WO2011005279A1

WO2011005279A1 - Method for producing high strength polyethylene fiber and high strength polyethylene fiber

Info

Publication number: WO2011005279A1
Application number: PCT/US2009/067074
Authority: WO
Inventors: Nobuyuki Taniguchi; Yasuo Ohta; Benjamin Chu; Benjamin S. Hsiao
Original assignee: Toyo Boseki Kabushiki Kaisha; The Research Foundation Of State University Of New York
Priority date: 2009-07-08
Filing date: 2009-12-08
Publication date: 2011-01-13

Abstract

The present invention provides a method for producing a high strength polyethylene fiber superior in stretchability and having a higher strength, a higher elastic modulus and high productivity, and a high strength polyethylene fiber produced by the method. The method includes (1) dispersing a chemically surface modified carbon nanofiber in a solvent for an ultrahigh molecular weight polyethylene, (2) preparing a mixed dope comprising the polyethylene, the modified carbon nanofiber and the solvent by mixing the polyethylene with the suspension obtained in (1), wherein the concentration of the polyethylene is not less than 0.5 wt% and less than 50 wt%, and (3) extruding the dope obtained in step (2) through a spinneret, cooling the dope, and then stretching the dope into a filament yarn at a deformation rate of not less than 0.005 s^-1 and not more than 0.5 s^-1.

Description

DESCRIPTION

METHOD FOR PRODUCING HIGH STRENGTH POLYETHYLENE FIBER AND HIGH STRENGTH POLYETHYLENE FIBER CROSS-REFERENCE TO THE RELATED APPLICATION

This .application claims the benefit of International patent application no. PCT/US2009/049879 filed July 8, 2009, the contents of which are incorporated in full herein by this reference.

TECHNICAL FIELD

[0001]

The present invention relates to a method for producing a high strength polyethylene fiber superior in stretchability and having a higher strength, a higher elastic modulus and high productivity, and a high strength polyethylene fiber produced by the method.

BACKGROUND ART

[0002]

Conventionally, many attempts have been made to achieve an organic fiber having high strength and high elastic modulus, and a technique for achieving high strength and high elastic modulus of a fiber is widely known, which comprises stretching a resin made of flexible molecules having a high molecular weight at a higher draw ratio. As a representative spinning method relating to such technique, what is called a "gel spinning method" using polyethylene having an ultrahigh

molecular weight as a starting material and enabling

ultradrawing by using a solvent is known and has already been widely used industrially (e.g., see patent reference 1, patent reference 2) .

[0003]

In recent years, a high strength polyethylene fiber is used not only for the above-mentioned application but also in a wide field, and more uniformity and higher strength/higher elastic modulus are strongly demanded to meet the properties requested for the fiber.

[0004]

As a means for satisfying these wide-ranged requests, a ^■ method using carbon nanotube (hereinafter to be referred to as CNT) as a composite has been proposed recently. As known well, in CNT, carbons having a 6-membered ring structure (graphite surface) form a cylindrical structure. Its diameter is about 0.5 nm. - about 100 nm, and the length is not less than about 50 nm. It has an extremely^' high aspect ratio, .and markedly high dynamic strength due to the constituted 6-membered ring structure. Such superior properties of CNT is highly promising as a filler for polymer matrix, and many studies have so far been made thereon (e.g., see patent reference 3).

[00053

However, as conflicting problems, carbon nanotube has high, surface crystallinity, and the intermolecular attractive force (to be sometimes referred to as π-π interaction) between nanotubes is extremely high. As a result, the dispersibility in polymer matrix is poor and, when formed into a composite, the properties do not show sufficiently. In addition, its higher cost than conventional fillers poses a major problem in industrialization.

[0006]

A carbon material having a similar form as carbon nanotube is carbon nanofiber (hereinafter to be referred to as CNF) . CNF is a fiber-like carbon material having a diameter of generally several 100 nm - 1 μm, and a length of several μm - several 100 μm. It has a greater diameter than CNT, and the inside thereof is constituted with a substantially crystalline carbon. While CNF has somewhat lower as compared to CNT, its dynamic properties are strikingly high as compared to

conventional polymer materials, and CNF is a material

comparable to CNT in terms of the properties of a filler. In addition, CNF shows smaller attractive intermolecular

interaction between CKFs since it has a greater diameter than CNT, and is advantageously superior in the dispersibility.

[0007]

The superiority of CNF is easiness of surface

modification by chemical reaction as compared to CNT.

Generally, the surface of CNT has high crystallinity,. which is the factor of the superior dynamic properties characteristic of CNT. On the other hand, high crystallinity means

inferiority in the chemical reactivity of the surface.

In contrast, the structure of CNF comprises the inside having high crystallinity, but the surface is covered with noncrystalline carbon (amorphous carbon) . Since the noncrystalline carbon has a weaker binding force between carbon atoms as compared to crystalline carbon, it is considered susceptible to chemical reaction. The property indicates that CNF, when chemically modifying the surface, permits easy chemical modification as compared to CNT.

