JPH0552323B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a solid catalyst for α-olefin polymerization. More specifically, the present invention relates to a solid catalyst preferably used for the polymerization of ethylene, propylene, butene-1,4-methylpentene-1, etc., which is composed of a supported catalyst component having high polymerization activity and an organoaluminum compound. Conventionally, JP-A-Sho has proposed a supported catalyst suitable for the stereoregular polymerization of α-olefins having 3 or more carbon atoms.
No. 48-16986, JP-A No. 49-86482, JP-A No. 50-
No. 108385, Japanese Patent Application Publication No. 126590, Japanese Patent Application Publication No. 1973-
Many methods have been proposed, including No. 28189, for producing a titanium-containing catalyst using a halogenated magnesium compound, preferably magnesium chloride, as a carrier raw material. Furthermore, the general formula used in the present invention is Mg(OR ¹ ) _o (OR ² ) _2-o ...[] (wherein, R ¹ and R ² represent an alkyl group, an aryl group, or an aralkyl group, and R ¹ and R ² may be the same or different; n indicates 2≧n≧0.
Although proposals have been made in Japanese Patent Publications No. 47-1768 and Japanese Patent Publication No. 47-42137, none have been found suitable for highly stereoregular polymerization of α-olefins having 3 or more carbon atoms. Various attempts have been made to improve the stereoregularity using a carrier represented by the general formula [], including JP-A No. 52-98076, which was previously proposed by the present applicant, as well as JP-A No. 53-2580, JP-A No. No. 1983-43094, Japanese Patent Application Publication No. 1983
-152710, JP-A-56-26904, etc. have been proposed, but these have not been fully satisfactory. The present inventors have arrived at the present invention as a result of studying a method for producing a titanium-containing solid catalyst using a carrier represented by the general formula [] and a polymerization method using the catalyst. That is, the present invention is based on the general formula Mg(OR ¹ ) _o (OR ² ) _2
-o (In the formula, R ¹ and R ² represent an alkyl group, an aryl group, or an aralkyl group, and R ¹ and R ² may be the same or different. n represents 2≧n≧0.) A titanium-containing solid catalyst component (a) obtained by treating a magnesium compound with three types of compounds consisting of a carboxylic acid ester, a silicon compound containing a halogen and an aryloxy group, and a chlorine-containing tetravalent titanium compound; This is a method for producing an olefin polymer, which comprises polymerizing or copolymerizing an olefin in the presence of a catalyst comprising an organoaluminum compound (b). The above-mentioned halogen-containing magnesium has a property of being hygroscopic or reacting with moisture, and therefore, the use of a support represented by the general formula [] has a great advantage in the catalyst manufacturing process. To explain the present invention in detail, (A) a magnesium compound represented by the general formula [ ], (B) a carboxylic acid ester, (C) a silicon compound containing a halogen and an aryloxy group, and (D) a chlorine-containing tetravalent titanium Solid catalyst component (a) obtained by treatment with three types of compounds consisting of
and an organoaluminum compound (b) as essential components,
This method of producing an olefin polymer is characterized in that the olefin is polymerized or copolymerized using a titanium-containing catalyst in combination with an appropriate carboxylic acid ester (c). Specifically, the magnesium compound A represented by the general formula [] used in the present invention is Mg
