JPS6096609A - Production of thermoplastic elastomer - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer excellent in polymerization activity and strength and low in stickiness, by copolymerizing ethylene with an alpha- olefin by using a catalyst system obtained from a specified solid catalyst component and an organoaluminum compound. CONSTITUTION:Ethylene is copolymerized with a 12C or lower alpha-olefin by using a catalyst system obtained from (A) a hydrocarbon-insoluble solid catalyst component obtained by reacting a magnesium compound (M) of formula I with an alkoxytitanium compound (T) of formula II, an alkoxyzirconium compound (Z) of formula III, and an aluminum halide compound (E) of formula IV, said compounds M, T, Z, and E being present in amounts satisfying the relationships (V) wherein Mg, Ti, Zr, X<1>, and X<2> are amounts (in g. equivalent) of Mg, Ti, Zr, and halogen used and (B) an organoaluminum compound. In this way, a copolymer having an ethylene content of 40-90wt%, a crystallinity of ethylene of 1-20%, and an intrinsic viscosity as measured in decalin at 135 deg.C of 1.0-20dl/g is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION [j,) OBJECTS OF THE INVENTION The present invention relates to a process for producing 7-terephine thermoplastic elastomers using a novel catalyst system. More specifically, the present invention relates to a method for producing a thermoplastic elastomer, in which at least ethylene and α-olefin are copolymerized using a novel solid catalyst component containing a titanium compound and a zirconium compound, and a catalyst component obtained from an organoaluminum compound. The purpose is to produce a thermoplastic elastomer that has excellent polymerization activity, less stickiness, and good strength.

[11] Background of the Invention In recent years, various processing methods similar to those for thermoplastic resins, such as injection molding, blow molding, rotary molding, and extrusion molding, can be used, and they have appropriate rubber-like flexibility. Thermoplastic elastomers are coated with thermoplastic elastomers and are beginning to be used in many applications due to their improved processing efficiency and ease of recycling compared to conventional crosslinked rubber.

A thermoplastic elastomer is a polymer system in which soft segments that exhibit comb-like properties at the operating temperature and hard segments that are considered pseudo-crosslinking points such as crystals, glass, etc. are appropriately arranged, and crosslinking occurs at the operating temperature. It is a glass resin whose molecular structure is such that it behaves similarly to rubber and behaves similarly to general thermoplastic resins at processing temperatures.

Among various thermoplastic nidistomers, polyolefin-based ones are mainly used in the automobile field and electric wire field because of their outstanding weather resistance and moderate heat resistance.

Polyolefin-based thermoplastic elastomers are generally referred to as ethylene-zoro♂lene terpolymer (hereinafter referred to as "EPDM").
) or ethylene-brohillencombe (hereinafter referred to as r
EPRj) and olefin resins such as polypropylene. For example, what can be seen in JP-A-47-18943 (EPR or EPDM'i = a method of partially crosslinking and blending with polyolefin (plastic), JP-A-48-18943)
A method of cross-linking while mixing a rubber component and a plastic component as in No. 26838, a method of cross-linking after kneading the two in advance as in JP-A-51-1386, and a method of cross-linking after kneading the two in advance as in JP-A-49-53938. JP-A-52-111952 and JP-A-52-12645 attempt to improve physical properties by using a high molecular weight comb component without crosslinking, or by adding a third component based on the above technology.
No. 0, JP-A-47-34739, JP-A-51-132
A technique such as No. 256 has been proposed. Also, recently,
JP-A-55-804-18 proposes a method for producing a zolopyrene-ethylene pro-copolymer.

However, in most of the above technologies, the rubber component and plastic component, which have been manufactured separately in advance, are combined and combined.
When the soft segment and the hard segment are properly arranged in the same molecule, it deviates considerably from the ideal form of a thermoplastic nidistomer. Therefore, there are still some points that require improvement in its properties as an elastomer (for example, the balance between strength and flexibility).

