KR20010013309A - Olefinic polymer - Google Patents

Abstract

A propylene polymer having specified relationships between a melt index and a molecular weight distribution and also between a melt tension and a limiting viscosity which is in a specified range and also having a long chain branch. It has properties equivalent or superior to those of conventional propylene polymers, and is excellent in melt processability and particularly suitable for blow molding or extrusion foam molding to give large-sized moldings. The polymer is suitable for use as a compatibilizer for a propylene homopolymer with a propylene copolymer.

Description

Olefin Polymer {OLEFINIC POLYMER}

Conventionally, polypropylene has (1) high mechanical strength such as rigidity, excellent physical property balance, (2) chemical stability, good weather resistance, hard to penetrate chemicals, etc., (3) high melting point, and high heat resistance. (4) Light weight and low cost, and at the same time excellent melt moldability, it is possible to apply melt molding methods such as extrusion molding, blow molding, injection molding, inflation molding, and so on. Was used.

By the way, many of the amorphous resins, such as polystyrene, have been used for the foam of thermoplastic resin by the point which can carry out extrusion foam molding comparatively easily. However, in recent years, there has been a demand for obtaining a foam having excellent heat resistance and impact resistance as well as quality of light weight, heat insulation, damping ability, etc., and thus a foam of polypropylene resin has been required.

However, polypropylene has a problem in that the crystallinity is relatively high, the viscoelasticity is greatly changed by a small temperature change, and the foaming optimum temperature range is very narrow. In addition, since the melt viscosity at a temperature above the crystal melting point is very low and the melt tension is insufficient, the foamed bubbles are not maintained and are easily broken. Therefore, it is difficult to obtain a foam having good mechanical properties and heat resistance having independent bubbles, and in order to extrude and foam a polypropylene resin like a polystyrene resin, the moldable temperature range is expanded and the melt viscoelasticity is higher than the melting point. Should be high.

In addition, polypropylene resins having the characteristics described above are actively used in automobile parts and the like taking advantage of their excellent properties, but there is a strong demand for further improvement in performance and cost reduction through simplification of the process for molding the resin. If a large part that has conventionally been produced by injection molding can be produced by blow molding, the manufacturing cost can be greatly reduced.

However, conventional polypropylene has low melt tension and melt viscoelasticity, poor parison stability when used for large blow molding, and drawdown phenomenon. Therefore, blow molding of large parts was difficult. In addition, when the molecular weight is increased in order to improve the melt tension, the melt fluidity is lowered, which leads to a problem in that it cannot be adapted to molding of a complicated shape.

As described above, in order to further expand the field of use of polypropylene, improvement of molding processability is required, and various attempts have been made to improve melt processability such as melt viscoelasticity of polyolefin.

In general, the introduction of a long chain branch into the polymer chain improves the melt processing properties by the branch. As a polymer branch constituting the branch with a monomer different from the polymer main chain, in the so-called composite material field composed of a heterogeneous polymer, It is possible to increase the dispersibility of the polymer by lowering the interfacial tension and to effectively impart incompatible physical properties such as impact strength and rigidity. In addition, because of the micro phase separation structure, it is possible to apply to various elastomers. However, in the field of polyolefins, there are limitations in the development of applications because of the limitation in introducing branches. When this is possible, it is expected that the field of application will be greatly expanded from the environmental suitability represented by the excellent mechanical properties and recycling properties inherent in polyolefins.

For example, (1) a method of mixing a high molecular weight high density polyethylene having a high melt tension (Japanese Patent Publication No. 94-55868, (2) a high melt tension high density polyethylene produced by a chromium-based catalyst is mixed. (Japanese Patent Application Laid-Open No. 96-92438, (3) A method of mixing low density polyethylene produced by a general high pressure radical polymerization method, (4) A method of increasing melt tension by irradiation with general polypropylene, (5 ) A method of increasing melt tension by irradiating general polypropylene in the presence of a crosslinking agent or a peroxide, (6) A method of grafting radical polymerizable monomers such as styrene to general polypropylene, and (7) A method of copolymerizing propylene and polyene. Japanese Patent Laid-Open No. 93-194778 and Japanese Patent Laid-Open No. 93-194779 have been tried.

However, in the above methods (1) to (3), the elastic modulus, strength, and heat resistance of the component that increases the melt tension are insufficient, so that the inherent characteristics of the polypropylene cannot be avoided, and the properties of the foam are also reduced. In addition, in the above methods (4) and (5), since it is difficult to control the crosslinking reaction occurring as a side reaction, the occurrence of gel causes adverse effects on appearance defects and mechanical properties, and also affects the formability between molecules. It is difficult to arbitrarily control the degree of crosslinking by the polymer reaction, and there is a problem that the control range is narrow. Moreover, in the method of said (6), the chemical stability of polypropylene is impaired, and also the problem of the recycling property of resin arises in a styrene type graft polymer. Moreover, in the method of said (7), the improvement result of melt tension is small, a sufficient effect cannot be exhibited, and a gel may be generated.

In addition, in the ethylene polymer, an ethylene polymer with improved melt tension has recently been proposed in spite of a narrow molecular weight distribution by a catalyst system combined with a metallocene catalyst and aluminoxane (Japanese Patent Publication No. 92-213306). Hobo publication). It is also disclosed that the ethylene polymer produced by a constrained geometric addition-type catalyst improves the melt tension even though the molecular weight distribution is similar (Japanese Patent Publication No. 91-163088). The presence of long chain branching has been suggested. In addition, the production of this long chain branch has been proposed a mechanism in which an ethylene polymer having a molecular chain terminal at the time of polymerization is produced with an ethylene polymer, which is polymerized again as a macromonomer.

Further, branched polyolefins having a homopolymer or copolymer of α-olefins having 2 to 30 carbon atoms as a main chain and branching to a homopolymer or copolymer of α-olefins having 250 or more carbon atoms have been disclosed (Japanese Patent Publication No. 96). -502303), a method of forming a branched branched olefin via a production of terminal vinyl macromonomers.

However, according to this publication, macromonomers are produced by the transfer of β hydrogen. However, according to this theory, when propylene is used for polymerization, the transfer of β hydrogen results in an internal olefin or vinylidene structure, and no macromonomer of terminal vinyl is produced. In addition, as a method of obtaining a macromonomer other than ethylene, a method of producing by capping with ethylene by adding ethylene in the final stage of the polymerization reaction has been suggested, and it is clear that ethylene is essential for producing the macromonomer. In addition, in this method, since the chain transfer reaction in the polymerization reaction field is very fast, even when ethylene is introduced, β hydrogen does not move to produce block-type macromonomer after producing a block copolymer with ethylene. Macromonomers of ethylene alone are produced. As mentioned above, it is clear that the technique disclosed in the said publication is a technique applicable only to an ethylene polymer, and the technique in which the alpha-olefin of propylene or more produces a macromonomer is not disclosed and is not suggested.

In addition, as a technique for introducing a propylene branch into a polyolefin polymer, (8) a method of copolymerizing a propylene oligomer produced by a catalyst system combining a specific metallocene catalyst and aluminoxane and the like (Patent No. 2554071) and (9) A method for producing a terminal vinyl type ethylene-propylene copolymer usable as a macromonomer by a catalyst system combining a specific metallocene catalyst and aluminoxane (Japanese Patent Publication No. 93-320260) is disclosed. It is.

However, in the method (8), since the propylene macromonomer introduced as a side chain is an oligomer of about dimer to hexamer, the improvement effect of melt tension is small and sufficient moldability cannot be obtained. Moreover, in the method of (9), since the propylene content of a terminal vinyl type ethylene-propylene copolymer is low about 10-30 mol%, and it is substantially no stereoregularity, the elasticity modulus, strength, and heat resistance of a copolymer become low. That is, there is a problem that the excellent properties of polypropylene inherently have to be compromised.

In addition, as the impact-resistant polypropylene composition, a mixture of a relatively low molecular weight and high stereoregular propylene homopolymer and a relatively high molecular weight ethylene / propylene random copolymer is used. Also in the packaging film, since the melting point of the polypropylene is relatively high, the propylene random copolymer obtained by copolymerizing the propylene homopolymer, propylene, ethylene or other α-olefin for the purpose of improving the heat sealing property at low temperature; Mixtures are used. However, in this case, since the crystallinity and molecular weight of the propylene homopolymer and the propylene random copolymer are different, both components are difficult to use and cause a decrease in impact resistance and rigidity. To improve this, it is effective to add a component compatible with both components, namely a block copolymer having a polypropylene block and a propylene / other α-olefin (including ethylene) copolymer block, or a graft copolymer. It is known.

Summary of the Invention

Under the circumstances, the present invention has physical properties equivalent to or higher than those of conventional propylene polymers, and have sufficient melt tension, melt viscoelasticity, melt flowability, and the like, and are excellent in melt processing characteristics. It is also suitable as a compatibilizer of a propylene homopolymer, a propylene block copolymer or a random copolymer, and is also suitable for forming, and for the purpose of providing a propylene copolymer that can be used for high performance of polyolefin composite materials, elastomers, and the like. It is.

The present inventors have diligently studied to develop a branched polyolefin having excellent melt processing properties, and found that a specific olefin polymer is suitable for the purpose.

The specific olefin polymer is firstly a propylene polymer having a predetermined intrinsic viscosity, for example, a propylene homopolymer or propylene and ethylene and / or carbon number, each having a specific relationship between melt index, molecular weight distribution, melt tension and intrinsic viscosity. It is a propylene copolymer which has a copolymerization part with four or more alpha-olefins as a graft chain.

Secondly, branched polyolefins in which the main chain and the side chain each have a specific structure and the stereoregularity of the side chain are in a specific range.

Thirdly, the propylene content, the melt index and the molecular weight distribution, the melt tension and the melt index have specific relations, respectively, and have a predetermined intrinsic viscosity, and an ethylene, an α-olefin having 3 to 20 carbon atoms, a cyclic olefin and a styrene. It is a branched polyolefin which has a copolymerization part with a kind or more selected from the graft chains.

The present invention has been completed according to the above findings.

That is, this invention provides the olefin polymer shown below.

(1) (a) Ratio of melt index MI ₅ (g / 10 min) measured at a temperature of 230 ° C. under a load of _5.0 kg and a melt index MI _2.16 (g / 10 min) measured under a load of 2.16 kg MI ₅ / The ratio Mw / Mn between MI _2.16 and the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography is expressed by the following equation.