_{( OCH3} ) ₂ , Mg( _OC2M5 ) ₂ , Mg( _OC3H7 ), _Mg
(OC ₄ H ₉ ) ₂ , Mg (OC ₆ H ₅ ) ₂ , Mg (OCH ₂ C ₆ H ₅ ) ₂ ,
Mg( _{OC6H5 )} ( _OC4H9 ) _, Mg( _{OC2H5 )} ( _{CO6H5 )} ,
Examples include dialkoxymagnesium, diaryloxymagnesium, dialkyloxymagnesium, and alkyloxyaryloxymagnesium such as Mg(OC ₄ H ₆ CH ₃ ) ₂ . As the carboxylic acid ester (B), ethyl acetate,
Methyl propionate, ethyl acrylate, ethyl oleate, ethyl stearate, ethyl phenyl acetate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, methyl toluate, ethyl toluate, propyl toluate, toluic acid Examples include butyl, methyl ethylbenzoate, ethyl ethylbenzoate, ethyl xylenecarboxylate, methyl anisate, ethyl anisate, methyl ethoxybenzoate, ethyl ethoxybenzoate, ethyl cinnamate, etc. Among them, aromatic Carboxylic acid esters are preferably used. The silicon compound (C) containing a halogen and an aryloxy group has the general formula SiRa(OAr)bXc (wherein R
represents an alkyl group, an aryl group, or an aralkyl group, Ar represents an aryl group, and a, b, and c are 0
≦a<4, 0<b<4, 0<c<4, a+b+c
= 4, and X represents a halogen), specifically, PhSi(OPh) ₂ Cl (Ph represents a phenyl group), PhSi
(OPh) _1.5 Cl _1.5 , PhSi (OPh) ₁ Cl ₂ , PhSi (OPh) _0.5 Cl _2.5 , MeSi (OPh) ₂ Cl (Me represents a methyl group), MeSi (OPh) _1.5 cl _1.5 , MeSi
(OPh) ₁ Cl ₂ , MeSi(OPh) _0.5 Cl _2.5 , Si(OPh) ₃ Cl,
Si (OPh) _2.5 , Cl _1.5 , Si (OPh) ₂ Cl ₂ , Si (OPh) _1.5
Examples include Cl _2.5 , Si(OPh) ₁ Cl ₃ , Si(OPh) _0.5 Cl _3.5 and the like. Furthermore, the phenyl group may be substituted with a halogen or an alkyl group. Among these, PhSi(OPh) _0.5 Cl _2.5 , PhSi
(OPh) ₁ Cl ₂ , PhSi(OPh−Cl) _0.5 Cl _2.5 , PhSi(OPh−Me) _0.5
Cl _2.5 , PhSi(OPh−Cl) ₁ Cl ₂ , PhSi(OPh−
Me) ₁ Cl ₂ etc. In the method of the present invention, the components (A), (B), (C), and (D) may be treated by mechanical pulverization or by contacting them in the presence or absence of a hydrocarbon solvent. After mechanically grinding, mixing or contacting components A), (B), (C), and (D) and washing with an inert hydrocarbon solvent.
Add (B), (C), and (D) and further mechanically crush or
A method of repeating the steps of contact-mixing (B), (C), and (D) under heating and washing with an inert hydrocarbon solvent at least once can also be preferably used. In addition, in the repeated treatment, as long as the halogen- and aryloxy-containing silicon compound is used at least once as component (C), other halogen-containing silicon compounds may be used. Furthermore, the amounts of each component used in the catalyst manufacturing process in one process are usually expressed in molar ratios as follows. Mg (OR ¹ ) _o (OR ² ) _2-o carboxylic acid ester 10 to 0.01, preferably 1 to
Silicon compound containing 0.1 halogen and aryloxy group 20-0.1, preferably 5-0.5 Chlorine-containing tetravalent titanium compound 100-0.1, preferably 40-1 and usually the amount of titanium in the product is 0.1-10% by weight, The amount of each of the above components used is preferably adjusted to 0.5 to 5% by weight. Mechanical pulverization in each of the above methods is performed using a pole mill,
Any conventional method such as an impact mill or a vibration mill may be used. The pulverization temperature may normally be around room temperature, and heating and cooling are not particularly required. The pulverization time depends on the type of pulverizer used, but is usually from several hours to 200 hours. In addition, the reaction in the presence or absence of an inert hydrocarbon solvent is usually carried out at room temperature to 200°C, preferably at 80°C.
