JPS621736A - Polyolefin powder composition - Google Patents

Abstract

PURPOSE:A powder composition, consisting of an ultrahigh-molecular weight polyolefin and low-molecular weight - high-molecular weight polyolefin and capable of remarkably improving the impact resistance and dynamic physical properties by addition thereof as a modifier to a thermoplastic resin, etc. CONSTITUTION:A polyolefin powder composition consisting substantially of (A) an ultrahigh-molecular weight polyolefin having at least 15dl/g intrinsic viscosity measured in decalin at 135 deg.C and (B) a low-molecular weight - high- molecular weight polyolefin having within 0.1-10dl/g intrinsic viscosity range measured in decalin at 135 deg.C. The amount of the component (A) is within 10-95wt% range based on the total weight of the whole components and has 1-50mum average particle diameter and further contains at least 50wt% particles having within 0.5-60mum particle diameter range. The incorporation of the composition with an ethylenic polymer provides a composition having improved moldability without fish eye.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a polyolefin powder composition consisting essentially of two polyolefins having widely different intrinsic viscosities.

More specifically, it has excellent uniform blendability and modification effects as a modifier for thermoplastic resins such as polyolefin resins. r
f Conventional technology related to IJ olefin powder compositions Because it is light in weight, economical, and has excellent melt moldability compared to polyolefins such as polyethylene and polyzolopyrene, it can be easily processed by melt molding such as extrusion molding, blow molding, and injection molding. It is used for general purpose purposes.

However, among these polyolefins, ethylene polymers containing ethylene as a main component, especially polymerized using Ziegler-type polymerization catalysts, have excellent melt moldability, but they are difficult to use, especially in the field of blow molding. Melt tension and melt elasticity are insufficient, and as a result, drawdown phenomenon easily occurs during molding, and weld lines occur in molded products.Therefore, there is a strong desire to improve these problems.

Conventionally, attempts to improve such physical properties of polyolefins have been proposed. Attempts have been made to achieve the same objective by blending V'X, or by partially crosslinking p-lyolefin.

However, both methods have drawbacks in that they are complicated and the degree of improvement is small. Therefore, despite the above proposals, polyolefins with even better melt tension and melt elasticity are required.

Also, among polyolefins, polypropylene and poly-
1-Butene etc. have V's in melt moldability and are crushed, but
There is a drawback that the molded product has poor impact resistance, especially low-duty impact resistance, and there is a desire to improve this. As a method to improve the impact resistance of polypropylene, poly(1-butene), etc., the purpose is to be achieved by improving the catalyst during polymerization, its composition, and the polymerization recipe. A method of attempting to achieve the same objective by copolymerization, a method of blending various modifiers such as a rubber-like polymer or a low-crystalline olefin polymer, etc. have been proposed.

However, although any of these methods improves the In1 impact resistance of polyzolopyrene, polybutene, etc., there is a drawback that other mechanical properties such as cleaving properties deteriorate. Therefore, despite the above proposals, there is a need for a modifier that can provide compositions with excellent impact resistance and mechanical properties next to polypropylene and poly-1-butene.

Problems to be Solved by the Invention The present inventors have discovered that polyethylene, polyzolopyrene, poly-
Recognizing that the physical properties of thermoplastic resins such as 1-butene each have the drawbacks mentioned above, and that the conventional techniques for modifying these resins are subject to the said situation, we have developed an excellent method for improving the properties of these polyolefins. As a result of extensive research into modifiers that can exhibit these effects, a specific polyolefin powder composition consisting essentially of ultra-high molecular weight polyolefins and low-molecular weight to high-molecular weight polyolefins has been developed that can be used to modify thermoplastic resins such as polyolefins. Therefore, it is an object of the present invention to provide a polyolefin powder composition containing ultra-high molecular weight polyolefin.

Another object of the present invention is that by blending it with an ethylene polymer containing ethylene as the main component, such as H5-liethylene, it is possible to eliminate the formation of fish eyes and have excellent uniformity in blending, and to improve melt tension, melt elasticity, etc. An object of the present invention is to provide a polyolefin powder composition that can form an ethylene polymer composition with excellent melt moldability.

Yet another object of the present invention is polyzolopyrene, poly-1
- A polyolefin powder composition that can be blended with a thermoplastic resin such as butene to form a thermoplastic resin that also has excellent uniform blendability, excellent impact resistance, and other mechanical properties. It depends on providing.

Further objects and advantages of the present invention will become apparent from the description below.

According to the present invention, the above objects and advantages of the present invention F'5-) (1) The intrinsic viscosity measured in decalin at 135° C. is at least 1 sat/f. Ultra-high molecular weight polyolefin and 1
Intrinsic viscosity measured in decalin at 35℃ is α1~10d
(2) The super-polymer polyolefin consists essentially of a polyolefin with a low molecular weight to a high molecular value in the range of t/l;
) The VC is in the range of 10 to 95 weights and 18 L based on the total weight with the olefin, and (6) the average particle size is in the range of 1 to 50 μm, and at least 501 particles are in the range of α1 to 60 μm. This is achieved by a particularly characterized polyolefin powder composition consisting of U) powder having a particle size.

The ultra-high molecular weight polyolefin referred to in the present invention includes 13
The intrinsic viscosity [η]U measured in decalin at 5° C. is at least 1 saz/f. Intrinsic viscosity [η]. Ultra-high molecular weight polyolefins with vJU in the range 15 to 5 saz/f are advantageous.

The other low molecular weight to high molecular weight polyolefin U referred to in the present invention is one whose fc cardinal viscosity [η]h is in the range of 01 to 1 odz/f when measured in decalin at 135°C. Intrinsic viscosity [η] h ranges from [12 to vat/y V
C is preferably a low molecular weight to high molecular weight polyolefin.

The polyolefins used in the present invention include ethylene, fluoropylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-f-cene, 1-dodecene, 4-methyl-1-pentene, 5-methyl- It is a homopolymer or copolymer of alpha-olefin such as 1-pentene. Homopolymers of ethylene or copolymers of ethylene and other α-olefins, with ethylene as the main component, are preferred.

The above ultra-high molecular weight i-polyolefin has [η]8 of 15 dt/
1 ultra high polymer - 1 m polyethylene, about 16
It has a viscosity average molecular weight of 50,000.

Further, when the above-mentioned low molecular weight MfL or high molecular weight 1 polyethylene is polyethylene in which [η]h is α1 to 10 dt/f, K has a viscosity average molecular weight of about 1,500 to about 950,000.

The quantitative ratio of the ultra-high molecular weight polyolefin and the low-molecular weight to high-molecular weight polyolefin is such that the ultra-high molecular weight polyolefin is 10 to 9% of the total weight of both polyolefins.
In other words, the low molecular weight to high molecular value polyolefin accounts for 90 to 5 weight % of the total weight of both polyolefins. A preferred quantitative proportion is such that the ultra-high molecular weight olefin accounts for 20 to 75% by weight based on the total weight of both polyolefins.

The polyolefin composition of the present invention essentially consists of an ultra-high molecular weight polyolefin and a low to high molecular weight polyolefin in the quantitative proportions as described above.

If the powder composition contains more than 95 weight Sx% of ultra-high molecular weight polyolefin and less than 5 weight units of low molecular weight or high molecular weight polyolefin, the uniform dispersibility in thermoplastic resins will be poor, and it will be especially difficult to blend into ethylene polymers. Shi7'C
In such cases, molded articles formed from the ethylene resin composition will have many fish eyes and the like, and the effect of improving melt moldability such as melt tension and melt elasticity will be reduced. Also, fc can be blended with polyolefins such as polyzolopyrene, poly-1-butene, or other engineering resins.
In some cases, the uniform dispersibility becomes poor, and the molded product often has fine eyes, uneven dispersion, hair cracks, etc., and the effect of improving impact resistance becomes small. However, in a powder composition in which the amount of ultra-high molecular weight polyolefin is less than 51% and the amount of low or high molecular weight polyolefin is more than 95%, when the olefin powder composition is blended with an ethylene polymer, In this case, the effect of improving melt moldability such as melt tension and melt elasticity of the ethylene polymer composition becomes small. Furthermore, when such polyolefin powder M1 powder is blended with polyolefins such as polyzolopyrene, poly-1-butylene, or other engineering resins, the effect of improving the impact resistance of molded products becomes small.

The powder properties of the polyolefin powder composition of the present invention include an average particle size of 1 to 50 μm, preferably 2 to 40 μm.
The powder is in the range of C10 to 60 μm and the particle size distribution is usually 50% by weight or more, preferably 80 to 100% by weight. Its bulk density is usually in the range of α1 to α5P/cm". Its shape can be in various forms. For example, when the polyolefin composition of the present invention is produced by the multi-stage polymerization method described later, the shape It is usually substantially spherical in shape, such as reeds, balls, panicles, and clusters of grapes.

In the polyolefin powder composition of the present invention, the ultra-high molecular weight polyolefin and the low- or high-molecular weight polyolefin may each form physically distinguishable separate powder particles, and each powder particle may have an ultra-high molecular weight polyolefin. Although it may be composed of a polyolefin and a low-molecular weight or high-molecular weight polyolefin, a polyolefin composition constituting the latter form is particularly preferred.

When each polyolefin forms separate powder particles, each polyolefin powder particle preferably has an average particle size of 1 to 50 μm, more preferably 2 to 4 μm.
The particle size distribution is in the range of 0μm, and the particle size distribution is between 15 and 60μm.
Powder in the range of m is preferably 50% by weight or more, υ
It is preferably in the range of μ80 to 100% by weight, and its bulk density is preferably α1 to α5 f/cM
The shape is, for example, a substantially spherical shape, such as a spherical shape, a panicle shape, a grape cluster shape, etc.

The polyolefin powder composition of the present invention contains an antioxidant, a lawn hydrogen absorbent,
Various additives such as an anti-aggregation agent, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent, a nucleating agent, a pigment, etc. may be added as necessary. The mixing ratio is appropriate.

The following method can be exemplified as a method for preparing the polyolefin powder composition of the present invention.

[A] A method of simply blending the ultra-high molecular weight polyolefin powder (2) and the low molecular weight to high molecular weight polyolefin powder (b) in the above ratio, (B) a specific highly active solid titanium catalyst component and an organoaluminum compound catalyst component A method for preparing the polyolefin powder composition of the present invention by carrying out a multi-stage polymerization in the presence of a catalyst formed from.

Among these 288 methods, if the latter multi-step polymerization method is adopted, the powder properties of the 4 lyolefin composition of the present invention can be easily controlled, and the resulting polyolefin powder composition can be individually coated. The powder particles form a composition in which ultra-high molecular weight polyolefin and low-molecular weight to high-molecular weight polyolefin are closely dispersed, and are suitable because they have excellent uniform dispersibility in thermoplastic resins such as polyolefins. This multi-step polymerization method will be explained below. There are two methods for this multi-step polymerization method:
Either method can be adopted.

[1] A slurry of polyolefin powder compositions with different intrinsic viscosities obtained by polymerizing olefins in a multi-stage polymerization process of at least two or more stages under specific conditions in the presence of a specific Ziegler type catalyst is further added with vC. A method of applying high-speed shearing.

[2] Olefin is produced in a multi-stage polymerization process of at least two stages under specific conditions in the presence of a specific finely dispersed Ziegler type catalyst obtained by roughly subjecting the specific catalyst to a double-speed shearing treatment. Polyolefin powder compositions with different intrinsic viscosities can also be directly obtained by polymerization. Furthermore, if necessary, the polyolefin powder composition obtained by this method can be subjected to a shearing treatment using a slurry K Koren, which is suitable because a polyolefin powder composition having excellent shape and properties can be obtained.

Next, these methods will be specifically explained.

The specific Ziegler type catalysts used in the VC methods of [1] and [2] above are catalysts with specific properties that are basically formed from a solid titanium catalyst component and an organic aluminum compound catalyst component. bl. The solid titanium catalyst component constituting the catalyst used in the method described in [1] has a narrow particle size distribution and an average particle size of α1 to α3.
It has been found that it is sufficient to use a highly active finely powdered catalyst component in which several microspheres of approximately .mu.m are fixed together. A highly active finely powdered titanium catalyst component having such properties is, for example, a solid titanium catalyst component disclosed in JP-A-56-811, in which a liquid magnesium compound and a liquid titanium compound are brought into contact to completely precipitate a solid product. For example, in the method disclosed in the publication, a hydrocarbon solution in which magnesium chloride and a higher alcohol are dissolved and titanium tetrachloride are mixed at a low temperature. , then 50 to 100°C
When the solid product is precipitated by raising the temperature to a certain degree, a small amount of monocarboxylic acid ester of about α01 to α2 mol is allowed to coexist for 1 mol of VC1 magnesium chloride, and the precipitation is carried out under strong stirring conditions. be. Further, if necessary, it may be washed with titanium tetrachloride. In this way, a solid catalyst component having satisfactory activity and particle properties can be obtained. Such a catalyst component contains, for example, about 1 to about 6 titanium, an oc:y/temen (atomic ratio) of about 5 to about 90, and a magnesium/titanium (atomic ratio) of about 4 to about 50. within the range of

In addition, the solid titanium catalyst fraction constituting the specific Ziegler type polymerization catalyst used in the method [2] above has a narrow h particle size distribution, and the average particle size is usually α01 to 5μ.
, preferably using microspheres in the range of α05 to 5μ, the highly active powdered titanium catalyst component having such properties is added to the solid prepared by one method of [1] above. It is obtained by shearing a slurry of titanium catalyst components at high speed. As a method of high-speed shearing treatment, specifically, for example, a method of treating a slurry of solid titanium catalyst components in an inert gas atmosphere for an appropriate time using a commercially available homomixer is adopted. At this time, for the purpose of preventing deterioration of catalyst performance, it is also possible to adopt a method in which an organic aluminum compound is added in advance in an equimolar amount to titanium. Alternatively, a method may be adopted in which the treated slurry is filtered through a sieve to remove coarse particles. By these methods, the highly active fine powdered titanium catalyst component having the fine particle size can be obtained.

The polyolefin powder composition of the present invention comprises the above-mentioned highly active fine powdered titanium catalyst component and an organoaluminum compound catalyst component, such as trialkylaluminum such as triethylaluminum and triisobutylaluminum,
Soethylaluminum chloride 9 Soaluminum chloride such as soimptylaluminum chloride, alkylaluminum sesquichloride such as ethylaluminum sesquichloride, or a mixture thereof, and if necessary in combination with an electron donor, can be used to produce Polyolefin powders with different limiting viscosities are obtained by subjecting olefins to chiller polymerization in a multi-stage polymerization process of at least two or more stages in a hydrocarbon medium such as hexane, hegetane, or kerosene, usually at a temperature in the range of 0 to 100°C. A slurry of the composition can be made.

The multi-stage polymerization process of the olefin includes 1 (multi-stage polymerization method in a bunch type in 21 polymerization tanks, or a multi-stage method in which 11 or more polymerization tanks are usually connected in a row). A polymerization method is adopted, for example, a two-stage polymerization method, a 5 & 2 polymerization method 1006, or an n-stage polymerization method. It is necessary to produce a high molecular weight polyolefin.The polymerization step to produce the ultra-high molecular weight +lτl olefin may be a first stage polymerization step, an intermediate polymerization step, or a final stage polymerization step. The polymerization process may be carried out in two or more stages or in several stages of plugs, but a one-stage bacterial polymerization process is preferable from the viewpoint of polymerization processing operation and control of the physical properties of the polyolefin produced. In the polymerization step VC, by polymerizing 10 to 95% by weight of the 1,000 fluorine to be polymerized in the entire process, the intrinsic viscosity [η] (at 135° C. in decalin medium) is
It is necessary to produce an ultra-high molecular weight polyolefin with an f directivity (measured in
H, especially by polymerizing 30 to 70 times the limiting viscosity [η]. is 15 to 55 dt/f, and (lc20.? to 50 dl/f (7) In one polymerization step, it is preferable to produce an ultra-high molecular weight J-polyolefin, the intrinsic viscosity [η] of the ultra-high molecular weight polyolefin produced. Even if 1 is less than 15 dl/f, the ultra-high molecular weight polyolefin produced in the polymerization step is 10 to 9
If the amount is outside the range of 5% by weight, the above-mentioned effects of the polyolefin powder composition of the present invention cannot be achieved.

In the multi-stage polymerization step, in the polymerization step for producing an ultra-high molecular weight polyolefin, polymerization is carried out in the presence of a catalyst consisting of the highly active titanium catalyst acid fraction and the organoaluminum compound catalyst component (B). The polymerization can be carried out either by a gas phase polymerization method or by a liquid phase slurry suspension polymerization method. In either case, in the polymerization process to produce ultra-high molecular weight polyolefins, the polymerization reaction is optionally carried out in the presence of an inert medium; Hcz is carried out in the presence of a diluent, and the liquid phase polymerization process is carried out in the presence of a 1G medium consisting of an inert medium if necessary.

In the polymerization step for producing the ultra-high molecular weight polyolefin, the highly active titanium catalyst component (4) is used as a catalyst, for example, about 101 to about 200 milligram atoms, particularly about 1105 to about 100 milligram atoms, based on titanium atoms per medium 1. , the organoaluminum compound catalyst component, At
/Ti (atomic ratio) is preferably used in a ratio of about 101 to about 1000, particularly about 01 to about 500.
The temperature of the synthesis step is usually in the range of about -20 to about 100°C, preferably about 5 to about 80°C, particularly preferably about 10 to about 60°C. In addition, the pressure during the polymerization reaction is within a pressure range that allows liquid phase polymerization or gas phase polymerization at the above temperature, for example, from atmospheric pressure to about 100 f/cy+
”, preferably from atmospheric pressure to about 50 K4/cm
In addition, in the polymerization time in the polymerization process,
The amount of polymerized polyolefin produced is about 1000 r or more per milligram atom of titanium in the highly active titanium catalyst component,
Preferably, it should be set to about 5000 f or more. In addition, in the polymerization step, in order to produce the ultra-high molecular weight polyolefin, it is preferable to carry out the polymerization reaction in the absence of hydrogen, and further, after carrying out the polymerization reaction, the polymer is inactivated. Once isolated under a medium atmosphere,
It is also possible to save it.

Inert media that can be used in the polymerization process to produce the ultra-high molecular weight polyolefin include, for example, aliphatic hydrocarbons such as propane, butane, pentane, hexa/, heptane, octane, decane, kerosene; cyclopentane, Examples include alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloroethane, methylene chloride, and chlorobenzenate; and mixtures thereof; The use of hydrocarbons is preferred.

Furthermore, in the method of the present invention, in the polymerization steps other than the polymerization step for producing the ultra-high molecular weight polyolefin, the polymerization reaction of the remaining olefin is carried out in the presence of hydrogen. If the polymerization process for producing an ultra-high molecular weight polyolefin is the first stage polymerization process, then the second stage and subsequent polymerization processes correspond to the polymerization process. When the polymerization step is located after a polymerization step for producing an ultra-high molecular weight polyolefin, a polyolefin containing the ultra-high molecular weight polyolefin is supplied to the polymerization step, and the polymerization step is performed to produce an ultra-high molecular weight polyolefin. ! When located after a polymerization step other than the J-olefin production polymerization step, the polyolefin produced in the previous step is supplied, and in either case, polymerization is carried out continuously. At that time, the raw material olefin and hydrogen are usually supplied to the polymerization step. When the polymerization step is the first stage polymerization step, a catalyst consisting of the highly active titanium catalyst component and the organic heptaluminium compound catalyst component is supplied, and the polymerization step is the second stage or later polymerization step. In this case, the catalyst contained in the polymerization product liquid produced in the previous step can be used as is, or the highly active titanium catalyst component and/or the organoaluminum compound catalyst component can be additionally replenished as necessary. 5 to 90% of the total olefin components polymerized in the entire polymerization step may be added to the proportion of the raw olefin to be polymerized in the polymerization step.
It ranges preferably from 25 to 80% by weight, particularly preferably from 50 to 70% by weight.

The hydrogen supply ratio in the polymerization steps other than the ultra-high molecular weight polyolefin production polymerization step is usually 101 to 50% per mole of olefin supplied to each polymerization step.
mol, preferably α1 to 50 mol.

The concentration of each catalyst component in the polymerization product liquid in the polymerization tank in the polymerization process other than the ultra-high molecular weight polyolefin production polymerization process is about 100 to 100% per polymerization volume, and the catalyst after the above treatment is converted into titanium atoms. Approximately α1 milligram atom,
Preferably, it is about α005 to about α1 milligram atom, and the Al/T1 (atomic ratio) of the polymerization system is about 1 to about 100.
0, preferably about 2 to about 500. For this purpose, an organoaluminum compound catalyst component can be additionally used as needed.1 The polymerization system also has molecular weight, molecular weight distribution, etc. Hydrogen, an electron donor, a halodanized hydrocarbon, etc. may be present in order to adjust the temperature.

The polymerization temperature is within a temperature range that allows slurry polymerization and gas phase polymerization, and is about 50°C or higher, more preferably about 60 to about 1
A range of 00° C. is preferred, and the polymerization pressure is preferably in the range of, for example, atmospheric pressure to about 100°C/P+”, particularly atmospheric pressure to about 50 Kf/lar”. The amount of polymer produced is about 5,000 V or more, especially about 100,009 V per milligram atom of titanium in the titanium catalyst component.
It is preferable to set the polymerization time so that the above is achieved.

Like the polymerization steps other than the ultra-high molecular weight polyolefin production polymerization described above, it can be carried out by gas phase polymerization, or it can be carried out by liquid phase suspension polymerization. Among the liquid phase polymerization methods that can also be employed, a slurry suspension enrichment method is preferably employed.

In either case, the polymerization reaction is usually carried out in the presence of an inert medium. 7'C is carried out in the presence of an inert medium diluent in a gas phase polymerization process and in the presence of an inert medium solvent in a liquid phase slurry suspension polymerization process. Examples of the inert medium include those exemplified in the polymerization process for producing the ultra-high molecular weight polyolefin.

[η] of the polyolefin powder composition obtained in the final polymerization step is usually α1 to 10 dt/t%, preferably 12 to 7 dt/fl, particularly preferably α5
The polymerization reaction is carried out until Sat/y is reached.

The multi-step polymerization method can be carried out in a batch, semi-continuous or continuous manner.

The olefins to which the multi-step polymerization method can be applied include:
ethylene, propylene, 1-butene, 1-pentene, 1
Examples of α-olefins include hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene, and 5-methyl-1-pentene, and these α-olefins alone It can be applied to a method for producing a polymer, and it can also be applied to a method for producing a comonomer consisting of two or more mixed components. The main α-olefin of the ultra-high molecular polyolefin and the main α-olefin of the polyolefin other than the ultra-high polymer 'N polyolefin may be different.

Among these α-olefins, it is preferable to apply the method of the present invention to a method for producing ethylene-based polymers, which are ethylene or copolymers of ethylene and other α-olefins, and whose main component is ethylene. .

The polyolefin powder composition prepared by the above method is subjected to high-speed shearing treatment in the form of a slurry of the polyolefin powder obtained by the above method in the method [1] or, depending on the required VC, in the method [2]. Manufactured by 4. Specific pcrtx as a method of high-speed shearing treatment
All examples of pulverization methods using a commercially available homomincline mill or the like can be given. For example, when using a commercially available pulverizer such as Homomic 2I/Mill, the stator clearance is set to CL2m, the slurry is continuously processed for 1 hour while being recycled, and then when the slurry is sent to the next aftertreatment process, Is the entire slurry passed through a homomincline and subjected to shearing treatment? It can be done efficiently. By these methods, the polyolefin powder composition of the present invention can be obtained by subjecting the slurry of the polyolefin powder described above to high-speed cutting.

The polyolefin powder composition of the present invention has thermoplastic properties*
It can be added to J fat as a modifier.

By blending the polyolefin powder composition of the present invention with an ethylene polymer containing ethylene as a main component, such as polyethylene, it is possible to improve the melt tension and melt elasticity during melt molding of the ethylene polymer, As a result, it is possible to suppress the drawdown phenomenon during melt molding, improve the swell ratio, and suppress the occurrence of weld lines in the molded product. Ethylene polymers include high density polyethylene, medium density polyethylene, low density polyethylene, ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-intene, 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-
Examples include copolymers with α-olefins having 5 to 20 carbon atoms such as octadecene and 1-eicosene, and ethylene copolymers containing ethylene as a main component. The intrinsic viscosity [η] measured in decalin at 135° C. is usually in the range α5 to 20 dt/2.

