KR100336338B1 - Propylene-based polymer, preparation method thereof, composition thereof, catalyst component for polymerization, and preparation method thereof - Google Patents

Abstract

(1) 99.0% by weight or more of xylene extraction insolubles (XI) at 25 ° C., and (2) 98.0% of isotactic pentad fraction (IP) measured by ¹³ C nuclear magnetic resonance spectroscopy. (3) the total amount of each fraction having an isotactic average chain length (N) of 500 or more and (4) an average chain length (N _f ) of 800 or more obtained by column separation of xylene insolubles. Provided is a propylene-based polymer composition prepared by combining 10% by weight or more of a propylene-based polymer, a method for producing the same, or at least one nucleating agent with the propylene-based polymer at 0.05-15% by weight. In addition, a polymerization catalyst component for producing such a propylene polymer, and a production method thereof are provided.

Description

Propylene-based polymer, preparation method thereof, composition thereof, catalyst component for polymerization, and preparation method thereof

1 shows an example of a ¹³ C-NMR spectral chart of the methyl region of homopolypropylene.

The present invention is a propylene polymer having excellent physical properties such as stiffness, surface hardness, heat resistance, water vapor barrier properties, etc. suitable for use in automobiles, home appliances and packaging materials, a method for preparing the same, a composition containing the same and a catalyst component for polymerization thereof, and It relates to a manufacturing method.

Propylene-based polymers are generally inexpensive and exhibit certain properties including transparency, mechanical strength, heat resistance, surface gloss, chemical resistance, oil resistance, rigidity, flex fatigue resistance, and the like, which is why they are used in industrial materials, food packaging materials, and cosmetics. It has a wide range of uses, such as packaging materials, pharmaceutical packaging materials, and the like.

As mentioned above, propylene-based polymers exhibit properties such as stiffness, impact resistance, and the like, and thus are widely used in various industries including automobiles, home appliances, sundries, and the like. Recently, manufacturers have been looking at the prospect of increasing the surface hardness to make the products thinner in order to make them lighter and lower their production costs, while preventing the surface damage. That is, there is an increasing demand for a propylene polymer having high rigidity, high surface hardness, and excellent layer resistance. In addition, the demand for physical properties and processability continues to increase, and there is a demand for maintaining rigidity and strength at high temperatures, durability, and improving moldability of large molded articles.

Regarding the high stiffness and transparency of the propylene crab polymer and the improvement of surface gloss, conventionally, the Group I _a and II _a metal salts of monocarboxylic acids (eg sodium benzoate), dicarboxylic acids (eg adipic acid) and aliphatic Method of using fillers such as group III-IV metal salts of dicarboxylic acids (e.g., aluminum adipate), dibenzylidene sorbitol derivatives, talc, and the like as nucleating agents (Japanese Patent Publication No. 39-1809, Japanese Unexamined) Japanese Patent Application Laid-Open No. 60-139731, etc., and a method for generating a wide distribution of molecular weight of a propylene polymer (Japanese Unexamined Patent Publication No. 56-2307, 59-172507, and 62-195007, etc.) are known. There is a bar.

However, although the use of these nucleating agents yields the improvement of the previously mentioned physical properties, it cannot be said that they are necessarily sufficient for all uses.

As a result, a propylene-based polymer suitable as a material for automobiles, home appliances and packaging materials having excellent mechanical strength including impact resistance, rigidity, etc., surface hardness and heat resistance, and at the same time, by reducing the amount of filler such as talc, etc. It has been desired to reduce the density of the product to thin the product.

In addition, it increases the stereoregularity (isotacti-city) of propylene-based polymers, broadens their molecular weight distribution, increases their strength and durability depending on the molecular weight distribution, extrusion molding, blow molding, etc. Efforts have been made to improve moldability.

Among these efforts, the development of catalysts which are particularly high in activity and exhibit high isotacticity has been recently studied in earnest. All are catalyst systems composed of a solid catalyst component containing magnesium, titanium, halogen, and electron donating compounds as essential components, and organoaluminum and other electron donating compounds. Examples thereof include Japanese Unexamined Patent Publication (Kokai) 57-63310, 58- 32604, 58-83006, 59-206408, 59-219311, 60-130607, 61-209207, 61-211309, 62-72702, 62-104811, 62-11705, 63-199703, 63-264609, 1-126306, 1-311106, 3-62805, 3-70710, 4-103604, 4-114009 and 4-202505.

The present inventors also recently disclosed Japanese Unexamined Patent Publications (Publication) 4-43407, 4-149217, 4-178406, 4-180903, 4-185613, 4-198202, 4-198204, 5-9209 and 5- As disclosed in 287019.

The propylene-based polymers disclosed in the prior publications are isotactic pentads of methyl groups in polypropylene, measured by up to 99% xylene-extraction insolubles and ¹³ C nuclear magnetic resonance spectroscopy (abbreviated hereinafter as ¹³ C-NMR). Isotactic pentad ratio (mmmm), at most about 93-98%, thus limiting the improvement of various physical properties such as stiffness and heat resistance.

An object of the present invention is a propylene-based polymer having excellent stiffness, surface hardness, heat resistance, transparency, surface gloss, water vapor barrier properties, and the like, suitable for use in automobile home appliances and packaging materials, without losing the original physical properties of the propylene-based polymer. And a method for producing the same, a composition containing the same, a catalyst component for polymerization, and a method for producing the same.

The present inventors have conducted a lot of research on how to overcome the above-mentioned problems, (1) the xylene extracting insoluble content is 99.0% by weight or more, and (2) the eye measured by ¹³ C nuclear magnetic resonance spectroscopy A soottic pentad fraction (IP) of 98.0% or more, (3) an isotactic average chain length (N) of 500 or more, and (4) an average chain length (N _f ) of 800 or more The problem mentioned above is overcome as a propylene-based polymer in which the total amount of each fraction obtained by column fractionation of the xylene insoluble portion is 10% by weight or more in total, thus completing the present invention.

A clear description will be given of the properties of the propylene-based polymer according to the invention.

(1) Xylene-extracted insoluble part (XI) is the weight% of the polymer which is insoluble in xylene at 25 degreeC. Specifically, it is the weight percent of polymer that is first dissolved in ortho-xylene at 135 ° C. and then precipitated at 25 ° C. The XI of the propylene polymer of the present invention is 99.0% or more, preferably 99.5% or more, and more preferably 99.7% or more. If XI is less than 99.0%, the polymer will lack the desired stiffness, heat resistance, surface hardness, surface glossiness, transparency, water vapor barrier properties, and the like.

(2) The isotactic pentad fraction (hereinafter sometimes abbreviated as IP) of the propylene molecular chain measured by ¹³ C nuclear magnetic resonance spectroscopy is measured according to the method of A, Zambelli, Macromolecules, 6, 925, 1973. . That is, it refers to the isotactic fraction of pentad units in the propylene polymer molecular chain, measured using nuclear magnetic resonance spectroscopy ( ¹³ C-NMR) as the isotope carbon. IP according to the invention is a measure for the actual polypropylene obtained by polymerization, not a measure for polypropylene after the aforementioned xylene extraction or other extraction, separation, etc. has been carried out.

Classification of the peaks was performed based on the revised edition of this document, described in Macromolecules, 8, 687, 1975, and IP was determined by the intensity fraction of the mmmm peak among the total absorption peaks of methyl carbon by ¹³ C-NMR.

The IP of the propylene-based polymer thus measured should be 98.0% or more, because if it is less than this value, the polymer will lack the desired rigidity, heat resistance, surface hardness, surface gloss, transparency, water vapor barrier properties, and the like. The IP of the propylene-based polymer is preferably 98.5% or more. Particular preference is given to propylene-based polymers having an IP of 99.0% or more.

