JP2007254575A - Hydroxyl group-containing propylene copolymer and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a propylene copolymer excellent in the balance of the physical properties of elastic modulus, rigidity, adhesiveness and so on. <P>SOLUTION: The hydroxyl group-containing propylene copolymer contains 99.8-99.99 mol% of propylene units of structural formula (I), 0.01-0.1 mol% of polar units of structural formula (II) and 0-0.1 mol% of nonpolar units of structural formula (III) and has a weight-average molecular weight Mw of 70,000-1,000,000. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel propylene copolymer having a small amount of hydroxyl groups in the side chain and high stereoregularity of the propylene chain portion.

  Polypropylene is used in many fields as one of the most important plastic materials because it has excellent mechanical properties, moldability, chemical stability, and is very cost effective. However, while chemically stable, there are problems such as poor adhesion and dyeability due to nonpolarity and poor miscibility with other plastic materials. In order to solve this problem, many attempts have been made to produce a propylene-based copolymer into which a polar group has been introduced.

  For example, a hydroxyl group-containing propylene copolymer obtained by copolymerizing propylene and 10-undecen-1-ol using a titanium trichloride catalyst in which titanium trichloride and diethylaluminum chloride are combined is known (patent) Reference 1, Example 1). However, polymers produced with titanium trichloride-based catalysts have a wide composition distribution and molecular weight distribution. When slurry polymerization or bulk polymerization is performed, low molecular weight, low stereoregular components are eluted, or gas phase polymerization is performed. In this case, there is a problem that the stable operation becomes impossible due to the aggregation of the particles and adhesion to the reactor wall surface or blockage of the extraction pipe.

On the other hand, a method of copolymerizing propylene and a hydroxyl group-containing comonomer using a highly stereoregular catalyst such as a MgCl ₂ supported catalyst or a metallocene catalyst is also known (see Patent Documents 2 to 6).

  However, these documents mainly disclose polyethylene-based copolymerization, and even if the disclosed highly stereoregular catalyst is used in a propylene-based polymer, the polar group content is required to provide adhesion and paintability. The polymer thus obtained is not sufficiently rigid, and the balance between the adhesion performance due to polar groups such as hydroxyl groups and the rigidity derived from high stereoregularity has been further improved. The appearance of a hydroxyl group-containing polypropylene copolymer has been awaited.

  More specifically, an ethylene / propylene / methyl acrylate ternary copolymer rich in an ethylene component produced by using a monomer in which a polar group is directly bonded to a terminal vinyl group (see Patent Document 4), undecene-1- Ethylene / butene / polar monomer ternary copolymer rich in ethylene component produced using polar monomers such as all (see Patent Document 5), polar groups using polar monomers such as undecen-1-ol A copolymer such as a binary copolymer (see Patent Documents 6 and 7) rich in an ethylene component or a propylene component containing 0.5 mol% or more has a polar group, but the type of polymer structural unit or Controlled by the content, the high rigidity of the propylene homopolymer cannot be maintained as it is. In other words, it can be said that the copolymer has been developed for different purposes from the present invention and has different performance.

In addition, in order to obtain high-rigidity polypropylene, a method for producing high-rigidity polypropylene by copolymerization of 0.005 to 0.5% by weight of an α-olefin component having 6 to 15 carbon atoms such as hexene and octene with propylene is known. (See Patent Document 8). However, although this copolymer has a small amount of hydrocarbon branching, it is not a polymer into which a polar group has been introduced, so that an effect of improving adhesiveness or paintability cannot be obtained.
JP 55-98209 A JP-A-8-53516 JP 2003-246820 A JP 2000-319332 A JP 2002-145944 A JP 2002-145947 A JP 2006-2072 A JP-A-4-363310

  It is an object of the present invention to provide a propylene copolymer having an improved balance between adhesion and rigidity, which is the above problem. Compared with a propylene homopolymer, both physical properties of adhesiveness and elastic modulus (rigidity) are improved.

As a result of studying in view of such circumstances, the present inventors have used a specific metallocene catalyst to copolymerize a specific trace amount of an alkenyldialkylaluminum with propylene, and perform post-reactions including oxidative decomposition thereto. By applying this, a dialkylaluminum group (—AlR ³ R ⁴ ) derived from an alkenyldialkylaluminum can be converted into a hydroxyl group, and a propylene copolymer having high stereoregularity and excellent balance between rigidity and adhesiveness can be obtained. Found that can be obtained.
Furthermore, it was found that even when a specific trace amount of a hydroxyl group-containing monomer is copolymerized with propylene, a propylene-based copolymer having an excellent balance between rigidity and adhesiveness can be obtained without using an oxidative decomposition method. The invention has been reached.

  That is, the gist of the present invention is that 99.8 to 99.99 mol% of propylene units represented by the following structural formula (I) and 0.01 to 0.1 mol of polar units represented by the structural formula (II). % And non-polar units represented by the structural formula (III) 0 to 0.1 mol%, and the weight average molecular weight Mw is 70,000 to 1,000,000. Exists in the copolymer.

Another gist of the present invention is the above-mentioned hydroxyl group-containing propylene copolymer in which the triad tacticity (mm fraction) of the monomer 3 chain portion centering on propylene composed of a head-to-tail bond is 97.0% or more. It exists in coalescence.

  Another gist of the present invention resides in the hydroxyl group-containing propylene copolymer in which the relationship between the number average molecular weight Mn and the weight average molecular weight Mw is 5 or less as a Q value (Mw / Mn).

  Another gist of the present invention resides in the above-mentioned hydroxyl group-containing propylene copolymer having a storage elastic modulus (G ′) at 25 ° C. of 730 to 2000 MPa obtained by solid viscoelasticity measurement.

Moreover, the other summary of this invention exists in the said hydroxyl-containing propylene copolymer whose carbon number of R < ¹ > and R < ² > is 4-8.

  Another gist of the present invention resides in the above-mentioned hydroxyl group-containing propylene copolymer in which the content of polar units per molecule of the polymer is 0.2 to 2 as an average value of the polymer.

Another gist of the present invention is propylene and the following general formula (1).
CH ₂ = CH—R—AlR ³ R ⁴ (1)
(In the formula, R represents an optionally branched divalent hydrocarbon group having 1 to 20 carbon atoms, R may contain a double bond, and R ³ and R ⁴ are carbon atoms. A propylene-alkenyldialkylaluminum copolymer or propylene-alkadienyldialkylaluminum copolymer obtained by copolymerization with an alkenyldialkylaluminum or alkadienyldialkylaluminum represented by formula (1) to (20). Propylene units 99.8 to 99.99 mol% represented by the following structural formula (I) and polar units 0.01 to 0 represented by the structural formula (II) are characterized by reacting the union with oxygen. 1 mol% and non-polar units represented by structural formula (III) 0 to 0.1 mol%, and the weight average molecular weight Mw is 70,000 to 1,000,000 It consists in the production method of the acid group-containing propylene copolymers.

  An object of the present invention is to provide a propylene copolymer having an improved balance between adhesion and rigidity. By introducing a small amount of a hydroxyl group into a propylene unit, not only the adhesion to a metal and the like is improved, but also a hydroxyl group-containing propylene copolymer having an improved elastic modulus (particularly storage elastic modulus) is provided.

  The hydroxyl group-containing propylene copolymer of the present invention contains units represented by the following structural formulas (I) to (III) at a specific ratio.

That is, 99.8 to 99.99 mol% of the propylene unit represented by the structural formula (I), 0.01 to 0.1 mol% of the polar unit represented by the structural formula (II), and the structural formula (III) Contains 0 to 0.1 mol% of the nonpolar units represented.

  The propylene copolymer of the present invention is essentially close to a propylene homopolymer and is characterized by containing a trace amount of hydroxyl units. If the content of the propylene unit represented by the structural formula (I) (the fraction of the unit in the total unit) is less than 99.8 mol%, the crystallinity is lowered and the elastic modulus and heat resistance are adversely affected. When it exceeds 99.99 mol%, it is difficult to introduce a desired amount of units represented by the structural formulas (I) and (II). Therefore, the preferable content of the propylene unit is selected from the range of 99.81 to 99.97 mol%.

