TW200831586A - Polyolefin compositions - Google Patents

Abstract

Polyolefin compositions, comprising (percent by weight): (1) 55-80% of a homopolymer or copolymer of propylene, said copolymer containing up to 15% of ethylene and/or C4-C10 α-olefin (s). (2) 20-45% of a copolymer of ethylene with one or more C4-C10 α-olefin (s) containing from 10 to 40% of said C4-C10 α-olefin (s); said compositions having values of MRF (230 DEG C , 2.16kg) up to 20 g/10 min, a total content of ethylene of 20% or more, a total content of C4-C10 α-olefin (s) of 4.5% or more, a ratio of the total content of ethylene to the total content of C4-C10 α-olefin (s) of 2.3 or more, a total fraction soluble in xylene at room temperature of 18 wt% or higher and flexural modulus, referred to composition as a reactor grade, or more than 700 Mpa.

Description

200831586 IX. Description of the Invention: [Technical Field] The present invention relates to a polyolefin composition comprising a propylene homopolymer and a propylene containing propylene and/or other α-storage as a comonomer A propylene polymer component of a random copolymer and a copolymer of ethylene and c 4 _ c ! 〇α-olefin. [Prior Art] The composition of the present invention can be easily converted into various finished or semi-finished products. In particular, the compositions of the present invention have a high melt flow rate (MFR) and are particularly suitable for use in finished articles produced by the use of injection molding techniques, substantially in combination with stiffness, high gloss and low shrinkage while exhibiting stress free whitening. . Therefore, the composition can be used in a variety of applications, including toys, packaging materials, and household goods, particularly for impact resistance at low temperatures and without rupturing the finished product. In addition, the finished product can be advantageously used in food container applications, examples of food containers suitable for use in refrigerators. The composition of the present invention has a low MFR 値 suitable for film applications, particularly for cast and double oriented films, in addition to the above-mentioned unique balance properties, low temperature impact, gloss and good shrinkage properties and exhibits high gas permeability (breathability), Low haze (good optical properties) and flexural modulus (stiffness). Therefore, the composition can be particularly used for such film applications requiring gas permeability, good optical properties and stiffness, such as packaging of fresh vegetables, laminating sterilization and packaging of flexible packaging and transparent sterilization bags. Compositions comprising a crystalline polypropylene matrix and a rubber phase formed from an elastomeric copolymer of ethylene and an alpha-olefin are known in the art and are described in particular in European Patent Nos. 170,255, 373,660, 603,723 and 1 135 440 and International Application No. 200831586. 04/003 0 73. The impact strength exhibited by this composition, and in the cases of European Patent Nos. 3, 73,660, 60 3,723, 1135,440 and WO 04/0030735, and the use of transparent enamel have attracted many applications. However, due to high market standards, the overall balance characteristics are still not fully met for all possible applications. A rare balance characteristic is obtained in the case of WO 0 4/003 073, but the impact stiffness balance is not fully satisfied in some applications, especially considering the use of a clarified nucleating agent (Mi 11 ad), still The better 値 of the flexural modulus is not satisfied. Therefore, there is still a continuing need for such compositions and the application of improved balance characteristics to specific targets. SUMMARY OF THE INVENTION Excellent balance properties are obtained by the polyolefin composition of the present invention, which comprises (relative to the sum of components 1) and 2), expressed as a percentage by weight: 1) 5 5 -8 0% propylene a homopolymer or copolymer comprising up to 15% ethylene and/or C4-C1G alpha-olefin; 2) 20-45% ethylene copolymer with one or more C4-C1Ga-olefins, The copolymer contains from 10 to 40% of the C4-C1Ga-olefin; the composition has an MFR 値 (230 ° C, 2.16 kg) of up to 20 g/10 min, and the total amount of E3 is 20% or more, C 4 - C 1 ο a - The total content of the commission smoke is 4, 5 % or more, and the ratio of the total ethylene content to the total content of total C4-C1G olefins is 23 or more 'Total fraction soluble in xylene at room temperature The rate of the composition is 18 wt% or higher, and the composition of the reaction grade has a flexural modulus of more than 700 MPa. In particular, the special characteristics of the composition of the present invention are: - the inherent viscosity of the dimethane soluble fraction at room temperature is 2 dl/g or less, and 200831586 is preferably 1.7 dl/g or less, more preferably i. 1 to ^1, preferably from l1 to 1.5 dl/g; • flexural modulus greater than 770 MPa' is more preferably greater than 800 MPa; - component 2) (decomposed) is 25_45%' preferably 25_40 %' is a percentage by weight and is expressed as the sum of components 1) and 2); - the content of the dimethane insoluble component polymer at room temperature (23. underarm component 1) is less than 90%, in particular no Less than 93%, which is a weight percentage and expressed by the weight of the component 1); - a total ethylene content of 20% by weight to 40% by weight; a total content of -C 4 - C 1 〇α - olefin of 6% by weight To 15% by weight; - the dimethane soluble fraction at room temperature is less than 35 wt%, more preferably less than 30 wt%; and the ductility of brittleness/brittleness is generally equal to or lower than -3 5 °C The lower limit has been indicated to be about -6 0 °C. The term "copolymer" throughout the specification also includes a polymer containing more than one other comonomer in addition to the main monomer. The composition of the present invention provides high impact strength (transfer temperature/brittle transfer temperature and Izod impact), high gloss, extremely high whitening resistance and low heat shrinkage, respectively, measured on the board, and A combination of high gas permeability measured on a film and good transparency. A preferred polyolefin composition of the article produced by injection molding is a flexible polyolefin composition having high fluidity, high stress-resistant whitening and low heat shrinkage, and the sum of components 1) and 2) is expressed by weight: 1) 5 5 - 80%, preferably 55-75%, more preferably 60-70% of a propylene homopolymer 200831586 or copolymer containing up to 15% higher ethylene and/or C4-C1G An α-olefin having an MFR of 15 g/l min or more, preferably 30 g/10 mi or more; and 2) 2 0-4 5 %, preferably 2 5 - 4 5 %, more preferably 3 0-40% of ethylene and one or more C 4 -C ! 