KR820001965B1 - Physically blended propylene polyme rcomposition - Google Patents

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Description

Physically Blended Propylene Polymer Compositions

The present invention relates to physically mixed propylene polymer compositions having excellent properties such as impact strength, hardness, gloss and high uniformity upon mixing and high dispersion of components in the resulting polymer composition.

More specifically, the present invention provides a propylene / ethylene random copolymer 1 comprising (A) 100 parts by weight of crystalline polypropylene containing 0 to 10 mol% of ethylene and / or other α-olefins, and (B) 30 to 85 mol% of propylene. To 30 parts by weight (this copolymer contains 0 to 10 mol% of diene components, (i) having a micro-isotaxy of at least 0.8 and (ii) 0 to 10% by weight of boiling n-cyclohexane insoluble), ( C) 0 to 30 parts by weight of polyethylene containing 0 to 15 mol% of α-olefins, and relates to a propylene polymer composition in which the above-mentioned components (A) and (B) are mixed with each other by a physical method.

Although crystalline polypropylenes prepared using stereoregular catalysts have excellent hardness and thermal stability, they have drawbacks of low impact strength, especially at low temperatures, which limit their use.

In order to overcome this drawback, a method of producing a polymer composition in which a polypropylene is mixed with a polyethylene and / or ethylene / propylene copolymer and physically mixed is proposed (for example, Japanese Patent Publication No. 7008/1960, US). German Patent No. 1,694,914 corresponding to Japanese Patent Publication No. 7345/1966 and Japanese Patent Publication No. 23416/1970. What can be done with a chemically mixed polymer composition obtained by chemical means multi-stage polymerization with a physically mixed polymer composition obtained by physically mixing means which initially produces different polymers or copolymers and then physically mixes them Likewise, it is difficult to obtain a high degree of uniformity upon mixing, and a high degree of dispersion of various components in the resulting polymer composition.

In addition, the physically mixed polymer composition as described above can not avoid the accidental degradation of the desired properties of the polypropylene itself, even slightly improving the impact resistance of the resulting polymer composition. In particular, it is difficult to have a suitable balance between high impact strength and high hardness of a conventionally physically mixed polymer composition. The polymer composition added and physically mixed has a difficulty that the gloss is remarkably insufficient compared with that of polypropylene. In addition, conventionally physically mixed polymer compositions have not used a carrier supported titanium catalyst which also contains donors such as magnesium, halogen and titanium, suitably organic acid esters.

In order to solve the shortcomings of the physically mixed polymer composition which is difficult to obtain a homogeneous mixture and difficult to obtain a suitable balance between high impact strength and high hardness, it is possible to prepare a polymer composition which is chemically mixed by a multistage polymerization method. There were two suggestions.

A first proposal of chemically blended polymer compositions is described in Japanese Patent Publication No. 2061 / l969, in which a polymer of propylene or propylene / ethylene copolymer is prepared and then a propylene-rich propylene / ethylene copolymer And a stereoregular catalyst comprising (a) a titanium tetrachloride composition obtained by reducing TiCl ₄ to metallic aluminum and (b) an organoaluminum compound. A polymer composition is produced that has improved impact strength at low temperatures. In order to further refine this process, another proposal was made later (see Japanese Patent Publication No. 24,593 / 1974), in which the polymer composition improved from the composition obtained in the first proposal using the same catalyst as the first proposal. First to produce polypropylene, followed by ethylene-rich ethylene / propylene copolymer, followed by a high ethylene / propylene copolymer. A third proposal, similar to the second proposal, was made (see Japanese Patent Publication No. 30264/1974), and in this method, the same catalyst as in the first and second proposals was used, initially using polypropylene in the presence of a chain transfer agent. And ethylene-rich ethylene / propylene copolymers were then prepared, and finally polyethylene or ethylene / propylene copolymers with high ethylene content. A fourth proposal, similar to the third proposal, is known or known (see DT-PS 2,417,093).

None of the first to fourth proposals of the chemically blended polymer composition utilized a carrier supported titanium catalyst component.

Further proposals for preparing chemically mixed polymer compositions are described in DT-OS 2, 700,774 (corresponding to US Pat. No. 4,128,606) and DT-OS 2,801,217. These proposals avoid the physical mixing of the polymer composition and include (a) a carrier-supported titanium catalyst component containing together magnesium, halogen and titanium, suitably organic acid esters, on the surface of the carrier and (b) an organoaluminum compound To chemically mix the polymer composition by three step polymerization.

These chemically blended polymer compositions have high hardness and impact strength, good balance, and high degree of uniformity that are difficult to obtain in conventional physically blended polymer compositions compared to the physically blended polymer compositions described above. Has the advantage. However, chemically mixed polymer compositions have been found to have the following drawbacks.

In preparing a chemically mixed polymer composition, after the completion of the first stage of the multistage polymerization, the reactive product containing the desired polymer composition is contained in the polymerization solvent, and then the solid polymer composition is separated from the reaction product, It collects and isolates and manufactures a desired polymer composition. In this case, the propylene / ethylene random copolymer (B) specified in the present invention is dissolved in a non-negligible amount of polymerization solvent, and after the above separation and recovery, a part of the random copolymer is dissolved in a liquid phase. It remains and has the drawback of losing the random copolymer content in the final product.

