JPH07508769A - Polypropylene resin and its manufacturing method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Polypropylene resin and its manufacturing method field of invention The present invention generally relates to polypropylene gas phase or The present invention relates to a slurry phase manufacturing method. The present invention further provides a film using this polypropylene. The present invention relates to a method for forming and molding a lume, and articles manufactured thereby.

Background of the invention A wide variety of polypropylenes, both crystalline and amorphous, are commercially available. . Economical methods for producing polypropylene generally use gas phase fluidized bed and slurry phase techniques. I am using it. Slurry phase processes are carried out in liquid propylene or other inert diluents. Gas phase methods, on the other hand, eliminate the need for costly solvent removal. done in the presence of The use of highly active catalysts in both processes results in expensive catalysts. Polypropylene with low levels of catalyst residue eliminating the need for removal Can be done. Unfortunately, prior to the present invention, polyamides produced by these methods were Propylene could not be used in certain film applications. film is an extremely valuable product and is suitable for gas phase technology and slurry using highly active catalysts. Since both the Lie phase technology and Lie phase technology are the important methods of producing most polypropylene, By phase technology or slurry phase technology, such as biaxially oriented polypropylene (BOPP) Produces polypropylene that can be economically converted into more film applications It is highly desirable to be able to do so.

Radiation sterilization is a method commonly used in medical applications. Furthermore, radiation sterilization Used in numerous food packaging applications. That is, any Polypropylene must also be radiation resistant. However, vapor phase method and Polypropylene produced using both rally phase processes is , susceptible to degradation initiated by, for example, gamma rays. For this, this polypropylene Pyrene cannot be used in applications that use high-energy radiation. Therefore Radiation resistant from polypropylene produced by vapor phase technology or slurry phase technology It would be highly desirable to be able to manufacture articles of this type. This means that gas phase or slurry phase Polypropylene produced by polypropylene produced by prior art methods (e.g. solution process) It has properties comparable to propylene, and even more so by using a highly active catalyst. This is especially true if it is economical.

Disclosure of invention The composition of the present invention comprises 99.8 mol% to 100 mol% propylene and 0 to 0.2 mol% propylene. A polypropylene composition comprising mol% of other α-olefins at 230°C. to achieve a melt flow rate of 0.01 to 20 g/10 min and a specific level of crystallinity. It is a polypropylene composition having

An additional aspect of the invention is that under gas phase fluidized bed reactor conditions, at temperatures of 75-90°C, At least 50 mol% propylene, comonomer/propylene molar ratio 0 to 0.00 5 and one other α-olefin comonomer and 0 to 50 mol% of an inert gas carrier. Hydrogen with a hydrogen/propylene molar ratio of 0.001 to 0.06 in the titanium Logen-supported magnesium halide catalyst, organoaluminum cocatalyst and electron donor (However, the aluminum/titanium molar ratio is 30 to 150, and the cocatalyst/electron (donor molar ratio is 3 to 6). This is a method for producing propylene.

An additional aspect of the invention provides that propylene is and one other α-olefin with a comonomer/propylene molar ratio of 0-0.005. comonomer and O to small mol% hydrogen/propylene mole in an inert gas carrier Hydrogen with a ratio of o, ooi ~ 0.06 is transferred to titanium halogen-supported halogenated magnes aluminum catalyst, organoaluminum cocatalyst and electron donor (however, aluminum/titanium the cocatalyst/electron donor molar ratio is 3 to 6). A process for producing polypropylene in a slurry phase comprising reacting in the presence of It is the law.

Another aspect of the invention includes biaxially oriented polypropylene articles and radiation resistant molded polypropylene articles. Pyrene articles and methods of making these articles from the polypropylene compositions of the present invention is included.

Detailed description of the invention The present inventors have surprisingly discovered that a porous material can be formed into an article with excellent orientation properties. A lipropylene composition has been discovered. These advantages of the polypropylene composition of the present invention The orientational properties determined by It can be easily observed using the tensile strength, elongation, etc. at the cut point. In addition, Excellent migration of additives (slip agents and anti-blocking agents) in the film ensures that the final film resulting in a lower coefficient of friction for the rubber substrate. Lower coefficient of friction results in better film Provides additional handling characteristics.