[0008],

An attempt to improve the dynamic properties of a material by chemically modifying the surface of CNF utilizing such property of CNF, and making a composite with

polypropylene and ultrahigh molecular weight polyethylene has been reported. However, no specific report relating to the application to a high strength polyethylene fiber is present, and specific, appropriate conditions and the like are unknown.

SUMMARY OF THE INVENTION

[0009]

The present inventors have conducted intensive studies and succeeded in providing a novel method for producing a high strength polyethylene fiber capable of affording a high draw ratio not obtainable by a conventional gel spinning method, by making a composite of CNF (m-CNF) having a chemically-modified surface arid optimizing the conditions therefor, as well as a high strength polyethylene fiber produced by such method, which resulted in the completion of the present invention.

[0010]

Accordingly, the present invention provides the following constitutions.

fl] A method for producing a high strength polyethylene fiber, comprising the steps of:

(1) dispersing a chemically surface modified carbon nanofiber ■ in a solvent for an ultrahigh molecular weight polyethylene, (2) preparing a mixed dope comprising the polyethylene, the modified carbon nanofiber and the solvent by mixing the polyethylene with the suspension obtained in step (1), wherein the concentration of the polyethylene is not less than 0.5 wt% and less than 50 wt%,

(3) extruding the dope obtained in step (2) through a

spinneret, cooling the dope, and then stretching the dope into a filament yarn at a deformation rate of not less than 0.005 s^" ¹ and not more than 0.5 s^"1.

[2] The method of [1], further comprising a step of preparing the surface modified carbon nanofibers comprising:

(4) generating a carboxylic group on a carbon nanofiber by oxidation of the carbon nanofiber,

^' (5) generating an alkyl chain on the carbon nanofiber by- reaction of an alkyl chain having amine as an end group with the carboxylic group of (4) .

[3] The method of [1], wherein the surface modified carbon nanofiber is modified with an alkyl chain and the ultrahigh molecular weight polyethylene has an intrinsic viscosity of 5 dL/g to 40 dL/g.

[4] The method of [3], wherein the content of the carbon nanofiber is 0.05 wt% to 10 wt% of the fiber.

[5] The method of [3] , wherein the weight fraction of the alkyl chain in the modified carbon nanofiber is 8% to 20%.

[6] The method of [3], wherein the alkyl chain in the modified carbon nanofiber is a linear alkyl chain having 8 or more carbon atoms.

[7] The method of [6], wherein the alkyl chain is an octadecyl chain having 18 carbon atoms.

[8] A high strength polyethylene fiber produced by the method of [I].

[9] A high strength polyethylene fiber produced by the method of [2].

[10] A high strength polyethylene fiber produced by the method of [3].

[11] A high strength polyethylene fiber produced by the method of [4].

[12] A high strength polyethylene fiber produced by the method of [5] .

[13] A high strength polyethylene fiber produced by the method of [6].

[14] A high strength polyethylene fiber produced by the method of [7].

[0011]

According to the present invention, a high draw ratio can be achieved by merely adding a trace amount of a surface- modified carbon nanofiber and, as a result, a high strength polyethylene fiber having a superior strength elastic modulus not obtainable by a conventional gel spinning technique can be advantageously provided.

[0012]

In addition, by the conventional gel spinning technique, broken threads occur, most in a multiple-stage stretching step, thus decreasing the productivity. However, since the

polyethylene fiber of the present invention increases the limit draw ratio at which the broken threads are developed, the incidence of broken thread can be decreased while

maintaining the conventional strength and elastic modulus, and

^■a polyethylene fiber having high productivity can be

advantageously provided. BRIEF DESCRIPTION OF DRAWINGS

[0013]

Fig. 1 is a schematic phase diagram of polyethylene near the melting point .

[0014]

Fig. 2 shows alkyl chain fraction dependency of hexagonal crystal fraction in fiber under stretch.

DETAILED DESCRIPTION OF THE INVENTION

[0015]

The present invention is described in detail in the following. As for the method of obtaining the fiber of the present invention, a novel method is necessary and, for • example, the following method is recommended, though the method is not limited thereto.

[0016]

First, the production method of a carbon nanofiber (m- CNF) having a surface chemically modified by alkyl chain is explained.

[0017]

The carbon nanofiber (CNF) in the present invention is, as mentioned above, a fiber-like carbon material, having a diameter of 100 nm - 1 μm, and a length of several μm - several 100 μra. It has a greater diameter as compared to CNT, and the inside is constituted with substantially crystalline carbon.

[0018]

Then, the chemical modification to be applied to CNF is explained. When an alkyl chain is introduced into the surface of CNF by chemical modification, the affinity for a spinning solvent and a polyethylene matrix increases to facilitate dispersing. Besides these, since the affinity for polyethylene increases, when the fiber is formed, stress transmission efficiency from polyethylene (the fiber inside)^' to CNF becomes high. Thus, chemical modification is important.

[0019] The first step of chemical modification is introduction of an acidic functional group such as carboxyl group (-COOH), hydroxyl group and the like into the surface of CNF using a strong acid. While the strong acid used for introduction of an acidic functional group is not particularly limited, for example, potassium chlorate, potassium perchlorate,

hydrochloric acid, sulfuric acid, nitric acid, and a mixture thereof can be mentioned. The necessary temperature for acid treatment is 0 - 100⁰C, preferably 30 - 7O⁰C;

[0020]

The time necessary for the acid treatment is particularly important since it affects, as mentioned below, the ratio of alkyl chain produced in the second step of the chemical

modification of the surface relative to the whole amount of surface-modified CNF (m-CNF) , and strongly affects the

stretchability of the fiber. The reason therefore is that acidic functional group introduced into the surface by acid treatment reacts with the molecule used in the second step of the chemical modification, whereby the alkyl chain is

introduced into the surface of CNF. The time necessary for the acid treatment is 10 min - 48 hr, preferably, 30 min - 24 hr. When the time of acid treatment is prolonged, a greater number of alkyl chains can be introduced later, but when the time of acid treatment is prolonged too much, CNF is unpreferably decomposed. Since the amount of surface area of CNF is limited, and the number of reaction sites is also limited, an acid treatment for a long time is meaningless .

[0021]

Then, as the second step of chemical modification, a step wherein an alkyl chain is introduced into CNF (hereinafter, oxidized CNF) , into which the acidic functional group has been introduced by the aforementioned acid treatment, to produce CNF having an alkyl chain introduced into the surface (m-CNF) is explained. The reagent for introducing an alkyl chain into oxidized CNF is not particularly limited as long as it can be bonded to an acidic functional group (carboxyl group, hydroxyl group and the like) . Examples thereof include alkyl chain having a chemical structure containing amine at the terminal (octylamine, decylamine, dodecylamine, hexadecylamine, octadecylamine, alkyl chain containing amine at the terminal etc.}- The structure of the alkyl chain is not particularly limited, and it may be branched.

[0022]

The reaction is performed by dispersing the oxidized CNF in the aforementioned reagent. At this time, a small amount of a solvent {e.g., dimethyl sulfoxide) may be concurrently used to disperse oxidized CNF.

[0023]

The reaction of the oxidized CNF with the aforementioned reagent is performed at 100⁰C - 300⁰C, preferably 150⁰C - 250⁰C, more preferably 170 - 200⁰C. In addition, the reaction can be carried out in an inert gas such as nitrogen and argon. The reaction time is 12 - 30 hr, preferably 15 - 25 hr.

[0024]

After the completion of the reaction, the reaction mixture is filtered, and the reaction product is washed with a wash solvent . The wash solvent is not particularly limited, and preferably, appropriately selected and used according to the reagent. For example, organic solvents such as

tetrahydrofuran, ethanol, chloroform, hexane and the like, or a mixture thereof can be mentioned. Then by vacuum drying (50 - 90⁰C) and removal of the residual solvent, m-CNF, wherein the surface is modified by alkyl chain, can be obtained.

[0025]

The amount of the alkyl chain modifying the surface of CNF can be measured by thermogravimetric analysis (TGA) . When the atmospheric gas is the air, a weight decrease is observed at a temperature (about 600⁰C) of decomposition of the original CNF and a weight decrease accompanying decomposition of alkyl chain is observed at 200 - 400⁰C depending on the kind of the alkyl chain used for modification. For example, when octadecyl chain is used as an alkyl chain, a weight decrease of

octadecyl chain occurs at about 370⁰C.

[0026]

The content of alkyl chain in the m-CNF is particularly important since it greatly influences the stretchability of the fiber in the present invention. Preferably, the weight fraction is 8 - 20%, more preferably 10 - 20%. When the content of the alkyl chain is less than 8%, the stress

transmission efficiency from polyethylene inside the fiber to CNF decreases during formation and stretching of the fiber, since the affinity between polyethylene and CNF becomes small. On the other hand, when the content of the alkyl chain exceeds 20%, the stress transmission efficiency is not improved, since the surface area of CNF is limited.

[0027]

Now, polyethylene, which is the starting material used in the present invention, is explained.

[0028]

For production of the fiber, high molecular weight polyethylene to be the starting material needs to have an intrinsic viscosity [η] of not less than 5 dL/g, preferably not less than 8 dL/g, more preferably not less than 10 dL/g. When the intrinsic viscosity is less than 5 dL/g, a desired high strength fiber having a strength exceeding 20 cN/dtex cannot be obtained. The upper limit needs to be not more than 40 dL/g, preferably not more than 35 dL/g, more preferably not more than 30 dL/g, still more preferably not more than 25 dL/g. When the intrinsic viscosity is too high, the proσessability is degraded to often make it difficult to produce a fiber.

[0029]

The ultrahigh molecular weight polyethylene in the present invention is characterized in that its repeat unit is substantially ethylene, and may be a copolymer with a small amount of other monomer, for example, α-olefin, acrylic acid and a derivative thereof, methacrylic acid and a derivative thereof, vinylsilane and a derivative thereof, and the like, or a copolymer of these copolymers, or a copolymer with an ethylene horαopolymer, or further, a blend with other

homopolymer such as α-olefin and the like. Particularly, it is more preferable to contain short chain or long chain branch to a certain extent by the use of a copolymer of α-olefin such as propylene, butene-1 and the like, since it stabilizes

production of the fiber, particularly yarn making by spinning and stretching. However, when the content of components other than ethylene increases too much, it prevents stretching. Thus, from the aspects of production of a fiber having high strength" high, elastic modulus, the monomer unit is desirably not more than 0.2 mol%, preferably not more than 0.1 mol%. Needless to say, it may be a homopolymer of ethylene alone.