In addition, the multistage reactions by the multistage polymerization stage have drawbacks that are complex to control. This control method, even if done carefully to obtain the final product of the predetermined composition, at least the deviation of the reaction conditions occurring in each step increases the deviation of the predetermined composition. Because of these phenomena affecting each other, and due to the partial loss of the random copolymer, it is difficult to obtain a final product of a predetermined composition with high reproducibility.

When the copolymer is prepared in a large amount in order to obtain a final composition having a relatively high content of copolymer in the propylene / ethylene random copolymer preparation step, the viscosity of the reaction mixture increases, making it difficult to perform the multistage polymerization mildly. You will have a difficult issue. Chemically mixed resulting polymer compositions often have the disadvantage of poor gloss.

The inventors have addressed the above drawbacks of chemically blended polymer compositions, and at the same time, conventionally physically blended polymer compositions such as difficulty of balance, lack of gloss and lack of uniformity between high impact strength and high hardness. As a result of intensive studies to prepare a physically blended polymer composition that solves the drawbacks of the polymer, physically obtained by mixing crystalline polypropylene with a specific amount of propylene / ethylene random copolymer having a specific range of propylene content by physical means The blended propylene polymer composition meets the following two characteristics: specific micro-isotaxy and specific content of boiling n-cyclohexane insolubles, and also optionally contain a maximum specific amount of polyethylene. Physically mixing with blended polymer composition It is a composition that has the advantages of both solving the crystals of polymerized polymer compositions and having not been able to meet them at the same time.

It is therefore an object of the present invention to provide a physically mixed propylene polymer composition which consists of crystalline polypropylene and a propylene / ethylene random copolymer and which optionally contains polyethylene and which has significantly improved properties.

The foregoing and other numerous objects and advantages of the present invention are described in detail below.

In the physically mixed propylene polymer composition of the present invention, the crystalline polypropylene (A) contains 0-10 mol% of ethylene and / or other α-olefins, and α having 4 to 10 carbon atoms as another α-olefin. -Olefins such as 1-butene, 1-hexane, 4-methylpentene-1,3-methylpentene-1, or 1-octene can be used.

The above-mentioned crystalline polypropylene (A) has an iso turbidity of 93% by weight, more preferably 90% by weight or more of boiling n-heptane insoluble content in the propylene copolymer, and has a propylene with ethylene and / or other α-olefins. For copolymers it is suitable to have an iso turbidity of at least 75% by weight, suitably 85% by weight. Such crystalline polypropylenes are commercially available and can be used in the original known processes, for example in the presence of a stereoregular catalyst comprising a titanium catalyst component containing an electron donor such as an ester, ether or alcohol and an organometallic compound catalyst component. It may be prepared by polymerizing or copolymerizing propylene with about 10 mol% of ethylene and / or other olefins.

As the organometallic compound described above, an organometallic compound of Group I to III metals of the Mandele Jeff Periodic Table (short period), preferably an organoaluminum compound can be used. As the above-mentioned titanium catalyst component, titanium trihalide such as titanium trichloride, suitably titanium trichloride obtained by reducing titanium tetrachloride and titanium tetrahalide with a metal aluminum, hydrogen or organoaluminum compound can be used. The resulting catalyst preferably contains a carrier-supported titanium catalyst component consisting of magnesium halogen and titanium and an organoaluminum compound on the surface of the carrier. The carrier supported catalyst component may be any one containing at least magnesium, halogen and titanium on the surface of the carrier, and treated with a donor and / or an active hydrogen-containing compound as necessary. Suitably the carrier supported catalyst component has a specific surface area of at least 100 m 2 / g. The carrier supported titanium catalyst component is suitably treated with a donor such as an organic carboxylic acid ester, in particular an aromatic carboxylic acid ester. In other words, it is convenient to use a carrier supported titanium catalyst component containing at least magnesium, halogen and titanium on the surface of the carrier and treated with an organic carboxylic acid ester, in particular an aromatic carboxylic acid ester.

Several proposals have been known regarding the preparation of such carrier supported titanium catalyst components (e.g., DT-PS 2, 153,520, DT-PS-2,230,672, DT-PS 2,230,728, DT-PS 2,2 30,752, DT). -PS 2,504,036, NL 75.10394, DT-PS 2,605,922 and Japanese Laid-Open Patent Publication Nos. 126590/1974, 20797/1976, 28189/1979, 57789/1976 and 15 1691/1977). Several production methods for producing a carrier supported titanium catalyst component containing at least magnesium, halogen and titanium on the surface of the carrier and treated with an organic carboxylic acid ester are described below.

(1) magnesium halides, preferably magnesium chloride or magnesium embrittlement and organic carboxylic acids, suitably aromatic carboxylic acid esters, are mechanically ground in the absence or presence of small amounts of inert liquid weights, silicone compounds or aluminum compounds; The milled product is reacted with titanium halide, suitably titanium chloride, and treated with or without organoaluminum compounds.

