 50 mg each insoluble in two The toluene component was dissolved in 0.5 ml of C2D2C14. The 13C nuclear magnetic resonance (NMR) spectrum was determined at Bruker DPX-400 (1 00.6 1 200403256 MHz, 90 ° pulse wave, 12 seconds delay between pulse waves) Measured. Approximately 3,000 transient data are stored for each spectrum; the mmmm five-element spike (21.8 ppm) is used as a reference. The microstructure analysis is performed as described in the literature [Polymer, 1 984, 25, 1640, author Inoue Y. et al., And Polymer, 1994, 35, 339, author Chujo R. et al.] Determination of xylene insoluble fraction (XI) 2.5 grams of polymer was stirred at 135 ° C for 30 minutes O-xylene , Then the solution was cooled to 25 ° C, and the insoluble polymer was filtered after 30 minutes. The obtained solution was evaporated under a stream of nitrogen, and the residue was dried and weighed to determine the percentage of soluble polymer, Then calculate the XI ·% according to the difference .. Temperature Rising and Fractionation (TREF) Method The polymer's temperature rising and fractionation (TREF) is by dissolving 1 g of propylene polymer in o-xylene at 135 ° C, and The glass bead-loaded extraction column was slowly cooled (20 hours) to 25 ° C. The elution using o-xylene (600 ml / hour) was first performed at 25 ° C for 1 hour to obtain xylene solubility Fractionation. Then, without elution, the temperature of the extraction column was increased from 25 ° C to 95 ° C at a rate of 0.7 ° C / min, and elution was performed at this temperature for 1 hour to produce a single fraction. Before the rate, the temperature was maintained at 95 ° C for 2 hours. Finally, the dialysis was continued while the temperature was increased from 95 ° C to 120 ° C at a rate of 3 CC / hour, and every 1 ° C temperature interval was collected Individual fractions. Stereoblock content according to the invention It is regarded as the total weight of the xylene-insoluble fraction at 25 ° C, which is washed out at a temperature below 1000200403256 ° c (based on the total weight of the polymer). Melt flow index L (Vi is measured according to IS 0 1 1 3 3 (2 3 0. C, 2 · 16 kg). Fen Wang Xuan (two and ml) by using gel permeation chromatography (GPC) at 1, 2 This property of the polydispersity index (P.I.) measured in, 4-trichlorobenzene is strictly related to the molecular weight distribution of the polymer under examination. In particular, it is inversely proportional to the latent resistance of the polymer in the molten state. This resistance is called modular separation at low modulus 500 (500 Pa), which is at a temperature of 200 ° C. Using a parallel plate rheometer, the model is RMS-800 (sold from Rheometrics (US A)), measured at vibration frequencies increased from 0.1 rad / s to 100 rad / s. From the modulus separation, we can derive the polydispersity index (P · 1 ·) by the following formula: P · Ι · = 54.6X (modulus separation) +76 where the modulus separation is defined as:

Modulus separation = (at G, = 500 Pa frequency) / (at G frequency) where G is the storage modulus and G, ′ is the loss modulus. Deflection modulus is measured according to ISO 178 method. Izod impact resistance Measured according to ISO 1 8 0/1 A method. -20- 200403256 Examples Examples 1 and 2 Preparation of solid catalyst components 250 ml of TiCl4 was added at 500 ° C to a 500 ml four-necked round flask purged with nitrogen. Under stirring, 10.0 grams of microspherical MgCl2 _-2.8C2H5OH (made according to the method disclosed in Example 2 of U.S. Patent No. 4,3 99,054, but operated at 3,000 rpm instead of 1 0.0000 rpm). Also added is a previously prepared diisobutyl phthalate (DIBP) containing racemic and meso forms containing 2,3- (diisopropyl) diethyl succinate (DIBIPS) 9 A mixture of the two was used as an internal donor. The content of the internal donor in the solid catalyst component is shown in Table 10. The temperature was increased to 100 ° C and maintained at this temperature for 120 minutes. The stirring was then interrupted, the solid product was allowed to settle and the supernatant liquid was siphoned off. 250 ml of fresh TiC 14 was added. The mixture was allowed to react at 120 ° C for 60 minutes with stirring, and then the supernatant liquid was siphoned off. The solid was washed six times with anhydrous hexane (100 ml each) at 60 ° C. · Polymerization: 75 ml of anhydrous n-hexane containing 7 millimoles of A1Et3, dicyclopentyldimethoxysilane as the external electron donor compound (the amount is shown in Table 1 below), and the solid catalyst component at 30 The propylene stream at ° C was added to a 4 liter autoclave washed with a nitrogen stream at 70 ° C. The autoclave was closed, and 5 N L of hydrogen was added, and then 1.2 kg of liquid propylene was fed under stirring. The temperature was raised to 70 ° C in 5 minutes, and the polymerization was carried out at this temperature for -21-200403256 for 2 hours. The unreacted propylene was discharged and the polymer was recovered at 70. c Dry under vacuum for 3 hours, then weigh and grade with o-xylene to determine at 25. (: Xylene insoluble (X.!.) Fraction and its microstructure. The polymerization reaction conditions are shown in Table 1 below.) Example 3 Repeat Example 1 'The exception is that during the polymerization reaction, a kind of A mixture containing 70% by weight of dicyclopentyldimethoxysilane and 30% by weight of cyclohexylmethyldimethoxysilane as an external electron donor compound. The polymerization reaction conditions are shown in Table 1 below. Examples 4 Example 1 was repeated, with the exception that the addition of MgCl2 and ethanol was dealcoholized as described in Example 1 of European Patent Application No. 728,769. The polymerization reaction conditions are shown in Table 1 