JP3338089B2 - Method for producing propylene random copolymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

The present invention relates to a method for producing a propylene random copolymer. More specifically, the present invention provides
The present invention relates to a method for producing a random copolymer having an unsaturated hydrocarbon bond containing propylene and a specific diene as essential components using a specific catalyst.

[0002]

2. Description of the Related Art Propylene homopolymers or copolymers (hereinafter sometimes collectively referred to as propylene polymers) are being developed for use in a wide range of fields because of their excellent properties. Is well known. On the other hand, since these polymers are essentially saturated hydrocarbons, they have poor chemical reactivity and are limited in graft reaction, cross-linking reaction, etc., and also have adhesiveness, paintability mainly derived from polar groups, It is also known that there is a problem that the printability is extremely poor. Various inventions have been proposed for the purpose of providing a solution to such a point (JP-A-55-165907, JP-A-56-30414, and JP-A-5-30414).
Nos. 6-36508, 62-115007, 62-
No. 115008, JP-A-2-145611).
These inventions relate to the copolymerization of propylene with a non-conjugated diene, and this copolymer has attracted attention as a reactive polypropylene because it has an unsaturated double bond in the side chain.

However, in these proposals, the copolymerizability of non-conjugated dienes is not always high, so that a large amount of expensive non-conjugated diene compounds must be used, and the amount of copolymer produced relative to the amount of catalyst used must be increased. (Ie, the catalytic activity) is low, and the production cost tends to be high. In addition, the copolymer according to such a proposal requires an unconjugated diene content of a certain level or more because almost all of the unsaturated double bonds in the side chain are tri-substituted internal olefins. It seems that there is a problem when a high degree of adhesiveness or adhesiveness is required or when it is used for applications such as foaming. On the other hand, it is well known that an α-olefin polymer can be obtained in a high yield by using a polymerization catalyst comprising a transition metal compound having a conjugated five-membered ring ligand and alumoxane (Japanese Patent Application Laid-Open No. 59-1984). No. 19309, No. 60-35007, No. 61-
Nos. 130314 and 63-295607;
No. 41303). Also, there has been proposed a method for producing a copolymer of propylene and a 1-olefin having 4 or more carbon atoms using these catalysts (Japanese Patent Laid-Open No. Sho 62-62).
119212, JP-A-1-266116, JP-A-2
173014, JP-A-2-247207). However, the polymers obtained by these proposals are:
As it is, the molecular weight distribution is narrow, so that the moldability may deteriorate and the melt strength may decrease. Further, Japanese Patent Laid-Open No. 4-2551
In Japanese Patent Publication No. 4, there is proposed a syndiotactic polypropylene-based α, ω-diene copolymer. However, since the polymer of this proposal is syndiotactic crystalline, there is a problem that it is inferior in compatibility with a conventional composite with an isotactic polypropylene resin.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a solution to the above problems.

[0005]

[Means for Solving the Problems]

[Summary of the Invention] <Summary> Consisting of repeating units (I) to (III) according to the present invention, the content of each of which is (I) 70 to 99.9 mol%,
(II) 0 to 15 mol% and (III) 0.1 to 15 mol%
And a method for producing a propylene random copolymer in which the [mm] fraction of triads by ¹³ C-NMR is 0.7 or more comprises a polymerization catalyst comprising the following components (A) and (B): And contacting with a monomer giving a repeating unit of the formula (1) to effect copolymerization.

[0006]

Embedded image

(Where m is 0 or an integer of 2 to 10,
n shows the integer of 1-20. ) Component (A) formula ^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b)
A transition metal compound represented by MeXY [provided that (C ₅ H _4-a R
¹ _a) and ^{_{(C 5 H 4-b R}} 2 b) , respectively ¹ and coordinating conjugated five-membered ring ligand ^(R in Me is ^{R 2} each 1 carbon atoms
20 monovalent groups selected from the group consisting of 20 hydrocarbon residues, halogen groups, alkoxy groups, silicon-containing hydrocarbon groups, phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups and boron-containing hydrocarbon groups (R ¹ And R ² may be the same or different, and two of R ¹ (or R ² ) are each bonded to form one fused six-membered ring to form an indenyl group)) Q is a divalent bonding group bridging the two conjugated five-membered ring ligands; Me is titanium, zirconium or hafnium; X and Y are each hydrogen, halogen, hydrocarbon, alkoxy, amino or amino. A is a monovalent group selected from the group consisting of a phosphorus-containing hydrocarbon group and a silicon-containing hydrocarbon group (X and Y may be the same or different), a is an integer of 2 ≦ a ≦ 4, b Represents an integer of 2 ≦ b ≦ 4. Component (B) Alumoxane.