(2) reacting the organic and coalesced between magnesium and aluminum on an organic containing a halogen atom and an alkoxy group with an organic carboxylic acid ester, preferably an aromatic carboxylic acid ester, and reacting the reaction product with a titanium compound, preferably titanium tetrachloride React with

(3) The product obtained in (1) or (2) is reacted with an organic carboxylic acid ester, preferably an aromatic carboxylic acid ester, followed by a titanium compound, preferably titanium tetrachloride.

(4) The product obtained in (1) or (2) is reacted with an organic carboxylic acid ester, preferably an aromatic carboxylic acid ester, followed by a titanium compound, preferably titanium tetrachloride and an organoaluminum compound.

Titanium in the titanium composite prepared using titanium tetrachloride in the above (1), (2) and (3) is usually tetravalent. When titanium tetrachloride is used in the method (4), the titanium in the titanium complex is usually a mixture of tetravalent titanium and trivalent titanium, which can vary depending on the amount of organoaluminum compound to be reacted.

The organic carboxylic acid esters used in the above method are, for example, (1) aliphatic carboxylic acid esters and halogenated aliphatic carboxylic acid esters or (ii) aromatic carboxylic acid esters.

Commonly used aliphatic carboxylic acid esters or halogenated aliphatic carboxylic acid esters (i) are saturated or unsaturated aliphatic carboxylic acids or halogen substitutions thereof containing 1 to 8 carbon atoms, suitably 1 to 4 carbon atoms. Product, saturated or unsaturated aliphatic primary alcohol having 1 to 8 carbon atoms, suitably 1 to 4 carbon atoms, saturated or unsaturated alicyclic alcohol having 3 to 8 carbon atoms, suitably 5 or 6 carbon atoms , A phenol having 6 to 10 carbon atoms, suitably 6 to 8 carbon atoms, or an ester formed between an alicyclic or unsaturated primary alcohol having 3 to 10 carbon atoms.

Aromatic carboxylic acid esters (ii) which are commonly used are aromatic carboxylic acids having 7 to 12 carbon atoms, preferably 7 to 10 carbon atoms, 1 to 8 carbon atoms, and preferably 1 to 4 carbon atoms. Saturated or unsaturated aliphatic primary alcohols having 3 to 8 carbon atoms, suitably phenols having 6 to 8 carbon atoms, or having 1 to 4 carbon atoms bonded to alicyclic or aromatic rings having 3 to 10 carbon atoms Esters formed between aliphatic saturated or unsaturated primary alcohols.

Specific examples of the aliphatic carboxyl acid esters (i) include alkenyl esters and methyls of saturated fatty acids such as methyl formate, ethyl acetate, n-amyl acetate, 2-ethylhexyl acetate, n-butyl formate and ethyl butyrate allyl acetate. And primary alkyl esters of unsaturated fatty acids such as acrylate, methyl methacrylate or n-butyl crotonate.

Specific examples of the aromatic carboxylic acid ester (ii) include methylbenzoate, ethylbenzoate, n-propylbenzoate, n- or i-butylbenzoate, n- or i-amylbenzoate, n-hexylbenzoate, Toluic acid, such as alkyl ester of benzoic acid, such as n-octyl benzoate or 2-ethylhexyl benzoate, methyltoluate, ethyltoluate, n- or i-butyl toluate, or 2-ethylhexyl toluate Alkyl esters of aniseic acids, such as alkyl esters of methyl esters, methyl aniseates, ethyl aniseates or n-propyl aniseates, and methyl naphthoates, n-propyl naphthoates, n-butylnaphthoates or 2-ethylhexyl naphtho And primary alkyl esters of naphthoic acid such as ate.

Of these, aromatic carboxylic acid esters are suitable. Particularly suitable aromatic carboxylic acid esters are C of monocyclic aromatic carboxylic acids such as methylbenzoate, ethylbenzoate, methyl p-toluate, ethyl p-toluate, methyl p-anisate and ethyl p-anisate. _1-8 alkyl esters are mentioned.

Examples of the inert liquid diluent used in the above method include hydrocarbons, halogenated hydrocarbons, and halogenated carbon liquid at room temperature. Specific examples include aliphatic hydrocarbons such as n-pentane, iso-pentane, n-hexane, iso-hexane, n-heptane, n-octane, 2-ethylhexane, n-decane and serine, cyclopentane and cyclohexane. Alicyclic hydrocarbons, methyl cyclohexane, benzene, toluene, xylene, ethylbenzene, cumene, simen, mesitylene, pseudocumene and butylbenzene aromatic hydrocarbons such as methylene chloride, ethyl chloride, ethylene chloride, trichloroethylene, Halogenated hydrocarbons such as chlorobenzene, n-propyl chloride, iso-propyl chloride and chloroform, and halogenated carbon such as carbon tetrachloride and the like can be used.