(3) The isotactic average chain length (N) is the isotactic average chain length of the methyl group in the polypropylene molecule, and J.C. It can be calculated based on the method reported by Randall (Polymer Sequence Distribution, Academic Press, New York, 1977, chapter 2).

Specifically, the polypropylene is dissolved by heating at a temperature of 130 ° C. so that the polymer concentration is 10% by weight in a mixed solvent of 1,2,4-trichlorobenzene / heaven benzene.

This solution was placed in a glass sample tube with an inner diameter of 10 mmφ and measured by ¹³ C-NMR under the same measurement conditions for the previous isotactic pentad fraction (IP).

Definition of the two-site model described in "Shan-Nong Zhu, Xiao-Zhen Yang, Riichiro Chujo: Polymer Journal, Vol. 15, No. 12, p.859-868, 1983", ie, two activities during polymerization. Assume that kind is included. One type is called catalyst controlled polymerization and the other is chain terminated polymerization (details on catalyst controlled and chain terminated polymerization are described by Junji Furukawa in Macromolecules: Essence and Topics 2, "Macromolecular Synthesis", p.73, published by Kagaku Dojin, KK., 1986).

The two-site model can be summarized as follows:

α: Catalytically controlled polymerization (enantiomorphic process): An index of the probability of D- and L-forms added at the end of the polymerization, that is, the degree of disorder of the isotactic component.

sigma: Chain end-controlled polymerization (Bernoulli process): The probability of mesoform formation by addition of the same kind as the end of the polymerization.

ω: ratio of α site

Homopolypropylene breaks down into ten peaks of the pentad due to isotacticity of the methyl group, but α, σ and ω are calculated by the least squares method so that the actual measurements match the calculated strength (area). The quantity A ₁ -A _{10 in} each pentad unit is measured by the following equation above.

* β = α (1-α)

Next, a definition formula (N = meso chain number / meso unit number) for the average chain length (N) described in the literature previously mentioned by JC Randall was added to each of the pentad units A ₁ -A ₇ calculated above. When applied, it can be calculated by the following equation.

The N value according to the invention is a measure for the actual polypropylene obtained by polymerization and is not a measure of polypropylene after carrying out the above-mentioned xylene extraction or other extraction, separation, or the like. N for the isotactic propyline-based polymer of the present invention is 500 or more, preferably 700 or more, and more preferably 800 or more. If N is less than 500, the polymer will lack the desired stiffness, heat resistance, and the like.

In general, ¹³ C-NMR of polypropylene provides three main peaks for methylene, methine and methyl.

When the peak of the methyl region is enlarged, the data shown in FIG. 1 is obtained. mmmmrmmmm... ,… mmmmmmrrmmmmm... And asymmetrical binding forms.

The crystalline isotactic fungal chain length is considered to have an inverse relationship with the asymmetric bond.

Larger number of asymmetrical bonds, ie more racemic structures between mmmm structures, will shorten the average chain length (N).

As mentioned above, the average chain length (N) calculated in this way gives the length of the sequence of the crystalline isotactic structure, and as such length becomes larger (less asymmetric bond), propylene-based It will be appreciated that the physical properties of the polymer, such as stiffness, heat resistance, water vapor barrier properties, etc., will be increased.

(4) The average chain length (N _f ) of the oil fraction obtained by column fractionation of the xylene insoluble portion was first dissolved in para-xylene at a temperature of 130 ° C. in the xylene-extraction insoluble portion of the polypropylene obtained in the above (1). Celite was added, and the temperature was lowered to 30 ° C. at a temperature-lowering rate of 10 ° C./hour to attach celite, and the column was filled, and the temperature was raised from 70 ° C. to 130 ° C. by 2.5 ° C. at a time, The fractions are fractionated and then found by calculating the average chain length (N) of each fractioned fraction by the previously mentioned method as the average chain length (N _f ) for each fraction.

In the propylene polymer according to the present invention, the total amount of each fraction obtained by column separation of xylene insolubles having an average chain length (N) of 800 or more is 10% by weight or more based on the total. Preferably it is 30 weight% or more, More preferably, it is 50 weight% or more.

If the total amount of oil having an average chain length (N _f ) of 800 or more is 10% by weight or less based on the total, the desired improvement effect on stiffness, surface hardness, heat resistance and water vapor barrier properties will be small.

A method for producing a propylene polymer according to the present invention will be described.

The propylene-based polymer according to the present invention (A) has a magnesium compound, a titanium compound, a halogen-containing compound and a first electron donor compound as essential components, and the molar ratio of the first electron donor compound and the titanium electron content supported as a polymerized solid catalyst component (D Solid catalyst component for polymerization in which / T) is D / T ≧ 1: (B) organoaluminum compound: and (C) propylene polymerization using a polymerization catalyst containing an electron donor compound.

Magnesium compounds here include magnesium halides such as magnesium dichloride, magnesium dibromide and magnesium diyodide; Alkoxy magnesium, such as dimethoxy magnesium, diethoxy magnesium, dipropoxy magnesium, dibutoxy magnesium and diphenoxy magnesium; Carboxylates such as magnesium laurate, magnesium stearate and magnesium acetate; And alkyl magnesium, such as diethyl magnesium and butylethyl magnesium. These various magnesium compounds may be used alone or in combination of two or more thereof. Preferably, magnesium halides or alkoxy magnesiums are used, or magnesium halides are formed during the formation of the catalyst. Most preferably the halogen mentioned above is chlorine.

Titanium compounds include titanium halides such as titanium tetrachloride, titanium trichloride, titanium tetrabromide and titanium tetraidide; Alkoxy titanium compounds such as tetramethoxy titanium, tetraethoxy titanium, tetrapropoxy titanium, tetrabutoxy titanium and tetraphenoxy titanium; And alkoxy titanium halides such as ethoxy titanium chloride, butoxy titanium chloride, phenoxy titanium chloride, dibutoxy titanium chloride and tributoxy titanium chloride, and the like. These various titanium compounds may be used alone or in combination of two or more thereof. Preferably, halogen tetravalent titanium compounds are used, more preferably titanium tetrachloride.

In halogen-containing compounds, halogen is fluorine, chlorine, bromine or iodine, preferably chlorine, and in actual examples the specific compound depends on the method of preparing the catalyst component; However, titanium halides such as titanium tetrachloride, titanium tetrabromide, and the like; Silicon halides such as silicon tetrachloride, silicon tetrabromide; And phosphorus halides such as phosphorus trichloride and phosphorus pentachloride may be provided by way of example, and halogenated hydrocarbons, halogen molecules or hydrohalogenic acids may also be used depending on the method of preparing the catalyst component.

As the first electron donating compound, there may generally be mentioned oxygen-containing compounds, nitrogen-containing compounds, phosphorus-containing compounds, sulfur-containing compounds, and the like. Oxygen-containing compounds include, for example, alcohols, ethers, esters, acid halides, acid anhydrides, and the like.

More specifically, methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, 2-ethyl alcohol, oleyl alcohol, benzyl alcohol, phenylethyl alcohol, Alcohols such as phenol, cresol, ethyl phenol and naphthol; Ethers and diethers such as methyl ether, ethyl ether, propyl ether, butyl ether, amyl ether, hexyl ether, tetrahydrofuran, anisole and diphenyl ether; Ethyl acetate, ethyl chloroacetate, ethyl propionate, ethyl butyrate, ethyl acrylate, ethyl crotonate, ethyl oleate, ethyl stearate, ethyl phenylacetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzo Ate, methyl toluate, ethyl toluate, propyl toluate, butyl toluate, methyl ethyl benzoate, methyl anate, ethyl aniseate, methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate, dimethyl phthalate, Esters such as diethyl phthalate, dipropyl phthalate, di-n-butyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, γ-butyrolactone, δ-valerolactone and ethylene carbonate, acetyl chloride, benzoyl Chloride, toluic acid chloride and phthalate Acid chlorides such as chloride; And acid anhydrides such as maleic anhydride, phthalic anhydride, and the like.

