CA1152272A - Filaments of high tensile strength and modulus - Google Patents
Filaments of high tensile strength and modulusInfo
- Publication number
- CA1152272A CA1152272A CA000345309A CA345309A CA1152272A CA 1152272 A CA1152272 A CA 1152272A CA 000345309 A CA000345309 A CA 000345309A CA 345309 A CA345309 A CA 345309A CA 1152272 A CA1152272 A CA 1152272A
- Authority
- CA
- Canada
- Prior art keywords
- polymer
- filament
- solvent
- filaments
- spinning
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/04—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/05—Filamentary, e.g. strands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0058—Liquid or visquous
- B29K2105/0073—Solution
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
- Woven Fabrics (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
PROCESS FOR MAKING POLYMER FILAMENTS
WHICH HAVE A HIGH TENSILE STRENGTH
AND A HIGH MODULUS
ABSTRACT
A process for making polymer filaments which have a high tensile strength and a high modulus by stretching a polymer filament which contains an appreciable amount of polymer solvent at a temperature between the swelling point and the melting point of the polymer.
WHICH HAVE A HIGH TENSILE STRENGTH
AND A HIGH MODULUS
ABSTRACT
A process for making polymer filaments which have a high tensile strength and a high modulus by stretching a polymer filament which contains an appreciable amount of polymer solvent at a temperature between the swelling point and the melting point of the polymer.
Description
~22~2 PROCESS FOR MAKING POLYMER FILAMENTS
WHICH HAVE A HIGH TENSILE STRENGTH
AND A HIGH MODULUS
BACKGROUND OF THE INVENTION
S The present invention relates to polymer filaments which have a high tensile strength and a high modulus, and to a process for making such filaments.
Filaments are usually made by spinning linear polymers. A polymer is first made into a liquid such as a melt or a solution and is then spun forming a filament. Although other substances are capable of being spun the chain formatîon of the macromolecules is an important consideration as side branches have an adverse effèct on filament formation and mechanical properties. Therefore, the production of filaments in accordance with the process of the present invention is premised on th~ use of linear polymers although a limited degree of branching is usually unavoidable and ~illhaveto be.accepted.
The rando,nly oriented chains of molecules in this filament must next be oriented lengthwise in the filament which is accomplished by stretching.
Stretching of the filament results in orienting the chain macromolecules lengthwise which also increases the strength of the filaments. However, in many cases the strength of the stretched filaments is still far below the value that is theoretically expected. Many attempts have already been made at producing filam~ents with a tensile strength and a modulus ~.
~52272 closer to what are theoretically possible. These attempts, of which a survey is given in publications by Juyn in Pla5tica 31 ~1978~ 262-270 and Bigg in Polymer Eng. Sci. 16 ~1976) 725~734, have ~ailed to yield satisfac~ory results.
In a number of cases the modulus was improved sufficiently, but not the tensile strength. There was an additional drawback in tha~ the filament formation was so slow that economic production would be impossible.
It has now been found that polymer filaments which have a high tensile strength and a high modulus can be made by stretching a polymer fila-ment containing an appreciable amount of polymer solvent at a temperature between the swelling point and the melting point of the polymer. Preferably a spinnable solution is spun by any of the known methods, the resultant fila-ment is cooled to below the solution temperature of the polymer, the tempera~
ture of the filament is then adjusted at a value between the swelling point of the polymer in the solvent and the melting point of the polymerJ and the filament is then stretched.
According to one aspect of the present invention there is provided a process for making polymer filaments which have a high tensile strength and a high modulus comprising the steps of:
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution tempera-ture of the polymer, either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the solvent in the filament, c) bringing said filament to a temperature between the swelling point of the polymer in the solvent and the melting point of the polymer, and
WHICH HAVE A HIGH TENSILE STRENGTH
AND A HIGH MODULUS
BACKGROUND OF THE INVENTION
S The present invention relates to polymer filaments which have a high tensile strength and a high modulus, and to a process for making such filaments.
Filaments are usually made by spinning linear polymers. A polymer is first made into a liquid such as a melt or a solution and is then spun forming a filament. Although other substances are capable of being spun the chain formatîon of the macromolecules is an important consideration as side branches have an adverse effèct on filament formation and mechanical properties. Therefore, the production of filaments in accordance with the process of the present invention is premised on th~ use of linear polymers although a limited degree of branching is usually unavoidable and ~illhaveto be.accepted.
The rando,nly oriented chains of molecules in this filament must next be oriented lengthwise in the filament which is accomplished by stretching.
Stretching of the filament results in orienting the chain macromolecules lengthwise which also increases the strength of the filaments. However, in many cases the strength of the stretched filaments is still far below the value that is theoretically expected. Many attempts have already been made at producing filam~ents with a tensile strength and a modulus ~.