〇 α-olefin copolymers containing 15 to 40% of the C4-Ci α α-olefin; the composition has 1 〇 MFR 20 (230 ° C, 2.16 kg) to 20 g/10 min, total ethylene content of 20% or more, total content of C4-C1G ct-olefins of 6% or more, total ethylene content of C4-C1G α - the ratio of the total content of olefins is 2.3 or more, the total fraction soluble in xylene at room temperature is 18 wt% or more, preferably at least 20 wt%, and the flexural modulus of the composition for the reaction grade It is greater than 7 〇〇 MPa. When the composition suitable for the injection molding application as described above is obtained by adding a nucleating agent such as Na benzoate (refer to the following). Improved mechanical properties, especially the discovery of very high E. sinensis without a balance that substantially affects gloss, resistance to whitening and shrinkage. The above polyolefin composition is preferably used for injection molding applications, and is particularly suitable for replacing AB S. Preferred polyolefin compositions for film applications, particularly for cast and double oriented films, exhibit high gas permeability, good optical properties and stiffness on the film, including (relative to component 1) and 2) The sum total, expressed as a percentage by weight): 1) 5 5 - 80%, preferably 5 5 - 7 5 %, more preferably 6 5 - 7 5 % of a propylene homopolymer or copolymer 'The copolymer contains Up to 15% ethylene and/or €4-(:1() 〇1-olefin; and 200831586 2) 2 0 - 4 5 %, preferably 2 5 - 4 5 %, more preferably 2 5 - 3 5% of ethylene and one or more C4-Ci〇 α-olefin copolymers. The copolymer contains 15 to 40% of the C 4 —C i 〇 α-olefin; the composition has a high l〇g/ M〇 値 (2 3 0 T:, 2.1 6 kg) of l〇min, preferably 1 to 4 g/10 min, total ethylene content of 20% or more, and total content of α-olefin of C4-C1 () is 6% Or above, the ratio of the total ethylene content to the total content of the C4-C1Ga-olefin is 2.3 or more, and the total fraction soluble in xylene at room temperature is 18% by weight or more, preferably at least 20% by weight. And the flexural modulus is greater than 700 MPa. In the composition and fraction of the composition of the present invention, a C4-C10a-olefin may exist or may exist as a comonomer represented by CH2=C HR wherein R is a linear or branched chain having 2 to 8 An alkyl or aryl group of a carbon atom (particularly a phenyl group). Examples of C4-C1Ga-olefins are butene, 1-pentene, 1-hexene, 4-methyl-1pentanyl and 1-octane. It is preferably 1-butene. The composition of the present invention is prepared by continuous polymerization comprising at least two consecutive steps wherein the components 1) and 2) are prepared in different sequential steps except that the operations of the first step are in the previous step The polymer formed and the catalyst used are carried out in the presence of a catalyst. Preferably, the catalyst is added only in the first step, however, its activity is still active in all successive steps. Preferably, component 1) is prepared prior to component 2). Accordingly, the present invention is further directed to the above process for the preparation of a polyolefin composition as described above, which process comprises at least two successive polymerization stages, and each polymerization reaction is carried out in the presence of a polymer material formed by the preceding polymerization reaction, wherein The polymerization stage of polymerizing the polymer into a polymer component 1) 200831586 is carried out in at least one stage, followed by copolymerization of at least one ethylene with one or more C4-C1Ga-olefin mixtures to synthesize the elastomeric polymer component 2). The polymerization stage can be carried out in the presence of a stereospecific Ziegler-Natta type catalyst. According to a preferred embodiment, all of the polymerization stages are carried out in the presence of a catalyst, including a trialkylaluminum component, optionally, an electron donor and a solid catalyst component, which comprise a halide of Ti or a halo-containing alcoholate and are supported An electron donor compound on anhydrous magnesium chloride. Catalysts having the above-mentioned features are known from the patent literature. Particularly advantageous catalysts are described in USP 4,399,054 and EP-A-45 977. Other examples can be found in USP 4,472,524. Preferably, the polymerization catalyst is a stereospecific Ziegler-Natta type catalyst comprising a solid catalyst component: a) Mg, Ti and a halogen and an electron donor (internal donor), b) an aluminum alkyl Ingredients and optionally (but preferably) c) one or more electron donor components (external donor). The internal donor is preferably selected from the group consisting of monoesters or dicarboxy organic acids such as benzoates, glycerides, phthalates and certain succinic esters. For example, it is described in U.S. Patent No. 4,522,293, European Patent No. 45,977, and International Patent Application Nos. WOOO/63261 and W001/57099. Particularly suitable for phthalates and succinates. Preferred are alkyl decanoates such as diisobutyl, dioctyl and diphenyl phthalate, and benzyl butyl phthalate. Among the succinates, it is preferably selected from the following formula (I): -10 200831586 〇 R3 IIΗ, # O' wherein Ri and R2 are Η ten c/〇, Η II Ο

