GB1594545A - Method of producing aritcles from melts of crystallizable polymers - Google Patents

Method of producing aritcles from melts of crystallizable polymers Download PDF

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Publication number
GB1594545A
GB1594545A GB11870/78A GB1187078A GB1594545A GB 1594545 A GB1594545 A GB 1594545A GB 11870/78 A GB11870/78 A GB 11870/78A GB 1187078 A GB1187078 A GB 1187078A GB 1594545 A GB1594545 A GB 1594545A
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United Kingdom
Prior art keywords
polymer
melts
melt
spinneret
temperature
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
Application number
GB11870/78A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
INST VYSOKOMOLEKULYARNYKH SOED
Original Assignee
INST VYSOKOMOLEKULYARNYKH SOED
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to DE2813012A priority Critical patent/DE2813012C2/en
Application filed by INST VYSOKOMOLEKULYARNYKH SOED filed Critical INST VYSOKOMOLEKULYARNYKH SOED
Priority to GB11870/78A priority patent/GB1594545A/en
Priority to FR7814812A priority patent/FR2425934A1/en
Publication of GB1594545A publication Critical patent/GB1594545A/en
Expired legal-status Critical Current

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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
    • 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
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
    • B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
    • 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
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
    • B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the 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
    • D01D5/08—Melt spinning methods
    • 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
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0018—Combinations of extrusion moulding with other shaping operations combined with shaping by orienting, stretching or shrinking, e.g. film blowing
    • 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
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Description