[■] Structure of the Invention Based on the above, the present inventors conducted various searches to improve these conventionally developed techniques, and as a result, (A) (1-in general formula Mg(oi)tx2-t) Magnesium compound (M) represented by (2) Alfuki/titanium compound (T) represented by general formula T 1 (OR2) 4 and (3) Alcogine zirconium compound represented by -T general formula zr (OR3) 4 ( Z) and (4) an aluminum halide compound (E) represented by the general formula AtIt.
At least ethylene and an α-olefin having at most 12 carbon atoms are copolymerized using a catalyst system obtained from an organoaluminum compound, so that the content of ethylene in the copolymer is 40 to 90% by weight. , the crystallinity of ethylene is in the range of 1 to 201 by weight,
and the intrinsic viscosity in decalin at a temperature of 135°C is 1
0 to 20 dt/fl "thermoplastic elastomer"
(hereinafter referred to as [TPF, j)], a TPF with excellent performance that is thought to have a soft segment and a hard segment appropriately arranged within the same molecule.
It was discovered that J could be obtained, and the present invention was achieved.

[■] Effects of the invention When producing TPE using the catalyst system of the present invention, the greatest feature (effect) is that the polymerization activity is high, so after the preparation of the TPE, the catalyst residue remaining in the TPE can be removed. Even without performing this process, the color of the TPE is good and there is almost no odor. Furthermore, the resulting TPE has less plating and has excellent strength.

[V, II Detailed Description of the Invention (A) Solid Catalyst Component The general formula of the magnesium compound used to produce the solid catalyst component of the present invention is represented by the following formula.

Mg(OR')tX,... (1) In formula (1), It1 is a saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group having at most 16 carbon atoms, and x+ is represents a location atom, and L is O~2. Among the magnesium compounds represented by formula (1), representative examples of preferred compounds include magnesium chloride, magnesium bromide, magnesium ethylate, magnesium butylade, ethoxymagnesium chloride, and butoxymagnesium chloride.

The titanium compound used to produce the solid catalyst component has the general formula shown below.

T 1 (OR2) 4 ([1) In the formula (n), R2O-1 is an aliphatic, alicyclic or aromatic hydrocarbon group having at most 16 carbon atoms,
Among the alkoxytitanium compounds represented by the formula (II),
Representative examples of suitable ones include ethyl titanate, isopropyl titanate, n-butyl titanate, inbutyl titanate, phenyl titanate, and the like.

Furthermore, the general formula of the zirconium compound is represented by the following formula.

Zr(OR3)4' (III) (I[I) In the formula, RJt is an aliphatic, alicyclic or aromatic hydrocarbon group having at most 16 carbon atoms, (
Among the alkoxynorconium compounds represented by formula (2), representative examples of preferred compounds include ethylzircone-1., n-probylnorconate, n-butylnorconate, and phenylzirconate.

The general formula of the aluminum halide compound is represented by the following formula.

AtR Eifu-m (IV) In the formula (IV), R4 is a saturated or unsaturated aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms, x2 represents a haloke atom, m is O~
Indicates the number 2.

Among the aluminum halide compounds represented by the formula (■), representative examples of preferred ones include methylaluminum rhamnochloride, ethylaluminum rhamnochloride, ethylaluminum sesquichloride, diethylaluminiumuno chloride, methylaluminum rhamnochloride, Examples include pteraluminum sesgichloride, aluminum chloride, and aluminum bromide.

The solid catalyst component of the present invention is the above-mentioned reactant (1).

(It), (III) and (IV) can be prepared by any method that results in a chemical reaction of these reactants. The reaction for producing the solid catalyst component is preferably carried out in a liquid quaternary agent. As a liquid diluent, Hegisan,
Aliphatic hydrocarbons such as hezotane, alicyclic hydrocarbons such as nclohexane, and aromatic hydrocarbons such as benzene, tolueno, and quinolene are used.

Although the order of addition of the reactants is arbitrary, reaction example (I) is used.

Reactant (IV) is added to the reaction mixture of (II) and (Ill).
) 'z is most preferably added. Reactant (I),
The reaction temperature and time of (It) and (III) are not particularly limited (depending on the type of reactants and their proportions), but are generally 40 to 180°C for 10 minutes to 3 hours, particularly preferably 60 to 180°C. The temperature is 140°C for 30 minutes to 2 hours. Reaction mixture of reactants and reactant (IV)
The reaction temperature and time are generally between -40°C and 120°C.
It takes 10 minutes to 5 hours at a temperature of 30°C to 80°C.
C. for 30 minutes to 2 hours is preferred.

The amount of each reactant used is strict, and compound (1)
, (II), (III) and (IV) must satisfy the formula.

Here, Mg, Ti, Zr, and X and X represent the amounts of magnesium, titanium, zirconium, and halogen, respectively, and these amounts are expressed in Durham light amount.

Therefore, in order to obtain a catalyst solid component according to the present invention, it is necessary to use these compounds so as to satisfy the above formula (V).

The equation (V) in formula (V) must be less than or equal to 15, and if this product is greater than 15, the resulting TPE
It is sticky (adhesive) and has low tensile strength, making it unsuitable for practical use.

The solid catalyst component prepared as described above may be thoroughly washed with an inert hydrocarbon, such as rl n-hexane, n-hezotane, etc., and may be supplied as it is as a slurry to the polymerization system, or after drying, Even if you use it in powder form
love.

The content of titanium atoms in the solid component obtained as described above is generally 01 to 30% by weight, and the content of zirconium atoms is O,]=20% by weight. or,
The content of magnesium atoms is 0.1 to 30 parts by weight, and the content of local atoms is at most 70 parts by weight.

Using the solid catalyst component purified as described above, TPF can be produced in a conventional manner using an organoaluminum compound or a catalyst system obtained from the compound and a third component.

(B) Organoaluminum Compound Among the organoaluminum compounds used in the present invention, the general formulas of typical ones are represented by the following formulas [Formula (■), Formula (■), and Formula (■)].

AtRRR (Vl) RRAA-0-AtRR (■) AtR1,5X1.5 (4) In formula (Vl), formula (■), and formula (■), R, R
and R7 may be the same or different, and are an aliphatic, alicyclic or aromatic hydrocarbon group having at most 12 carbon atoms;
is a hydrogen atom or a hydrogen atom, at least one of which is the above hydrocarbon group, R8, R9, R1
0 and R11 are the same but different types i,? / First mark
H shi shi 4shi trigram jt ii f-h, T21
2 Jr1 is a negative square dihydrogen group, and X3 is a halokene atom.

Among the aluminum compounds represented by the formula (Vl), typical examples include trialgyl aluminum such as triethyl aluminum, trialgyl aluminum, tributyl aluminum, trimyl aluminum and trioctyl aluminum, diethyl aluminum hydride, etc. Examples thereof include alkylaluminum hydrides such as No. 14 and cynobutylaluminum hydride, as well as noethylaluminum chloride and noethylaluminum bromide.

Further, among the organoaluminum compounds represented by the formula (■), representative examples include alkylnoalumoxanes such as tetraethyldialumoxane and tetrabutylnoalumoxane.

Furthermore, among the organoaluminum compounds represented by the formula (■), ethylaluminum sesquichloride is a typical example. Among organoaluminum compounds, particularly preferred are compounds represented by formula (■).

In carrying out the present invention, the solid catalyst component and the organoaluminum compound, or the reactant or mixture of these and the electrodynamic organic compound may be separately introduced into the reactor (polymerization vessel). , two or all of them may be mixed in advance. Alternatively, it may be used after being diluted in advance with an inert solvent used as a solvent in the polymerization described later.

(C) Polymerization (1) Amount of solid catalyst component and organoaluminum compound used In carrying out the polymerization of the present invention, there is no restriction on the amount of the solid catalyst component and organoaluminum compound obtained as described above, but Solvents used in polymerization and "polymerization equipment that also functions as a solvent" (hereinafter referred to as 1 polymerization monomer solvent) 11 adashi, 1 m9 ~ 1 (9
A proportion of the solid catalyst component of 0.1 to 10 mmol of the organoaluminum compound is preferred. Further, the amount of the organoaluminum compound used is generally in the range of 1 to 1000 mol per 1 atomic equivalent of the transition metal element contained in the solid catalyst component. Further, when an electron-donating compound or the like is used, the ratio of the electron-donating compound or the like to the organoaluminum compound is (7 to 100 times at most) by weight.

(2) α-Olefin In carrying out the present invention, it can be obtained by total copolymerization of at least ethylene and α-olefin. The α-olefin used is a hydrocarbon having a double bond at the end and having at most 12 carbon atoms.

Representative examples include glolene, butene-1,4-methylindene-1, hexene-1 and octene-1, and the so-called Swanto B-B fraction produced by the Nafbu cracking furnace. The copolymerization ratio of the above α-olefin in the obtained TPE is generally 10 to 50.
The weight ratio is preferably 15 to 40 inches.

Although the TPE of the present invention can be obtained by copolymerizing ethylene and the above-mentioned α-olefin, it can also be produced by copolymerizing ethylene, α-olefin, and the polyunsaturated hydrocarbon monomer described below. Typical examples of polyunsaturated hydrocarbon monomers that can be used include fatty acids such as 1, hexadiene, 1,4-,5,7-nomethyloctadiene-1,6, decatriene-1,4,9, and non-conjugated tsenes. or polyenes, 4-vinylcyclohexene-193 (2-phthynyl)-cyclobutene, alkenylcycloalkenes, non-conjugated monocyclic dienes such as diene-1,4, such as nocyclobentadiene, 5-butenyl-norbornene; -Polycyclic 1/domethylene polyenes such as -2,5-inzorobenyl-norbornene-2゜5-ethylidenenorbornene-1,
4,9,7.8-Tetrahydroindene, 6-# Chiru 4.9,7.8-Tetrahydroindene, 5,6-
polycyclic polyenes having fused rings in which each pair of fused rings has two carbon atoms in common, such as dimethyl-4.9,7.8-tetrahydroindene, novinylcyclobutane;
Examples include di- or polyalkenylcycloalkanes such as trivinylcyclohexane.

The copolymerization ratio of these polyunsaturated hydrocarbon monomers in the resulting TPE is preferably 10 molar at most, preferably 5 molar or less.

In the present invention, magnesium compounds, titanium compounds, norconium compounds, aluminum haloke octane compounds, etc. used for producing the solid catalyst component, and TPE f: solid catalyst component used for producing the organoaluminum compound, The electron-donating compound crab (if used), the α-olefin, and the polyunsaturated hydrocarbon monomer (if used) may each be used alone or in combination of two or more. Furthermore, when producing the solid catalyst component and TPE in an inert solvent, each inert solvent may be used alone or in combination of two or more.

(3) Other polymerization conditions Although polymerization can be carried out by dissolving at least ethylene and α-olefin in an inert solvent or a polymerization monomer solvent, it may also be carried out by a known so-called melting method. Considering economic efficiency, it is particularly preferable to polymerize in a slurry state using α-olefin itself such as zolopyrene or butene-1 as a solvent. In this case, in order to maintain a good slurry condition, it is particularly preferable to use a tubular circulation reactor. Furthermore, if necessary, a molecular weight regulator (generally hydrogen) may be present.

The polymerization temperature is generally from -10°C to 300'°C, and practically from 0°C to 250°C. In the case of slurry polymerization, H is preferably 50°C or lower.

In addition, the conditions used in the production of general ethylene polymers may be applied to the type of polymerization solvent and the proportions of ethylene and α-olefin or these and polyunsaturated hydrocarbon monomers.

Additionally, the configuration of the polymerization reactor, polymerization control method, post-treatment method, ratio of monomers (ethylene, α-olefin and polyunsaturated hydrocarbon monomers) to inert organic solvent used in polymerization, and organoaluminum Regarding the ratio of compounds, the type of inert organic solvent, the post-treatment method after completion of polymerization, etc., there are no limitations specific to this catalyst system, and all known methods can be applied.

(4) TPE The ethylene content (hereinafter referred to as "Cv: J") in the TPE obtained as described above is /IO~90 weight ratio,
A weight ratio of 55 to 85 is appropriate. If this ratio is low, the product will be soft, and if it is high, it will be hard. When the CE is 40 or less, there are no ethylenic crystals, that is, hard segments of the thermoplastic elastomer, so the uncrosslinked sulfurized resin also becomes a sticky polymer, which prevents the polymerization reaction. It is impossible to maintain a slurry state inside the slurry, otherwise it will stick together and form a lump, making stable production impossible. When the CE is 90 or higher, it is not very hard and no longer falls within the range of thermoplastic nidistomers.

A further important factor is the proportion of ethylenic crystals in the reaction product. This ethylenic crystallinity is measured by DSC (scanning differential thermal analyzer), and the detailed measurement method will be described later.

The ethylenic crystallinity is between 1 and 20. If the number of threads is less than one, the uncrosslinked rubber exhibits similar physical properties because the amount of knot segments is insufficient, and the tensile strength is also low, causing so-called cold flow and making it difficult to maintain the shape.

Furthermore, if the ethylenic crystallinity is less than 1%, it becomes virtually impossible to carry out the entire reaction in a slurry form.

On the other hand, if the ethylenic crystallinity exceeds 20, there will be no problem in carrying out the polymerization reaction, but the product will be hard and
It becomes close to resin and has properties as a thermoplastic nidistomer.
For example, flexibility and low compression set cannot be obtained.

The molecular weight of the thermoplastic elastomer produced by this method is that the intrinsic viscosity [η] measured in decalin at 135°C is 1.
0 to 20 (dll/g), preferably 2 to 20 (dll/g)
7 is appropriate. When the tensile strength is lower than 10, sufficient tensile strength cannot be obtained, and on the other hand, when it exceeds 20, sufficient moldability cannot be imparted.

Thanks to this invention! If TpE is required to have properties similar to those of the patented sulfur comb, which is characterized by having sufficient physical properties without crosslinking, it can be partially crosslinked to form a crosslinked type. For these, crosslinking can be carried out using a known organic peroxide (the amount added is generally 1" in total, 0.01 to 1.0% by weight relative to the combined amount) or a combination of the organic peroxide and a crosslinking aid. Furthermore, the 1゛yen C of the present invention can be blended with other resins, inorganic materials, and Ietsuki filler materials to meet the final use purpose.As a resin to be mixed with is +1″! Liolefin is common.

[VI) Examples and Comparative Examples The present invention will now be described in more detail with reference to Examples.

In addition, in Examples and Comparative Examples, Menoret Flow Index (hereinafter referred to as "MFI, J") and JI
Based on SK-6758, measurements were made under the conditions of a temperature of 230°C and a load of 2.16K9, and CE was measured by infrared absorption spectroscopy. In addition, the tensile strength test is JISK-
Measured based on 6301. Furthermore, the permanent elongation is J
According to ISK-6301, press plate with thickness of 1 mist.
Punch out a JI No. 83 dumbbell and test it with a tensile tester.
It was stretched by 100 inches at a temperature of 0° C. and held for 10 minutes, and the permanent elongation was measured 10 minutes after returning it. The degree of ethylenic crystallinity is determined by the heat of fusion ΔH (c
at/g) and the heat of fusion of perfectly crystalline polyethylene (68c
aA/g) using the following formula (see Polymer End Book, 2nd edition).

α (Crystallinity) = (ΔH/68)X100 (H) Examples 1 to 7. Comparative Example 1.2 (1) Production of solid catalyst component Magnesium ethyla ~ 1., n in the proportions shown in Table 1
-Butyl ticunate, n-butylsolcone-1, and n-hezotane were used as a solvent, and the reaction was carried out at 70°C for 1 hour. Then, a predetermined amount of ethylaluminum dichloride was added at 80°C.