MI ₅ / MI _2.16 ? 0.240 x Mw / Mn + 3.1... (Ⅰ)

And (b) the melt viscosity MS (g) measured at a temperature of 230 ° C and the ultimate viscosity [η] (dl / g) measured at a temperature of 135 ° C in a tetralin solvent.

logMS? 3.17 x log [?]-0.68... (Ⅱ)

The intrinsic viscosity [η] is in the range of 0.1 to 15.0 dl / g while satisfying the relationship of propylene-based polymer.

As the propylene polymer, for example, a propylene copolymer having a copolymerization portion of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms as a graft chain, preferably Mw / Mn is 1.5 to 4.0, and furthermore, A propylene copolymer whose content of a copolymerization part with ethylene and / or a C4 or more alpha-olefin is 3 weight% or more is mentioned. This propylene copolymer can be used as a compatibilizer between a propylene homopolymer and a propylene block copolymer or a propylene random copolymer.

As another example, a propylene homopolymer, Preferably, the Mw / Mn is 1.5-4.5 and the melting point measured with the differential scanning calorimeter is 120-165 degreeC.

(2) a main chain composed of a polymer of at least one monomer selected from ethylene, alpha -olefins having 4 to 20 carbon atoms, cyclic olefins and styrenes, propylene homopolymer or propylene and ethylene, alpha -olefins having 4 to 20 carbon atoms, and cyclic Those having side chains composed of copolymers of at least one monomer selected from olefins and styrenes, and having an isotactic triad fraction [mm] of not less than 80% indicating stereoregularity of propylene linkages in the side chains. Vapor phase polyolefin, or

(3) a main chain composed of a polymer of at least one monomer selected from α-olefins, cyclic olefins and styrenes having 2 to 20 carbon atoms, and selected from propylene and ethylene, α-olefins having 4 to 20 carbon atoms, cyclic olefins and styrenes; A branched polyolefin having an isotactic triad fraction [mm] having a side chain composed of a copolymer with one or more monomers and showing stereoregularity of propylene linkages in the side chain.

In the branched polyolefin of (2) or (3), the weight average molecular weight of polyethylene equivalent measured by gel permeation chromatography (GPC) method is 5,000 to 1,000,000, and melt tension MS has the same copolymer composition and melt index MI. The melt tension MS (g) measured at a temperature of 230 ° C. and the melt index MI (g / l 0 min) are larger than the melt tension MS of the linear polyolefin.

logMS? -0.907 x logMI + 0.375? (Ⅰ)

It is preferable that the content of propylene in the range of 60-99.9 mol%, the main chain and side chain constituent monomers which comprise a branched polyolefin are the same, and substantially do not contain a gel, satisfying the relationship of

(4) (a) the content of propylene is in the range of 60 to 99.9% by weight, and (b) measured under a melt index MI ₅ (g / 10 min) and a load of 2.16 kg measured at a temperature of 230 ° C. under a load of _5.0 kg. The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn measured by the gel permeation chromatography to the melt index MI _2.16 (g / 10min) MI ₅ / MI _2.16

MI ₅ / MI _2.16 ≥ 0.240 × Mw / Mn + 3.10 (Ⅰ)

(C) melt tension MS (g) and melt index MI (g / 10min) measured at a temperature of 230 ° C

logMS> -0.907 × logMI + 0.375 (II)

Intrinsic viscosity [η] measured at a temperature of 135 ° C. in a tetralin solvent while satisfying the relationship of, and is selected from α-olefins, cyclic olefins and styrenes having 2 to 20 carbon atoms. A branched polyolefin having a main chain (except propylene homopolymer chain) composed of the above, and a copolymerization portion of ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrene as graft chains.

In this branched polyolefin, it is preferable that content of the copolymerization part of ethylene and one or more types chosen from C3-C20 alpha-olefin, cyclic olefin, and styrene is 3 weight% or more, while Mw / Mn is 1.5-4.0.

This branched polyolefin is preferable as a compatibilizer between a propylene homopolymer and a propylene block copolymer or a propylene random copolymer.

The present invention relates to propylene polymers, in particular branched propylene polymers, more particularly to physical properties equivalent to or greater than those of conventional propylene polymers, and at the same time excellent in melt processing properties, in particular large blow molding or extrusion. The present invention relates to a propylene polymer suitable for use in foam molding and the like.

The present invention also relates to a propylene polymer having a function as a compatibilizer between polyolefin resins in a composite material composed of a propylene polymer, a propylene block copolymer, a random copolymer, and the like, and which can be used for high performance of a composite material, elastomerization, and the like. .

The propylene polymer which is 1st aspect of this application is a long-chain branched propylene polymer which is narrow in molecular weight distribution and excellent in the balance of a physical property and workability because it can control the non-Newtonian property of melt flow and melt tension. Specific examples thereof include a long-chain branched propylene homopolymer made of only a propylene monomer, a long-chain branched propylene copolymer made of propylene and ethylene and / or an α-olefin having 4 or more carbon atoms.

Moreover, the propylene polymer which is this invention has the property shown below.

First, a melt index measured at a temperature of 230 ℃ under a load of 5.0kg MI ₅ (g / 10min) and the melt index under the load of 2.16kg MI _2.16 (g / 10min) Non-MI with ₅ g / MI _2.16 g and a gel The ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn measured by permeation chromatography (GPC) is

MI ₅ / MI _2.16 ? 0.240 x Mw / Mn + 3.10... (Ⅰ)

It is necessary to satisfy the relationship.

When MI ₅ / MI _2.16 is smaller than the value of “0.240 × Mw / Mn + 3.1”, the melt workability is poor and the object of the present invention cannot be achieved. In terms of melt processability, preferably,

MI ₅ / MI _2.16 ≥ 0.240 × Mw / Mn + 3.8

More preferably

MI ₅ / MI _2.16 ≥ 0.240 × Mw / Mn + 4.5

to be.

In addition, melt index MI measured MI in the temperature of 230 degreeC, and 2.16 kg of loads based on ASTMDl238. In the measurement, 4000 ppm by weight of a mixture of Irganox 1010 (Irganox 1010) and BHT 1: 1 by weight ratio was previously added as an antioxidant. Although measurement temperature is 230 degreeC normally, you may set arbitrarily in the range of 190-300 degreeC with the monomer to comprise, and when molecular weight is large and melt fluidity is low, you may measure at high temperature in this range.

In addition, said Mw / Mn is the value computed by the weight average molecular weight (Mw) and number average molecular weight (Mn) of polyethylene conversion measured by the following apparatus and conditions by the gel permeation chromatography (GPC) method.

Device: Main Body Waters ALC / GPC 150C

Column dosing TSK MH + GMH 6 × 2

Condition: Temperature 135 ℃

Solvent 1, 2, 4-trichlorobenzene

Flow rate 1.0ml / min

Next, the melt viscosity MS (g) measured at a temperature of 230 ° C and the ultimate viscosity [η] (dl / g) measured at a temperature of 135 ° C in a tetralin solvent are expressed by the following equation.

logMS> 3.17 x log [η]-0.68... (Ⅱ)

It is necessary to satisfy the relationship.

When logMS is smaller than the value of "3.17 x log [η]-0.68, the melt workability is inferior to the objective of this invention. In terms of melt processability

Preferably

logMS> 3.17 x log [η]-0.57

More preferably

logMS> 3.17 x log [η]-0.46

Particularly preferably

logMS> 3.17 x log [η]-0.35

to be.

In addition, the intrinsic viscosity [η] needs to be in the range of 0.1 to 15.0 dl / g. If this [η] is less than 0.1 dl / g, melt workability will be inferior, and mechanical strength will be insufficient at the same time, and if it exceeds 15.0 dl / g, melt viscosity will be high and melt workability will fall. In view of the balance between melt processability and mechanical strength and the like, 0.4 to 10.0 dl / g is preferable as this [η], and a range of 0.6 to 6.0 dl / g is particularly preferable.

In addition, the said melt tension MS is the value measured on condition of the following using Capirograph 1B by a Toyo Seiki company.

Capillary: diameter 2.095 mm, length 8.0 mm

Cylinder diameter: 9.6 mm

Cylinder Extrusion Speed: 10mm / min

Winding Speed: 3.14 m / min

Temperature: 230 ℃

In addition, the propylene polymer of the present invention preferably has a ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn in the range of 1.5 to 4.5. The Mw / Mn of more than 4.5 is difficult to obtain a physical property that can be sufficiently satisfied because the molecular weight distribution is too wide. In addition, it is difficult to manufacture substantially that Mw / Mn is less than 1.5. In terms of physical properties, more preferred Mw / Mn is in the range of 1.5 to 4.0, particularly preferably in the range of 1.5 to 3.5.

In addition, it is preferable that melting | fusing point Tm measured with the differential scanning calorimeter (DSC) exists in the range of 120-165 degreeC. If the melting point is less than 120 ° C, the heat resistance is insufficient. On the other hand, if the melting point exceeds 165 ° C, the molding temperature becomes too high and economically undesirable. In consideration of heat resistance and economical efficiency of molding, a more preferable range of this melting point is 130 to 165 캜.

In addition, this melting | fusing point Tm is the value measured by the following method using the differential scanning calorimeter "DSC-7" by a Perkin Elmer Co., Ltd. product. That is, using a sheet obtained by hot pressing at 190 ° C as a sample, after melting for 5 minutes at 200 ° C with the DSC-7, the temperature was lowered to 20 ° C at a rate of 10 ° C / min and maintained for 5 minutes, The temperature is raised at a rate of 10 ° C./min, and the melting point Tm is obtained from the endothermic peak shown in the process.

Moreover, it is preferable that the propylene polymer of this invention has a low molecular weight component or an atactic part. For example, it is preferable that content of the component soluble in diethyl ether is 2 weight% or less, and it is especially preferable that it is 1 weight% or less. In addition, content of the component soluble in this diethyl ether is the value measured by the following method.

That is, about 3 g of powdered polymer was put into a Soxlet's extractor, and extracted with 160 ml of diethyl ether for 6 hours. Thereafter, the extraction solvent was distilled off by a rotary evaporator, and the component soluble in diethyl ether was further recovered by vacuum drying to measure the weight.