Ri or a straight or branched alkyl, alkenyl, arylalkyl or alkylaryl group of different Ci-Cu optionally containing halogen or C1 in which the heterologous R6 groups are the same or different from each other -C20

a compound, an alkenyl group, a ring-based group, an aryl group, an aryl group or a yard comprising a hetero atom; and a R3 to R6 group bonded to the same carbon to form a ring; and the condition is that when R3 to R5 are simultaneously selected from a group of 3 to 20 carbon atoms, a branched chain, a dioxacycloalkyl group, an aryl group, an arylalkyl group or an alkylaryl group or a formula (II): I are the same as each other, a cycloalkyl group, an aromatic F Wherein to a straight or branched aryl group, when the atom may be hydrogen together, R6 is a or tertiary alkyl group,

4 0 Η〆 〆, R! H (3⁄4 wherein the 1^ and R2 groups are the same or different from each other, Cl- (the alkyl, alkenyl, cycloalkyl, aryl, aryl fluorenyl group of the chain optionally comprises The heteroatom, and the r3 group have at least 4 alkyl groups, optionally containing a hetero atom. The A 1 -alkyl compound is used as a co-catalyst, wherein the package name is A1-triethyl, A1-triisobutyl a linear or branched or alkylaryl group of A1-di-n-butyl 20, a straight chain 'A1-trialkyl group of any carbon atom, and a linear or cyclic group of 200831586 containing two or more aluminum atoms by hydrazine Or an A1-alkyl compound in which N atoms are bonded to each other, or an S04 or S03 group. The A1-alkyl component generally uses an Al/Ti ratio of from 1 to 1,000. The external donor (c) may be the same form or different a succinate of formula (I) or (II). Suitable external electron donor components comprise a hydrazine compound, an ether, such as a phthalate, a benzoate, a succinic acid having a different structure from formula I) or II) An amine, a heterocyclic compound, especially a 2,2,6,6-tetramethylpiperidone of the general formula (III), a ketone and a l,3-diether. Huan / 丨丨