  The polar unit represented by the structural formula (II) is a unit mainly composed of a hydrocarbon group having a hydroxyl group in the side chain, and the content thereof is 0.01 to 0.1 with respect to all units of the polymer. It is selected from a very narrow range of mol%. When this content exceeds 0.1 mol%, the effect of improving the adhesiveness is saturated, and adversely affects the excellent elastic modulus, heat resistance, etc. of the propylene copolymer. On the other hand, if it is less than 0.01 mol%, the effect of improving adhesiveness cannot be obtained. Therefore, the preferable content of the polar unit is selected from the range of 0.02 to 0.09 mol%.

R ¹ in the structural formula (II) is a C1-C20 aliphatic, alicyclic or aromatic hydrocarbon group having a hydroxyl group, which may have a branch, and is substituted on the aromatic ring. It may have a group and may have an unsaturated bond inside.

R ¹ is preferably an aliphatic hydrocarbon group. More preferably, it is a linear saturated hydrocarbon group. The hydroxyl group may be bonded to the primary carbon, or may be bonded to the secondary or tertiary carbon. In the case of an aromatic system, a substituent may be present on the ring. Preferably, it is a hydroxyl group present at the side chain end position bonded to the primary carbon. R ¹ preferably has 2 to 10 carbon atoms, more preferably 4 to 8 carbon atoms.

A specific example of R ¹ is shown in FIG. 1 as a chemical structural formula. In the figure, P represents the main chain of the propylene copolymer and is represented as R ¹ bonded thereto.

  In the hydroxyl group-containing propylene copolymer, the distribution of the polar unit represented by the structural formula (II) is arbitrary and is not particularly limited, and a hydroxyl group is mainly formed at the side chain position of the polymer. However, when the polar unit represented by the structural formula (II) is bonded to the terminal position of the polymer, a hydroxyl group is formed at the terminal position, which is naturally included in the present invention.

  The number of hydroxyl groups in the hydroxyl group-containing propylene copolymer depends on the molecular weight of the copolymer, but is usually 0.2 to 2, preferably 0.3 to 1, as an average value per polymer molecule. .Select from 5 ranges. At least one hydroxyl group is not necessary for all polymer molecules, and the average value per polymer molecule is 0.2 to 2 and the effects of the present invention can be sufficiently achieved.

  Here, “average number of hydroxyl groups per molecule of polymer” (N) is calculated by the following formula.

N = (Molar concentration of polar unit) * (Number average molecular weight of the polymer determined by GPC) / 42
The unit represented by the structural formula (III) is a nonpolar unit having only a hydrocarbon group in the side chain, and its content is 0 to 0.1 mol%, preferably 0.01 to 0.1 mol%. is there. The content of the unit represented by the structural formula (III) may be zero, but conversely, if it exceeds 0.1 mol%, the elastic modulus, heat resistance, etc. of the hydroxyl group-containing propylene copolymer are lowered, so it is selected from the above range. Is done.

R ² in the structural formula (III) is an aliphatic, alicyclic or aromatic hydrocarbon group having 2 to 20 carbon atoms, may have a branch, and has a substituent on the aromatic ring. And may have an unsaturated bond inside. R ² is preferably an aliphatic hydrocarbon group, more preferably a linear saturated hydrocarbon group. R ² has 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. A specific example of R ² is shown in FIG.

The abundance ratio of each unit represented by structural formulas (I), (II) and (III) can be determined using analytical methods such as ¹³ C-NMR and ¹ H-NMR. ^When determining using ¹³ C-NMR, for example, when R ² and R ³ in (II) and (III) are linear saturated hydrocarbon structures and a hydroxyl group is present at the side chain terminal position of R ² , By referring to the relationship between the chemical shift value and the structure described in the document “Macromolecules 2002, 35 卷, p. 6760”, peak assignment can be performed and the abundance ratio of each unit can be calculated. Specific measurement conditions are as follows.

Device used: JSX-400 manufactured by JEOL Ltd.
Measurement temperature: 130 ° C
Solvent type: o-dichlorobenzene 80% by volume + total deuterated benzene 20% by volume
Decoupling: Proton complete decoupling Sample amount: 375mg
Integration count: 10000 times Pulse angle: 90 °
Pulse interval: 10 seconds Sample tube: 10 mmφ
Amount of solvent used: 2.5 ml
Peak assignments can be made according to various literature. For example, when R ^{1 of the} unit represented by the structural formula (II) is an n-butanol group (4-hydroxybutyl group) or an n-nonanol group (9-hydroxynonyl group), Journal of Polymer Science: Part A; Polymer Chemistry, 37, 2457 (1999). In the case of n-hexanol group (6-hydroxyhexyl group), the peak derived from structural unit (II) with reference to Macromolecules, 35, 6760 (2002) Should be attributed. For the peak derived from the structural formula (III), when R ¹ is an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group or i-butyl group, Macromolecular Chemistry and Physics, Volume 204, p. 1738 (2003).

  The abundance ratio of the polar unit represented by Structural Formula (II) is obtained by using the sum of the peak intensities of methylene carbon in the main chain portion of the polymer as the denominator and the intensity of the characteristic peak derived from Structural Formula Unit (II) as the numerator. The obtained value is further divided by the number of moles of carbon that produce the characteristic peak used in the calculation contained in 1 mole of structural unit (II). Here, in many cases, the peak derived from the carbon atom adjacent to the polar group in the side chain portion of the structural formula unit (II) may be used as the characteristic peak used in the molecule.

  The abundance ratio of the nonpolar unit represented by the structural formula (III) is obtained by using the sum of the peak intensities of methylene carbon in the main chain portion of the polymer as the denominator and the intensity of the characteristic peak derived from the structural formula unit (III) as the numerator. The obtained value is further divided by the number of moles of carbon that causes the characteristic peak used in the calculation contained in 1 mole of structural formula unit (II). Here, in many cases, the peak of the terminal methyl carbon of the side chain portion may be used as the characteristic peak used for the molecule.

Further, as a more specific example below, when R ¹ is an n-hexanol group (6-hydroxyhexyl group) and R ² is an n-hexyl group, the following calculation formula is obtained.
Ratio of n-hexanol group = [o1] / [Sp + Spo + Soo]
Ratio of n-hexyl group = [h1] / [Sp + Spo + Soo]
FIG. 3 shows an example of a partial chemical structure of the polymer in this case.

Here, the meaning of each symbol is as follows.
o1: represents a carbon adjacent to a hydroxyl group in a hexanol group.
h1: represents the terminal methyl carbon of the hexyl group.
Tp: represents a methine carbon adjacent to a methyl group derived from propylene in the main chain.
To: represents a methine carbon adjacent to a hexyl group or hexanol group derived from a comonomer in the main chain.
Sp: Methylene carbon having methine carbon Tp adjacent to the methyl group derived from propylene in the main chain at both ends.
Spo: Methylene carbon having both ends of a methine carbon Tp adjacent to a methyl group derived from propylene in the main chain and a methine carbon To adjacent to a hexyl group or hexanol group derived from a comonomer.
Soo: represents a methylene carbon having both ends of a methine carbon To adjacent to a hexyl group or hexanol group derived from a comonomer in the main chain.
[] Represents the peak intensity, and the peak assignment was in accordance with the method described in Macromolecules 2002, 35 ,, page 6760.

  The hydroxyl group-containing propylene copolymer of the present invention needs to have a weight average molecular weight Mw of 70,000 to 1,000,000. If it is less than the lower limit, mechanical properties such as impact strength and tensile strength are lowered. On the other hand, when the upper limit is exceeded, the flowability at the time of molding deteriorates and is not practical. Mw is preferably 100,000 to 500,000.

  The ratio (Mw / Mn) between the weight average molecular weight Mw and the number average molecular weight Mn is an index representing the extent of the molecular weight distribution of the polymer, and is also called the Q value. In the hydroxyl group-containing propylene copolymer of the present invention, the Q value is preferably in the range of 5 or less, preferably 2-5. When this upper limit is exceeded, the storage elastic modulus described later cannot be improved due to the presence of the units represented by the structural formulas (I) and (II), and therefore the rigidity cannot be improved, and the process operation is not performed. When slurry polymerization or bulk polymerization is performed on the top, low molecular weight, low stereoregular components are eluted, or when gas phase polymerization is performed, the particles aggregate to each other, causing adhesion to the reactor wall surface. There is an inconvenience that stable operation is impossible due to blockage of the extraction pipe. On the other hand, if the molecular weight distribution is too narrow, the rigidity improving effect may not be exhibited. Therefore, the Q value is more preferably in the range of more than 3.0 and 4.8 or less. If it is 3 or less, orientation crystallization is less likely to occur, so the orientation of the polar group is also reduced, and the effect of improving the rigidity is reduced and the effect of the polar group such as adhesiveness is also reduced.

