EP0233667A1 - Verfahren zur Herstellung einer Synthesefaser und einer orientierten Synthesefaser sowie nach diesem Verfahren hergestellte orientierte Synthesefaser - Google Patents

Verfahren zur Herstellung einer Synthesefaser und einer orientierten Synthesefaser sowie nach diesem Verfahren hergestellte orientierte Synthesefaser Download PDF

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Publication number
EP0233667A1
EP0233667A1 EP87200155A EP87200155A EP0233667A1 EP 0233667 A1 EP0233667 A1 EP 0233667A1 EP 87200155 A EP87200155 A EP 87200155A EP 87200155 A EP87200155 A EP 87200155A EP 0233667 A1 EP0233667 A1 EP 0233667A1
Authority
EP
European Patent Office
Prior art keywords
synthetic
resin fibre
oligomeric compound
starting material
molecularly oriented
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.)
Granted
Application number
EP87200155A
Other languages
English (en)
French (fr)
Other versions
EP0233667B1 (de
Inventor
Dirk Jan Broer
Grietje Neeltje Mol
Cornelis Marinus Gerrit Jochem
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.)
Koninklijke Philips NV
Original Assignee
Philips Gloeilampenfabrieken NV
Koninklijke Philips Electronics NV
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
Application filed by Philips Gloeilampenfabrieken NV, Koninklijke Philips Electronics NV filed Critical Philips Gloeilampenfabrieken NV
Publication of EP0233667A1 publication Critical patent/EP0233667A1/de
Application granted granted Critical
Publication of EP0233667B1 publication Critical patent/EP0233667B1/de
Expired legal-status Critical Current

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Classifications

    • 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
    • D01D5/38—Formation of filaments, threads, or the like during polymerisation
    • 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
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • 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
    • D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products