Wherein R1 and R11 are the same or different and are (^ to C18 alkyl, C3 to C18 cycloalkyl or C7 to C18 aryl; wherein R111 and RIV are the same or different and are (^ to C4 alkyl) Or a carbon atom in the position 2 consists of a cyclic or polycyclic structure consisting of 5, 6 or 7 carbon atoms, and a 1,3-diether consisting of 2 or 3 unsaturations. A preferred electron donor compound can be used as an external donor comprising an aromatic quinone component comprising at least one Si-OR bond, wherein R is a hydrocarbyl group, as disclosed in the European Patent Application Nos. 3 6 1 493 and 728 769. A particularly preferred external donor compound is an anthracene compound of the formula Ra7Rb8Si(OR9)c wherein a and b are integers from 0 to 2, c is an integer from 1 to 3 and the sum of (a + b + c) is 4; , R 8 and R 9 are a hydrocarbon group of C! to C18, optionally containing a hetero atom. In a particularly preferred ruthenium compound, a is 1, b is 1, c is 2, and R 7 and R 8 are at least one selected from a branched alkyl group. An alkenyl group, an alkylene group, a cycloalkyl group or an aryl group having 3 to 10 carbon atoms, optionally containing a hetero atom, and R9 is an alkyl group of Ci-C1〇-12-200831586, particularly a methyl group. Examples of preferred ruthenium compounds are cyclomethoxyoxane, tert-butyltrimethoxydecane, third hexyltrimethoxycyclohexylmethyldimethoxydecane, 3,3,3-trifluoropropyl-2-ethylpiperidin [methoxy oxane, diphenyl dimethoxy decane, methyl tert-butyl dimethyl dicyclopentyl dimethoxy decane, 2-ethylpiperidinyl-2-tributyl dioxane, trifluoro -2-propyl)-methyldimethoxydecane and (1,1,1-propyl)-2-ethylpiperidinyldimethoxydecane. Further, it is preferred that c is 3 and R8 is a branch. An alkyl group or a cycloalkyl group of an anthracene compound, optionally an atom, and R9 is a methyl group. Particularly preferably, a specific component of the oxime component > butyl butyl hSi(OCH3) 2, (cyclohexyl) (methyl Si(OCH3)2, Si(〇CH3)2 and (cyclopentyl)2Si(OCH3)2. Preferably, the electron donor compound (C) uses this amount to provide an aluminum component and the electron donor compound ( The molar ratio between C) is 500, more preferably 1 to 300, and particularly preferably 3 to 30. As explained above, the solid catalyst component contains the above-mentioned electric body, Ti, Mg, and halogen. In particular, the catalyst component comprises a Ti-halogen bond and is supported at Mg The above electron donor compound on the halide. The magnesium halide is preferably M g C 12 in the active form, and the patent document is known to use a stereospecific Ziegler-Natta type catalyst. Patent USP 4,298,718 and USP 4,495,338 is the use of a first compound such as a stereospecific Ziegler-Natta type catalyst. The patent teaches that in the activator of a catalyst for polymerizing olefins, it is used as an active form of a co-support. Magnesium dihalide characterized by X-ray, wherein the most hexyl trioxane, decyl-monopropane, methoxytrifluoro-2_a present in the spectrum of the inactive halide is 0, including The compound is (tris(phenyl) 2 to give 0.1 to the organic group to give at least one component of titanium to the ground from the support for the support from the support of the 'line spectrum: strong diffraction-13-200831586. The line is weakened in strength, and It is replaced by a halogen with a maximum intensity and a fine distribution at a lower angle relative to a stronger line. Preferably, the titanium compound is TiCl4 and 11 (:13, and further, a Ti-halo alkoxide of the formula Ti(OR)n_yXy, wherein n is a valence of titanium, y is a number between 1 and η, and X is a halogen And R is a hydrocarbon group having from 1 to 10 carbon atoms. The preparation of the solid catalyst component can be carried out according to several known and described prior art methods. According to a preferred method, the solid catalyst component can be reacted by Ti ( Manufactured as a titanium compound of OR)n_yXy, wherein η is the valence of titanium, y is a number between 1 and η, preferably TiCl4 having an adduct of magnesium chloride derived from the formula MgCl2 · pROH, wherein p is 0.1 and The number between 6 is preferably 2 to 3.5, and R is a hydrocarbon group having 1 to 18 carbon atoms. It is operated under stirring in the presence of an inert hydrocarbon which is immiscible with the adduct, and is added. The melting temperature of the substance (100 to 130 ° C) can be suitably prepared into a spherical shape by mixing an alcohol and magnesium chloride. Thereafter, in the form of spherical particles, the emulsion is rapidly quenched, thereby causing an adduct. Curing. An example of the preparation of a globular adduct according to this procedure is described in USP 4,399,054 and USP 4,469,648. The resulting adduct can be directly reacted with the Ti compound, or first subjected to thermal control to dealcoholate (80 to 130 ° C) to obtain an adduct, and the amount of the alcoholic mole of the adduct is usually less than 3, Preferably, it is between 1 and 2.5. The reaction with the Ti compound can be carried out by suspending the adduct (dealcoholation or maintenance) in cold TiCl4 (usually 〇 ° C); the mixture is heated to 80 to 130 °C and maintaining this temperature for 0.5 to 2 hours. One or two -14-200831586 times and Tic 14 treatment can be carried out. The electron donor compound can be added during the treatment with TiCl4. Regardless of the preparation method used, the electron donor compound The final amount is preferably such that the molar ratio with respect to MgCl2 is from 0.01 to 1, more preferably from 0.05 to 0.5. The catalyst is precontacted with a small amount of olefin (prepolymerization) to maintain catalyst suspension in a hydrocarbon solution at a polymerization temperature of room temperature. To 60 ° C, the amount of polymer produced is 〇 5 to 3 times the weight of the catalyst. The amount of polymer which is operated in a liquid monomer and in this case is 1000 times that of the catalyst is obtained by using the above catalyst. a polyolefin composition in the form of spherical particles having The average diameter is from 250 to 700 μm, the fluidity is less than 30 seconds and the bulk density (tight) is greater than 0.4 g/ml. The polymerization stage may occur in the liquid phase, in the gas phase or in the liquid-gas phase. The polymerization of the polymer component 1) (for example, using liquid propylene as a diluent) is carried out in a liquid monomer, and the copolymerization phase of the elastomeric copolymer component 2) is carried out in the gas phase. Alternatively, all successive polymerization stages are carried out in the gas phase. The reaction temperature in the polymerization stage in which the polymer component 1) and the elastomeric copolymer component 2) are prepared may be the same or different, preferably 40 to 100 ° C, and more preferably, the reaction temperature of the polymer component 1) is prepared. The temperature ranges from 50 to 80 ° C ' and the polymer component 2) is prepared to a temperature of 70 to 100 ° C. If the preparation of polymer component 1) is carried out in a liquid monomer, the pressure in the polymerization stage is equivalent to the vapor pressure of liquid propylene at the operating temperature used, and can be inerted by using a small amount of feed to the catalyst mixture. The pressure of the component 1) is adjusted by the vapor pressure of the diluent, by overpressure of any monomer, and by using hydrogen as a molecular weight regulator. 200831586 If carried out in the liquid phase, the polymerization pressure is preferably in the range of from 3 3 to 4 3 bar, and in the gas phase, from 5 to 30 bar. The residence time of each stage depends on the desired ratio between polymer components 1) and 2) and typically ranges from 15 minutes to 8 hours. Conventional molecular weight regulators known in the art can be used, such as chain transfer agents (e.g., gamma hydrogen or ZnEt2). The composition of the present invention can be obtained by separately preparing the components 1) and 2) by operating in the same catalyst and essentially the same polymerization conditions as described above (except that not all of the continuous polymerization methods are carried out, but The component is prepared in a separate polymerization step, and the component is mechanically bent in a molten or softened state. Conventional mixing equipment such as screw extruders, in particular, can be used with twin screw extruders. The compositions of the present invention may also comprise the use of additives generally found in the art, such as antioxidants, light stabilizers, heat stabilizers, nucleating agents, colorants and tanning agents. In particular, the addition of nucleating agents provides significant improvements in important physico-mechanical properties such as flexural modulus, heat distortion temperature (HDT), ratio of tensile strength, and transparency. Typical examples of nucleating agents are sodium benzoate, talc and 1,3- and 2,4-dibenzyl sorbitol. With respect to the total weight, the amount of the nucleating agent to be added to the composition of the present invention is preferably in the range of 0.01 to 2% by weight, more preferably 0.05 to 1% by weight. The addition of inorganic materials such as talc, calcium carbonate and inorganic fibers also contributes to improved mechanical properties such as flexural modulus and HDT. The following specific examples are given to illustrate the invention but not to limit it. -16- 200831586 [Embodiment] Example 1 - 2 In a factory which was continuously operated according to the mixed liquid-gas polymerization technique, samples were subjected to the conditions described in Table 1. The polymerization is carried out in the presence of a catalyst system in which a device equipped with two reactors is present, and the product is immediately transferred from one reactor to the other. Preparation of Solid Catalyst Component A Ziegler-Natta type catalyst was prepared according to Example 5 of the European Patent E P 7 2 8 7 6 9th, 4th to 5th. Triethylaluminum (TEAL) was used as the co-catalyst and dicyclopentyldimethoxydecane as the external donor, and the weight percentage thereof is shown in Table 1. Catalyst system and prepolymerization treatment The above solid catalyst component was used as an outer-electron-donating component at 12 ° C for 24 minutes with triethylaluminum (TEAL) and dicyclopentyldimethoxydecane (DCPMS). Table 1 details the weight ratio between TEAL and solid catalyst components and the weight ratio between TEAL and DCPMS. Next, the catalyst system is subjected to prepolymerization by maintaining the catalyst system in 2 (TC liquid propylene for about 5 minutes) before introducing the catalyst system into the first polymerization reactor. The reactor unit continuously treats the polymerization operation, and the product is immediately transferred from one reactor to the other. The first reactor is a liquid phase reactor, and the second reaction is a fluidized bed gas phase reactor. The reactor prepared polymer component 1) while preparing the poly 1 200831586 component 2) in the second reactor. The temperature and pressure of all processes in the reaction are maintained constant. Hydrogen is used as a molecular weight regulator. The gas phase (propylene, ethylene and hydrogen) was continuously analyzed via gas phase analysis. The extremely dry powder was discharged at the end of the operation in a stream of nitrogen. The relevant data for the xylene solubility and comonomer content of the final polymer composition are reported in Tables 1 and 2, and measurements were made on the stabilized polymer obtained when needed. Next, polymer particles were introduced into the extruder, which was mixed with 500 mg of Irganox B 215 (composed of 1 part of Irganox 1010 and 2 parts of Irgafos 168) and 500 ppm of calcium stearate. The aforementioned irganox loio is neopentyl sulphate 3-(3,5-di-t-butyl-4-hydrocarbon phenyl) propionate, and Irgafos 168 is ginseng (2,4-di-third butyl) Phenyl phenyl) phosphites, all marketed by Giba-Geigy. In Example lb, a nucleated composition was obtained by treating with calcium stearate and 900 ppm sodium benzoate. The polymer particles were extruded under nitrogen in a twin screw extruder at a rotation speed of 25 rpm and a melting temperature of 200 to 25 °C. Data relating to the physico-mechanical properties of the final polymer composition are reported in Table 2 'measured on the polymer so extruded to obtain relevant data. The data obtained by using the following test methods are shown in the table. - Feed gas grass g rate is determined by gas chromatography. The ethylene and 1-butene content of the compound was determined by IR spectroscopy. -18- 200831586 - Melt flow rate (MFR) According to ASTM D 1 23 8 and condition L (MFR "L, 'measured) - Dimethane soluble and insoluble fractions are determined as follows. 2.5 g of polymer and 25 0 ml The methane is introduced into a glass dosing bottle equipped with a cooler and a magnetic stirrer. The temperature rises to the boiling point of the solvent within 30 minutes. Then, the obtained transparent liquid is further maintained at reflux for 30 minutes and then stirred. The vial was allowed to stand at 1 ° C for 10 to 15 minutes and allowed to stand in a constant temperature water bath at ® 25 ° C for 30 minutes. The solid formed was filtered on a fast filter paper. 10 〇 m 1 The filtrate was poured onto a pre-weighed aluminum vessel which had been heated on a hot plate in a stream of nitrogen to remove the solvent by evaporation. The vessel was then maintained at 80 ° C in vacuum until constant weight was obtained. Calculate the weight percentage of soluble polymer in dimethane at room temperature - Intrinsic viscosity Π. V.) Determined in tetrahydronaphthalene at 135 ° C. - Flexural modulus ^ Determined according to IS Ο 1 7 8 - Ehrlich's impact strength (marked) Determined according to IS Ο 1 8 0 /1 A. - Plate sample It is used to measure D/B board and stress-resistant whitening, and has a size of 1 27 x 1 27x 1.5mm prepared as follows. Negri BossiTM (NB90) type with injection pressure of 90 tons. The model is a rectangular plate. ( 1 27x 1 27χ1. 5 mm) 19, 200831586 The main program parameters are recorded as follows: Back pressure (bar): 2 0 Injection time (s): 3 Maximum injection pressure (MPa): 14 Injection hydraulic pressure (MPa): 6 -3 First pressurizing hydraulic pressure (MPa): 4 soil 2 First pressurizing time (s): 3 Second pressurizing hydraulic pressure (MPa): 3±2 Second pressurizing time (s): 7 Cooling time (s ) : 20 Molding temperature (°C ) : 60 Melting temperature between 220 and 2 80 ° C. Thickness 1 is prepared by injection molding at 1 second injection time, temperature 2 30 ° C, and molding temperature 40 °C. Mm plate to measure haze. The injection press is BattenfeldTM BA 503 CD type, with two molds with a closing force of 50 tons inserted (each piece is 5 5 x 6 0 XI mm). Preparation of cast film samples By using a single-spiral Colin extruder (helix length/diameter ratio: 30) at a film stretching speed of 7 m/min and a melting temperature of 210 to 260 °C, Each of the polymer compositions was pressed to prepare a film thickness of 50 μm. The ruthenium film was prepared by OTR measurement at 230 ° C, and the polymer composition was extruded on a CARVER machine to obtain a plate having a thickness of 1 mm and 60 x 60 mm, and then, At an oven temperature of 1 50 ° C, a BOPP film thickness of 30 μm was obtained using TM-Long mechanical stretching -20-200831586 having a biaxial stretching ratio of 6 x 6 in. The ductility/brittle transfer temperature (D/B) was determined according to the following method. Biaxial impact resistance was determined by the impact of an automated computerized hammer. A circular test sample was obtained from a plate prepared as described above by a circular hand punch (diameter: 38 mm). It was at 23 ° C, 50 RH for at least 12 hours, and was placed in a constant temperature bath for 1 hour at the test temperature. The force-time curve is detected during the impact of a hammer (5.3 kg, 1.27 cm hemispherical ^ punch) on a circular sample placed on the annular support. The CEAST 6758/000 model was used. The D/B transfer temperature means the temperature at which 50% of the samples produced brittle fracture during the impact test. The stress-anti-whitening anti-whitening system was measured at room temperature (about 23 ° C), and the polymer small disc (made from the plate as described above, diameter 38) was measured by the impact of darts falling from different heights. Mm, thickness 1.5mm). The dart has a diameter of 1.27 mm and a weight of 2 63 g. ® The diameter of the white area (average 値 of 10 samples tested from each drop height) indicates stress-anti-whitening. Table 2 records and details both the height and width (diameter) of the whitened area. Longitudinal and transverse heat shrinkage has a rectangular test specimen of size 1 0 0 X 2 0 0 X 2 · 5 mm, which is produced by using "Sandretto Serie Sette 190" (where 190 is the closing force of 190 gantry) Formed to make. The main processing parameters are detailed as follows: -21 - 200831586 - Back pressure: lObar - injection time + retention time: 30 sec - total cycle time: 55 sec