  In the present invention, Mw and Mn are determined by gel permeation column chromatography (GPC). The specific measurement conditions are as follows.

Model used: Waters 150C
Measurement temperature: 140 ° C
Solvent: orthodichlorobenzene (ODCB)
Column: Shodex 80M / S, manufactured by Showa Denko Co., Ltd. Flow rate: 1.0 mL / min Injection volume: 0.2 mL
Sample preparation: The sample was prepared as a 1 mg / mL solution using ODCB (containing 0.5 mg / mL BHT (2,6-di-t-butyl-4-methylphenol)), Dissolve in 1 hour.

Calculation of molecular weight: standard polystyrene method Conversion from retention capacity to molecular weight is performed using a calibration curve prepared in advance with standard polystyrene.
The standard polystyrenes used are the following brands manufactured by Tosoh Corporation.
F380, F288, F128, F80, F40, F20, F10, F4, F1, A5000, A2500, A1000. A calibration curve is created by injecting 0.2 mL of a solution dissolved in ODCB (containing 0.5 mg / mL BHT) so that each is 0.5 mg / mL. The calibration curve uses a cubic equation obtained by approximation by the least square method.
The viscosity equation [η] = K × Mα used for conversion to molecular weight uses the following numerical values.
PS: K = 1.38 × 10 ⁻⁴ , α = 0.7
PE: K = 3.92 × 10 ⁻⁴ , α = 0.733
PP: K = 1.03 × 10 ⁻⁴ , α = 0.78
Detector: MIRAN 1A IR detector manufactured by FOXBORO (measurement wavelength: 3.42 μm)
Column: AD806M / S (3 pieces) manufactured by Showa Denko KK
An example of the baseline and the section of the obtained chromatogram is shown in FIG.

  The hydroxyl group-containing propylene copolymer of the present invention has a triad tacticity (mm fraction) of a monomer 3 chain part (provided excluding ethylene) centering on propylene composed of a head-to-tail bond, being 97.0% or more, Preferably it is 98.0% or more, More preferably, it is 99% or more. If the mm fraction is less than the above, the crystallinity of the propylene portion is insufficient and there are problems in the elastic modulus, heat resistance, and the like.

The mm fraction is measured using a ¹³ C-NMR spectrum measured under the above conditions.

In addition to the above-mentioned literature, spectral assignments were made with reference to Macromolecules, (1975) 8 pp. 687, Polymer, 30 pages 1350 (1989).
A more specific method for determining the mm fraction will be described below.
Peaks derived from the methyl group of the three-chain central propylene bonded head-to-tail around the propylene unit are generated in three regions depending on the configuration.
mm: about 22.5 to about 21.2 ppm
mr: about 21.2 to about 20.5 ppm
rr: about 20.5 to about 19.5 ppm
The chemical shift range of each region slightly shifts depending on the molecular weight and the copolymer composition, but the above three regions can be easily identified. The standard of chemical shift is that the peak of isotactic propylene 5-chain (mmmm) is 21.8 ppm.
Here, mm, mr, and rr are each represented by the following structure.

However, X and Y are any of a methyl group, R < ¹ > of Structural formula (II), and R < ² > of Structural formula (III).
When the polar group-containing propylene copolymer of the present invention contains only the above partial structure, its mm fraction is
mm fraction = peak area of mm region / (peak area of mm region + peak area of mr region + eye peak area of rr region) × 100 [%] (IV)
As required.

  Moreover, as a partial structure containing a position irregular unit, it may have the following structure (i) and structure (ii).

Among these, the carbon A and A ′ peaks appear in the mr region, and the carbon C and C ′ peaks appear in 16.8 to 17.8 ppm. Therefore, it is necessary to reduce the peak area based on the carbons A and A ′ appearing in the mr and rr regions at the peak not based on the head-to-tail three-linked chain.

  The peak areas based on carbon A are carbon D (resonance around 42.4 ppm), carbon E and G (resonance around 36.0 ppm), and carbon F (38.7 ppm) in the position irregular substructure [structure (i)]. It can be evaluated from 1/4 of the sum of the peak areas of resonance in the vicinity.

  The peak area based on carbon A ′ can be evaluated by 1/2 of carbon L (resonance at around 27.7 ppm).

  Note that the positions of the carbon C peak and the carbon C ′ peak need not be considered because they are not related to the focused mm, mr, and rr regions.

  Further, when the structural formulas (II) and (III) have a methyl group, the peak position derived from the methyl group is not considered because it does not relate to the region of interest.

  Since the peak areas of mm, mr, and rr can be evaluated as described above, the mm fraction of the triple chain portion composed of the head-to-tail bond with the propylene unit as the center can be obtained according to the above formula (IV).

Next, a method for producing the hydroxyl group-containing propylene copolymer of the present invention will be described.
The method for producing a hydroxyl group-containing propylene copolymer of the present invention is obtained by copolymerizing propylene with a specific hydroxyl group-containing monomer or an alkenyl dialkylaluminum monomer capable of introducing a hydroxyl group by post-treatment using a specific stereoregular catalyst. Manufacture is possible by converting the obtained polymer into a hydroxyl group by post-treatment. Details of the available catalyst, specific copolymerization monomer, its production method and copolymerization method will be described below.

1. Polymerization Catalyst The hydroxyl group-containing propylene copolymer of the present invention is not particularly limited in its production method as long as it contains a predetermined amount of the above-described structural unit and has a predetermined weight average molecular weight. Although it can be produced using a specific Ziegler-Natta catalyst (ZN catalyst) known as a highly stereoregular catalyst, it can be preferably produced using a metallocene catalyst.

  Examples of such highly stereoregular catalysts include solid components (component A) and organoaluminum compounds (component B) that require titanium, magnesium, halogen, and specific electron donating compounds, and electron donating compounds as optional components. A so-called ZN catalyst such as a catalyst comprising (C component), a metallocene complex (A ′ component), and a so-called co-catalyst component (B ′ component) such as an organoaluminum oxy compound, Lewis acid, anionic compound, or clay mineral. A metallocene catalyst is used.

The organoaluminum compound (component B) in the ZN catalyst has a general formula R ¹ _m AlX _3-m (wherein R ¹ is a hydrocarbon group having 1 to 12 carbon atoms, X represents a halogen, and m represents 1 to 3). Can be used. Examples thereof include trialkylaluminums such as trimethylaluminum, triethylaluminum, and triisobutylaluminum, alkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, and ethylaluminum sesquichloride, and alkylaluminum hydrides such as diethylaluminum hydride. Also, alumoxanes such as methylalumoxane and butylalumoxane can be used.

In addition, as a titanium compound serving as a supply source of titanium constituting a solid component (component A) which essentially contains titanium, magnesium, halogen and a specific electron donating compound, a general formula Ti (OR ² ) _4-n X _n (Wherein R ² is a hydrocarbon residue having 1 to 10 carbon atoms, X is a halogen, and n is a number from 0 to 4). Among them, titanium tetrachloride, tetra Ethoxy titanium, tetrabutoxy titanium and the like are preferable.

  Examples of the magnesium compound that serves as the supply source of magnesium include dialkyl magnesium, magnesium dihalide, dialkoxy magnesium, and alkoxy magnesium halide, among which magnesium dihalide is preferable. Examples of the halogen include fluorine, chlorine, bromine, and iodine. Among them, chlorine is preferable, and these are usually supplied from the titanium compound or the magnesium compound, but aluminum halide, silicon halide, It may be supplied from other halogen sources such as tungsten halide.

