JPS642127B2 - - Google Patents

Description

[Detailed description of the invention]

[1] Background of the Invention The present invention relates to a method for producing an unsaturated copolymer by copolymerizing an α-olefin and a specific non-conjugated diene. More specifically, the present invention relates to a method for efficiently producing a copolymer with good reproducibility by subjecting a specific non-conjugated diene to a specific treatment. If a copolymer with a C=C bond in the side chain can be produced efficiently, crosslinking or various polar groups can be easily introduced by addition reaction to the C=C bond, oxidation reaction, or substitution reaction to the allyl position. This is a breakthrough in the development of new polyolefin materials. [2] Summary and Purpose of the Invention The present inventors have made several proposals regarding such polymers and methods for producing the same. However, when a highly active Ziegler-Natsuta catalyst in which the transition metal component is a halogen-containing titanium compound or a composition thereof is used as a polymerization catalyst, when the catalyst concentration is reduced in order to increase the copolymer yield per unit weight of the catalyst, Even when high-purity monomers are used, polymerization becomes unstable, making it difficult to produce copolymers efficiently and with good reproducibility. Summary The present invention was achieved as a result of extensive research to solve these problems. That is, the present invention provides (1) olefin and (2) general formula (Here, R' represents an alkyl group having 8 or less carbon atoms, and R ² and R ³ each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms.) The 1,4 diene represented by Or an unsaturated copolymer characterized in that the 1,4 diene is treated with alumina in advance before polymerization when copolymerizing using a Ziegler-Natsuta catalyst in which the composition and organoaluminium are combined. This is the manufacturing method. [3] Specific Description of the Invention 1 Olefin (A) The olefin to be copolymerized with the 1,4-diene used in the present invention is selected from α-olefins having 2 to 12 carbon atoms. Specifically, for example, ethylene, propylene, butene-1, 3-methylbutene-1,
Pentene-1, 3-methylpentene-1, 4-methylpentene-1, hexene-1, octene-
1, decene-1, dodecene-1, and styrene. Thus, the term "α-olefin" as used in the present invention includes arylethylene (particularly a hydrocarbon compound) such as styrene or cycloalkylethylene, in addition to ethylene and ethylene homologues or alkylethylene.
The α-olefin used in the present invention may be a mixture of two or more selected from these. In particular, α-olefins selected from ethylene, propylene, butene-1, hexene-1, 4-methylpentene-1, octene-1, and decene-1 are commercially available as copolymers with 1,4-diene. It is an α-olefin that is important and preferred in the present invention. 2 1,4-Diene (B) General formula that is one of the features of the present invention (Here, R' is an alkyl group having 8 or less carbon atoms,
R ² and R ³ are each hydrogen atom or carbon number 8
Represents the following alkyl group. ) Examples of 1,4-dienes are 1,
4-hexadiene, 1,4-heptadiene, 4-
Methyl 1,4-hexadiene, 5-methyl-1,
4-hexadiene, 4-ethyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 4-methyl-1,4-heptadiene, 4-ethyl-1,4-heptadiene, 5-methyl- 1,
4-heptadiene, 4-ethyl-1,4-octadiene, 5-methyl-1,4-octadiene, 4
-n-propyl 1,4-decadiene and the like. Among these, particularly preferred examples of 1,4-dienes include 1,4-hexadiene,
4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene. These dienes may be a mixture of two or more types, and a mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene is particularly suitable. 3. Alumina treatment The most distinctive feature of the present invention is the above-mentioned 1.
- The diene is pre-treated with alumina prior to polymerization. 1 Alumina Any alumina can be used as long as it is suitable for the purpose. Among them, porous activated alumina having a surface area of 50 m ² /g or more, particularly about 100 to 500 m ² /g is preferred. Activated alumina has various crystal forms depending on its manufacturing method, such as x-form, γ-form, and η-form, but the γ-form is preferably used because it is easily available. Activated aluminas include acidic, neutral, and basic types, with neutral and basic types being particularly preferred. When using highly acidic activated alumina, 1,4-diene may undergo cationic polymerization or oligomerization depending on the processing conditions, so care must be taken. Depending on the manufacturing method, activated alumina may contain small amounts (usually less than 5%) of impurities such as sodium oxide and iron oxide.
Permissible as long as 1,4-diene does not react. Activated alumina is commercially available in various shapes, such as powder of about 300 mesh, diameter of 1
There are spherical objects or cylindrical objects of about 10 mm, and any of them can be used in the present invention. 2 Treatment method There is no particular restriction on the method for treating 1,4-diene with alumina as long as it is suitable for the purpose, but usually, alumina is packed in a column and treated with 1,4-diene under a stream of inert gas such as nitrogen gas or argon gas. Efficient treatment can be achieved by passing 4-diene through. In this case, if the column diameter/column length is too large, it will be difficult to obtain a treatment effect, and the smaller the column diameter/column length, the greater the treatment effect. However, this does not mean that the processing effect will be improved. Therefore, the value of column diameter/tower length is usually
About 0.001 to 5, preferably about 0.005 to 1, etc.
Approximately 0.01 to 0.5 is preferable. 1,4 flowing inside the tower
- If the diene linear velocity is too high, the processing effect will be small, and if it is too low, it will take time and be inefficient.
Usually 0.01~1000cm/min, preferably 0.1~500cm/min
min, especially 0.5 to 100 cm/min. If the processing temperature is too high, the processing effect will be reduced, usually -100~
100℃, preferably -50~70℃, especially -30~50℃
is preferred. Alumina saturated with impurities that adversely affect polymerization activity should be washed with alcohol, acetone, water (including water vapor), etc. after removing the liquid, and then being washed under a stream of air or inert gas.
About 100 to 1000℃, preferably about 200 to 900℃,
In particular, the adsorption capacity can be regenerated by firing at about 250 to 800°C. By alumina treatment of this 1,4-diene, α
-Copolymerization with olefins can be carried out with high activity and good reproducibility, but the detailed reason for this is unknown. The present inventors assume the following reason for this. The hydrogen atom of the methylene group sandwiched between the two double bonds of 1,4-diene is active against radicals and easily reacts with oxygen to first form hydroperoxides, followed by formation of conjugated ketones and others. Disassemble. It is thought that as a result of selective adsorption and removal of these hydroperoxides and conjugated ketones by alumina, high activity and good reproducibility are achieved in copolymerization with α-olefin. In titanium-based Ziegler-Natsuta catalysts, which are highly active and highly reactive with oxygen compounds, the presence of just a few ppm of hydroperoxides or conjugated ketones significantly inhibits polymerization activity. Furthermore, it is of course possible to separate and remove hydroperoxides and their decomposition products by distillation, but in order to reduce the concentration of these impurities to a few ppm or less, it is necessary to considerably increase the number of theoretical plates in the rectification column. Therefore, the alumina treatment of the present invention is much more efficient, does not require the addition of heat, is low cost, and is effective in terms of energy saving. Furthermore, alumina saturated with impurities that adversely affect polymerization activity can be industrially advantageous because its adsorption capacity can be regenerated by removing the liquid, preferably washing with a polar solvent such as alcohol or acetone, and then calcination. It is. The effects of the alumina treatment of 1,4-diene according to the present invention can be fully enjoyed particularly when copolymerizing using a highly active titanium-based Ziegler-Natsuta catalyst. 4 Polymerization Catalyst 1 Transition Metal Component The Ziegler-Natsuta catalyst to be used in the present invention is not particularly limited as long as the transition metal component is a halogen-containing titanium compound or a composition thereof, and any suitable conventionally known combination may be used. be able to. Examples of halogen-containing titanium compounds or compositions thereof include (a) halogenated titanium compounds such as titanium tetrachloride, titanium trichloride and compositions thereof (e.g. 3TiCl ₃ .AlCl ³ ), titanium dichloride and compositions thereof; (b) Titanium halogen compounds such as titanium tetrachloride, ethoxytitanium trichloride, titanium trichloride, etc. are used as carriers (here, carrier is not only a compound that simply functions as a carrier, but also a titanium compound and additives as necessary). It also means a compound that forms a complex complex with other components in the compound and has subtle effects on polymerization activity, stereoregularity, molecular weight distribution, etc.For example, silica, alumina, silica-alumina, titania, Magnesia, magnesium chloride and compositions thereof (for example, compositions consisting of magnesium chloride and a Lewis acid, compositions consisting of magnesium chloride and a metal oxide, etc.) magnesium oxychloride, reaction products of magnesium oxychloride and alkyl aluminum dichloride etc.) may include so-called supported catalyst components, which are optionally supported together with electron-donating compounds such as organic acid esters, water, amines, amides, ethers, and alcohols. In the present invention, when referring to a halogen-containing titanium compound as a "composition," it mainly consists of a halogen-containing titanium compound, and usually contains up to 30% by weight of a Lewis acid (e.g., aluminum chloride, antimony trichloride, halogen In addition to the composition containing a phosphorus compound, etc.) and/or an electron donor (for example, ethers, organic acid esters, organic acid amides, phosphoric acid amides, amines, phosphines, etc.), the supported catalyst It also means ingredients. Suitable for use in the present invention are, for example:
Titanium tetrachloride, titanium trichloride or titanium trichloride composition (e.g. TiCl ₃ nAlCl ₃ ) obtained by reducing titanium tetrachloride with various reducing agents (e.g. hydrogen, aluminum, titanium, organic aluminum, etc.),
A titanium trichloride composition obtained by co-pulverizing this titanium trichloride (composition) with an electron donor such as an organic acid ester, ether, phosphoric acid amide, amine, etc., titanium tetrachloride reduced with organoaluminium. After that, a titanium trichloride composition obtained by ether treatment and Lewis acid treatment, a reaction product of magnesium oxychloride and alkyl aluminum dichloride (a compound obtained by further reacting this with a siloxane compound if desired), or magnesium chloride. as a carrier, an electron donor (selected from organic acid esters, alcohols, amines, organic acid amides, ethers, and water), and a halogen-containing titanium compound (e.g., titanium tetrachloride, titanium trichloride, alkoxy trichloride). This is a supported catalyst component in which titanium, etc.) is supported as an essential component. 2 Reducing Agent Component Organoaluminum is used as the other component of the Ziegler-Natsuta catalyst to be combined with the halogen-containing titanium compound or its composition. Examples of organoaluminum compounds that are usually preferably used include compounds represented by the following formula. R ⁴ _o AlX _3-o where R ⁴ is a hydrocarbon residue having about 1 to 10 carbon atoms,
X represents a hydrogen atom, a halogen atom, an alkoxy group having about 1 to 10 carbon atoms, an aryloxy group, or a siloxy group, and n is a number expressed as 0<n≦3. Examples of these organoaluminum compounds include (a) trialkyl aluminum such as trimethylaluminum, triethylaluminum, triisobutylaluminum, triisoprenylaluminum, and tri-n-hexylaluminum; (b)
dialkylaluminum halides such as diethylaluminum chloride, di-n-propylaluminum chloride, diisobutylaluminum chloride, (c) dialkylaluminum hydrides such as diethylaluminum hydride and diisobutylaluminum hydride, (d) methylaluminum sesquichloride, ethylaluminum sesquichloride, Alkylaluminum sesquihalides such as n-propylaluminum sesquichloride, (e) alkylaluminum dihalides such as methylaluminum dichloride, ethylaluminum dichloride, isopropylaluminum dichloride, (f)
Dialkyl aluminum alkoxides or aryl oxides such as diethylaluminum ethoxide, diethylaluminium isopropoxide, di-n-propylaluminium-2,6-di-tert-butylphenoxide, (t)dimethylaluminum trimethylsiloxide, diethylaluminium dialkyl aluminum siloxides such as trimethyl siloxide, and the like. Alternatively, it may be a reaction product of these organoaluminum compounds and water or a secondary amine. These organoaluminum compounds may be used alone or in a mixture of two or more. 3 Optional Components In the copolymerization according to the present invention, in order to obtain a copolymer with particularly excellent stereoregularity, various compounds such as iodine or electron-donating substances (such as ethers, It may be convenient to use organic acid esters, amines, phosphoric acid amides, phosphines, etc.). 4. Composition Ratio There is no particular restriction on the composition ratio of the catalyst, and any suitable quantitative ratio may be used. Usually, about 0.1 to 2000 mol, preferably 0.5 to 1000 mol, and more preferably 1.0 to 500 mol of the organometallic compound is used per titanium atom. The amount of the electron-donating compound used as the third component of the catalyst varies depending on the amount of the organometallic compound, but it is usually about 0.01 to 1.0 mol per 1 mol of the organometallic compound. It's normal. 5 Copolymerization Polymerization conditions using a Ziegler-Natsuta catalyst in which the transition metal component is a halogen-containing titanium compound or a composition thereof can generally be used. That is, the polymerization temperature is 0 to 250°C, preferably 20 to 250°C.