When blending the polyolefin powder composition of the present invention with the ethylene polymer, the ethylene polymer 1
The amount is usually 115 to 20 parts by weight, preferably 121 to 10 parts by weight. The ethylene polymer composition (if necessary, an antioxidant, a hydrochloric acid absorbent, an anti-aggregation agent, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent, a nucleating agent, a pigment) Various additives such as fillers and fillers may also be blended.The blending ratio thereof is appropriate.The ethylene polymer 111M can be subjected to A'JI according to a conventionally known method.

-Also, by blending the uninvented polyolefin 7 with a crystalline olefin-based polymer other than the ethylene-based polymer, :J: It is important to improve the impact resistance of carvings, especially the impact resistance of low-walled surfaces. Specifically, the crystalline olefin polymer other than the ethylene polymer includes polypropylene, poly-1-guti/, z-4-methyl-1-pentene, poly-1-hexeno, and propylene.・Ethylene copolymer, propylene/1-butene copolymer, 1
-Butylene, 1-butene, 1-butylene, 1-butene, 1-butene, etc.
α-olefins (aS) such as hexene and etele/, propylene, 1-butene, 1-hexene, 4-methyl-1
- α-olefins having 2 to 20 carbon atoms, such as lindene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene; Self α-
α-olefin (,,) different from olefin (a,)
,! Examples include crystalline α-olefin copolymers consisting of: 1 of the crystalline olefin polymer! The intrinsic viscosity [η] determined at 91 in decalin at I5° C. is usually in the range of α5 to 1 odz/r, and the degree of crystallinity is 5% or more, preferably 120% or more.

When blending the polyolefin powder composition of the present invention with the crystalline α-olefin polymer, the blending ratio is usually 1 to 100 parts by weight of the crystalline α-olefin polymer.
It ranges from 115 to 20 parts by weight, preferably from 1 to 10 parts by weight. The crystalline α-olefin polymer composition may optionally contain an antioxidant, a hydrochloric acid absorber, an anti-aggregation agent, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent, and a nucleating agent. Various additives such as pigments, fillers, etc. can also be blended. The crystalline α-olefin polymer composition can be produced by a conventionally known method.

Furthermore, by blending the polyolefin powder composition of the present invention with various engineering resins, it is possible to improve the physical properties of the engineering resins, such as impact resistance and sliding properties.

When the engineering resin is an engineering resin having a polar group, maleic acid, citraconic acid,
Using a modified polyolefin powder composition obtained by graft copolymerizing an unsaturated cardanic acid or its derivative component such as itaconic acid, maleic anhydride, citraconic anhydride, itaconic anhydride, dimethyl maleate, dimethyl citraconate, and dimethyl itaconate. is preferable, and the grafting ratio of the unsaturated dicarpic acid or its derivative component C is usually (10 parts by weight) per 100 parts by weight of the polyolefin powder composition.
It ranges from 2 to 50 parts by weight. Specific examples of engineering resins include polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides such as hexamethylene upamide, octamethylene upamide) decamethylene 7, dodecamethylene upamide, polycaprolactone, and polyphenylene oxyto 9. Examples include polyarylene oxide, boria heptatal, ABS, AES, polycarbonate, etc. The blending ratio of the polyolefin powder composition or its modified product is usually in the range of 12 to 20 parts by weight per 100 parts by weight of the engineering resin.The engineering resin composition may optionally contain an antioxidant, Hydrochloric acid absorber, anti-agglomeration agent, heat stabilizer, ultraviolet absorber, lubricant, weather stabilizer, antistatic agent, nucleating agent, pigment,
Various additives such as fillers can be blended. The engineering resin composition can also be prepared according to conventionally known methods.

By blending the polyolefin powder composition of the present invention with various rubbery polymers, it is possible to improve the physical properties of the rubbery polymers, such as chemical resistance and rigidity. Specifically, the rubbery polymers include, for example, ethylene O propylene/non-conjugated tsene copolymer, ethylene/1-butene/non-conjugated tsene copolymer, polygetatsuene rubber, polyingrene rubber, styrene O-butatsuene/styrene. Examples include block copolymers. The blending ratio of the polyolefin powder composition is 100 parts by weight of the rubbery polymer (usually in the range of 1 to 100 parts by weight based on C).The rubbery polymer composition may optionally contain fillers and crosslinking agents. ,
Various fillers such as crosslinking aids, pigments, and stabilizers can be blended. The rubbery polymer composition can be prepared according to conventionally known methods.

〔Example〕

Next, the polyolefin powder composition of the present invention will be specifically explained using examples. In addition, in Examples and Comparative Examples, particle size distribution, average particle diameter, and bulk density were measured by the following methods.