Examples of electron donating compounds include alcohols, phenols, ketones, ethers, aldehydes, carboxylic acids, oxygen-containing compounds such as organic acids or inorganic acids and their derivatives, ammonia, amines, nitriles, isocyanates, etc. And the like. Among them, ethers, inorganic acid esters, organic acid esters, organic acid halides, organic silicon compounds and the like are preferable, silicic acid esters, substituted succinic acid esters, More preferred are polyvalent carboxylic acid esters such as phthalic acid esters, acetic acid cellosolve esters, phthalic acid halides, diethers, and organic alkoxysilicon compounds. For example, the general formula R ³ R ⁴ ₃₋ such as t-butyl-methyl-dimethoxysilane, t-butyl-methyl-diethoxysilane, cyclohexyl-methyl-dimethoxysilane, cyclohexyl-methyl-diethoxysilane, dicyclopentyldimethoxysilane, etc. _p Si (OR ⁵ ) _p (wherein R ³ is a branched aliphatic hydrocarbon residue having 3 to 20 carbon atoms, preferably 4 to 10 carbon atoms, or cyclic having 5 to 20 carbon atoms, preferably 6 to 10 carbon atoms. Represents an aliphatic hydrocarbon residue, R ⁴ represents a branched or straight-chain aliphatic hydrocarbon residue having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and R ⁵ represents 1 to 10 carbon atoms, preferably 1 -4, and p is a number from 1 to 3.), for example, 2,2-diisopropyl-1,3-diether, 2,2-diisobutyl -1,3-die 1,3-diethers having 2,2-substituents such as ether, polyvalent carboxylic acid esters such as butyl phthalate, octyl phthalate and dibutyl 1,2-diisopropyl succinate, and phthalic halides such as phthalic chloride Is preferred. It is also possible to use a plurality of these in combination. Particularly preferred are 1,3-diethers, coexistence of 1,3-diethers, combined use of 1,3-diethers and organosilicon compounds represented by the above general formula, or phthalic acid esters and phthalic acid chlorides. The combined use of a phthalic acid derivative such as the above and an organosilicon compound represented by the above general formula is particularly preferable. These preferable electron donors can be used as an electron donating compound (component C) not only during the production of the solid catalyst component but also during the polymerization in contact with the organoaluminum. In addition, since the structure of formula (II) is introduced, a three-dimensional structure that can maintain substantial practical physical properties without causing deterioration of physical properties such as rigidity even when interpolymers with good copolymerization or some different monomers are introduced. ZN-based catalysts having excellent regularity are preferred.

  As for these ZN catalysts, for example, JP-A-57-63310, JP-A-60-23404, JP-A-62-187706, JP-A-62-212407, JP-A-63-235307, JP-A-2-160806, JP-A-2-163104, JP-A-3-234707, JP-A-3-706, JP-A-3-294304, JP-A-7-258328, JP-A-8-20607, It is described in each gazette such as Kaihei 8-151407.

  Next, the metallocene catalyst will be described. The metallocene compound (A ′ component) in the metallocene catalyst has carbon bridge, silicon bridge, germane bridge group, etc., and substituted or unsubstituted cyclopentadiene, indene, fluorene, azulene or the like as a ligand. Group 4 transition metal compounds.

  Non-limiting specific examples include: (1) Carbon bridges include ethylene bis (2,4-dimethylindenyl) zirconium chloride, ethylenebis (2,4,7-trimethylindenyl) zirconium dichloride, isopropylidene ( 3-methylindenyl) (fluorenyl) zirconium chloride, isopropylidene (2-methylcyclopentadienyl) (3-methylindenyl) zirconium dichloride, and the like.

  (2) Examples of the silicon bridge include dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, diphenylsilylene (2-ethyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-isopropyl-4). -(3,5-diisopropylphenyl) indenyl) zirconium dichloride, dimethylsilylenebis (2-propyl-4- (9-phenanthryl) indenyl) zirconium dichloride, (9-silafluorenyl) bis (2-ethyl-4- (4- t-butylphenyl) indenyl) zirconium dichloride, dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4H-azurenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4- (4-chloropheny) ) -4H-azurenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4- (4-t-butyl-3-chlorophenyl) -4H-azurenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4- (2) -Fluorobiphenylyl) -4H-azurenyl) zirconium dichloride, dimethylsilylenebis (2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl) zirconium dichloride, and the like.

  (3) As the germane crosslinking, a compound in which the silicon-crosslinked silylene of the above (2) is replaced with germanylene is used. A compound in which zirconium is replaced with hafnium is exemplified as a suitable compound as it is. Furthermore, the dichloride of the exemplified compound can be exemplified by other halides, compounds substituted with methyl group, isobutyl group, phenyl group, hydride group, dimethylamide, diethylamide group, etc. as suitable compounds.

  As a co-catalyst (B ′ component) used for the metallocene catalyst, an organoaluminum oxy compound, a Lewis acid, an ionic compound, and a clay mineral can be used.

  (1) Examples of organoaluminum oxy compounds include methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, aluminum tetraisobutyl butylboronate, methylaluminum bispentafluorophenoxide, diethylaluminum pentafluorophenoxide and the like.

(2) As the Lewis acid, a compound represented by BR ₃ (wherein R is a phenyl group or a fluorine atom which may have a substituent such as a fluorine atom, a methyl group or a trifluoromethyl group). For example, trifluoroborane, triphenylborane, tris (4-fluorophenyl) borane, tris (3,5-difluorophenyl) borane, tris (4-fluoromethylphenyl) borane, tris (pentafluorophenyl) Examples include borane, tris (p-tolyl) borane, tris (o-tolyl) borane, tris (3,5-dimethylphenyl) borane, and inorganic compounds such as magnesium chloride and aluminum oxide.

  (3) Examples of the ionic compound include a trialkyl-substituted ammonium salt, an N, N-dialkylanilinium salt, a dialkylammonium salt, and a triarylphosphonium salt. Specifically, as the trialkyl-substituted ammonium salt, for example, triethylammonium tetra (phenyl) borate, tri (n-butyl) ammonium tetra (phenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, Examples thereof include dimethylanilinium tetrakis (pentafluorophenyl) borate and dimethylanilinium tetrakis (pentafluorophenyl) aluminate. Examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetra (phenyl) borate. Examples of ionic compounds other than ammonium salts include triphenylcarbenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium tetrakis (pentafluorophenyl) aluminate, ferrocenium tetra (pentafluorophenyl) borate and the like.

  (4) Examples of clay minerals include montmorillonite, mica, teniolite, hectorite, modified products treated with acid / salt thereof, and composites with other inorganic oxides. Of these, in the promoter system using clay mineral, the effect of the composition of the present invention is particularly remarkable.

  In the propylene copolymer of the present invention, the amount of the component (A), the component (B) and the component (C) used may be arbitrary as long as the effect of the present invention is recognized. The inside is preferable. Component (A) contains 0.01 to 10000 mol. Of titanium in component (A) with respect to propylene supplied to the reactor. The amount of component (B) used is 0.1 to 10,000 mol. per propylene fed to the reactor. ppm, preferably 1-1000 mol. ppm, more preferably 10 to 300 mol. Within the ppm range. Moreover, the usage-amount of a component (C) is 0-100 mol. With respect to the propylene supplied to a reactor. ppm, preferably 0 to 50 mol. ppm, particularly preferably 0 to 20 mol. Within the ppm range.

  On the other hand, the component (A ′) and the component (B ′) in the case of the metallocene catalyst have a component (A ′) of 0.001 to 100 mol. As for the usage-amount of ppm and a component (B '), 1-10000 (weight ratio) with respect to a component (A') is common. In order to introduce the units (II) and (III) without degrading the performance such as activity and stereoregularity, it is preferable that the copolymerization is excellent, and in particular, a metallocene catalyst is used. Is preferred.

2. Techniques for Producing Copolymers There are various methods for producing a propylene-based copolymer containing a hydroxyl group. Typical examples are illustrated below.
2-1. Propylene-alkenyldialkylaluminum copolymer intermediate intermediate method A method of oxygen decomposition after copolymerization of propylene and alkenyldialkylaluminum or alkadienyldialkylaluminum by the method described in JP-A-2003-246820 can be employed.

  The alkenyldialkylaluminum or alkadienyldialkylaluminum used is a special monomer, but its production method is known and disclosed in, for example, JP-A-2003-246820.