The polypropylene compositions of the present invention also have excellent radiation resistance.

This radiation resistance is believed to be due to the reduced crystallinity to a certain level. high Polypropylene produced using active catalysts is highly crystalline. high crystallization The stiffness is advantageous for many applications where high stiffness is required. However, For certain applications, such as radioactive articles, crystallinity reduced to a certain level may be seems important.

This polypropylene composition surprisingly showed a melting rate of 0.1 to 20 g/10 minutes at 230°C. have a high flow rate and a certain level of crystallinity. Crystallinity can be measured in several ways, That is, xylene soluble content (Xs), carbon-13 nuclear magnetic resonance (NMR) It can be measured by isotoughness measured by Furthermore, crystallinity can be measured using dynamic mechanical thermal analysis (DMTA). of a certain value The measurement is T0.

To is the temperature where the complex modulus of elasticity (E”) = 1.4XIO “dyne/am” be. The polypropylene compositions of the present invention have a T1 of less than 318°F (159°C). has.

This combination of melt flow rate and specific crystallinity level (To) surprisingly , the polypropylene composition of the present invention can be used in industrial fibres, such as in the production of BOPP. The present invention is useful for producing oriented polypropylene by a lume-forming method. Furthermore, this Articles molded using the composition have improved resistance to radiation-initiated degradation. Shows high resistance.

This composition is generally prepared using a gas phase fluidized bed process or a slurry phase process using a titanium catalyst and an organic alcohol. Produced with hydrogen in the presence of a minium cocatalyst. Polypropylene composition of the invention The product is generally unmodified and contains between 0.1 and 20 g/1 when taken directly from the reactor. Melt flow at 230°C measured by ASTM method DI238-85 in 0 min. -rate and a certain level of crystallinity as measured by DMTA (T'') are doing.

Polypropylene produced by gas phase or slurry phase technology is known to those skilled in the art. be. The compositions of the present invention can be made using standard gas phase technology or slurry phase technology reactors. can be built. Catalysts, cocatalysts and electron donors are known to those skilled in the art. An example is U.S. Patent No. 3.418.346, U.S. Patent No. 4.400.302, U.S. Pat. No. 4,414.132 and U.S. Pat. No. 4,329.253 (the disclosures of which are incorporated herein by reference) (incorporated herein by reference in their entirety).

Preferred titanium halogen-supported magnesium halide used in the gas phase method of the present invention The catalyst is titanium tetrachloride on magnesium chloride.

Organoaluminum compounds are used in all known catalyst systems consisting of titanium halides. activators can be selected from. That is, a trialkyl aluminum compound, Dialkyl aluminum rhamno 1ride and dialkyl aluminum alkoxide can be used successfully. Trialkylaluminum compounds, especially alkyl Each group has 2 to 6 carbon atoms, such as triethylaluminum, triethylaluminium, -n-propyl aluminum, triisobutyl aluminum, tri-n-propyl aluminum aluminum, triisopropylaluminum and dibutyl-n-amylaluminum Minimum is preferred. A preferred organoaluminum cocatalyst is trialkylaluminium aluminum compounds, with triethylaluminum being most preferred.

Suitable electron donors are ethers, esters, ketones, phenols, amines, amides. , imine, nitrile, phosphine, phosphite, stibine, arsine, phosphorus Ruamide and Alcolade. Examples of suitable electron donors are U.S. Pat. No. 36.243 and German Published Patent Application No. 2.729.196. It is something that exists. Preferred electron donors are ethyl benzoate, methyl benzoate, Ethyl para-methoxybenzoate, Methyl para-ethoxybenzoate, Para-ethoxy Ethyl benzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, dicarbonate Methyl, dimethyl adipate, dihexyl fumarate, dibutyl maleate, sulphate Ethyl isopropyl urate, ethyl para-chlorobenzoate, para-aminobenzoic acid hexyl, isopropyl naphthenate, n-amyl toluate, cyclohexanoic acid Ethyl (ethylcyclohexanoate), propyl pivalate, N , N, N', N'-tetramethylethylenediamine, 1. 2. 4-Tori such as methylpiperazine and 2,3.4.5-tetraethylpiperidine compounds. , esters and amines, especially esters of aromatic carboxylic acids; Ethyl toxybenzoate is most preferred.