below. Comparison Example 1 (1 c) Preparation of solid catalyst component The solid catalyst component was prepared according to the method of Example 1 above, with the exception that it contained a diether, that is, 9,9-bis (methoxymethyl) ) Manganese is used as an internal electron donor compound to replace phthalate and succinate derivatives. The internal donor content in the solid catalyst component is shown in Table 1. Polymerization Polymerization is continuous, Ordered in two sets The reactor is equipped with a device for transferring the products from the front reactor to the reactor immediately after -22- 200403256. The hydrogen and monomers in the gas phase are continuously analyzed and fed so that I get what I want The concentration will be kept constant. A mixture containing triethylaluminum active agent and dicyclopentyldimethoxysilane as the external electron donor compound and the solid catalyst component in a container at 40 ° C The contact lasts for 1 to 3 minutes. The catalyst is then transferred to a reactor containing excess liquid propylene and prepolymerized at 20 ° C for a period ranging from about 1.5 to 2 minutes. · The prepolymer is then transferred to Another reactor, in which the polymerization reaction takes place in the gas phase to form component (A). The product of the above reactor is sent to the second reactor in the gas phase to form component (B). The polymerization reaction conditions are shown in the following table. -23- Table 1 Example 1 Example 2 Example 3 Example 4 Comparative Example lc Internal DIBIPS content, military halo% 4.54 6.79 6.79 4.63 0 Electronic Drop content, weight% 12.8 11.68 11.68 6.63 0 Donor II ether Content,% by weight 0 0 0 0 16.4 DIBIPS / DIBP Molar ratio 0.35 0.63 0.63 0.75 0 Solid catalyst component input, g / hour 8.2 7 6.6 6-AlEt3 / solid catalyst component, g / g 10 13 14 13 6.1 AlEt3 / external body weight halo ratio 30 15 4 8 5.8 Polymerization reaction temperature, ° c 70 70 70 75 70 200403256 The physical and chemical properties of Examples 1 to 4 and Comparative Example 1 are shown in Table 2 below. The mechanical properties are measured on injection-molded test specimens. The plates of Examples 1 to 3 and Comparative Example 1 were extended at a temperature increase of 5 ° C in a temperature range of 140 to 155 W.

-24- 200403256 Table 2 Example 1 Example 2 Example 3 Example 4 Comparative Example lc mmmm% > 98 98.52 > 98 98.61 98.43 Mw / Mn 9.2 9.6 8.7--Mz / Mw 4.2 4.1 4.8--Main wash Analytical peak temperature, ° C-114-117 113 Stereoblock content up to 95 ° C, wt%-5.2--6.4 Stereoblock content up to 98 ° C, wt%-5.2 6.2 6.2 Elution fraction up to 94. (:, Wt%---4.6 4.1 MFR, g / 10min 3.5 3.5 2.6 2.6 3.5 soluble xylene fraction, wt% 1.7 1.6 1.4 1.5 1.3 Polydispersity Index (PI) 4.8 5 4.9 4.6 5.5 Melting temperature C 163 163 163 165.7 162 Mechanical properties of polymer Flexural modulus, MPa 1,725 1,770 1 to 850 1,780 to 1,940 1,810 to 1,885 Izod impact resistance at 23 ° C, W / m2 4.5 4.6 6 5.1 4.6 The polymers of Example 5 and Comparative Example 4 and Comparative Example 1 were processed on a B OPP tenter experimental plant line to make a 20 micron flat biaxially oriented film. The polymer is It is extruded through a flat die like a sheet and is cooled on the casting device under controlled conditions. After leaving the casting device, the sheet is reheated to the appropriate temperature, and then the film is run at different speeds by passing the film through The heating roller system is extended 4 X 1.1 in the longitudinal direction. The extension in the transverse direction is subsequently completed by a continuous stretching frame enclosed in a hot air oven. The film is preheated in this oven (the preheating temperature is as shown in the table) (Shown) and then by expanding the orbital system The moving chain clamp device system is extended 8 times in the horizontal direction. After the extension of -25-200403256, the film is quenched and corona treated. The sides are cut off and the film is finally wound on a roller. Line The speed is 70 meters / minute. Table 3 Example 5 Comparative Example 2c Minimum oven preheating temperature, 0C 162 164 Optimum oven preheating temperature, C 174 174 The deviation of 20 μm thick film, micron 1 ~ 2 0 · 5 to 3 According to the deviation 値, Example 5 shows that the film according to the present invention has a more uniform thickness than the film of the comparative example. Compared to Comparative Example 2, it also shows that the polymer can be applied at a lower oven preheating temperature By extension, an acceptable film can still be obtained, which means that the polymer according to the present invention is easier to process than the polymer of the comparative example. Examples 6 to 8 and Comparative Example 3 (3c) Examples 1 to 3 and Comparative Example 1 are compression-molded into a 1.0 mm plate, and subsequently biaxially aligned on a TM (tenter frame) long extension frame. The extension is at a fixed extension ratio of 7 times in the longitudinal direction and 7 times in the transverse direction. Simultaneous. Biaxial alignment is thin The final film thickness is 20 microns. The film properties are measured on an oriented film sample that is stretched at the optimum elongation temperature, which corresponds to 5 samples that failed the test at each temperature 0%. The properties of the film are Shown in Table 4. Table 4 (biaxially oriented film obtained from an extended frame) Example 6 7 8 3c Elongation at break,% 26 28 28 21 Tensile stress at break, MPa 140 145 146 135 Tensile modulus, MPa 2,970 2/730 2? 955 3,180 200403256 Compared with the comparative sample, the film according to the present invention shows a higher elongation at break and a higher tensile stress at break .