The propylene polymer of the present invention includes a propylene copolymer. The propylene copolymer is preferably one having a copolymerized portion of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms as a graft chain, and in particular, one having a main chain made of a propylene homopolymer and the copolymerized portion as a graft chain. Do. Here, it is preferable that content of a copolymerization part is 3.0 weight% or more. If the content is less than 3.0% by weight, it is difficult to obtain an excellent balance between physical properties and melt processability, and the performance as a compatibilizer between the propylene homopolymer and the propylene block copolymer or the propylene random copolymer is not sufficiently exhibited. In addition, when there is too much content, there exists a possibility that the intrinsic physical property of polypropylene resin may be impaired. In consideration of physical properties, melt processability, performance as the compatibilizer, and the like, more preferable content of this copolymerization portion is in the range of 5 to 50% by weight, particularly preferably in the range of 4.0 to 30% by weight.

In addition, when a graft chain consists of a copolymerization part of propylene and ethylene and / or the C4 or more alpha-olefin, content of each component can be calculated | required according to the method mentioned later.

In the propylene copolymer, the content of comonomer units other than propylene in this copolymer portion is usually in the range of 1.0 to 50% by weight, preferably 2.0 to 30% by weight.

Moreover, as comonomer, C4 or more alpha olefins including ethylene, for example, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, decene-1, dodecene -1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1, etc. are used, These may be used independently and may be used in combination of 2 or more type.

The manufacturing method of the propylene polymer of this invention should just be a method which can obtain the propylene polymer which satisfy | fills the said requirements, and there is no restriction | limiting in particular. For example, when producing a propylene homopolymer, the desired propylene polymer is efficiently polymerized by polymerizing propylene with a reactive macromonomer obtained by reacting propylene in the presence of a catalyst for olefin polymerization in the presence of a catalyst for olefin polymerization. It can manufacture. In the case of producing a propylene copolymer, for example, a reactive macromonomer and propylene obtained by reacting propylene with ethylene and / or an α-olefin having 4 or more carbon atoms in the presence of a catalyst for olefin polymerization can be used as a catalyst for olefin polymerization. By polymerizing in the presence of, a desired propylene copolymer can be efficiently produced.

At this time, various catalysts can be used without particular limitation as the catalyst for olefin polymerization, but a metallocene catalyst composed of a transition metal compound shown below and a compound capable of forming an ionic complex by reacting with it is preferably used.

Representative of the transition metal compound, a transition metal compound of Group 4 of the periodic table having a ligand in which two indenyl groups having substituents, which can regulate the steric structure of the polymer, are crosslinked by five or more rings with one or two crosslinking groups Can be mentioned. As the transition metal of Group 4 of the periodic table, titanium, zirconium, and hafnium are preferable.

As the transition metal compound of Group 4 of the periodic table having the indenyl skeleton, for example, (i) Hoechst, BASF-type complex, (B) double-crosslinked complex and the like can be used.

As the above-mentioned hobst and BASF type complexes, for example, rac-dimethylsilylene-bis (2-methyl-4-phenylindenyl) zirconium dichloride and rac-dimethylsilylene-bis (2-methyl-5 And titanium and hafnium compounds corresponding to these zirconium compounds, such as 6-benzoindenyl) zirconium dichloride and rac-ethylenebisindenyl zirconium dichloride. On the other hand, as the double-crosslinked complex of (B), for example, (1, 2'-ethylene) (2, 1'-ethylene) -bis (4, 7-dimethylindenyl) zirconium dichloride, (1 And titanium or hafnium compounds corresponding to these zirconium compounds, such as 2'-ethylene) (2,1'-ethylene) -bis (4-phenylindenyl) zirconium dichloride.

On the other hand, examples of the compound capable of reacting with the transition metal compound to form an ionic complex include, for example, an aluminum oxy compound, an ionic compound composed of a cation and an anion bonded to a plurality of groups, and a Lewis acid. Among these, aluminum oxy compounds are preferable, and aluminoxane is particularly preferable. Examples of this aluminoxane include methylaluminoxane, ethylaluminoxane, n-propylaluminoxane, isobutylaluminoxane, methyl-ethylaluminoxane, methyl-n-propylaluminoxane, methyl-isopropylaluminoxane and ethyl-n -Propyl aluminoxane, ethyl-isopropyl aluminoxane, etc., and those in which 2 or more types were mixed are mentioned.

The propylene macromonomer used in this method is preferably a macromolecule and a propylene homopolymer continuously produced using a single reactor, but only the macromonomer may be prepared and added in the preparation of the propylene homopolymer, and a single step In polymerization, a macromonomer and a propylene homopolymer can also be manufactured simultaneously. In this case, the catalyst for producing the propylene homopolymer and the catalyst used for producing the macromonomer are preferably the same, but other catalysts may be used.

There is no restriction | limiting in particular about a polymerization method, You may use any method of a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and suspension polymerization method. In addition, during the polymerization, the molecular weight of the polymer obtained can be controlled by using a commonly used chain transfer agent such as hydrogen.

In addition, when using a polymerization solvent in solution polymerization method, slurry polymerization method, etc., what is necessary is just to be inert to superposition | polymerization as this solvent, and there is no restriction | limiting in particular, For example, aromatic hydrocarbons, such as benzene, toluene, xylene, pentane, hexane, heptane And alicyclic hydrocarbons such as aliphatic hydrocarbons such as octane, cyclopentane, and cyclohexane.

In addition, polymerization temperature may be suitably selected suitably in the range of 0-250 degreeC normally according to a polymerization method, and polymerization pressure is normally 0.01-100 kg / cm <^2> G, Preferably it is 0.2-60 kg / cm <^2> G. It is good to select from. Moreover, polymerization time is about 1 minute-about 10 hours normally.

The propylene polymer of the present invention thus obtained has physical properties comparable to or higher than those of conventional propylene polymers, and at the same time have sufficient melt tension, melt viscoelasticity, melt flowability, and the like, and excellent melt processing properties, especially large Blow molding, extrusion foam molding, etc. can be used suitably.

Further, a propylene copolymer having a copolymerization portion of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms as a graft chain may be a propylene homopolymer and a propylene random copolymer or a block copolymer (propylene and ethylene and / or 4 or more carbon atoms). -Random copolymer with olefin, block copolymer).

Next, the second invention of the present application will be described.

The branched polyolefin of the present invention is composed of a main chain and a side chain of a specific structure, is made of α-olefin, cyclic olefin and / or styrenes, and can control the non-newtonability and melt tension of the melt flow, so that the physical properties and processability It is a polyolefin excellent in the balance, and has a structure and a characteristic shown below.

The main chain and the side chain of the branched polyolefin of the present invention include (1) a main chain composed of a polymer of ethylene, an α-olefin having 4 to 20 carbon atoms, a cyclic olefin, and one or more monomers of styrene, a propylene homopolymer or propylene and ethylene, and a carbon number. Side chains composed of copolymers of 4 to 20 α-olefins, cyclic olefins and styrenes with one or more monomers, or (2) polymers of one or more monomers of α-olefins, cyclic olefins and styrenes having 2 to 20 carbon atoms And a side chain comprising a copolymer of propylene and ethylene, at least one monomer of olefins having 4 to 20 carbon atoms, cyclic olefins and styrenes.

As alpha-olefin which is a structural monomer of this main chain and a side chain, For example, ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 4-methyl-1- pentene, 1- Octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicocene and the like are cyclic olefins, for example, cyclopentene, cyclohexene, norbornene, 1 -Methylnorbornene, 5-methylnorbornene, 7-methylnorbornene, 5, 6-dimethylnorbornene, 5, 5, 6-trimethylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5-phenyl Norbornene and the like are styrenes, for example, alkyl styrenes such as styrene, p-methyl styrene, m-methyl styrene, o-methyl styrene, 2, 5-dimethyl styrene and pt-butyl styrene, p-chloro styrene, m-chlorostyrene, o-chlorostyrene, p-bromostyrene, m-bromostyrene, o-bromostyrene, p-fluorostyrene, m-fluorostyrene, o-fluorostyrene, o-methyl- halogenated styrenes such as p-fluorostyrene, 4 Vinyl biphenyls, such as -vinyl biphenyl, 3-vinyl biphenyl, and 2-vinyl biphenyl, etc. are mentioned.

In the present invention, the olefins may be used in one kind or in combination of two or more kinds so as to meet the above conditions of ① or ②. When using 2 or more types of olefins, the said olefins can be combined arbitrarily.

In a side chain, it is preferable that propylene content is 50 mol% or more, It is more preferable that it is 60 mol% or more, It is further more preferable that it is 70 mol% or more. When the propylene content is within the above range, sufficient mechanical properties can be obtained. In addition, there is no restriction | limiting in particular about the primary structure of a side chain, Any structure, such as a branched form which has a linear or long chain branch, may be sufficient.

Regarding stereoregularity, any of atactic, isotactic, and syndiotactic structures may be used in monomers other than ethylene in the main chain, and therefore, any of amorphous and crystalline structures may be used. In the side chain, it is necessary that the isotactic triad fraction [mm] indicating the stereoregularity of the propylene linkage is 80% or more. If it is lower than 80%, the mechanical strength is lowered, which is not preferable. In terms of mechanical strength, 85% or more is more preferable, and 90% or more is more preferable.

The isotactic triad fraction [mm] used in the present invention refers to the polypropylene molecular chain measured by ¹³ C nuclear magnetic resonance spectra described in the Polymer Handbook, Japanese Society for Analytical Chemistry Polymer Analysis Research. Mean isotactic fraction in triad units. In addition, the method of determining the peak attribution in the measurement of the ¹³ C nuclear magnetic resonance spectrum was in accordance with the attribution proposed in A. Zambelli et al., "Macromolecules, 8, 687 (1975)".

The weight average molecular weight Mw of the branched polyolefin of the present invention is preferably 5,000 to 1,000,000, more preferably 10,000 or more, still more preferably 15,000 or more, and particularly preferably 20,000 or more. If the weight average molecular weight is lower than 5,000, the mechanical strength is lowered, which is not preferable.

There is no restriction | limiting in particular about the molecular weight distribution of the branched polyolefin of this invention, Usually, ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 1.5-30, Preferably it is 1.5-15, More preferably Preferably 1.5 to 10, more preferably 1.5 to 5, particularly preferably 1.5 to 4.5. Within this range, sufficient mechanical strength can be obtained.