After thoroughly washing the generated precipitate with n-hexane,
Vacuum drying was performed at °C to obtain solid catalyst powders A-F.

(2) Manufacture of TPE Into a 1304 stainless steel autoclave, the amount of the solid catalyst component shown in Table 2 and 200 mm of tri-butylaluminum were added, and the amounts of Titecomonomer 30K9 and hydrogen shown in Table 2 were added, and polymerization was carried out. Raise the temperature to the temperature shown in Table 2. Then, ethylene was fed under pressure to maintain the ethylene concentration in the autoclave (the ethylene concentration is shown in Table 2), and the polymerization was continued for 1 hour.

Then, the feed of ethylene to the polymerization system was stopped, and the contents were discharged into the furnace to terminate the polymerization. The obtained polymer was dried in a hollow chamber while flowing nitrogen gas. stomach! ) The yield and polymerization activity of the polymer thus obtained are shown in Table 2. (3) Physical properties of the polymer To 100 parts by weight of the polymer thus obtained, 005 parts by weight of 2,6-di and monobutyl Lacresol and 02
part by weight of similistyrylthionopropione), 0.0
5 parts by weight of tetrakis [methylene-3-(3',5'-
Nort-butyl-4'-hydroxyphenyl)propionate dimethane and 0.2 parts by weight of calcium stearate were added, and the wire was rolled at 180 DEG C. for 5 minutes using a 3-inch roll. The obtained sheet-like Sansol is compression molded,
Tensile test and/or Yoar hardness were measured. Various physical property values are shown in Table 3. Furthermore, the CE I MFI of the polymer,
α and intrinsic viscosity are shown in Table 3.

Example 8 A solid catalyst component (G) was obtained in exactly the same manner as in Example 1, except that magnesium chloride was used instead of magnesium ethylate. TPE was produced and characterized in exactly the same manner as in Example 1, except that a predetermined amount of this solid catalyst component was used. The results are shown in Tables 2 and 3.

Example 9 TPE was produced in exactly the same manner as in Example 1 except that 2Q0 mmol of triethylaluminum and 100 mmol of tetrahydrofuran were used instead of triisobutylaluminum.

The polymerization results are shown in Table 2, and the physical property evaluation results are shown in Table 3.

Example 10 TPE was produced in exactly the same manner as in Example 1, except that 5-ethylidenenorbornene-1 was further added as a comonomer in an amount of 67 mol based on zololene. The polymer was washed with methanol and then dried under a nitrogen stream. The yield and polymerization property of the obtained positive polymer were determined by the second
Table 3 shows the physical property evaluation results.

Claims (1)

[Claims] (A) (1) The general formula Mg (OR1) is expressed as
1 is a saturated or unsaturated aliphatic, alicyclic, or aromatic hydrocarbon group having at most 16 carbon atoms;
・A magnesium compound (M) represented by the general formula Ti(OR2)4 (wherein R2 is an aliphatic or aliphatic compound having at most 16 carbon atoms) Alkoxytitanium compounds (T) represented by a cyclic or aromatic hydrocarbon group
) and (3) alkoxyzirconium compounds (Z ) and 2 (4) General formula AtRm a hydrocarbon-insoluble solid catalyst component obtained by reacting an aluminum halide compound (E) represented by
(T), (Z) and (E) are respectively expressed by the following formulas (wherein, Mgr Tiz Zr p
Table 1 shows the amounts of magnesium, titanium, zirconium, and zirconium used, each expressed in Durham equivalent. ) and CB) A catalyst system obtained from an organoaluminum compound is copolymerized with at least ethylene and an α-olefin having at most 12 carbon atoms, and the ethibine in the copolymer is The content is 40 to 90% by weight, the crystallinity of ethylene is 1 to 20%, and the intrinsic viscosity in decalin at a temperature of 135°C is 1.0.
A method for producing a thermoplastic elastomer, the method comprising producing a thermoplastic elastomer having a density of 20 dt/g.