~52272 closer to what are theoretically possible. These attempts, of which a survey is given in publications by Juyn in Pla5tica 31 ~1978~ 262-270 and Bigg in Polymer Eng. Sci. 16 ~1976) 725~734, have ~ailed to yield satisfac~ory results.
In a number of cases the modulus was improved sufficiently, but not the tensile strength. There was an additional drawback in tha~ the filament formation was so slow that economic production would be impossible.
It has now been found that polymer filaments which have a high tensile strength and a high modulus can be made by stretching a polymer fila-ment containing an appreciable amount of polymer solvent at a temperature between the swelling point and the melting point of the polymer. Preferably a spinnable solution is spun by any of the known methods, the resultant fila-ment is cooled to below the solution temperature of the polymer, the tempera~
ture of the filament is then adjusted at a value between the swelling point of the polymer in the solvent and the melting point of the polymerJ and the filament is then stretched.
According to one aspect of the present invention there is provided a process for making polymer filaments which have a high tensile strength and a high modulus comprising the steps of:
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution tempera-ture of the polymer, either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the solvent in the filament, c) bringing said filament to a temperature between the swelling point of the polymer in the solvent and the melting point of the polymer, and
-2-~ . .
d) stretching the filament, that still contains at least 25% by ueight of solvent relative to the polymer, at a stretching ratio of at least 5.
According to another aspect of the present invention there is provided a process for making polymer filaments which have a high tensile strength and a high modulus comprising the steps of:
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution tempera-ture of the polymer to form a polymer gel filament either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the sdlvent in the filament, c~ adjusting the temperature of said polymer gel filament at a value between the swelling point of the polymer in the solvent and the melting point of the polymer, d) stretching the filament, that still contains at least 25% by weight of solvent relative to the polymer, at a stretching ratio of at least 5, wherein there is at least a partial evaporation of the solvent, and e) recovering a substantially solvent-free filament.
In the dry spinning process which is widely applied on a technical scale, a solution of a spinnable polymer is spun in a shaft through which air is blown to evaporate all or most of all of the solvent to form the filament.
While the air is usually heated the temperature in the shaft is kept below the melting point of the polymer in order to increase the mechanical strength of the filament, which is veTy low as it exits the spinning aperture.
-2a-''~3~ ;
~227Z
The mechanical strength can be further increased in the subsequent stretching step at temperatures below the melting point of the polymer.
DESCRIPTION OF THE INVENTION
According to the present invention, the evaporation of the solvent from the filament immediately after spinning is not promoted during the cooling phase. The filament can be cooled to below the solution temperature, and particularly to below the swelling point of the polymer in the solvent by any suitable way, inclùding for e~ample, by passing the filament through a water bath, or through a shaft without any air or only minimal amounts of air being blown through the shaft. Some evaporation of the solvent from the filament will often take place spontaneously and cannot be prevented. This is acceptable as long as the evaporation is not actively promoted and the amount of solvent in the filament is not reduced~to a low value, e.g., to less than 25% by weight of solvent relative to the polymer.
Preferably the amount of solvent will not be less than equal amounts by weight of solvent and polymer. If desired, the evaporation of the solvent may be reduced or suppressed by carrying out the spinning in an atmosphere containing solvent vapor.
In cooling to below the solution temperature, in particular to below the swelling temperature of the polymer in the solvent, the polymer precipitates from the solution, and a gel is formed. A filament consisting of this polymer 1~ 5~;~72 gel has sufficient mechanical strength for further processing, for example, by means of the guides, rolls, and the like customarily used in spinning techniques. A filament of this kind is heated to a temperature between the swelling point of the filament in the solvent and the melting point of the polymer, and is then stretched at that temperature. This can be effected by passing the filament into a zone containing a gaseous or liquid medium kept at the required temperature. A
tubular oven with air for the gaseous medium is very suitable, but it is also possible to use a liquid bath or any other suitable device. A
gaseous medium is easier to handle, and is therefore preferable.
When the filament is being stretched in a gaseous medium, solvent evaporation will occur.
If a liquid medium is used, there will be dissolution of the solvent in the liquid.