As the alkenyldialkylaluminum or alkadienyldialkylaluminum used in the present invention, the following general formula (1)
CH ₂ = CH—R—AlR ³ R ⁴ (1)
(In the formula, R represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a branch, and R may contain a double bond or a phenylene group; R ³ , R ⁴ represents an alkyl group having 1 to 20 carbon atoms.) Alkenyldialkylaluminum or alkadienyldialkylaluminum represented by the following formula can be used. Particularly preferably, the following general formula (2)
_{CH 2 = CH- (CH 2)} n -AlR 3 R 4 ····· (2)
(Wherein R ³ and R ⁴ are alkyl groups having 1 to 20 carbon atoms, and n is an integer of 1 to 20). Specifically, R ³ and R ⁴ are each an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. N is an integer of 1 to 20, preferably an integer of 2 to 6, more preferably 4 or 6.

  Alkenyl dialkyl aluminum and alkadienyl dialkyl aluminum whose dialkyl is diisobutyl (iBu) are illustrated in FIG.

[Method for producing alkenyldialkylaluminum compound, etc.]
The alkenyldialkylaluminum used in the present invention can be obtained by many known methods. For example, hydroalumination reaction of non-conjugated diene or non-conjugated triene, cross-coupling reaction of alkenyl halide, alkadienyl halide and organoaluminum compound, organometallic compound such as alkenyl (or alkadienyl) lithium and alkenyl (or alkadienyl) magnesium There are transmetalation reactions with organoaluminum compounds. Among these, a preferable method is a hydroalumination reaction of a nonconjugated diene or a nonconjugated triene, and an alkenyldialkylaluminum can be produced by reacting a nonconjugated diene or nonconjugated triene with a dialkylaluminum hydride under mild conditions. .

[Method of copolymerizing propylene and alkenyldialkylaluminum]
Since a catalyst for obtaining a copolymer of propylene and alkenyldialkylaluminum requires high stereoregularity (high mm) and high copolymerization performance, it is preferable to use a so-called metallocene catalyst. Moreover, it is necessary to employ | adopt appropriate polymerization conditions according to the ligand structure of a metallocene complex. Copolymerization of propylene and alkadienyl dialkylaluminum can be similarly performed.

[Production of hydroxyl group-containing propylene copolymer]
The hydroxyl group-containing propylene-based copolymer of the present invention can be produced by reacting a propylene-alkenyldialkylaluminum copolymer or a propylene-alkadienyldialkylaluminum copolymer with various decomposing agents. That is, it can be obtained by converting a dialkylaluminum group (carbon-aluminum bond) in the copolymer into a carbon-hydroxyl bond. The reaction with the decomposing agent can be carried out according to a known method relating to the reaction between a low molecular weight organoaluminum compound and an inorganic compound (example: R. Rienacker and G. Ohloff, Angew.chem., 1961, 73 卷, 240, P. Tesseire and M. Plattier, Recherches, 1963, 13 卷, 34 [Chem. Abstr., 1964, 60 卷, 15915]). Examples of the decomposing agent include oxygen and peroxide.

2-2. Masking method In this method, the hydroxyl group of a hydroxyl group-containing olefin monomer such as 5-hexen-1-ol or 7-octen-1-ol is masked with organoaluminum, then copolymerized with propylene, and finally the masking is removed. Here, the masking means that the hydroxyl group does not act as a catalyst poison during the polymerization reaction by bringing the hydroxyl group-containing olefin monomer into contact with the organic aluminum. Further, during polymerization, the masked hydroxyl group can be returned to the original hydroxyl group while removing the AL atom by contacting with a compound containing active hydrogen after polymerization. Examples of the compound containing active hydrogen include alcohols such as methanol and ethanol, and water. Regarding this method, reference can be made to JP-A-55-98209, JP-A-8-53516 and the like.

[Copolymerization of propylene and masked hydroxyl group-containing olefin monomer]
Since the copolymer of propylene and a masked hydroxyl group-containing olefin monomer requires high stereoregularity (high mm) and high copolymerization performance, it is preferable to use a so-called metallocene catalyst. Moreover, it is necessary to employ | adopt appropriate polymerization conditions according to the ligand structure of a metallocene complex. Moreover, the part of (III) can be introduce | transduced by making a C4-C22 alpha olefin coexist in the case of copolymerization.

[Specific polymerization methods and formats]
This is a common matter between the above-described (1) propylene-alkenyldialkylaluminum or propylene-alkadienyldialkylaluminum copolymer intermediate method and (2) masking method.

  In the production method described above, any polymerization method can be adopted as long as the catalyst component and each monomer come into contact efficiently. Specifically, a slurry method using an inert solvent, a bulk method using substantially no inert solvent and propylene as a solvent, a solution polymerization method, or a gas phase method using substantially no liquid solvent can be employed. . Further, a method of performing continuous polymerization, batch polymerization, or prepolymerization is also applied. In the case of slurry polymerization, a saturated aliphatic or aromatic hydrocarbon such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used alone or as a mixture as a polymerization solvent. The polymerization temperature is −50 to 200 ° C., and hydrogen can be used supplementarily as a molecular weight regulator. The polymerization pressure can be carried out in the range of greater than 0 to 5 MPa, but as described above, it is important to employ appropriate polymerization conditions depending on the metallocene complex used.

[Introduction of Unit Represented by Structural Formula (III)]
In the present invention, as a method for introducing the unit represented by the structural formula (III) into the copolymer, an α-olefin having 4 or more carbon atoms coexists in addition to the alkenyldialkylaluminum or alkadienyldialkylaluminum as a comonomer. However, as another method, there is a technique in which the ratio of converting a dialkylaluminum group to a hydroxyl group is not 100%. That is, in the decomposition reaction, when oxygen or the like is brought into contact with the propylene-alkenyldialkylaluminum copolymer, alcohol or water is mixed, oxygen or the like is brought into contact with the content of alkenyldialkylaluminum or less (equivalent or less), or By changing the temperature and time during the reaction, the carbon-aluminum bond of the dialkylaluminum group that is not converted to a hydroxyl group is simply hydrolyzed (converted to a carbon-hydrogen bond) and converted to the unit of structural formula (III). Is possible. In this way, the propylene copolymer of the present invention can be produced by partial decomposition without adding an α-olefin having 4 or more carbon atoms during the copolymerization reaction.

[Storage modulus G ']
The storage elastic modulus G ′ is assumed to be at a temperature of 25 ° C. obtained by solid viscoelasticity measurement. Specifically, the solid viscoelasticity measurement is performed by applying a sinusoidal strain of a specific frequency to a strip-shaped sample piece and detecting the generated stress and the phase difference between the strain and the stress. Here, the frequency is 1 Hz, and the measurement temperature is raised in a step shape from −60 ° C. until the sample is melted and cannot be measured. Further, it is recommended that the magnitude of distortion is about 0.1 to 0.5%. From the obtained stress, the storage elastic modulus G ′ is obtained as a component having the same phase as the strain by a known method.

  The storage elastic modulus of the polypropylene homopolymer not containing the structural units (II) and (III) is about 730 MPa as apparent from the comparative examples described later, but according to the present invention, the storage elastic modulus is increased to a level exceeding 800 MPa. Can be improved.

[G 'control method]
As a method for controlling G ′, the following method can be exemplified.
(1) Increase / decrease in “stereoregularity: isotactic triad tacticity (mm fraction)” The mm fraction is determined by the stereoregular performance of the catalyst used, and in the case of a ZN catalyst, phthalate improves steric regulation. A catalyst using a titanium-containing solid catalyst component that has been subjected to internal donor treatment such as acid ester or 1,3-diether, and further using a silicon compound that enhances stereoregularity as an external donor is preferably used. When a metallocene catalyst system is used, the mm fraction can be increased and G ′ can be improved by using a metallocene complex having high isotactic stereoregular performance.

  Specifically, a transition metal compound having a specific ligand structure described later is used. It is more preferable to use a racemate in the form of a crosslinked complex. As a preferred ligand structure, a bridging group bisindenyl type or bridged bisazulenyl type ligand is used.

  By introducing a specific bulky substituent such as a phenyl group or a substituted phenyl group at the 4-position having a methyl group, an ethyl group or an isopropyl group at the 2-position, the mm fraction has a high value of about 99%. Then, by controlling the polymerization temperature and the polymerization pressure, the mm fraction value can be controlled to a desired value between 97% and 100%.