(54) METHOD OF PRODUCING ARTICLES FROM MELTS OF CRYSTALLIZABLE POLYMERS (71) We, INSTITUT VYSOKO MOLEKULYARNYKH SOEDINENY AKEDEMII NAUK SSSR, Bolshoi prospekt, 31, Leningrad, Union of Soviet Socialist Republics, a State Enterprise organised and existing under the laws of the U.S.S.R., do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:- The present invention relates to methods of producing articles from polymers and more particularly to a method of producing articles from melts of crystallizable polymers.
It is most expedient to use the present invention for producing articles from polyolefins, for example, from high-density polyethylenes and polypropylenes.
Known in the art are methods of producing articles from melts of crystallizable polymers (see Japanese Patent No. 28979, cl. DOlif of 23.08.71) by extruding the polymer melt through a spinneret with subsequent solidification and drawing thereof.
It is known that industrial methods of producing polymer articles are based on the crystallization process. The structure of the polymer being crystallized determines the strength and other properties of a readymade article.
Crystallization of polymers from the melt without an external action is accompanied, as a rule, by the folding of the macromolecular chains which are twisted in the melt and form coils. The structure of the article obtained is a set of folded crystals connected with one another by separate chains which pass from one crystal to another and take up the main load in use of the article. These are so-called stressed chains (bonds). Mechanical and, in particular, tensile properties of the polymer article in this case are completely determined by the number of the bonds (per unit of the cross section surface area).
To improve the above-cited properties of the articles, the polymers are subjected to drawing. When the articles are prepared by the known method, drawing is performed in two stages: first, when the polymer is extruded through a spinneret and, second, after the polymer is solidified. In the first stage the melt, which is in a viscous-flow state, is subjected to some drawing (spinneret drawing). In this case spinneret drawing is limited because of the viscousflow state of the polymer (due to high overheating with respect to the crystallization point). Therefore, deformation of the coils of twisted macromolecules does not attain values sufficient for straightening of the macromolecules. Due to the high mobility of the macromolecules in the overheated melt, drawing only accelerates slipping of the macromolecule coils with respect to one another. This is accompanied by unfolding of the coils, and during subsequent solidification of such deformed melt, the number of chains connecting separate crystals decreases. As a result, with an increasing degree of spinneret drawing, the properties of the article produced deteriorate.
The next stage of drawing is performed after solidification of the polymer with or without heating. This makes it possible to improve somewhat the mechanical characteristics, i.e. to increase the strength and elasticity modulus with a simultaneously reduction in elongation.
But, nevertheless, the articles (fibres, films) obtained by the known method do not possess sufficiently low elongation and high Young's modulus and strength, which limits their application in industry and shortens the service-life especially in such branches as the tyre industry, production of fibrous plastics, etc.
It is an object of the invention to eliminate the above disadvantages.
The principal object of the invention is to provide a method of manufacturing articles from melts of crystallizable polymers, which will increase the strength of the articles and their Young's modulus and decrease elongation.
This object is accomplished by providing a method of producing articles from melts of crystallizable polymers comprising extruding a polymer melt through a spinneret so that extruded melt flows from the spinneret, decelerating the extruded melt at a location adjacent to the spinneret so that the decelerated extruded melt flows from said location, and effecting drawing of the decelerated extruded melt within a treating zone whereof the temperature is in the range between the crystallization temperature of the polymer and 50"C below same, to effect solidification of the decelerated extruded melt.
Due to such technological solution, even at the earliest stages of polymer solidification, a larger (as compared with the known method) number of macromolecules straighten and become oriented in the direction of elongation with a simultaneous fixing of this orientation, i.e. solidification. This is accompanied by the formation of crystals from the stretched chains connected with one another by a comparatively large number of stressed bonds. As a result, the number of (stressed) bonds, taking the load, per unit of the cross section surface area increases, thus increasing the strength and elasticity modulus and decreasing considerably the elongation of the polymer.
Specific examples of a method of producing articles from crystallizable polymers in accordance with the invention are given hereinafter by way of illustration with reference to the accompanying drawing which shows a principal diagram of a device for realizing said method.
Example 1 To obtain an elementary filament from a melt, a polymer, for example, high-density polyethylene, having the following .characteristics is used: melt index, 26.2 g/10 min; density, 0.941 g/cm3; melting point (m.p.), 1300C.
The polymer granules are charged into a conventional moulding device containingan extruder (1) (Fig. 1) and a spinneret assembly (2).
The temperature of heating zones in the extruder and the temperature of the forming head are as follows: I zone, 1700C; II zone, 200"C; III zone, 240"C; moulding head IV, 210 C.
Melt (3) is extruder through a spinneret hole (4) 0.24 mm in diameter; the rate of the extruder-melt flow from the spinneret hole is 3m/min.
At a distance of 20 cm from the spinneret hole (4) a decelerating device (5) is mounted, said device comprising one pair of actively rotating thermostatically controlled rollers (5) of a cylindrical form.
The gap between the rollers (5) is adjusted to the values from zero to the filament diameter. The decelerating device is placed at a depth of 50 mm into a thermostatically controlled bath (6) of any heated fluid which is chemically inert towards the polymer.
The temperature of the heated fluid (for example, silicone oil) is established as equal to that on the surface of the rollers 5, namely, 1 100C. As can be seen from the above, the polymer-melt extrusion near the exit from the spinneret hole 4 flows through a region corresponding to the crystallization zone and having a temperature within a range between the crystallization temperature of the polymer and 50"C below said temperature.
The pre-solidified filament is clamped between the rotating rollers of the decelerating device. The gap between the rollers is 0.17 mm and the rotation speed is chosen so that the ratio between the rate of the polymer flow from-the spinneret hole and the linear speed of the rollers is 1.5.
Then the filaments fed to a stretching and receiving device 6 which rotates with a linear speed equal to 40 m/min.
Thus, the aforesaid decelerating device ensures deceleration of the pre-solidified filament at the entry to a region of required temperature with a force sufficient for ensuring solidification of the polymer by the subsequent drawing thereof in said region.
The diameter of the elementary filament thus obained is 0.07 mm. The tensile strength ert of the ready-made filament is 0.90-0.95 GPa; Young's modulus E.21 GPa; and elongation E, 9--10%.
Example 2 The conditions of forming an elementary filament are similar to those described in Example 1. But the temperature of the surface of the thermostatically controlled rollers 5 of the decelerating device and that of the heat carrier in the thermostatically controlled bath 6 is 85 C.
Thus, in this case as well, the polymer melt near the exit from the spinneret and at the entry to a region corresponding to the crystallization zone has a temperature whose value is within a range of 50 C from the crystallization temperature of the polymer.
The diameter of the elementary filament obtained is 0.07 mm.
The tensile strength of the ready-made filament is ~ 0.70-0.75 GPa; Young's modulus E, 13 GPa; elongation #, 13-16%.
Hence, in spite of the fact that solidification of the filament is performed by its drawing under non-optimum conditions, the mechanical characteristics of the ready-made filament are higherlthan those of a filament manufactured by the known method.
Example 3 To prepare an elementary filament from a melt, isotactic polypropylene is used having the following characteristics: melt index, 42 g/10 min; content of the atatic part, 0.2 and of stereoblock part, 4.2 weight %; melting point (m.p.), 175 C.
The conditions of forming an elementary filament from the polymer are similar to those described in Example 1 but; (1) the temperature of the heating zones in the extruder is 190 C in the I zone, 230 C in the II zone, 270 C in the III zone and 250 C of the forming head IV.
(2) the temperature of the surface of the thermostatically controlled rollers of the decelerating device, as well as the temperature of the heating fluid in the thermostatically controlled bath, is 150 C.
The diameter of the elementary filament thus prepared is 0.062 mm; tenacity at 0.95-1.00 GPa; Young's modulus E, 26--28 GPa; elongation E, 810%.
Example 4 The conditions of forming an elementary filament from a polymer melt are similar to those described in Example 3, but the temperature of the surface of the thermostatically controlled rollers, as well as the temperature of the heat carrier in a thermostatically controlled bath, is 127 C.
Thus, in this case as well, the polymer melt near the exit from the spinneret and within the region corresponding to the crystallization zone has a temperature which is within the range of 50 C below the crystallization temperature.
The diameter of the obtained elementary filament is 0.069 mm; tensile strength at, 0.80-0.85 GPa; Young's modulus E, 19-20 GPa; elongation #, 15-17%.
In conclusion, a table is given for comparing the mechanical properties of elementary filaments obtained by following the known and the hereinbefore described methods.
TABLE Proposed Method as described Proposed Method as described in Example 1 in Example 2 Polymer #T-20 C #T-45 C Known method High-density #t E # #t E # #t E # polyethylene 0.90-0.95 21 9-10 0.70-0.75 13 13-16 0.55-0.65 9-11 13-16 Isotatic 0.95-1.00 26-28 8-10 0.80-0.85 19-20 15-17 0.70-0.75 12-14 13-16 polypropylene Thus, the mechanical properties of the elementary filament, obtained by extruding the polymer melt through a spinneret with subsequent solidification thereof by drawing within the crystallization zone at a temperature whose values is within a range of 50"C below the crystallization temperature, are considerably improved as compared with those of a filament obtained by known methods.