(1) Particle size distribution It was measured using a Coulter counter TAU type.

(2) Average particle size Same as above (3) Bulk density JIS K6721-1966 (ASTMD1895-
657).

(4) Angle of repose Polykawamicron powder tester (PT-E type) and was measured by the angle of incidence method.

Example 1 <vI4g of solid titanium catalyst component> Anhydrous magnesium chloride 47.6 t (α5 mol),
Decane α251 and 2-ethylhexyl alcohol α
251 (1.5 mol) was heated at 150°C for 2 hours to form a homogeneous solution, and then mixed with benzoic acid ether 7.4Tr.
Add Lt (50 mmol). Add 50% of this homogeneous solution.
1.5 tons of TiCl4 kept at 0.degree. C. was poured under stirring for 1 hour. The reactor used was a glass 51 C. Serapul flask with a stirring speed of 950 rpm. After one drop, the temperature was raised to 90°C, and the reaction was carried out at 90°C for 2 hours.
After the reaction was completed, the solid portion was collected by filtration and thoroughly washed with hexane to obtain 1 highly active finely powdered titanium catalyst acid.

The catalyst component contained 58 WT% titanium atoms.

Kushige Kim> Into a polymerization vessel with an internal volume of 53 tons, 50 tons of n-hexane, 50 mmol of triethylaluminum (TEA), and 6 milligram atoms of cL (calculated as titanium atoms) of a particulate titanium catalyst were added, and the temperature was raised to 55°C. Gas was introduced into the polymerization vessel at a rate of 1470 NL/Hr. Hot water was flowed through the jacket of the polymerization vessel, and the polymerization temperature was set at 40°C.
I kept it below.

The polymerization pressure was 1-5 to 4/2G. When the cumulative amount of ethylene introduced reached 240 ONL, ethylene was fed and cut, and then 2 fL was added for 1 hour to obtain ultra-high molecular weight polyethylene.

Subsequently, H, was introduced into this polymerization vessel to produce 13F4/(-
The temperature of the 1st polymerization vessel pressurized to 1"G was set to 80°C, and hot water was flowed through the jacket of the 6th polymerization vessel into which ethylene gas was introduced at a rate of 147°N/Hr, and the polymerization temperature was increased to 80°C.
The polymerization pressure maintained at 15 to 16°C was 4/cya"G. When the cumulative value of ethylene introduction reached 240 ONL, the ethylene feed was cut and post-polymerization was carried out for 50 minutes, followed by cooling and desorption. By pressing, a slurry of the desired polyethine composition was obtained. After carrying out high-speed shearing treatment of this slurry for 1 hour using a commercially available homomixer,
The solvent was separated and drying was performed under reduced pressure under a nitrogen atmosphere. The resulting polymer had a molecular weight of 15990 f and a molecular weight of 135.
with an intrinsic viscosity of 1 sodl/l, measured in decalin of
In addition, the average particle diameter was 18 microns, and the particle size distribution was 81% between 11 and 60 microns. Also, the bulk density is −(
The angle of repose of L 282 f 7 cm" was 45°C. In addition, the molecular weight of the ultrahigh molecular weight 1N edene polymerized in the first stage was s4.udl/l in terms of intrinsic viscosity, and the ultrahigh molecular weight polyethylene was 5 in proportion to the weight of
I got 0%. The molecular weight of the polyethylene polymerized in the second stage was α4 d l/r in terms of intrinsic viscosity, and the amount was 50% of the total.1 The polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2. fc .

Example 2 Contents: 1800t of n-to-Φsan in a polymerization vessel of g2ysol,
) After adding 1800mMole of ethylaluminum and 15rnMole of particulate titanium catalyst, ethylene gas was introduced into the polymerization vessel at a rate of 2ONm3/Hr.1 Cooling water was poured into the jacket of the polymerization vessel to keep the polymerization temperature below 40°C. The polymerization pressure was 1 to 5 2b/Ql"G at 0 polymerization pressure maintained at The polymerization conditions were shown in Table 1, and the results obtained are shown in Table 2.

Once the pressure is released, the polymerization vessel is filled with H! 2.5K
The temperature of the polymerization reactor, which had been pressurized to 1 g/crm''Q, was raised to 65°C, and ethylene gas was introduced at a rate of 5ONm''/Hr. Hot water was poured into the jacket of the polymerization vessel to maintain the polymerization temperature at 65°C. 2.5-4.1Kf for polymerization pressure
/11G Dera fc, cumulative amount of ethylene is 1100
When the temperature reached N'', the ethylene feed was cut, and after post-polymerization, cooling and depressurization were performed to obtain a slurry of the desired polyethylene composition. Using a commercially available homomic line mill, this slurry was After high-speed shearing treatment for 2 hours three times, the solvent was separated and dried under reduced pressure under N28FM.The obtained if7'c polymer was 2461
0 polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2.
Shown below.

Example 5 In Example 1, the cumulative amount of ethylene introduced into the first stage polymerization reaction was 360 ONt, the amount of ethylene introduced into the second stage polymerization reaction was 9'xii120 ONt, and the polymerization conditions listed in Table 1 were adopted. Other than that, the same procedure as in Example 1 was carried out to obtain a polyethylene powder composition.

The polymerization conditions are shown in Table 1, and the results obtained are shown in Table 2.

Example 4 In Example 1, the cumulative amount of ethylene introduced into the first stage polymerization reaction was 120 ONt, the cumulative amount of ethylene introduced into the second stage polymerization reaction was 560 ONt, and the polymerization conditions listed in Table 1 were adopted. Other than that, the same procedure as in Example 1 was carried out, and Table 1 shows the results obtained from the 0M polyethylene powder composition, and Table 2 shows the obtained results.

Example 5 In Example 1, triisobutylaluminum (TIBA) was used instead of triethylaluminum,
The same procedure as in Example 1 was carried out except that the soft polymerization conditions listed in Table 1 were used to obtain a polyethylene powder husate. KI polymerization conditions
V? The results are shown in Table 2'Ic.

Example 6 In Example 1, when the shearing treatment of the slurry was omitted, some of the slurry coagulated with each other, resulting in a slurry with poor fluidity. The results are shown in Table 1+.

Example 7 In Example 1, using 1.0 mMol of ultrafine titanium catalyst d in terms of titanium atoms, the polymerization conditions listed in Table 1 were adopted, and in addition, the same procedure as in Example 1 was carried out, Polyethylene powder: The polymerization conditions for obtaining the m-acid are shown in Table 1, and the results obtained are shown in Table 1.

Comparative Example 1 In Example 1, the first stage polymerization temperature was 80°C, the polymerization conditions listed in Table 1 were adopted, and the holes and other conditions were the same as in Example 1, and a polyethylene powder composition was obtained under zero polymerization conditions. are shown in Table 1, and the obtained results are shown in Table 2.

Comparative Example 2 In the same manner as in Example 1, ethylene was introduced into the first stage 3.
! A polyethylene composition was obtained by introducing ethylene in an amount of 24"0 Nts and a calculated amount of 4 sbONt in the second stage. The results are shown in Table 1.

Comparative Example 5 In Example 1, the titanium catalyst had an average particle size of 8 to 8.
It was weighed using a 10 μm weight. The results are shown in Table 1.

Evaluation examples 1 to 10. Evaluation Comparative Examples 1 to 5 The thermoplastic resin shown in Table 3 and the d lyolefin powder composition were triblended using a Henschel mixer in the proportions shown in Table 3, and then kneaded with an extruder to obtain pellets. Table 5 shows the physical properties of this thermoplastic resin composition.

Evaluation examples 11-12. Evaluation Comparative Example 6 The thermoplastic resin shown in Table 4 and the 1F 1J olefin powder composition were tri-blended using a Henschel mixer, kneaded using an extruder, mixed, and then press-molded to a thickness of 10 m. A press sheet was created. Table 4 shows the physical properties of this press sheet.

Tewa V Kei 1 Seisho July 30, 1985 Mochishi 1 Office Commissioner Uga Hebe 1, Indication of the incident 1985 Patent Application No. 141320 2 Name of the invention Polyolefin 13) Kigumi acid compound 3, Person to be amended f1 - Which relationship Patent applicant name (588) Mitsui Oil (Higaku Kogyo Co., Ltd. 4, Agent 107 Telephone: 585-2256 5, Date of amendment order None 6, Target of amendment as per attached sheet) .

(1), on page 41 of the specification, in 1, in the blanks in the 5th line, 8th line, 9th line, 10th line, and 12th line from the top of the column for Example 4, respectively, r 1470 yo. , "80 yo," 13-1
6", r1470J, "13Jf: Join.

Claims (1)

[Claims] 1. (1) An ultra-high molecular weight polyolefin having an intrinsic viscosity of at least 15 dl/g as measured in decalin at 135°C and an intrinsic viscosity of 0.1 to 10 dt as measured in decalin at 135°C. (2) The ultra-high molecular weight polyolefin has a content of 10 to 95% based on the total weight of the ultra-high molecular weight polyolefin and the low molecular weight to high molecular weight polyolefin. % by weight, and (3) the average particle size is in the range from 1 to 50 μm, and at least 50% by weight has a particle size in the range from 0.5 to 60 μm. polyolefin powder composition. 2. (1) An ultra-high molecular weight polyolefin having an intrinsic viscosity of at least 15 dt/g as measured in decalin at 135°C and an intrinsic viscosity in the range of 0.1 to 10 dt/g as measured in decalin at 135°C. (2) The ultra-high molecular weight polyolefin is in the range of 10 to 95% by weight based on the total weight of the ultra-high molecular weight polyolefin and the low-molecular weight to high molecular weight polyolefin. , and (3) a polyolefin powder composition comprising a powder having an average particle size in the range of 1 to 50 μm and at least 50% by weight having a particle size in the range of 0.5 to 60 μm. A modifier for thermoplastic resins.