The temperature is ~150°C, and the reaction time is about 0.5 to 4 hours. In the present invention, the reaction product obtained as described above is then washed with an inert hydrocarbon solvent,
Remove components soluble in the solvent. and the thus obtained catalyst component (a) and organoaluminum compound (b),
Further, if necessary, a catalyst system containing a carboxylic acid ester (c) is used to carry out polymerization or copolymerization of the olefin to produce a polyolefin. At this time, there is no particular restriction on the order in which the components (a), (b), and (c) are added. Next, the organoaluminum compound [component (b)] used in this catalyst system preferably has the general formula
Examples include compounds represented by AlR ² _o X _3-o . In the above formula, R ² is a hydrocarbon group having 1 to 20 carbon atoms,
In particular, it is an aliphatic hydrocarbon group, where X is a halogen, n
indicates a number of 2 to 3. Specific examples of this organoaluminum compound include triethylaluminum,
Examples include tripropyl aluminum, triisobutyl aluminum, trihexyl aluminum, trioctyl aluminum, monovinyl diethylaluminium, diethylaluminium monoclide, and preferably trialkyl aluminum alone or a mixture with dialkyl aluminum monohalide is used. Further, as the catalyst system component (c), the component (B) used in the production of the solid catalyst component (a) described above is used, but aromatic carboxylic acid ester is preferable. The ratio of catalyst components to be used is such that the molar ratio of titanium in catalyst component (a) to aluminum compound in component (b) to carboxylic acid ester in component (c) is 1:3 to 500:0 to 100.
Preferably, the ratio is selected to be 1:20 to 200:3 to 50. Olefins include ethylene, propylene,
Examples include butene-1,3-methylbutene-1,4-methylpentene-1, preferably 3 carbon atoms.
The above-mentioned α-olefins, especially propylene, can be mentioned. In addition to homopolymerization, the polymerization can also be applied to random or block copolymers. The polymerization reaction is carried out using an inert hydrocarbon, such as hexane,
Slurry polymerization is preferably carried out using heptane, cyclohexane, benzene, toluene, pentane, butane, or a mixture thereof, or a liquefied product of α-olefin to be polymerized as a solvent, but polymerization may also be carried out in a gas phase. can. The temperature is
The temperature is 50 to 100°C, preferably 60 to 90°C, and the pressure is not particularly limited, but is usually selected from within the range of atmospheric pressure to 100 atm. Hydrogen can also be present as a molecular weight regulator in the polymerization system, which results in a melt flow index (MFI, measured by ASTM-D1238) of 50
~0.1 polymers can be easily produced.
Other methods commonly used for the polymerization and copolymerization of α-olefins can also be applied to the method of the present invention. For example, the three catalyst components (a), (b),
(c) or a method of pretreating with α-olefin using two components (a) and (b). Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples unless it deviates from the gist thereof. It should be noted that FIG. 1 is a flowchart diagram to help understand the technical content included in the present invention, and the present invention is not limited in any way by the flowchart diagram as long as it does not exceed the gist thereof. In the examples, the polymerization activity (denoted as K) is the amount of polymer produced (g) per 1 g of titanium per 1 kg/cm ² of α-olefin pressure per hour,
Catalytic efficiency (expressed as CE) is the amount of polymer produced (g) per gram of titanium in the catalyst component. The isotactic index (denoted as