Claims (4)

WHAT WE CLAIM IS:
1. A method of producing articles from melts of crystallizable polymers, comprising extruding a polymer melt through a spinneret so that extruded melt flows from the spinneret, decelerating the extruded melt at a location adjacent to the spinneret so that the decelerated extruded melt flows from said location, and effecting drawing of the decelerated extruded melt within a treating zone whereof the temperature is in the range between the crystallization temperature of the polymer and 50"C below same to effect solidification of the decelerated extruded melt.
2. A method of producing articles from melts of crystallizable polymers, as claimed in the above Claim and substantially as hereinbefore described.
3. A method of producing articles from melts of crystallizable polymers, substantially as hereinbefore described with reference to any one of the Examples.
4. Articles whenever produced from melts of crystallizable polymers by the method according to any one of the preceding claims.
GB11870/78A 1978-03-28 1978-03-28 Method of producing aritcles from melts of crystallizable polymers Expired GB1594545A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE2813012A DE2813012C2 (en) 1978-03-28 1978-03-23 Process for the manufacture of products from melts of crystallizable polymers
GB11870/78A GB1594545A (en) 1978-03-28 1978-03-28 Method of producing aritcles from melts of crystallizable polymers
FR7814812A FR2425934A1 (en) 1978-03-28 1978-05-18 PROCESS FOR OBTAINING ARTICLES FROM CRYSTALLIZABLE POLYMER FUSION BATHS

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB11870/78A GB1594545A (en) 1978-03-28 1978-03-28 Method of producing aritcles from melts of crystallizable polymers

Publications (1)

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GB1594545A true GB1594545A (en) 1981-07-30

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GB11870/78A Expired GB1594545A (en) 1978-03-28 1978-03-28 Method of producing aritcles from melts of crystallizable polymers

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DE (1) DE2813012C2 (en)
FR (1) FR2425934A1 (en)
GB (1) GB1594545A (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3539185A1 (en) * 1984-12-01 1986-06-05 Barmag Barmer Maschinenfabrik Ag, 5630 Remscheid Process for the production of polypropylene threads

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT202689B (en) * 1956-10-26 1959-03-25 Montedison Spa Process for the production of stretch-oriented fiber material or continuous fibers
US3258515A (en) * 1963-05-07 1966-06-28 Fmc Corp Process for quenching films
US3511905A (en) * 1967-08-22 1970-05-12 Viscose Suisse Soc Process for the preparation of synthetic polymer filaments
US3518722A (en) * 1967-10-31 1970-07-07 Fmc Corp Guide for incompletely solidified polymeric article
NL6902959A (en) * 1969-02-26 1970-08-28
US3605162A (en) * 1969-03-14 1971-09-20 Ind Brush Co Brush filament and construction therefor
BE759802A (en) * 1969-12-04 1971-05-17 Snia Viscosa METHOD AND DEVICE FOR THE CONTINUOUS SPINNING AND EXTENSION OF SYNTHETIC FILAMENTS, MORE PARTICULARLY OF POLYESTER FILAMENTS
DE2513385A1 (en) * 1975-03-26 1976-10-07 Kabel Metallwerke Ghh High grade stress free cable insulation - produced by cooling sprayed on polymer in stages without stretching
JPS54289A (en) * 1977-05-19 1979-01-05 Shigeji Tanigaki Motor twooblade saw

Also Published As

Publication number Publication date
FR2425934A1 (en) 1979-12-14
DE2813012A1 (en) 1979-09-27
DE2813012C2 (en) 1985-04-18
FR2425934B1 (en) 1981-04-30

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PS Patent sealed [section 19, patents act 1949]
PCNP Patent ceased through non-payment of renewal fee