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Claims (1)

403256 The scope of application and patent application 1 · ~ Propene polymers, which have the following characteristics: 1) The content of the same five-element group measured by nuclear magnetic resonance (NMR) is higher than 97%; 2) Gw The molecular weight distribution represented by the / 5n ratio is equal to or higher than 6 •, and 3) the M z / M w ratio 値 is equal to or lower than 5 · 5. 2. The polymer according to item 1 of the patent application scope is a propylene homopolymer. 3. The polymer according to item 1 of the scope of patent application, which has a stereoblock content of 10% or less, as measured by using a temperature-increasing elution fractionation (TREF) method. 4 · If the polymers in claims 1 and 2 have a content of five elements in the same row, the content is higher than 97.5%. 5. The polymer according to claims i to 3 of the patent application range has a molecular weight distribution from 6 to 11. 6. The polymer as claimed in claims 1 to 4 has a Mz / Mw 値 equal to or lower than 5. 7. The polymer as claimed in claims 1 to 5 has a melting temperature of 164. C or more. 8. — A method for manufacturing a polymer such as the one in the scope of the patent application, which comprises only a single polymerization stage in the presence of a Ziegler-Natta catalyst The Geller-Nata catalyst system contains:-A solid catalyst component, which contains magnesium (Mg), titanium (Ti), halogen, and at least two kinds of electron donor compounds. The characteristics of the catalyst component are: at least one The electron donor compound is based on the total amount of the electron donor compound, and its content is from 15 to 50 mole%. It is an ester selected from succinic acids and it cannot be extracted under the following conditions. . The above (ie, non-extractable succinates), and at least one other electron donor compound which is extractable at more than 30 mol% (ie, extractable electron donor compound) under the same conditions; -An organometallic compound;-A highly stereoregular electron donor compound (external donor) ° 9 · The method according to item 8 of the patent application, wherein the ester of the succinic acid is selected from the following formula (I) Succinates shown: Among them, the groups R, and r2 are the same or different from each other, and each of the lines c "c2. Linear or branched alkyl, alkenyl, cycloalkyl, aryl, aralkyl, or alkaryl groups, as required May contain heteroatoms; and the groups & and R4 are the same or different from each other; each is Ci_c2. Alkyl, cycloalkyl, aryl, aralkyl, or alkaryl groups may contain heteroatoms as necessary, and its limitations Provided that at least one of them is a branched alkyl group; the two -29-200403256 asymmetric carbon atoms identified in the structure of formula (1), these compounds are of a pure state or a mixture type (S5 R) or (R, S) stereoisomers. I 〇. The method according to claims 8 and 9, wherein the extractable electron donor compound in the solid catalyst component is selected from aromatic carboxyl groups. The esters of acids. 1 1. The manufacturing method according to items 8 to 10 of the patent application range, wherein the external electron donor compound is selected from the group consisting of Ra5Rb6Si (〇R7). The a and b are from Integers from 0 to 2, c is an integer from 1 to 4, and the sum (a + b + c) is 4; R5, R6, and R7 are the base, The ring base or square base has 1 to 18 carbon atoms, and contains heteroatoms as needed. 02 · The film or sheet includes the polymer as described in the claims 1 to 7. 1 · The film or sheet It includes a composition containing a polymer and a hard resin such as those in the scope of claims 1 to 7. I4. Multi-layer laminated products, which include a film or sheet such as the ones in claims 12 or 13 of the scope of patent application. -30- 200403256 (1) Designated representative map (1) The designated representative map in this case is: None. (2) Brief description of the component representative symbols in this representative map 捌 If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention