JPH0662810B2 - Polyolefin powder composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a polyolefin powder composition consisting essentially of two types of polyolefins having widely differing intrinsic viscosities.
More specifically, conventional techniques related to polyolefin powder compositions that have excellent uniform mixing properties and modification effects as modifiers for thermoplastic resins such as polyolefin resins Polyolefins such as polyethylene and polypropylene are lightweight, economical and have excellent melt moldability. Because of its excellent properties, it is easily molded by melt molding such as extrusion molding, blow molding, and injection molding, and is used for general purposes. However, among these polyolefins, ethylene-based polymers containing ethylene as a main component, especially ethylene-based polymers polymerized by a Ziegler-type polymerization catalyst have excellent melt moldability, but especially in the field of blow molding. Has a drawback that melt tension and melt elasticity are insufficient and, as a result, a draw-down phenomenon easily occurs during molding and a weld line is generated in a molded product, and improvements thereof are strongly demanded. Conventionally, attempts have been proposed to improve such physical properties of polyolefin. For example, a method for achieving the object by improving the catalyst and its composition or polymerization formulation during the production of polyolefin, a method for achieving the same object by incorporating a modifier, or a method for partially modifying the polyolefin. Attempts have been made to achieve the same purpose by crosslinking with.

However, each method has a drawback that it is complicated and the degree of improvement is small. Therefore, in spite of the above proposals, there has been a demand for a polyolefin having excellent melt tension and melt elasticity.

Among the polyolefins, polypropylene and poly-
Although 1-butene is excellent in melt moldability, it has a drawback that the molded product is inferior in impact resistance, particularly low temperature impact resistance, and improvement thereof is desired. As a method for improving impact resistance of polypropylene, poly-1-butene, etc., a method for achieving the object by improving the catalyst and its composition during polymerization and the polymerization formulation, different olefin components such as ethylene A method for achieving the same purpose by copolymerization, a method for incorporating various modifiers such as a rubbery polymer and a low crystalline olefin polymer, and the like have been proposed.

However, although impact resistance of polypropylene or polybutene is improved by any of these methods, there is a drawback that other mechanical properties such as creep characteristics are deteriorated. Therefore, in spite of the above proposal, there is a demand for a modifier capable of giving a composition excellent in impact resistance and mechanical properties for polypropylene and poly-1-butene.

Problems to be Solved by the Invention The present inventors have found that polyethylene, polypropylene, poly-
Recognizing that the physical properties of thermoplastic resins such as 1-butene have the above-mentioned drawbacks, respectively, and recognize that the conventional techniques relating to these modifications are in the above-mentioned situation, they are excellent in improving the properties of these polyolefins. As a result of earnest research on a modifier capable of exhibiting, a specific polyolefin powder composition consisting essentially of ultra-high molecular weight polyolefin and low-molecular weight or high-molecular weight polyolefin is used as a modifier for a thermoplastic resin such as the polyolefin. They have found that they are excellent and have reached the present invention.

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 to add an ethylene-based polymer containing ethylene as a main component such as polyethylene to
It is an object of the present invention to provide a polyolefin powder composition capable of forming an ethylene-based polymer composition which is excellent in uniform blending property without forming a fisheye and has excellent melt moldability such as melt tension and melt elasticity.

Still another object of the present invention is polypropylene, poly-1-
Providing a polyolefin powder composition capable of forming a thermoplastic resin having excellent uniform blending property, impact resistance, and other mechanical properties by being mixed with a thermoplastic resin such as butene To do.

Further objects and advantages of the present invention will be apparent from the following description.

Means and Actions for Solving Problems According to the present invention, the above objects and advantages of the present invention are as follows: (1) The intrinsic viscosity measured in decalin at 135 ° C. prepared by multistage polymerization is at least 15 dl / g. And a low molecular weight to high molecular weight polyolefin having an intrinsic viscosity in the range of 0.1 to 10 dl / g measured in decalin at 135 ° C. The ultrahigh molecular weight polyolefin is in the range of 10 to 95% by weight based on the total weight of the ultrahigh molecular weight polyolefin and the low to high molecular weight polyolefin, and (3) the polyolefin composition has an average particle shape. Diameter is in the range of 1-50 μm and at least 50% by weight
Is a powder having a particle size in the range of 0.5 to 60 μm, which is achieved by a polyolefin powder composition.

The ultrahigh molecular weight polyolefin referred to in the present invention has a viscosity of 135
At least the intrinsic viscosity [η] u measured in decalin at ℃
It is 15 dl / g. Intrinsic viscosity [η] u is 15 to 55
Ultra high molecular weight polyolefins in the dl / g range are preferred.

The other low molecular weight to high molecular weight polyolefin referred to in the present invention has an intrinsic viscosity [η] h measured in decalin at 135 ° C. in the range of 0.1 to 10 dl / g. Low molecular weight or high molecular weight polyolefin having an intrinsic viscosity [η] h in the range of 0.2 to 7 dl / g is preferable.

Polyolefin in the present invention, for example, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-1-pentene,
It is a homopolymer or copolymer of α-olefin such as 3-methyl-1-pentene. A homopolymer of ethylene or a copolymer composed of ethylene and another α-olefin and having ethylene as a main component is preferable.

When the above ultrahigh molecular weight polyolefin is an ultrahigh molecular weight polyethylene having [η] u of 15 dl / g, it has a viscosity average molecular weight of about 1.65 million. When the low molecular weight or high molecular weight polyolefin has a [η] h of 0.1 to 10 dl / g, it has a viscosity average molecular weight of about 1500 to about 950,000.

The quantitative ratio of the ultrahigh molecular weight polyolefin and the low molecular weight or high molecular weight polyolefin is a range in which the ultrahigh molecular weight polyolefin accounts for 10 to 95% by weight based on the total weight of both polyolefins, in other words, the low molecular weight or high molecular weight. Polyolefin is based on the total weight of both polyolefins
The range is 90 to 5% by weight. A preferred quantitative ratio is a range in which the ultrahigh molecular weight polyolefin accounts for 20 to 75% by weight based on the total weight of both polyolefins.

The polyolefin composition of the present invention consists essentially of ultra-high molecular weight polyolefin and low- to high-molecular weight polyolefin in the above quantitative ratios.

Powder compositions containing more than 95% by weight of ultra-high molecular weight polyolefin and less than 5% by weight of low- or high-molecular weight polyolefin have poor uniform dispersibility in a thermoplastic resin, and are particularly blended with an ethylene polymer. In this case, a molded product formed from the ethylene-based resin composition has a large amount of formation of fibers and the effects of improving melt moldability such as melt tension and melt elasticity are reduced. In addition, even when blended with polyolefin, such as polypropylene and poly-1-butene, or other engineering resins, the uniform dispersibility becomes inferior, and the molded products often have formation of fisheye, uneven dispersion, hair cracks, etc. The impact improvement effect is reduced. Further, in a powder composition containing less than 5% by weight of ultra-high molecular weight polyolefin and more than 95% by weight of low to high molecular weight polyolefin, when the polyolefin composition is blended with an ethylene-based polymer, the ethylene-based The effect of improving melt moldability such as melt tension and melt elasticity of the combined composition becomes small. Further, when such a polyolefin powder composition is blended with a polyolefin such as polypropylene or poly-1-butene, or another engineering resin, the effect of improving the impact resistance of the molded article becomes small.

The powder properties of the polyolefin powder composition of the present invention have an average particle size of 1 to 50 μm, preferably 2 to 40 μm, and a particle size distribution of 0.5 to 60 μm. Preferably 80 to 100
It is in the range of% by weight. Its bulk density is usually 0.1 to 0.5
It is in the range of g / cm ³ . The 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 thereof is usually substantially spherical, and spherical, lumpy sugar-like, grape tuft-like or the like.

In the polyolefin powder composition of the present invention, the ultrahigh molecular weight polyolefin and the low molecular weight to high molecular weight polyolefin may form separate powder particles which are physically distinguishable from each other, and the individual powder particles may form the ultrahigh molecular weight polyolefin. And a low molecular weight or high molecular weight polyolefin, but a polyolefin composition constituting the latter form is particularly preferable.

When each polyolefin has formed a separate powder particle, the powder particle of each polyolefin has an average particle size of preferably 1 to 50 μm, more preferably 2 to 40 μm.
powder having a particle size distribution of 0.5 to 60 μm, preferably 50% by weight or more, more preferably 80 to 100% by weight, and a bulk density of 0.1 to 0.5 g. It is in the range of / cm ³ . The shape is, for example, a shape substantially close to a sphere, such as a sphere, a sugary sugar-like shape, and a grape tuft shape.

The polyolefin powder composition of the present invention contains an antioxidant, a hydrogen halide absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, an antistatic agent, and a core in a range that does not impair its physical properties. If necessary, various additives such as agents and pigments can be blended. 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 method for preparing the polyolefin powder composition of the present invention by carrying out multi-step polymerization in the presence of a catalyst formed from a specific high activity solid titanium catalyst component and an organoaluminum compound catalyst component.

Employing the multi-step polymerization method described above, the powder properties of the polyolefin composition of the present invention can be easily controlled, and the obtained polyolefin powder composition has individual powder particles with ultra-high molecular weight polyolefin and low molecular weight or It is suitable because it forms a composition in which a high molecular weight polyolefin is closely dispersed, and is excellent in uniform dispersibility in a thermoplastic resin such as polyolefin. The multistage polymerization method will be described below. This multi-step polymerization method has the following 2
There are two methods, and either method can be adopted.

[1] A slurry of a polyolefin resin powder composition having different intrinsic viscosities, which is obtained by polymerizing olefin in a multi-step polymerization process of at least two stages or more under specific conditions in the presence of a specific Ziegler type catalyst, A method of performing high-speed shearing treatment.

[2] In the presence of a specific fine dispersion type Ziegler type catalyst obtained by further subjecting the specific catalyst to a high-speed shearing treatment, under a specific condition, at least two or more stages of multi-step polymerization process are performed to obtain olefin. It is also possible to directly obtain a polyolefin powder composition having different intrinsic viscosities by polymerizing. Further, if necessary, by subjecting the slurry of the polyolefin powder composition obtained by this method to a shearing treatment at a high speed, a polyolefin powder composition excellent in shape and properties can be obtained, which is preferable.

Next, these methods will be specifically described.

The specific Ziegler type catalysts used in the above methods [1] and [2] are basically catalysts of specific properties formed from a solid titanium catalyst component and an organoaluminum compound catalyst component. The solid titanium catalyst nodes constituting the catalyst used in the method [1] have a narrow particle size distribution and an average particle size of 0.1 to 3 μm.
It has been found that a highly active fine powdery catalyst component having several microspheres adhered may be used. The highly active fine powder titanium catalyst component having such properties is, for example, in the solid titanium catalyst component disclosed in JP-A-56-811, a magnesium compound in a liquid state and a titanium compound in a liquid state are brought into contact with each other to precipitate a solid product. It can be produced by strictly adjusting the deposition conditions during the process. For example, in the method disclosed in this publication, a hydrocarbon solution in which magnesium chloride and a higher alcohol are dissolved and titanium tetrachloride are mixed at a low temperature, and then the temperature is raised to about 50 to 100 ° C. to precipitate a solid product. When using magnesium chloride 1
A small amount of about 0.01 to 0.2 mol of monocarboxylic acid ester is allowed to coexist with the mol, and the precipitation is performed under a strong stirring condition. If necessary, it may be washed with titanium tetrachloride. Thus, 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% by weight of titanium, and has a halogen / titanium (atomic ratio) of about 5 to about 90,
The magnesium / titanium (atomic ratio) is in the range of about 4 to about 50.

The solid titanium catalyst component constituting the specific Ziegler-type polymerization catalyst used in the above method [2] has a narrow particle size distribution and an average particle size of usually 0.01 to 5 μm.
It has been found that microspheres preferably in the range 0.05 to 3μ may be used. The highly active powdery titanium catalyst component having such properties can be obtained by shearing the slurry of the solid titanium catalyst component prepared by the method [1] at high speed. As a method of the high-speed shearing treatment, specifically, for example, a method of treating a slurry of a solid titanium catalyst component in an inert gas atmosphere with a commercially available homomixer for an appropriate time is adopted. At this time, for the purpose of preventing the deterioration of the catalyst performance, a method of previously adding an organoaluminum compound in an equimolar amount with titanium can be adopted. Further, a method of filtering coarse slurry after treatment to remove coarse particles can also be adopted. By these methods, the highly active fine powdery titanium catalyst component having the fine particle size can be obtained.

The polyolefin powder composition of the present invention is a highly active fine powder titanium catalyst component and an organoaluminum compound catalyst component as described above, for example, triethylaluminum, trialkylaluminum such as triisobutylaluminum,
Diethylaluminum chloride, dialuminium chloride such as diisobutylaluminum chloride, alkylaluminum sesquichloride such as ethylaluminum sesquichloride, or a mixture thereof, if necessary, together with an electron donor, pentane, hexane, heptane, Slurry of a polyolefin powder composition having different intrinsic viscosities by thriller-polymerizing olefins in a hydrocarbon medium such as kerosene in a temperature range of 0 to 100 ° C. in a multi-step polymerization step of at least two stages. Can be manufactured.

In the multi-stage olefin polymerization step, a batch-type multi-step polymerization method in one polymerization tank, or a multi-step polymerization method in which at least two or more polymerization tanks are usually connected in series is adopted. For example, two-step polymerization method, three-step polymerization method, ...
·, N-stage polymerization method is adopted. It is necessary to produce a certain amount of ultra high molecular weight polyolefin in at least one polymerization tank of the multi-step polymerization process. The polymerization step for producing the ultrahigh molecular weight polyolefin may be a first-stage polymerization step, an intermediate polymerization step, or a final-stage polymerization step,
Although it is possible to use two or more stages, it is preferable to use the first stage polymerization step in terms of the polymerization treatment operation and the control of physical properties of the produced polyolefin. In the polymerization process, 10 to
By polymerizing 95% by weight, the intrinsic viscosity [η] u
It is necessary to produce an ultrahigh molecular weight polyolefin (value measured at 135 ° C in decalin solvent) of 15 dl / g or more.
By polymerizing 25 to 75% by weight, particularly 30 to 70% by weight, the intrinsic viscosity [η] u is 15 to 55 dl / g,
In particular, it is preferred to produce 20 to 50 dl / g of ultrahigh molecular weight polyolefin. In the polymerization step, the intrinsic viscosity [η] u of the ultrahigh molecular weight polyolefin produced is 15 dl
/ G or less than the range of 10 to 95% by weight of ultrahigh molecular weight polyolefin produced in the polymerization step, the effects of the above-mentioned polyolefin powder composition of the present invention cannot be achieved.

In the multi-step polymerization process, the high activity titanium catalyst component is used in the polymerization process for producing ultra high molecular weight polyolefin.
Polymerization is carried out in the presence of a catalyst comprising (A) and the organoaluminum compound catalyst component (B). The polymerization can be carried out by a gas phase polymerization method or a liquid phase slurry suspension polymerization method. In any case, in the polymerization step for producing ultra-high molecular weight polyolefin, the polymerization reaction is carried out in the presence of an inert medium, if necessary, and, for example, in the gas phase polymerization method, a dilution containing an inert medium is carried out as necessary. It is carried out in the presence of an agent, and in the liquid phase polymerization method, if necessary, it is carried out in the presence of a solvent consisting of an inert medium.

In the polymerization step for producing the ultra-high molecular weight polyolefin, the highly active titanium catalyst component (A) is used as a catalyst, for example, about 0.01 to about 200 mg atom, and particularly about 0.05 to about 100 mg atom, of titanium atom per medium 1. The aluminum compound catalyst component has an Al / Ti (atomic ratio) of about 0.01 to about 1000, particularly about 0.1 to about 500.
It is recommended to use it in such a ratio that The temperature of the polymerization process to form the ultra high molecular weight polyolefin is usually about −
The range is 20 to about 100 ° C, preferably about 5 to about 80 ° C, particularly preferably about 10 to about 60 ° C. Further, the pressure during the polymerization reaction is in the range of pressure capable of liquid phase polymerization or gas phase polymerization at the temperature, for example from atmospheric pressure to about 100 Kg
/ Cm ² , preferably from atmospheric pressure to about 50 kg / cm ² . The polymerization time in the polymerization step is such that the amount of the polymerized polyolefin produced is about 1000 g or more, preferably about 500 g per 1 mg atom of titanium in the highly active titanium catalyst component.
It may be set to be 0 g or more. Further, in the polymerization step, in order to produce the ultrahigh molecular weight polyolefin, it is preferable to carry out the polymerization reaction in the absence of hydrogen. Furthermore, after carrying out the polymerization reaction, the polymer may be isolated and stored once in an inert medium atmosphere.

Examples of the inert medium which can be used in the polymerization step for producing the ultra high molecular weight polyolefin include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane and kerosene; cyclopentane, cyclohexane, etc. Alicyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as diglorethane, methylene chloride and chlorobenzene; or mixtures thereof, but especially aliphatic hydrocarbons. Use of is preferred.

Further, in the method of the present invention, the polymerization reaction of the remaining olefin is carried out in the presence of hydrogen in a polymerization step other than the polymerization step for producing the ultrahigh molecular weight polyolefin. If the polymerization process for producing ultrahigh molecular weight polyolefin is the first-stage polymerization process, the second and subsequent polymerization processes correspond to the polymerization process. When the polymerization step is located after the ultra-high molecular weight polyolefin-forming polymerization step, the polymerization step is supplied with polyolefin containing the ultra-high molecular weight polyolefin, and the polymerization step is other than the ultra-high molecular weight polyolefin-forming polymerization step. When it is located after the polymerization step (1), the polyolefin produced in the previous step is supplied, and in any case, the polymerization is continuously carried out.
At that time, the raw material olefin and hydrogen are usually supplied to the polymerization step. When the polymerization step is the first step polymerization step, a catalyst comprising the highly active titanium catalyst component and the organoaluminum compound catalyst component is supplied, and when the polymerization step is the second or subsequent polymerization step. The catalyst contained in the polymerization product liquid produced in the previous step can be used as it is, or the high activity titanium catalyst component and / or the organoaluminum compound catalyst component can be additionally supplemented if necessary. I don't mind. The proportion of the raw material olefins polymerized in the polymerization step is 5 to 90% by weight, preferably 25 to 80% by weight, particularly preferably 30 to 70% by weight based on the total olefin components polymerized in the entire polymerization step.
It is in the range of% by weight.

The hydrogen supply rate in the polymerization steps other than the ultra-high molecular weight polyolefin-forming polymerization step is usually 0.01 to 50 moles, preferably 0.1 to 30 moles per 1 mole of olefin supplied to each polymerization step.

The concentration of each catalyst component in the polymerization product liquid in the polymerization tank in the polymerization step other than the ultra-high molecular weight polyolefin formation polymerization step is about 0.001 to about 0.1 in terms of titanium atom of the treated catalyst per polymerization volume. It is preferable to prepare it so that the amount of milligram atom is preferably about 0.005 to about 0.1 milligram atom and the Al / Ti (atomic ratio) of the polymerization system is about 1 to about 1000, preferably about 2 to about 500. Therefore, if necessary, an organoaluminum compound catalyst component can be additionally used. In the polymerization system, hydrogen, an electron donor,
Halogenated hydrocarbon and the like may coexist.

The polymerization temperature is a temperature range in which slurry polymerization and gas phase polymerization are possible, and about 50 ° C. or higher, more preferably about 60 to about 100.
The range of ° C is preferred. The polymerization pressure is, for example, from atmospheric pressure to about 100 kg / cm ² , particularly from atmospheric pressure to about 50 kg / c.
A range of m ² is recommended. The amount of polymer produced is about 5000 g per 1 mg of titanium atom in the titanium catalyst component.
It is preferable to set the polymerization time so that it is about 10,000 g or more.

Like the polymerization step other than the ultra-high molecular weight polyolefin formation polymerization, it can be carried out by a gas phase polymerization method, a liquid phase slurry suspension polymerization method, or of course, a different polymerization method at each polymerization step. It is also possible to adopt. Among the liquid phase polymerization methods, the slurry suspension polymerization method is preferably adopted. In any case, in the polymerization step, the polymerization reaction is usually carried out in the presence of an inert medium. For example, in the gas phase polymerization method, it is carried out in the presence of an inert medium diluent,
The liquid-phase slurry suspension polymerization method is carried out in the presence of an inert medium solvent. As the inert medium, the inert medium exemplified in the polymerization step for forming the ultra high molecular weight polyolefin can be similarly exemplified.

The [η] of the polyolefin powder composition obtained in the final polymerization step is usually 0.1 to 10 dl / g, preferably 0.2.
The polymerization reaction is carried out up to -7 dl / g, particularly preferably 0.3 to 5 dl / g.

The multi-stage polymerization method can be carried out by any of batch method, semi-continuous method and continuous method.

As the olefin to which the multi-step polymerization method can be applied,
Ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, 1-dodecene, 4-methyl-
Examples include α-olefins such as 1-pentene and 3-methyl-1-pentene, which can be applied to the production method of homopolymers of these α-olefins, and are composed of two or more kinds of mixed components. It can also be applied to a method for producing a copolymer. Major .ALPHA.-Olefins of Ultra-High Molecular Weight Polyolefins and Major .ALPHA.-of Polyolefins Other than Ultra-High Molecular Weight Polyolefins
The olefin may be different. Among these α-olefins, it is preferable to apply the method of the present invention to a process for producing ethylene or a copolymer of ethylene and other α-olefins and having an ethylene component as a main component. .

The polyolefin resin powder composition prepared by the above method is subjected to shearing treatment at high speed in the slurry state of the polyolefin powder obtained by the above method in the above method [1] or optionally in the method [2]. It is manufactured accordingly. Specific examples of the method of high-speed shearing treatment include a method of pulverizing using a commercially available homomic line mill or the like. For example, when pulverizing with a commercially available homomix line mill, etc., is used, the clearance of the stator is 0.2 mm, the slurry is continuously recycled for 1 hour, and the slurry is further fed to the next post-treatment step. The entire amount can be passed through the homomix line, and the shearing treatment can be efficiently performed. According to these methods, the slurry of the polyolefin powder is subjected to high-speed shearing treatment to obtain the polyolefin powder composition of the present invention.

The polyolefin powder composition of the present invention can be blended with various thermoplastic resins as a modifier thereof.

By blending the polyolefin powder composition of the present invention with an ethylene-based polymer containing ethylene as a main component such as polyethylene, it is possible to improve melt tension and melt elasticity during melt molding of the ethylene-based polymer, As a result, it becomes possible to suppress the drawdown phenomenon during melt molding, improve the swell ratio, and suppress the formation 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-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, etc. are copolymers with α-olefins having 3 to 20 carbon atoms. Examples thereof include ethylene-based copolymers containing ethylene as a main component. Part 135
The intrinsic viscosity [η] measured in decalin at ℃ is usually 0.5
To 20 dl / g.

The blending ratio when blending the polyolefin powder composition of the present invention with the ethylene polymer is 10
It is usually 0.5 to 20 parts by weight, preferably 1 to 0 parts by weight.
To 10 parts by weight. The ethylene-based polymer composition may include an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather stabilizer, if necessary.
Various additives such as an antistatic agent, a nucleating agent, a pigment and a filler can also be blended. The mixing ratio is appropriate. The ethylene polymer composition can be prepared according to a conventionally known method.

Further, by blending the polyolefin powder composition of the present invention with a crystalline olefin polymer other than the ethylene polymer, impact resistance of a molded product of the crystalline olefin polymer, particularly low temperature impact resistance. Can be improved. Specific examples of the crystalline olefin polymer other than the ethylene polymer include polypropylene, poly-1-butene, poly-4-methyl-1-pentene, poly-1-hexene, and propylene ethylene. Copolymer, propylene / 1-butene copolymer, 1-butene / ethylene copolymer, 1-
Α-olefin (a ₁ ) such as propylene, 1-butene, 1-hexene and ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, such as butene / propylene copolymer 1-octene, 1-decene, 1-
Dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene shall apply in to 20 α- olefin having 2 to carbon atoms, such as the α- olefin (a ₁₎ is different from the α- olefin (a ₂ ) And crystalline α-
Examples include olefin copolymers. The intrinsic viscosity [η] of the crystalline olefin polymer measured in decalin at 135 ° C. is usually in the range of 0.5 to 10 dl / g, and the crystallinity is 5% or more, preferably 20% or more.

The blending ratio when blending the polyolefin powder composition of the present invention into the crystalline α-olefin polymer is usually 0.5 to 20 parts by weight, preferably 100 parts by weight of the crystalline α-olefin polymer. Is in the range of 1 to 10 parts by weight. In the crystalline α-olefin polymer composition, if necessary, an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, Various additives such as pigments and fillers can also be blended. The crystalline α-olefin polymer composition can be prepared by a conventionally known method.

Furthermore, by blending the polyolefin powder composition of the present invention with various engineering resins, the physical properties of the engineering resin, such as impact resistance and sliding characteristics, can be improved. When the engineering resin is an engineering resin having a polar group, maleic acid, citraconic acid, and itaconic acid are added to the polyolefin powder composition of the present invention in order to improve the affinity or dispersibility to the engineering resin. It is preferable to use a modified polyolefin powder composition obtained by graft-copolymerizing an unsaturated carboxylic acid such as maleic anhydride, citraconic anhydride, itaconic anhydride, dimethyl maleate, dimethyl citraconate, or dimethyl itaconic acid, or a derivative component thereof. . The graft ratio of the unsaturated dicarboxylic acid or derivative component thereof is 100% by weight of the polyolefin powder composition 100.
It is usually in the range of 0.02 to 50 parts by weight with respect to parts by weight.
Specific examples of engineering resins include polyesters such as polyethylene terephthalate and polybutylene terephthalate, hexamethylene adipamide, octamethylene adipamide, decamethylene adipamide, dodecamethylene adipamide, polycaprolactone, and other polyamides, poly Examples thereof include polyarylene oxide such as phenylene oxide, polyacetal, ABS, AES and polycarbonate. The blending ratio of the polyolefin powder composition or its modified product is usually in the range of 0.2 to 20 parts by weight with respect to 100 parts by weight of the engineering resin. The engineering resin composition may include an antioxidant, a hydrochloric acid absorbent, an anticoagulant, a heat resistance stabilizer, an ultraviolet absorber, a lubricant, a weather resistance stabilizer, an antistatic agent, a nucleating agent, a pigment, a filler, etc., if necessary. Various additives can be blended.
The engineering resin composition can also be prepared according to a conventionally known method.

By blending the polyolefin powder composition of the present invention with various rubber-like polymers, the physical properties of the rubber-like polymer, such as chemical resistance and rigidity, can be improved. Specific examples of the rubber-like polymer include ethylene / propylene / non-conjugated diene copolymer, ethylene / 1-butene /
Examples thereof include non-conjugated diene copolymer, polybutadiene rubber, polyisoprene rubber, and styrene / butadiene / styrene block copolymer. The proportion of the polyolefin powder composition is usually in the range of 1 to 100 parts by weight based on 100 parts by weight of the rubber-like polymer. If necessary, various fillers such as a filler, a cross-linking agent, a cross-linking aid, a pigment and a stabilizer can be added to the rubber-like polymer composition. The rubbery polymer composition can be prepared according to a conventionally known method.

〔Example〕

Next, the polyolefin powder composition of the present invention will be specifically described with reference to examples. In the examples and comparative examples, the particle size distribution, average particle size and bulk density were measured by the following methods.

(1) Particle size distribution It was measured using Coulter Counter TAII type.

(2) Average particle size Same as above (3) Bulk density Measured according to JIS K6721-1966 (ASTM D1895-657).

(4) Angle of repose The angle of repose was measured using a powder tester (PT-E type) made by Horikawa Micron.

Example 1 <Preparation of solid titanium catalyst component> Anhydrous magnesium chloride 47.6 g (0.5 mol), decane 0.25
And 2-ethylhexyl alcohol 0.23 (1.5mol)
Was heated at 130 ° C. for 2 hours to give a homogeneous solution, and 7.4 ml (50 mmol) of ethyl benzoate was added. This homogeneous solution is added dropwise to 1.5 TiCl ₄ kept at −5 ° C. with stirring over 1 hour. The reactor used is glass 3
The stirring speed was set to 950 rpm in the separable flask. After the dropping, the temperature was raised to 90 ° C., and the reaction was carried out at 90 ° C. for 2 hours. After completion of the reaction, the solid part was collected by filtration and further sufficiently washed with hexane to obtain a highly active fine powdery titanium catalyst component. The catalyst component contained 3.8 WT% titanium atoms.

<Polymerization> n-Hexane 30, triethylaluminum (TEA) 30 mMol and fine particle titanium catalyst were converted into titanium atoms and 0.6 mg atom was added to a polymerization vessel having an internal volume of 53, and the temperature was raised to 35 ° C. After that, ethylene gas was introduced into the polymerization vessel at a rate of 1470 NL / Hr. Warm water was poured into the jacket of the polymerization vessel to keep the polymerization temperature at 40 ° C or lower. Polymerization pressure is 1-Kg /
It was cm ² G. When the cumulative amount of ethylene introduced reached 2400 NL, ethylene was fed cut and post-polymerization was carried out for 1 hour to obtain ultrahigh molecular weight polyethylene.

Subsequently, H ₂ was introduced into this polymerization vessel, and the pressure was increased to 13 kg / cm ² G. The temperature of the polymerization vessel was raised to 80 ° C., and ethylene gas was introduced at a rate of 1470 NL / Hr. Hot water was poured into the jacket of the polymerization vessel to keep the polymerization temperature at 80 ° C. Polymerization pressure is 13
It was about 16 Kg / cm ² G. The cumulative amount of ethylene introduced is 2400
When NL is reached, ethylene is fed cut and post-polymerization is performed.
After carrying out for 30 minutes, it was cooled and depressurized to obtain a slurry of the target polyethyne composition. The slurry was subjected to high-speed shearing treatment for 1 hour using a commercially available homomixer, then the solvent was separated, and vacuum drying was performed under an N ₂ atmosphere. The obtained polymer had a yield of 5990 g and a molecular weight of 15.0 dl / g as measured in decalin of 135, and its properties were an average particle size of 18μ and a particle size distribution of 0.1-60μ.
There was 81% during the period. The bulk density was 0.282 g / cm ³ and the angle of repose was 45 ° C. The molecular weight of the ultrahigh molecular weight polyethylene polymerized in the first step was 34.0 dl / g in intrinsic viscosity, and the ratio of the ultrahigh molecular weight polyethylene to the total weight was 50%. The polyethylene polymerized in the second stage had an intrinsic viscosity of 0.4 dl / g, and the amount was 50% of the whole. The polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2.

Example 2 n-Hexane 1800, triethylaluminum 1800 mMol and particulate titanium catalyst 15 mMol were placed in a polymerization vessel having an internal volume of 2750.
Then, ethylene gas was introduced into the polymerization vessel at a rate of 20 Nm ³ / Hr. Cooling water was flown through the jacket of the polymerization vessel to keep the polymerization temperature at 40 ° C or lower. Polymerization pressure is 1 ~ 3.2Kg / cm ²
It was G. When the cumulative amount of ethylene introduced reached 100 Nm ³ , ethylene was fed cut and post-polymerization was carried out to obtain ultrahigh molecular weight polyethylene. The polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2.

Once depressurized, H ₂ was introduced into the polymerization vessel to give a pressure of 2.5 kg / cm 2.
Pressurized to ³ G. The temperature of the polymerization vessel was raised to 65 ° C., and ethylene gas was introduced at a rate of 30 Nm ³ / Hr. Warm water was poured into the jacket of the polymerization vessel to keep the polymerization temperature at 65 ° C. The polymerization pressure was 2.5 to 4.1 kg / cm ³ G. The cumulative amount of ethylene
When 100Nm ³ is reached, ethylene is fed cut,
After carrying out post-polymerization, cooling and depressurization were carried out to obtain a slurry of the intended polyethylene composition. This slurry was subjected to high-speed shearing treatment for 2 hours using a commercially available homomic line mill, and then the solvent was separated and dried under reduced pressure in an N ₂ atmosphere. The obtained polymer was 246 Kg. The polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2.