[0030]

An ultrahigh molecular weight polyethylene and surface- modified CNF (m-CNF) can be mixed by a known method. To be specific, a solution mixing method wherein m-CNF is dispersed in a solvent of an ultrahigh molecular weight polyethylene to give an m-CNF dispersion, which is mixed with a solution of the ultrahigh molecular weight polyethylene, a method wherein an ultrahigh molecular weight polyethylene is mixed with a dispersion of m-CNF, a method wherein ultrahigh molecular weight polyethylene and m-CNF are mixed in a twin screw

kneader, and the like can be used. To facilitate dispersion of m-CNF in the finally-obtained fiber, a method using a

dispersion of m-CNF is preferable.

[0031]

. While the method of dispersing m-CNF in a solvent of polyethylene is not particularly limited, ultrasonication affords a dispersion wherein the m-CNF is uniformly dispersed therein. For ultrasonication, a commercially available

ultrasonic washing machine and an ultrasonication dispersion machine can be used. [ 0032]

For the subsequent step for affording a composite with an ultrahigh molecular weight polyethylene, mixing of a

polyethylene solution with the above-mentioned surface CNF dispersion, or a method including directly feeding

polyethylene into an m-CNF dispersion and stirring the mixture can be employed. In the present invention, the latter method including directly feeding polyethylene into an m-CNF

dispersion and stirring the mixture is preferable. When a powder of ultrahigh molecular weight polyethylene is fed into an m-CNF dispersion and the mixture is stirred with heating, a fog-like precipitate of a polyethylene and m-CNF composite is produced in the liquid at around 100⁰C, and the solvent and the composite are separated once. Further stirring with heating results in dissolution of the fog-like composite in the

solvent to give a gel for spinning.

[0033]

In contrast, in the method including mixing a

polyethylene solution and the above-mentioned surface CNF dispersion, the resulting gel has a low polyethylene

concentration and the production efficiency is not good.

[0034]

The amount of m-CNF (B) relative to ultrahigh molecular weight polyethylene resin (A) in a weight ratio is

(A) : (B}=90:10 - 99.95:0.05, preferably (A) : <B)=95:5 - 99.9:0.1, more preferably (A) : (B}=99.5:0.5 - 99.9:0.1. When the content of the m-CNF is small, the stretchability improving effect is low. Conversely, too high a content of m-CNF is not preferable, since undispersed m-CNF acts as a foreign substance to induce broken thread during spinning and/or stretching, and degrades the stretchability and fiber properties .

[0035]

In the production method recommended in the present invention, a volatile organic solvent such as decalin and/or tetralin and the like is preferably used as a solvent for dissolving the above-mentioned ultrahigh molecular weight polyethylene. Use of a solvent which is solid at ambient temperature or a non-volatile solvent markedly degrades the productivity during spinning. A volatile solvent evaporates somewhat in an early stage of spinning from the surface of a gel yarn after delivery from the spinneret. It is

inconclusively assumed that a cooling effect produced by the evaporative latent heat due to the evaporation of the solvent at that time stabilizes the spinning state. The concentration is preferably not more than 30 wt%, preferably not more than 20 wt%, more preferably not more than 15 wt%. It is necessary to select an optimal concentration according to the intrinsic viscosity [η] of ultrahigh molecular weight polyethylene, the starting material. Furthermore, it is preferable to set, in spinning step, the spinneret temperature to not less than 30⁰C plus the melting point of polyethylene and not more than the boiling point of the solvent used. In the temperature range near the melting point of polyethylene, the viscosity of polymer becomes too high, and the polymer cannot be taken up rapidly. In addition, at a temperature not less than the boiling temperature of the solvent used, since the solvent boils immediately after delivery from the spinneret, broken thread is frequently developed unpreferably immediately below the spinneret.

[0036]

The obtained unstretched yarn is further heated, and stretched several folds while removing the solvent or, where necessary, stretched for multiple stages, whereby the

aforementioned high strength polyethylene fiber having superior stretchability can be produced. At this time, the deformation rate of the fiber during stretching is an

important parameter. When the deformation rate of the fiber is too fast, the fiber is unpreferably broken before reaching a sufficient draw ratio. When the deformation rate of the fiber is too slow, molecular chain relaxation occurs during stretching. This is not preferable since the fiber becomes thin due to stretching but a fiber having high strength and high modulus properties cannot be obtained. Preferably, a deformation rate of not less than 0.005 s^"1 and not more than 0.5 s^"1 is preferable and not less than 0.01 s^"1 and not more than 0.1 s^"1 is more preferable . The deformation rate can be calculated based on the draw ratio of the fiber, stretching rate and the length of heating section in an oven. That is, the deformation rate (s^"1) ={1—1/draw ratio) stretching

rate/length of heating section. To obtain a fiber having a desired strength, the recommended draw ratio of the fiber is not less than 10-fold, preferably not less than 12-fold, more preferably not less than 15-fold,

[0037]

The stress transmission from polyethylene matrix to m-CNF can be observed based on changes in crystal morphology of polyethylene under stretch. A hexagonal crystal, which is a metastable phase, appears near the melting point of

polyethylene depending on the temperature range, and the stress range applied to the inside of polyethylene due to compression or stretching. By studying how the hexagonal crystal appears, the stress state of polyethylene during stretching can be known.

[0038]

The outline of the phase diagram near the melting point of polyethylene., is shown, for example, in Macromolecules, 1996, vol. 29, page 1540 (non-patent reference 2} and Macromolecules, 1998, vol. 31, page 5022 (non-patent reference 3).

Polyethylene used in these non-patent references differs from the polyethylene preferable for the present invention.

Accordingly, specific temperature, stress and pressure differ from those for the fiber of the present invention. However, the outline of the phase diagram is essentially the same. The schematic view is shown in Fig. 1. A hexagonal crystal appears at a temperature not less than a given temperature (hereinafter to be temporarily referred to as Tl) and only in a given stress range. When the temperature is not more than Tl, a hexagonal crystal does not appear. With stress of not more than the phase transition line, it becomes a molten liquid, and with stress of not less than the phase transition line, an orthorhombic crystal is obtained. On the other hand, when the temperature is not less than Tl, the behavior is a molten liquid with stress'pressure of not more than phase transition line Ll, a hexagonal crystal in the region of not less- than Ll and not more than L2, and an orthorhombic crystal with stress* pressure of not less than L2.

[0039]

The changes in the crystal morphology of polyethylene fiber under stretch can be known by X-ray diffraction test using strong X-rays. Such test can be performed using a large radiation facility. Such test is possible using a drawing machine provided with a slit type heater and by irradiating strong X-rays to the fiber passing through a heating region in the slit. A wide-angle X-ray diffraction (WiAXD) pattern

"obtained by such test appears as a mixed pattern of

orthorhombic crystal and hexagonal crystal. By separating the peak of the pattern, the fraction of the peaks occupied by respective crystals can be calculated.

[0040]

Of the diffraction patterns obtained in this manner, a peak fraction of hexagonal crystal reflecting the stress condition applied to polyethylene is noted. The polyethylene fiber under stretch is subjected to a greater stress as the draw ratio increases. Therefore, when the polyethylene fiber is stretched at a temperature of not less than Tl and the draw ratio is high, only an orthorhombic crystal appears. However, when the draw ratio is low, a hexagonal crystal also appears in a mixture.

[0041]

By comparison of a polyethylene fiber produced under preferable conditions in the present invention and a

polyethylene fiber produced otherwise, the fraction occupied by the hexagonal crystal becomes higher for the polyethylene fiber of the present invention. This is considered to be attributable to a decreased stress applied to a polyethylene matrix, which is caused by propagation of a part of the stress to be applied to the whole fiber due to stretching, to an m- CNF composite. EXAMPLES

[0042]

The present invention is explained in detail by the following Examples, which are not to be construed as

limitative.

[0043]

The measurement methods and measurement conditions of the property values in the present invention are as follows.

(Alkyl chain content of m-CNF)

[0044]

The alkyl chain content of m-CNF was measured using a thermogravimetric analyzer (TGA) , TGA-7 manufactured by Perkin Elmer, under the conditions of the air atmosphere and a temperature rise rate of 20°C/min, and a thermogravimetric curve was obtained- Assuming the weight decrease (200 - 400⁰C) observed at a temperature lower than the decomposition (about 600⁰C) of original CNF as the decomposition of alkyl chain, the weight decrease in this part was taken as the alkyl chain content .

[0045]

(Intrinsic viscosity)

The intrinsic viscosity of polyethylene was determined by measuring specific viscosity of various dilute solutions using decalin at 135°C and Ubbelohde capillary viscosity tube, and from the extrapolation point at the zero concentration of the straight line obtained by least mean square approximation of the plot of the values resulting from dividing the specific viscosity by the concentration, relative to the concentration. For the measurement, 1 wt% antioxidant (trade mark "YOSHINOX BHT" manufactured by Yoshitomi Pharmaceutical Industries) 5 relative to the polymer was added -to a sample, and the mixture was dissolved by stirring at 135°C for 24 hr to prepare the measurement solution.

[0046]

(Strength and elastic modulus of fiber)

io The strength in the present invention was determined by determining a strain-stress curve using "TENSILON"

manufactured by ORIENTIC Co,, Ltd., under conditions of sample length 100 mm (length between chucks), stretching rate

100%/min, atmospheric temperature 20°C and relative humidity

15 65%, and calculating the strength (cN/dTex) from the stress and elongation at fracture point. In addition, the elastic modulus (cN/dTex) was calculated from the tangent line

defining the maximum gradient near the point of origin of the curve . Each value is an average of ten measurements .

20. [0047]

For the measurement of fineness, about 2 m of each single yarn was cut out, and the weight of the single yarn (1 m) was measured and converted to 10000 m to give a fineness (dTex) .

[0048]

25 (X-ray structural analysis of fiber under stretch)

The X-ray structural analysis of polyethylene fiber under stretch was performed using Synchrotoron Light Source, X27C beamline, in US Brookhaven National Laboratory (Upton, NY, USA) . A drawing machine having a slit heater (gap 2 mm, length

30 30 mm) was set in such a manner that the X-ray would pass

through the center of the slit heater in the gap. A yarn was passed through the gap of the heater, the position of the drawing machine was slightly adjusted so that the fiber under stretch would be exposed to the X-ray, and X-ray diffraction

35 images were photographed using a Mar-CCD two-dimensional X-ray detector (Mar USA, Inc) as an X-ray detector. The wavelength of the X-ray was 0.1371 nm, and the distance between fiber and X-ray detector was about 10 cm (varied depending on the test).

[0049]

(Example 1) Surface oxidation of carbon nanofiber

An acidic functional group (carboxyl group, hydroxyl group) was produced on the surface of carbon nanofiber (CNF) using a mixed acid (a mixture of sulfuric acid and nitric acid). A mixture of carbon nanofiber (0.5 q, Pyrograf PR-24- HHT), concentrated sulfuric acid (37.5 mL, 95%, Sigma-Aldrich Corporation) and concentrated nitric acid (12.5 mL, Sigma- Aldrich Corporation) was ultrasonicated for 10 min to disperse CNF, and stirred at 60⁰C for 24 hr. The CNF suspension was diluted with pure water, and filtered through a membrane filter having a pore size of 0.2 μm. The obtained product was washed with pure water and methanol, and dried overnight in vacuo at 70⁰C to give an oxidized CNF.

[0050]

(Example 2)

In the same manner as in Example 1 except that the stirring time at 6O⁰C was set to 18 hr, an oxidized CNF was obtained.

[0051]

(Example 3)

In the same manner as in Example 1 except that the stirring time at 60⁰C was set to 10 hr, an oxidized CNF was obtained.

[0052]

(Example 4)

In the same manner as in Example 1 except that the stirring time at 60⁰C was set to 6 hr, an oxidized CNF was obtained.

[0053]

(Example 5) Modification of oxidized carbon nanofiber with alkyl chain A mixture of the oxidized carbon nanofiber obtained in Example 1 (0.4 g), dimethyl sulfoxide (8 mL, Sigma-Aldrich Corporation) and 1-octadecylamine (0.4 g, Sigma-Aldrich

Corporation) was ultrasonicated for 10 min, and 1- octadecylamine (1.8 g) was added. The mixture was stirred at 18O⁰C for 24 hr, and filtered through a membrane filter having a pore size of 0.2 μm, and the obtained product was washed with a mixed solvent of ethanol/chloroform (volume ratio:2/l), and dried overnight in vacuo at 7O⁰C to give an m-CNF.

[0054]

(Example 6)

In the same manner as in Example 5 except that the oxidized carbon nanofiber obtained in Example 2 was used, an m-CNF was obtained.

[0055]

(Example 7)

In the same manner as in Example 5 except that the oxidized carbon nanofiber obtained in Example 3 was used, an m-CNF was obtained.

[0056]

(Example 8)

In the same manner as in Example 5 except that the oxidized carbon nanofiber obtained in Example 4 was used, an m-CNF was obtained.

[0057]

(Example 9)

The m-CNF (0.018 g) obtained in Example 5 was fed into decahydronaphthalene (291 g, a mixture of cis-form and transform) , and the mixture was ultrasonicated for 1 hr to disperse the m-CNF in decahydronaphthalene. To the dispersion were added ultrahigh molecular weight polyethylene having an intrinsic viscosity of 21.0 dL/g (8.982 g) and BHT as an antioxidant (1 wt% relative to polyethylene) , and mixture was stirred to give a slurry liquid. While dispersing the

substance, the substance was dissolved in a mixer type kneader provided with two impellers and set to 160⁰C to give a gel substance. Without cooling, the gel substance was filled in a cylinder set to 17O⁰C, and extruded at a discharge rate of 0.8 g/min from a spinneret set to 17O⁰C and having one hole with a diameter of 0.8 ram. The discharged dope filament was cast in a water bath via 7 cm air gap, cooled and wound up at a spinning rate of 20 m/miii without removing the solvent. Then, the dope filament was vacuum dried at 40⁰C for 24 hr and the solvent was removed. The obtained fiber was stretched at a deformation rate of 0.1 s^"1 using a slit type drawing machine set to 80⁰C at a draw ratio of 4 and the stretched yarn.was wound up. Then, the stretched yarn was further stretched at a deformation rate of 0.1 s^"1 at 143°C, the draw ratio immediately before yarn breakage was measured, and the obtained value was multiplied by 4 to give a maximum draw ratio. The maximum draw ratio and various properties of the obtained polyethylene fiber are shown in Table 1.