- Molding temperature '· 40°C

- Melting temperature: 2 5 0 °C The size of the test sample was measured using a 3D measuring system with a "Mi cr oval 3D". The shrinkage is the difference between the initial sample size after injection and the size after 48 hours at 23 °C and is expressed as a percentage of the initial sample. Longitudinal contraction measures its contraction in the direction of injection flow; transverse contraction measures its contraction across the direction of injection flow. The haze on the plate was measured according to the method described below. The panels were prepared as described above under conditions of 12 to 48 hours, relative humidity of 50 ± 5%, and temperature of 23 ± 1 °C. The instrument used for the test was a Gardner luminometer equipped with a G.E. 1209 light source and a color filter C with a smog meter UX-10. The instrument is calibrated by measuring no sample (〇% haze) and measuring the intercepting beam (100% haze). The principles of measurement and calculation are provided in accordance with standard ASTM-D 1 003. Haze measurements were made on 5 panels. The gloss on the plate was extruded into 10 rectangular samples (5 5 χ 60 X 1 mm) by using an injection press Battenfeld BA5 00CD, which was operated under the following conditions: Spiral rotation speed: 120 rpm Back pressure: lObar _ 22 · 200831586

Molding temperature · 40 °C

Melting temperature: 2 60 °C Injection time: 3 sec First retention time: 5 sec Second retention time: 5 sec Cooling time (after the second retention time): l〇sec During the above indicated time, the injection pressure should be Enough and fully expand the model. The incident angle is 60 by the gloss meter'. The optical fraction is measured by the surface reflection of the sample. The enthalpy described in Table 2 indicates the average gloss 値 of 1 α samples of each of the polymers tested. The gloss meter used sets the angle of incidence to 60. Zehntner type ZGM1020 or 1022. Measured according to the measurement guidelines provided in the standard ASTM D2457. A sample with a known gloss 使用 is used for device calibration. The haze on the film was measured on a 50 μm thick film of the test composition and prepared as described above. A portion cut from the central portion of the film into a 50 x 50 m portion was measured thereon. The instrument used for the test was a Gardner luminometer equipped with a g.E. 1209 light source and a filter C with a smog meter UX-10. The measurement of the instrument and the measurement of the occlusion beam (1 〇 〇 % haze) were performed as the calibration of the instrument. The gloss on the film was measured on the sample as smog. The instrument used for the test is a model for incident testing 1020 -23- 200831586

Zehutner photometer. By at an incident angle of 60. A blank glass with a standard gloss of 96.2%; and an incident angle of 45. Measurements were made with blank glass with a standard gloss of 5 5.4%. - Hydrogen transport (OTR) Measured at 23 ° C, relative humidity (RH) of 0% and 100%, in Mocon OX-TRAN 2/61 unit (commercially available from the company Moc on). Comparative Example 1 c Details the final properties of the composition of Example 3 of International Application WO 04/003073, the purpose of which is to be compared. According to the composition of the present invention having a higher stiffness (higher flexural modulus), there is a rare balance between impact and optical properties, and even in the non-nucleated form of Example 1 a is thermal stability. Comparative Example 2c The final properties of the propylene heterophasic copolymer manufactured by Basell under the trade name Moplen 2000 HEXP are detailed in Table 2, the purpose of which is to compare. Moplen 2 000 HEXP is a heterophasic copolymer formed by a crystalline propylene polymer matrix and an ethylene-propylene rubber component (EPR). Comparative Example 3 c Table 2 also details the final properties of the blend comprising: 40% by weight of a commercially available propylene heterophasic copolymer with about 25 % of a crystalline propylene polymer matrix and about 7 It consists of 5% ethylene/propylene rubber composition (EPR). The crystalline propylene homopolymer, manufactured by Basell under the trade name Moplen HP522H, is 60% by weight. The example illustrates the use of a heterogeneous composition obtained by mixing a propylene polymer in the film of -24-200831586, which comprises the ethylene-propylene rubber component ratio of the present invention compared with the ethylene-α-olefin rubber component (2), not provided The equilibrium nature of the valuable enthalpy of the composition according to the invention.

-25- 200831586 Table 1 polymerization method

Example, 1 2 TEAL / solid catalyst component weight ratio 20 12 TEAL / DCPMS Mohr ratio 10 8 1st liquid phase reactor: propylene homopolymer matrix polymerization temperature °c 67 70 pressure M pa 3 8 39 residence time min 3 9 6 1 H2 feed mol ppm 4 15 0 9 10 MFG “L” g /1 0 min 34 2 fraction soluble in xylene wt % 1.4 1.7 decomposition wt % 63 6 7 first gas phase reactor - ethylene Butene-1 copolymer rubber polymerization temperature °C 85 8 5 Pressure bar 2 0 18 Residence time min 47 23 h2/c2" Mo ratio 0.309 0.258 C4-/(C4- + C2·) Mo ratio 0.607 0.503 fraction Wt % 37 33 Butene-1 wt % in rubber 26 26 Fractions soluble in xylene wt % 23.4 22.9 Note: H2 feed = calculated relative to propylene molar flow, C plant = ethylene; c3_ Dipropylene; c4_ = butene-1 -26 - 200831586 Table 2 Examples and Comparative Example 1 2 1 c 2c 3c la lb (nucleation) MFR "L" g / 1 0 min 15 16 3.3 19.4 18 3 soluble in two The fraction of toluene wt % 23.4 22.9 22.6 - 20 The fraction of soluble xylene is IV· dl/g 1.4 1 1.23 1 .09 - 1.9 Ethylene content wt % 27.7 24.3 25.4 7 -1 content wt % 9.6 8.5 8.0 flexural modulus MPa 8 16 995 775 760 997 730 anti-Ehrlich impact 2 3 °C KJ/m2 12.2 40.4 42.2 37.9 17.5 34 o°c KJ/m2 4.8 16.8 23.4 12.0 7.7 -2 0°C KJ/m2 4.0 6.2 7.9 8.8 3 . 1 k D/B transfer temperature °C < -50 < -50 -50 -50 < -50 Anti-whitening: white due to falling of the column from a height Area radius 7 6 cm mmx 1 0 120 130 190 30 cm mm x 1 0 90 9 0 170 2 0cm mm x 1 0 80 70 140 10cm mmx 1 0 50 60 110 5cm mm x 1 0 10 20 - - 90 Shrinkage (portrait % 0.67 0.6 1 丨1.24 -27 - 200831586 Shrinkage (lateral) % 0.80 0.90 1 .40 Haze of the board (1 Π1 m ) % 48 60 28 23.7 >90 53.2 Gloss at 60° plate (1mm) % 95 92 106 - 52 9 1.8 Haze of cast film (50 μm ) % - - 8 - - 13 Gloss of film cast at 45 ° (50μπι) % - - 62 - - 3 9.2 1 Double oriented film Oxygen transfer ratio (thickness 30 μm) cc/m2/ 曰- - 493 9 - 3 8 17