The side chain of the branched polyolefin is usually a chain length having a weight average molecular weight of 2,000 to 500,000 of 100 to 40,000 carbon atoms or a macromonomer which is a raw material of the side chain.

As the number of branches, it usually has a branch of 0.001 to 10 / 1,000 carbon atoms.

In addition, the said weight average molecular weight was measured by the gel permeation chromatography (GPC) method demonstrated in 1st invention of this application. The measurement apparatus and the measurement conditions are also the same as those described in the first invention.

Moreover, it is preferable that melt tension MS (branch) of the branched polyolefin of this invention is larger than melt tension MS (linear) of linear polyolefin which made copolymerization composition and melt index MI the same. In other words,

MS (branch) ＞ MS (straight chain)

to be. If this relationship is within the above range, sufficient melt processability can be obtained. In terms of melt processability, more preferably,

MS (branch) ≥ 1.03 MS (straight chain)

More preferably,

MS (branch) ≥ 1.05 MS (straight chain)

Particularly preferably,

MS (branch) ≥ 1.07 MS (straight chain)

More preferably,

MS (branch) ≥ 1.09 MS (straight chain)

to be.

Herein, the linear polyolefin is a polypropylene prepared by using an organic aluminum as a cocatalyst as a main catalyst of all polyolefins prepared using a titanium compound and an organoaluminum compound as essential components, for example, titanium tetrachloride supported on magnesium chloride. It refers to the ethylene propylene copolymer etc., and the whole polyolefin which does not contain a C50 or more side chain. In addition, the comparison between MS (branch) and MS (straight chain) was performed by adjusting the copolymer composition and melt index MI of the linear polyolefin to be within ± 5% of the copolymer composition and melt index MI of the branched polyolefin.

In addition, melt tension MS (g) and melt index MI (g / 10min) measured at the temperature of 230 degreeC of the branched polyolefin of this invention are a mathematical formula.

logMS ≧ −0.907 × logMI + 0.375... (Ⅰ)

It is preferable that propylene content exists in the range of 60-99.9 mol%, satisfying the relationship of the.

If 1ogMS is smaller than the value of -0.907 x logMI + 0.375, melt workability is inferior and it is not preferable. More preferably in terms of melt processability

1ogMS ≥ -0.907 × 1ogMI + 0.450

More preferably,

1ogMS ≥ -0.907 × logMI + 0.50

Particularly preferably,

1ogMS ≥ -0.907 × 1ogMI + 0.60

to be.

The melt index MI and melt tension MS were measured by the methods and conditions described in the first invention herein.

As a specific example of the branched polyolefin of this invention, although the following structure is mentioned by the structure of a principal chain, it is not limited to this.

(1) ethylene-based

(1) A branched polyethylene having a copolymer of isotactic polypropylene or propylene and ethylene or an α-olefin having 4 to 20 carbon atoms as a branch relative to the main chain polyethylene.

(2) A branched polyethylene having a copolymer of propylene with cyclic olefins or styrenes as a branch relative to the main chain polyethylene.

(3) The main chain is copolymerized polyethylene of ethylene and alpha -olefins having 4 to 20 carbon atoms, cyclic olefins or styrenes, and isobranched polypropylene or propylene as a branch copolymer of ethylene or alpha -olefin having 4 to 20 carbon atoms. Having branched polyethylene.

(4) A branched polyethylene whose main chain is a copolymerized polyethylene of ethylene with an alpha -olefin, cyclic olefin or styrene having 4 to 20 carbon atoms and which has a copolymer of propylene with a cyclic olefin or styrene as a branch.

Said branched polyethylene is crystalline or amorphous, and when it is crystalline, it has melting | fusing point normally at 60-135 degreeC. In addition, the ethylene content of a principal chain exceeds 50%.

(2) propylene

(1) Branched polypropylene having isotactic polypropylene as branch to the main chain polypropylene. However, the stereoregularity of the main chain is an atactic or syndiotactic structure.

(2) A branched polypropylene having a copolymer of propylene and ethylene or an α-olefin having 4 to 20 carbon atoms as a branch to the main chain polypropylene. However, the stereoregularity of the main chain is an atactic, syndiotactic or isotactic structure.

(3) Branched polypropylene having a copolymer of propylene with cyclic olefins or styrenes as a branch to the main chain polypropylene. However, the stereoregularity of the main chain is an atactic, syndiotactic or isotactic structure.

(4) The main chain is copolymerized polypropylene of propylene with ethylene, α-olefin having 4 to 20 carbon atoms, cyclic olefins or styrenes, and isotactic polypropylene or propylene as a branch with ethylene or α-olefin having 4 to 20 carbon atoms. Branched polypropylene with copolymers. However, the stereoregularity of the main chain is an atactic, syndiotactic or isotactic structure.

(5) Branched polypropylene in which the main chain is propylene and ethylene, copolymerized polypropylene of alpha -olefin, cyclic olefin or styrene having 4 to 20 carbon atoms, and has a copolymer of propylene and cyclic olefin or styrene as a branch. However, the stereoregularity of the main chain is an atactic, syndiotactic or isotactic structure.

The branched polypropylene is crystalline or amorphous, and in the case of crystallinity, usually has a melting point at 60 to 163 ° C. In addition, the propylene content of a principal chain exceeds 50%.

(3) higher α-olefin type

(1) A branched polyolefin in which the main chain is a polymer of? -Olefins of 4 to 20 carbon atoms, and has isotactic polypropylene or propylene as a branch and a copolymer of ethylene and? -Olefins of 4 to 20 carbon atoms.

(2) A branched polyolefin in which the main chain is a polymer of? -Olefins having 4 to 20 carbon atoms and has a copolymer of propylene with cyclic olefins or styrenes as a branch.

(3) The main chain is a copolymerized polyolefin of an alpha -olefin having 4 to 20 carbon atoms and an alpha -olefin, cyclic olefin or styrene having 4 to 20 carbon atoms except for this olefin, and isotactic polypropylene or propylene and ethylene or 4 carbon atoms as a branch. Branched polyolefin having a copolymer with? -Olefins of from 20 to 20.

(4) The main chain is a copolymerized polyolefin of an alpha -olefin having 4 to 20 carbon atoms and an alpha -olefin, cyclic olefin or styrene having 4 to 20 carbon atoms excluding the olefin, and a branched copolymer of propylene and a cyclic olefin or styrene. Having branched polyolefins.

The branched polyolefin is crystalline or amorphous. The stereoregularity of the main chain is atactic, syndiotactic or isotactic structure. In addition, the higher α-olefin content of the main chain is more than 50%.

(4) cyclic olefins

(1) A branched polycyclic olefin having a copolymer of isotactic polypropylene or propylene and ethylene or an α-olefin having 4 to 20 carbon atoms as a branch to the main chain polycyclic olefin.

(2) A branched polycyclic olefin having a copolymer of propylene and a cyclic olefin or styrenes as a branch relative to the main chain polycyclic olefin.

(3) The main chain is a copolymer of a cyclic olefin and an α-olefin having 2 to 20 carbon atoms or styrene, and is a branched copolymer of isotactic polypropylene or propylene and ethylene or an α-olefin having 4 to 20 carbon atoms. Branched polycyclic olefin having.

(4) The branched polycyclic olefin having a main chain is a cyclic olefin and a copolymerized polycyclic olefin having 2 to 20 carbon atoms or styrene and having a copolymer of propylene and a cyclic olefin or styrene as a branch.

Said branched polycyclic olefin is crystalline or amorphous. The stereoregularity of the main chain is atactic, syndiotactic or isotactic structure. In addition, the cyclic olefin content of a principal chain exceeds 50%.

(5) styrene

(1) Branched polystyrene having a copolymer of isotactic polypropylene or propylene and ethylene or an α-olefin having 4 to 20 carbon atoms as a branch to the main chain polystyrene.

(2) Branched polystyrene having a copolymer of propylene with cyclic olefins or styrenes as a branch to the main chain polystyrene.

(3) The main chain is styrene and copolymerized polystyrene of C2-C20 olefins, cyclic olefins or styrenes other than styrene, and isotactic polypropylene or propylene as a branch of ethylene or C4-C20 alpha-olefin Branched polystyrene with copolymers.

(4) The branched polystyrene whose main chain is copolymerized polyethylene of styrene and styrene except C2-C20, cyclic olefin, or styrene, and has a copolymer of propylene and cyclic olefin or styrene as a branch.

The branched polystyrene is crystalline or amorphous. The stereoregularity of the main chain is atactic, syndiotactic or isotactic structure. In addition, styrene content of a principal chain exceeds 50%.

The method for producing a branched polyolefin of the present invention may be a method for obtaining a branched polyolefin that satisfies the above requirements. For example, propylene, or propylene and ethylene, having 4 to 20 carbon atoms in the presence of a catalyst for olefin polymerization. Terminal vinyl propylene macromonomers obtained by polymerizing one or more of α-olefins, cyclic olefins and styrenes, propylene or propylene or ethylene, α-olefins having 4 to 20 carbon atoms, cyclic olefins and styrenes The desired branched polyolefin can be efficiently produced by polymerizing one or more kinds of in the presence of a catalyst for olefin polymerization.

In this case, various catalysts can be used as the catalyst for producing the propylene macromonomer and the catalyst for the propylene macromonomer copolymerization, but the metallocene catalyst described in the first invention of the present application is preferably used. Since the typical thing of the catalyst for propylene-type macromonomer manufacture and the typical catalyst for propylene-type macromonomer copolymerization are the same as what was demonstrated by 1st invention of this application, detailed description here is abbreviate | omitted.

There is no restriction | limiting in particular about a superposition | polymerization method and superposition | polymerization conditions, It can select from the range demonstrated by the 1st invention of this application suitably, and can implement.

Moreover, in this invention, a macromonomer and a branched polyolefin can be manufactured continuously using a single reactor. Moreover, only a macromonomer may be manufactured and this may be added at the time of manufacture of a branched polyolefin, and also a macromonomer and a branched polyolefin can be manufactured simultaneously in a single step of superposition | polymerization. At this time, the catalyst for producing a branched polyolefin may be the same as or different from the catalyst used for producing a macromonomer.

Next, the branched polyolefin which is the third invention of the present application will be described.