Example 3 In Example 1, the introduction amount of ethylene introduced into the first stage polymerization reaction was 3600 Nl, and the introduction amount of ethylene introduced into the second stage polymerization reaction was 1200 Nl, and the polymerization conditions shown in Table 1 were adopted. Others were carried out similarly to Example 1, and obtained the polyethylene powder composition. The polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2.

Example 4 In Example 1, the introduction amount of ethylene introduced into the first stage polymerization reaction was 1200 Nl, and the introduction amount of ethylene introduced into the second stage polymerization reaction was 3600 Nl, and the polymerization conditions shown in Table 1 were adopted. Otherwise in the same manner as in Example 1 to obtain a polyethylene powder composition. The polymerization conditions are shown in Table 1, and the results obtained are shown in Table 2.
It was shown to.

Example 5 A polyethylene powder composition was obtained in the same manner as in Example 1 except that triisobutylaluminum (TIBA) was used in place of triethylaluminum and the polymerization conditions shown in Table 1 were adopted. The polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2.

Example 6 In Example 1, when the shearing treatment of the slurry was omitted, some of them aggregated with each other, and a powder having poor fluidity was obtained. The results are shown in Table 1.

Example 7 A polyethylene powder composition was obtained in the same manner as in Example 1, except that 1.0 mMol in terms of titanium atom was used as the ultrafine particulate titanium catalyst and the polymerization conditions shown in Table 1 were adopted. It was The polymerization conditions are shown in Table 1, and the results obtained are shown in Table 1.
It was shown to.

Comparative Example 1 In Example 1, the first stage polymerization temperature was set to 80 ° C.
A polyethylene powder composition was obtained in the same manner as in Example 1 except that the described polymerization conditions were adopted. The polymerization conditions are shown in Table 1, and the obtained results are shown in Table 2.

Comparative Example 2 A polyethylene composition was obtained in the same manner as in Example 1 except that the introduction amount of ethylene in the first stage was 240 Nl and the introduction amount of ethylene in the second stage was 4560 Nl. The results are shown in Table 1.

Comparative Example 3 In Example 1, the titanium catalyst has an average particle size of 8 to
The 10 μ was used for stacking. The results are shown in Table 1.

Evaluation Examples 1 to 10 and Evaluation Comparative Examples 1 to 5 The thermoplastic resin shown in Table 3 and the polyolefin powder composition were dry blended at a ratio shown in Table 3 using a Henschel mixer and kneaded with an extruder. I got a pellet. The physical properties of this thermoplastic resin composition are shown in Table 3.

Evaluation Examples 11 to 12 and Evaluation Comparative Example 6 The thermoplastic resin shown in Table 4 and the polyolefin powder composition were dry blended using a Henschel mixer, kneaded with an extruder to form pellets, and then pressed to obtain 10
A press sheet having a thickness of mm was prepared. The physical properties of this press sheet are shown in Table 4.

Claims (2)

[Claims] (1) 135 ° C. prepared by multistage polymerization
From ultra-high molecular weight polyolefins with an intrinsic viscosity of at least 15 dl / g as measured in decalin and low molecular weight or high molecular weight polyolefins with an intrinsic viscosity in the range of 0.1-10 dl / g as measured in decalin at 135 ° C. (2) The ultrahigh molecular weight polyolefin is substantially in the range of 10 to 95% by weight based on the total weight of the ultrahigh molecular weight polyolefin and the low to high molecular weight polyolefin. (3) The above polyolefin composition has an average particle size in the range of 1 to 50 μm and is at least 50% by weight.
Is a powder having a particle size in the range of 0.5 to 60 μm, a polyolefin powder composition. 2. (1) 135 ° C. prepared by multistage polymerization
From ultra-high molecular weight polyolefins with an intrinsic viscosity of at least 15 dl / g as measured in decalin and low molecular weight or high molecular weight polyolefins with an intrinsic viscosity in the range of 0.1-10 dl / g as measured in decalin at 135 ° C. (2) The ultrahigh molecular weight polyolefin is substantially in the range of 10 to 95% by weight based on the total weight of the ultrahigh molecular weight polyolefin and the low to high molecular weight polyolefin. (3) The above polyolefin composition has an average particle size in the range of 1 to 50 μm and is at least 50% by weight.
Is a powder having a particle size in the range of 0.5 to 60 μm. A modifier for thermoplastic resin, comprising a polyolefin powder composition.