Examples of the organoaluminum compound used in the above method include the general formula R ′ _3-m AlX _m where R ′ is a hydrogen atom or an alkyl or aryl group, X is a halogen atom, and m is an amount of 0 or 3 or less An integer), general formula R ' _3-n Al (OR) _n (wherein R is an alkyl or aryl group, R' is as defined above, n is a positive integer of 0 or greater and 3 or less) and general formula RAl And compounds of (OR) X (wherein R and X are as defined above). Specific examples include alkylaluminum halides such as trialkylaluminum, alkylaluminum dihalide, dialkylaluminum halides, alkylaluminum sesquihalides, alkylaluminum hydrides and alkylaluminum alkoxides. Specific examples include triethyl aluminum, diethyl aluminum hydride, tripropyl aluminum, tributyl aluminum, diethyl aluminum chloride, diethyl aluminum bromide, diethyl aluminum ethoxide, diethyl aluminum phenoxide, ethyl aluminum ethoxy chloride, ethyl Aluminum sesquichloride, diethyl aluminum ethoxide, ethyl aluminum diethoxide, etc. can be illustrated.

In the process of the present invention, it is carried out in the presence of the above-mentioned catalyst which consists of a carrier-supported titanium catalyst component containing at least magnesium, halogen and titanium and an organoaluminum compound on the surface of the reaction carrier to prepare the desired polymer composition.

Examples of the organoaluminum compound used to prepare this catalyst include trialkylaluminum, dialkylaluminum halides, alkylaluminum sesquihalides or alkylaluminum dihalides having 1 to 12 carbon atoms in alkyl groups. It is suitable to use trialkylaluminum. Examples of suitable organoaluminum compounds are (C ₂ H ₅ ) Al, (iC ₄ H ₉ ) ₃ Al, (nC ₄ H ₉ ) ₃ Al, [CH ₃ CH (CH ₃ ) CH ₂ CH ₂ CH ₃ ] ₃ Al, (C ₁₂ H ₂₅ ) ₃ Al and (C ₂ H ₅ ) ₂ AlOAl (C ₂ H ₅ ) ₂ .

Polymerization of crystalline polypropylene (A) containing 0 to 10 mol% of ethylene and / or other α-olefins is carried out in the presence of a stereocatalyst comprising a titanium catalyst component which may contain an electron donor and the organometallic compound catalyst component described above. I can do it. The polymerization can usually be carried out in the presence of a polymerization solvent or in the absence of a polymerization solvent. Examples of such a polymerization solvent may include pentane, hexane, heptane, kerosine and the like.

The polymerization can be carried out at room temperature to about 90 ° C., suitably at about 20 ° C. to about 80 ° C. and at atmospheric pressure to about 40 kg / cm 2 gauge pressure, suitably about 3 to about 15 kg / cm 2 gauge pressure.

The polymerization can be carried out in the presence of an organic carboxylic acid ester, preferably an aromatic carboxylic acid ester. The same ester as described above for the preparation of the carrier-supported titanium catalyst can be used as the organic carboxylic acid ester for this purpose. These esters increase the proportion of high-stereoregular polymers formed when the polymerization is carried out in the presence of hydrogen as a chain-transfer agent. The carrier-supported titanium catalyst component, the organometallic compound catalyst component, the organometallic compound catalyst component, suitably the organoaluminum compound catalyst component and the organic carboxylic acid ester may be introduced into the reaction zone and mixed in the desired order. The amount of free organic carboxyl acid ester to be used is, for example, about 1 mole or less, preferably about 0.01 to about 0.5 mole per aluminum atom of the organoaluminum compound in the catalyst.

Suitable concentrations of the catalyst are from about 0.01 to about 10 mmol / liter when the amount of the titanium catalyst component is calculated as titanium atoms, and the amount of the organoaluminum compound is from about 0.01 to about 30 mmol / liter, both of which It is based on volume. As the chain transition, hydrogen is most suitable. However, the use of chain transfer agents is not critical. The amount of hydrogen as the chain transfer agent is about 20 mol% based on the monomers supplied to the polymerization vessel.

In the present invention, 30 to 85 mol% of propylene, preferably 40 to 80 mol%, more preferably 50 to 80 mol% and optionally diene components such as ethylidene norbornene, dicyclopentadiene or 1.4-hexadiene It contains 0 to 10 mol%, and has two properties: (i) micro-isotaxy of at least 0.8, suitably at least 0.9, more suitably at least 0.9 and (ii) boiling n-cyclohexaneinsolubles A propylene / ethylene random copolymer (B) having 0 to 10% by weight, suitably 0 to 5% by weight, particularly suitably less than, 1 to 30 parts by weight per 100 parts by weight of crystalline polypropylene (A), Is used in an amount of 3 to 20 parts by weight.

When the amount of the propylene / ethylene random copolymer (B) (except the block or graft copolymer) is less than or equal to the above-described bottom limit, the resulting polymer composition is excellent in hardness but low in impact strength. If this amount is above the upper limit described above, the resulting polymer composition will have a high impact strength but low hardness.

If the propylene content of the above-mentioned random copolymer is too low compared to its specific range, the resulting polymer composition will have excellent impact strength and hardness, but will be weak in gloss, uneven in color, and have defects indicated by markings on the surface. . The use of the aforementioned random copolymers with greater amounts of propylene than a certain range results in polymer compositions with good hardness but low impact strength.

In the present invention, the propylene / ethylene random copolymer (B) satisfies two different properties (i) and (ii), while the combination of the two conditions described above, namely crystalline polypropylene (A) and its propylene content It is important to meet their mixing amount based. Failure to meet either of (i) and (ii) properties under the above bonding conditions results in a physically mixed polymer composition having excellent uniformity, a good balance between high hardness and high impact strength, and a satisfactory gloss. Hard to get

In the present invention, the microiso Turbidity of the propylene / ethylene random copolymer (B) means a value measured by the method described later.

Micro-Iso Turbidity

The 13c nuclear magnetic resonance spectrum of the propylene / ethylene random copolymer (B) is an indefinite indication due to the stereoregularity of methine carbon atoms of three or more consecutive propylene chain moieties present in the random copolymer (B) (isotactic structure, Syndiotactic structure, heterotactic structure). Subsequently, the micro-iso Turbidity was calculated by the following equation.

Here, iso, syndio and hetero represent the peak portions of the notice corresponding to the isotactic, syndiotactic and heterotactic structures, respectively.

In the present invention, the content of the boiling cyclohexane insolubles of the propylene / ethylene random copolymer (B) refers to the numerical value measured by the method described below.

Boiling Cyclohexaneinsoluble content

The fine particles of the random copolymer (B) each having about 1 mm × 1 mm × 1 mm and each having glass beads of about 1 mm × 1 mm × 1 mm are placed in a cylindrical glass filter (G ₃ ) and 14 at the boiling point of cyclohexane. Extracted into cyclohexane by Soxhleet's extractro for hours. In this case, the solvent was refluxed at a rate of once for 5 minutes. After extraction, the weights of the dissolved and insoluble portions were measured and the content of boiling cyclohexane insolubles was calculated from the results as weight percent.

The content of boiling n-heptane insoluble matter of the crystalline polypropylene (A) of the present invention is not glass beads, n-heptane instead of cyclohexane, cylindrical filter paper instead of cylindrical glass filter, and extraction is performed. A numerical value is indicated by the same method as described above except that it is carried out for 6 hours.

A propylene / ethylene random copolymer (B) having a specific propylene content and two properties (i) and (ii) used in the present invention can be prepared using a catalyst selected from known α-olefin polymerization or copolymerization catalysts. have. That is, the random copolymer (B) contains magnesium, halogen, titanium and electron donor, suitably organic carboxylic acid ester, and has a specific surface area (measured by the BET method) of about 100 m 2 / g, which is a suitable carrier-supported solid phase. The titanium catalyst component containing the titanium catalyst component, the electron donor and the organometallic compound catalyst component described above for the preparation of the crystalline polypropylene (A) may be prepared using a catalyst comprising an organoaluminum compound catalyst component selected from stereoregular catalysts. Can be. This catalyst is exemplified above and described, for example, in (1)-(4) in DT-PS 2.153.520 and in many other known literature.

For example, when using a catalyst containing a titanium catalyst component of the non-carrier-supported titanium trihalide (titanium chloride) type obtained by reducing titanium tetrahalide, such as titanium tetrachloride, with a metal aluminum, hydrogen, or organoaluminum compound, The propylene / ethylene random copolymer (B) has a boiling n-cyclohexane insoluble content of about 20% by weight or more, as in the characteristic value (ii), its composition is heterogeneous, and the random copolymer (B) is a crystalline polypropylene ( It is difficult to mix uniformly with A), and the resulting polymer composition has a disadvantage of a poor balance between high hardness and high impact strength and unsatisfactory gloss.

For example, when using an organoaluminum compound catalyst component which is a catalyst commonly used in the preparation of a vanadium catalyst component and a propylene / ethylene random copolymer, the resulting random copolymer is too small as in the case of the characteristic value (i), namely Typically it has a micro-iso Turbidity of 0.6 or less. Such a random copolymer also has a high hardness and impact strength of the resulting polymer composition because it is difficult to uniformly mix with the crystalline polypropylene (A), but has a disadvantage that the balance and gloss of the composition are not satisfactory.

The method for producing a propylene ethylene random copolymer using the specific catalyst described above is known per se and can be carried out under the same polymerization conditions as those exemplified for the production of crystalline polypropylene (A).

The propylene / ethylene random copolymer (B) of the present invention preferably has an intrinsic viscosity [η] of about 1 to 15, and preferably about 1.5 to 13.5, as measured in decalin at 135 ° C. The random copolymer (B) has a melting point of about 130 ° C. or less, suitably about 30 to about 120 ° C., a Shore hardness of 40 to 97, and suitably 50 to 90 as measured by different scanning calorimetry (DSC). Do.