The branched polyolefin of the present invention is a main chain consisting of at least one selected from α-olefins having 2 to 20 carbon atoms, cyclic olefins and styrene (except for homopolymerization chains of propylene), ethylene and α-olefins having 3 to 20 carbon atoms, It is a long-chain branched polyolefin that has a copolymerization part with at least one selected from cyclic olefins and styrene, has a narrow molecular weight distribution, and can control non-Newtonianity and melt tension of melt flow, and has excellent balance between physical properties and processability. And has the properties shown below.

First, it is necessary that the propylene content in a branched polyolefin exists in the range of 60-99.9 weight%. When the propylene content is less than 60% by weight, heat resistance is impaired or compatibility problems occur. When the propylene content exceeds 99.9% by weight, the component contributing to the commercialization decreases, so that the commercialization performance is lowered. Propylene content is preferably in the range of 65 to 99.5% by weight, more preferably 70 to 99% by weight in view of the compatibility and heat resistance.

Next, the gel permeability of the ratio MI ₅ / MI _2.16 between the melt index MI ₅ (g / 10 min) and the melt index MI _2.16 (g / 10 min) at a load of 2.16 kg measured at a temperature of 230 ° C. under a _5.0 kg load. The ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn measured by chromatography (GPC) is

MI ₅ / MI _2.16 ≥ 0.240 × Mw / Mn + 3.10 (Ⅰ)

It is necessary to satisfy the relationship.

When MI ₅ / MI _2.16 is smaller than the value of “0.240 × Mw / Mn + 3.10”, melt workability is poor and the object of the present invention cannot be achieved. In terms of melt processability, preferably,

MI ₅ / MI _2.16 ≥ 0.240 × Mw / Mn + 3.50

More preferably

MI ₅ / MI _2.16 ≥ 0.240 × Mw / Mn + 3.86

to be.

In addition, the measurement apparatus and measurement conditions of the gel permeation chromatography (GPC) method used for the measurement of said Mw / Mn are the same as that of what was demonstrated by the 1st invention of this application.

In addition, melt tension MS (g) measured at the temperature of 230 degreeC, and melt index MI (g / 10min) (same as _MI2.16 above) by 2.16 kg of load measured at the temperature of 230 degreeC are mathematical formulas.

logMS≥ -0.907 × logMI + 0.375 (II)

It is necessary to satisfy the relationship.

If 1ogMS is "-0.907 x logMI + 0.375" or less, melt workability is inferior, and the objective of this invention cannot be achieved. In terms of melt processability, preferably

1ogMS≥-0.907 × 1ogMI + 0.40

More preferably

1ogMS≥-0.907 × 1ogMI + 0.45

Particularly preferably,

1ogMS≥-0.907 × logMI + 0.50

to be.

In addition, the intrinsic viscosity [eta] measured at the temperature of 135 degreeC needs to exist in the range of 0.1-15.0 dl / g. If this intrinsic viscosity [η] is less than 0.1 dl / g, melt workability will be inferior, and mechanical strength will be insufficient at the same time, and if it exceeds 15.0 dl / g, melt viscosity will become high and melt workability will fall. In view of the balance of melt processability and mechanical strength, the limiting viscosity [η] is preferably 0.4 to 10.0 dl / g, particularly preferably in the range of 0.6 to 6.0 dl / g.

In addition, the melt index MI and melt tension MS were measured by the methods and conditions described in the first invention of the present application.

The branched polyolefin of the present invention preferably has a ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn in the range of 1.5 to 4.0. If Mw / Mn exceeds 4.0, the molecular weight distribution is too wide, and it is difficult to obtain sufficient physical properties. In addition, Mw / Mn of less than 1.5 is practically difficult to manufacture. In terms of physical properties, more preferred Mw / Mn is in the range of 1.5 to 3.5.

In addition, although the branched polyolefin of this invention has a copolymerization part of ethylene and at least 1 sort (s) chosen from the C3-C20 alpha olefin, cyclic olefin, and styrene, it is preferable that content of this copolymerization part is 3.0 weight% or more. . When the content is less than 3.0% by weight, it is difficult to obtain an excellent balance between physical properties and melt processability, and the performance as a compatibilizer between the propylene homopolymer and the propylene block copolymer or the propylene random copolymer is not sufficiently exhibited. In addition, when there is too much content, there exists a possibility that the intrinsic physical property of polypropylene resin may be impaired. In consideration of physical properties, melt processability, performance as the compatibilizer, and the like, a more preferable content of this copolymerization portion is in the range of 3.5 to 50% by weight, particularly preferably in the range of 4.0 to 30% by weight.

In addition, content of the copolymerization part of the said ethylene and at least 1 sort (s) chosen from C3-C20 alpha olefin, cyclic olefin, and styrene can be calculated | required according to the method mentioned later.

In the branched polyolefin of the present invention, the content of comonomer units in the copolymer is usually in the range of 1.0 to 50% by weight, preferably 2.0 to 30% by weight.

Moreover, it is preferable that the branched polyolefin of this invention has few low molecular weight components and an atactic part. For example, it is preferable that content of the component soluble in diethyl ether is 2 weight% or less, and 1 weight% or less is especially preferable. In addition, content of the component soluble in this diethyl ether is the value measured by the following method.

That is, about 3 g of powdery copolymer was put into a Soxhlet extractor and extracted with 160 ml of diethyl ether for 6 hours. Thereafter, the extraction solvent was distilled off by a rotary evaporator, and the component soluble in diethyl ether was further recovered by vacuum drying to measure the weight.

The main chain of the branched polyolefin of the present invention includes ethylene and α-olefins having 3 to 20 carbon atoms, for example, propylene, butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 , Decene-1, dodecene-1, tetradecene-1, hexadecene-1, octadecene-1, eicosene-1 and the like, cyclic olefins such as cyclopentene, cycloheptene, norbornene, 5-ethyl- One selected from styrene, such as 2-norbornene and tetracyclo dodecene, is polymerized independently or two or more types are copolymerized. However, the case where the propylene is polymerized alone is excluded.

In the graft chain of the branched polyolefin of the present invention, as the comonomer, one or more selected from α-olefins having 3 to 20 carbon atoms, the same cyclic olefins and styrenes as described above, or a combination of two or more thereof and ethylene are used. .

The method for producing the long-chain branched polyolefin of the present invention may be a method capable of obtaining a branched polyolefin that satisfies the above requirements, and is not particularly limited. For example, by reacting propylene and ethylene in the presence of a catalyst for olefin polymerization. The desired branched polyolefin can be efficiently produced by polymerizing the obtained reactive macromonomer and propylene / ethylene in the presence of a catalyst for olefin polymerization.

In this case, various catalysts can be used as the catalyst for producing the propylene macromonomer and the catalyst for the propylene macromonomer copolymerization, but the metallocene catalyst described in the first invention of the present application is preferably used. Since the typical thing of the catalyst for propylene-type macromonomer manufacture and the typical catalyst of the propylene-type macromonomer copolymerization are the same as what was demonstrated by 1st invention of this application, detailed description here is abbreviate | omitted.

There is no restriction | limiting in particular about a polymerization method and superposition | polymerization conditions, It can select from the range demonstrated by 1st invention of this application suitably, and can implement.

The propylene-based copolymer of the present invention thus obtained has physical properties comparable to or higher than that of conventional propylene-based polymers, and has sufficient melt tension, melt viscoelasticity, melt flowability, and the like. It can be used suitably for blow molding, extrusion foam molding, sheet molding and the like.

In addition, as a graft chain, the propylene homopolymer and the propylene random copolymer or the block copolymer (propylene and ethylene and the like) have a copolymerization portion of ethylene and at least one selected from α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrene. / Or a random copolymer with an alpha -olefin having 4 or more carbon atoms, a block copolymer).

Next, although an Example demonstrates this invention still in detail, this invention is not limited at all by these examples.

In addition, the physical property evaluation of the olefin polymer obtained by each Example was performed according to the following method about 4000 ppm by weight of the mixture of Irganox 1010 and BHT 1: 1 by weight ratio as an antioxidant previously added.

(1) Melt Index (MI ₅ , MI _2.16 )

In accordance with ASTM D1238, MI ₅ at a load of 5.0 kg and MI _2.16 at a load of 2.16 kg were measured at a temperature of 230 ° C.

(2) melt tension (MS)

It measured according to the method described in the specification body.

(3) Intrinsic viscosity ([η])

It measured at the temperature of 135 degreeC in the tetralin solvent.

(4) melting point (Tm)

It is the value measured according to the following method using the differential scanning calorimeter "DSC-7" by a Perkin Elmer company. That is, after using a sheet obtained by hot pressing at 190 ℃ as a sample, and melted for 5 minutes at 200 ℃ in the DSC-7, after lowering the temperature to 20 ℃ at a rate of 10 ℃ / min, and maintained for 5 minutes, The temperature is raised at a rate of 10 ° C./min to determine the melting point Tm from the endothermic peak shown in this process.

(5) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)

It measured according to the method (gel permeation chromatography (GPC) method described in the specification body.

(6) stereoregularity [mm]

It measured according to the method described in the specification body.

(7) propylene content

^It calculated from the ratio of a methyl group and a methylene group from 1H-NMR spectrum. (8) terminal vinyl group

Presence was confirmed by the presence or absence of the absorption in 907 cm <^-1> of an IR spectrum using the film produced by heat press.

Examples 1 to 6 and Comparative Examples 1 to 3 below are examples corresponding to the first invention of the present application.

Example 1

(1) Preparation of ethylene / propylene copolymerized macromonomer

In a 1.6 liter stainless pressure autoclave equipped with a stirring device, 600 ml of dehydrated toluene and 1.45 mol / liter toluene solution of methylaluminoxane (manufactured by Tosho Akuzo Co.) under nitrogen stream were converted into aluminum atoms in 6 Millimole was added. Stirring was started at 500 rpm while controlling the temperature to 20 ° C., and propylene was fed until saturated at a gauge pressure of 7.0 kg / cm ² G. Thereafter, ethylene was continuously supplied until saturated at a pressure of 2.0 kg / cm ² at a partial pressure. In addition, through the balance line, injection of the bis-pentamethyl cyclopentadiene diethyl hafnium dichloride (Cp ^* ₂ HfC1 ₂₎ of a toluene solution containing 20 μmol 20 ㎖ in the autoclave, which was then initiate the copolymerization at 20 ℃. At this time, the supply of ethylene was continuously introduced for 10 minutes so that the voltage became constant.

