JPH0118084B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a compound having ethylene or a mixture of ethylene and one or more α-olefins, and two or more conjugated or non-conjugated unsaturated olefin bonds (preferably a conjugated diene or a non-conjugated diene). A method for obtaining a copolymer in high yield using a conjugated diene (conjugated diene) as a raw material, in which (i) an organometallic compound of a metal belonging to Group 3 of the periodic table and (ii) a titanium compound of magnesium metal or manganese metal is used. and a halogen donor.

The product obtained from the copolymerization reaction of ethylene and a polyunsaturated compound has crystallinity.

The applicant has disclosed that ethylene and conjugated or non-conjugated polyolefins, in particular butadiene and ethylidene-
It is known that there are various methods for obtaining crystalline copolymers by polymerization with norbornene (for example, JP-A-51-37983, JP-A-51-37984,
(Japanese Patent Application Laid-open No. 11983/1983). These methods involve the use of vanadium-coordinated anionic catalysts, and although these catalysts give high polymerization yields, it is difficult to obtain catalytic activity levels and it is very difficult. However, if the transition metal residue is not removed from the copolymer, the transition metal residue may impair the oxidation stability of the copolymer and cause undesirable coloring. Become.

The applicant has developed an organometallic compound of a metal belonging to Group 1 of the Periodic Table by (i) vaporizing or sublimating magnesium in vacuum and (ii) condensing this vapor with titanium tetrahalide and a halogen donor. The existence of JP-A-52-94891, which relates to a catalyst composition (active in the polymerization and copolymerization of mono-α-olefins) obtained by reacting with a composition prepared by condensing it into a phase. I also know. According to this, the activity of this catalyst composition in polymerization and copolymerization of α-olefin is such that the amount of vaporized metallic magnesium can give an atomic ratio Mg/Ti in the condensed phase of 0.5 or more, And by adding an excessive amount of halogen to metallic magnesium, MgX ₂ 2TiX ₃ (X is halogen)
If there is a compound capable of forming a complex with an atomic ratio of Mg/Ti of 0.5, the value is extremely high. In this case, additional MgX ₂ is produced, which reacts with the equivalent complex to form one or more new active complexes containing titanium.

By appropriately varying the conditions for magnesium vaporization and selecting the reactants and reaction conditions, the inventors have discovered that ethylene or ethylene and other α
-Found that mixtures with olefins can be copolymerized with compounds containing one or more unsaturated olefinic bonds and that highly crystalline polymers are obtained when ethylene alone is used. , led to the present invention. In this case, in addition to magnesium, manganese can also be used in the preparation of the components of the catalyst system.

The activity of the above catalyst system is 50% copolymer per 1g of titanium.
It is enough to generate more than Kg.

The components of this catalyst system vaporize magnesium or manganese in a metallic or alloyed state,
This vapor can be prepared by condensing it into a cold solution obtained by dissolving the titanium compound and the halogenated compound in an inert diluent.

The metal (M) can be used in powder, granule or lump form, and is preferably vaporized in vacuum by sublimation. For magnesium, pressure 2 to 10 ^-4
For torr, the temperature is selected in the range of about 650°C to 300°C depending on the pressure.

Manganese requires even harsher conditions, with temperatures ranging from 800°C to 10 ^-1 to 10 ^-4 Torr.
The temperature is 1100℃.

If the operation is carried out at higher temperatures, the metal can be vaporized from the molten state even under atmospheric pressure.

The solution in which the vapor is condensed is stirred at a low temperature.
Depending on the solvent used, the temperature in this case is −120
℃ to 0℃, generally -80℃ to -20℃. For inert diluents, it is not necessary to use low volatility hydrocarbons with low freezing points (e.g. Normal-heptane, normal-
There is no need to use octane, toluene, etc.).

A liquid titanium compound suitable for this purpose is tetrachlorotitanium, while alkyl halides are suitable as halogenated compounds, used in excess to form the reaction medium.