The physically mixed propylene polymer of the present invention is, in addition to crystalline polyproppropylene (A) and propylene / ethylene random copolymer (B), 30 parts by weight of polyethylene containing α-olefin, 0 to 15 mol%, suitably Up to 15 parts by weight, for example, may contain 1 to 15 parts by weight. Examples of α-olefins other than ethylene which may contain up to 15 mole% are α-olefins having 3 to 10 carbon atoms, for example propylene, 1-butene, 4-methylpentene-1, 1-hexene, or 1- Octene can be mentioned. The method of manufacturing polyethylene which may contain alpha -olefins other than ethylene is well-known, This polyethylene can be marketed. The polyethylene may be any one produced by the high pressure method, the medium pressure method or the low pressure method. Suitable polyethylenes have a density of 0.90 to 0.98 g / cm 3, and particularly suitable are those having a density of 0.94 to 0.98 g / cm 3. The intrinsic viscosity of polyethylene measured in 135 degreeC decalin is 1.0-10, More preferably, it is 2.0-6.0.

When the amount of polyethylene (C) added is above the maximum amount described above, a polymer composition with improved impact strength but lacking hardness and gloss is obtained.

The physically mixed propylene polymer composition of the present invention also has a number of conventional additives. Examples of such additives are tetrakis [methylene- (3.5-di-tertbutyl-4-hydroxy) hydrocinnamate methane, tri (mono- or di-norylphenyl) phosphite, or 36-di-tert-butyl cresol Antioxidants such as 2, (2'-hydroxy-3'-tertbutyl-5'-methyl-phenyl) -5-chlorobenzotriazole, or bis (2.26.6-tetramethyl-4-piperidyl) Charging agents such as ultraviolet absorbers such as sebacate, calcium stearate or synthetic hydrotalcite, nucleating agents such as aluminum hydroxy-di-para-tert-butylbenzoate, or aluminum benzoate, and charging such as stearyl monoglycerides Inhibitors, flame retardants such as ethylenebis [tris- (2-cyanoethyl) -phosphonium bromide], ammonium polyphosphate, or antimony trioxide, isoindole is a colorant, quinacridone colorant, cyanine colorant, or carbon black Colorants such as talc, calcium carbonate, Fillers such as barium sulfate or mica can be used.

The amount of these additives may be appropriately selected, but for example, about 0.05 to about 0.8 wt% of an antioxidant, about 0.05 to about 0.5 wt% of an ultraviolet absorber, about 0.05 to about 0.5 wt% of a lubricant, about 0.05 to about 0.5 wt% of a nucleating agent, About 0.1 to about 0.8 wt% of an antistatic agent, about 5 to about 30 wt% of a flame retardant, about 0.3 to about 2 wt% of a colorant, or about 5 to about 50 wt% of a filler may be used. It is based on the total weight of A), (B) and (C).

Crystalline polypropylene (A), propylene / ethylene random copolymer (B) and polyethylene (C) and additives can be mixed by suitable means to prepare the physically mixed propylene polymer composition of the present invention.

Examples of such mixing means are described below.

In the present invention, component (A) and component (B) are physically mixed together. The component (C) may be chemically mixed with the component (A) in advance, and the component (C) is obtained by preparing the component (A) in a multistage polymerization system and then preparing the component (C) in the presence of the component (A). It is a chemically mixed mixture.

Alternatively, the separately synthesized components (B) and (C) can be first mixed together and then the mixture can be mixed with component (A) or mixed with component (A).

Mixing is, for example, each component is thoroughly stirred by a Henschel mixer followed by mixing with a single screw or double screw extruder and then pelletized.

)약 11∼약 17×10^-3kg/㎠ 및 광택도 약 50∼약 75x를 갖는 물리적으로 혼합시킨 프로필렌 중합체 조성물을 제조할 수 있다.Good balance between high impact strength and high hardness, expressed in satisfactory gloss and drop daart strength (FD) by the present invention, about 130 to about 200 kg / cm (0 ° C.), initial bending coefficient (

A physically mixed propylene polymer composition having about 11 to about 17 × 10 ⁻³ kg / cm 2 and gloss of about 50 to about 75 × can be prepared.

The present invention will be described in detail based on the following examples.

Example 1

Preparation of Carrier Supported Titanium Catalyst Component

30 g of commercially available anhydrous magnesium chloride, 7.5 ml of ethylbenzoate, and methyl polysiloxane (20 C.S at a viscosity of 25 DEG C) and 4.5 ml were contacted by a vibratory mill for 40 hours in the presence of nitrogen. 20 g of the resulting solid was suspended in 200 ml of TiCl ₄ and stirred at 80 ° C. for 2 hours. After the reaction was completed, the supernatant was decanted and the residue was washed with purified hexane. This method was repeated until no chlorine was detected in the supernatant nucleic acid.

The resulting titanium catalyst component contains 1.9 weight percent titanium and 65 weight percent chlorine, all of which are calculated as atoms. The titanium catalyst component was then polymerized as described below.

Polymerization of Polypropylene (A)

Titanium catalyst component synthesized as described above, calculated as 3 l / hr hexane dehydrated in a continuous polymerization vessel having a volume of 24 L, 5.9 mmol / hr triethylaluminum, 2.1 mmol / hr methyl p-toluate and titanium atoms 0.11 mmol / hr was fed continuously. Propylene was continuously supplied to the polymerization vessel to continuously polymerize propylene at a polymerization temperature of 70 ° C. at a pressure of about 9 kg / cm 2 for an average residence time of 3 hours. The melt index (MI) of the resulting polypropylene was controlled by supplying hydrogen. As a result, crystalline polypropylene (A) having the properties shown in Table 1 below was obtained.