Preferably, the evaporation is promoted by suitable means such as removal of the solvent vapor, by for instance leading a gas or air current past the filament in the stretching zone. At least part of the solvent should be evaporated, but preferably at least the greater part of the solvent is evaporated, so that by the end of the stretching zone there will be at most only a small amont, e.g., not more than a few percent, calcu].ated on a solid-substance basis of solvent contained in the fi~lament. The filament 5J~ould PrQ ~: e ra bJ
B which is eventually obtained must be free of solvent, and it is advantageous to apply such conditions that it is free, or virtually free, of solvent by the time it exits from the stretching zone.
llSZZ7Z
Surprisingly, the process in accordance with the present invention can produce filaments - that are considerably stronger, i.e. are filaments with considerably higher tensile~strength and s higher modulus than filaments of the same material made by any of the usual dry spinning processes.
By means of the methods described in the above-mentioned publications by Juyn and Bigg filaments of higher modulus have been obtained, but the tensile strength is still unacceptable. Moreover, the productivity of these methods is low.
The process in accordance with the present invention differs from the usual dry spinning processes in that a filament containing an appreciable amount of solvent is stretched with removal of solvent at a temperature at which the spinnable material will at least swell in the solvent, whereas in the usually applied spinning processes solvent free filaments are subjected to stretching.
One requirement of dry spinning is that the linear polymer be soluble in a suitable solvent. For any given soluble polymer a number of different solvents are available. A suitable solvent is one with a boiling point not too high so that it will not be difficult for the solvent to be evaporated from the filament, and not too low so that it is not too volatile and thus hinder filament formation because of rapid evaporation~
Also, if it is too volatile, it may have to be processed under pressure to prevent rapid evaporation.
115~27Z
Dissolution of a polymer in a suitable solvent involves swelling. While the solvent is being absorbed and the volume increases, a swollen gel is formed, which, however, because of its consistency and stability of shape is still regarded as a kind of solid substance. It is generally assumed that the polymer is composed of ordered or crystalline areas and less ordered or amorphous areas. The ordered areas are believed to act as anchoring points and thus lend stability of shape to the gel. The formation of the gel and the dissolution are time dependent. A given polymer can be dissolved in a given solvent only above a given temeprature. Below this solution temperature only swelling takes place, and according as the temperature is lowered, the swelling becomes less, until at a certain temperature the swelling will be negligible. The swelling point or swelling temperature is considered to be that temperature at which a distinct increase in volume and a distinct absorption of solvent in an amount of about 5 to 10% of the polymer weight occur. A simple rule of thumb is that the swelling temperature above which the stretching is to be effected is the temperature at which 10% of solvent is unquestionably absorbed into the swelling polymer.
In dry spinning processes usually 5-30~
wt. solutions are used ~or technical and economic reasons. Such solutions are also suitable for the process of the present invention, although generally solutions of lower concentration may be used. Solutions in the range of about 1 to 5% by ` 1152272 weight of polymer to solvent can be advantageously used while still lower concentrations can be used at times but these do not present advantages and are economically disadvantageous.
Suitable stretching ratios can be easily determined by experiment. Tensile strength and modulus of the ~ilaments are, within certain limits, about proportional to the stretching ratio. Accordingly as the filaments are to be stronger, a greater stretching ratio will have to be selected.
The stretching ratio is at least 5, by preferance at least 10, and more in particular at least 20. High stretching ratios such as 30 to 40 and even higher can be applied without objection, and will result in filaments whose tensile strength and modulus are appreciably higher than those of filaments made by the usual dry spinning processes.
In dry spinning proce~ses the diameters of the spinning apertures in the spinning nozzles are usually small. In general, these diameters range from about 0.02 mm to about 1.0 mm. When small spinning apertures of les than about 0.2 mm are used, the spinning process is highly sensitive to the presence of impurities in the spinning solution. Therefore the spinning solution shouid be carefully freed and kept free of solid impurities. In most cases, filters are placed on the spinning nozzles, but regardless the spinning nozzles need to be cleaned after a short time, and blockage still occurs frequently. One significant advantage of the process of the present invention is that larger spinning apertures can be used.
Spinning apertures of for example about 0.5 mm to --~` 115227Z
2.0 mm or larger can be used because considerably higher stretching ratios can be applied and, additionally, generally lower polymer concentrations in the spinning solution are used.
The process of the present invention has a wider application and can be used in general for any materials that can be dry spun to filaments.
Polymers that can be spun by the process according to the present invention are, for instance, polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, polyoxymethylene, polyethylene oxide; polyamides, ` ~ such as the various types of nylon; polyesters, such as polyethyleneterephtalate, poly-acrylonitrile: vinyl polymers such as polyvinyl-alcohol, polyvinylidenefluoride.
Polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers and higher polyolefins can without objection be dissolved in hydrocarbons such as saturated aliphatic and cyclic hydrocarbons as well as aromatic hydrocarbons, or mixtures thereof such as mineral oil fractions. Very suitable are aliphatic or cyclic hydrocarbons such as nonane, decane, undecane, dodecane, tetralin, decalin, etc., or mineral oil fractions corresponding in boiling range. Polyethyelene or polypropylene is preferably dissolved in decalin or dodecane. The present method is particularly suitable for the preparation of filaments of polyolefins, preferably polyethylene.