The first electron donating compound may be used alone or in combination of two or more thereof. Preferably esters are used, more preferably phthalic esters.

Obviously, a single compound may contain two or more of four compounds, including magnesium compounds, titanium compounds, halogen compounds and first electron donor compounds.

The amount of the components to be used mentioned above may be preferred as long as the effects of the present invention are provided, but generally the following ranges are preferred.

The amount of titanium compound to be used may be 0.0001-1000, and preferably 0.01-100 in molar ratio, with respect to the amount of magnesium compound used. Halogen compounds are used as necessary, in which case they are used in molar ratios 0.01-1000, and preferably 0.1-100, with respect to the amount of magnesium used, regardless of whether the halogen is contained in the titanium compound or the magnesium compound. The amount of the electron donating compound to be used is 0.001-10, preferably 0.01-5, in molar ratio with respect to the amount of the magnesium compound mentioned above.

The process for preparing the solid catalyst component to be used according to the present invention is a conventional solid catalyst component obtained by contacting and reacting a magnesium compound, a titanium compound and a first electron donor compound, and also a halogen-containing compound at a time or in several steps as a preparation if necessary. It may be a manufacturing method of.

As specific examples of known production methods, the following may be mentioned.

(1) Magnesium halide, if necessary the best electron donating compound and titanium compound are contacted together.

(2) A method in which a solid component obtained by contacting magnesium halide, tetraalkoxy titanium and a specific polymer silicon compound is contacted with a halogenated titanium compound and / or a halogenated silicon compound.

(3) A method in which a tetraalkoxy titanium and a first electron donor compound and a magnesium compound are dissolved, followed by contacting the titanium compound with a solid component obtained by precipitation as a halide or titanium halide compound.

(4) A method of treating alumina or magnesia as a phosphorus halide compound and contacting the product with a magnesium halide first electron donor compound and a halogenated titanium compound.

(5) A method of contacting an organomagnesium compound, represented by a Grignard reagent, with a reducing or halogenating agent, followed by contact with a first electron donor compound and a titanium compound.

(6) A method of bringing an alkoxy magnesium compound into contact with a halogenating agent and / or a titanium compound in the presence or absence of a first electron donor compound.

(7) A method of dissolving a magnesium compound with tetraalkoxy titanium and treating as a polymer silicon compound, followed by treating as a halogenated silicon compound and an organometallic compound.

(8) A method of treating a spherical magnesium compound / alcohol chelate with a first electron donating compound, a halogenated titanium compound, or the like.

The above-mentioned method for preparing the solid catalyst component may be used for the preparation of the propylene polymer according to the present invention, but the solid catalyst component may be a mole of the first electron donating compound and titanium electron content supported on the solid catalyst component (D / It should be a solid catalyst component for polymerization with T) of at least D / T ≧ 1. It is more preferable if D / T?

If D / T <1, it would be difficult to obtain the high isotactic propylene polymer of the present invention.

Therefore, according to the present invention, the essential components are magnesium compound, titanium compound, halogen compound and first electron donor compound, and the molar ratio (D / T) of the first electron donor compound (D) and titanium (T) contained in the solid catalyst component A solid catalyst fraction for α-olefin polymerization with D / T ≧ 1 is provided. This solid catalyst component has been developed for the production of polypropylenes with the highly isotacticity mentioned above, but it is also useful as a solid catalyst component for the normal polymerization of α-olefins which are not general propylene-based polymers or propylene-based polymers. . In particular, in order to obtain a propylene polymer having a high degree of isotacticity and the required rigidity and heat resistance, D / T is preferably 1.5 or more.

In addition, in the case of solid catalyst components which do not match the above conditions (D / T? 1) when prepared by the conventional method, they can be made to meet the above conditions by the following further treatment.

In this case, the molar ratio (D / T) of the first electron donor compound and titanium atom content in the solid catalyst component before further treatment for modification and the molar ratio (D / T) of the first electron donor compound and titanium atom content in the improved catalyst component _m should have a relationship of (D / T) _m / (D / T) _i > 1, more preferably if (D / T) _m / (D / T) _i ≥ 2.

For example, the solid catalyst component prepared by the above-mentioned known method and whose essential components are magnesium, titanium, halogen and the first electron donating compound may be further treated as the first electron donor compound and / or the halogen-containing compound before treatment. / T is increased above its value, so that the catalyst can be improved. The order and frequency of the treatment as the first electron donor compound and the halogen-containing compound are not particularly limited, but in the method of treating a solid catalyst component generally used, the first treatment is carried out as a supported first electron donor compound, followed by treatment as a halogen-containing compound. It is then washed further as a hydrocarbon.

Used for Modification of Catalyst Components The first electron donor compound may be the same or different as used during the preparation of the solid catalyst component prior to further processing. The first electron donor compound may be used in a single kind or in combination of two or more. Preferred for use are esters, particularly phthalic esters.

The amount of the first electron donor compound used is 0.001-500 mol, and preferably 0.01-50 mol, with respect to the titanium atom in the solid catalyst component.

If the amount of the first electron donor compound is very small, it will be difficult to achieve the relationship (D / T) _m / (D / T) _i > 1, whereas if it is very high the polymerization activity will be lowered, so the conditions Not desirable

The halogen containing compound to be used for the modification of the catalyst may be the same or different as used during the preparation of the solid catalyst component prior to further treatment. Of these, titanium halides, silicon halides and halogenated hydrocarbons are preferred. The halogen containing compound may be used in a single kind or in combination of two or more.

The amount of the halogen-containing compound used is a molar ratio of 0.1-10,000, preferably a molar ratio of 1-3000, and more preferably a molar ratio of 5-500 with respect to the titanium atom in the solid catalyst component. If the amount of halogen-containing compound is very small, it will be difficult to achieve the relationship (D / T) _m / (D / T) _i > 1, whereas if it is very large the polymerization activity will be lowered and the amount of waste solution will be Will be increased, and thus the condition is undesirable.

For the modification, the treatment of the solid catalyst component as the first electron donating compound is carried out at a temperature of -30-150 ° C, preferably 0-100 ° C. In addition, the treatment of the solid catalyst component as the halogen-containing compound is carried out at a temperature of 0-200 占 폚, and preferably 50-150 占 폚. Temperatures outside this range are undesirable because the resulting polymerization activity will be reduced.

Treatment for the modification of the solid catalyst component using the first electron donating compound and the halogen containing compound can usually be carried out in a hydrocarbon solvent. Hydrocarbons to be used here are preferably inert hydrocarbons, for example aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, and the like or aromatic hydrocarbons such as benzene, toluene, xylene, and the like. These hydrocarbons can also be used as solvents for washing solid catalyst components after their treatment as first electron donor compounds and halogen containing compounds.

After the solid catalyst component before the treatment has been treated as the first electron donating compound and washed as the halogen containing compound, the washing of the olefin polymerization improving catalyst using the above-mentioned hydrocarbon is carried out at a temperature of 0-200 ° C., and preferably 60-140 ° C. Is performed in Here, it will be difficult to achieve the relation (D / T) _m / (D / T) _i > 1 if the washing temperature is very low, and if it is very large the relation (D / T) _m / (D / T) _i > 1 will be achieved but the polymerization activity will be lowered and therefore the conditions are undesirable.

If the solid catalyst component is not treated (washed) as a halogen-containing compound after its treatment as the first electron donating compound, the polymerization activity will be greatly reduced and the effect of the present invention will not be exhibited. The frequency of treatment (washing) as the halogen-containing compound is not particularly limited, but should be performed 2-4 times for the effect of the present invention to be appropriately shown. A single wash will not adequately show the effects of the present invention, while too many washes will degrade the polymerization activity and are therefore undesirable.