Copolymerization of propylene and ethylene (B)

10 liters of hexane dehydrated and purified in a 24 liter continuous polymerization vessel, 4 mmol of triethyl aluminum, hr 1.33 mmol of ethylene acetate, and 0.045 mmol of hr titanium catalyst component obtained as calculated above as titanium atom Was charged continuously. Propylene and ethylene were continuously fed to the polymerizer to prepare a propylene-ethylene copolymer having the composition shown in Table 1. To continuously polymerize, the pressure maintained about 7 kg / cm 2 residence time at about 1 hour and polymerization temperature at 60 ° C. MI of the resulting copolymer was controlled by continuously feeding H ₂ . The resulting copolymer had a micro-isotaxy of 0.92 and a boiling cyclohexane insoluble content of 2.3 wt% by 13 C-NMR. Moreover, this copolymer showed melting | fusing point 40-70 degreeC by Shore A hardness 59 and DSC. Other properties of the copolymer are shown in Table 1 below.

Blend of Polypropylene and Propylene / Ethylene Copolymer

Crystalline polypropylene (A) and the propylene / ethylene copolymer obtained as described above were well stirred by a Henschel mixer and then pelletized with a mill at 230 ° C. The pellets were molded into 120 cm x 130 cm x 0.2 cm test pieces by a molding machine, and the properties of the test pieces were measured. Initial bending coefficient (FM) and gloss were measured by ASTM-D-790-66 and ASTM-D-523-62T, respectively. The falling daart strength (FD) was measured and the impact strength (kg / cm) was measured as follows. The mixed daart was dropped from a constant height on a test piece placed horizontally at 0 ° C. The drop test was repeated until the specimen was ruptured by varying the daart of the daart. The energy required to rupture half of a certain number of test pieces was measured, and the impact strength (kg / cm) of this test piece was measured from the results.

TABLE 1

Example 2

Polymerization of Crystalline Polypropylene and Polyethylene Mixtures (A ')

Two continuous polymerization vessels connected in series and having a capacity of 24 L and 8 L, respectively, were used in this polymerization. Crystalline polypropylene (boiling n-heptane insoluble content 94.2% by weight) in the first polymerization vessel was polymerized in the same manner as in Example 1, followed by polymerization of polyethylene in the second polymerization vessel to produce a chemical mixture of crystalline polypropylene and polyethylene (MI : 24.1, C ₂ ^μ content: 8.8 mol%) of the target compound. M1 of the obtained polymer was adjusted by adding hydrogen, and the amount of polyethylene to be polymerized was controlled by feeding ethylene.

The propylene ethylene copolymer obtained in the same manner as in Example 1 except that the physically mixed polymer composition was methyl p-toluate instead of the chemical mixture (A ') of polypropylene and polyethylene obtained above and ethyl benzoate ( B ') It was prepared in the same manner as in Example 1 using a micro-isotaxy 0.92, boiling cyclohexane insoluble content 1.8% by weight, Shore hardness A56, melting point 40 ~ 70 ℃ by DSC. Other properties of the polymer composition are shown in Table 2.

TABLE 2

Example 3

Copolymerization of Propylene and Ethylene

A autoclave with an internal volume of 30 L was charged with 20 L of purified hexane and 4 mmol of triethylaluminum, and the system was heated to 70 ° C. On the other hand, an ethylene / propylene mixed gas (C ^μ ₂ / C ₃ ^μ molar ratio: 40/60) was passed and the pressure of the system was maintained at 5 kg / 'cm 2 G, and the polymerization was calculated as titanium atom, which was obtained in Example 1 0.4 mmol of the titanium catalyst was added and carried out for 1 hour. After the polymerization was terminated, the pressure was reduced, and the polymer solution was poured into a large amount of methanol to precipitate the polymer. As a result, propylene-ethylene copolymer (B ^μ) to give a 4500g. The copolymer showed a viscosity [?] Of 2.98 and a C ₂ ^μ content of 42.5 mol%. The micro-isotaxy of the copolymer was 0.93 and its boiling cyclohexane insoluble content was 3.6% by weight.

Preparation of Polypropylene and Polyethylene Mixtures (A ^μ ) by Polymerization

The polymerization was carried out in the same manner as in Example 2 to obtain a chemical mixture (A ^μ ) having crystalline polypropylene (boiling n-heptane insoluble content 96.2%) and polyethylene having a content of MI 12.7 and C ₂ ^μ , and polyethylene.

The products (A ^μ ) and (B ^μ ) thus obtained were treated in the same manner as in Example 1 at a ratio of 100 / 11.1 to prepare a physically mixed polymer composition. The composition was measured in the same manner as in Example 1, and the composition showed an average FM of 13.9 10 ⁻³ kg / cm 2, FD (0 ° C.) 170 kg.cm, and glossiness 53.