It is also possible to make filaments of solutions of two or more polymers in a common solvent by the present process. For this purpose the polymers need not be miscible with each ```~ 115227~
other. For instance, it is possible to dissolve together in decalin or dodecane polyethylene and polypropylene whose melts are i~miscible, and to spin the solutions thus obtained.
The fila~ents according to the invention can be used for many purposes. They can be applied as reinforcement in many kinds of materials for which reinforcement with fibers or filaments is known, such as tire yarnsJ
and for all possible applications in which low weight combined with high strength is a desirable feature.
The invention will be further described with reference to the accompanying drawings showing by way of example a preferred embodiment of the:invention in which:
Figure 1 is a diagram showing the process for making polymer filaments according to the invention, wherein A refers to the polymer solution B refers to a cooling bath C refers to a wet filament D refers to a feed reel E refers to an oven F refers to a stretching reel Figure 2 is a diagram showing the dependency of the tensile strength (a) in GPa versus the stretching ratio ~b).
Figure 3 is a diagrAm showing the dependency of the modulus (b~
in GPa versus the stretching ratio (b).
The invention will be elucidated by means of the following examples, without being restricted thereby.
lS2272 EXA~PLES
Example 1 A polyethylene of high molecular weight, with Mw Y 1.5 x 106, was dissolved in decalin at 145C to fo~m a 2% wt. solution. This solution was spun through a spinning nozzle with a spinning aperature of 0.5 mm dia., at 130C. The filament was passed into a water bath kept at room temperature, where it was cooled. The cooled, 0.? mm thick filament, which was gel-like in appearance and still contained about 98% solvent, was next passed through a tubular oven heated at 120C, and stretched, with the use of various stretch-ing ratios. This process is shown in diagram in Figure 1.
Figures 2 and 3 show, respectively, the tensile strength and themodulus plotted against the stretching ratio. A modulus of more than 60 -9a-~ ~ZZ72 GPa and tensile strength of almost 3 can be attained using the process of the present invention whereas the modulus of polyethylene filaments madè in the conventional way is-2-3 GPa, and the tensile strength about 0.1 GPa.
The values of modulus and tensile strength of polyethylene filaments made with different stretching ratios as polotted in Figures 2 and 3 are given in Table 1.
Polyethylene filaments having a tensile strength of over 1.2 GPa can easily be produced by means of the present process.
.
Table 1 Expt. Stretching Modulus, Tensile strength ratio GPa GPa 1 1 2.4 0.09 2 3 5.4 0.27
d) stretching the filament, that still contains at least 25% by ueight of solvent relative to the polymer, at a stretching ratio of at least 5.
According to another aspect of the present invention there is provided a process for making polymer filaments which have a high tensile strength and a high modulus comprising the steps of:
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution tempera-ture of the polymer to form a polymer gel filament either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the sdlvent in the filament, c~ adjusting the temperature of said polymer gel filament at a value between the swelling point of the polymer in the solvent and the melting point of the polymer, d) stretching the filament, that still contains at least 25% by weight of solvent relative to the polymer, at a stretching ratio of at least 5, wherein there is at least a partial evaporation of the solvent, and e) recovering a substantially solvent-free filament.
In the dry spinning process which is widely applied on a technical scale, a solution of a spinnable polymer is spun in a shaft through which air is blown to evaporate all or most of all of the solvent to form the filament.
While the air is usually heated the temperature in the shaft is kept below the melting point of the polymer in order to increase the mechanical strength of the filament, which is veTy low as it exits the spinning aperture.
-2a-''~3~ ;
~227Z
The mechanical strength can be further increased in the subsequent stretching step at temperatures below the melting point of the polymer.
DESCRIPTION OF THE INVENTION
According to the present invention, the evaporation of the solvent from the filament immediately after spinning is not promoted during the cooling phase. The filament can be cooled to below the solution temperature, and particularly to below the swelling point of the polymer in the solvent by any suitable way, inclùding for e~ample, by passing the filament through a water bath, or through a shaft without any air or only minimal amounts of air being blown through the shaft. Some evaporation of the solvent from the filament will often take place spontaneously and cannot be prevented. This is acceptable as long as the evaporation is not actively promoted and the amount of solvent in the filament is not reduced~to a low value, e.g., to less than 25% by weight of solvent relative to the polymer.