Furthermore, according to the invention, the first electron donor compound is of the general formula TiX _a Y Y _b where X is a halogen atom such as Cl, Br or I; a is 3 or 4; Y is the electron donating compound (1) It may be a titanium compound represented by 0 <b ≦ 3), and after treatment of the catalyst component for supporting, washing is again performed as a hydrocarbon as a halogen-containing compound to increase the solid catalyst component to D / T ≧ 1. Therefore, when carrying out the treatment of the solid catalyst component using the first electron donor compound, the treatment (wash) frequency as the halogen-containing compound according to the invention should generally be at least twice, as mentioned previously; However, if TiX _a · Y _b is used, the effect of the present invention will suitably appear as a halogen-containing compound as the frequency of treatment (washing) 1-2 times. Further, as mentioned later, since the amount of halogen-containing used amount can be reduced, it is possible to greatly reduce the waste solution displacement during the washing of the improved solid catalyst component as hydrocarbon.

TiX _a (where X is a halogen atom such as Cl, Br or I and a is 3 or 4) is for example RSP Coutts, PC Wailes, Advan, Organometal. Chem., 9, 135, 1970: Shinjikken Kagaku Koza, 4th edition, 17, Inorganic Complexes / Chelated Complexes, Nihon Kagakukai Maruzen, 1991, p. 35; HK Kakkoen, J. Pursiainen, TA Pkkanen, M. Ahlgren, E. Ilskola, J. Organomet. Chem., 453, 175, 1993; As described, etc., it is generally known to easily form chelates with the electron donating compound.

X of TiX _a · Y _b is a halogen atom such as Cl, Br or I, the Cl is preferred. The letter "a" is 3 or 4, preferably 4. Y (first electron donor compound) may be selected from those previously mentioned and may be the same as or different from that used during the preparation of the solid catalyst component before improvement. In the manufacture of TiX _a · Y _b, the first electron-donating compound used may be a single species or a combination of two or more. Y is preferably an ester, more preferably a phthalic acid ester. TiX _a · added mole ratio of Y to TiX _a during the preparation of Y _b is a "a" of the Y in the third il "b" mentioned above 0 <b ≤ 3, "a" is 0 is 4 <b ≤ 2, and therefore the number of electron donating groups of Y depends on the original value of Ti. Most preferably, a is 4 and b is 1.

The amount of TiX _a · Y _b used is 0.001-500 in molar ratio, preferably 0.01-50 in molar ratio, and more preferably 0.1-10 in molar ratio with respect to the titanium atoms in the solid catalyst component before its modification. If the amount of the TiX _a · Y _b is very small, equation _{(D / T) m / (} D / T) i> will be difficult is to achieve the first, on the other hand will be the polymerization activity decreases if it is very large, and thus the conditions This is not desirable.

The usage-amount of a halogen containing compound is 0.1-1000 in molar ratio with respect to titanium atom in a solid catalyst component, Preferably it is 1-500 in molar ratio, More preferably, it is 5-100 in molar ratio.

In addition, the treatment temperature of the solid catalyst component as TiX _a · Y _b may be the same as the above temperature for treatment as the first electron donating compound, and the washing temperature of the solid catalyst component as the halogen-containing compound may be as mentioned above.

Treatment of the solid catalyst component as TiX _a · Y _b and washing as the halogen containing compound are the same as treatment as the first electron donating compound described above and washing as the halogen containing compound.

TiX _a · treated and the particular restriction for the three frequencies as a halogen-containing compound with a Y _b are, but, the effect of the invention as referred to above TiX _a · Y _b single or twice by a halogen-containing compound after the treatment as Will appear appropriately as a wash. If no washing is carried out as the halogen containing compound, no significant properties according to the invention will be obtained.

Prepolymerization

The improved solid catalyst component prepared in the manner described above is used for the polymerization of propylene in combination with the organoaluminum compound and the second electron donor compound described below; Small amounts of monomer may be prepolymerized prior to polymerization. This is typically about 0.01-1000 g per gram of the improved solid catalyst component prepared in advance, and the prepolymerization temperature may be -30-80 ° C. Prepolymerization is usually carried out in the presence of an organoaluminum compound and a second electron donor compound to be used in the polymerizations described hereinafter. In general, prepolymerization may be carried out in an inert hydrocarbon solvent, but may also be carried out in liquid monomers, gas phase monomers, and the like.

The monomers to be used for the prepolymerization are propylene or for example ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene Α-olefins such as vinyl cyclopentane, vinyl cyclohexane, and the like; Styrene derivatives such as styrene or α-methylstyrene, and the like; Dienes such as butadiene, 1,9-decadiene, and the like; Or allyltrialkylsilane. These monomers need not be used alone, since two or more thereof may be used in several steps or in combination. Hydrogen may be used as molecular weight regulator for prepolymerization.

Propylene polymerization

The above-mentioned improved solid catalyst component can be used to polymerize the propylene-based polymer in the presence of an organoaluminum compound and a second electron donor compound.

Organoaluminum compounds to be used according to the invention include trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, tripropylaluminum, tributylaluminum, trihexylaluminum and trioctylaluminum; Alkylaluminum hydrides such as dimethylaluminum hydride, diethylaluminum hydride and dibutylaluminum hydride; Alkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, diethylaluminum bromide and ethylaluminum sesquichloride; Alkylaluminum alkoxides such as diethyl aluminum ethoxide and diethylaluminum phenoxide; And aluminoxanes such as methyl aluminoxane, ethyl aluminoxane and propyl aluminoxane. These organoaluminum compounds may be used alone or in combination of two or more. Preferably, trialkylaluminum compounds are used.

The second electron donating compound to be used according to the present invention may be the same as or different from the first electron donating compound, but as a representative example thereof, an aromatic carboxylic acid ester, a silicon compound having an Si-OC or Si-NC bond, an acetal compound, Ge-OC Germanium compounds having a bond and heterocyclic compounds of nitrogen or oxygen having an alkyl substituent may be mentioned.

Specific examples of these compounds include aromatic carboxylic acid esters such as ethyl benzoate, ethyl p-toluate and ethyl p-anisate; Phenyl trimethoxysilane, diphenyl methoxysilane, di-n-propyl dimethoxysilane, di-i-propyl dimethoxysilane, di-t-butyl dimethoxysilane, dicyclohexyl dimethoxysilane, dicyclopentin dimethoxy Silicone compounds such as methoxysilane, cyclohexylmethyl dimethoxysilane, t-butyl trimethoxysilane, cyclohexyl trimethoxysilane, dexyl trimethoxysilane, tetramethoxysilane and tetraethoxysilane; Acetal compounds such as benzophenone dimethoxyacetal, benzophenone diethoxyacetal, acetophenone dimethoxyacetal and acetophenone diethoxyacetal; Germanium compounds such as diphenyldimethoxy germanium and phenyltriethoxy germanium; And heterocyclic compounds such as 2,2,6,6-tetramethylpiperidine and 2,2,6,6-tetramethylpyran.

These electron donating compounds may be used alone or in combination of two or more thereof. Preferably, silicon compounds or acetal compounds are used, more preferably silicon with Si—O—C bonds.

The polymerization preparation method according to the present invention is not particularly limited and may be a known method including liquid phase polymerization such as slurry polymerization or bulk polymerization, and gas phase polymerization. In addition, batch polymerization, and other methods using continuous polymerization and batch polymerization may be applied. The polymerization solvent to be used for the slurry polymerization is alone or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, cyclohexane, toluene, and the like. In the production according to the invention the polymerization process can also be used for multistage polymerization in two or more polymerization reactors.

The polymerization temperature is about −50 ° C.-200 ° C., preferably 20-150 ° C., and the polymerization pressure is from atmospheric pressure to 100 kg / cm 2 G, preferably 3-50 kg / cm 2 G. In addition, the molecular weight can be controlled by adding an appropriate amount of hydrogen during the polymerization.