<Effect> According to the present invention, adhesiveness, paintability,
A propylene random copolymer having excellent printability or having reactivity such that it is easily modified according to its purpose, at a low cost without using a large amount of expensive non-conjugated diene compounds, and having a molecular weight distribution. The production can be performed without causing much decrease in the melt strength due to the narrowing. Further, the propylene random copolymer according to the present invention can be used in the form of a complex with a commercially available isotactic polypropylene as a modifier.

[Detailed Description of the Invention] Polymerization catalyst The polymerization catalyst used in the present invention comprises the component (A) and the component (B). Here, “consisting of”
The use of the component (A) and the component (B) does not exclude the coexistence of an optional third component as long as the effect is not deteriorated.

[0010] <Component (A)> Component (A) is a general formula ^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b) a transition metal compound represented by Mexy. Where Q is
It is a divalent linking group that bridges two conjugated five-membered ring ligands. Specifically, (a) an alkylene group such as a methylene group, an ethylene group, an isopropylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclohexylene group,
(B) silylene group, dimethylsilylene group, phenylmethylsilylene group, diphenylsilylene group, disilylene group,
A silylene group such as a tetramethyldisilylene group, (c) a hydrocarbon group containing germanium, phosphorus, nitrogen, boron or aluminum (specifically, a (CH ₃ ) ₂ Ge group, (C
₆ H _{5) 2} Ge group, _(CH 3) P _group, (C _{6 H} 5) P
Group, (C ₄ H ₉ ) N group, (C ₆ H ₅ ) N group, (CH ₃ )
B group, (C ₄ H ₉ ) B group, (C ₆ H ₅ ) B group, (C ₆ H
₅ ) Al group, (CH ₃ O) Al group, etc.). Preferred are an alkylene group and a silylene group.

[0011] ^{_{(C 5 H 4-a R}} 1 a) and _(C 5 H _4-b
Although the conjugated five-membered ring ligand represented by R ² _b ) is defined separately, the definitions of a and b and R ¹ and R ² are the same (details described later). It goes without saying that the five-membered ring groups may be the same or different. One specific example of R ¹ (or R ² ) is a hydrocarbon group (C ₁ -C ₂₀ , preferably C ₁
To C ₁₂ ), and two of the hydrocarbon groups are bonded to each other to form one condensed six-membered ring together with a part of the cyclopentadienyl group to form an indenyl group. _{^{That, C 5 H 5 R 1 a}} ( or _C 5 _H 5 ^R _{2 b),} the
It is a substituted or unsubstituted indenyl group.

R ¹ and R ² each represent the above-mentioned C ₁
-C _20, preferably outside of the _C 1 -C _12, hydrocarbon radical,
A halogen group (for example, fluorine, chlorine, bromine), an alkoxy group (for example, _one of C _{1 to} C ₁₂ ), a silicon-containing hydrocarbon group (for example, when a silicon atom is -Si- (R)
(R) a group having about 1 to 24 carbon atoms contained in the form of (R)), a phosphorus-containing hydrocarbon group (for example, a phosphorus atom represented by -P- (R)
A group having about 1 to 18 carbon atoms in the form of (R)), a nitrogen-containing hydrocarbon group (for example, a group having about 1 to 18 carbon atoms containing a nitrogen atom in the form of -N (R) (R)) or Boron-containing hydrocarbon group (for example, when a boron atom is -B- (R)
(R) containing about 1 to 18 carbon atoms in the form of (R). a
(Or b) is 2 or more and R ¹ (or R ² )
When a plurality of are present, they may be the same or different. At least ^{one of} R ¹ (or R ² ) is located at the second position from the carbon having a bridging group. Me
Are titanium, zirconium and hafnium. X and Y each represent hydrogen, a halogen group, a hydrocarbon group having 1 to 20, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and 1 carbon atom. To 20, preferably 1 to 12 phosphorus-containing hydrocarbon groups (specifically, for example, diphenylphosphine groups) or silicon-containing hydrocarbon groups having 1 to 20, preferably 1 to 12 carbon atoms (specifically, Is, for example, a trimethylsilyl group). X and Y may be the same or different. Of these, a halogen group and a hydrocarbon group are preferred.

Specific examples of the transition metal compound when Me is zirconium are as follows. (A) transition metal compounds having a five-membered ring ligand bridged by an alkylene group, such as (1) methylenebis (indenyl) zirconium dichloride, (2) ethylenebis (indenyl) zirconium dichloride, (3) ethylenebis (indenyl) Zirconium monohydride monochloride, (4) ethylene bis (indenyl) methyl zirconium monochloride, (5) ethylene bis (indenyl) zirconium monomethoxy monochloride, (6) ethylene bis (indenyl) zirconium diethoxide, (7) ethylene Bis (indenyl) zirconium dimethyl, (8) ethylenebis (4,5
6,7-tetrahydroindenyl) zirconium dichloride, (9) ethylenebis (2-methylindenyl)
Zirconium dichloride,

(10) Ethylene bis (2-ethylindenyl) zirconium dichloride, (11) isopropylidene bis (indenyl) zirconium dichloride and the like.