This is the remaining amount (% by weight) when extracted over time. Since the amorphous polymer is soluble in boiling n-heptane, it indicates the yield of crystalline polymer. Bulk density (ρ _B
Shown as The unit (g/cc) was measured according to JIS-K-6721. Melt flow index (denoted as MFI) was determined according to ASTM-D-1238. Example 1 (A) Production of catalyst 5 (g) of commercially available Mg(OC ₂ H ₅ ) ₂ was collected under a purified N ₂ seal in a 300 ml flask equipped with a stirrer and a thermometer, and the composition was C ₆ H ₅ Si ( OC ₆ H ₅ ) _0.5 Cl _2.5 silicon compound 10.5 (g) r, ethyl benzoate 1.3 (g) r,
83 (g) r of TiCl ₄ was added under a N ₂ blanket and the temperature was gradually increased with stirring. After raising the temperature to 130℃ and keeping it at the same temperature for 1 hour,
The supernatant was thoroughly washed with purified n-heptane and the supernatant was separated and dried to obtain a solid product. Then 10.5 (g) r of silicon compound of C ₆ H ₅ Si (OC ₆ H ₅ ) _0.5 Cl _2.5 , 1.3 (g) r of ethyl benzoate, TiCl ₄ 83
(g)r was added and the solid product was treated at 130°C for 1 hour. Thereafter, it was thoroughly washed with purified n-heptane, and the supernatant liquid was separated and dried to obtain a solid catalyst. The amount of Ti supported was 2.5% by weight. (B) Polymerization of propylene 1.3 mmol of triethylaluminum and 0.46 mmol of methyl p-methylbenzoate were added to the induction stirring autoclave ( ₂₎ which had been sufficiently purged with purified N2 at room temperature under a _N2 seal, and then _H2 was added at room temperature. 700(g)r of liquid propylene was added to the mixture so that the amount was 1.8Kg/cm ² . Raise the temperature while stirring,
25 mg of the above solid catalyst was added at 70°C to initiate polymerization. After being held at 70° C. for 1 hour, excess propylene was purged to obtain 400 (g) r of white powder polypropylene, including all the atactic polypropylene. The catalyst efficiency CE was 640 Kg-PP/g-Ti, and the polymerization activity K was 21,300. ρ _B was 0.43 g/cc, 96.1%, and MFI was 8.9. Example 2 In (A) of Example 1, as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that 11.8 (g)r of C ₆ H ₅ Si(OC ₆ H ₅ )Cl ₂ was used. Supported Ti
The amount was 2.6% by weight. When propylene was polymerized in the same manner as in Example 1 (B), the catalyst efficiency was
CE=600Kg-PP/g-Ti, polymerization activity K=20000. ρ _B is 0.42g/cc, is 95.9%, and MFI is
It was 9.8. Example 3 In (A) of Example 1, as a silicon compound
A solid catalyst was obtained in the same manner as in _Example 1(A) except that _C6H5Si ( _OC6H4 - _CH3 ) _0.5Cl2.510.8 ( _{g )} r was used. The amount of Ti supported was 2.3% by weight. When propylene was polymerized in the same manner as in Example 1 (B), catalyst efficiency CE=580Kg-PP/g-Ti, polymerization activity K=
19300, ρ _B =0.42g/cc, =95.8%, MFI=8.8
The result was Example 4 In (A) of Example 1, as a silicon compound
_A solid catalyst was obtained in the same manner as in Example 1(A) except that 12.4(g ₎ r of _{C6H5Si ( OC6H4} - _CH3 )Cl2 was used. carrying
The amount of Ti was 2.4% by weight. When propylene was polymerized in the same manner as in Example 1 (B), catalyst efficiency CE = 550 Kg-PP/g-Ti, polymerization activity K = 18300
It was hot. ρ _B =0.41g/cc, =95.4%, MFI=
It was 11.0. Example 5 As a silicon compound in Example 1 (A)
A solid catalyst was obtained in the same manner as in Example 1(A) except that _11.3gr of _C6H5Si ( _{OC6H4 -} Cl _{) 0.5Cl2.5} was used. Supported Ti
The amount was 2.5% by weight. Polymerization of propylene was carried out in the same manner as in Example 1 (B), and the catalyst efficiency was CE = 540 Kg.