In addition to the homopolymerization of propylene in the preparation according to the invention, the propylene is represented by the general formula R-CH = CH ₂ , where R is a hydrocarbon residue of 1-20 carbon atoms, which may be hydrogen or a side chain. May be copolymerized with. Specific examples thereof are ethylene, 1-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, vinyl cyclopentane, vinyl cyclone Hexane, and the like. Further examples include styrene derivatives such as styrene and α-methylstyrene, dienes such as butadiene, 1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, and allyltrialkylsilanes. These monomers may be used in combination of two or more thereof, and thus need not be used alone.

Among the propylene-based polymers according to the invention, the propylene-ethylene block copolymers can be produced by multistage polymerization in two or more polymerization reactors, where it is particularly preferred to produce the single polypropylene in the first stage.

In this case, if the single polypropylene obtained after completion of the first stage of polymerization meets the constituent requirements of the present invention, the finally obtained copolymer will overcome the problems aimed by the present invention and will have the properties obtained.

In addition, the propylene-based polymer obtained according to the present invention can be made into a resin composition in which crystallinity and high-speed moldability are further improved by addition of known nucleating agents.

Examples of nucleating agents include Group I _a and II _a metal salts of monocarboxylic acids (eg sodium benzoate), dicarboxylic acids (adipic acid) and group III-IV metal salts of aliphatic dicarboxylic acids (eg aluminum pt -Butylbenzoate), dibenzylidene sorbitol derivatives, talc and the like.

1,3,2,4-dibenzylidyl sorbitol, 1,3,2,4-di- (p-methylbenzylidene) sorbitol, 1,3,2,4-di- (p-ethylbenzylidene) sorbitol , 1,3,2,4-di- (p-chlorbenzylidene) sorbitol, 1,3-p-chlorbenzylidene-2,4-p-methylbenzylidene sorbitol, sodium-bis- (4-t- Butylphenyl) phosphate, sodium-2,2-methylene-bis- (4,4-di-t-butylphenyl) phosphate, sodium-2-2'-ethylidene-bis- (4,6-di-t- Particular preference is given to inorganic fillers such as butylphenyl) phosphate, and the like, and talc, calcium carbonate.

The effect of the present invention will be quite satisfactory if the amount of nucleating agent used is at least 0.05-15% by weight in the propylene-based polymer.

It is preferably added in an amount of 0.08-0.8% by weight, and more preferably 0.1-0.5% by weight. However, since inorganic compounds such as talc have less nucleation effect than the nucleating agents described above, they are in an amount of 1-15% by weight, preferably 2-13% by weight, and more preferably 5-10% by weight. Must be added.

Propylene-based polymers according to the present invention, so long as other additives commonly used for thermoplastics (e.g. antioxidants, weathering stabilizers, antistatic agents, dyes, pigments, oils, waxes, etc.) do not impair the object of the present invention. Or it can mix | blend with a resin composition suitably.

Examples of such additives are 2,5-di-t-butylhydroxyquinone, 2,6-di-t-butyl-p-cresol, 4,4-thiobis- (6-t-butylphenol), 2, 2-methylene-bis (4-methyl-6-t-butylphenol), octadecyl-3- (3 ', 5'-di-t-butyl-1'-hydroxyphenyl) propionate and 4,4 Antioxidants such as' -thiobis (6-butylphenol); Ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, 2- (2'-hydroxy-5-methylphenyl) benzotriazole and 2-hydroxy-4-octoxybenzophenone; Plasticizers such as dimethyl phthalate, diethyl phthalate, wax, liquid paraffin and phosphate esters; Antistatic agents such as monostearate, sorbitan monopalmitate, sulfated oleic acid, polyethylene oxide and carbon waxes; Lubricants such as ethylene bis-stearomide, butyl stearate, and the like; Colorants such as carbon black, phthalocyanine, quinacridone, indolin, azo pigments, titanium oxide, iron oxide red, and the like, and fillers such as fiberglass, asbestos, mica, pallastonite, calcium silicate, aluminum silicate, and the like. . In addition, many other high molecular compounds can be blended with them as long as the effects of the present invention are not impaired.

Melt index (MFR-JIS-7210, Table 1, Condition 14) of the propylene polymer according to the present invention is not particularly limited and may be selected according to the molding method and the intended use, but a suitable range is usually 0.1-500 g / 10 Minutes.

The propylene-based polymer according to the present invention may be molded into an injection molded body, a film, a sheet, a tube, a bottle, or the like using a known melt molding method or a compression molding method, and may be used alone or laminated with other materials.

For example, this lamination method uses a polyurethane, polyester or others based on dry laminate adhesives to laminate another thermoplastic resin layer on a single layer of a propylene-based polymer or resin composition according to the invention. , So-called dry lamination molding and sandwich lamination methods, or separately, co-extrusion lamination, co-extrusion (feed-block method, multi-manifold system), extrusion molding or co-extrusion pipe molding Can be used.

The multilayer laminate obtained in this manner can be used in a method performed in an operation for reheating and stretching using a vacuum molding machine, a compression molding machine or a drawing blow apparatus, or the like, or the multilayer laminate or a single layer molding using a single or biaxial drawing machine. By heat stretching operation.

More detailed description of the invention will be provided in connection with the examples.

Example

The methods and equipment used to measure each physical property value according to the invention are set out below.

(1) Xylene insoluble part (XI)

A 2.5 g portion of the puller was dissolved at 135 ° C. in ortho-xylene (250 ml) and the amount of polymer precipitated at 25 ° C. (wt%) was determined as xylene insolubles (XI).

(2) isotactic pentad fraction (mmmm)

The MMMM fraction is the isotactic ratio of pentad units of methyl groups in the molecular chain of the propylene polymer. Measurements were performed using Nihon Denshi, KK's product, JNM-CSX400 ( ¹³ C nuclear magnetic resonance frequency of 100 MHz). Each signal was classified according to A. Zambelli et al., Macromolecules, 13, 267, 1980. The measurement conditions were as follows.

Measurement mode: Proton decoupling method

Pulse width: 8.0 ㎲

Pulse repetition time: 3.0 ㎲

Cumulative recovery: 20,000 times

Solvent: Mixed solvent of 1,2,4-trichlorobenzene / vaporbenzene (75/25% by volume)

Internal standard: hexamethyldisiloxane

Sample concentration: 300 mg / 3.0 ml solvent

Measuring temperature: 120 ℃

(3) isotactic average chain length (N)

Calculate the isotactic average chain length (N) based on the method reported by J.C Randall (Polymer Sequence Distribution, Academic Press, New York 1977, chapter 2). Specifically, the polypropylene is heated at 130 ° C. in a mixed solvent of 1,2,4-trichlorobenzene / heavybenzene to dissolve at 10 wt% of the polymer concentration.

This solution is placed in a glass sample tube with an inner diameter of 10 mmφ and measured by ¹³ C-NMR on the isotactic pentad fraction (IP) under the same measurement conditions as described above. Next, as described previously, the average chain length 4 can be calculated from the number of meso chains and the number of meso units according to the following definition.

N = number of meso chains / number of meso units

(4) column separation

The xylene insoluble portion of the propylene-based polymer is dissolved in para-xylene at a temperature of 130 ° C., and celite is added thereto, and then the temperature is lowered to 30 ° C. at a temperature-lowering rate of 10 ° C./hour and adhered to celite. The deposit is charged to the column, the temperature is raised from 70 ° C. to 130 ° C. by 2.5 ° C. at a time and the oil is separated.

(5) injection molding

Izod impact test specimens, flexural modulus test specimens, thermal strain temperature test specimens and surface gloss test specimens (15 cm x 11 cm flat plate 2 mm thick) were prepared using Toshiba Kikai, KK. . They were left for 2 days in a constant temperature room at 50% humidity and 23 ° C. and then their physical properties were measured.