Examples of alkyl halides that can be used include:
These include 1-chlorobutane, 1-chlorohexane, and 1-bromohexane, as well as secondary or tertiary alkyl halides and aryl or alkylaryl halides. The most preferred inorganic halides are SnCl ₄ , SbCl ₅ , GeCl ₄ and POCl ₃ .

Among the titanium compounds, in addition to the tetrachlorides, other halides can be usefully used, such as trihalides, alcoholates, halogen alcoholates, chelates and organometallic compounds. In fact, any titanium compound can be used, with only slight differences in reaction rates.

In order to prepare components of highly active catalyst systems, the atomic ratio M/Ti is greater than or equal to 0.5, in particular greater than or equal to 4. The value of this ratio is between 15 and 30, and it is not advantageous for M to be greater than this.

The amount of halogen donor compound present during the reaction is determined depending on the amount of M, with 1 halogen per molecule.
In the case of monohalogenated organic compounds, the number is 2 or more, and in the case of inorganic compounds, the number is 1 or more so that more than atomic atoms can be produced.

The reaction of the metal vapor, Ti compound and halogenated compound is partially carried out at the low temperatures mentioned above.
In order for this reaction to complete, it can be left for a long time (several days) at room temperature or at a selected temperature (50-50°C).
180°C) for several hours (1-5 hours). The reaction is fast when the halogen donor is inorganic. Also, it is not necessary for the halogen donor to be present in a solution kept at a low temperature to condense the metal vapor. It can also be added later, but in this case the solution must be heated to a higher temperature beforehand to complete the reaction.

Normally, when any component or by-product present in excess in the raw materials substantially constitutes a dispersant in catalyst production, the fine suspension prepared as described above is used as described below. It can be used directly as a component of a catalyst system for polymerization.

Alternatively, the suspension is filtered and the solids are resuspended in the most suitable dispersant (generally the solvent used when the polymerization is carried out). The solids are then dispersed onto a solid inert carrier, such as a polymer.

As mentioned above, other components of the catalyst system are organometallic compounds of elements from Groups of the Periodic Table. Among these elements, aluminum is most advantageously used in terms of effectiveness and availability.

Examples of compounds _that can be used include Al( _C2H5 ) ₃ ,
trialkyl and triarylaluminums such as Al(iso-C ₃ H ₇ ) ₃ , Al(C ₆ H ₅ ) ₃ , alkyl aluminum hydrides such as AlH(iso-C ₃ H ₇ ) ₂ , and Al(C ₂ There are alkyl or arylaluminum halides such as H ₅ ) ₂ Cl and Al(C ₂ H ₅ )Cl ₂ .

Trialkyl derivatives are preferred, but these are also very effective in the form of mixtures with halogenated derivatives.

The molar ratio of organometallic compound to titanium compound should be greater than or equal to 3 to obtain the highest intrinsic activity.

For practical reasons, taking into account that very small amounts of titanium compound are used in the polymerization reaction, the molar ratio may be very large, e.g.
The value will be 500.

The process for preparing the above-mentioned catalyst system is shown as a flowchart in FIG.

As mentioned above, the copolymerization according to the present invention involves the copolymerization of ethylene with conjugated and non-conjugated polyolefins, using the above catalyst system, in the presence of an inert diluent, at a temperature of 40 to 120°C, and a pressure of 1 to 20°C.
It is carried out at Kg/ ^cm2 .

In batch tests, starting monomers are fed into a reactor and polymerization is carried out in the presence of a mixture of these two monomers to form a catalyst system, or polymerization is carried out by bringing the catalyst system into contact with this mixture. can be done.

There are actually two types of operating methods, both of which are effective. In the first method, the titanium-containing catalyst component is introduced last, and in the second method, the reaction of the catalyst component, which is added continuously to the monomer mixture, is carried out separately. In the latter case, a pre-contact time is required, and although this is not critical, this time should not be too long, especially when the Al/Ti ratio is high.

Aliphatic hydrocarbons can preferably be used as inert diluents. However, the presence of a diluent is not necessarily required, since the polymerization stage can be operated in gaseous form by using a catalyst dispersed in a slightly lower boiling solvent.

Monomers selected for implementing the copolymerization method will be described later.