Preferably the amount of solvent will not be less than equal amounts by weight of solvent and polymer. If desired, the evaporation of the solvent may be reduced or suppressed by carrying out the spinning in an atmosphere containing solvent vapor.
In cooling to below the solution temperature, in particular to below the swelling temperature of the polymer in the solvent, the polymer precipitates from the solution, and a gel is formed. A filament consisting of this polymer 1~ 5~;~72 gel has sufficient mechanical strength for further processing, for example, by means of the guides, rolls, and the like customarily used in spinning techniques. A filament of this kind is heated to a temperature between the swelling point of the filament in the solvent and the melting point of the polymer, and is then stretched at that temperature. This can be effected by passing the filament into a zone containing a gaseous or liquid medium kept at the required temperature. A
tubular oven with air for the gaseous medium is very suitable, but it is also possible to use a liquid bath or any other suitable device. A
gaseous medium is easier to handle, and is therefore preferable.
When the filament is being stretched in a gaseous medium, solvent evaporation will occur.
If a liquid medium is used, there will be dissolution of the solvent in the liquid.
Preferably, the evaporation is promoted by suitable means such as removal of the solvent vapor, by for instance leading a gas or air current past the filament in the stretching zone. At least part of the solvent should be evaporated, but preferably at least the greater part of the solvent is evaporated, so that by the end of the stretching zone there will be at most only a small amont, e.g., not more than a few percent, calcu].ated on a solid-substance basis of solvent contained in the fi~lament. The filament 5J~ould PrQ ~: e ra bJ
B which is eventually obtained must be free of solvent, and it is advantageous to apply such conditions that it is free, or virtually free, of solvent by the time it exits from the stretching zone.
llSZZ7Z
Surprisingly, the process in accordance with the present invention can produce filaments - that are considerably stronger, i.e. are filaments with considerably higher tensile~strength and s higher modulus than filaments of the same material made by any of the usual dry spinning processes.
By means of the methods described in the above-mentioned publications by Juyn and Bigg filaments of higher modulus have been obtained, but the tensile strength is still unacceptable. Moreover, the productivity of these methods is low.
The process in accordance with the present invention differs from the usual dry spinning processes in that a filament containing an appreciable amount of solvent is stretched with removal of solvent at a temperature at which the spinnable material will at least swell in the solvent, whereas in the usually applied spinning processes solvent free filaments are subjected to stretching.
One requirement of dry spinning is that the linear polymer be soluble in a suitable solvent. For any given soluble polymer a number of different solvents are available. A suitable solvent is one with a boiling point not too high so that it will not be difficult for the solvent to be evaporated from the filament, and not too low so that it is not too volatile and thus hinder filament formation because of rapid evaporation~
Also, if it is too volatile, it may have to be processed under pressure to prevent rapid evaporation.
115~27Z
Dissolution of a polymer in a suitable solvent involves swelling. While the solvent is being absorbed and the volume increases, a swollen gel is formed, which, however, because of its consistency and stability of shape is still regarded as a kind of solid substance. It is generally assumed that the polymer is composed of ordered or crystalline areas and less ordered or amorphous areas. The ordered areas are believed to act as anchoring points and thus lend stability of shape to the gel. The formation of the gel and the dissolution are time dependent. A given polymer can be dissolved in a given solvent only above a given temeprature. Below this solution temperature only swelling takes place, and according as the temperature is lowered, the swelling becomes less, until at a certain temperature the swelling will be negligible. The swelling point or swelling temperature is considered to be that temperature at which a distinct increase in volume and a distinct absorption of solvent in an amount of about 5 to 10% of the polymer weight occur. A simple rule of thumb is that the swelling temperature above which the stretching is to be effected is the temperature at which 10% of solvent is unquestionably absorbed into the swelling polymer.
In dry spinning processes usually 5-30~
wt. solutions are used ~or technical and economic reasons. Such solutions are also suitable for the process of the present invention, although generally solutions of lower concentration may be used. Solutions in the range of about 1 to 5% by ` 1152272 weight of polymer to solvent can be advantageously used while still lower concentrations can be used at times but these do not present advantages and are economically disadvantageous.
Suitable stretching ratios can be easily determined by experiment. Tensile strength and modulus of the ~ilaments are, within certain limits, about proportional to the stretching ratio. Accordingly as the filaments are to be stronger, a greater stretching ratio will have to be selected.
The stretching ratio is at least 5, by preferance at least 10, and more in particular at least 20. High stretching ratios such as 30 to 40 and even higher can be applied without objection, and will result in filaments whose tensile strength and modulus are appreciably higher than those of filaments made by the usual dry spinning processes.
