JPS6341512A - Production of polyethylene material having high strength and high modulus of elasticity - Google Patents

Abstract

PURPOSE:To obtain the titled material such as high-strength yarn having high modulus of elasticity, etc., simply and in reduced energy, by extruding under a specific condition in a solid phase ultra-high-molecular-weight polyethylene powder obtained by combining a specific catalyst with a specified polymerization method and drawing. CONSTITUTION:First, ethylene is polymerized by the use of a catalyst consisting of a solid catalytic component containing Mg, Ti and/or V and an organometallic compound at < the melting point of polyethylene, preferably 0-90 deg.C to give polyethylene powder having 5-50dl/g intrinsic viscosity at 135 deg.C in decalin. The the polyethylene powder is extruded in a solid phase at < the melting point and drawn to give the aimed material. The above- mentioned solid catalytic compound, for example, is obtained by supporting titanium chloride, etc., on a Mg-containing inorganic solid compound such as magnesium chloride, etc. Triethylaluminum, etc., are preferable as the organometallic compound.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention is directed to high strength and high modulus polyethylene MRA.
Or, regarding the method of producing films, etc., more specifically, ultra-polymers obtained by combining a specific catalyst and a specific polymerization method...High strength polymers such as fibers or films can be produced by stretching voriconidylene powder under specific conditions. The present invention relates to a method of manufacturing high modulus polyethylene material.

Problems to be solved by the conventional technology and the invention So-called ultra-high molecular weight polyethylene, which has an extremely high molecular weight of about 1 million or more, has characteristics such as excellent impact resistance and abrasion resistance, and also has self-lubricating properties]- As a linear plastic, it is used in a wide range of fields, including food machinery, civil engineering machinery, chemical machinery, agriculture, mining, sports and leisure fields, etc., as well as for making potsupah, silver, various gears, lining materials, and cedar egg lining.

Ultra-high molecular weight polyethylene has a significantly higher molecular weight than general-purpose polyethylene, so if it can be highly oriented, it may be possible to obtain a stretched product with unprecedented strength and elasticity. Various orientations have been studied. However, since ultra-high molecular weight polyethylene has an extremely high melt viscosity compared to general-purpose polyethylene, it is currently almost impossible to extrude it using normal methods, nor can it be highly oriented by stretching.

Paul Smith, Beater Yarn Lemstra, etc. made 1 from a decalin solution (dope) of ultra-high molecular weight polyethylene.
IJA with high strength and high elastic modulus is produced by stretching the qda gel to a high magnification.
A method for producing N (Japanese Unexamined Patent Publication No. 15408/1983) has been proposed. The polymer concentration in the dope is 3% by weight for a weight average molecular weight of 1.5 x 106, and 1% by weight for a weight average molecular weight of 4 x 10G, which is only an extremely low concentration.-CJ
However, in practical use, a large amount of solvent is used, and the preparation method and handling of a highly viscous solution are extremely disadvantageous in terms of economy.

In order to overcome the above-mentioned problems, various proposals have been made regarding methods for highly stretching and highly oriented ultra-high molecular weight polyethylene by methods such as extrusion, stretching or rolling below its melting point [JP-A-59] -187614, JP-A No. 60-15120, JP-A No. 60-97836, Proceedings of the Society of Polymer Science, p. 1148873 (1985), etc.1° However, in the conventionally known method, ultra-high molecular weight polyethylene is pre-coated with xylene, A dilute solution of a solvent such as decalin or kerosene is used, followed by cooling and isothermal crystallization to obtain a single crystal mat, which is then subjected to in-phase extrusion and stretching. The problem of having to use a large amount of solvent remains unsolved.

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have developed an ultra-high molecular weight polyethylene powder obtained by combining a specific catalyst and a specific polymerization method. The present invention was completed based on the discovery that fibers or films with high strength and high modulus of elasticity can be produced by drawing the polyester fibers or films in a solid state using a specific method.

In other words, the present invention provides a method for preparing ethylene in decalin at 135° C., which is obtained by combining ethylene at a temperature below the melting point of polyethylene with a catalyst consisting of a solid catalyst component containing at least Mg, Ti and/or V and an organometallic compound. polyethylene powder with an ultimate viscosity of 5 to 50 dl, /Q,
The present invention relates to a method for producing a high-strength, high-modulus polyethylene material, which comprises in-phase extrusion at a temperature below the melting point of the polyethylene powder, followed by stretching.

The present invention also relates to a method for producing a high-strength, high-modulus polyethylene material, which comprises compression-molding the polyethylene powder at a temperature below the melting point of the polyethylene powder, followed by rolling and stretching.

Effects of the Invention In the method of the present invention, high strength and high modulus of elasticity can be achieved by using the ultra-high molecular weight polyethylene powder obtained by the above-mentioned catalyst system in a solid state without dissolving or melting it in any way. This method proposes an excellent manufacturing method that is extremely simple, energy-saving, and can produce polyethylene materials such as fibers, films, and sheets.

In addition, the highly oriented polyethylene material obtained by the method of the present invention can be obtained by dissolving it in a solvent and stretching it as a gel, or a material obtained by heating and melting it to a temperature higher than the melting point of polyethylene and then stretching it. It is characterized by having strength and elastic modulus that are equivalent to or even superior to that of

The method of the present invention will be specifically explained below.

First, the intrinsic viscosity in decalin at 135° C. obtained by polymerizing ethylene at a temperature below the melting point of polyethylene using a catalyst consisting of a solid catalyst component containing at least M (1, Ti and/or V and an organometallic compound) A polyethylene powder with a hardness of 5 to 50 df/a is produced.The resulting polyethylene powder is then subjected to solid-phase extrusion and further stretched to obtain a high-strength, high-modulus polyethylene material.At this time, prior to solid-phase extrusion, Preferably, the polyethylene powder is compression-molded in advance at a temperature below its melting point.

In addition, by further stretching the polyethylene powder after rolling, -C can also preferably be used to obtain a high-strength, high-modulus polyethylene material. At this time, it is preferable that the polyethylene powder is compression-molded in advance at a temperature below its melting point prior to rolling.

The features of the present invention are polymerization and molding processes (compression molding,
Polyethylene must not be heated above its melting point during solid-phase extrusion or stretching, that is, it must never be melted or dissolved in a solvent. By doing so, a polyethylene material having excellent physical properties can be easily obtained.

The ultra-high molecular weight poly-L titanium used in the present invention is produced by slurry polymerization in an inert solvent using a specific catalyst or gas phase polymerization in the substantial absence of an inert solvent. Ultra-high molecular weight polyethylene suitable for the purpose of the present invention cannot be produced by high temperature polymerization methods in which polyethylene melts and dissolves.

The polymerization catalyst used at this time is at least Ma, T
It is composed of a solid catalyst component containing i and/or
0K (1/clN2.01 degree of polymerization is carried out at a temperature below the melting point of polyethylene, and is carried out at -20 to 110°C, preferably 0 to 90°C.

Although a polymerization solvent may or may not be used, an organic solvent inert to the Ziegler type catalyst is used as the solvent. Specifically, saturated hydrocarbons such as butane, pentane, hexane, heptane, octane, and cyclohexane, benzene,
Examples include aromatic hydrocarbons such as toluene and xylene, and high-boiling organic solvents such as decalin, tetralin, decane, and kerosene, depending on the necessity of molding the ultra-high molecular weight polyethylene obtained.

Further, the molecular weight of the obtained ultra-high molecular weight poly-[titanium] can be adjusted by changing the polymerization temperature, but hydrogen may be used as necessary.

The solid catalyst component used in the present invention is one in which a titanium compound is supported on an inorganic solid compound containing magnesium by a known method.

Inorganic solid compounds containing magnesium include metal magnesium, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium chloride, etc., and double salts and complex oxides containing magnesium atoms and metals selected from silicon, aluminum, and calcium. Carbonates, chlorides, or hydroxides, as well as these inorganic solid compounds, can be combined with organic oxygen-containing compounds such as water, alcohols, phenols, ketones, aldehydes, carboxylic acids, esters, polysiloxanes, acid amides, etc.; metal alkoxides. , inorganic oxygenated compounds such as metal oxyacids; thiols,
Organic sulfur-containing compounds such as thioethers, sulfur dioxide,
Inorganic sulfur-containing compounds such as sulfur trioxide and sulfur; benzene,
Monocyclic and polycyclic aromatic hydrocarbon compounds such as toluene, xyμne, anthracene, and phenanthrene; those treated or reacted with halogen-containing compounds such as chlorine, hydrogen chloride, metal chlorides, and organic halides. Guaru.

The titanium compounds supported on this inorganic solid compound include titanium halides, alkoxy halides,
These include alkoxides, halogenated oxides, etc., and tetravalent or trivalent titanium compounds are preferred. Specifically, the tetravalent titanium compound has the general formula % (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents a []gen atom). , r+1.to≦n≦4), titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytric [10ditane, dimethoxydichlorotitanium, 1-rimethoxymonochlorotitanium] are preferred. , tetramethoxytitanium, monoethoxytrichlorotitanium, dimethoxydichlorotitanium, triethoxymonochloro[]titanium, tetra-11hexytitanium, monoisoprop[]]hoxytrichlorotitaniumdiisoproboxydichloroditane, triisopropoxymonochlorotitanium, de 1-lysopoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichloro[1titanium, diphenoxydidic[][1titanium, trinoenoxymonochlorotitanium,
Examples include tetravalent titanium compounds such as tetraphenoxy titanium. In addition, trivalent titanium compounds include titanium tetrachloride, titanium tetrabromide, and other titanium oxides that are reduced with hydrogen, aluminum, titanium, or organometallic compounds of metals from groups 1 to 2 of the periodic table. The resulting trivalent titanium compound has the general formula % (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 2 carbon atoms, X represents a halogen atom, and m represents 0<m< A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide, which is 4), with an organometallic compound of a metal of groups ① to ② of the periodic table can be mentioned. Among these titanium compounds, tetravalent titanium compounds are particularly preferred. In addition, vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, Axyvanadium trichloride, orthoalkyl vanade-1
Examples include trivalent vanadium compounds such as ~ and trivalent babdium compounds such as vanadium trichloride. Specific solid catalyst components are disclosed in Japanese Patent Publication No. 5'L-3514, Japanese Patent Publication No. 550-23864, Japanese Patent Publication No. 51-1983.
No. 152, Japanese Patent Publication No. 52-15111, Japanese Patent Application Publication No. 49-106581, Japanese Patent Publication No. 11710-1980, Japanese Patent Publication No. 51-153, Japanese Patent Application Publication No. 1987-959
Examples include those specifically exemplified in Publication No. 09 and the like.

Further, as other solid catalyst components, for example, reaction products of Grignard compounds and titanium compounds can also be used, and are disclosed in Japanese Patent Publication Nos. 50-39470 and 1983. -12953
@Publication, Japanese Patent Publication No. 5112954, Japanese Patent Application Publication No. 57-7
Examples include those specifically described in Publication No. 9009, etc.
In addition, JP-A-56-47407, JP-A-57
A solid catalyst component in which an inorganic oxide is used together with an optionally used organic carboxylic acid ester described in Japanese Patent No. 187305, Jikai [1n58-21405, etc.] can also be used.

The organoaluminum compound of the present invention has the general formula % (where R represents an alkyl group, aryl group, or aralkyl group having 1 to 20 carbon atoms, and X represents a halogen atom,
R may be the same or different. ) Preferred are compounds represented by the following, including triJ delaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diethylaluminum ethoxide, ethylaluminum sesquichloride, and mixtures thereof.

There is no particular restriction on the usage period of the organoaluminum compound, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound.

Using the above catalyst system, the ultra-high molecular weight polyethylene powder of the present invention is synthesized.

The ultra-high molecular weight polyethylene powder thus obtained has a melting point (main peak temperature) determined by differential scanning calorimetry (DSC, heating rate of 5°C/+nin), preferably 138°C or higher, more preferably 138°C or higher, without any particular heat treatment. is 139
It is desirable that the temperature is at least 140°C, most preferably at least 140°C. It is important to use such ultra-high molecular weight polyethylene as it is; once heated and melted, the effects of the present invention cannot be obtained.

The ultra-high molecular weight polyethylene powder is then solid phase extruded, preferably compression molded beforehand. The method at this time is not particularly limited, but when solid phase extrusion is performed, the polyethylene powder is put into a cylinder of a solid phase extrusion device and compressed at a temperature below the melting point to form a rond-shaped polyethylene molded product.

The pressure at this time can be selected widely, but it is usually 10MP.
a ~2GPa, preferably 20~500Mpa is desirable. Further, when solid-phase coextrusion is performed in combination with a resin other than the polyethylene of the present invention, a sheet-like polyethylene molded product with a thickness of 1 mm to 2 mm is formed by pressing at a temperature below melting point. The pressure at this time is preferably in the same range as described above.

Furthermore, for the compression molding method for forming into a film or sheet prior to rolling, various known methods can be used as appropriate, but for example, the above-mentioned pressing method can be preferably adopted. .

Then, the obtained 1=compression molded product is subjected to solid phase extrusion. As a solid phase extrusion method, for example, the above-mentioned ultra-high molecular weight polyethylene powder or compression molded product thereof is placed in a cylinder of a solid phase extrusion device equipped with a die at the bottom, 20-130°C, preferably 90-120°C and a pressure of 0.01-0. An example is a method of pre-pressing with IGPa and then extruding at a temperature lα of 20° C. or higher and lower than the melting point, preferably 90° C. or higher and lower than the melting point. The stretching ratio (extrusion ratio) varies depending on the molecular weight of the polymer, the type of catalyst used, the compounding conditions, etc., but can be arbitrarily selected by changing the die diameter, and is usually 2 to 100 times, preferably 3 to 50 times. , more preferably at a magnification of 3 to 25 times.

Examples of the tensile stretching performed subsequent to solid-phase extrusion include leek 1 stretching and roll stretching, but among these, nip stretching is more preferred.

The temperature during tensile stretching is 20 to 150°C, preferably 2
It is carried out at 0-130°C.

The tensile speed varies depending on the molecular weight and composition ratio of the polymer, but is 1 to 100 mm/min, preferably 5 to 50 mm.
7 mrn.

The higher the stretching ratio, the higher the strength and the higher the modulus of elasticity. Therefore, it is desirable to increase the stretching ratio as much as possible.
It is possible to stretch twice as much.

By the above stretching method, a fiber or film having a tensile modulus of 120 GPa or more and an L1 strength of 2 GPa or more can be obtained.

Further, as a rolling method, a known method can be used, but a rolled sheet or film is obtained by holding the polyethylene described in the present invention in the same phase state without melting it and pressing it with rolling rolls having different circumferential speeds. .

At this time, the deformation ratio of the material due to the rolling operation can be selected from a wide range, and is usually 1.2 to 30 in terms of rolling efficiency (length after rolling/length before rolling), preferably 1.5 to 20. It is desirable to do so. At this time, the temperature is preferably 20° C. or higher]-lower than the melting point, preferably 90° C. or higher, and the rolling operation is desirably carried out without swirling. Of course, the above rolling operation may be carried out in multiple stages at least once.

The tensile stretching carried out after rolling is carried out in the same manner and under the same conditions as the tensile stretching carried out subsequent to solid phase extrusion.

That is, the temperature during tension stretching is 20 to 150°C, preferably 20 to 130°C.

The tensile speed varies depending on the molecular weight and composition ratio of the polymer, but is 1 to 100 mm/min, preferably 5 to 5 Q mm.
/min.

The higher the stretching ratio, the higher the strength and the higher the elasticity ratio. Therefore, it is desirable to increase the stretching ratio as much as possible.
0 times stretching is possible.

By the above stretching method, #A fibers or films having a tensile modulus of 120 GPa or more and a strength of 2 GPa or more can be obtained.

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited thereto.

EXAMPLES Example 1 (a) Preparation of solid catalyst components Internal volume 400111 containing 25] stainless steel balls having a diameter of 1/2 inch! Commercially available anhydrous magnesium chloride 100 in a stainless steel pot.
Then, 4.3 g of aluminum triethoxide was added thereto, and ball milling was performed at room temperature for 5 hours under a nitrogen atmosphere. Thereafter, 2.7 g of titanium tetrachloride was added, and ball milling was performed for an additional 16 hours.

Solid catalyst component 1 obtained after ball milling! ] is 40
It contained mQ of titanium.

(b) Polymerization A stainless steel A-trirep with an induction stirrer at 2°C was replaced with nitrogen, and 1000 m of hexane was used! .

1 mmol of triethylaluminum and 10 mg of the solid catalyst component were added thereto, and the mixture was heated to 70° C. with stirring. The vapor pressure of hexane is 1°6Kg/cfl1.
2.Gauge pressure (hereinafter expressed as Kg/clI2・G)
However, when the total pressure of ethylene is 10K (1/ClI2・G
Polymerization was started by straining the mixture until it reached . Total pressure is OK!
-[Tyrene was continuously introduced so that the ratio was +/cm2·G, and polymerization was carried out for 20 minutes. After the polymerization was completed, the polymer slurry was transferred to a beaker, and the polymer was removed under reduced pressure to obtain white polyethylene 72(+).

The ultimate stone [η] in decalin at 135°C is 15,
It was 2 dl,/Q. In addition, the temperature was measured at 5°C/
The melting point (main peak temperature) measured at a heating rate of min was 141.0°C.

(C) A die with an inner diameter of 0.46 cm and a thickness of 1 cm was attached to a capillary rheometer (cylinder inner diameter 0.9525 cm) manufactured by Solid Phase Extrusion and Tensile Stretching Instrument 1. Approximately 50 were filled. After compression for 10 minutes at 120℃ and 0.02GPa pressure, 0.24cm/min at 130℃
It was extruded at a constant speed. The deformation ratio (stretching ratio) is expressed as the ratio of the cross-sectional area of the cylinder to the cross-sectional area of the die, and in this case was 4 times.

The obtained extrudate was tested at 120°C using a tensile tester with a constant temperature bath.
Stretching was carried out at a crosshead speed of 40 mm/min at a temperature of 25 times.

The elastic modulus and strength of the obtained stretched product were measured according to conventional methods. The results are shown in Table 1.

Comparative Example 1 When carrying out the solid phase extrusion and tensile stretching of Example 1 (C) using the ultra-high molecular weight polyethylene obtained in Example 1 (b), the solid phase extrusion temperature was changed to that of the polyethylene powder. A pressed product was obtained under the same conditions as in Example 1(C) except that the temperature was 200° C., which was higher than the melting point.

The obtained extrudate was subjected to tensile stretching under the same conditions as in Example 1(c), but it could only be stretched twice, and the elastic modulus and strength were lower than those shown in Table 1. Therefore, it was not possible to create a high-modulus, high-strength polyethylene material.

Example 2 Ultra-high molecular weight poly 1 obtained in Example 1(b). Solid-phase extrusion and tensile stretching of Example 1(c) using Dilene were carried out under the same conditions as Example 1(c) except that a die with an inner diameter of 0.28 cm and a length of 1C1ll was used. An extrudate with a deformation ratio of 12 times was obtained.

When the obtained extrudate was subjected to tensile stretching under the same conditions as in Example 1(c), it was possible to stretch it 8 times. The elastic modulus and strength of the stretched product are shown in Table 1.

Example 3 (a) Preparation of solid catalyst component In Example 1 (a), aluminum triethoxide 4
．． 2.2g of aluminum triethoxide instead of 3g
A Method C catalyst was prepared in the same manner as in Example 1(a) except that 3.2 g of silicon tetra J1-oxide was used. 1 g of the obtained solid catalyst component contained 32 m (l) of titanium.

(b) Polymerization Using the same autoclave as in Example 1 <b), hexane 1000 m, i! 1 to 1 mmol of riconithylaluminium and 10 mole of the solid catalyst component were added, and the mixture was heated to 60° C. with stirring.

The vapor pressure of hexane was 1.5 KO/c-.G, but ethylene was charged until the total pressure reached 10 kg/cII2#G to start polymerization. Ethylene was continuously introduced so that the total pressure was 10 Ko/cn12·G, and polymerization was carried out for 30 minutes. After the polymerization was completed, the polymer slurry was transferred to a beaker, and hexane was removed under reduced pressure to obtain white polyethylene 75o. The intrinsic viscosity [η] in decalin at 135°C is 1
8.9 tJ! , /a.

(C) Solid-state extrusion and tensile stretching This polymer was subjected to solid-state extrusion (130
℃, deformation ratio 4 times) and then tensile stretching at 120° C., it was possible to stretch 22 times. Table 1 shows the elastic modulus and strength of the stretched product.

Chemical Comparative Example 2 In performing the solid-phase extrusion and tensile stretching of Example 3(c) using the ultra-high molecular weight polyethylene obtained in Example 3(b), the in-phase extrusion temperature was set to be higher than the melting point of the polyethylene powder. Extrudates were obtained under similar conditions to Example 3(c), except that 200'C'c was carried out.

The obtained extrudate was subjected to tensile stretching under the same conditions as in Example 3(c), but the stretching was only 1.5 times, and the elastic modulus and strength were only low as shown in Table 1. Therefore, it was not possible to create a high-modulus, high-strength polyethylene material.

Example 4 A die with an inner diameter of 0.340 m and a length of 1 cm was used to perform the solid phase extrusion and tensile stretching of Example 1 (c) using the ultra-high molecular weight polyethylene obtained in Example 3 (b). The extrusion was carried out under the same conditions as in Example 1(c) except for , and an extrudate with a deformation ratio of 8 times was obtained.

When the obtained extrudate was subjected to tensile stretching under the same strip ft as in Example 1(c), it was possible to stretch it 10 times.

Table 1 shows the elastic modulus and strength of the stretched product.

Example 5 The ultra-high molecular weight polyethylene obtained in Example 1(b) was
Pressed at 25℃ and 0.02GPa to a thickness of 0.2mm.
A film was produced. This film was rotated at 130°C in opposite directions at different circumferential speeds.
The film was supplied between a pair of rolling rolls with a diameter of 0 mm and a surface length of 500 mm and rolled to obtain a film with a rolling efficiency of 6 times. The obtained rolled film 11 was heated to 120°C using a constant temperature bath and a tensile tester.
, stretching was carried out at a blackhead speed of 4Qmm/1n,
Stretching of 20 times was possible. Table 1 shows the elastic modulus and strength of the stretched product.

A rolled film was obtained in the same manner as in Example 5, except that the temperature of the rolling roll was 200°C, which is higher than the melting point of the polyethylene. was subjected to tensile stretching under the same conditions as in Example 5, but 1
．． It could only be stretched 3 times, and the elastic modulus and strength were only low values as shown in Table 1, and a high elastic modulus/high strength polyethylene material could not be obtained.

Example 6 (a) Preparation of solid catalyst component In Example 1 (a), 0.5 (l) of VO (OC2Hs) and 2.0 (] of titanium tetrachloride were used instead of 2.7 g of titanium tetrachloride. Example 1 (a) except for
) The catalyst was produced in a similar manner.

1 g of the obtained solid catalyst component contained 7.6 mo of vanadium and 30.6 mo of titanium.

(b) Polymerization Using the same autoclave as in Example 1(b), 1000 m of hexane! , triethyl-24 = 1 mmol of aluminum and 10 mg of the solid catalyst component
was added and heated to 60°C while stirring.

The vapor pressure of hexane (J) is 1.5 K (1/cm2・G, but polymerization was started by pumping ethylene until the total pressure reached 10 K(]/c−・G.The total pressure was 10 K(] /clI2
・Ethylene was continuously introduced so that G was obtained, and polymerization was carried out for 30 minutes. After polymerization, the polymer slurry was transferred to a beaker, hexane was removed under reduced pressure, and white polyethylene 60
(+ was obtained. Intrinsic viscosity in decalin at 135°C [
η] was 14.2 rlelo.

(C) Rolling and tensile stretching This polymer was rolled according to Example 5 (130°C, rolling efficiency 4 times) and then tensile stretched at 120°C, and it was possible to stretch 25 times. . Table 1 shows the elastic modulus and strength of the stretched product.

Table--1 Procedural amendment November 17th, 1985 Method for manufacturing polyethylene abrasive 3. Person who makes corrections Relationship to the incident: Patent applicant Name (444) Nippon Oil Co., Ltd. 4, Agent 8. Contents of amendment

Claims (1)

[Scope of Claims] [1] A catalyst comprising a solid catalyst component containing at least Mg, Ti and/or V and an organometallic compound,
The intrinsic viscosity in decalin at 135°C obtained by polymerizing ethylene at a temperature below the melting point of polyethylene is 5-5.
A method for producing a high-strength, high-modulus polyethylene material, comprising solid-phase extrusion of 50 dl/g polyethylene powder at a temperature below the melting point of the polyethylene powder, and then stretching. [2] The method for producing a high-strength, high-modulus polyethylene material according to claim 1, which comprises performing compression molding at a temperature below the melting point prior to solid-phase extrusion. [3] With a catalyst consisting of a solid catalyst component containing at least Mg, Ti and/or V and an organometallic compound,
The intrinsic viscosity in decalin at 135°C obtained by polymerizing ethylene at a temperature below the melting point of polyethylene is 5-5.
A method for producing a high-strength, high-modulus polyethylene material, which comprises compression molding 50 dl/g of polyethylene powder at a temperature below the melting point of the polyethylene powder, followed by rolling and stretching.