The various conditions described above are general ones, and based on detailed suggestions regarding the copolymer described below,
Various ethylene copolymers can be produced by applying the method of the present invention without departing from the spirit of the present invention. Moreover, those skilled in the art can easily select the most appropriate operating conditions in relation to the desired polymer.

One of the monomers used is ethylene, and the others are cyclic hydrocarbons or alicyclic hydrocarbons having one or more (conjugated or non-conjugated) unsaturated bonds.

Among these hydrocarbons, 1,3-butadiene and 5-ethylidene (2,2,1)- are representative from the viewpoint of reactivity and cost.
Dicyclopent-2-ene (ethylidene norbornene). Since these have lower reactivity than ethylene in the polymerization reaction, they are supplied in an excess amount (50 times or more) than the amount required to obtain the copolymer. Any excess can be utilized by recycling the solution.

The amount of ethylene present in the copolymer is actually a few percent (less than 10 mole percent).

The molecular weight of the copolymer can be controlled by changing the reaction conditions as well as by introducing hydrogen.

The copolymers obtained by the method of the present invention have various properties depending on their composition. For example, ethylene-butadiene copolymers contain trans unsaturation, but no or virtually no cis vinyl unsaturation (as evidenced by the 1,4-trans addition of butadiene units). . Ethylene-rich ethylene-butadiene copolymer has a density of 0.940 to 0.960 and a melting point of about 130°C.
It has the configuration of unsaturated bonds as shown in the ¹³ C-NMR spectrum (for a copolymer containing 12.3 mol% of butadiene) in the accompanying drawing. This NMR spectrum shows three peaks due to butadiene units with different structures along the polymer chain (a = 32.6 ppm, b = 32.7 ppm,
c=32.9ppm (peak due to methylene group in butadiene).

It is known that crystalline poly-α-olefins such as polyethylene, isotactic polypropylene, isotactic polybutene, etc. are widely used. These poly-α-olefins are either homopolymers or copolymers containing small amounts of second α-olefins to improve certain properties. The amount of the second olefin is generally small enough not to excessively reduce crystallinity compared to the homopolymer, since important mechanical properties such as modulus and ultimate tensile strength are associated with a high degree of crystallinity. It is.

In copolymers of ethylene and butadiene, the compatibility of the two types of units within the same crystal means that crystalline polymers can be obtained over a wide composition range, from pure polyethylene to pure trans polybutadiene. enable. in this case,
There are no such limitations as in the case of copolymers of mono-α-olefins (ie, the olefins must be included in very small amounts to maintain a high level of crystallinity).

A very important advantage of the copolymers obtained by the process of the invention is that they contain unsaturated bonds (in the main chain in the case of butadiene and in the side chains in the case of ethylidenenorbornene). That's true.
Due to these unsaturated bonds, it is easily crosslinked (with sulfur or other reagents) to further improve its properties such as heat resistance, impact resistance, and resistance to chemicals (which induce cracking). Unsaturated bonds allow special modifying effects (eg frothing, heat generation of sheets) that would otherwise be impossible or very difficult.

Example 1 A catalyst system component containing titanium was prepared in a glass rotating flask (volume 1) mounted horizontally. Note that an aluminum crucible that was electrically heated by a tungsten filament was placed in the center of the flask.

240 ml of normal heptane and 0.2 ml of TiCl ₄ were placed in a flask, and 0.9 g of magnesium pieces were placed in a crucible. The solution was cooled to -70°C.

After reducing the pressure in the rotating flask (10 ^-3 torr), the crucible was heated by applying a voltage to the filament with sufficient intensity to cause scorching heat. Mg is vaporized to obtain a brown suspension, which is then added to n-butyl chloride (1
-8.2m of chlorobutane) was added. It was then heated at 80° C. for 3 hours using a reflux condenser.

Copolymerization reaction: Evacuate a volume 5 autoclave equipped with a stirrer and constant temperature heater, add 2200 ml of anhydrous normal heptane, 200 g of butadiene and Al(C ₂ H ₅ ) ₃ 15
A millimolar solution was introduced by suction.