In dry spinning proce~ses the diameters of the spinning apertures in the spinning nozzles are usually small. In general, these diameters range from about 0.02 mm to about 1.0 mm. When small spinning apertures of les than about 0.2 mm are used, the spinning process is highly sensitive to the presence of impurities in the spinning solution. Therefore the spinning solution shouid be carefully freed and kept free of solid impurities. In most cases, filters are placed on the spinning nozzles, but regardless the spinning nozzles need to be cleaned after a short time, and blockage still occurs frequently. One significant advantage of the process of the present invention is that larger spinning apertures can be used.
Spinning apertures of for example about 0.5 mm to --~` 115227Z
2.0 mm or larger can be used because considerably higher stretching ratios can be applied and, additionally, generally lower polymer concentrations in the spinning solution are used.
The process of the present invention has a wider application and can be used in general for any materials that can be dry spun to filaments.
Polymers that can be spun by the process according to the present invention are, for instance, polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers, polyoxymethylene, polyethylene oxide; polyamides, ` ~ such as the various types of nylon; polyesters, such as polyethyleneterephtalate, poly-acrylonitrile: vinyl polymers such as polyvinyl-alcohol, polyvinylidenefluoride.
Polyolefins such as polyethylene, polypropylene, ethylene-propylene copolymers and higher polyolefins can without objection be dissolved in hydrocarbons such as saturated aliphatic and cyclic hydrocarbons as well as aromatic hydrocarbons, or mixtures thereof such as mineral oil fractions. Very suitable are aliphatic or cyclic hydrocarbons such as nonane, decane, undecane, dodecane, tetralin, decalin, etc., or mineral oil fractions corresponding in boiling range. Polyethyelene or polypropylene is preferably dissolved in decalin or dodecane. The present method is particularly suitable for the preparation of filaments of polyolefins, preferably polyethylene.
It is also possible to make filaments of solutions of two or more polymers in a common solvent by the present process. For this purpose the polymers need not be miscible with each ```~ 115227~
other. For instance, it is possible to dissolve together in decalin or dodecane polyethylene and polypropylene whose melts are i~miscible, and to spin the solutions thus obtained.
The fila~ents according to the invention can be used for many purposes. They can be applied as reinforcement in many kinds of materials for which reinforcement with fibers or filaments is known, such as tire yarnsJ
and for all possible applications in which low weight combined with high strength is a desirable feature.
The invention will be further described with reference to the accompanying drawings showing by way of example a preferred embodiment of the:invention in which:
Figure 1 is a diagram showing the process for making polymer filaments according to the invention, wherein A refers to the polymer solution B refers to a cooling bath C refers to a wet filament D refers to a feed reel E refers to an oven F refers to a stretching reel Figure 2 is a diagram showing the dependency of the tensile strength (a) in GPa versus the stretching ratio ~b).
Figure 3 is a diagrAm showing the dependency of the modulus (b~
in GPa versus the stretching ratio (b).
The invention will be elucidated by means of the following examples, without being restricted thereby.
lS2272 EXA~PLES
Example 1 A polyethylene of high molecular weight, with Mw Y 1.5 x 106, was dissolved in decalin at 145C to fo~m a 2% wt. solution. This solution was spun through a spinning nozzle with a spinning aperature of 0.5 mm dia., at 130C. The filament was passed into a water bath kept at room temperature, where it was cooled. The cooled, 0.? mm thick filament, which was gel-like in appearance and still contained about 98% solvent, was next passed through a tubular oven heated at 120C, and stretched, with the use of various stretch-ing ratios. This process is shown in diagram in Figure 1.
Figures 2 and 3 show, respectively, the tensile strength and themodulus plotted against the stretching ratio. A modulus of more than 60 -9a-~ ~ZZ72 GPa and tensile strength of almost 3 can be attained using the process of the present invention whereas the modulus of polyethylene filaments madè in the conventional way is-2-3 GPa, and the tensile strength about 0.1 GPa.
The values of modulus and tensile strength of polyethylene filaments made with different stretching ratios as polotted in Figures 2 and 3 are given in Table 1.
Polyethylene filaments having a tensile strength of over 1.2 GPa can easily be produced by means of the present process.
.
Table 1 Expt. Stretching Modulus, Tensile strength ratio GPa GPa 1 1 2.4 0.09 2 3 5.4 0.27
3 7 17.0 0.73
4 8 17.6 0.81 11 23.9 1.32 6 12 37.5 1.65 7 13 40.9 1.72 8 15 41.0 1.72 9 17 43.1 2.11 69.0 2.90 11 32 90.2 3.02 ... . . . . . . .. _ _ _ _ _ _ Example 2 In accordance with the process described in Example 1, a 2% wt. solution of a mixture of equal parts of high-molecular-weight polyethylene, with Mw ~ 1.5 x 106, and a high-molecular-weight ~152272 polypropylene, with Mw ~ 3.0 x 106, was spun at 140C and stretched at 130C, using a stretching ratio of 20. The filaments had a tensile strength of 1.5 GPa.