-28-

Claims (1)

200831586 X. Patent application scope: 1 · An olefin composition comprising (relative to the sum of components i) and 2), expressed as a percentage by weight): 1) 5 5 - 80% of propylene homopolymer or copolymerization The copolymer contains up to 5% by weight of ethylene and/or C4-C1G alpha-olefin; 2) 20-45% of ethylene with one or more (:: 4-(:1()) olefins Copolymer 'The copolymer contains 10 to 40% of the α-olefin of the c4_Cl(); the composition has an MFR 値 (230 ° C, 2.16 kg) up to 20 g/l 〇 min, and the total ethylene content is 20% or Above, the total content of the α-olefin of c4-C1G is 4.5% or more, and the ratio of the total ethylene content to the total content of the 〇1-olefin of (:4-^() is 2·3 or more, at room temperature The total fraction soluble in xylene is 18 wt% or more, and the flexural modulus of the composition for the reaction grade is more than 700 Μ P a 〇 2 · The olefin composition as in claim 1 The intrinsic viscosity of the fraction soluble in xylene at room temperature is 2d Ι / g or less. 3 · The olefin composition of claim 1 wherein the flexural modulus is greater than 770 MPa. 4. The olefin composition of claim 1, wherein the copolymer of ethylene and one or more C 4 - C 〇 α-olefins is from 25 to 45 wt% of the total composition. The olefin composition of the first aspect of the patent, which has ductility/brittleness, has a transfer temperature of equal to or less than -3 5 ° C. 6. The olefin composition of claim 1 is included (relative to ingredient 1) And the sum of 2), expressed as a percentage by weight): -29- 200831586 1) 55-80% of a propylene homopolymer or copolymer containing up to 15% ethylene and/or C 4 - C ! The α-olefin' and having an MFR 値 of 15 g/l 〇 min or more; and 2) 2 0 - 4 5 % of ethylene and a copolymer having one or more C 4 - C 〇 α - olefins, the copolymer The composition contains 15 to 40% of the C 4 -C i α α-olefin; the composition has an MFR 10 (23 (TC, 2.1 6 kg) from 10 to 20 g/10 min, and the total ethylene content is 2 0 % or more, the ratio of the total content of α-olefins of C 4 -C i G is 6% or more, and the ratio of the total content of ethylene to the total content of C4-C1Ga-olefins is 2.3 or more, in the room The total fraction soluble in xylene is 18 wt% or higher, and the flexural modulus of the composition for the reaction grade is greater than 700 MPa. 7. The olefin composition according to claim 1 of the patent scope, which includes ( Relative to the sum of components 1) and 2), expressed as a percentage by weight: 1) 5 5 - 80% of a propylene homopolymer or copolymer containing up to 15% higher ethylene and/or C4-C1G Α-olefin; and 2) 20-45% of ethylene with a copolymer of one or more (: 4_(:1()〇1_olefins), the copolymer containing 15 to 40% of the (:4-( : 1 () 〇 1-olefin; the composition has a MFR 至 (230 ° C, 2.16 kg) up to l〇g / l 〇 min, total ethylene content of 20% or more, c4_Cl (> a olefin The total content of the total content of ethylene is 2.6 or more, and the ratio of the total content of ethylene to the total content of C4-C1Ga-olefin is 2.3 or more. The total fraction of soluble xylene at room temperature is 18% by weight or more, and the reaction is The composition of the grade has a flexural modulus of greater than 700 MPa. 8. A method of producing an olefin composition as claimed in claim 1 by sequential polymerization, which is carried out in at least two successive polymerization stages, A -30-200831586 and each of the subsequent polymerization stages described above The presence of polymeric material formed in the immediately preceding polymerization stage proceeds. An injection molded article comprising the polyolefin composition as claimed in claim 1 or 6. A film comprising a polyolefin composition as claimed in claim 1 or 7. 200831586 VII. Designation of representative representatives: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: Μ . y ν,, 8. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: