JPH042602B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ethylene copolymer wax.

When blending additives (hereinafter sometimes collectively referred to as pigments) that can be dispersed without being substantially dissolved in the polymeric material, such as pigments, fillers, or similar substances, the pigments are added to the polymeric material. Dispersants are often used for the purpose of uniformly blending into materials. For example, when coloring synthetic resins with pigments,
It is necessary to uniformly disperse the pigment in the synthetic resin to avoid undesirable uneven coloring. For this purpose, for example, a method is known in which a master batch of a pigment and a dispersant is prepared in advance and the master batch is blended into synthetic resins.

Various waxes are commercially available as dispersants used in such cases. Synthetic products are also known as such commercially available waxes, such as waxes obtained by thermal decomposition of high-pressure polyethylene, high-pressure polymerized polyethylene waxes obtained by radical polymerization of ethylene at high pressures, and furthermore, waxes made from ethylene or ethylene. Ethylene-based waxes, such as waxes obtained by low-pressure polymerization of olefins and α-olefins such as propylene and 1-butene using a Ziegler type catalyst, are often used.

Conventionally, the above-mentioned pyrolytic polyethylene wax and Ziegler type polymerized polyethylene wax are
It is assumed that this is due to differences in molecular structure and other factors, but there are differences in pigment dispersion ability depending on the type of polymer compound to be colored, and the fields of suitability of each are slightly different. Among conventional waxes, pyrolyzed polyethylene waxes and high-pressure polymerized polyethylene waxes have the drawbacks of poor thermal stability and discoloration, so they are not necessarily good pigment dispersants. However, it was hoped that other substitutes would emerge. On the other hand, Ziegler type polymerized polyethylene wax has the advantage of excellent thermal stability and low tendency to discolor, but as mentioned above, conventional products of this type lack pyrolytic polyethylene wax in terms of pigment dispersibility, etc. For example, pyrolytic polyethylene wax is used as a pigment dispersant for high-pressure polyethylene due to its dispersion performance. Conventional Ziegler type polymerized polyethylene wax could not be used as a substitute.

The present inventors did not lose the advantages of Ziegler-type polymerized polyethylene wax, which has good thermal stability and little tendency to discolor, but rather promoted it, and further improved the performance by making pigment dispersibility comparable to that of pyrolyzed polyethylene wax. We have conducted research to provide a new type of ethylene copolymer wax that has excellent pigment dispersibility in high-pressure polyethylene, such as waxes having the following properties.

As a result, it was discovered that an ethylene copolymer wax having the above-mentioned improved performance could be produced. Furthermore, the wax that can be produced under specific polymerization conditions, which will be detailed later, has the following characteristics (A) to (F).
It was discovered that this is a unique ethylene copolymer wax that is distinguishable from conventional ethylene copolymer waxes.

The wax has: (A) an intrinsic viscosity of 0.06 measured in decalin at 135°C;
~0.6 dl/g, (B) Density 0.87 to 0.94 g/cm ³ , (C) 120°C or less of the endothermic spectrum with respect to the total area σ ₀ surrounded by the endothermic spectrum line and its baseline by differential scanning calorimeter The area σ surrounded by the endothermic spectrum line and its baseline
(≦120℃) Ratio σ (≦120℃) / σ ₀ is 0.82 or more, (D) Ethylene content 88 to 98 mol%, (E) Methylene chain in which the number of methylene chains in the polymer chain is 7 or more An ethylene copolymer wax of ethylene and C ₄ to _{C 10} α-olefin with the following characteristics: the average number of methylene chains is 60 or less, and (F) the number of double bonds per 1000 carbon atoms is 0.7 or less. be.

Therefore, an object of the present invention is to provide an ethylene copolymer wax having both the above properties (A) to (F).

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

The ethylene copolymer wax of the present invention has (A) an intrinsic viscosity of 0.06 to 0.6 dl/g, preferably about 0.1 to about 0.4
dl/g. If the intrinsic viscosity is too small or too large outside the above range, pigment dispersibility will deteriorate.