After the completion of the reaction, the unreacted monomer was sent out of the autoclave system by depressurization, further removed by nitrogen purge, and then the catalyst component was lost with a small amount of methanol.

The reaction mixture containing the recovered ethylene / propylene copolymerized macromonomer was demineralized with dilute hydrochloric acid / methanol / water. After washing five times with ion-exchanged water, drying with anhydrous magnesium sulfate, and recovering the ethylene / propylene copolymerized macromonomer by evaporation drying, the yield was 59.5 g.

(2) Copolymerization of propylene with ethylene / propylene copolymerized macromonomer

The macromonomer obtained in the above (1) was dissolved in toluene and only the room temperature soluble portion was fractionated. The proportion of soluble part was 76% by weight. The toluene solution of this soluble part was further dehydrated and deoxygenated by nitrogen bubbling.

Into a 0.5 liter stainless pressure resistant autoclave equipped with a stirring device, 6 mL of dehydrated toluene 200 ml and a 1.45 mol / liter toluene solution (manufactured by Toso Akujozu) of methylaluminoxane (manufactured by Toso Akujozu) in a nitrogen atom was charged therein, A toluene solution of 16 g of copolymerized macromonomer was added thereto and left for 10 minutes while stirring at 25 ° C.

To 2 μmol of rac-dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride (rac-Me ₂ Si [2-Me-4-Ph-Ind] ₂ ZrC1 ₂ ) After adding 0.5 ml of toluene solution, propylene was continuously supplied at 25 ° C. at a gauge pressure of 1.0 kg / cm ² G for 60 minutes to obtain a propylene copolymer.

After completion of the reaction, the unreacted propylene was removed by depressurization and nitrogen purge, and then exposed to air to stir to lose the activity of the catalyst. 300 ml of toluene was further added to the toluene solution of the reaction mixture, and it stirred at 30 degreeC for 2 hours, the propylene-type copolymer was collect | recovered by filtration, and the same operation was performed 3 times. After drying by wind, vacuum drying at 80 ° C. resulted in a yield of 58.7 g.

Table 1 shows the results of evaluation of the physical properties of this propylene copolymer.

In addition, content of the ethylene / propylene copolymerization macromonomer in a copolymer was calculated | required by the following method.

^From the ratio of methyl carbon / methylene carbon obtained by ¹ H-NMR measurement, the ethylene / propylene composition of the ethylene / propylene copolymerized macromonomer prepared in the above (1) and the propylene copolymer obtained in the above (2) were respectively It calculated and calculated | required content of the ethylene / propylene copolymerization macromonomer in the propylene-type copolymer obtained by said (2). The results are shown in Table 1.

Example 2

(1) Preparation of ethylene / propylene copolymerized macromonomer

In Example 1- (1), it carried out similarly to Example 1- (1) except having changed the injection time of bispentamethyl cyclopentadienyl hafnium dichloride into 5 micromol, and making polymerization time 30 minutes. Thus, 103 g of macromonomer was obtained. In addition, the ratio of the toluene soluble part at room temperature of this macromonomer was 67.7 weight%.

(2) Copolymerization of propylene with ethylene / propylene copolymerized macromonomer

Copolymerization was carried out in the same manner as in Example 1- (2) except that the polymerization time was changed to 4 hours while using the 8 g of toluene-soluble macromonomer prepared in the above (1), to obtain 44.3 g of a propylene copolymer. . This evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

Example 3

In Example 2- (2), 0.25 mmol of triisobutylaluminum is newly used, and 2.5 mmol of methylaluminoxane and rac-dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride The polymerization was carried out in the same manner as in Example 2- (2), except that 0.2 μmol of the reaction product was subjected to polymerization temperature of 70 ° C., propylene pressure of 7.0 kg / cm ² G, and polymerization time of 60 minutes. g was obtained. This evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 1

The physical property evaluation was carried out about the commercially available propylene polymer "Idemitsu Polypro E-185G" made by Idemitsu Seki Yugaku Co., Ltd. The results are shown in Table 1.

Example 1 Example 2 Example 3 Comparative Example 1 Molecular Weight Mw 203,000 309,000 203,000 406,000 Mw / Mn 2.2 2.0 2.5 6.3 Intrinsic viscosity [η] (dl / g) 1.94 2.65 1.74 3.15 Melt Tension MS (g) Actual value 4.3 14.3 5.1 5.4 Calculation value ¹⁾ 1.71 4.59 1.21 7.94 MI ₅ (g / 10min) 4.80 0.52 4.75 1.49 MI _2.16 (g / 10min) 0.87 0.02 0.93 0.38 MI ₅ / MI _2.16 Actual value 5.52 26.00 5.15 3.92 Calculated value ²⁾ 3.63 3.58 4.34 4.61 Melting Point Tm (℃) 152 157 154 161 Macromonoma Content (wt%) 4.5 3.5 4.0 - Ethylene Unit Content (wt%) 2.7 2.4 2.7 - Note 1) Calculated from logMS = 3.17 x log [η] -0.68 2) Calculated from MI ₅ / MI _2.16 ≥ 0.240 x Mw / Mn + 3.1

Comparative Example 2

Polypropylene ([η] = 0.82 d1 / g) and ethylene propylene random copolymer (29% by weight of ethylene, [η] = 3.65 d1 / g) in a blast mill with the composition shown in Table 2 in Table 2 5 minutes melt-kneading on the conditions of 100 degreeC and rotation speed 100 degreeC. The obtained kneaded material was press-molded on condition of 230 degreeC, and the sheet | seat of thickness 2mm was created. The test piece was cut out from this sheet, and physical property evaluation was performed. In addition, the phase separation structure was observed under a transmission microscope. The results are shown in Table 2.

Example 4

Polypropylene ([η] = 0.82 d1 / g), ethylene propylene random copolymer (ethylene content 29 wt%, [η] = 3.65 d1 / g), and the propylene copolymer obtained in Example 3 are listed in a blast mill. The composition shown in 2 was melt-kneaded for 5 minutes on 200 degreeC and the conditions of rotation speed 100rpm. Using the obtained kneaded material, a test piece was prepared in the same manner as in Comparative Example 2 to evaluate physical properties, and the phase-separated structure was observed with a transmission microscope. The results are shown in Table 2.

As is apparent from Table 2, the test piece of Example 4 has improved compatibility in that the average particle diameter on the ethylene propylene copolymer is smaller than that of Comparative Example 2. As a result, the Izod impact strength was also improved.

Comparative Example 2 Example 4 Polypropylene amount (weight part) 84 76 Ethylene propylene copolymer amount (part by weight) 16 14 Propylene Copolymer - Copolymer Use of Example 3 Propylene copolymer amount (part by weight) 0 10 Izod impact strength (KJ / m ² ) (notched, 23 ° C) 5.6 6.4 Average particle diameter (μm) on ethylene propylene copolymer 4.1 1.4

Example 5

Into a 1.6 liter stainless steel pressure autoclave equipped with a stirring device, 400 ml of dehydrated toluene and methylaluminoxane (toluene solution manufactured by Toso Akujo Co., Ltd.) were charged in an atomic ratio of aluminum under nitrogen stream, and then stirring was started at 500 rpm. The temperature was raised to 90 ° C. and stirring was continued for 5 minutes.

A toluene solution of rac-dimethylsilylenebis- (2-methyl-4-phenyl-indenyl) zirconium dichloride (rac-Me ₂ Si [2-Me-4-Ph-Ind] ₂ ZrC1 ₂ ) was added thereto. After 2 µmol was charged, propylene was continuously supplied at a gauge pressure of 2.0 kg / cm ² G and polymerized at 90 ° C. for 30 minutes (first step reaction). Thereafter, the polymerization temperature was lowered to 60 ° C, and at the same time, propylene was continuously supplied at a gauge pressure of 7.0 kg / cm ² G and polymerized at 60 ° C for 30 minutes (second step reaction).

After the completion of the reaction, the unreacted propylene was removed by depressurization, the catalyst activity was lost with a small amount of methanol, and then the propylene homopolymer was recovered by filtration, yielding 117 g of water as a result of air drying and vacuum drying. Table 1 shows the results of evaluation of the physical properties of this propylene copolymer.

Example 6

In Example 1, the reaction of the first stage was carried out under the conditions of propylene pressure 1.0 kg / cm ² G, the polymerization temperature of 85 ° C., and the polymerization time of 45 minutes, and the reaction of the second stage was 3.0 kg of propylene pressure. 84.0 g of propylene homopolymers were obtained in the same manner as in Example 1, except that the reaction was carried out under the condition of / cm ² G, a polymerization temperature of 55 deg. Table 1 shows the results of evaluation of the physical properties of this propylene homopolymer.

Comparative Example 3

The physical property evaluation was carried out about the commercially available propylene polymer "Idemitsu Polypro E-185G" manufactured by Idemitsu Seki Yuga Chemical Co., Ltd. The results are shown in Table 3.

Examples 7 to 9 and Comparative Examples 4 and 5 below are examples corresponding to the second invention of the present application.

Example 7

(1) Preparation of Methyl Aluminoxane Supported Silica

Toluene was distilled off from the methylaluminoxane toluene solution (1.45 mol / liter) by Albemal company, and it further pressure-reduced at 45 degreeC for 4 hours. Dehydrated toluene was added to this until it reached the capacity before toluene distillation, and it stirred and dissolved. It was left to stand overnight and the symbol part in which methylaluminoxane was completely dissolved was used for preparation.

4.67 g of silica (CARIACT P-10, manufactured by Fuji Silysia Chemical Co., Ltd.) calcined under reduced pressure at 200 ° C. for 4 hours was dispersed in 200 ml of dry toluene, and 30 ml of the methylaluminoxane toluene solution subjected to the treatment was 0 ° C. It was dripped at 60 minutes, stirring. After completion of the dropwise addition, stirring was continued for 60 minutes, and further stirred at 20 ° C for 30 minutes and at 80 ° C for 120 minutes. Thereafter, using 100 ml of dry toluene, the solid component was washed by two decantations at 60 ° C. Furthermore, the same washing was performed once using 100 ml of dry hexane. This was made into 230 ml of full volume with dry hexane, and the silica which supported methyl aluminoxane was obtained.