In the reaction process of the present invention, the aluminum/titanium molar ratio is preferably 30 to 150. It is preferably 35 to 70, most preferably 40 to 60. Al greater than 150 The molar ratio of aluminum/titanium is wasteful with respect to organoaluminum components, and the ratio results in excessively high levels of residual aluminum in the polymer. less than 30 If the aluminum/titanium molar ratio is less than 30, the production rate is low, low Titanium catalyst productivity results in a very slow reaction with high levels of titanium catalyst residue.

In the reaction process of the present invention, the cocatalyst/electron donor molar ratio is 3 to 6, preferably 3. ．． 2 to 5.0, most preferably 3.5 to 4.0. Cocatalyst significantly larger than 6 Excessively high levels of xylene solubles content polymers form in the molar ratio of electron donors to will be accomplished. This xylene soluble content polymer is sticky and transferable from the reactor. difficult to do.

If the xylene solubles content is high enough, polymer transfer from the reactor is not practical. becomes practically impossible. Even higher xylene solubles content polymers can be used to form thin films. exhibits undesirable emissions when extruded. Cocatalyst to electron donor molar ratio is greater than 3 is small enough, it will not produce a satisfactorily oriented film and the present invention will fail. Polymers are produced that are out of range, ie, have a T1 that is too high.

In the process of producing homopolymers or near-homopolymers, hydrogen/propylene is The pyrene molar ratio is between 0.001 and 0.06, and the comonomer is preferably ethylene. ethylene with a comonomer/propylene molar ratio of 0.001 or less, or comonomer/propylene molar ratio of 0.001 or less. 1-butene, ■-hexene or 4-methylene with a lopylene molar ratio of 0.005 or less Leu-1-pentene. The hydrogen/propylene molar ratio during the polymerization step is preferably 0. ．． The ratio is from 0.002 to 0.03, and more preferably from 0.005 to 0.01.

The method of the present invention is performed at a temperature of 75 to 90°C and a total pressure of 300 to 1000 psi; It should preferably be carried out at 75-80°C and 400-600 psi.

The amount of propylene used in the gas phase process of the present invention is limited to 50 mol% or less of inert nitrogen such as nitrogen. at least 50 mole % in the presence of a neutral carrier gas. propylene in reactor If monomers or comonomers are used, the total amount of monomers is preferably 6 It is 0 to 100 mol%. Higher levels of inert gas reduce the amount of fluidization from added fluidization. The reaction rate is reduced without gaining much benefit. Inert carrier gas is mono This is not a requirement as the mer can provide fluidization to the catalyst bed.

In the slurry process, the reaction occurs in a liquefied pool of propylene.

The method can also be carried out in an inert diluent. Diluent is alkyl aluminum It must not contain any functional groups that can react with the catalyst of the nitrogen agent. Examples of suitable diluents include Includes isopentane, hexane, heptane, and octane. Common slurry phase The description of the law is in The Encyclopedia of Polymer 5cie nce and IEngineering, volume 13, pages 502-510. I can put it out.

Although the polypropylene produced by the method of the invention is actually crystalline, it Limited level of crystallinity and limited melt flow as measured by To - rate. As mentioned above, the xylene soluble content of polypropylene varies with the cocatalyst/electron donor molar ratio. T0 value for polypropylene is below 318°F (159°C), preferably between 311’F (155°C) 318°F (159°C) and 312°F (156°C) to 315°F ( 157° C.) is more preferable. For comparison purposes, a typical gas or slurry phase The manufactured polypropylene has a T” = 321°F (>160°C) . The inventors have determined that polypropylene with a T9 greater than 318°F (159°C) It has also been observed that when inferior BOPP is made into molded articles, it exhibits inferior radiation resistance. I discovered that.