[0058]

(Example 10)

In the same manner as in Example 9 except that the obtained fiber and the stretched yarn were stretched at a deformation rate of 0.01 s^"1, a polyethylene fiber was obtained. The maximum draw ratio and various properties of the obtained polyethylene fiber are shown in Table 1.

[0059]

(Example 11}

In the same manner as in Example 9 except that the m-CNF obtained in Example 6 was used, a polyethylene fiber was obtained. The maximum draw ratio and various properties of the obtained polyethylene fiber are shown in Table 1.

[0060]

(Example 12)

In the same manner as in Example 9 except that the m-CNF obtained in Example 7 was used, a polyethylene fiber was obtained. The maximum draw ratio and various properties of the obtained polyethylene fiber are' shown in Table 1.

[0061]

(Comparative Example 1)

In the same manner as in Example 9 except that the m-CNF obtained in Example 8 was used, a polyethylene fiber was obtained. The maximum draw ratio and various properties of the obtained polyethylene fiber are shown in Table 1.

[0062]

(Comparative Example 2)

In the same manner as in Example 9 except that a surface- unmodified CNF was used, a- polyethylene fiber was obtained.

The maximum draw ratio and various properties of the obtained polyethylene fiber are shown in Table 1.

[0063]

(Comparative Example 3)

In the same manner as in Example 9 except that an m-CNF was not used, a polyethylene fiber was obtained. The maximum draw ratio and various properties of the obtained polyethylene fiber are shown in Table 1.

[0064]

Table 1

[0065 ]

(Comparative Example 4}

In the same manner as in Example 9 except that the obtained fiber and the stretched yarn were stretched at a deformation rate of 0.001 s^"1, a polyethylene fiber was obtained. The maximum draw ratio and various properties of the obtained polyethylene fiber are shown in Table 1.

[0066]

{Comparative Example 5)

In the same manner as in Example 9 except that the obtained fiber and the stretched yarn were stretched at a deformation rate of 0.8 s^'1, a polyethylene fiber was obtained. Various properties of the obtained polyethylene fiber are shown in Table 1. Since the fiber could not be stretched, the maximum draw ratio was not obtained.

[0067]

As shown in Table 1, it was found that the fibers of the embodiment of the present invention had higher maximum draw ratio, higher strength and higher elastic modulus than those of the comparative examples.

[0068]

(Example 13)

The m-CNF {0.018 g) obtained in Example 5 was fed into decahydronaphthalene (291 g, a mixture of cis-forra and trans- ^■ form) , and the mixture was ultrasonicated for 1 hr to disperse the m-CNF in decahydronaphthalene. To the dispersion was added ultrahigh molecular weight polyethylene having an intrinsic viscosity of 21.0 dL/g (8.982 g) , and mixture was stirred to give a slurry liquid. While dispersing the substance, the substance was dissolved in a mixer type kneader provided with two impellers and set to 160⁰C to give a ^'gel substance.

Without cooling, the gel substance was filled in a cylinder set to 170⁰C, and extruded at a discharge rate of 0.8 g/min from a spinneret set to 17O⁰C and having one hole with a ■ diameter of 0.8 mm. The discharged dope filament was cast in a water bath via 7 cm air gap, cooled and wound up at a spinning rate of 20 m/min without removing the solvent. Then, the dope filament was vacuum dried at 4O⁰C for 24 hr and the solvent was removed. The obtained fiber was stretched at a deformation rate of 0.1 s^"1, using a slit type drawing machine set to 80⁰C at a draw ratio of 4 and the stretched yarn was wound up and used as intermediate stretch yarn A.

The intermediate stretch yarn A was stretched at a deformation rate of 0.1 s^"1 at draw ratios of 2, 3 and 4 at 143⁰C, and a wide-angle X-ray diffraction pattern was taken for each in the center of a drawing oven {slit heater) . The background was subtracted from the diffraction profile

obtained by integration of the range of ±5° of the diffraction pattern from the equator line. Each crystal .peak was separated by curve fitting and the peak area was determined. The fraction of hexagonal crystal at each draw ratio is shown in Fig. 2 as dependency on the content of alkyl chain for surface modification.

[0069]

(Example 14)

In the same manner as in Example 13 except that the m-CNF obtained in Example 7 was used, an intermediate stretch yarn of a polyethylene fiber was obtained. This was used as intermediate stretch yarn B.

The intermediate stretch yarn B was drawn at draw ratios of 2, 3 and 4 at 143°C, and a wide-angle X-ray diffraction pattern was taken for each in the center of a drawing oven (slit heater) . The background was subtracted from the

diffraction profile obtained by integration of the range of ±5° of the diffraction pattern from the equator line. Each crystal peak was separated by curve fitting and the peak area was determined. The fraction of hexagonal crystal at each draw ratio is shown in Fig. 2 as dependency on the content of alkyl chain for surface modification.

[0070]

(Comparative Example 6)

In the same manner as in Example 13 except that the m-CNF obtained in Example 8 was used, an intermediate stretch yarn of the polyethylene fiber was obtained. This was used as ' intermediate stretch yarn C.