(B) Transition metal compounds having a 5-membered ring ligand of a silylene group, such as (1) dimethylsilylenebis (indenyl) zirconium dichloride, (2) dimethylsilylenebis (4,5,6,7-tetrahydro (Indenyl) zirconium dichloride, (3) dimethylsilylenebis (2-methylindenyl) zirconium dichloride, (4) phenylmethylsilylenebis (indenyl) zirconium dichloride, (5) phenylmethylsilylenebis (4,5,6,7
-Tetrahydroindenyl) zirconium dichloride, (6) diphenylsilylenebis (indenyl) zirconium dichloride, (7) tetramethyldisilylenebis (indenyl) zirconium dichloride,

(8) dicyclohexylsilylenebis (indenyl) zirconium dichloride, (9) dicyclohexylsilylenebis (2-methylindenyl) zirconium dichloride, (10) dicyclohexylsilylenebis (2,4,7-
Trimethylindenyl) zirconium dichloride, and the like.

(C) Transition metal compounds having a five-membered ring ligand bridged by a hydrocarbon group containing germanium, aluminum, boron, phosphorus or nitrogen, such as (1) dimethylgermanium bis (indenyl) zirconium dichloride, 2) methyl aluminum bis (indenyl) zirconium dichloride, (3) phenyl aluminum bis (indenyl) zirconium dichloride, (4) phenylphosphinobis (indenyl) zirconium dichloride, (5) ethylboranobis (indenyl) zirconium dichloride, (6) phenyl Aminobis (indenyl) zirconium dichloride; (D) In addition, compounds obtained by replacing chlorine in the compounds (a) to (c) with bromine, iodine, hydride, methyl, phenyl, benzyl and the like can also be used.

Of these, preferred are zirconium compounds and hafnium compounds cross-linked with alkylene or silylene groups. Particularly preferred are zirconium compounds having an indenyl group.

<Component (B)> The component (B) is alumoxane. Alumoxanes are products obtained by the reaction of one trialkylaluminum or two or more trialkylaluminums with water. Specifically, methylalumoxane, ethylalumoxane, butylalumoxane obtained from one type of trialkylaluminum,
Examples thereof include isobutylalumoxane and the like, and methylethylalumoxane, methylbutylalumoxane, and methylisobutylalumoxane obtained from two kinds of trialkylaluminums and water. These alumoxanes may be used in combination of two or more, and may be used in combination with other alkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum, and dimethylaluminum chloride. It is also possible to use an alumoxane modified by reacting two kinds of alumoxanes or one kind of alumoxane with another organoaluminum compound. Of these, preferred are methylalumoxane, isobutylalumoxane, methylisobutylalumoxane, and a mixture of these alumoxane and trialkylaluminum. More preferred are methylalumoxane and methylisobutylalumoxane. Particularly preferred is a chemical shift of ²⁷ Al-NMR of 160
Methylisobutylalumoxane (having a peak at 3,000 Hz or more at a peak of ２５０250 ppm) (obtained by the following alumoxane preparation method (e) or (g).
16583).

These alumoxanes can be prepared under various known conditions. Specifically, the following method can be exemplified. (A) a method in which a trialkylaluminum is directly reacted with water using an appropriate organic solvent such as toluene, benzene or ether; (b) a salt hydrate having a trialkylaluminum and water of crystallization such as copper sulfate or aluminum sulfate (C) a method of reacting trialkylaluminum with water impregnated in silica gel or the like; (d) a method of mixing trimethylaluminum and triisobutylaluminum to form an appropriate mixture such as toluene, benzene, or ether. A method of directly reacting with water using an organic solvent, (e) a method of mixing trimethylaluminum and triisobutylaluminum and heating and reacting with a salt hydrate having water of crystallization, for example, a hydrate of copper sulfate or aluminum sulfate. , (F) Impregnate silica gel, etc. with water, and triisobutylaluminum After treatment, a method of adding treated with trimethylaluminum, method (g) synthesized in methylalumoxane and isobutyl alumoxane known methods, these two components are mixed predetermined amounts, reacted under heating.