The melt flow rate of the polypropylene of the present invention (measured in the characterization section below) is ) 0.1 to 20 g/10 minutes at 230°C, preferably 2 to 10 g/10 minutes and more preferably 3 to 8 g/10 minutes. Less than 0.1g710min Melt flow rates give polymers that are difficult to process. On the other hand, 20 Melt flow rates greater than g/10 min foster low melt strength and low melt viscosity. This results in a polymer that is too soft for film-forming applications.

The polypropylene produced by the gas phase method and slurry phase method of the present invention has the above-mentioned differences. properties (melt flow rate and T”), but standard vapor phase and slug It retains many of the properties of polypropylene produced by the Lie phase process. other mind The polypropylene of the present invention, like phase and slurry phase manufactured polypropylene, It has significantly higher stereoregularity than polypropylene produced by the method.

An example of a solution method is disclosed in US Pat. No. 3,272,788.

The polypropylene produced by the gas phase or slurry phase process and according to the invention is It has other properties that are different from polypropylene produced by the solution method. . These include residues from highly active catalysts; a higher melting point (2°C higher, e.g. the melting point of a homopolymer is typically higher than 159°C); higher crystallinity as measured by X-ray diffraction; Low heptane solubles content (at least 10% lower) + ASTM method D-633 Includes high tensile strength as measured by

The polymers of the present invention contain antioxidants that inhibit deterioration due to heat, ultraviolet light, and outdoor exposure. stabilizers, opacifying pigments such as titanium dioxide and carbon black; Plastics, slip agents, antiblocking agents, tackifying resins and small amounts (less than 20%) ) can be compounded with additives such as other compatible polymers. can.

Blend compositions include triblends, triblends and subsequent compounding. passing through a mixing extruder, compounding on kneading rolls, or a Banbury mixer - can be produced in various ways, such as by melting or by solution blending. Wear. Any method by which the ingredients can be blended together will also produce the desired blend. will build. For example, less than 20% of the pellets have a diameter of 1/8 inch (0,32 cm) and some pellets are smaller than 1/16 inch (0,16 cm). Fine pellets of each polymer with an average size of /16 inches (0,16 cm) mechanically mix the blend and feed the blend to an extruder where it is melted and extruded. put out.

The melt is converted into a film such as BOPP at a melting temperature below 325°C. however, a melting temperature in the range of 210-295°C is preferred, resulting in maximum It has been found to give excellent results with a usable linear velocity of .

Thus, another aspect of the invention includes 99.8-100 mole percent propylene and 0-0. Polypropylene composition consisting of 2 mol % of at least one other α-olefin , polypropylene has a melt flow of 0.1 to 20 g/10 minutes at 230°C. Polypropylene compositions having a T9 of less than 318°F (159°C) A method of forming a film or forming a molded article by extrusion or injection molding at high temperature law is included.

The invention is further illustrated by the following examples of preferred embodiments thereof, which examples are intended to be illustrative only. are included solely for the purposes of this invention and do not limit the scope of the invention unless otherwise indicated. It goes without saying that this is not intended to be limiting.

Example The slurry reactor used was obtained from Autoclave Engineers. It was a gallon capacity autoclave. Purified (polymerization grade) propylene used. Triethyl aluminum (TEAL) is manufactured by Aldrich Chemical Obtained from Al Company as a 25% (wt) solution in toluene.

l! Rose-ethoxybenzoin obtained from lan Chemical Company Ethyl acid (PEEB) was used as received. Titanium (Ti) content ~0.5% (weight) of catalyst (TiC1 supported on MgC+2), TEAL and P The EEB was weighed in a dry box using an analytical balance and dried (80°C (heated overnight) was added to the charge bomb. This charge cylinder is Ameri Improved check valve without certification, suitable for can Instruments valves It was bu. The autoclave was "broken in" before each operation.