The temperature of the autoclave and the partial pressure of each
70℃ before feeding at 3.5Kg/cm ² and 4.5Kg/cm ²
was controlled. Then titanium prepared as described above
10 ml of heptane suspension containing 0.075 mmol,
Steel container (100ml) with supply and discharge valves
was used to introduce the autoclave with overpressure of ethylene.

During the first 5 minutes of the reaction, a solution of Al(C ₂ H ₅ )Cl ₂ (7.5 mmol) in heptane (50 ml) was added to the mixture already present in the autoclave using a piston pump. It was observed that ethylene was being rapidly absorbed, and at a temperature of 70° C., the ethylene feed was carried out continuously so that the pressure was maintained constant.

Even after 3 hours, ethylene was absorbed to almost the same extent as at the beginning of the reaction. However, the reaction was now stopped and the suspension contained in the autoclave was removed and filtered.

MFI _2.16 = 49.5, butadiene unit content = 3.3
%, melting point Tm (measured by differential temperature analysis) = 131° C. 388 g of dry polymer was obtained. This polymer (which has a white solid appearance very similar to that of polyethylene) is mixed with the following compound (number of grams per 100 grams of polymer):
mixed with.

Zinc oxide 5 Stearic acid 1 2,2-methylene-bis(4-methyl-tertiary butylphenol) (AO2246) 1 N-oxydiethylbenzothiazole-2-sulfenamide (NOBS Special) 1.5 Dibenzothiazyl disulfide ( Vulkacit
DM) 0.5 Sulfur 3 The mixture was treated in a press at 180° C. for 30 minutes, resulting in a residue of 40% of the main product after extraction with boiling xylene (completely dissolved before vulcanization).

Example 2 Using the same autoclave as in Example 1, the reaction was carried out in the same manner at a temperature of 85°C.

In this case, the partial pressures of ethylene and hydrogen are each
5Kg/cm ² and 3Kg/cm ² and butadiene 250
g was introduced.

The amounts of other components are the same as in Example 1.

After 3 hours of polymerization reaction, 250 g of dry polymer having the following properties was obtained.

Butadiene unit content 3.3% MFI _2.16 0.84 MFI _21.6 /MFI _2.16 32.5 Melting point 129°C Impact resistance 13.7 Kg/cm ^{2Crosslinking} was carried out in the same manner as in Example 1, resulting in a product with impact resistance = 50.4 Kg/cm ² . It was done.

Example 3 A polymerization reaction was carried out using the same equipment and method as in the previous example and using the following raw materials.

Normal-heptane 1840 ml Butadiene 102 g Al(C ₂ H ₅ ) ₃ 17.6 mmol H ₂ 3.5 Kg/cm ² Ethylene 5.0 Kg/cm ² Ti complex (see Example 1) 0.06 mmol Consumed during gas introduction and during polymerization reaction While replenishing the ethylene that has been removed, the autoclave is
A temperature of 85°C was maintained.

After 4 hours, the reaction was stopped and the product was collected and dried to obtain 285 g.

The analysis results are as follows.

Butadiene unit content 1.5% (mol) MFI _2.16 0.99 g/10 min MFI _21.6 27.4 Tm (DSC) 133°C Example 4 400 ml of n-heptane and bicyclo(2,
A solution prepared from 40 ml of 2,1)-5-ethylidene-2-heptane (ethylidene norbornene),
The mixture was suctioned into an autoclave made of stainless steel (volume 2) of the same type as in Example 1.

The temperature of the autoclave was controlled at 85° C. and then ethylene and hydrogen were introduced at partial pressures of 5 Kg/cm ² and 3 Kg/cm ² , respectively.

Then, in the same manner as in Example 1, Al (iso-
C ₄ H ₉ ) ₃ 5 mmol and titanium of the type of Example 1
A catalyst consisting of a heptane suspension of the product obtained by reaction with 0.012 mol of the product for 60 minutes at room temperature was introduced using a steel vessel and an excess of N ₂ .

The reaction continued for 1 hour, during which time the consumed ethylene was replenished to keep the partial pressure constant. The solid product obtained by filtering the suspension was dried and weighed 35 g.

The properties of this product are as follows.

Ethylidene norbornene 3.3% (weight) MFI _2.16 3.4 g/10 min MFI _21.6 33 σ20 min 0.9633 g/cm ³ Example 5 The titanium-containing catalyst component was the same as in Example 1, but using the following raw materials: Prepared.

1-chlorooctane 120ml TiCl ₄ 0.088ml Magnesium metal 1.5g The solution was cooled to -50°C and reduced pressure (10 ^-4 torr).
Then, the magnesium was vaporized and condensed. A thick dark brown suspension was obtained, which was then heated at 100° C. for 1 hour.

According to chemical analysis, the homogenized suspension is
Ti5.10 mmol/, Mn186.2 mmol/,
It contained Cl390.0 mmol/.

Copolymerization Reaction Using the apparatus of Example 1, a copolymerization reaction of butadiene and ethylene was carried out.

The solution fed to the reactor was prepared from the following ingredients:

Normal-heptane 2200ml Butadiene 250g Al (iso-C ₄ H ₉ ) ₃ 22.5 mmol Control the temperature at 85°C and heat the autoclave with hydrogen 3
Pressurized with Kg/cm ² and 5 Kg/cm ² of ethylene.

15 cm ³ of the suspension containing the titanium compound prepared as described above were then introduced. Pressure initial value 10
The reaction was carried out for 3 hours while adding fresh ethylene to maintain the temperature at Kg/cm ² (at 85° C.), after which the reaction was stopped and the product was collected and dried.

200 g of polymer with the following properties were obtained.

1,4-trans-butadiene unit content
5.15% (mol) MFI _2.16 0.05g/10min Tm (DSC) 132°C [η] 105°C Decalin 1.75 Example 6 A titanium-containing catalyst system component was prepared from the following raw materials in an apparatus similar to Example 1. .

Normal-octane 300 ml TiCl ₄ 0.187 ml SnCl ₄ 8 ml Mg metal 1.2 g Magnesium was vaporized at a pressure of 5 x 10 ^-2 torr and condensed into a solution maintained at about -50°C. The temperature of the resulting suspension was raised to room temperature. After 24 hours, the solution above the precipitated solids was removed from the titanium. This homogenized suspension contains 6.32 mmol of Ti, 187 mmol of Mg, and 207 mmol of Sn.
and 863 mmol/.

Copolymerization Reaction In the autoclave of Example 1, using the method of Example 5 and the same raw materials, but with the suspension
Using a titanium-containing catalyst system component consisting of 11.85ml
Reactions were carried out at 85°C. Polymers with the following properties
180g was obtained.

MFI _2.16 0.1g/10min Tm (DSC) 131℃ Butadiene unit content 3.34% (mol)

[Brief explanation of drawings]

Figure 1 is a flowchart showing the preparation process of the catalyst system used in the present invention, and Figure 2 is a flow chart showing the preparation process of the catalyst system used in the present invention.
FIG. 3 is a diagram showing an NMR spectrum.

Claims (1)