(2) Number of branches in the polymer The branch in the polymer means a side chain portion based on the structural unit (II) or (III). In the region where the total number of branches is 0.2 mol% or less, the degree of crystallinity is higher than that of polypropylene having no branch, and G ′ is improved. When the number exceeds 0.2 mol%, the degree of crystallinity is reversed. By decreasing, G ′ becomes smaller. This phenomenon is also a phenomenon that is particularly noticeable when the molecular weight distribution (Q value) is lower than 5 due to the influence of the molecular weight distribution of PP. The number of branches can be controlled by the comonomer concentration, temperature and pressure during copolymerization.

[Application of this copolymer]
(1) Since the hydroxyl group-containing propylene copolymer of the present invention has an effect of improving the affinity with a polar compound, for example, an EVOH layer that imparts gas barrier properties in a laminate, or adhesion to nylon or metal It is suitable for. More specifically, metals such as iron and aluminum, polyamide, polyester, polyacetal, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS), polymethacrylate, polycarbonate, polyphenylene oxide, polyvinyl chloride, polyvinylidene chloride, polyacetic acid Adhesiveness with polar group-containing polymers such as vinyl, polyvinyl alcohol, ethylene-vinyl acetate copolymer completely or partially saponified, and ethylene- (meth) acrylate copolymer is good. Moreover, since the main chain structure is polyolefin, it is excellent in adhesiveness with polyolefin, and can be used as an adhesive resin between the polar substances or between the polar substances and polyolefin.

(2) Moreover, since affinity with an ink improves, for example, it is suitable for molded objects, such as a film which needs printing. As the ink, common ones can be used. For example, letterpress printing ink, flat printing ink, flexographic ink, water-based ink, soybean ink, gravure ink, liquid crystal ink, crystal ink, glass color, perfume ink, magnetic ink, Ink such as UV curable ink. As a printing method, a general printing method is used, and examples thereof include offset printing, letterpress printing, screen printing, and gravure printing.

(3) Furthermore, the compatibility with the coating material is improved, and the coating material is likely to adhere without applying a primer or plasma treatment in advance. Therefore, it is suitable for a molded body requiring painting. Examples of paints that can be used include organic solvent paints and water-soluble resin paints, water-dispersible resin paints, water-based emulsion paints, and the like that are widely used. Specifically, acrylic paints, epoxy paints, polyester paints, urethane paints, melamine paints, alkyd paints and the like can be used as the resin component or crosslinking component of these paints. Examples of the method for applying the paint include spray painting by spraying, brush painting, and application by a roller, and any method can be used.

(4) When the hydroxyl group-containing olefin copolymer according to the present invention is used as a modifier for a resin, there are reforming effects such as hydrophilicity, antistatic property, paintability, and printability. Moreover, since it has the effect as a compatibilizer of polypropylene and a polar compound (nylon, polyester) which are nonpolar compounds, it is suitable as a modifier for forming a polymer alloy. When the polar group-containing olefin copolymer according to the present invention is used, polyolefin and a thermoplastic resin containing a hydroxyl group can be mixed at an arbitrary ratio. Since the hydroxyl group-containing olefin copolymer according to the present invention has a polyolefin main chain and a side chain having a hydroxyl group, components that were originally incompatible can be mixed with each other. The elongation at break can be remarkably improved as compared with the case where no coalescence is used.

(5) Even when an inorganic compound filler is used as the polar compound, it has an effect of improving its dispersibility, and therefore is suitable as a filler dispersion material. The filler dispersant is used, for example, when mixing a thermoplastic resin and a filler. Examples of the thermoplastic resin include the thermoplastic resins described above, and polyolefin is preferable. Fillers used in the present invention include organic fillers such as wholly aromatic polyamide fibers, aliphatic polyamide fibers, polyester fibers, and cellulose fibers, and fine dispersions such as liquid crystal polyester and polyamide, and silica, diatomaceous earth, and alumina. , Titanium oxide, magnesium oxide, pumice powder, pumice balloon, aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate, dolomite, calcium sulfate, calcium titanate, barium sulfate, calcium sulfite, talc, clay, mica, asbestos, glass Examples of inorganic fillers include fibers, glass flakes, glass beads, calcium silicate, montmorillonite, bentonite, graphite, aluminum powder, and molybdenum sulfide. Although the usage-amount of a filler dispersing agent is not specifically limited, For example with respect to 100 weight part of thermoplastic resins, it is 0.01-100 weight part, Preferably it is the quantity of 0.1-20 weight part.

  EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited to these Examples. In addition, the measuring method of the physical property in a following example is as follows.

[Measurement method of physical properties]
(1) Content of units represented by structural formulas (I), (II), and (III) (mol%)
NMR method as described above.
(2) Average molecular weight (Mw, Mn) and molecular weight distribution (Q value)
GPC method mentioned above.
(3) Storage elastic modulus (G ')
The sample used was a hot-press molded sheet of 2 mm thickness cut into a strip shape of 10 mm width × 18 mm length × 2 mm thickness. The apparatus used was ARES manufactured by Rheometric Scientific. The frequency is 1 Hz. The measurement temperature was raised in steps from −60 ° C., and measurement was performed until the sample melted and became impossible to measure. The strain was performed in the range of 0.1 to 0.5%.

(4) Adhesive strength [Create film]
A 0.1 mm thick polyethylene terephthalate sheet and a 100 μm thick stainless steel sheet with a 16 cm × 16 cm square cut in the order are laid in this order on the press plate, and a 4.0 g sample is placed in the center (the cut part). (Polar group-containing olefin copolymer) was placed. Subsequently, a polyethylene terephthalate sheet and a press plate were further stacked in this order.

The sample sandwiched between the press plates was placed in a hot press at 190 ° C., preheated for about 5 minutes, then pressurized to 100 kg / cm ² -G and heated under pressure for 5 minutes. After depressurization, it is removed from the press machine of the press plate, transferred to another press machine where the crimping part is kept at 20 ° C., pressurized and cooled at 100 kg / cm ² -G for 5 minutes, depressurized, and the sample is removed. I took it out. A uniform part of the obtained film having a thickness of about 150 to 170 μm was used for measuring the adhesive strength.
[Measurement of Al adhesive strength]
An aluminum sheet (thickness 50 μm) and a stainless steel sheet 100 μm thick with the center cut into a 16 cm × 16 cm square are laid in this order on the press plate, and the sample film is placed on the center (the cut part). It was. Next, an aluminum sheet (thickness 50 μm) and a press plate were stacked in this order. Next, the aluminum sheet and the sample film were bonded together under the same pressing conditions as in the above “Film creation”. The obtained laminate was cut into 15 mm width strips, and the adhesive interface between the aluminum sheet and the sample film was peeled in the 180 ° direction, and the peel strength was measured.

(5) Measurement of melting peak temperature (Tm) Using a differential scanning calorimeter (DSC6200 manufactured by Seiko Instruments Inc.), a sample piece made into a sheet is packed in a 5 mg aluminum pan and once heated from room temperature to 200 ° C, the heating rate is 100 ° C. The maximum melting temperature (° C.) when the temperature was raised to 200 ° C. at 10 ° C./min after being crystallized by lowering to 40 ° C. at 10 ° C./min. ).

[Example 1]
[Production of metallocene compounds]
Dimethylsilylenebis (2-methyl-4- (4-chlorophenyl) -4H-azurenyl) zirconium dichloride was synthesized by the method described in Example 1 of JP-A-11-240909.
[Production of octenyl diisobutylaluminum]
1,7-octadiene (200 ml: 1.40 mol) and diisobutylaluminum hydride (25.0 ml: 0.14 mol) were added to a 500 ml glass reactor equipped with a stirrer and reacted at 60 ° C. for 6 hours. Thereafter, the remaining 1,7-octadiene was removed under reduced pressure to obtain a reaction product. This reaction product was analyzed by gas chromatography (GC) and NMR. In the GC analysis, 0.5 ml of the reaction product was diluted with 2 ml of metaxylene (internal standard), and then decomposed by adding distilled water and hydrochloric acid and used for the analysis. As a result, it was confirmed that octenyl diisobutylaluminum was quantitatively produced.
[Production of chemically treated montmorillonite]
In a separable flask, 96% sulfuric acid (750 g) was added to 1130 g of ion-exchanged water, and then 300 g of a commercially available granulated montmorillonite (manufactured by Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 27.0 μm) was added to 390 at 90 ° C. It was made to react for minutes. Thereafter, it was washed to pH 3 with ion exchange water. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed and further dried under a nitrogen stream at 200 ° C. to obtain 140 g of chemically treated montmorillonite. The composition of this chemically treated montmorillonite is Al: 4.6 wt%, Si: 41.5 wt%, Mg: 0.60 wt%, Fe: 0.9 wt%, Na <0.2 wt%, Al /Si=0.115 [mol / mol].
[Catalyst / Prepolymerization Catalyst Preparation]
The inside of the 1 L three-necked flask was replaced with dry nitrogen, 20 g of the chemically treated smectite obtained above was added, and 116 mL of heptane was further added to form a slurry, to which trinormal octyl aluminum (50 mmol) was added for 1 hour. After stirring, the mixture was washed with heptane (washing rate: 1/100), and heptane was added so that the total volume became 200 mL.