That is, 1600 mL of 0.5% TEAL solution was placed in an autoclave and heated under N2. Heated to 100°C, cooled to ambient temperature and discharged the TEAL. After cooling , 2 L of liquid propylene and 15 psi of N2 were added. Autoclave 5 Heated to 0°C. The contents of the charge cylinder were pressurized into the autoclave with nitrogen. . Heat the autoclave to the desired temperature, maintain it at that temperature for 1 hour, and Cooled to temperature. The contents were removed and analyzed (see below).

gas phase reactor A continuous reactor for the production of polypropylene (PP) powder was used. Known catalyst poisons All gas components were purified to remove them. Propylene gas composition 70 mol% maintained. Hydrogen to produce PP with desired melt flow rate (VFR) The concentration was varied. The remainder of the gas composition consists of nitrogen and small amounts of inert impurities. Ta. Reactor bed temperature was maintained at 67°C. The total pressure was 535 ps i. Psych Maintains a gas flow of 19,000 cubic feet/hour (150,000 cm’/second) The bed was fluidized by Catalyst was continuously fed to the reactor. TEA L was supplied as a dilute solution in isopentane. Aluminum/Titanium (AI/ The molar ratio of Ti) was 50-60. Electron donor, PEEB in isopentane It was supplied continuously as a diluted solution. TEAL/ The molar ratio of PEEB was varied. Polypropylene powder to give constant floor weight The powder was discharged from the reactor at periodic intervals. Lose the powder by steaming I made it come alive.

combination 3.5 inch Modern Plastics Machinery Single Axis Screen either a screw extruder or a 40 mm Berstorff twin screw extruder. The powder was formulated with the selected additive system. The selected additive system can be determined by a person skilled in the art. The selection can be based on well-known techniques. Attachments found to be effective Examples of additive systems include 0 to 2. OOppm primary antioxidant, e.g. hindered Phenol; 0-2. OOOppm secondary antioxidant, e.g. phosphorous acid ester 0~3. OOOppm synergistic antioxidant, e.g. thioester; 0-2 ．． 000 ppm acid scavenger blend (amounts are based on the weight of the total extrusion coating system) standard). A specific example of hindered phenol is tetrakis [methylene] 3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propione Tocomethane (registered trademark Irga OX) 1010 Cibaga (available from Iggy). Specific examples of phosphorous esters include tri(mono and di) nonylphenyl) phosphite (registered trademark Naugard PHR Uniro yal Chemical Company). Thio Esthe A particular example of a metal is distearyl thiodipropionate (DSTDP). acid sulfur A specific example of a scavenger is calcium stearate.

thin film composition Compositions for thin films typically include an intimate mixture of polymers, antioxidants, Extrusion compounding with acid scavengers and coefficient of friction reducers well known in the industry. It is made by. A suitable additive package is 0.1% Irganox (Ir ganox) 1010.0.1% Irgafos 168. 0.04% Hydrotalcite DHT4A and 0 ．． 3% Amide E. This composition was processed using a twin screw extruder. Extrusion and pelletization at a melt temperature of 225°C.

thin film manufacturing Relatively thick sheets (15-40 mils) are processed in a continuous process on chill rolls or immersed in cold water. Cast by soaking. This is then passed through a series of oil-heated take-off rolls. sheet at a ratio of 4 to 6:l by moving the rolls and increasing the speed between the rolls. Make it thinner. These machine direction dimensional changes are then measured at the oil heated roll location. The annealed and thinned sheet is contacted with a width ratio clamp that grips the edge of the sheet. Do a hot air pass through the oven. sheet above 250°F but above the melting point After being pulled through a preheating section that heats at a low temperature, the sheet is laterally rolled through the final Stretch to desired film thickness. This final stretch is as large as IO:1. Good too. After this, the stretched film is passed through an annealing section to fix the width, and then passed through a width pressing machine. Take it out and wind it up as a thin film on a pair of take-up rolls.

Characteristic measurement The resins were characterized using standard analytical test methods. VFR is ASTM method D1 Measured using 238-85. Xs is due to the dissolution of the polymer in refluxing xylene. was measured. The solution was cooled to 25°C to allow crystallization to occur. Xs and Decari The soluble matter was determined by measuring the concentration of polymer remaining in the solvent at 25°C. I met. Melting points were determined using Differential Scanning Calorimetry (DSC) using ASTM Method D Method 418. ). Melting point (Tm), heat of fusion (Δ1(f), crystallization temperature (TC ) and heat of crystallization (ΔHc) were obtained in the second heating cycle. Physical property evaluation of test piece Manufactured by injection molding using an Arbug 305 S injection molding machine for . Physical properties were obtained using standard methods (see Table 1).