The intermediate stretch yarn C was drawn at draw ratios of 2, 3 and 4 at 143⁰C, and a wide-angle X-ray diffraction ^■ pattern was taken for each in the center of a drawing oven

(slit heater) . The background was subtracted from the

diffraction profile obtained by integration of the range of

±5° of the diffraction pattern from the equator line. Each crystal peak was separated by curve fitting and the peak area was determined. The fraction of hexagonal crystal at each draw ratio is shown in Fig. 2 as dependency on the content of alkyl chain for surface modification.

[0071J

(Comparative Example 7)

In the same manner as in Example 13 except that a surface-unmodified CNF was used, an intermediate stretch yarn of a polyethylene fiber was obtained. This was used as intermediate stretch yarn D.

The intermediate stretch yarn D was drawn at draw ratios of 2, 3 and 4 at 143°C, and a wide-angle X-ray diffraction pattern was taken for each in the center of a drawing oven

(slit heater) . The background was subtracted from the

diffraction profile obtained by integration of the range of

[0072]

(Comparative Example 8)

In the same manner as in Example 13 except that an m-CNF was not used, an intermediate stretch yarn of a polyethylene fiber was obtained. This was used as intermediate stretch yarn

E.

The intermediate stretch yarn E was drawn at draw ratios of 2, 3 and 4 at 143⁰C, and a wide-angle X-ray diffraction pattern was taken for each in the center of a drawing oven (slit heater) . The background was subtracted from the

■ diffraction profile obtained by integration of the range of

[0073]

As is clear from Fig. 2, as the draw ratio increases, the fraction of hexagonal crystal depends on the alkyl chain content of rα-CNF. That is, as the amount of alkyl chain increases, the fraction of hexagonal crystal increases, approaching the fraction at a low draw ratio. This indicates that a greater alkyl content of ia-CNF means that the state of stress inside a polyethylene fiber is approaching the state of low draw ratio, i.e., decrease of stress applied to

polyethylene. The stress decrease suggests propagation of stress to m-CNF.

INDUSTRIAL APPLICABILITY

[0074]

The fiber obtained by the production method of a high strength polyethylene fiber of the present invention is

industrially applicable to a wide range including high

performance textile such as various sportswear, bulletproof* protective clothing'protective gloves, various safety products and the like, various rope products such as tag rope-mooring rope, yacht rope, rope for construction and the like, various braided rope products such as fishing line, blind cable and the like, net products such as fish net*net for preventing balls and the like, further, reinforcement members of chemical filter-battery separator and the like, various non-woven fabric, curtain materials such as tent and the like, reinforcing fibers for sports such as helmet, ski and the like, speaker cone, composite such as prepreg, concrete reinforcement etc., and the like.

Citation list

Patent Literture

[0075]

patent reference 1: JP-B-60-47922

patent reference 2: JP-B-64-8732

patent reference 3: WO00/69958

patent reference 4: WO03/69032

patent reference 5: WO05/84167

Non Patent Literture

[0076]

non-patent reference 1: Macromolecules, 2005, vol. 38, page 3883

Claims

1. A method for producing a high strength polyethylene fiber, comprising the steps of:

(1) dispersing a chemically surface modified carbon nanofiber in a solvent for an ultrahigh molecular weight polyethylene,

(2) preparing a mixed dope comprising the polyethylene, the modified carbon nanofiber and the solvent by mixing the polyethylene with the suspension obtained in step (1) , wherein the concentration of the polyethylene is not less than 0.5 wt% and less than 50 wt%,

(3) extruding the dope .obtained in step (2) through a

spinneret, cooling the dope, and then stretching the dope into a filament yarn at a deformation rate of not less than 0.005 s^" * and not more than 0.5 s^"1.

2. The method of claim 1, further comprising a step of preparing the surface modified carbon nanofibers comprising:

(4) generating a carboxyliσ group on a carbon nanofiber by oxidation of the carbon nanofiber,

(5) generating an alkyl chain on the carbon nanofiber by reaction of an alkyl chain having amine as an end group with the carboxylic group of (4) .

3. The method of claim 1, wherein the surface modified carbon nanofiber is modified with an alkyl chain and the ultrahigh molecular weight polyethylene has an intrinsic viscosity of 5 dL/g to 40 dL/g.

4. The method of claim 3, wherein the content of the carbon nanofiber is 0.05 wt% to 10 wt% of the fiber.

5. The method of claim 3, wherein the weight fraction of the alkyl chain in the modified carbon nanofiber is 8% to 20%.

6. The method of claim 3, wherein the alkyl chain in the modified carbon nanofiber is a linear alkyl chain having 8 or more carbon atoms.

5 7. The method of claim 6, wherein the alkyl chain is an

octadecyl chain having 18 carbon atoms.

8. A high strength polyethylene fiber produced by the method of claim 1.

10

9. A high strength polyethylene fiber produced by the method of claim 2.

10. A high strength polyethylene fiber produced by the method 25 of claim 3.

11. A high strength polyethylene fiber produced by the method of claim 4.

20 12. A high strength polyethylene fiber produced by the method of claim 5.

13. A high strength polyethylene fiber produced by the method of claim 6.

25

14. A high strength polyethylene fiber produced by the method of claim 7.