[Scope of Claims] 1. A method of copolymerizing ethylene or a mixture of ethylene and one or more α-olefins with a polyolefin selected from non-conjugated dienes or conjugated dienes in high yield, comprising: and the polyolefin, 1 magnesium vapor or manganese vapor with a titanium compound and a halogen donor in an atomic ratio M/
of an ethylene copolymer, characterized in that it is brought into contact with a catalyst system consisting of a composition prepared by reacting with 4 or more Ti (where M is magnesium or manganese) and an organometallic compound of 2 aluminum. Manufacturing method. 2. In the manufacturing method described in claim 1,
A composition in which component 1) of the catalyst system is prepared by vaporizing magnesium or manganese or an alloy thereof and condensing the vapor in a diluent solution containing a titanium compound and possibly a halogen donor. A method for producing ethylene copolymer, which is a product. 3. In the method according to claim 1 or 2, component 1) of the catalyst system comprises magnesium in a vacuum of 2 to 10 ^-4 Torr and at a temperature of 300 to 650 Torr.
A method for producing an ethylene copolymer, prepared by sublimation at °C. 4. In the method according to claim 1 or 2, component 1) of the catalyst system comprises manganese in a vacuum of 10 ^-1 to 10 ^-4 Torr and a temperature of 800 to 1100 Torr.
A method for producing an ethylene copolymer, prepared by sublimation at °C. 5. In the method according to claim 1 or 2, component 1) of the catalyst system is a metal compound in an inert solvent selected from aliphatic or aromatic hydrocarbons at a temperature of -120°C to 0°C. A process for making ethylene copolymers, which are prepared by condensing steam. 6. In the method according to any one of claims 1 to 5, component 1) of the catalyst system is prepared by completing the reaction at a temperature of 20 to 180°C. , a method for producing ethylene copolymers. 7 In the manufacturing method described in claim 1,
A method for producing an ethylene copolymer, wherein the titanium compound in the catalyst system is selected from trivalent or tetravalent titanium halides, alcoholates, halogenoalcoholates, or organometallic compounds. 8. In the manufacturing method described in claim 1,
A method for producing an ethylene copolymer, wherein the halogen donor is selected from organic or inorganic halides. 9 In the manufacturing method described in claim 8,
A method for producing an ethylene copolymer, wherein the organic halogen donor compound is selected from chloroalkanes, bromoalkanes, chloroarenes, and bromoarenes. 10. A method for producing an ethylene copolymer according to claim 1 or 9, wherein the molar ratio of the organic halogen donor compound to the vaporized metal is 2 or more. 11. The method according to claim 8, wherein the inorganic halogen donor compound is SnCl ₄ ,
A method for producing an ethylene copolymer selected from SbCl ₄ , GeCl ₄ , and POCl ₃ . 12. A method for producing an ethylene copolymer according to claim 1 or 11, wherein the molar ratio of the inorganic halogen donor compound to the vaporized metal is 1 or more. 13. The method for producing an ethylene copolymer according to claim 1, wherein the atomic ratio M/Ti is 15 to 30. 14. In the production method according to any one of claims 1 to 13, by reacting ethylene or the ethylene mixture with the polyolefin selected from non-conjugated dienes or conjugated dienes, highly A process for producing ethylene copolymers that produces crystalline copolymers. 15. A method for producing an ethylene copolymer according to claim 14, wherein the copolymerization reaction of ethylene or the ethylene mixture with the polyolefin is carried out in the presence of an inert solvent. 16. The method of claim 15, wherein the inert solvent is the same as that used in the preparation of component 1) of the catalyst system. 17. The method for producing an ethylene copolymer according to any one of claims 14 to 16, wherein the copolymerization reaction is carried out at a temperature of 40°C to 120°C. 18. The method for producing an ethylene copolymer according to any one of claims 14 to 17, wherein the copolymerization reaction is carried out at a pressure of 1 to 20 atmospheres. 19. A method for producing an ethylene copolymer according to claim 14, wherein ethylene or the ethylene mixture and the polyolefin are supplied in gaseous form to a catalyst system in the absence of a solvent. 20 In the production method according to any one of claims 14 to 19, the copolymerization reaction of ethylene or the ethylene mixture with the polyolefin is carried out after dispersing the catalyst system on an inert carrier. , a method for producing ethylene copolymers. 21. The method for producing an ethylene copolymer according to any one of claims 19 to 20, wherein the copolymerization reaction is carried out at a pressure of 1 to 30 atmospheres. 22 In the production method according to any one of claims 19 to 21, the copolymerization reaction is carried out at a temperature ranging from room temperature to a temperature slightly lower than the melting point of the resulting copolymer. , a method for producing ethylene copolymers. 23. The method for producing an ethylene copolymer according to any one of claims 1 to 22, wherein the polyolefin is 1,3-butadiene. 24. In the manufacturing method according to any one of claims 1 to 22, the polyolefin is ethylidenenorbornene (5-ethylidene(2,2,1)-bicyclohept-2-ene).
A method for producing an ethylene copolymer.