Table 1 Physical property measurement method Test ASTM method Curvature rate 0790-66 Tensile D-638 Density D-1505 Melt flow rate D-1238-85 Biforce - Softening point D-1525 0 hardness D-785 Izotsu Impact D-256 Heat deformation D-648 Gardner Impact D-3029 Melting points were measured by differential scanning calorimetry (DSC). Isotaft City is Triad element level using JEOL GSX 270 at 270 MHz Measurements were made by carbon-13 nuclear magnetic resonance (NMR) using an analytical method.

19, the peak at 85-20.50 ppm is designated as rr, 20.50-21 ．． The peak at 20 ppm is designated as mr, and the peak at 21.20 to 22.50 ppm is designated as mr. Peaks were designated as mm.

Isotuffity is defined as [mm/(mm+mr+rr)]X100 I justified it. Productivity is determined by the amount of residual T from the polymer produced/catalyst fed or in the PP. It can be calculated from the level of i. T1 is rheometrics (Rheom etrics) Using the R3A-II device, the dimensions are approximately 0.75 mm x 23 mm. Dynamic Mechanical Thermal Analysis (DMTA) using die-cut thick film samples with method Measured using. This film was compression molded using an automatic PHI press. specimen 120 to 1 at 1”C/min in dynamic tension at 0.1% strain at 17.5 rad/sec Tested in temperature gradient mode at 70°C. T″ is the complex modulus of elasticity (E″) = 1 ．． The temperature is 4×10 “dynes/cm”.

The molecular weight distribution of the PP sample was measured using a Waters 150CGPC with a refractive index detector. Analyzed by size exclusion chromatography (SEC) using the system.

The column set consists of two Waters' Linear (1 0'/10'/10') from "Microstyragel-HT" column It had become. Calibration is Mw=267000. Single with Mn=43000 This was done using Broad PP standard product. The sample was 143% in 0-dichlorobenzene. Processed at °C. That is, the results are relative, and the Mn number by other methods should not be compared quantitatively. The SPC range for standard products is shown below.

Average Sigma (n=43) Mw: 272000 11000 Mn: 44000 2200 Mw/Mn: 6.3 0.3 Slurry method The following four examples were prepared by the slurry phase process.

Example 1 Contents of charge bomb: 1.05g TEAL solution, 0.13g PE EB and 0.31 g of catalyst were placed in an autoclave. Increase temperature to 80°C I set it. Analysis of the product was as follows. 688g, residue, Ti=4.0p pm, AI=271ppmXC1=32ppm, PEEB=169ppm ; MFR=10.1g/10min; Xs=12.4%, T"=310 ．． 4°F (154°C); Tm = 160.3°C; ΔHf = 82.5Hf- Le/g; Tc=110.4°C: Isotafticity; 91.9%, MWd=6.4; Productivity=10.600 bond (kg) PP/bond (k g) Catalyst (dry basis).

Example 2 (comparison) Contents of charge bomb: 0.99g TEAL solution, 0.17g PE EB and 0.28 g of catalyst were placed in the autoclave. Raise the temperature to 60℃ I set it. Analysis of the product was as follows. 295g; Residue, Ti-4,6 ppm, AI=240ppm, C1=50ppm SPFEB=8929p m; MFR=1.23g/10min; X5=4.4%, T”=321.5 °F (161'C); Tm = 159.4°C; ΔHf = 84.3Hf-ru/ g; Tc = 109.0°C; Isotuffity = 95.1%; M Wd=4.5; Productivity=5000 bond (kg) PP/bond (kg) touch Medium (dry base).

