CA1147518A - Filaments of high tensile strength and modulus and process for their preparation - Google Patents

Abstract

A B S T R A C T

The invention relates to the preparation of filaments with a high tensile strength and a high modulus and to the filaments thus prepared. A solution of a linear polyethylene with a weight-average mole-cular weight of at least 4 x 105 is spun and the filaments, from which the solvent may have been removed in whole or in part, are drawn using a draw ratio of at least (12 x 106/?w) + 1. The filaments are drawn at a tem-perature such that the modulus is at least 20 GPa.
The invention allows filaments to be prepared at high drawing rates, of 0.5 sec-1 or more, with a modulus of at least 20 GPa and a ten-sile strength of at least 1 GPa.

Description

1~L~7518 3107 FILAMENTS aF HIGH TENSILE STRENGTH AND MOOULUS AND PROCESS FQR THEIR
PREPARATION

The invention relates to filaments of high tensile strength and modulus and to a process for preparing filaments by spinning a solution of a high-molecular linear polymer and drawing the filaments.
Filaments can be prepared by spinning linear polymers. A
suitable polymer is then reduced to a 1iquid state tmelt, solution) and spun. The arbitrarily oriented molecular chains in the filament formed ~ are then aligned longitudinally in the filament by drawing~ Chainstruc-- tured macromolecules are a major prerequisite for spinnability to fila-ments, although other substances may also be spinnable. Branches influence filament formation and mechanical properties adversely. For this reason, as linear as possible polymers are used for the drawing of filaments, even though a limited degree of branching will often be una-voidable and in fact permissible.
The most economic and most frequently applied method for pro-ducing filaments is melt spinning, i.e. molten polymer is spun tofilaments. The melt spinning of linear polyethylene and other polymers is known per se. The material to be spun must for this purpose be meltable and be stable in the molten state. The viscosity of the melt must permit of a reasonable spinning rate. For a meltable polymer, the spinnability ; 20 decreases with increasing molecular weight.
Polymers that melt above the decomposition temperature or are relatively unstable in the molten condition are frequently spun from a solution. In spinning from a solution, the filaments can be fed into an evaporating chimney, so-called dry spinning, or into a precipitation or cooling bath, so-called wet spinning. The solvent can be washed out in the cooling bath.
In dry sp~nning hot air is usually blown through the eva-porating chimney, to evaporate the solvent completely or to a large - extent from the filament. The temperature in the chimney is - at any rate over part of the chimney - below the polymer melting point. The mechani-cal strength of the filaments, which is still very low when a filament leaves the spinning aperture, increases in the chimney, but reamins re~a-tively low. The strength oi the iilaments is lncreased by the subsequent , 7S~3 drawing, one of the major after-treatments of spun filaments. As a result of the slight, or even zero orientation of the chain molecules of the linear polymer filaments possess a great deformability in the undrawn state, i.e. the modulus is low. By drawing, the macromolecules are oriented longitudinally and the strength and the modulus of the filaments then increase.
The spun filaments must in general be drawn above the glass transition temperature Tg of the polymer. Gn the other hand, drawing should preferably be performed below the melting point of the polylmer, because above this temperature the motion of the macromolecules soon becomes so great that the desired orientation cannot be achieved, or the orientation is insufficient.

It is often advisable to effect drawing at a temperature that is at least - 10C below the melting point. The intramolecular heat generation resulting from the drawing work performed on the filaments must be taken into account.
At high drawing speeds the temperature of the filaments can thus rise sharply, and it should be ensured that it does not approach or even exceed the melting point.
The strength of drawn filaments in many cases remains far below the values that could be expected theoretically, however.

Many attempts have already been made to produce filaments the tensile strength and modulus of which approximate the theoretical potential more closely. These attempts, a review of which is given in publications by Juyn in Plastica 31 (1978) 262-270 and by Bigg in Polymer Eng. Sci. 16 (1976) 725-734, have not yet produced satisfying results: the modulus or tensile strength often leave much to be desired, or there are technical or economic objections that render the proposed methods unattractive. In particular, the processing rates are low, as is mentioned in the article by Juyn.
Attempts to prepare polyethylene filaments with a high strength and

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~147S1~3 modulus are described, inter alia, in Netherlands Patent Applications 74.02956 (Canadian Patent 1059278) and 74.13069 (United States Patent 3962205), which relate to the melt spinning of polyethylene with a weight-average molecular weight of less than 300,000. According to Netherlands Patent Application 76.12315 (United States Patent 4268470) by the same applicant, polyethylene with a higher molecular weight of up to 2,000,000 can also be processed. The examples describe only the extremely slow drawing of moulded dumb-bell polyethylene samples with a molecular weight of at most 800,000 in an Instron tensile strength tester, or the drawing of filaments melt-spun from polyethylene with a molecular weight (Mw) of 312,000 or lower.
Netherlands Patent Application 65.01248 (Canadian Patent 860839) describes the preparation of filaments of heat-sensitive polymers by spinning solutions thereof. According to this application, heat-sensitive polymers are, e.g., polyethylene or polypropylene with such a high molecular weight that they do not melt without severe decomposition. The filaments produced by spinning a solution of, say, a polyethylene with a molecular weight of 1 to 3 million are reeled. Nothing is said about the drawing method (draw ratio, drawing speed, etc.), or about the final strength. The reeled threads must first be subjected to a laborious washing treatment. Shrinkage occurs in washing the gel-like threads on the reel,which leads to greatly varying stretch in the reeled thread and may even result in rupturing.
Netherlands Patent Application 76.05370 ~United States Patent 4137394) describes a method by which polyethylene filaments with very good mechanical properties, in particular with a high modulus and tensile strength, can be prepared. The production rate is, however, less than 1 m/min and economic production is not feasible by this method.
The present invention aims to provide an economic method for

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~47518 preparing filaments with a hi~h modulus and high strength from a linear polymer, in particular from polyethylene.
According to the invention, filaments with a high strength and high modulus can be produced by spinning a linear polyethylene with a weight-average molecular weight (Mw) of at least 4 x 105 and preferably at least 8 x 105 and drawing the resulting filaments with a draw ratio of at least (12 x 106/MW) + l, at a temperature such that at the draw ratio chosen the filaments acquire a modulus of at least 20 GPa. The modulus is defined as the stress required to effect a unit deformation. The deformation may be a change in length (Young's modulus), a torsion or shear, or a chan~e in volume. The modulus is here measured on filaments at 23C on an Instron tensile strength tester. The sample length between the clamps was 15 cm and the elongation rat~ during the test 10 cm/min. The modulus values given below are the initial moduli.
Solutions of high-molecular-weight linear polyethylene (Mw ~ 4 x 105) in general contain at least 1 and most ~0 wt.% polyethylene. Solutions with concentrations below l wt.% may be spun, but - 3a -', .

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the spinning thereof does not in general bring any advantages, although with very-high-molecular-weight polyethylene it may sometimes be favourable to process solutions with concentrations of less than 1 wt.g.
High-molecular-weight polyethylene is-here taken to mean polyethylene that may contain minor amounts, preferably at most 5 moles ~, of one or more other alkenes copolymerized therewith, such as propy-lene, butylene, pentene, hexene, 4-methyl pentene, octene, etc., with less than one side chain per 100 carbon atoms, and preferably with less than 1 side chain per 300 carbon atoms, and with a weight-average molecu-lar weight of at least 4 x 105, preferably at least 8 x 105. The polyethylene may contain minor amounts, preferably at most 25 wt.%, of one or more other polymers, in particular an alkene-1-polymer such as polypropylene, polybutylene or a copolymer of propylene with a minor amount of ethylene.
The filaments spun by the method according to the invention are upgraded according to usual methods. They may be fed into a chimney through which hot air can be passed, and in which all or part of the solvent may be evaporated. The solvent can also be washed out of the filaments in whole or in part, or further removed from them by evapara-tion in a zone following the chimney. The filaments from which all or part of the solvent has been evaporated or removed by washing, that is to say the filaments containing in general less than 25 wt.~ and preferably less than 10 wt.~ solvent, are then highly drawn. The filaments leaving the spinneret may also be fed into a space in which they are cooled without substantial solvent evaporation until a gel-like filament is formed, and this filament is drawn. When solvent-containing filaments are drawn it is advisable to evaporate or wash from the filaments as much of the solvent as possible during drawing, although it may also be removed from the filaments after drawing.
It has been found that as ~he draw ratio increases, the modulus and the tensile strength~increase. The draw ratio cannot be increased indefinitely, as rupturing occurs at too high draw ratios. It can be easily established experimentally at what draw ratio filament rupturing is so frequent as to interfere with production continuity to an unaccep-table degree.
It has also been found that unusually high draw ratios can be applied when the present method is applied. The draw ratio is preferably at least (14 x 106/MW) + 1, more specifically at least (18 x 106/MW) + 1.

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The high draw ratios can with the present method be attained at high drawing speeds. The drawing speed is the difference between the rate of take-off (from the drawing roller) and the rate of feed (onto the feed roller) per unit drawing zone, and is expressed in sec~1. With the pre-sent method, the drawing speed can amount to, e.g. 0.5 sec-1 or even 1 sec~1 or more.
To obtain the high modulus values required, drawing must be performed below the melting point of the polyethylene. The drawing tem-perature is in general at most 135 C. With drawing below 75 ~C, results are no longer satisfactory and the drawing temperature should therefore be at least 75 ~C.
It has furthermore been found that as the molecular weight increases, the attainable moduli, but especially the attainable tensile strengths, increases. It is therefore preferable to process a polyethy-lene with a molecular weight (Mw) of at least 8 x 105. As the molecularweight of the polyethylene increases, it becomes more difficult to process. Dissolution in a suitable solvent becomes more time-consuming, the solutions become more viscous at given concentration, and the attainable spinning rates consequently decrease, while rupturing during drawing occurs more readily. For this reason, polyethylene with a molecu-lar weight (Mw) above 15 x 106 will not in general be used, although the present method is feasible with higher molecular weights. The weight-average molecular weight (Mw) can be determined by known methods by gel permeation chromatography or light scattering.
The choice of solvent is not critical. Any suitable solvent may be used, e.g. halogenated or non-halogenated hydrocarbons. In most solvents, polyethylene is soluble only at temperatures of at least 90 ~C.
In conventional spinning processes, the space in which the filaments are spun is at atmospheric pressure. Low-boiling solvents are therefore less desirable, because they can evaporate so rapidly from the filaments that they come to act more or less as foaming agents and interfere with the structure of the filaments.
The temperature of the solution in spinning is preferably at least 100 ~C, more specifically at least 120 ~C, and the boiling point of the solvent is preferably at least 100 C, more specifically at least equal to the spinning temperature. The boiling point of the solvent ~- should not be so high as to render it difficult to evaporate it from the -11'~7S~

spun filaments. Suitable solvents are aliphatic, cycloaliphatic and aro-matic hydrocarbons with boiling points of at least 100 VC, such as octane, nonane, decane or isomers thereof, and higher branched or unbranched hydrocarbons, petroleum fractions with boiling ranges above 100 ~C, toluenes or xylenes, naphthalene, hydrogenated derivatives thereof, such as tetralin, decalin, but also halogenated hydrocarbons and other known solvents. In view of the low cost price, preference will usually be given to non-substituted hydrocarbons, including hydrogenated derivatives of aromatic hydrocarbons.
The spinning temperature and the temperature of dissolution must not be so high as to lead to considerable thermal decomposition of the polymer. In general, the temperatures applied will therefore not be above 240 C.
Surprisingly, it is found that filaments with a greater modulus and strength can be produced by the present method than by melt spinning of the same polymer, drawing conditions being as far as possible the same, e.g. with the same drawing temperature and drawing rate.
In conventional methods for spinning solutions, the diameters of the spinning apertures in the spinnerets are often small. In genèral, the diameters are 0.02-1.0 mm. Especially if small spinning apertures ~ 0.2 mm) are used, it is found that the spinning process is very sen-sitive to contaminants in the spinning solution, and this solution must be carefully freed and kept free of solid contaminants. The spinnerets are usually provided with filters. Nevertheless, it is found that the spinnerets have to be cleaned after a short time and blockage is still often found to occur. With the present method larger spinning apertures, of more than 0.2 mm, for example 0.5-2.0 mm or more, can be used, as the drawing ratios can be large and, additionally, fairly low polymer con-centrations are used in the spinning solution.
The filaments according to the invention are suitable for a variety of applications. They can be used as reinforcement in a variety of materials for which reinforcement with fibres or filaments is known, for tyre cords, and for all applications in which low weight combined with high strength is desired, such as rope, nets, filter cloths etc.
If so desired, minor quantities, in particular quantities of 0.1-10 wt.% relative to the polymer, of conventional additives, stabili-zers, fibre treatment agents and suchlike can be incorporated in or 7~1~