In the present invention, the intrinsic viscosity is a value determined by measurement in decalin at 135°C.

The ethylene copolymer wax of the present invention has (B) a density of 0.87 to 0.94 g/cm ³ , preferably about 0.89 to about
It is 0.93g/ ^cm3 . Waxes whose density is too high, exceeding the above-mentioned upper limit, have poor pigment dispersibility, and waxes whose density is too low, exceeding the above-mentioned lower limit, have blocking defects and are unsuitable due to poor workability.

In addition, in the present invention, the density is determined according to ASTM D-1505.
Measured using the density gradient tube method in accordance with .

The ethylene copolymer wax of the present invention comprises (C) an endothermic spectrum line of 120°C or less of the endothermic spectrum measured by a differential scanning calorimeter and its base line with respect to the total area σ ₀ surrounded by the endothermic spectrum line and its base line; The ratio σ (≦120°C)/σ ₀ of the area surrounded by the line σ (≦120°C) is 0.82 to 1.0, preferably about 0.82 to 1.0.

If the above ratio is less than 0.82, the pigment dispersibility is poor and it is inappropriate.

In addition, in the present invention, the measurement and determination of the above-mentioned σ (≦120°C)/σ ₀ is as follows.

The measurement is performed using a differential scanning calorimeter (DSC) [Model 990 manufactured by DuPont]. Sample wax approx. 4mg
Place it in the measurement sample case, weigh it, and attach it to the measuring instrument. Next, leave it at 200℃ for 5 minutes, then 10℃/
Cool to 0°C at a rate of min and leave for 2 minutes.
Using this sample wax, raise the temperature at a rate of 10°C/min to obtain its endothermic spectrum chart. The total area σ ₀ surrounded by the endothermic spectrum line of the obtained chart and its baseline, and the area σ (≦120°C) surrounded by the endothermic spectrum line below 120°C of the endothermic spectrum and its baseline. ,
Measure the chart and use the formula σ (≦120℃)/σ ₀
Calculate and determine the value of.

An example of the above-mentioned endothermic spectrum chart is shown in FIG. 1 of the accompanying drawings. An example of the measurement determination method described above will be explained in more detail using this figure.

Since the portion A in FIG. 1 where no endotherm is observed on the high temperature side is almost a straight line, this is extended to the point where it intersects with the endothermic spectrum on the low temperature side. The area surrounded by the straight line AB and the endothermic spectrum is σ ₀ , and the area surrounded by the straight line AB, the endothermic spectrum, and 120℃
The area of the low temperature side part surrounded by the line C drawn above is σ
(≦120℃).

When the ethylene copolymer wax of the present invention is produced according to the production method that will be specifically described later, multiple peaks are often observed in the DSC endothermic spectrum of the obtained wax. Even if one is at 120°C or higher, as in the example in Figure 1, if the above ratio is 0.82 or higher,
Pigment dispersibility is good.

The ethylene copolymer wax of the present invention has (D) an ethylene content of 88 to 98 mol%, preferably about 90 to 98 mol%.
It is about 96 mol%. If the ethylene content is too low outside the above range, pigment dispersibility will deteriorate. On the other hand, if the amount is too large, blocking defects occur, resulting in poor workability and unsuitability.

In the present invention, the ethylene content is determined by quantifying the amount of _C4 to _C10 α-olefin components from an infrared absorption spectrum.

In the ethylene copolymer wax of the present invention, the average number of methylene chains in the polymer chain (E) is 7 or more, and the average number of methylene chains is 60 or less, preferably about 55 or less. For example, it is about 20 to 60. A wax whose average number of methylene chains is larger than the above upper limit means that it has a large number of polyethylene blocks, and the pigment dispersibility is poor.

In addition, in the present invention, the average number of methylene chains is
The number of methylene chains with a methylene chain number of 7 or more is calculated from the ¹³ C nuclear magnetic resonance spectrum. That is, in the ethylene copolymer wax with the following structure, (R is a branch of C ₂ or more) From the signal area S〓 of α carbon and the area S〓 of signal of δ carbon, the average number of methylene chains of methylene chains with 7 or more methylene chains is S〓/S〓 It is determined by the formula x2+6.

The ethylene copolymer wax of the present invention has (F)
The number of double bonds per 1000 carbon atoms is 0.7 or less, preferably about 0.5 or less, and more preferably about 0.3 or less. For example, the number is about 0.01 to 0.7. Waxes with too large double bonds exceeding the above upper limit have poor heat resistance and are unsuitable.

In the present invention, the number of double bonds per 1000 carbon atoms is determined as follows. Sample film formed by compression molding machine (thickness 50-100μm)
From the IR spectrum of terminal vinyl (910 cm ^-1 ), trans vinyl (965 cm ^-1 ), vinylidene (880 cm ^-1 )
The amount of double bonds per 1000 carbon atoms is determined from the absorbance determined from the absorption intensity and film thickness using each calibration curve, and the total amount is determined.

As mentioned above, the ethylene of the present invention and C ₄ ~
The ethylene copolymer wax with _C10 α-olefin has properties (A) to (F), but in a particularly preferred embodiment, (G) the (E) average methylene chain number; The ethylene copolymer wax exhibits a characteristic in which the difference in the number of methylene chains of a completely random copolymer having the same monomer composition is 30 or less, more preferably about 25 or less. For example, it is about 10 to 30.

This characteristic (G) is one of the measures expressing the randomness of the wax of the present invention, and the difference from the value for a completely random copolymer (calculated and determined by the content of ethylene and α-olefin) is small. This means that the randomness is better.

According to a preferred embodiment of the present invention, the ethylene copolymer wax of ethylene and _C4 to _C10 α-olefin of the present invention has a maximum melting point of (H) as measured by differential scanning calorimetry (DSC).
The temperature is 105°C or higher, more preferably about 1.10°C or higher.

For example, it exhibits a maximum melting point (the highest temperature in the peak of the DSC spectrum) in a range such as 105 to 120°C. In addition, in many cases, the preferred ethylene copolymer wax of the present invention has a melting point (the point at which the maximum endotherm is observed in the DSC spectrum) of approximately 80°C.
That's all.

In the present invention, copolymerized with ethylene
Examples of _C4 to _C10 α-olefins include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3
-Methyl-1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 6-methyl-
Examples include 1-heptene. In particular, alpha-olefins having 5 to 10 carbon atoms, especially branched alpha-olefins, are preferred.

The ethylene copolymer wax of the present invention comprises (A) a highly active titanium catalyst component activated with a magnesium compound, (B) halogen/Al (atomic ratio) of 1 to 2,
Copolymerizing ethylene and an α-olefin having 4 to 10 carbon atoms at a temperature of 100°C or higher in the presence of hydrogen in the presence of a catalyst preferably formed from an organoaluminum compound of 1.05 to 1.4 and (C) ether. It can be obtained by doing.

The highly active titanium catalyst component (A) is a titanium catalyst component that has been highly activated by using a magnesium compound, and the magnesium compound and titanium compound may be allowed to interact with each other before use, or the magnesium compound may be added in a polymerization system. High activation can be achieved by bringing the titanium compound into contact with the titanium compound.

The catalyst component (A) may be a titanium catalyst component supported on a magnesium compound, or the magnesium compound and the titanium compound may be dissolved in a hydrocarbon or the like by using a solubilizing agent such as an alcohol. It can be something. Titanium in the catalyst component (A) is usually tetravalent and/or trivalent. The solid catalyst component (A) usually preferably has a titanium content of about 0.2 to about 18% by weight, more preferably about
0.3 to about 15% by weight, and the halogen/titanium (molar ratio) is preferably about 4 to about 300,
More preferably from about 5 to about 200. Furthermore,
The specific surface area is preferably about 10 m ² /g or more, more preferably about 20 to about 1000 m ² /g, even more preferably about 40 to about 900 m ² /g.

Such a solid highly active titanium catalyst component (A) is widely known, and basically, a reactant with a large specific surface area is obtained by reacting a magnesium compound and a titanium compound, or a reactant with a large specific surface area is obtained. A method of reacting a titanium compound with a magnesium compound is often used. For example, co-pulverization of a magnesium compound and a titanium compound, a thermal reaction between a magnesium compound with a sufficiently large specific surface area and a titanium compound, a thermal reaction between an oxygen-containing magnesium compound and a titanium compound, and a magnesium compound treated with an electron donor. Typical examples include a method in which the material is treated in advance with an organic aluminum compound or a halogen-containing silicon compound, or is reacted with a titanium compound without treatment.

There are various magnesium compounds used for producing the solid highly active titanium catalyst component (A). For example, magnesium chloride, magnesium bromide, magnesium iodide, magnesium fluoride, magnesium hydroxide, magnesium oxide, magnesium hydroxyhalide, alkoxymagnesium, alkoxymagnesium halide, allyloxymagnesium, allyloxymagnesium halide, alkylmagnesium halide, or these. Examples include mixtures. These may be made by any manufacturing method. The magnesium compound may also contain other metals, electron donors, and the like.

Ti(OR) ₄ −mXm(R
is a hydrocarbon group, such as a _C2 - _C6 alkyl group,
C ₆ - C ₁₂ aryl group, X is halogen, 0≦m≦
The tetravalent titanium compound shown in 4) can be exemplified. Examples of such titanium compounds are
_TiCl4 , _TiBr4 , Ti( _OC2H5 ) _{Cl3 ,} Ti
(OC ₂ H ₅ ) ₂ Cl ₂ , Ti(OC ₆ H ₅ ) ₃ Cl, Ti(OC ₂ H ₅ ) ₄ ,
Examples include Ti( _{OC4H9 )4 .} Furthermore,
Titanium tetrahalide, aluminum, titanium,
Examples include various titanium trihalides obtained by reduction with a reducing agent such as hydrogen or an organic aluminum compound, such as titanium trichloride. Two or more of these tatin compounds can be used in combination.

Typical methods for obtaining such a solid highly active titanium catalyst component (A) include, for example, Japanese Patent Publication No. 46-34092, Japanese Patent Publication No. 46-34094, Japanese Patent Publication No. 46-34098, Japanese Patent Publication No. 47-1986.
41676, Japanese Patent Publication No. 47-46269, Japanese Patent Publication No. 50-32270, Japanese Patent Publication No. 53-1796, etc., and can be used in the present invention.

An example of a soluble highly active titanium catalyst component is
This is shown in Japanese Patent Application No. 53-151998.

The organoaluminum compound used together with the titanium catalyst component (A) has a halogen/Al (atomic ratio) in the range of 1 to 2, preferably 1.05 to 1.4;
A mixture of two or more types may be used, or trialkylaluminum, trihalogenated aluminum, etc. may be used as one component when used in combination. Such organoaluminum compounds include dialkylaluminum halides such as diethylaluminum chloride, dibutylaluminum chloride, diethylaluminium bromide, ethylaluminum sesquichloride, propylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, octylaluminum sesquichloride, etc. Typical examples include alkylaluminum sesquichlorides such as chloride, alkylaluminum dichlorides such as ethylaluminum dichloride, butylaluminum dichloride, mixtures thereof, and mixtures of these with trialkylaluminum and/or trihalogenated aluminum. I can do that. Even if a trialkylaluminium or the like is used in place of such an organoaluminum compound, the wax of the present invention cannot be obtained.

As the ether (C), diethyl ether, diisopropyl ether, di-n-propyl ether,
Di-n-butyl ether, ethyl n-butyl ether, diisobutyl ether, diisoamyl ether, dihexyl ether, dioctyl ether,
Ethers having 2 to 20 carbon atoms such as ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, tetrahydrofuran and anisole are preferably used. The amount of ether used is preferably such that the ether/halogen-containing organoaluminum compound (molar ratio) ranges from about 0.05 to about 1, particularly from about 0.1 to about 0.8.

The ethylene copolymer waxes of the present invention can also be formed in other manners. For example, the highly active titanium catalyst component (A) can be obtained by reacting a complex of magnesium halide and alcohol directly with a titanium compound, or by reacting the complex with an organoaluminum compound and then reacting with a titanium compound. When the organoaluminum compound (B) is a halogen/Al (atomic ratio) between 1 and 1.5, preferably between 1.05 and 1.4, the above ether (C) can be used in combination. It can be manufactured without

The copolymerization reaction is carried out in the presence of hydrogen at a temperature of 100°C or higher, preferably from about 120 to about 230°C, under conditions such that the wax produced dissolves in the reaction medium. The copolymerization is preferably carried out under conditions that provide a homogeneous phase. Hydrocarbons are preferably used as reaction medium, for example hexane, heptane, octane,
Decane, kerosene, cyclohexane, benzene, toluene, xylene, etc. can be used. Although it can be changed as appropriate depending on the ethylene content, intrinsic viscosity or polymerization temperature, catalyst supply amount, etc. of the target ethylene copolymer wax, the supply ratio (molar ratio) of α-olefin having 4 to 10 carbon atoms to ethylene ) is about 0.02 to about 0.30, and the hydrogen/ethylene (mole ratio) in the gas phase in the polymerization vessel is about 0.1.
It is preferable to set the value to about 10 to about 10.
The copolymerization reaction is preferably carried out in a continuous manner. The catalyst in the wax obtained by the copolymerization reaction can be removed by known means such as filtration and washing.

The ethylene copolymer wax of the present invention exhibits excellent performance as a pigment dispersant. When used as a dispersant, for example, about 100 parts by weight of the ethylene-based copolymer wax of the present invention may be added with a pigment, etc.
Mixing in a proportion of about 20 to about 140 parts by weight, kneading at a temperature above the melting point of the wax, cooling and solidifying,
A color base can then be prepared by crushing the powder to a suitable particle size, for example, about 20 to about 200 mesh. Next, the material may be melted and diluted in advance with the polymer compound to be colored, or may be directly added to the polymer compound in an amount that will give the required degree of coloring, and then molded. The pigments used may be organic or inorganic, and typical examples include those listed in the Latest Pigment Handbook (published by Seibundo Shinkosha on January 10, 1978), pages 216 to 221. can be mentioned. As well as pigments, the waxes of the invention can also be used for dispersing other additives, such as fillers, to be dispersed in polymeric compounds. Examples of these pigments or fillers include titanium oxide, iron oxide, magnesium hydroxide, calcium carbonate, talc, carbon black, silica, magnesium carbonate, aluminum hydroxide, kaolin, asbestos, glass fiber, hydrotalcite, and zinc oxide. Examples include inorganic materials such as azo-based, isoindolinone-based, anthrone-based, phthalocyanine-based, dioxazine-based, perylene-based, perinone-based, and quinophthalone-based organic pigments. Various polymer compounds can be selected as the polymer compound to be colored, but polyolefin resins, such as polyethylene, polypropylene, poly-1-butene, poly-4-methyl-1-pentene, among others,
Preferably it is applied to low density polyethylene.

The ethylene copolymer wax of the present invention can be used as a lubricant, a hot melt resin, an ink, a paint, etc. by itself or after reacting with maleic anhydride.

Next, an example will be explained.

The viscosity average molecular weight Mv in the examples was calculated from the limiting viscosity [η] using the following formula.

Mv = 2.51 × 10 ⁴ × [η] ^1.235 Example 1 Under a nitrogen seal, 10 kg of dehydrated hexane and 10 kg of anhydrous magnesium chloride (average particle size 150 μ) were charged into a 50 glass-lined reactor equipped with a stirrer, and ethanol was added at room temperature while stirring. 5 kg was dropped in 1 hour, and stirring was continued for 3 hours. Next, the stirring was stopped and the mixture was allowed to stand still. After removing the supernatant hexane layer, 20 kg of titanium tetrachloride was added to form a reslurry, and the temperature was raised to 110°C.
After reacting with stirring for 2 hours, let stand,
After removing the supernatant, rinse once with cold titanium tetrachloride,
Titanium tetrachloride was replaced with hexane. The solid catalyst thus obtained contained 42 mg of titanium per gram.

Dehydrated hexane at 100/hr, the above solid catalyst at 2.8 mM/hr, ethylaluminum sesquichloride at 30 mM/hr, and diisoamyl ether at 10 mM/hr were continuously fed into a pressurized continuous device equipped with a stirrer. In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the total pressure was 32 at a polymerization temperature of 140°C.
Continuous polymerization was carried out at a rate of Kg/cm ² and an average residence time of 1 hour in hexane, and the mixture was discharged from the reactor. The molecular weight of the wax obtained by continuously flashing hexane from the polymer solution is adjusted by the hydrogen/ethylene molar ratio in the reactor, and the density is adjusted by the 4-methyl-1-pentene/ethylene supply ratio. average molecular weight
5500 (ethylene-4-methyl-1- with intrinsic viscosity 0.29 dl/g, density 0.906, ethylene content 93.8 mol%)
A pentene copolymer wax was obtained at a rate of 14 kg/hr. σ(≦
120℃)/σ ₀ = 0.98, DSC main peak 112℃, ^13C
The average methylene chain length determined from NMR was 42. The number of double bonds determined by infrared absorption spectrum was 0.1 per 1000 carbon atoms.

The above wax (particle size: about 60 mesh) and pigment (phthalocyanine blue) were mixed in a 1:1 ratio and kneaded at 120°C using a triple roll. After kneading 1 g of this material and 38 g of high-pressure polyethylene using a Brabender Plastograph, it was made into a 100μ thick 24mm x 34mm.
Create a press sheet with a size of
Judgment was made in four stages: 2, 3, and 4 (5 or less items of 10μ or more). A pigment dispersion rating of 2 or less is poor and causes many practical problems, and the higher the number, the better the degree of dispersion. The degree of dispersion of this wax was 3-4.
Create a 2mm thick press sheet of this,
When a bending test was performed at room temperature with a span distance of 32 mm, the maximum bending deflection was 5.7 mm, indicating excellent flexibility.

Example 2 Dehydrated hexane 50/hr, solid catalyst of Example 1 3mM/hr, ethylaluminum sesquichloride 43.5mM/hr in a pressurized continuous device equipped with a 200° stirrer.
hr, triethyl aluminum 6.5mM/hr (halogen/Al ratio 1.31), diisoamyl ether 10mM/hr
hr was continuously supplied. Furthermore, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and 170
Continuous polymerization was carried out at a polymerization temperature of ℃ at a total pressure of 38 Kg/cm ² and an average residence time of 2.4 hours in hexane, and then extracted from the reactor.
Treated in the same manner as in Example 1, the viscosity average molecular weight was 4500.
(intrinsic viscosity 0.25 dl/g), density 0.897 g/cm ³ , ethylene content 91.6 mol% ethylene-4-methyl-
A 1-pentene copolymer wax was obtained at a rate of 18 kg/hr. σ analyzed from the DSC curve of this
(≦120℃)/σ ₀ = 0.88, DSC main peak 120℃,
¹³ Average methylene chain length determined from CNMR31
It was hot. The number of double bonds determined by infrared absorption spectrum was 0.03 per 1000 carbon atoms. The pigment dispersion performance of this product was 3 to 4.

Example 3 Dehydrated hexane 50/hr, solid catalyst of Example 1 0.7mM/hr,
Diethylaluminum chloride 45mM/hr, ethylaluminum sesquichloride 5mM/hr, and diisoamyl ether 10mM/hr were continuously supplied.
In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the total pressure was increased at a polymerization temperature of 170°C.
Continuous polymerization was carried out at 37 Kg/cm ² and an average residence time of 2.4 hours in hexane, and the mixture was extracted from the reactor and treated in the same manner as in Example 1, resulting in a viscosity average molecular weight of 4300 (intrinsic viscosity 0.24 dl/
g), an ethylene-4-methyl-1-pentene copolymer wax having a density of 0.897 g/cm ³ and an ethylene content of 92.9 mol% was obtained at a rate of 15.3 Kg/hr. σ (≦120℃) / σ ₀ = analyzed from the DSC curve of this product
0.82, the main peak of DSC was 115°C, and the average methylene chain length determined from ¹³ CNMR was 36. In addition, the number of double bonds determined by infrared absorption spectrum is
The number was 0.08 per 1000 carbon atoms. Pigment dispersibility was 3.

Example 4 1 kg of anhydrous magnesium chloride (100 mesh passes, specific surface area 4 m ² /g) and 100 g of titanium tetrachloride were co-milled in a vibrating ball mill at room temperature for 6 hours. 24 mg of Ti was fixed on this co-pulverized solid catalyst.

Dehydrated hexane 100/hr, the above solid catalyst 3.6 mM/hr, ethylaluminum sesquichloride 90 mM/hr, and diisoaluminum ether 30 mM/hr were continuously fed to a pressurized continuous device equipped with a stirrer. In addition, ethylene, 1-butene and hydrogen were continuously supplied, and the polymerization was carried out continuously at a polymerization temperature of 150° C. under a total pressure of 31 Kg/cm ² and an average residence time of hexane of 1 hour. Viscosity average molecular weight 4600 (intrinsic viscosity 0.25 dl/g), density 0.910 g/g
cm ³ , ethylene-1- with ethylene content of 93.5 mol%
A butene copolymer wax was obtained at a rate of 14 Kg/hr. The DSC curve of this is analyzed σ (≦120
°C)/σ ₀ = 0.97, DSC main peak 97 °C, highest melting point
The average methylene chain length determined from ¹³ CNMR at 112°C was 40. The number of double bonds determined by infrared absorption spectrum is 0.05 per 1000 carbon atoms.
The pigment dispersion score was 3 to 4.

Comparative Example 1 Dehydrated hexane 50/hr, solid catalyst of Example 1 2.5mM/hr,
Triethylaluminum was continuously supplied at 50mM/hr. In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the mixture was continuously polymerized at a polymerization temperature of 180°C with an average residence time of 2.4 hours in hexane, and then extracted from the reactor and treated in the same manner as in Example 1. , viscosity average molecular weight 4900 (intrinsic viscosity 0.27 dl/g), density
An ethylene-4-methyl-1-pentene copolymer wax having a weight of 0.903 g/cm ³ and an ethylene content of 92.0 mol% was obtained at a rate of 17.5 kg/hr. σ (≦120°C)/σ ₀ =0.78, which was analyzed from the DSC curve of this product. The pigment dispersion rating for this product was 2.

Comparative Example 2 Dehydrated hexane 50/hr, solid catalyst of Example 1 2.2mM/hr,
Triethylaluminum was continuously supplied at 50mM/hr. Furthermore, ethylene, propylene, and hydrogen were continuously supplied, and the total pressure was 38 Kg/cm ² at a polymerization temperature of 180°C.
Continuous polymerization was carried out in hexane with an average residence time of 2.4 hours, and the polymer was extracted from the reactor and treated in the same manner as in Example 1.
15.2Kg/hr of ethylene-propylene copolymer wax with 0.916g/cm ³ and ethylene content of 95.8mol%
obtained at a rate of Despite the fact that σ (≦120° C.)/σ ₀ =1.0 was analyzed from the DSC curve of this product, and the average methylene chain length determined from ¹³ CNMR was 32, the pigment dispersion score was 1 to 2.

Comparative Example 3 Dehydrated hexane 100/hr, solid catalyst of Example 1 4.4mM/hr,
Ethylaluminum sesquichloride 60mM/
hr, diisoamyl ether 15mM/hr was continuously supplied. In addition, ethylene, propylene and hydrogen were continuously supplied, and the total pressure was 27.5Kg/at a polymerization temperature of 140℃.
cm ² , continuous polymerization in hexane average residence time of 1 hour,
It was extracted from the reactor and treated in the same manner as in Example 1.
Viscosity average molecular weight 4000 (intrinsic viscosity 0.23 dl/g), density
0.920g/cm ³ , 7.5Kg/hr of ethylene-propylene copolymer wax with ethylene content of 96.0mol%
obtained at a rate of Despite the fact that σ (≦120°C)/σ ₀ =1.0 as analyzed from the DSC curve of this product, the pigment dispersion score was 2.

Comparative Example 4 Dehydrated hexane 50/hr, solid catalyst of Example 1 2.5mM/hr,
Triethylaluminum was continuously supplied at 50mM/hr. In addition, ethylene, 4-methyl-1-pentene and hydrogen were continuously supplied, and the mixture was continuously polymerized at a polymerization temperature of 180°C with an average residence time of 2.4 hours in hexane, and then extracted from the reactor and treated in the same manner as in Example 1. , viscosity average molecular weight 6000 (intrinsic viscosity 0.31 dl/g), density
An ethylene-4-methyl-1-pentene copolymer wax having a weight of 0.920 g/cm ³ and an ethylene content of 93.0 mol% was obtained at a rate of 19.0 Kg/hr. σ (≦120℃) / σ ₀ = 0.82, DSC analyzed from the DSC curve of this product
The main peak is 120℃, the average methylene chain length determined from ¹³ CNMR is 72, and the pigment dispersion rating is 2~
It was 3.

[Brief explanation of drawings]

FIG. 1 is a drawing showing an example of an endothermic spectrum in a wax differential scanning calorimeter according to the present invention.

Claims (1)

[Scope of Claims] 1 The following (a) to (c) (a) A highly active titanium catalyst component activated with a magnesium compound (b) An organoaluminum compound having a halogen/Al (atomic ratio) of 1 to 2; c) In the presence of a catalyst formed from ether, ethylene and α-olefin having 4 to 10 carbon atoms in the coexistence of hydrogen,
Copolymerized at a temperature of 100 to 230°C, with an intrinsic viscosity of 0.06 measured in decalin at 135°C as shown below (A) to (F)
~0.6 dl/g, (B) Density 0.87 to 0.94 g/cm ³ , (C) 120°C or less of the endothermic spectrum with respect to the total area σ ₀ surrounded by the endothermic spectrum line and its baseline by differential scanning calorimeter The area σ surrounded by the endothermic spectrum line and its baseline
(≦120℃) Ratio σ (≦120℃) / σ ₀ is 0.82 or more, (D) Ethylene content 88 to 98 mol%, (E) Methylene chain in which the number of methylene chains in the polymer chain is 7 or more An ethylene copolymer wax of ethylene and a C ₄ to _{C 10} α-olefin has the following characteristics: the average number of methylene chains is 60 or less, and (F) the number of double bonds per 1000 carbon atoms is 0.7 or less. 1. A method for producing an ethylene copolymer wax, which comprises forming an ethylene copolymer wax. 2 (G) The difference between the average number of methylene chains in (E) and the number of methylene chains in a completely random copolymer having the same monomer composition as the ethylene copolymer wax is 30 or less. A method for producing an ethylene copolymer wax according to item 1. 3. The method for producing an ethylene copolymer wax according to claim 1, wherein the _C4 to _C10 α-olefin is a branched olefin. 4. (H) The method for producing an ethylene copolymer wax according to claim 1, which has a maximum melting point of 105° C. or higher as measured by a differential scanning calorimeter.