S Example 3 In accordance with the process described in Example 1, a 2% wt. solution of isotactic polypropylene, with Mw - 3.0 x 106, was spun at 140C and stretched at 130C, using a stretching ratio of 20. The tensile strength of the resulting filaments was 1 GPa.
S Example 3 In accordance with the process described in Example 1, a 2% wt. solution of isotactic polypropylene, with Mw - 3.0 x 106, was spun at 140C and stretched at 130C, using a stretching ratio of 20. The tensile strength of the resulting filaments was 1 GPa.
Claims (5)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for making polymer filaments which have a high tensile strength and a high modulus comprising the steps of:
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution tem-perature of the polymer, either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the solvent in the filament c) bringing said filament to a temperature between the swelling point of the polymer in the solvent and the melting point of the polymer, and d) stretching the filament, that still contains at least 25%
by weight of solvent relative to the polymer, at a stretching ratio of at least 5.
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution tem-perature of the polymer, either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the solvent in the filament c) bringing said filament to a temperature between the swelling point of the polymer in the solvent and the melting point of the polymer, and d) stretching the filament, that still contains at least 25%
by weight of solvent relative to the polymer, at a stretching ratio of at least 5.
2. A process for making polymer filaments which have a high tensile strength and a high modulus comprising the steps of:
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution temperature of the polymer to form a polymer gel filament either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the solvent in the filament c) adjusting the temperature of said polymer gel filament at a value between the swelling point of the polymer in the solvent and the melting point of the polymer, d) stretching the filament, that still contains at least 25%
by weight of solvent relative to the polymer, at a stretching ratio of at least 5, wherein where is at least a partial evaporation of the solvent, and e) recovering a substantially solvent-free filament.
a) spinning a solution of a linear polymer, ranging from about 1% to about 5% by weight of polymer to solvent, through a spinning aperture to form a filament, b) cooling said filament of step (a) to below the solution temperature of the polymer to form a polymer gel filament either in a zone containing a gas without promoting the evaporation of the solvent or with a cooling liquid that does not dilute or extract the solvent in the filament c) adjusting the temperature of said polymer gel filament at a value between the swelling point of the polymer in the solvent and the melting point of the polymer, d) stretching the filament, that still contains at least 25%
by weight of solvent relative to the polymer, at a stretching ratio of at least 5, wherein where is at least a partial evaporation of the solvent, and e) recovering a substantially solvent-free filament.
3. The process of claim 1 or 2 wherein the spun filament is cooled below the swelling point and then stretched at a temperature between the swelling point and the melting temperature.
4. The process of claim 1 or 2 wherein a filament containing at least about an equal amount by weight of solvent relative to the polymer is stretched.
5. The process of claim 1 or 2 wherein the stretching ratio is at least 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL7900990 | 1979-02-08 | ||
| NLAANVRAGE7900990,A NL177840C (en) | 1979-02-08 | 1979-02-08 | METHOD FOR MANUFACTURING A POLYTHENE THREAD |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1152272A true CA1152272A (en) | 1983-08-23 |
Family
ID=19832598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000345309A Expired CA1152272A (en) | 1979-02-08 | 1980-02-08 | Filaments of high tensile strength and modulus |
Country Status (19)
| Country | Link |
|---|---|
| JP (4) | JPS6047922B2 (en) |
| AT (1) | AT380033B (en) |
| AU (1) | AU532451B2 (en) |