<Formation of Catalyst> The catalyst of the present invention is prepared by subjecting the above-mentioned component (A) and component (B) in a polymerization vessel or outside the polymerization vessel in the presence or absence of a monomer to be polymerized. It can be obtained by contact. The amounts of component (A) and component (B) used in the present invention are arbitrary, but generally, the atomic ratio (Al / Me) of the aluminum atom in component (B) to the transition metal of component (A). ) At 0.01 to 100,000, preferably 1 to 30,000.
0. The contacting method is optional and may be introduced separately during the polymerization and brought into contact, or may be brought into contact in advance. As described above, the catalyst of the present invention can include other components in addition to the components (A) and (B), but can be added to the components (A) and (B). As the three components (optional components), for example, H
₂ O, active hydrogen-containing compounds such as methanol, ethanol, and butanol; electron-donating compounds such as ethers, esters, and amines; and alkoxy such as phenyl borate, dimethylmethoxyaluminum, phenyl phosphite, tetraethoxysilane, and diphenyldimethoxysilane. Examples of contained compounds can be given.

2. Production of Random Copolymer Monomer which gives repeating units (I), (III) and optional component (II) to the polymerization catalyst already described in detail,
Propylene, the formula _{CH 2 = CH-C n H} 2n -CH = C
Α, ω-non-conjugated diene (hereinafter, non-conjugated diene) represented by H ₂ and, if necessary, a general formula CH ₂ ＣＨCH—C _m H
The random copolymer of the present invention can be obtained by mixing and contacting _{2m + 1} α-olefin, ie, ethylene or α-olefin having 4 to 12 carbon atoms (hereinafter abbreviated as α-olefins). . The amount ratio of each monomer in the system does not need to be constant over time, it is convenient to supply each monomer at a constant mixing ratio, and it is also possible to change the mixing ratio of the supplied monomers over time. It is possible.
In addition, one of the monomers, particularly a non-conjugated diene, can be added in portions in consideration of the copolymerization reaction ratio. α, ω
-As non-conjugated dienes, 1,4-pentadiene, 1,
5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 4-methyl-1,7-octadiene, 4-
Ethyl-1,7-octadiene, 1,8-nonadiene,
1,9-decadiene, 1,10-undecadiene, 1,
11-dodecadienes, 1,13-tetradecadienes,
1,15-hexadecadiene and 1,19-eicosadiene. Of these, particularly preferred are
1,7-octadiene, 1,9-decadiene, 1,11
-Dodecadiene and 1,13-tetradecadiene.

However, among the above α, ω-non-conjugated dienes,
Since 1,5-hexadiene and 1,6-heptadiene are susceptible to cyclopolymerization during the polymerization, they need to be used in larger amounts than other α, ω-nonconjugated dienes, and therefore 1,5-hexadiene.
The use of hexadiene and 1,6-heptadiene is more costly than using other α, ω-nonconjugated dienes. Representative examples of α-olefins used as needed include ethylene, 1-butene,
Examples thereof include 1-pentene, 3-methyl-butene-1, 1-hexene, 4-methylpentene-1, 1-heptene, 1-octene, 1-nonene and 1-decene. One or more of these can be supplied to the system as a mixture and used. Of these, linear α-
Olefins are preferred, particularly preferably ethylene,
1-butene, 1-hexene.

The polymerization mode can be any mode as long as the catalyst component and each monomer are in efficient contact. Specifically, a slurry method using an inert solvent, a slurry method using propylene and a non-conjugated diene as a solvent without substantially using an inert solvent, a solution polymerization method, or each monomer without using a substantially liquid solvent is used. A gas phase method of substantially maintaining a gaseous state can be employed. Further, the present invention is also applicable to a method of performing continuous polymerization, batch polymerization or preliminary polymerization. As a polymerization solvent in the case of slurry polymerization, a single or a mixture of saturated aliphatic or aromatic hydrocarbons such as hexane, heptane, pentane, cyclohexane, benzene, and toluene is used. The polymerization temperature is about −78 ° C. to about 200 ° C., preferably 0 ° C. to 150 ° C. At that time, hydrogen can be used as a molecular weight regulator in an auxiliary manner. At the time of slurry polymerization, the amount of the component (A) used is 0.0001 to 1.0.
It is preferably within the range of gram component (A) / liter solvent.
The polymerization pressure is 0 to 90 kg / cm ² G, preferably 0 to 60 kg.
/ Cm ² G, particularly preferably 1 to 50 kg / cm ² G.