  In another flask (volume: 200 mL), 87 ml of heptane containing 3% toluene was added to dimethylsilylenebis (2-methyl-4- (p-chlorophenyl) -4H-azurenyl) zirconium dichloride (218 mg; 0.3 mmol). After making the slurry, triisobutylaluminum (3 mmol: 4.26 mL of a heptane solution having a concentration of 145 mg / mL) was added, and the mixture was reacted by stirring at room temperature for 60 minutes. This solution was placed in a 1 L flask containing a slurry of chemically treated montmorillonite reacted with the above-described tri-normal octyl aluminum and stirred for 1 hour. To the flask containing the pre-prepolymerization catalyst slurry, 213 mL of 3% toluene-containing heptane was added, and this slurry was introduced into a 1 L autoclave.

Propylene was fed to the autoclave at a rate of 10 g / hour for 4 hours, and prepolymerization was performed while maintaining 40 ° C. Thereafter, the propylene feed was stopped, the internal temperature was raised to 50 ° C. in 5 minutes, and the remaining polymerization was further performed for 2 hours. The supernatant of the obtained catalyst slurry was removed by decantation, and triisobutylaluminum (12 mmol: 17 mL of a heptane solution having a concentration of 140 mg / mL) was added to the remaining portion, followed by stirring for 10 minutes. This solid was dried under reduced pressure at 40 ° C. for 3 hours to obtain 68.4 g of a dry prepolymerized catalyst. The prepolymerization ratio (value obtained by dividing the amount of prepolymerized polymer by the amount of solid catalyst) was 2.42.
[Copolymerization with propylene]
The inside of a 1 L stainless steel autoclave equipped with a stirring and temperature control apparatus was thoroughly dried, and then replaced with sufficiently dried propylene, and then thoroughly dehydrated heptane and triisobutylaluminum heptane solution (140 g / l) in 400 mg. And 0.031 mol of octenyl diisobutylaluminum synthesized previously (AL atom conversion) was added to adjust the total liquid volume to 500 ml. Thereafter, after introducing 1000 mg of the previously prepared solid catalyst component, propylene was supplied so that the propylene pressure became 0.5 MPa, and polymerization was carried out at 65 ° C. for 2 hours.
[Post-treatment of copolymer]
After copolymerization with propylene, the slurry solution containing the polymer was drawn into a 1 L flask under a nitrogen atmosphere using a siphon tube, and then 60 L of dry oxygen was blown in over 2 hours. Thereafter, 200 ml of methanol, 20 ml of concentrated hydrochloric acid, and 100 ml of distilled water were added, heated to reflux for 1 hour, and allowed to stand, and the lower layer (aqueous phase) was removed. Further, 200 ml of distilled water was added and the mixture was stirred and allowed to stand, and the operation of removing the lower layer (aqueous phase) was performed three times. The upper layer (organic phase) was filtered and dried at 90 ° C. under reduced pressure for 2 hours to obtain 58 g of a propylene copolymer. When this polymer was analyzed and evaluated, the content of the unit of structural formula (I) was 99.85 mol%, the content of the unit of structural formula (II) was 0.08 mol%, and structural formula (III) The content of the unit was 0.07 mol%, and the weight average molecular weight was 209,000. The results are shown in Table 1 together with other results.

[Example 2]
In Example 1, copolymerization of propylene was carried out in the same manner as in Example 1 except that octenyl diisobutylaluminum used for copolymerization with propylene was changed to 0.0080 mol (in terms of Al atom). The resulting copolymer was post-treated in the same manner. As a result, 75 g of polymer was obtained. The results are shown in Table 1.

[Comparative Example 1]
In Example 1, instead of copolymerization with propylene, propylene polymerization was carried out in the same manner as in Example 1 except that octenyl diisobutylaluminum was not used. When the resulting polymer was post-treated in the same manner, 140 g of polymer was obtained. The results are shown in Table 1.

[Comparative Example 2]
In Example 1, copolymerization was performed in the same manner as in Example 1 except that octenyl diisobutylaluminum used for copolymerization with propylene was changed to 0.124 mol (in terms of Al atom), and the obtained copolymer was When the post-treatment of the coalescence was performed in the same manner, 17 g of a propylene copolymer was obtained. The results are shown in Table 1.

[Example 3]
[OH group masking and propylene copolymerization]
After the inside of a 1 L stainless steel autoclave equipped with a stirrer and a temperature controller is thoroughly dried, it is replaced with sufficiently dried propylene, and then sufficiently dehydrated heptane is introduced, and then 7-octene-1- Introducing 2.3 ml (15 mmol) of all (8-hydroxy-1-octene), followed by 16 mmol of heptane solution of triisobutylaluminum (140 g / l) in terms of aluminum atoms, and adjusting the total liquid volume to 500 ml did. Ten minutes later, 1000 mg of the prepolymerized solid catalyst used in Example 1 was introduced, and then propylene was supplied so that the propylene pressure became 0.5 MPa, and polymerization was performed at 65 ° C. for 2 hours.
[Unmasking]
After the polymerization, the slurry solution containing the polymer was extracted into a 1 L flask under a nitrogen atmosphere using a siphon tube. Thereafter, 200 ml of methanol, 20 ml of concentrated hydrochloric acid, and 100 ml of distilled water were added, heated to reflux for 1 hour, and allowed to stand, and the lower layer (aqueous phase) was removed. Further, 200 ml of distilled water was added and the mixture was stirred and allowed to stand, and the operation of removing the lower layer (aqueous phase) was performed three times. The upper layer (organic phase) was filtered and dried at 90 ° C. for 2 hours under reduced pressure to obtain 70 g of the desired polymer. The results are shown in Table 1.

[Example 4]
[Production of solid catalyst]
200 ml of dehydrated and deoxygenated n-heptane was introduced into a fully nitrogen-substituted flask, and then 0.4 mol of MgCl ₂ and 0.8 mol of Ti (On-C ₄ H ₉ ) ₄ were introduced. The reaction was carried out at 95 ° C. for 2 hours. After completion of the reaction, the temperature was lowered to 40 ° C., and then 48 ml of methylhydropolysiloxane (20 centistokes) was introduced and reacted for 3 hours. The resulting solid component was washed with n-heptane.

Next, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, and 0.06 mol of the solid component synthesized above was introduced in terms of Mg atoms. Next, 0.1 mol of SiCl ₄ was mixed with 25 ml of n-heptane, introduced into the flask at 30 ° C. for 30 minutes, and reacted at 70 ° C. for 3 hours. After completion of the reaction, washing with n-heptane was performed. Next, 0.006 mol of phthalic acid chloride was mixed with 25 ml of n-heptane, introduced into the flask at 70 ° C. for 30 minutes, and reacted at 90 ° C. for 1 hour. After completion of the reaction, washing with n-heptane was performed. Then, 2.5 mol of TiCl ₄ was introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, it was thoroughly washed with n-heptane, and further 2.5 mol of TiCl ₄ was introduced and reacted at 90 ° C. for 3 hours. After completion of the reaction, the solid component (A1) for producing the component (A) was thoroughly washed with n-heptane. The titanium content of this product was 2.6% by weight.