(2) Preparation of Propylene / 1-Octene Copolymer

After drying and nitrogen-substituting the stainless pressure-resistant autoclave equipped with the stirring apparatus, 400 ml of dehydrated heptane, 2 ml of 1-octene, and 0.5 ml of triisobutylaluminum heptane solution (0.5 mmol in terms of aluminum atoms) were added under a nitrogen stream. After starting stirring at 500 rpm and raising the temperature to 80 ° C., propylene was continuously supplied at a pressure of 2.0 kg / cm ² G.

Separately, 15 ml of a heptane slurry containing 0.8 mmol of the methylaluminoxane-supported silica prepared in (1) in terms of aluminum atoms, and rac-dimethylsilylenebis- (2-methyl-4-phenyl-indenyl) zirconium dichloride ( 1.0 ml (equivalent to 5 μmol) of a heptane solution of rac-Me ₂ Si [2-Me-4-Ph-Ind] ₂ ) was added and contacted for 10 minutes at room temperature. This catalyst mixture was added to the autoclave via a balance line to initiate polymerization. After polymerization for 60 minutes, unreacted propylene was removed by depressurization. Here, the copolymer was taken out with 15 ml of heptane solution to obtain Copolymer I.

Next, propylene was continuously fed at a gauge pressure of 7.5 kg / cm ² G and further polymerized at 70 ° C for 2 hours. After completion of the polymerization, unreacted propylene was removed by depressurization. The reaction mixture was poured into a large amount of methanol, 61.5 g of propylene / l-octene copolymer was recovered by filtration and drying to give Copolymer II.

(3) Evaluation of Propylene / 1-Octene Copolymer

The evaluation result of copolymer I is shown in Table 4, and the evaluation result of copolymer II is shown in Table 5.

Example 8

(1) Preparation of Propylene / Ethylene Copolymer

After drying and nitrogen-substituting the stainless pressure-resistant autoclave equipped with the stirring apparatus, 400 ml of dehydrated heptane and 0.5 ml of triisobutylaluminum heptane solution (0.5 mmol in terms of aluminum atoms) were added under nitrogen stream, and stirring was started at 500 rpm. After raising the temperature to 80 ° C, ethylene was supplied at a flow rate of 0.15 milliliter / min and propylene at 2.9 liter / min, and the total pressure was 2.0 kg / cm ² G in gauge pressure.

Separately, 15 ml of a heptane slurry containing 0.8 mmol of the methylaluminoxane-supported silica prepared in Example 7 in terms of aluminum atoms, and rac-dimethylsilylenebis- (2-methyl-4-phenyl-indenyl) zirconium dichloride ( 1.0 mL (equivalent to 5 μmol) of a heptane solution of rac-Me ₂ Si [2-Me-4-Ph-Ind] ₂ ZrCl ₂ ) was added and contacted at room temperature for 10 minutes. This catalyst mixture was added to the autoclave via a balance line to initiate polymerization. After polymerization for 60 minutes, unreacted ethylene and propylene were removed by depressurization. Here, the copolymer was taken as 15 mL of heptane solution to obtain copolymer III.

Next, ethylene was supplied at a flow rate of 0.15 L / min and propylene at a flow rate of 3.06 L / min, the total pressure was adjusted to a gauge pressure of 7.5 kg / cm ² G, and further polymerized at 55 ° C for 2 hours. After the end of the polymerization, unreacted ethylene and propylene were removed by depressurization. The reaction mixture was poured into a large amount of methanol, 97 g of propylene / ethylene copolymer was recovered by filtration and drying to obtain Copolymer IV.

(2) Evaluation of Propylene / Ethylene Copolymer

The evaluation result of copolymer III is shown in Table 4, and the evaluation result of copolymer IV is shown in Table 5.

Example 9

(1) Preparation of Propylene / Ethylene Copolymer

In the same manner as in Example 8, copolymer III was obtained.

Next, 1.0 kg / cm ² G of hydrogen was introduced, and ethylene was continuously supplied at a partial pressure of 6.5 kg / cm ² G, and further polymerized at 60 ° C. for 1 hour. After completion of the polymerization, unreacted ethylene was removed by depressurization. The reaction mixture was poured into a large amount of methanol, 164 g of propylene / ethylene copolymer was recovered by filtration and drying to obtain Copolymer V.

(2) Evaluation of Propylene / Ethylene Copolymer

Table 5 shows the evaluation results of the copolymer V.

Comparative Example 4

(1) Preparation of solid catalyst component

After sufficiently replacing the reactor equipped with the 500 ml stirrer with nitrogen gas, 30 g of magnesium diethoxide, 150 ml of purified heptane, 4.5 ml of silicon tetrachloride, and 5.4 ml of di-n-butyl phthalate were added to start stirring. While maintaining the inside of the system at 90 ° C, 144 ml of titanium tetrachloride was added, and further stirred at 110 ° C for 2 hours, and then the solid component was separated and washed with purified heptane at 80 ° C. Further, 228 ml of titanium tetrachloride was added, the mixture was stirred at 110 ° C for 2 hours, and then the solid component was separated and sufficiently washed with 80 ° C purified heptane to obtain a solid catalyst component.

(2) pretreatment

After sufficiently replacing the reactor equipped with a 500 ml stirrer with nitrogen gas, 230 ml of purified heptane, 25 g of the solid catalyst component prepared in (1), 1.0 mol / mol of triethylaluminum to the titanium atom in the solid catalyst component, and dish Clopentyl dimethoxysilane was added at a rate of 1.8 mol / mol. Next, propylene was introduced to a partial pressure of 0.3 kg / cm ² G and polymerized at 25 ° C for 4 hours. After the completion of the polymerization, the solid catalyst component was washed several times with purified heptane, and further carbon dioxide was supplied and stirred for 24 hours.

(3) Preparation of Propylene / 1-Octene Copolymer

After drying and nitrogen-substituting a stainless steel pressure-resistant autoclave equipped with a stirring device, 400 ml of dehydrated heptane, 10 ml of 1-octene, 0.25 mmol of dicyclopentyl dimethoxysilane, and 2.0 ml of triethylaluminumheptane solution (aluminum) under a nitrogen stream. 2.0 mmol in terms of atoms) was added, stirring was started at 500 rpm, and the temperature was raised to 70 ° C.

Next, the catalyst prepared in (2) was introduced into a 5 µmol autoclave in terms of titanium atoms, and hydrogen was introduced to a gauge pressure of 0.5 kg / cm ² G. Further, propylene was continuously fed at a gauge pressure of 7.0 kg / cm ² G and polymerized for 6 hours. After completion of the polymerization, unreacted propylene was removed by depressurization. The reaction mixture was poured into a large amount of methanol, and 83.5 g of a propylene / 1-octene copolymer was recovered by filtration and drying.

Table 5 shows the evaluation results of the copolymer.

Comparative Example 5

Preparation of Propylene / Ethylene Copolymer

After drying and nitrogen-substituting a stainless pressure resistant autoclave equipped with a stirring device, 400 ml of dehydrated heptane, 0.25 mmol of dicyclopentyldimethoxysilane, and 2.0 ml of triethylaluminum heptane solution (2.0 mmol in terms of aluminum atom) were added under nitrogen stream. After the reaction was initiated at 500 rpm and the temperature was raised to 70 ° C., 0.8 L / min of ethylene, 2.9 L / min of propylene and 0.2 L / min of hydrogen were supplied, and the total pressure was 7.0 kg / cm. ^It was set as 2G.

Next, the catalyst prepared in Comparative Example 4 was added to a 5 μmol autoclave in terms of titanium atoms to initiate polymerization. After polymerization for 6 hours, unreacted ethylene and propylene were removed by depressurization. The reaction mixture was poured into a large amount of methanol, and 70.5 g of a propylene / ethylene copolymer was recovered by filtration and drying.

Table 5 shows the evaluation results of the copolymer.

Propylene Content (mol%) Number average molecular weight Mw [Mm] (%) Terminal vinyl group Example 7 Copolymer I 99.5 97,000 95.4 existence Example 8 Example 9 Copolymer III 96.3 122,000 98.2 existence

Propylene Content (mol%) Melt Index MI (g / 10min) Melt Tension MS (g) log (MS) (%) -0.907 x log (MI) +0.375 Example 7 Copolymer II 99.8 6.6 1.4 0.82 -0.37 Comparative Example 4 99.2 6.8 0.2 -0.70 -0.38 Example 8 Copolymer IV 98.5 16.1 1.5 -0.30 -0.72 Comparative Example 5 98.0 15.1 <0.1 <-1.0 -0.69 Example 9 Copolymer V 9.3 0.8 - - -

The following Examples 10, 11 and Comparative Example 6 are examples corresponding to the second invention of the present application.

Example 10

(1) Preparation of ethylene / propylene copolymerized macromonomer

In a 1.6 liter stainless steel pressure autoclave equipped with a stirrer, 600 ml of dehydrated toluene and a 1.45 mol / liter toluene solution (manufactured by Toso Akujozu) of methylaluminoxane (6 to 6 mmol) in terms of aluminum atom were charged under nitrogen stream. Stirring was started at 500 rpm while controlling the temperature to 20 ° C., and propylene was fed until saturated at a gauge pressure of 7.0 kg / cm ² G. Thereafter, ethylene was continuously supplied until saturated at a pressure of 2.0 kg / cm ^{2 at} a partial pressure. Further via a balance line, 20 ml of a toluene solution containing 20 μmol of bispentamethylcyclopentadienyl hafnium dichloride (Cp ^* ₂ HfCl ₂ ) was injected into the autoclave and copolymerization was started at 20 ° C. At this time, the supply of ethylene was continuously introduced for 10 minutes so that the total pressure became constant.

After the completion of the reaction, the unreacted monomer was released out of the autoclave system by depressurization, further removed by nitrogen purge, and then the activity of the catalyst component was lost with a small amount of methanol.

The reaction mixture containing the recovered ethylene / propylene copolymerized macromonomer was demineralized with dilute hydrochloric acid / methanol / water. After washing five times with ion-exchanged water, and then drying with anhydrous magnesium sulfate, the ethylene / propylene copolymerized macromonomer was recovered by evaporation drying, and the yield was 59.5 g.