| BE (1) | BE881587A (en) |
| BR (1) | BR8000775A (en) |
| CA (1) | CA1152272A (en) |
| CH (1) | CH650535C2 (en) |
| CS (1) | CS235001B2 (en) |
| DE (2) | DE3051066C2 (en) |
| ES (1) | ES488304A1 (en) |
| FR (1) | FR2448587B1 (en) |
| GB (1) | GB2042414B (en) |
| IN (1) | IN152729B (en) |
| IT (1) | IT1144056B (en) |
| MX (1) | MX6124E (en) |
| NL (1) | NL177840C (en) |
| SE (1) | SE446105B (en) |
| SU (1) | SU1138041A3 (en) |
| ZA (1) | ZA80528B (en) |
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| DE2713456C2 (en) * | 1977-03-26 | 1990-05-31 | Bayer Ag, 5090 Leverkusen | Process for the production of hydrophilic fibers |
| NL177840C (en) * | 1979-02-08 | 1989-10-16 | Stamicarbon | METHOD FOR MANUFACTURING A POLYTHENE THREAD |
| US6020230A (en) * | 1998-04-22 | 2000-02-01 | Texas Instruments-Acer Incorporated | Process to fabricate planarized deep-shallow trench isolation having upper and lower portions with oxidized semiconductor trench fill in the upper portion and semiconductor trench fill in the lower portion |
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1979
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1980
- 1980-01-29 ZA ZA00800528A patent/ZA80528B/en unknown
- 1980-02-01 AU AU55148/80A patent/AU532451B2/en not_active Expired
- 1980-02-04 CH CH874/80A patent/CH650535C2/en not_active IP Right Cessation
- 1980-02-06 FR FR8002571A patent/FR2448587B1/en not_active Expired
- 1980-02-06 CS CS80810A patent/CS235001B2/en unknown
- 1980-02-06 ES ES488304A patent/ES488304A1/en not_active Expired
- 1980-02-06 AT AT0065280A patent/AT380033B/en not_active IP Right Cessation
- 1980-02-07 IT IT47840/80A patent/IT1144056B/en active
- 1980-02-07 MX MX808636U patent/MX6124E/en unknown
- 1980-02-07 SU SU802878003A patent/SU1138041A3/en active
- 1980-02-07 JP JP55014245A patent/JPS6047922B2/en not_active Expired
- 1980-02-07 GB GB8004157A patent/GB2042414B/en not_active Expired
- 1980-02-07 BE BE0/199295A patent/BE881587A/en not_active IP Right Cessation
- 1980-02-07 BR BR8000775A patent/BR8000775A/en not_active IP Right Cessation
- 1980-02-07 SE SE8000997A patent/SE446105B/en not_active IP Right Cessation
- 1980-02-08 DE DE3051066A patent/DE3051066C2/de not_active Expired
- 1980-02-08 CA CA000345309A patent/CA1152272A/en not_active Expired
- 1980-02-08 DE DE19803004699 patent/DE3004699A1/en active Granted
- 1980-02-08 IN IN149/CAL/80A patent/IN152729B/en unknown
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1984
- 1984-08-10 JP JP59168737A patent/JPS6075606A/en active Pending
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1986
- 1986-07-31 JP JP61181840A patent/JPS6245714A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7141301B2 (en) | 2000-12-11 | 2006-11-28 | Toyo Boseki Kabushiki Kaisha | High strength polyethylene fiber |
| US7056579B2 (en) | 2001-08-08 | 2006-06-06 | Toyo Boseki Kabushiki Kaisha | High-strength polyethylene fiber |
| US7811673B2 (en) | 2003-12-12 | 2010-10-12 | Toyo Boseki Kabushiki Kaisha | High strength polyethylene fiber |
Also Published As
| Publication number | Publication date |
|---|---|
| CH650535A5 (en) | 1985-07-31 |
| AU532451B2 (en) | 1983-09-29 |
| IT8047840A0 (en) | 1980-02-07 |
| JPS6047922B2 (en) | 1985-10-24 |
| DE3051066C2 (en) | 1987-12-10 |
| AT380033B (en) | 1986-03-25 |
| BE881587A (en) | 1980-08-07 |
| JPS6075607A (en) | 1985-04-30 |
| IN152729B (en) | 1984-03-24 |
| CH650535C2 (en) | 1998-02-27 |
| MX6124E (en) | 1984-11-21 |
| DE3004699A1 (en) | 1980-08-21 |
| ES488304A1 (en) | 1980-08-01 |
| JPS6245714A (en) | 1987-02-27 |
| DE3004699C2 (en) | 1987-10-29 |
| JPS648732B2 (en) | 1989-02-15 |
| FR2448587A1 (en) | 1980-09-05 |
| NL7900990A (en) | 1980-08-12 |
| GB2042414B (en) | 1982-12-22 |
| IT1144056B (en) | 1986-10-29 |
| ZA80528B (en) | 1981-01-28 |
| SE446105B (en) | 1986-08-11 |
| JPS6075606A (en) | 1985-04-30 |
| AU5514880A (en) | 1980-08-14 |
| ATA65280A (en) | 1985-08-15 |
| SU1138041A3 (en) | 1985-01-30 |
| JPS55107506A (en) | 1980-08-18 |
| FR2448587B1 (en) | 1985-08-23 |
| SE8000997L (en) | 1980-08-09 |
| BR8000775A (en) | 1980-10-21 |
| NL177840B (en) | 1985-07-01 |
| GB2042414A (en) | 1980-09-24 |
| NL177840C (en) | 1989-10-16 |
| CS235001B2 (en) | 1985-04-16 |
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