applied on the filaments.
The invention is elucidated further by the following examples and attached drawings, without being thereby restricted.
In these drawings:
Figure 1 is a modulus (ordinate) against draw ratio ~abscissa) diagram of filaments prepared according to example I-III;
Figure 2 is a tensile strength against draw ratio diagram of said filaments of examples I-III;
Figure 3 is a modulus/draw ratio diagram of filaments prepared according to examples IV-V;
Figure 4 is a tensile strength/draw ratio diagram of said filaments of examples IV-V;
Figure 5 is a modulus/draw ratio diagram of filaments prepared according to examples VI-VIII;
Figur0 6 is a tensile strength/draw ratio diagram of said filaments of examples VI-VIII;
Figure 7 is a modulus ~ordinate) against tensile strength ~abscissa) diagram of the filaments prepared according to example V, VI and IX and of filaments of comparative examples A and B.
Examples I-III
A high-molecular-weight linear polyethylene of Mw ~ 1.5 x 106 is dissolved at 145C in decalin to a 2 wt.% solution. This solution is spun at 130C by a spinneret with a spinning aperature of 0.5 mm diameter through an evaporating-type spinning chimney.
I. In one series of experiments no air was blown through the spinning chimney.
The filament was only cooled in the chimney, resulting in a gel-like filament being obtained from the chimney that still contained more than 90% solvent.
This filament was drawn in l-m long drawing chamber kept at 120C. The drawing ,, _ 751~

speed was about 1 sec 1 The draw ratio was varied between 2 and more than 30. lhe modulus and tensile strength were determined for filaments drawn at different draw ratios. The values of modulus and draw ratio are represented in Figures 1 and 2 by open circles (o ~, withthe modulus, resp. the tensile strength, in GPa, being plotted along the ordinate and the draw ratio along the abscissa.
II. In one experimental series air heated to 60C was blown through the evaporating-type spinning chimney. The filament emerging f~om the chimney still contained 6 wt.% solvent and was drawn in the same way as in Example I.
The values of modulus (ordinate) and the draw ratio (abscissa) are represented in Figures 1 and 2 by solid circles ( ).
III. In one experimental series air heated to 60C was blown through the evaporating-type spinning chimney. The filament emerging from the chimney was fed through a methanol bath, in which the solvent was washed out of the filament. The filament was then draw as in Example I. The values of modulus and draw ratio are represented in Figures 1 and 2 by solid triangesl ( ).
Somewhat higher draw ratios can be achieved in drawing solvent-containing filaments (Example I) than with filaments containing little or no solvent (Examples II and III). In the former case the values of the modulus and tensile strength attainable are therefore greater.

Example IV-V
A high-molecular-weight linear polyethylene of Mw Y 1.0 x 106 was dissolved at 145C in decalin to a 3 wt.% solution. The solution was - 7a -~,..