(2) Copolymerization of ethylene / propylene and ethylene / propylene copolymerized macromonomers

The macromonomer obtained in the above (1) was dissolved in toluene, and only the room temperature soluble part was fractionated. The ratio of soluble part was 76 weight%. The toluene solution of this soluble part was dehydrated and deoxygenated by nitrogen bubbling.

After drying and nitrogen-substituting a 0.5 liter stainless pressure autoclave equipped with a stirring device, 400 ml of dehydrated heptane, a toluene solution of 3.1 g of the copolymerized macromonomer and 0.5 ml of heptane of triisobutylaluminum (0.5 in terms of aluminum atoms) Mmol) was added, stirring was started at a rotational speed of 500 rpm, and the temperature of the reaction system was raised to 70 ° C.

Next, 15 ml of a heptane slurry solution containing 0.8 mmol of methylaluminoxane supported on silica (SiO ₂ ) in terms of aluminum atoms and rac-dimethylsilylenebis (2-methyl-4-phenyl-indenyl) zirconium dichloride 1.0 mL (equivalent to 5 μmol) of a heptane solution of (rac-Me ₂ Si [2-Me-4-Ph-Ind] ₂ ZrCl ₂ ) was contacted at room temperature for 10 minutes, and then the catalyst mixture was placed in an autoclave.

Next, ethylene was continuously supplied at a flow rate of 0.15 L / min and propylene 3.06 L / min, and the total pressure was polymerized at a gauge pressure of 7 kg / cm ² G for 2 hours. After the completion of the polymerization, the unreacted monomer was removed by depressurization, and then 1 ml of methyl alcohol was injected into the reaction mixture to deactivate the catalyst. Furthermore, 300 ml of heptanes were added, and after stirring at 30 degreeC for 2 hours, a copolymer was collect | recovered and the same operation was performed 3 times. After air drying, 47 g of a copolymer was obtained by drying under reduced pressure. Table 6 shows the evaluation results of the physical properties of this copolymer.

In addition, content of the ethylene / propylene copolymerization macromonomer in a copolymer was calculated | required by the following method.

^From the ratio of methyl carbon / methylene carbon obtained by ¹ H-NMR measurement, the ethylene / propylene composition of the ethylene / propylene copolymerized macromonomer prepared in the above (1) and the copolymer obtained in the above (2) were respectively calculated and And content of the ethylene / propylene copolymerized macromonomer in the propylene copolymer obtained in the above (2). In addition, the ethylene content in the macromonomer was determined from the ethylene / propylene composition ratio of the ethylene / propylene copolymerized macromonomer. The results are shown in Table 6.

Example 10 Molecular Weight Mw 388,000 Mw / Mn 2.6 Intrinsic viscosity [η] (dl / g) 2.19 Melt Tension MS (g) Actual value 5.7 Calculation value ¹⁾ 3.3 MI ₅ (g / 10min) 3.1 MI _2.16 (g / 10min) 0.69 MI ₅ / MI _2.16 Actual value 4.49 Calculated value ²⁾ 3.76 Melting Point Tm (℃) 149 Macromonoma Content (wt%) 1.8 Ethylene Unit Content (wt%) 97.5 Note 1) Calculated from logMS = -0.907 x log [MI] + 0.375 2) Calculated from MI ₅ / MI _2.16 ≥ 0.240 x Mw / Mn + 3.10

Comparative Example 6

Polypropylene ([η] = 0.82 dl / g) and ethylene propylene random copolymer (ethylene content 29 wt%, [η] = 3.65 dl / g) are the compositions shown in Table 7 with a blast mill, and are 200 degreeC and rotation speed 100rpm Melting and kneading was carried out for 5 minutes under the condition of. The obtained kneaded material was press-molded on condition of 230 degreeC, and the sheet | seat of thickness 2mm was created. The test piece was cut out from this sheet, and physical property evaluation was performed. In addition, the phase separation structure was observed by a transmission microscope. The results are shown in Table 7.

Example 11

Polypropylene ([η] = 0.82 dl / g), ethylene propylene random copolymer (ethylene content 29% by weight, [η] = 3.65 dl / g) and the copolymer obtained in Example 10 are shown in Table 7 with a blast mill. In the composition, melt kneading was carried out for 5 minutes under conditions of 200 ° C and a rotation speed of 100 rpm. Using the obtained kneaded material, the test piece was produced like Example 6, the physical property evaluation was carried out, and the phase-separated structure was observed with the transmission microscope. The results are shown in Table 7.

As is apparent from Table 7, the test piece of Example 11 was improved in that the average particle diameter on the ethylene propylene copolymer was smaller than that of Comparative Example 6. As a result, the Izod impact strength was also improved.

Comparative Example 6 Example 11 Polypropylene amount (weight part) 84 76 Ethylene propylene copolymer amount (part by weight) 16 14 Propylene Copolymer - Copolymer Use of Example 10 Propylene copolymer amount (part by weight) 0 10 Izod impact strength (KJ / m ² ) (notched, 23 ° C) 5.6 7.0 Average particle diameter (μm) on ethylene propylene copolymer 4.1 1.2

The propylene polymer of the present invention maintains physical properties equivalent to or higher than those of conventional propylene polymers, and has sufficient melt tension, melt viscoelasticity, melt flowability, and the like, and excellent melt processing properties and control of melt tension. Suitable for foam molding, sheet molding, blow molding and the like. Moreover, it is excellent in melt processing property, and can be applied to the shaping | molding method which used the restriction | limiting in the conventional propylene polymer, for example, large blow molding, extrusion foam molding, etc.

Moreover, it is also suitable as a compatibilizer of a propylene homopolymer, a propylene random copolymer, or a block copolymer.

Claims (16)

(a) Melt index MI ₅ (g / 10 min) and melt index MI _2.16 (g / 10 min) measured under a load of _5.0 kg at a temperature of 230 ° C. and a gel of MI ₅ / MI _2.16 and gel The ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn measured by permeation chromatography is MI ₅ / MI _2.16 ? 0.240 x Mw / Mn + 3.1... (Ⅰ) Satisfy the relationship (b) The melt viscosity MS (g) measured at a temperature of 230 ° C and the ultimate viscosity [η] (dl / g) measured at a temperature of 135 ° C in a tetralin solvent logMS? 3.17 x log [?]-0.68... (Ⅱ) The intrinsic viscosity [η] is in the range of 0.1 to 15.0 dl / g while satisfying the relationship of propylene-based polymer. The method of claim 1, A propylene polymer, wherein the propylene polymer is a propylene copolymer having a copolymerized portion of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms as a graft chain. The method of claim 2, A propylene copolymer having a Mw / Mn of 1.5 to 4.0 and a content of a copolymerization portion of propylene with ethylene and / or an α-olefin having 4 or more carbon atoms of 3% by weight or more. The method of claim 2, A propylene copolymer in which a propylene homopolymer and a propylene block copolymer or a propylene random copolymer are used as a compatibilizer. The method of claim 1, A propylene polymer wherein the propylene polymer is a propylene homopolymer. The method of claim 5, Propylene polymer having Mw / Mn of 1.5 to 4.5. The method of claim 5, A propylene homopolymer having a melting point of 120 to 165 ° C. measured by a differential scanning calorimeter. A main chain composed of a polymer of at least one monomer selected from ethylene, alpha -olefins of 4 to 20 carbon atoms, cyclic olefins and styrenes, propylene homopolymer or propylene and ethylene, alpha -olefins of 4 to 20 carbon atoms, cyclic olefins and styrene A branched polyolefin having a side chain composed of a copolymer with at least one monomer selected from the group, and having an isotactic triad fraction [mm] showing a stereoregularity at the side chain of 80% or more. A main chain composed of a polymer of at least one monomer selected from α-olefins, cyclic olefins and styrenes having 2 to 20 carbon atoms, and at least one selected from propylene and ethylene, α-olefins, cyclic olefins and styrenes having 4 to 20 carbon atoms A branched polyolefin having a side chain composed of a copolymer with a monomer, and having an isotactic triad fraction [mm] having a stereoregularity in the side chain of 80% or more. The method according to claim 8 or 9, A branched polyolefin having a weight average molecular weight of 5,000 to 1,000,000 in terms of polyethylene measured by gel permeation chromatography (GPC). The method according to claim 8 or 9, A branched polyolefin having a melt tension MS greater than the melt tension MS of the linear polyolefin having the same copolymerization composition and melt index MI. The method according to claim 8 or 9, Melt tension MS (g) and melt index MI (g / l 0 min) measured at 230 ° C logMS ≧ -0.907 × log MI + 0.375... (Ⅰ) The branched polyolefin having a propylene content in the range of 60 to 99.9 mol% while satisfying the relationship of. The method of claim 9, A branched polyolefin in which the constituent monomers of the main chain and the side chain constituting the branched polyolefin are the same and are substantially free of a gel. (a) the content of propylene is in the range of 60 to 99.9% by weight, (b) the ratio MI ₅ / MI _2.16 between the melt index MI ₅ (g / 10 min) measured at a temperature of 230 ° C. under a _5.0 kg load and the melt index MI _2.16 (g / 10 min) measured under a load of 2.16 kg, The ratio Mw / Mn between the weight average molecular weight Mw and the number average molecular weight Mn measured by gel permeation chromatography is MI ₅ / MI _2.16 ≥ 0.240 × Mw / Mn + 3.10 (I) Satisfy the relationship (c) Melt tension MS (g) and melt index MI (g / 10 min) measured at a temperature of 230 ° C logMS> -0.907 × logMI + 0.375 (II) Intrinsic viscosity [η] measured at a temperature of 135 ° C. in a tetralin solvent while satisfying the relationship of 1 and selected from α-olefins, cyclic olefins and styrenes having 2 to 20 carbon atoms Characterized in that the graft chain having a main chain consisting of more than one species (except propylene homopolymer chain), and copolymerization of ethylene and at least one selected from α-olefins, cyclic olefins and styrene having 3 to 20 carbon atoms Vapor phase polyolefin. The method of claim 14, The branched polyolefin having Mw / Mn of 1.5 to 4.0 and a content of a copolymerization portion of ethylene and at least one kind selected from α-olefins having 3 to 20 carbon atoms, cyclic olefins and styrene at least 3% by weight. The method of claim 14, A branched polyolefin in which a propylene homopolymer and a propylene block copolymer or a propylene random copolymer are used as a compatibilizer.