Example 3 (comparison) Contents of the charge bomb: 0.99 g TEAL solution, 0.15 g P EEB and 0.29 g of catalyst were placed in the autoclave. Increase temperature to 70°C I raised it. Analysis of the product was as follows. 591g; residue, Ti=2. 2ppm, AI=128pI)m, CI=43ppm, PEEB=27 81) I) m; MFR=0.98g710min; X5=4.2%, T”= 321.1°F (161°C): Tm = 159.6°C: ΔHf = 89. 0Hf-ru/g; Tc=111.2°C: Isotafticity=95 ．． 0%; MWd=5.3; Productivity=9700 Bond (kg) PP/Bond (kg) Catalyst (dry basis).

Example 4 (comparison) Contents of charge bomb: 1.01g TEAL solution, 0.17g PE EB and 0.28 g of catalyst were placed in the autoclave. Raise the temperature to 80℃ I set it. Analysis of the product was as follows. 223g; residue, Ti=7. lp pm, AI=240ppm, CI=6611pm, PEEB=937p pm; MFR=1.06g/10min; X5=2.2%, T”=325. 2°F (163°C); Tm = 160.6°C; ΔHf = 100.3 joules / g ; Tc = 111.5°C; Isotafticity = 98.4%; MWd = 4.5, productivity = 3800 bond (kg) PP/bond (kg ) Catalyst (dry basis).

stiffness Gas phase method The five examples below were prepared using a gas phase method.

Example 5 The gas phase reactor was heated to a TEAL/PEEB molar ratio of 4.0. Temperature = 80°C, H, /Pro It was operated at a pyrene molar ratio = 0.003. Analysis of the product is shown below. residue, Ti=2.4ppm, Al=54ppm, PEEB=119ppm; M FR=4.5g/10min; X5=7.5%; Ds=9.3%, T'=3 18.0°F (159°C); Tm = 160, 1″C; ΔHf = 90.0Hf-le /g: Tc=114.7°C; Isotafticity=92.6%, MWd=4.0, productivity=8700 bond (kg) PP/bond (kg) Catalyst (dry base).

Example 6 (comparison) The gas phase reactor was equipped with TEAL/PEEB molar ratio = 2.5, temperature = 80°C, Hl/P It was operated at a ropyrene molar ratio=0.015. Analysis of the product is shown below. residue, Ti=7.4ppm, AAl-74pp, PEEB=203ppm; M FR=5.0g/10min; X5=5.5%; Ds=6.9%, T"=3 21.6°F (161°C); Tm = 163, 6°C; ΔHf = 81.1Hf- Le/g; Tc=112.2°C; Isotuffity=94.7% , MWd=4.8, Productivity=7200 bond (kg) PP/bond (kg ) Catalyst (dry basis).

Example 7 (comparison) The gas phase reactor was equipped with TEAL/PEEB molar ratio = 3.5, temperature = 60°C, Ha/propylene It was operated at a ren mole ratio of 0.022. Analysis of the product is shown below. residue, T i=2.2ppm, AI=43ppm, PEEB=1101)pm; M FR=5.0g/10min; X5=6.3%; Ds=7.5%, T"=3 22.0°F (161'C); Tm = 163, 4°C: ΔHf = 77.6 units 1 l/g; Tc = 113.4°C; Isotoughness = 95.6%, MWd=8.6; Productivity=10500 bond (kg) PP/bond (kg ) Catalyst (dry basis).

Example 8 (comparison) The gas phase reactor was equipped with TEAL/PEEB molar ratio = 2.5, temperature = 60°C, Hl/P It was operated at a ropylene molar ratio of 0.030. Analysis of the product is shown below. residue , Ti=3. lppm, Al=55ppm, PEEB=250ppm; MFR=4.9g/10min: X5=6.7%; Ds=8.0%, T”= 319.4°F (160°C); Tm = 162.1°C: ΔHf = 74.7Hf - Le/g; Tc = 111.7°C; Isotuffity = 96.4% , MWd=5.8, Productivity=7400 Bond (kg) PP/Bond (kg ) Catalyst (dry basis).

Example 9 (comparison) The gas phase reactor was equipped with TEAL/PEEB molar ratio = 4.0, temperature = 70°C, H8/propylene It was operated at a ren mole ratio = 0.005. Analysis of the product is shown below. residue, T i=1.9ppm, AI=45ppm, PEEB=250pHm; MF R = 1.6g/l.