spun at 130 ~C through a spinning aperture with a diameter of 0.5 mm into an evaporating-type spinning chimney.
lV. As in Example I, the filament was only cooled in the chimney. The yel-like filament, containing more than 90 % solvent, was drawn in two series of experiments in the way described in Example I, at 93 ~C and at 106 ~C. An attempt to perform a third series of experiments at a drawing temperature of 142 ~C failed due to the filament continually melting away and consequently rupturing.
V. Air heated 60 ~C was blown through the evaporating-type spinning chimney. The filament emerging from the spinning chlmney contained about 6 wt.~ solvent. Three series of experiments were performed. The filaments were drawn at 93 ~C, 106 C and 142 ~C.
The moduli and the tensile strengths were determined for filaments pre-pared according to Examples IY and V with varying draw ratios, from 2 to more than 40. Fig. 3 and Fig. 4 show the moduli, resp. the tensile str-engths in GPa (along the ordinate~ plotted versus the draw ratios (along the abscissa).
The values measured for gel-like filaments drawn at 93 ~C are represented by open circles (O ).
The values measured for gel-like filaments drawn at 106 ~C are repre-sented by open triangles ( ~ ).
The values measured for substantially dry filaments drawn at 93 vc are represented by solid circles (- ).
The values measured for substantially dry filaments (i.e. filaments con-taining approx. 6 wt.~ solvent) drawn at 106 ~C are represented by solidtriangles ( ~ ).
The values measured for substantially dry filaments drawn at 142 ~C are presented by semi-solid circles ( O ).
A modulus of 20 GPa cannot be achieved at a drawing temperature of 142 ~C
and as a result the value of the tensile strength also remains considerably below 1 GPa.

Example VI
A polyethylene A of molecular weight ~w ~ 1.5 x 106 was dissolved at 145 ~C in decalin to a 2 wt.~ solution and then spun as in Example II and drawn at varying draw ratios.
In Figs. 5 and 6 the moduli, resp. the tensile-strenghts, in GPa (alon~

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g ~he ordinate), plotted versus the draw ratios (a1Ong the abscissa), are indicated by semi-solid circles.( O ) Example VII
Example VI was repeated with a polyethylene B of molecular weight Mw ~ 8 x 105 dissolved in decalin to a 4 wt.~ solution.
The moduli and tensile strengths measured are represented in Fig. S and F;g. 6 by open circles IO ).

Examplé VIII
Example YI was repeated with a polyethylene C of molecular weight Mw # 600,000 dissolved in decalin to an 8 wt.% solution.
The moduli and tensile strengths are represented in Fig. 5 and Fig. 6 by solid circles ( ).

Example IX
Example VI was repeated with a polyethylene of molecular weight Mw Y 4 x I06 dissolved in decalin to a 1 wt.% solution.
The moduli and tensile strengths of filaments drawn at varying draw ratios were measured and plotted versus each other along the abscissa and along the ordinate, respectively, of Fig. 7. The relation is shown by curve IX in that figure.
The moduli and tensile strengths of filaments prepared as in Examples V
and VI are represented by Curves V and VI in Fig. 7.
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Comparative examples A en B
According to the method of Example II, filaments of a polyethy-lene of Mw = 280,000 and a polyethylene of Mw = 60,000 were spun from respectively 20 and 50 wt.~ solutions in decalin. The relation between modulus and tensile strength is represented in Fig. 7 by Curve A for the polyethylene of Mw = 280,000 and by Curve B for the polyethylene of MW =
60,000.
Fig. 7 shows that, with decreasing molecular weight, a tensile strength ' ~ 30 of 1 GPa is achieved only at an ever higher modulus and an accordingly - higher draw ratio and in the long run can no longer be achieved at all.
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Claims (7)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Process for the preparation of filaments of high modulus and tensile strength by spinning a solution of a high-molecular-weight linear polymer and drawing the filaments, characterized in that a solution of a linear polyethylene with a weight-average molecular weight ?w ? 4 x 105 is spun and the filaments are drawn using a draw ratio of at least (12 x 106/?w) + 1, at a drawing temperature such that at the draw ratio used the modulus of the filaments is at least 20 GPa.

2. Process according to Claim 1, characterized in that the draw ratio is at least (14 x 106/?w) + 1.

3. Process according to Claim 2, characterized in that the draw ratio is at least (18 x 106/?w) + 1.

4. Process according to Claims 1 to 3, characterized in that a linear polyethylene with a weight-average molecular weight of at least 8 x 105 is used.

5. Process according to Claims 1 to 3, characterized in that the drawing rate is at least 0.5 sec-1.

6. Process according to Claims 1 to 3, characterized in that the filaments are drawn at temperatures of 75-135°C.

7. Filaments prepared according to the process of claim 1.