Further, 50 ml of n-heptane purified in the same manner as described above was introduced into a sufficiently nitrogen-substituted flask, 5 g of the solid component synthesized above was introduced, and (t-C ₄ H ₉ ) Si (CH ₃ ) ( 1.2 ml of OCH ₃ ) _{2 and} 1.7 grams of Al (C ₂ H ₅ ) ₃ were contacted at 30 ° C. for 2 hours. After completion of the contact, the product was sufficiently washed with n-heptane to obtain a component (A) mainly composed of magnesium chloride. The titanium content of this product was 2.3% by weight.

[Propylene copolymerization]
The inside of a 1 L stainless steel autoclave equipped with a stirrer and a temperature controller was thoroughly dried, and then replaced with sufficiently dried propylene, and then sufficiently dehydrated heptane was introduced, and then a triethylaluminum hexane solution (72 0.5 g / l) was introduced in an amount of 125 mg, and octenyldiisobutylaluminum was further introduced in an amount of 0.062 mol (in terms of AL atom) to adjust the total liquid volume to 500 ml. Thereafter, 20 mg of the previously prepared solid catalyst component was introduced, propylene was supplied so that the propylene pressure was 0.5 MPa, and polymerization was performed at 70 ° C. for 2 hours.
[Post-processing]
After the polymerization, the slurry solution containing the polymer was extracted into a 1 L flask under a nitrogen atmosphere using a siphon tube, and then 60 L of dry oxygen was blown in over 2 hours. Thereafter, 200 ml of methanol, 20 ml of concentrated hydrochloric acid and 100 ml of distilled water were added, and the mixture was heated and refluxed for 1 hour and then allowed to stand, and the lower layer (aqueous phase) was removed. Further, 200 ml of distilled water was added and the mixture was stirred and allowed to stand, and the operation of removing the lower layer (aqueous phase) was performed three times. The upper layer (organic phase) was filtered and dried at 90 ° C. for 2 hours under reduced pressure to obtain 59 g of the desired polymer. The results are shown in Table 1.

[Example 5]
[Production of metallocene compounds]
Dimethylsilylenebis (2-ethyl-4- (4-trimethylsilyl-3,5-dichlorophenyl) -4H-azurenyl) hafnium dichloride was synthesized by the method described in Example 1 of JP-A-2005-126679.
[Production of chemically treated montmorillonite]
Into a 3 L separable flask equipped with a stirring blade and a reflux apparatus, 500 g of ion-exchanged water is added, and 249 g (5.93 mol) of lithium hydroxide monohydrate is added and stirred. Separately, 581 g (5.93 mol) of sulfuric acid was diluted with 500 g of ion-exchanged water and slowly dropped into the lithium hydroxide aqueous solution using a dropping funnel.
Further, 350 g of commercially available granulated montmorillonite (Mizusawa Chemical Co., Ltd., Benclay SL, average particle size: 28.0 μm) was added and stirred. Thereafter, the temperature is raised to 108 ° C. over 30 minutes and maintained for 150 minutes. Then, it cooled to 50 degreeC over 1 hour. Thereafter, it was washed to pH 3 with ion exchange water. The obtained solid was preliminarily dried at 130 ° C. for 2 days under a nitrogen stream, and then coarse particles of 53 μm or more were removed and further dried under a nitrogen stream at 200 ° C. to obtain 275 g of chemically treated montmorillonite. The composition ratio of the chemically treated montmorillonite was Al / Si = 0.21, Mg / Si = 0.046, and Fe / Si = 0.022.
[Catalyst / Prepolymerization Catalyst Preparation]
The same procedure as in Example 1 except that the metallocene complex produced in Example 5 and the chemically treated montmorillonite were used was prepared. As a result, 63.4 g of a dry prepolymerization catalyst having a prepolymerization ratio of 2.17 was obtained.
[Propylene copolymerization / post-treatment]
Except that the catalyst used was the catalyst prepared in Example 5, copolymerization was carried out in the same manner as in Example 1, and the post-treatment of the obtained copolymer was also carried out in the same manner. As a result, 87 g of polymer was obtained. The results are shown in Table 1.

[Comparative Example 3]
In an oil bath, dissolve 0.7 liter of xylene and 90 g of homopolypropylene (product name: Novatec PP, FY4, manufactured by Nippon Polypro Co., Ltd.) as a reaction solvent at 140 ° C. in a 1 L glass flask equipped with a stirrer. I let you. Next, a maleic anhydride xylene solution (0.058 g / 30 ml) and a dicumyl peroxide (DPC) xylene solution (4.8 mg / 6 ml) were gradually fed to the toluene solution from separate conduits over 4 hours. . After the feed yield, the reaction was continued for another 30 minutes and then cooled to room temperature to precipitate the polymer. The precipitated polymer was filtered, washed repeatedly with acetone, and dried under reduced pressure at 80 ° C. overnight to obtain a modified propylene polymer. This modified propylene homopolymer was subjected to elemental analysis and the amount of maleic anhydride grafted was measured. As a result, maleic anhydride corresponding to 0.1 mol% was graft polymerized. The results for the modified propylene homopolymer are shown in Table 1.

An example of R ¹ in Structural Formula (II) is shown. An example of R ² in the structural formula (III) is shown. An example of the partial chemical structure of a polymer is shown. An example of an alkenyl dialkyl aluminum compound and an alkadienyl dialkyl aluminum compound is shown. An example of the baseline and interval of a chromatogram is shown.

Explanation of symbols

P: represents the main chain of the propylene copolymer.
o1: Carbon adjacent to the hydroxyl group in the hexenol group is represented.
h1: represents the terminal methyl carbon of the hexyl group.
Tp: represents a methine carbon adjacent to a methyl group derived from propylene in the main chain.
To: represents a methine carbon adjacent to a hexyl group or hexanol group derived from a comonomer in the main chain.
Sp: Methylene carbon having methine carbon Tp adjacent to the methyl group derived from propylene in the main chain at both ends.
Spo: Methylene carbon having both ends of a methine carbon Tp adjacent to a methyl group derived from propylene in the main chain and a methine carbon To adjacent to a hexyl group or hexanol group derived from a comonomer.
Soo: represents a methylene carbon having both ends of a methine carbon To adjacent to a hexyl group or hexanol group derived from a comonomer in the main chain.

Claims (7)

99.8 to 99.99 mol% of propylene units represented by the following structural formula (I), 0.01 to 0.1 mol% of polar units represented by the structural formula (II), and structural formula (III) A hydroxyl group-containing propylene copolymer containing 0 to 0.1 mol% of a nonpolar unit represented, and having a weight average molecular weight Mw of 70,000 to 1,000,000.
  2. The hydroxyl group-containing propylene copolymer according to claim 1, wherein triad tacticity (mm fraction) of a monomer 3 chain portion centering on propylene composed of a head-to-tail bond is 97.0% or more.   The hydroxyl group-containing propylene copolymer according to claim 1 or 2, wherein the relationship between the number average molecular weight Mn and the weight average molecular weight Mw is 5 or less as a Q value (Mw / Mn).   The hydroxyl group-containing propylene copolymer according to any one of claims 1 to 3, wherein the storage elastic modulus (G ') at 25 ° C obtained by solid viscoelasticity measurement is 730 to 2000 MPa. The hydroxyl group-containing propylene copolymer according to any one of claims 1 to 4, wherein R ¹ and R ² have 4 to 8 carbon atoms.   6. The hydroxyl group-containing propylene copolymer according to claim 1, wherein the content of polar units per molecule of the polymer is 0.2 to 2 as an average value of the polymer. Propylene and the following general formula (1)
CH ₂ = CH—R—AlR ³ R ⁴ (1)
(In the formula, R represents an optionally branched divalent hydrocarbon group having 1 to 20 carbon atoms, R may contain a double bond, and R ³ and R ⁴ are carbon atoms. A propylene-alkenyldialkylaluminum copolymer or propylene-alkadienyldialkylaluminum copolymer obtained by copolymerization with an alkenyldialkylaluminum or alkadienyldialkylaluminum represented by formula (1) to (20). Propylene units 99.8 to 99.99 mol% represented by the following structural formula (I) and polar units 0.01 to 0 represented by the structural formula (II) are characterized by reacting the union with oxygen. A hydroxyl group containing 1 mol% and 0 to 0.1 mol% of a nonpolar unit represented by the structural formula (III) and having a weight average molecular weight Mw of 70,000 to 1,000,000 Method for manufacturing perforated propylene copolymer.