(6) Izod impact strength (notching)

The measurement was performed according to JIS K7110. The device used was Uejima Seisakusho, KK. Product, U-F impact tester.

(7) flexural modulus

The measurement was performed according to JIS K7203.

(8) ethylene content

The calculation was based on the ¹³ C-NMR method reported by CJ Carman et al. (Nacromolecules, 10, 537, 1977).

(9) MFR (melt flow rate)

The measurement was performed according to JIS K7210, Table 1, Condition 14. The apparatus used was Takara, KK, Melt Indexer.

(10) heat deflection temperature

The measurement was performed in accordance with JISK7207B method using Toyo Seiki Seisakusho, product of KK, HDTεVSPT tester.

(11) Rockwell Surface Hardness

The measured samples were prepared by a press molding machine at a temperature of 230 ° C. and measured using a Rockwell hardness tester of Toyo Seiki Seisakusho, KK., Model AR-10, according to JIS K7202.

12 film forming

Under conditions of a die temperature of 230 ° C., a cooling temperature of 30 ° C., and a drawing speed of 10 m / min, a 40 mmφ T-die film forming machine manufactured by Yoshii Tekko, KK. Was used to produce a film having a thickness of 60 μm. haze and surface glossiness were measured.

(13) haze

The measurement was performed in accordance with JIS K7105, using a haze meter of Suga Shikenki, KK., Model HGM-2D.

(14) surface glossiness

Measurements were performed according to JTS K7105 using a gloss meter of Nihon Denshoku Kogyo, KK., Model VG-ID.

(15) water vapor transmission rate

Measurements were performed according to ASTM-E96 using PERMATRAN W, a product of Modern Controls, Inc., under conditions of temperature 37.8 ° C. and relative humidity 90%.

(16) catalyst analysis

Before the solid catalyst component and the solid catalyst component for olefin polymerization were dissolved in dilute sulfuric acid, the organic portion was extracted with heptane. Ti in the aqueous layer was measured using an atomic absorption spectrometer of product model AA610S from Shimazu Seisakusho, KK. The electron donating compound in the heptane layer was measured using Hitachi Seisakusho, product of KK., Gas Chromatography 263-50.

Example 1

(1) Preparation of solid catalyst components before improvement (common practice)

56.8 g of anhydrous magnesium dichloride in 100 g (174 mmol) of absolute ethanol at 500 ° C., 500 ml of CP15N waseline oil from Idemizu Kosan, KK. And 500 ml of KF96 silicone oil from Shinetsu silicone, KK. 597 mmol) portion was completely dissolved. The mixture was stirred for 3 minutes at 3000 rpm using a TK homomixer, manufactured by Tokushu-Kika Kogyo, KK. Thereafter, stirring was transferred to 2 liters of anhydrous heptane so that the temperature did not exceed 0 ° C. The white solid obtained was washed with a sufficient amount of anhydrous heptane and the material was vacuum dried at room temperature.

30 g portions of the obtained spherical solid MgCl ₂ · 2.5C ₂ H ₅ OH were dispersed in 200 ml of anhydrous heptane. While stirring at 0 ° C., 500 ml (4.5 mol) of titanium tetrachloride were added dropwise over a period of one hour. Then heating was started and when the temperature reached 40 ° C., 4.96 g (17.8 mmol) of diisobutyl phthalate were added and the temperature was raised to 100 ° C. over a period of about one hour. After the reaction was performed at 100 ° C. for 2 hours, the solid portion was collected by filtration while heating. Thereafter, 500 ml (4.5 mol) of titanium tetrachloride was dispersed in the reaction product and reacted at 120 ° C. for one hour. After completion of the reaction, the solid portion was collected by filtration with heating again and washed 7 times with 1.0 liter of hexane at 60 ° C. and 3 times with 1.0 liter of hexane at room temperature. The titanium content of the obtained solid catalyst component was measured and found to be 2.25% by weight. The component also contained 7.81% by weight of electron donating compound (1).

(2) Preparation of Improved Solid Catalyst Components

A 20 g portion of the pre-improved solid catalyst component obtained above was dispersed in 300 ml of toluene and reacted with 2.78 g (10 mmol) of diisobutyl phthalate at 25 ° C. for one hour. After the reaction was completed, 100 ml (900 mmol) of titanium tetrachloride were added for reaction at 90 ° C. for one hour. After completion of the reaction, the solid portion was collected by filtration with heating, 300 ml of toluene and 100 ml (900 mmol) of titanium tetrachloride were dispersed in the reaction product and reacted at 90 ° C. for one hour. After completion of the reaction, the solid portion was collected by filtration with heating again and washed seven times with 500 ml of toluene at 90 ° C. and three times with 500 ml of hexane at room temperature. The titanium content of the obtained solid catalyst component was measured and found to be 1.01% by weight. The component also contained 12.0% by weight of the first electron donating compound. A comparison of the analytical results of the catalyst components before and after their modifications is provided in Table 1.

(3) prepolymerization

500 ml of n-heptane, 6.0 g (53 mmol) of triethyl aluminum, 3.9 g (17 mmol) of dicyclopentyl dimethoxysilane and a catalyst component for the improved olefin polymerization obtained in (2) above in a 3-liter autoclave. 10 g was charged and the mixture was stirred at a temperature of about 0-5 ° C. for 5 minutes. Propylene was then fed to a polymerization autoclave of 10 g of propylene per gram of the improved olefin polymerization catalyst component for one hour of prepolymerization at a temperature of about 0-5 ° C. The obtained solid catalyst component for prepolymerization was washed three times with 500 ml of n-heptane and used for the preparation of the following propylene polymer.

(4) main polymerization

Under a nitrogen atmosphere, 2.0 g of a solid catalyst component for prepolymerization, 11.4 g (100 mmol) of triethylaluminum and 6.84 g (30 mmol) of dicyclopentyl dimethoxysilane, prepared by the method described above, were added to an autoclave with a 60-liter stirrer. The flask was then fed with hydrogen at 18 kg propylene and 13,000 mol ppm relative to propylene and the temperature was raised to 70 ° C. for polymerization for one hour. After one hour unpolymerized propylene was removed to terminate the polymerization. The result was 6.56 kg polypropylene, or 32.8 kg of polymer activity per gram of solid catalyst component, with a MFR of 33.0 g / 10 min. The results of the evaluation of the physical properties of the polymers are provided in Table 2.

Example 2

(1) Preparation of solid catalyst component before improvement

It was carried out in the same manner as in Example 1.

(2) Preparation of TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ]

Diisobutyl phthalate over a period of about 30 minutes while maintaining a temperature of 0 ° C. in a 1.0 liter solution of hexane containing 19 g (100 mmol) of titanium tetrachloride; 27.8 g (100 mmol) of C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ was added dropwise. After dropping, the temperature was raised to 40 ° C. for 30 min reaction. After the reaction was completed, the solid portion was collected and washed three times with 500 ml of hexane to obtain the desired material.

(3) Preparation of Improved Olefin Polymerization Catalyst Component

20 g portion of the solid catalyst component obtained in (1) was dispersed in 300 ml of toluene, and 5.2 g of TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ] at 25 ° C. for 1 hour to carry. 11 mmol). After completion of the loading, the solid part was collected by filtration while heating and redispersed in 10 ml (90 mmol) of titanium tetrachloride, stirred at 90 ° C. for one hour for washing, and then collected by filtration while heating the solid part. The reaction product was then washed 5 times with 500 ml of toluene at 90 ° C. and 3 times with 500 ml of hexane at room temperature. The titanium content of the obtained solid catalyst component was measured and found to be 0.91% by weight. The component also contained 10.6% by weight of the first electron donating compound. Table 1 provides a comparison of the analytical results of catalysts before and after their modifications.