Minutes; "C); Tm = 159, 3°C; ΔHf = 94.0 joules/g; T c = 110.0°C; Isotuffity = 95.0%, MWd = 5.1 , Productivity = 17300 Bond (kg) PP/Bond (kg) Catalyst (Dry base).

Although the invention has been described in detail with particular reference to preferred embodiments thereof, variations and modifications thereof It goes without saying that this may be done without departing from the spirit and scope of the invention.

Claims (19)

[Claims] 1. At a temperature of 75 to 90 °C, at least 50 mol% propylene, comonomer/ one other α-olefin comonomer with a propylene molar ratio of 0 to 0.005; and Hydrogen/propylene molar ratio in 0-50 mol% inert gas carrier is 0.00 1 to 0.06 of hydrogen, titanium halogen-supported magnesium halide catalyst, organic Aluminum cocatalyst and electron donor (however, the aluminum/titanium molar ratio is 30 ~150 and the cocatalyst/electron donor molar ratio is 3 to 6). A method for producing polypropylene, comprising: 2. The comonomer is ethylene with an ethylene/propylene molar ratio of 0.001 or less. 1-butene, 1-butene or comonomer/propylene molar ratio of 0.005 or less; The method according to claim 1, which is hexene or 4-methyl-1-pentene. . 3. The titanium halogen catalyst is titanium tetrachloride and the organoaluminum cocatalyst is trichloride. ethylaluminum and the electron donor is ethyl para-ethoxybenzoate The method according to claim 1. 4. Triethylaluminum/ethyl para-ethoxybenzoate molar ratio is 3.2~ 5. The method according to claim 3, wherein 5. 2. The method according to claim 1, wherein the temperature is 75-80<0>C. 6. 2. The method of claim 1, wherein the total reaction pressure is 300 to 1000 psi. 7. 2. A method according to claim 1, wherein the reaction is carried out under gas phase fluidized bed reactor conditions. 8. The reaction is carried out under slurry phase reactor conditions, with very small amounts of inert gas carrier 2. The method of claim 1, wherein the method is present in an amount not exceeding . At a temperature of 9.75-80°C, at least 75 mol% propylene, comonomer/ one other α-olefin comonomer with a propylene molar ratio of 0 to 0.001; and Hydrogen/propylene molar ratio of 0.00 to 25 mol% in an inert gas carrier 1 to 0.02 of hydrogen, titanium halogen-supported magnesium halide catalyst, organic Aluminum cocatalyst and electron donor (however, the aluminum/titanium molar ratio is 40 ~70 and the cocatalyst/electron donor molar ratio is 3 to 4). A method for producing polypropylene, comprising: 10.99.8-100 mol% propylene and 0-0.2 mol% at least Contains 1 type of other α-olefin, polypropylene is 0.1-20g at 230°C /10 minutes melt flow rate and T* below 318°F (159°C) polypropylene composition. 11. Claims where T* is between 311°F (155°C) and 318°F (159°C) The composition according to item 10. 12. Claim No. 2, wherein the melt flow rate is 2 to 10 g/10 minutes at 230°C. Composition according to item 10. 13. Up to 10% by weight of antioxidants, stabilizers, slip agents, block inhibitors, selected from pigments, plasticizers, tackifying resins, compatible polymers and mixtures thereof. 11. The composition of claim 10 further comprising at least one additive. 14.99.8 to 100 mol% propylene and 0 to 0.2 mol% at least Contains 1 type of other α-olefin, polypropylene is 0.1-20g at 230°C /10 minutes melt flow rate and T* below 318°F (159°C) A method of forming an article comprising extruding a polypropylene composition at an elevated temperature. 15. Melt flow of polypropylene composition at 230°C for 2 to 10 g/10 minutes 15. The method of claim 14, comprising: 16. 15. The method of claim 14, wherein the composition is extruded into a thin film. 17. 15. The method of claim 14, wherein the composition is extruded into a mold. 18. An article of manufacture comprising a film made from the composition of claim 10. . 19. The molded article according to claim 10.