-PP/g-Ti, polymerization activity K=18000, ρ _B =0.42
Results of g/cc = 95.5% and MFI = 9.2 were obtained. Example 6 In Example 1(A), as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that _13.3 (g)r of _C6H5Si ( _{OC6H4 -} Cl ₎ Cl2 was used. When propylene was polymerized in the same manner as in Example 1 (B), the catalyst efficiency was CE = 530 Kg-PP/g-Ti, polymerization activity K = 17700, ρ _B = 0.41 g/cc, = 95.3
%, MFI=10.0. Comparative Example 1 (A) Production of catalyst In (A) of Example 1, a solid was prepared by performing the same operation as in Example 1 (A) except that phenyltrichlorosilane 9.2 (g) r was used as the silicon compound. I got a catalyst. The amount of Ti supported was 2.1% by weight. (B) Polymerization of propylene Using 25.0 mg of the solid catalyst obtained in (A) above, propylene polymerization was carried out in the same manner as in Example 1 (B). Catalytic efficiency CE = 400 Kg - PP/g −
The polymerization activity K for Ti was 13,300. ρ _B is 0.40
g/cc = 94.4%, MFI = 10.0. Comparative Example 2 A solid catalyst was synthesized in the same manner as in Example 1, except that no silicon compound was used in Example 1(A), and propylene was polymerized in the same manner as in Example 1(B). As a result, the catalyst efficiency CE = 280Kg−
PP/g-Ti, polymerization activity K=9300, ρ _B =0.38g/
cc, = 91.0%, MFI = 5.3. Examples 7 and 8, Comparative Examples 3 and 4 In Examples 7 and 8, the catalyst of Example 1 was used, and in Comparative Examples 3 and 4, the catalyst of Comparative Example 1 was used, and the amount of methyl para-methylbenzoate added during propylene polymerization was Polymerization was carried out with the changes shown in Table 1. The results are shown in Table-1.

[Table] Example 9 (A) Production of catalyst _N2 was added to a 300 ml flask equipped with a stirrer and a thermometer.
Under a seal, 5 g of Mg (OC ₂ H ₅ ) was collected, and 9.2 g of phenyltrichlorosilane and ethyl benzoate were collected.
1.3 g and 83 g of TiCl ₄ were added. While stirring, the temperature was gradually raised to 130°C, and then maintained at the same temperature for 1 hour.
Thereafter, the mixture was thoroughly washed with purified heptane, and the supernatant liquid was separated and dried to obtain a solid product. Next, 11.8 g of C ₆ H ₅ Si (OC ₆ H ₅ ) Cl ₂ as silicon compounds, 1.3 g of ethyl benzoate, and 83 g of TiCl ₄ were added to the obtained solid organism, and the mixture was treated at 130° C. for 1 hour. Thereafter, it was thoroughly washed with n-heptane, and the supernatant liquid was separated and dried to obtain a solid catalyst. The amount of Ti supported was 2.7% by weight. (B) Polymerization of propylene Using 25.0 mg of the solid catalyst obtained in (A) above,
Polymerization of propylene was carried out in the same manner as in Example 1(C). As a result, catalyst efficiency EC=580Kg−PP/
g-Ti, polymerization activity K=19300, ρ _B =0.43g/cc,
= 95.8%, MFI = 9.5. Comparative Example 5 In Example A, as a silicon compound
A solid catalyst was obtained in the same manner as in Example 1(A) except that 11.8 g of C ₆ H ₅ SiCOC ₆ H ₅ )Cl ₂ was used and ethyl benzoate was not added. The amount of Ti supported was 6.9% by weight. When propylene was polymerized in the same manner as in Example 1 (B), the catalyst efficiency CE = 150Kg-
PP/g-Ti, polymerization activity K=5000. teeth
67.1%, MFI was 50, and ρ _B was not measurable. Example 2 in which ethyl benzoate was added to the above values
Compare with the value of

[Table] As shown above, the polymerization activity and stereoregularity were dramatically improved by the addition of the electron donating compound, and the effect of the addition of the electron donating compound is obvious.

[Brief explanation of the drawing]

FIG. 1 is a flowchart showing one embodiment of the present invention.

Claims (1)

[Claims] 1 General formula Mg (OR ¹ ) _o (OR ² ) _2-o (wherein R ¹ and R ² represent an alkyl group, an aryl group, or an aralkyl group, and R ¹ and R ² are the same (n indicates 2≧n≧0.) Magnesium compounds represented by Production of an olefin polymer characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst consisting of a titanium-containing solid catalyst component (a) obtained by treatment with a compound and an organoaluminum compound (b) Method. 2. The method according to claim 1, wherein the olefin is polymerized or copolymerized in the coexistence of the carboxylic acid ester (c).