(4) prepolymerization

Under a nitrogen atmosphere, 3-liter 500 ml of n-heptane, 6.0 g (53 mmol) of triethylaluminum, 3.8 g (17 mmol) of dicyclopentyl dimethoxysilane and 10 g of the improved olefin polymerization catalyst component obtained in the above (3) were used. The crab was charged and the mixture was stirred for 5 minutes at a temperature of about 0-5 ° C. For one hour of prepolymerization at a temperature of about 0-5 ° C., propylene was fed to a polymerization autoclave of 10 g of propylene for 1 g of the improved olefin polymerization catalyst component. The obtained solid catalyst component for prepolymerization was washed three times with 500 ml of n-heptane and used for the polymerization of the following propylene polymer.

(5) Main polymerization

In a nitrogen atmosphere, 2.0 g of a solid catalyst component for prepolymerization prepared by the method described above, 11.4 g (100 mmol) of triethylaluminum and 6.84 g (30 mmol) of dicyclopentyl dimethoxysilane were autoclaved with a 60-liter stirrer. Hydrogen was supplied at 18 kg propylene and 13,000 mol ppm relative to propylene and the temperature was raised to 70 ° C. for polymerization for one hour. After one hour unpolymerized propylene was removed to terminate the polymerization. The result was 6.64 kg of polypropylene, or 34 kg of polymerization activity per gram of solid catalyst component, with a polymer MFR of 34.2 g / 10 min. The evaluation results for the physical properties of the polymers are provided in Table 2.

Comparative Example 1

Under a nitrogen atmosphere, 6.0 g of AA-type titanium trichloride and 23.5 g of diethylaluminum chloride (195 mmol), manufactured by Toso Akuzo, KK., Were placed in an autoclave with a 60-liter stirrer, 18 kg of propylene and 8000 for propylene. Hydrogen was supplied at mol ppm and the temperature was raised to 70 ° C. for polymerization for one hour. After one hour unpolymerized propylene was removed to terminate the polymerization. The result was 6.23 kg polypropylene and the MFR of the polymer was 32.2 g / 10 min. The results of the evaluation of the physical properties of the polymers are provided in Table 2.

Comparative Example 2

Example 1 Prepolymerization and polymerization were carried out under the same methods and conditions as in Example 2 except that the pre-improved solid catalyst component prepared in (1) was used for polymerization and hydrogen was charged at 9300 mol ppm. The result was 6.88 kg polypropylene, with an MFR of 33.0 g / 10 min. The results of the evaluation of the physical properties of the polymers are provided in Table 2.

Example 3-5

The same methods and conditions as in Example 2 except that the charge of hydrogen was adjusted so that the MFR of the polypropylene product obtained during the production of the propylene polymer was 10.5 g / 10 minutes, 2.7 g / 10 minutes and 0.7 g / 10 minutes, respectively. Polypropylene was prepared. Table 2 provides the evaluation results for the physical properties of the obtained polymer.

Comparative Example 3

A propylene polymer was prepared in the same manner and in the same manner as in Comparative Example 1 except that the charge of hydrogen was controlled so that the MFR of the polymer obtained during the production of the propylene polymer was 3.2 g / 10 min. Table 2 provides the evaluation results for the physical properties of the obtained polymer.

Example 6

(1) Preparation of solid catalyst component before improvement

Under a nitrogen atmosphere, 47.6 g (500 mmol) of anhydrous magnesium dichloride, 250 ml of decane and 234 ml (1.5 mol) of 2-ethylhexyl alcohol were heated together at 130 ° C. for 2 hours for reaction to form a homogeneous solution, followed by anhydrous 11.1 g (75 mmol) of phthalic acid was added to the stirred solution at 130 ° C. for one hour to dissolve phthalic anhydride in a homogeneous solution. After the obtained homogeneous solution was cooled to room temperature, the total amount thereof was added to 2.0 liters (18 mol) of titanium tetrachloride maintained at -20 ° C over a period of one hour. After completion of the dropwise addition, the temperature of the mixed solution was raised to 110 ° C. over a period of 4 hours, when reaching 110 ° C., 26.8 ml (125 mmol) of diisobutyl phthalate was added and the mixture was 110 ° C. for reaction. Stirred for 2 h. After the reaction was completed, the solid portion was collected by filtration while heating, and 2.0 liters (18 mol) of titanium tetrachloride were dispersed in the reaction product and reacted at 110 ° C. for 2 hours. After completion of the reaction, the solid portion was collected by filtration with heating again, washed 7 times with 2.0 liters of decane at 110 ° C. and 3 times with 2.0 liters of hexane at room temperature, to obtain a solid catalyst component. The analysis results of the catalysts are provided in Table 1.

(2) Preparation of TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ]

This was carried out as in Example 2 (2).

(3) Preparation of Improved Olefin Polymerization Catalyst Component

40 g portion of the solid catalyst component obtained in (1) was dispersed in 600 ml of toluene, and TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ] 10.3 obtained at (2) at 90 ° C. for supporting. treated as g (22 mmol) for one hour, after completion of the loading, the solid portion was collected by filtration with heating and redispersed in 600 ml of toluene and 20 ml (180 mmol) of titanium tetrachloride and for one hour at 90 ° C. for washing. After stirring, the solid portion was collected by filtration while heating, and then the reaction product was washed 5 times with 1 liter of toluene at 90 ° C and 3 times with 1 liter of hexane at room temperature to obtain an improved olefin polymerization catalyst component. The analysis results of the catalysts are provided in Table 1.

(4) prepolymerization

Under nitrogen atmosphere, 500 ml of n-heptane, 6.0 g (53 mmol) of triethylaluminum, 4.15 g (17 mmol) of diphenyl dimethoxysilane and 10 g of the improved olefin polymerization catalyst component obtained in Example 2 (3) were added to 3 -Liter autoclave was charged and the mixture was stirred for 5 minutes at a temperature of about 0-5 ° C. For one hour of prepolymerization at a temperature of about 0-5 ° C., propylene was fed to an autoclave for the polymerization of 10 g of propylene per gram of the improved olefin polymerization catalyst component. The obtained prepolymerized solid catalyst component was washed three times with 500 ml of n-heptane and used for the preparation of the following propylene polymer.

(5) present propylene polymerization

Under a nitrogen atmosphere, 2.0 g of solid catalyst component for prepolymerization prepared by the method described above and 11.4 g (100 mmol) of triethylaluminum were placed in an autoclave with a 60-liter stirrer, 18 kg of propylene and 5300 mol for propylene. Hydrogen was supplied at ppm and the temperature was raised to 70 ° C. for polymerization for one hour. After one hour unpolymerized propylene was removed to terminate the polymerization. The polymerization activity was 22.0 kg per gram of solid catalyst component. Moreover, MFR of obtained polypropylene was 14.5 g / 10min. The evaluation results for the physical properties of the polymers are provided in Table 2.

Example 7

(1) Preparation of solid catalyst component before improvement

50.0 g (440 mmol) of diethoxy magnesium and 15.3 g (55 mmol) of di-n-butyl phthalate were stirred at reflux in 250 ml of methylene chloride for 1 hour under a nitrogen atmosphere. The resulting dispersion was sent to 2.0 liters (18 mol) of titanium tetrachloride and the temperature was raised to 110 ° C. for 2 hours for reaction. After completion of the reaction, the precipitated solid was reacted with 2.0 liters (18 mol) of titanium tetrachloride at 110 ° C. for 2 hours. After completion of this reaction, the product was rinsed three times as 2.0 liters of n-decane at 110 ° C. and then as 2.0 liters of n-hexane at room temperature until no more chloride ions were detected. Thereafter, the resultant was dried under reduced pressure at 40 ° C. to obtain the desired solid catalyst component. The analysis results of the catalysts are provided in Table 1.

(2) Preparation of TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ]

This was done as in Example 2 (2).

(3) Preparation of Improved Olefin Polymerization Catalyst Component

40 g of the solid catalyst component obtained in the above (1) was dispersed in 600 ml of toluene, and TiCl ₄ [C ₆ H ₄ (COO ⁱ C ₄ H ₉ ) ₂ ] 10.3 obtained in the above (2) at 90 ° C. for supporting. Treated as g (22 mmol) for one hour. After completion of the loading, the solid part was collected by filtration with heating and redispersed in 600 ml of toluene and 20 ml (180 mmol) of titanium tetrachloride, stirred at 90 ° C. for washing for 1 hour, and the solid part was filtered The reaction product was then washed 5 times as 1 liter of toluene at 90 ° C. and 3 times as 1 liter of hexane at room temperature. The catalytic analysis results are provided in Table 1.

Prepolymerization and propylene polymerization were carried out in the same manner and in the same manner as in Example 6. The result was 21.1 kg of polymerization activity per gram of solid catalyst component. Moreover, MFR of obtained polypropylene was 16.3 g / 10min. The evaluation results for the physical properties of the polymers are provided in Table 2.

Table 1-Catalyst Analysis

Table 2-1

Table 2-2

Example 8

After propylene was polymerized in an autoclave with a 60-liter stirrer in the same manner as in Example 2 (step 1), the liquid propylene was removed and a mixed gas of ethylene / propylene = 40/60 (molar ratio) was 2.2 Nm ³ / hour. And hydrogen were fed at 75 ° C. for copolymerization for 40 minutes at a rate of 20 NL / hour (second step). After 40 minutes, the unreacted gas was removed to stop the polymerization. As a result, 8.0 kg of propylene / ethylene block copolymer was obtained. The ethylene content measured by ¹³ C-NMR was 9.7 wt% and the MFR was 17.8 g / 10 min. The evaluation results for the physical properties of the polymers are provided in Table 3. In the table, XI, IP and N shown are for the homopolypropylene obtained after completion of the first stage polymerization.

Comparative Example 4

After propylene was polymerized in an autoclave with a 60-liter stirrer in the same manner as in Comparative Example 1, liquid propylene was removed and a mixed gas of ethylene / propylene = 40/60 (molar ratio) was added at a rate of 2.2 Nm ³ / hour and hydrogen Was fed at 65 ° C. for 40 minutes copolymerization at a rate of 20 NL / hour. After 40 minutes, the unreacted gas was removed to stop the polymerization. As a result, 7.7 kg of propylene / ethylene block copolymer was obtained. The ethylene content measured by ¹³ C-NMR was 9.6% by weight and the MFR was 18.3 g / 10 min. The evaluation results for the physical properties of the polymers are provided in Table 3. In the table, XI, IP and N shown are for the homopolypropylene obtained after completion of the first stage polymerization.

Table 3-1

Table 3-2

Examples 9, 10 and Comparative Example 5

0.05% by weight of propylene-based polymer and di-t-butyl-p-cresol obtained according to the present invention as a propylene-based polymer composition using a 20-liter supermixer (model SMV20) from Kawata Seisakusho Co. for mixing, penta 0.05% by weight of erytrityl-tetrakis [3- (3,5-dibutyl-4-hydroxyphenyl)] propionate and 0.10% by weight of calcium stearate, product of Nakatani Kikai Co., 30 mmφ A twin screw extruder was used to make the pellets. The following compound was used as nucleating agent and its amount was changed appropriately.

(Form of nucleating agent)

Nucleating agent A: aluminum p-t-butylbenzoate

Nucleating agent B: Sodium 2,2-methylenebis (4,6-di-tert-butylphenyl) phosphate

Table 4 shows the composition prepared by combining the above-mentioned nucleating agent with the polypropylene obtained in Example 2 (Examples 9 and 10) and the composition prepared by combining the nucleating agent with the polypropylene obtained in Comparative Example 1. The evaluation results for the physical properties of 5) are presented.

Example 11 and Comparative Example 6

Table 4 also shows the results of evaluation of the physical properties of the composition obtained by combining the nucleating agent in the same manner as in Example 9 with the propylene / ethylene block copolymers obtained in Example 8 and Comparative Example 4.

Table 4-1

Table 4-2

The present invention enables the production of propylene-based polymers and compositions suitable for automobiles, home appliances and packaging materials having superior physical properties, including stiffness, surface hardness, heat resistance, water vapor barrier properties, and the like, to those of the prior art. The industrial value is great.

Claims (12)

(1) 99% by weight or more of xylene extraction insolubles (XI) at 25 ° C, and (2) 98.0% or more of isotactic pentad fraction (IP) as measured by ¹³ C nuclear magnetic resonance spectroscopy. More than (3) an isotactic mean chain length (N) of 500 or more, and (4) a total amount of each fraction having an average chain length (N _f ) of 800 or more obtained by column separation of xylene insolubles. The propylene polymer which is 10 weight% or more of all these. 2. The isotactic pentad fraction (IP) measured by ¹³ C nuclear magnetic resonance spectroscopy according to claim 1, wherein (1) the xylene extracting insoluble portion (XI) is at 99% by weight or more at 25 ° C. ) Is 98.5% or more, (3) the isotactic average chain length (N) is 500 or more, and (4) the average chain length (N _f ) obtained by column separation of xylene insolubles is 800 or more. A propylene-based polymer in which the total amount of each of the above components is 30% by weight or more in total. Essential components are a magnesium compound, a titanium compound, a halogen-containing compound and a first electron donor compound, and the solid catalyst component for polymerization in which the molar ratio of the first electron donor compound (D) to the titanium content (T) is (D / T) _i . Forming a solid catalyst component for polymerization and preparing an improved solid catalyst component for polymerization in which the molar ratio of the supported electron donating compound (D) and titanium content (T) is (D / T) _m ; , (D / T) _m / (D / T) _i > 1 method for producing a solid catalyst component for propylene polymerization. The process according to claim 3, wherein (D / T) _i / (D / T) _m > 2. 4. A process according to claim 3, wherein the treatment of the solid catalyst component consists of treating as a first electron donor compound for mixing thereof, followed by treatment as a halogen containing compound and washing, further washing as a hydrocarbon. The method of claim 3 wherein the solid catalyst component The formula for mixing TiX _a · Y _b (X is a halogen atom such as Cl, Br and / or I; a is 3 or 4; Y is a first electron-donating compound And 0 ≤ b ≤ 3), followed by washing with a halogen containing compound and further washing with a hydrocarbon. Propylene-based polymer composition prepared by combining at least one nucleating agent with 0.05-15% by weight with the propylene-based polymer according to claim 1. i) The molar ratio (D / T) m of the first electron donating compound (D) and the titanium compound (T) supported on the solid catalyst component for polymerization is any one of claims 3 to 6 wherein (D / T) m ≥ 1; A solid catalyst component prepared by the process according to claim 1, ii) an organoaluminum compound, and iii) polymerizing propylene using a solid catalyst component for polymerization containing the second electron donating compound. 9. A process according to claim 8 wherein D / T &gt; 1.5 in the solid catalyst component. 9. The isotactic pentad fraction (IP) measured by ¹³ C Nuclear Magnetic Resonance Spectroscopy according to claim 8 wherein (1) the xylene extraction insolubles (XI) are at or above 99% by weight at 25 ° C. ) Is 98.0% or more, (3) the isotactic average chain length (N) is 500 or more, and (4) the average chain length (N _f ) obtained by column separation of xylene insolubles is 800 or more A manufacturing method characterized in that for the production of propylene-based polymers in which the total amount of each of the above components is 10% by weight or more. A solid catalyst component for propylene polymerization prepared by the method according to any one of claims 3 to 6, comprising as an essential component a magnesium compound, a titanium compound, a halogen-containing compound and a first electron donating compound. 12. The solid catalyst component of claim 11 wherein D / T &gt;