About 180°C, particularly preferably about 30 to 150°C, polymerization pressure from normal pressure to 150Kg/cm ² , preferably from normal pressure to 90°C
Kg/cm ² , particularly preferably normal pressure to 50 Kg/cm ² , is suitable. There are no particular restrictions on the polymerization method, and (a) a slurry method or solution method using an inert solvent, and (b) a method in which α-olefin and/or 1,4-diene serve as the solvent without substantially adding a solvent. Slurry or solution methods that accomplish the following, or (c) gas phase methods that carry out the copolymerization reaction without using a substantially liquid solvent and keeping the monomer in a substantially gaseous state, are all applicable to the present invention. can do. Furthermore, hydrogen can be added to control the molecular weight during copolymerization. The manner in which α-olefin and diene are supplied is also arbitrary. From the viewpoint of ease of operation, it is convenient to mix both in a predetermined ratio, and either one (in particular, α-olefin) can be added in portions, taking into account the copolymerization reaction ratio of both. 6 Produced Copolymer 1 Copolymer Composition In the method according to the present invention, in addition to a binary copolymer of one kind of α-olefin and one kind of 1,4-diene, multiple copolymers, such as one kind of α- Ternary or quaternary or more copolymerization of olefin and two or more types of 1,4-dienes, two or more types of α-olefin and two or more types of 1,4-dienes
- Quaternary or quinary or more copolymerization with diene is possible. The content of 1,4-diene units represented by formula () in the copolymer is usually 0.01 to 50 mol%, preferably 0.02 to 30 mol%, particularly preferably 0.1 to 15 mol%. This content can be controlled by changing the ratio of α-olefin and 1,4-diene in the copolymerization reaction system. 2. Shapes and uses of copolymers The present invention allows copolymers to be produced with various molecular weights and shapes depending on the combination of α-olefin and 1,4-diene, selection of catalyst system, amount of hydrogen added during copolymerization, etc. Although unsaturated copolymers can be produced efficiently, they are particularly suitable for producing thermoplastic resins. Examples of copolymer shapes include wax-like products,
Examples include liquid rubber-like materials, solid rubber-like materials, thermoplastic elastomers, thermoplastic resins, and the like. The copolymer that can be produced by the method of the present invention is
to the side chain

[Formula] An α-olefin copolymer with freely controlled molecular weight.
Therefore, crosslinking, introduction of various polar groups, graft polymerization, etc. are easy through addition reactions to C=C bonds, substitution reactions to oxidation allyl positions, etc., and it is useful for base resins for paints, paintability, and adhesiveness. As a new polyolefin-based material such as modified polyolefin, which has significantly improved properties such as flexibility, printability, and gas barrier properties, its uses are immeasurable. Example 1 Preparation of supported catalyst 3 g of the product obtained by co-pulverizing 20 g of magnesium chloride and 14 g of ethoxytrichlorotitanium in a vibration mill for 24 hours was made into a slurry in 70 ml of 1,2-dichloroethane, and 0.1 g of iodine trichloride was added. The mixture was stirred at 80°C for 2 hours. The solid product was separated from the liquid phase and thoroughly washed with hexane to obtain a supported catalyst. This supported catalyst contained 9.1% by weight of titanium. Alumina treatment 8: 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene with a purity of 99.5%:
2 mixture (hereinafter this mixture will be abbreviated as methyl-1,4-hexadiene) was degassed by argon bubbling. Next, this methyl-1,4-hexadiene was transferred to a column (column diameter 30 mm, packing length) packed with activated alumina (300 mesh) for chromatography.
1000 mm), the linear velocity of methyl-1,4-hexadiene in the alumina packed column was set to 1.0 under an argon flow.
cm/min and then packed with molecular sieve (5A) (column diameter 30mm, packing length 1000mm)
Purified methyl-1,4-
Hexadiene was obtained. Copolymerization of ethylene and methyl-1,4-hexadiene 1. Place 0.4 of well-dried n-heptane and 0.1 of the above purified methyl-1,4-hexadiene in an autoclave, and add 200 mg of triethylaluminum.
Add 10 mg of the above supported catalyst, and reduce the hydrogen partial pressure to 0.5.