It is also preferable to use a catalyst in which propylene is previously polymerized before copolymerization for the purpose of improving the activity and reducing the amount of solvent-soluble by-product polymers. At this time, the proportion of the propylene homopolymerized portion in the total copolymer is usually 10% by weight or less, preferably 5% by weight.
The following is sufficient, and it is preferable that the peak of the DSC based on the propylene homopolymer is not recognized in the product polymer. In this case, the polymerization temperature at the time of propylene homopolymerization is generally equal to or lower than the temperature of the subsequent copolymerization. Therefore, the temperature during propylene homopolymerization is -30 to 70 ° C,
Preferably it is 0-50 degreeC. The pressure is usually between normal pressure and 2
0 kg / cm ² G, preferably normal pressure to 5 kg / cm ² G, can be adopted, but it is not necessarily limited to this as long as the ratio of the propylene homopolymer part to the target copolymer is within the above-mentioned predetermined range. The molecular weight of the copolymer can be controlled by adding hydrogen to the polymerization system.

3. Copolymer (1) Composition The copolymer obtained by the present invention is a random copolymer, and (I) a repeating unit derived from propylene,

[0027]

Embedded image

Is 70 to 99.9 mol%, preferably 87
-99.9 mol%, more preferably 90-99.5 mol%, (II) repeating units derived from α-olefins,

[0029]

Embedded image

(Where m = 0 or an integer of 2 to 10) is 0
１５15 mol%, preferably 0-10 mol%, more preferably 0-6 mol%, and (III) a repeating unit derived from a non-conjugated diene,

[0031]

Embedded image

(N is an integer of 1 to 20) is 0.1
To 15 mol%, preferably 0.1 to 10 mol%, more preferably 0.5 to 7 mol%.
Here, “consisting of” indicates that it may contain other suitable components other than the above three components or other components inevitably coexist. Further, since the copolymer according to the present invention is a random copolymer, the repeating units (I) to (III)
Are randomly (ie, randomly) arranged. If the propylene unit is less than 70 mol%, the crystallinity is excessively reduced, and the rubbery substance is formed. On the other hand, when this unit exceeds 99.9 mol%, the content of the non-conjugated diene unit does not decrease so that the reactivity based on the unsaturated bond in the side chain intended by the present invention cannot be sufficiently exhibited. When the non-conjugated diene unit has a plurality of non-conjugated diene units, it is expressed as the sum of both units. If the unit of the non-conjugated diene is less than 0.1 mol%, sufficient reactivity cannot be obtained for the same reason as described above. On the other hand, if it exceeds 15 mol%, the crystallinity becomes too low and the ratio of causing a crosslinking reaction during polymerization increases, which is not preferable.

In the present invention, the α-olefin unit (II) is required for the purpose of adjusting or improving physical properties required for the copolymer, for example, transparency, flexibility and melting point, depending on the use of the copolymer. Are introduced arbitrarily according to. Therefore, the content of the α-olefin units is appropriately determined according to the use of the copolymer and other circumstances. However, if the ethylene unit content exceeds 15 mol%, a copolymer satisfactory in crystallinity cannot be obtained.
Therefore, a preferred composition has a propylene unit of 87-9.
9.9% by mole, 0 to 10% by mole of α-olefin units, 0.1 to 10% by mole of α, ω-non-conjugated diene unit, and particularly preferably 90 to 99.99% by weight of propylene unit.
5 mol%, α-olefin units are 0 to 6 mol%, and α, ω-non-conjugated diene units are 0.5 to 7 mol%.

(2) Molecular Weight The molecular weight of the copolymer of the present invention is 0.01 to 1000 g / 10 at a melt flow rate (MFR) measured at 230 ° C. under a load of 2.16 kg according to JIS K-6758.
Molecular weight, preferably 0.02 to 300 g / 10 min, particularly preferably 0.05 to 200 g / 10 min. If it is less than this range, molding is difficult, and if it exceeds this range, the mechanical properties are significantly reduced, and both are not preferred. The molecular weight can also be measured by gel permeation chromatography, and the number average molecular weight is 1000.
１０００1,000,000, preferably 2,000 to 50,000
0, more preferably 5,000 to 200,000.

(3) Melting point The melting point of the copolymer of the present invention is a melting point peak of 60 to 160 ° C., preferably 90 to 155 ° C. by DSC.
° C, particularly preferably in the range of 100 ° C to 150 ° C. If it is less than this range, the heat resistance of the propylene-based resin cannot be exhibited, and furthermore, it becomes a rubber-like substance, which is not preferable. (4) Crystallinity The copolymer of the present invention has a crystallinity of 10 by X-ray diffraction.
% By weight, preferably in the range of 20 to 55% by weight. Below this range, the heat resistance of the propylene-based resin cannot be exhibited.