Example 4

Copolymerization of Propylene and Ethylene

10 l / hr of hexane purified by dehydration in a 24-l continuous chamber polymerization vessel. 2 mmol / hr of tri-isobutylaluminum, 0.04 mmol / hr of the titanium catalyst obtained in Example 1 as calculated by titanium atom, and 0.15 mmol / hr of methyl p-toluate were continuously fed. The polymerization temperature was 60 deg. Propylene and ethylene were continuously fed (average pressure of 7 kg / cm 2 G) to obtain a propylene / ethylene copolymer (B) having 37 mol% ethylene content and [η] 3.10. In this case, no hydrogen was used. This copolymer (B) exhibited a melting point or transition point (Tm) of 40 to 70 ° C. by micro-isotaxy 0.91, boiling cyclohexaneinsoluble content 2.3 wt%, Shore A hardness 56 and DSC.

Preparation of Polypropylene and Polyethylene Mixtures (A) by Polymerization

The polymerization was carried out in the same manner as in Example 2 to obtain crystalline polypropylene (boiling n-heptane insoluble content 96.3 wt%) and polyethylene, and a chemical mixture (B) having MI 6.6 and C ₂ ^mu content 9.2 mol%.

The products (A) and (B) obtained as above were prepared in the same manner as in Example 1 100/11. A polymer composition was prepared by mixing in one proportion and physically mixing. The composition was measured in the same manner as in Example 1, and the composition showed 151 kg / cm FD (0 ° C.), average FM 13.0 × 10 ⁻³ kg / cm 2, and glossiness 59.

Example 5

An ethylene / propylene copolymer having a C ₂ ^mu content of 25 mol% and [η] 2.98 was repeatedly synthesized with the exception of the propylene / ethylene copolymerization of Example 4 except that the supply amount of methyl p-toluate was changed to 0.18 mmol / hr. In addition, the propylene-ethylene feed ratio was also changed. The resulting ethylene / propylene copolymer had a micro-isotaxy 0.94 and a boiling cyclohexane insoluble content of 2.5% by weight. This copolymer was mixed with the chemical mixture of crystalline polypropylene and polyethylene obtained in Example 4, and a physically mixed polymer composition was prepared by adjusting the ratio of copolymer to mixture described above to 100 / 11.1. As a result of measuring its properties, the composition showed an FD (0 ° C.) 134 kg cm, an average FM of 12.5 × 10 ⁻³ kg / cm 2 and glossiness 64.

Example 6

The propylene / ethylene copolymerization of Example 4 was repeated but no methyl p-toluate was supplied, tri-isobutyl aluminum was used in an amount of 1 mmol / hr, and the titanium catalyst of Example 1 was calculated as titanium atom It used as the quantity of 0.03 mmol / hr, The feed ratio of propylene and ethylene was changed, and it changed to polymerization temperature-55 degreeC. As a result, a propylene / ethylene copolymer having [?] 2.76 and a C ^mu ₂ content of 58 mol% was obtained. This copolymer exhibited a micro-isotaxy 0.91, a boiling cyclohexane insoluble content 2.7% by weight, Shore A hardness 87 and 97 ° C. by DSC. This copolymer was mixed with a chemical mixture of the polypropylene polyethylene obtained in Example 4, and a physically mixed polymer composition was prepared by adjusting the ratio of copolymer to chemical mixture to 100 / 11.1. The composition of this composition is as follows. FD (0 ° C.) = 130 kg.cm. Average FM = 13.4 × 10 ⁻³ kg / cm 2, glossiness = 50.

Comparative Example 1

20 liters of hexane, Al (C ₂ H ₅ ) ₂ Cl and 15 mmol of TiCl ₃ AA15 mmol (commercially available from Toho Titanium Corporation as trade name TAC-131) were placed in the same autoclave as used in Example 3. The system was heated to 60 ° C. Ethylene / propylene mixed gas (C ^µ ₂ / C ₃ ^µ / molar ratio 40/60) was passed through hydrogen, and polymerization was carried out for 12 hours while maintaining the pressure of the system at 5 kg / cm 2 G. After the completion of the polymerization, the resulting polymer solution was contacted with a large amount of methanol for polymer precipitation to give 2200 g of propylene ethylene copolymer. The analysis showed that the polymer had a [η] 2.7, 52 mol% C ₂ ^μ content, a 23 wt% boiling cyclohexane insoluble content and 0.90 microiso Turbidity.

The mixture was prepared by mixing the propylene / ethylene copolymer obtained above with the chemical mixture in crystalline polypropylene / polyethylene 100 / 11.1 ratio obtained in Example 3. As a result of measuring its properties, the mixture exhibited an ID (0 ° C.) 110 kg · cm, an average FM of 13.6 10 ⁻³ kg / cm 2 and glossiness 36.

Claims (1)

100 parts by weight of crystalline polypropylene containing 0-10 mol% ethylene and / or other α-olefins. Propylene / ethylene random air containing 30-85 mol% of propylene and 0-10 mol% of diene, having a micro-isotacticity of 0.8 or more and a boiling n-cyclohexane insoluble content of 0-10 wt% A propylene polymer composition containing 0 to 30 parts by weight of polyethylene containing 1 to 30 parts by weight of copolymer and 0 to 15 mol% of α-olefin, and mixing the crystalline polypropylene and the propylene / 'ethylene copolymer.