Kg/cm ² , 85℃ with ethylene partial pressure kept at 4.5Kg/cm ²
Copolymerization was carried out for 1.5 hours. The results are shown in Table 1. Comparative Example 1 Ethylene and methyl-1,4-hexadiene were copolymerized by the same method as in Example 1, except that methyl-1,4-hexadiene was not treated with alumina. The results are shown in Table 1. Example 2 Preparation of supported catalyst 100g of magnesium oxychloride was added to n-hexane.
A slurry of 1.5% was prepared, 205 ml of ethylaluminum dichloride was added, and the mixture was heated and refluxed to react for 6 hours. A solid product was separated, 150 ml of hexamethyldisiloxane was added thereto, and the mixture was heated and refluxed for 4 hours to obtain a solid support. 20 g of this solid support, 9 ml of ethyl benzoate, and 3 g of trimethylsiloxyaluminum dichloride.
8g of powder obtained by co-pulverizing with a vibration mill for 12 hours,
A slurry of 40 ml of 1,2-dichloroethane was prepared, 40 ml of titanium tetrachloride was added, and the mixture was reacted at 80° C. for 2 hours. A supported catalyst was prepared by thoroughly washing the solid product with n-hexane. This supported catalyst contained 2.3% by weight of titanium. Copolymerization of propylene and methyl-1,4-hexadiene 1.0.4 n-heptane in an autoclave,
0.1 of methyl-1,4-hexadiene obtained in the same manner as the alumina treatment in Example 1 was charged, and 300 mg of triethylaluminum and ethyl p-toluate were added to 1 mole of triethylaluminum.
An amount equivalent to 0.26 mol and 61 mg of the above supported catalyst were added in this order, and hydrogen was added in an amount equivalent to 100 ml under standard conditions, and propylene was pressurized to bring the total pressure to 1.
After maintaining the temperature at Kg/cm ² and reacting at 15 to 20℃ for 15 minutes,
The temperature was raised to 60°C, and propylene was further pressurized to maintain the total pressure at 7 kg/cm ² and copolymerization was carried out for 1.5 hours. The results are shown in Table 1. Comparative Example 2 Copolymerization of propylene and methyl-1,4-hexadiene was carried out by the method of Example 2 except that methyl-1,4-hexadiene not treated with alumina was used. The results are shown in Table 1. Example 3 Preparation of titanium trichloride composition In two flasks containing 0.6 of hexane and 0.15 of titanium tetrachloride, 0.173 of diethylaluminum chloride was added to 0.45 of hexane under stirring (160 rpm).
The solution was added dropwise over 4 hours while keeping the temperature inside the flask at 1°C. After the dropwise addition, the temperature was maintained at 1℃ for 15 minutes with stirring, and then the temperature was maintained at 65℃ for 15 minutes.
Stir for hours. The resulting solid was separated from the liquid phase and washed five times with 0.5 hexane. This solid was then made into a slurry of 1.7 hexane,
0.26 diisoalumyl ether was added and stirred at 35°C for 1 hour. separating the solid reactants from the liquid phase;
Washed five times with hexane at 25°C. This solid reaction product was suspended in 0.85% of a hexane solution containing 40% by volume of titanium tetrachloride, and stirred at 65°C for 2 hours. Separate the solid product from the liquid phase and add 0.5 ml of hexane.
was washed five times to obtain a titanium trichloride composition. Copolymerization of propylene and methyl-1,4-hexadiene: n-heptane 0.25, methyl-1,4-hexadiene 0.25 obtained by treatment similar to the alumina treatment in Example 1, diethylaluminum chloride 4
Copolymerization of propylene and methyl-1,4-hexadiene was carried out in the same manner as in Example 2 using 0.43 g of the above titanium trichloride composition.
The results are shown in Table 1. Comparative Example 3 Copolymerization of propylene and methyl-1,4-hexadiene was carried out in the same manner as in Example 3 except that methyl-1,4-hexadiene not treated with alumina was used. The results are shown in Table 1.

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【table】

Claims (1)

[Claims] 1. Olefin and 2. General formula (Here, R ¹ is an alkyl group having 8 or less carbon atoms,
R ² and R ³ are each hydrogen atom or carbon number 8
Represents the following alkyl group. ) When copolymerizing a 1,4-diene represented by A method for producing an unsaturated copolymer, which comprises treating it with alumina.