(5) [mm] Fraction of Triad The propylene random copolymer obtained in the present invention has a ¹³ C
-The [mm] fraction of the triad is 0.7 as measured by NMR.
Or more, preferably 0.8 or more. here,
The [mm] fraction of the triad is a monomer unit in the α-olefin polymer, which is the minimum unit of the steric structure `` triad '', that is, a `` trimer unit '', three possible stereoisomeric structures, That is, [mm] (isotactic),
The ratio (y / x) of the number y of triads having the [mm] structure in the total number x of [mr] (heterotactic) and [rr] (syndiotactic). In addition,
The measurement of ¹³ C-NMR was conducted by JEOL JEOL. FX-2
Using 00, measurement temperature 130 ° C, measurement frequency 50.1MH
z, spectral width 8000 Hz, pulse repetition time 2.
0 seconds, pulse width 7μs, integrating circuit 10000-5000
This was performed under the condition of 0 times. The analysis of the spectrum was performed according to Macromolecules 21 617 (198
8) and Tetsuro Asakura's Proceedings of the Society of Polymer Science of Japan 36 (8) 2408 (198
It was performed based on 7).

[0037]

The following examples and comparative examples further illustrate the present invention. These examples are polymerized by a slurry polymerization method, but embodiments of the present invention are not limited to this method. The experimental methods used in the following Examples and Comparative Examples are as follows. (1) MFR (230 ℃, 2.16Kg) JIS K-6758 [g / 10 min] (2) Crystallinity X-ray diffraction method (3) Melting point DSC peak value [° C.] (4) comonomer composition ¹ H -NMR [mol%] ¹³ C-NMR [mol% and stereoregularity mm]

Example 1 Preparation of Component (A) Ethylene bis (indenyl) zirconium dichloride was synthesized according to the literature of J. Orgmet. Chem. (288) 63-67 1985 . Preparation of Catalyst Component (B) 5 g of copper sulfate pentahydrate at 0 ° C. was added to 565 ml of a toluene solution containing 48.2 g of trimethylaluminum at 0 ° C. while stirring.
Feed every 5 minutes. After the completion, the temperature is slowly raised to 25 ° C., and the reaction is performed at 25 ° C. for 2 hours and further at 35 ° C. for 2 days. The remaining copper sulfate solid is separated to obtain a toluene solution of alumoxane. The concentration of methylalumoxane was 27.3 mg / ml (2.7 w / v%).

Preparation of Copolymer In a 1.0 liter stainless steel autoclave equipped with a stirring and temperature control device, 400 ml of sufficiently dehydrated and deoxygenated toluene, 10 ml of 1,9-decadiene, methylalumoxane Of aluminum bis (indenyl) zirconium dichloride in an amount of 0.418 milligrams (0.0
01 mmol), propylene pressure = 5 kg / cm
Polymerization was performed at ² G at a polymerization temperature of 50 ° C. for 2 hours. After the polymerization is completed, the polymerization solution is withdrawn into 3 liters of methanol,
The polymer was filtered off and dried, recovering 84.5 grams of polymer. As a result of measurement by gel permeation chromatography, this was found to have a number average molecular weight (M
n) 25.4 × 10 ³ , molecular weight distribution is weight average molecular weight /
The ratio of the number average molecular weight was 11.0. JEOL. FX
As a result of measurement of ¹³ C-NMR by -200, the [mm] fraction of the triad was 0.910. Also, 1,9
The decadiene content was 1.16 mol%; MFR: 41 g / 10 min, melting point by DSC: 119.2 ° C., X
The crystallinity determined by the line diffraction method was 30.5% by weight.

Example 2 Preparation of Catalyst Component (A) Dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride was prepared according to J. Orgmet. Chem. (342) 21-29.
1988 and J. Orgmet. Chem. (369) was synthesized according to 359-370 19 89. Specifically, in a 300 ml flask purged with nitrogen, 5.4 g of bis (indenyl) dimethylsilane was diluted to 150 ml of tetrahydrofuran, cooled to −50 ° C. or lower, and then n-butyllithium (1.6 M / L) Was added dropwise over 30 minutes. After completion of the dropwise addition, the temperature was raised to room temperature over 1 hour, and the reaction was carried out at room temperature for 4 hours to synthesize a reaction solution A. 200 ml of tetrahydrofuran was introduced into a 500 ml flask purged with nitrogen, cooled to -50 ° C or lower, and 4.38 g of zirconium tetrachloride was slowly introduced. Next, after introducing the entire amount of the reaction solution A, the temperature was slowly raised to room temperature over 3 hours. After reacting at room temperature for 2 hours, the temperature was further raised to 60 ° C. and reacted for 2 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was dissolved in 100 ml of toluene and distilled off again to obtain 3.86 g of crude crystals of dimethylsilylenebis (indenyl) zirconium dichloride. Next, the crude crystals were dissolved in 150 ml of dichloromethane, introduced into a 500 ml autoclave, and platinum-carbon (0.5% by weight platinum supported).
After introducing 5 g of the catalyst, a hydrogenation reaction was carried out for 5 hours under the conditions of H ₂ = 50 kg / cm ² G and 50 ° C. After completion of the reaction, the catalyst was filtered off, the solvent was distilled off under reduced pressure, extracted with toluene, and recrystallized to obtain 1.26 g of the target dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride.

Production of Component (B) 1 equipped with a stirrer and a reflux condenser sufficiently purged with nitrogen.
100 ml of dehydrated and deoxygenated toluene was introduced into a 000 ml flask. Then, one of the two dropping funnels was filled with 0.72 of trimethylaluminum.
G (10 mmol) and 1.96 g (10 mmol) of triisobutylaluminum were diluted in 50 ml of toluene, and toluene containing saturated water was introduced into the other, and a mixed aluminum solution and saturated water were added at 30 ° C. The contained toluene was fed in equimolar amounts of Al and H ₂ O over 3 hours. After the feed, the temperature was raised to 50 ° C and
Allowed to react for hours. After completion of the reaction, the solvent was distilled off under reduced pressure.
9 grams of a white solid were obtained. Production of Copolymer All of the copolymers of Example 1 were used except that 0.46 mg of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride synthesized above and 3 mmol of methylisobutylalumoxane as aluminum atoms were used as polymerization catalysts. Polymerization was carried out under the same conditions as for the production of the coalescence. Table 1 shows the results.

Example 3 Preparation of Catalyst Component (A) Synthesis of Dimethylsilylenebis (2-methylindenyl) zirconium Dichloride In a 500 ml glass reaction vessel, 4.3 g (33 mmol) of 2-methylindene was added in 80 ml. Was dissolved in tetrahydrofuran, and under cooling, 21 ml of a 1.6 M hexane solution of n-butyllithium was slowly dropped into the reaction vessel. After stirring at room temperature for 1 hour, the mixture was cooled again, and 2.1 g of dimethyldichlorosilane was slowly added dropwise. After stirring at room temperature for 12 hours,
50 ml of water was added, and the organic phase was separated and dried to obtain 3.5 g of dimethylbis (2-methylindenyl) silane. Dissolve 3.5 g of dimethylbis (2-methylindenyl) silane obtained by the above method in 7.0 ml of tetrahydrofuran,
Under cooling, 1.6 M hexane solution of n-butyllithium 1
3.9 ml were slowly added dropwise. After stirring at room temperature for 3 hours,
The solution was slowly dropped into a solution of 2.6 g (11 mmol) of zirconium tetrachloride / 60 ml of tetrahydrofuran, stirred for 5 hours, blown with hydrogen chloride gas, and dried. Subsequently, methylene chloride was added to separate a soluble portion, and crystallized at a low temperature to obtain 0.45 g of an orange powder. Production of copolymer Polymerization was carried out under the same conditions as in the production of the copolymer of Example-2 except that 0.48 mg of dimethylsilylenebis (2-methylindenyl) zirconium dichloride synthesized above was used as the polymerization catalyst. did. Table 1 shows the results.

<Comparative Example-1> 0.2 g of the catalyst with a carrier disclosed in Example-1 of JP-A-2-145611 was used as the component (A), and triethylaluminum was used instead of the component (B). A copolymer was produced under the same conditions as in Example 1 except that 0.25 g was used. Table 1 shows the results. Comparing Example 1 with Comparative Example 1,
It can be seen that when the transition metal compound according to the present invention was used, the content of 1,9-decadiene in the produced polymer was higher than when the supported catalyst shown in Comparative Example 1 was used.

<Comparative Example 2> The polymerization temperature of Comparative Example 1 was 6
The temperature was raised to 5 ° C., and 100 N ml of hydrogen was added for polymerization. Table 1 shows the results. In this comparative example, the catalyst with a carrier used in Comparative Example 1 was polymerized at a temperature usually used. However, even at this temperature, the content of 1,9-decadiene in the produced polymer was lower than that in Example 1. I understand.

Comparative Example 3 Polymerization was carried out under the same conditions as in Example 2 except that 10 ml of 1-decene was used instead of 1,9-decadiene. Table 1 shows the results. It can be seen that by using 1-decene, the Mw / Mn value of the produced polymer is smaller than that in the case of using 1,9-decadiene, that is, the molecular weight distribution of the produced polymer is narrower.

[0046] Using 400 ml of n- heptane in place of manufacture toluene solvent <Example -4～6> copolymer, 1,9-usage decadiene, 5 ml 10 ml modify a 20 ml ,
0.46 mg of dimethylsilylenebis (tetrahydroindenyl) zirconium dichloride obtained in Example-2 and 5 mmol of methylisobutylalumoxane in terms of aluminum atom were used, and a propylene pressure of 5 kg / cm ² G at 50 ° C. for 2 hours A polymerization operation was performed. After completion of the polymerization, the same post-treatment as described in Example 1 was performed. Table 2
Indicates the result.

<Examples 7 to 8> Preparation of copolymer The same conditions as in Example 5 were used except that a predetermined amount of α, ω-nonconjugated diene shown in Table 2 was used instead of 1,9-decadiene. The polymerization was carried out. Table 2 shows the results.

[0048]

[Table 1]

[0049]

[Table 2]

[0050]

According to the present invention, a propylene random copolymer having excellent adhesiveness, coatability and printability, or having reactivity such that it is easily modified according to the purpose thereof, can be produced by using an expensive non-conjugated diene compound. It is possible to produce at low cost without using a large amount of, and without significantly lowering the melt strength due to narrowing of the molecular weight distribution, and the polypropylene random copolymer according to the present invention is a modifier As described above in the section of “Summary of the Invention”, it is also possible to use the compound as a complex with commercially available isotactic polypropylene.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-63-66206 (JP, A) JP-A-4-25514 (JP, A) JP-A-4-331214 (JP, A) JP-A-4- 142309 (JP, A) JP-A-1-301704 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 4/60-4/70

Claims (2)

(57) [Claims] 1. The repeating units (I) to (I), wherein a polymerization catalyst comprising the following components (A) and (B) is brought into contact with a monomer which gives the following repeating units and copolymerized. III), each having a content of (I) 70
９９99.9 mol%, (II) 0-15 mol% and (III)
A method for producing a propylene random copolymer having 0.1 to 15 mol% and a [mm] fraction of triad of 0.7 or more by ¹³ C-NMR. Embedded image (Where m is 0 or an integer of 2 to 10, n is 1 to 20)
Indicates an integer. ) Component (A) formula ^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b)
A transition metal compound represented by MeXY [provided that (C ₅ H _4-a R
¹ _a) and ^{_{(C 5 H 4-b R}} 2 b) , respectively ¹ and coordinating conjugated five-membered ring ligand ^(R in Me is ^{R 2} each 1 carbon atoms
20 monovalent groups selected from the group consisting of 20 hydrocarbon residues, halogen groups, alkoxy groups, silicon-containing hydrocarbon groups, phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups and boron-containing hydrocarbon groups (R ¹ And R ² may be the same or different, and two of R ¹ (or R ² ) are each bonded to form one fused six-membered ring to form an indenyl group)) Q is a divalent bonding group bridging the two conjugated five-membered ligands; Me is titanium, zirconium or hafnium; X and Y are each hydrogen, halogen, hydrocarbon, alkoxy, amino or amino A is a monovalent group selected from the group consisting of a phosphorus-containing hydrocarbon group and a silicon-containing hydrocarbon group (X and Y may be the same or different), a is an integer of 2 ≦ a ≦ 4, b Represents an integer of 2 ≦ b ≦ 4. Component (B) Alumoxane. 2. The repeating units (I) to (I), wherein a polymerization catalyst comprising the following components (A) and (B) is brought into contact with a monomer giving the following repeating units to copolymerize them. III), each having a content of (I) 70
９９99.8 mol%, (II) 0.1-15 mol% and (I)
II) 0.1 to 15 the molar%, and ¹³ the preparation of propylene random copolymer is C-NMR [mm] fraction of the triad is 0.7 or more by. Embedded image (Here, n is an integer of 1-20.) Component (A) formula ^{_{Q (C 5 H 4-a}} R 1 a) (C 5 H 4-b R 2 b)
A transition metal compound represented by MeXY [provided that (C ₅ H _4-a R
¹ _a) and ^{_{(C 5 H 4-b R}} 2 b) , respectively ¹ and coordinating conjugated five-membered ring ligand ^(R in Me is ^{R 2} each 1 carbon atoms
20 monovalent groups selected from the group consisting of 20 hydrocarbon residues, halogen groups, alkoxy groups, silicon-containing hydrocarbon groups, phosphorus-containing hydrocarbon groups, nitrogen-containing hydrocarbon groups and boron-containing hydrocarbon groups (R ¹ And R ² may be the same or different, and two of R ¹ (or R ² ) are each bonded to form one fused six-membered ring to form an indenyl group)) Q is a divalent bonding group bridging the two conjugated five-membered ring ligands; Me is titanium, zirconium or hafnium; X and Y are each hydrogen, halogen, hydrocarbon, alkoxy, amino or amino. A is a monovalent group selected from the group consisting of a phosphorus-containing hydrocarbon group and a silicon-containing hydrocarbon group (X and Y may be the same or different), a is an integer of 2 ≦ a ≦ 4, b Represents an integer of 2 ≦ b ≦ 4. Component (B) Alumoxane.