Definitions

  • the invention relates to a method of manufacturing a synthetic-resin fibre.
  • the invention further relates to a method of manufacturing a molecularly oriented synthetic-resin fibre and to a molecularly oriented synthetic-resin fibre manufactured by this method.
  • synthetic-resin fibres are frequently used in, for example, textile fibres, as a reinforcing means in optical telecommunication cables and as a filler in synthetic-resin composite materials.
  • the expression "molecularly oriented” is to be understood to mean herein that the material concerned contains anisotropic molecules having a preferred orientation.
  • the polymer molecules are elongated, the preferred orientation being the longitudinal direction of the fibre.
  • the polymer molecules In a non-oriented synthetic-resin, the polymer molecules generally have the shape of an isotropic cluster or coil.
  • a molten polymer is extruded through a narrow aperture after which the liquid thread is led through a cooling means in which the polymer solidifies to form a solid thread. Due to the high temperature of the melt chemical decomposition in the melting and extrusion process is hard to avoid.
  • a further object of the invention is to provide a method in which no solvents have to be used.
  • a starting material which comprises at least one oligomeric compound is extruded from the melt to form a liquid thread, after which the starting material is polymerized by subjecting it to actinic radiation.
  • an oligomeric compound also has a lower viscosity than the corresponding polymeric compound.
  • the oligomeric compound may be a monomeric compound or a compound consisting of a small number of monomeric units. It should be noted, however, that the compound is not polymerized until the desired fibre shape has been imparted to the starting material.
  • actinic radiation is to be understood to mean herein radiation using light, in particular UV-light, X-rays, gamma-rays or radiation using high-energetic particles, such as, electrons or ions.
  • the starting material may comprise a mixture of various oligomeric compounds.
  • the starting material may comprise one or more other suitable components, such as, for example, catalysts, (light sensitive) initiators, stabilizers, co-reacting monomers and surface-active compounds.
  • a synthetic-resin fibre is stretched.
  • the said fibre is manufactured in the usual way, for example, by spinning from a melt.
  • creep and relaxation of the stretched polymer molecules is precluded in a known manner by fixing the stretched conformation by means of cross-links between the polymer molecules.
  • Such a cross-linking reaction may be caused, for example, by radiation using high-energetic particles, such as electrons.
  • a starting material which at least comprises one oligomeric compound is extruded from the melt to form a liquid thread, after which the starting material is polymerized by subjecting it to actinic radiation, which method is further characterized in that the oligomeric compound is oriented immediately after the extrusion process by subjecting the liquid thread to an elongational flow, after which the starting material is polymerized prior to relaxation of the oriented oligomeric compound.
  • the invention is based on the experimentally established phenomenon that in a liquid having a relatively low viscocity an orientation can be brought about very effectively by means of an elongational flow.
  • the not yet polymerized molecules are small enough to form regular, almost crystalline structures, which in the case of a polymer is possible only to a limited extent, in particular, if there are cross-links between the molecules in the said polymer.
  • actinic radiation is used to start the polymerization process.
  • actinic radiation is not used to form cross-links in an existing polymeric material, but to form the polymer.
  • An additional advantage of the method in accordance with the invention is the efficient use of actinic radiation when it is simultaneously used to form the polymer and to form cross-links between the polymer molecules. In this case it is not necessary to carry out a separate operation after a fibre has been formed, in which operation the fibre is reinforced and cross-links are formed.
  • a further advantage of the method in accordance with the invention is that, as a result of the regular molecular structure, it is possible to form very many cross-links in the polymeric material, as a result of which a very strong fibre is obtained which is hardly subject to creep.
  • the oligomeric compound used and the processing temperature are selected so that the oligomeric compound exhibits liquid crystalline proporties at the processing temperature.
  • the orientation is enhanced by applying an electric or magnetic field.
  • the field is applied longitudinally or perpendicularly to the fibre to be manufactured. Due to this measure, the relaxation time of the molecules is increased and the curing time is less critical.
  • suitable compounds are aromatic polyamides and polyesters on the basis of p-hydroxy-benzoic acid. These materials are liquid crystalline with the mesogenic or smectic group in the main chain of the polymer. Further, it is possible to select a fast-curing starting material which comprises a mixture of oligomers, for example, a mixture in which the polymerization reaction is a reaction between a vinyl group and a thiol group.
  • the oligomeric compound used is selected from the group formed by oligo-esteracrylates and oligo­etheracrylates having a molecular weight of less than 3000 and comprising at least two acrylate-ester groups per molecule.
  • an oligomeric compound which consists of unbranched chains containing 1 to 12 rod-like, rigid chemical groups which enhance liquid crystalline properties, and 2 to 15 flexible chemical groups, and in which the acrylate-ester groups are attached to the chains via such flexible groups.
  • a high degree of molecular orientation is possible because the chains are unbranched and because of the presence of the rigid chemical groups in the main chains of the polymer molecules.
  • the acrylate-ester groups permit a high polymerization rate, consequently, these groups must possess a certain degree of mobility.
  • a polymer network can be formed because there are at least two polymerizing acrylate-ester groups in each molecule.
  • the rod-liked, rigid chemical groups are preferably selected from the group formed by :
  • the flexible chemical groups are preferably selected from the group formed by : in which p has a value of from 2 to 10, q has a value of from 1 to 10 and r has a value of from 1 to 6.
  • the chemical groups can be interconnected in the linear molecular chain in various ways, for example, directly, via oxygen atoms (ether bond), via ester groups or via urethane groups.
  • Figure 1 is the structural formula of an oligo­esterurethane acrylate which is suitable for use in the method in accordance with the invention, and which has 2 rigid, rod-like chemical groups per molecule, different types of flexible groups, urethane groups as coupling elements and 2 acrylate-ester groups per molecule. Due to the regular construction of the molecules, this material is crystalline in a non-polymerized condition at room temperature. In order to be able to cure the material by subjecting it to UV-light, it is mixed with 2 % by weight of 1-hydroxy-1-methyl-ethylphenylketone by stirring the components together at a temperature of 70°C.
  • the viscocity of the mixture at 80°C is almost independent of the rate of shear and amounts to 5 to 6 Pa.s.
  • the starting material may contain mono- or polyfunctional acrylate compounds which are incorporated into the polymer network. Such compounds increase the rate of the polymerization reaction and reduce the viscocity of the starting material. Suitable examples are 2-phenoxy-ethylacrylate, hexanedioldiacrylate and trimethylolpropanetriacrylate.
  • the starting material is extruded at a temperature of 80°C, in an arrangement as shown in Figure 2, from a vessel 10 which is provided with heating elements 11 and a plunger 12.
  • a stable liquid thread 13 is obtained, for example, under the following conditions : the bore of the nozzle 14 has a diameter of 0.5 mm and a length of 5 mm, the liquid pressure is 1.73 MPa and the rate of flow is 102 mm3/s.
  • the desired molecular orientation is obtained by means of an elongational flow at the location of the arrow 15, for example, under the influence of gravity but, preferably, by drawing the fibre 16, for example, via one or more rollers 17 after the fibre has cured.
  • the diameter of the liquid thread decreases from 0.5 to 0.2 mm, in which region the liquid thread is exposed to UV-light having a wavelength of from 300 to 400 nm, for example, by means of an electrodeless mercury lamp 18, marketed by Fusion System Inc., in combination with an elliptical-cylindrical mirror 19.
  • the molecular orientation of the cured fibre can be made visible in a polarization microscope having crossed polarizers.
  • the oriented synthetic-resin fibre distinguishes itself by a large modulus of elasticity in the longitudinal direction (axially), a great breaking strength and a small thermal coefficient of expansion.
  • the oriented material exhibits 8.7 x 1020 cross-links per cm3 between the polymer chains, which corresponds to a degree of conversion of 95 % of the acrylate-ester groups.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
  • Reinforced Plastic Materials (AREA)
EP19870200155 1986-02-10 1987-02-03 Verfahren zur Herstellung einer Synthesefaser und einer orientierten Synthesefaser sowie nach diesem Verfahren hergestellte orientierte Synthesefaser Expired EP0233667B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8600307A NL8600307A (nl) 1986-02-10 1986-02-10 Werkwijze voor het vervaardigen van een kunststofvezel en van een moleculair georienteerde kunststofvezel, en moleculair georienteerde kunststofvezel verkregen volgens de werkwijze.
NL8600307 1986-02-10

Publications (2)

Publication Number Publication Date
EP0233667A1 true EP0233667A1 (de) 1987-08-26
EP0233667B1 EP0233667B1 (de) 1990-10-24

Family

ID=19847543

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870200155 Expired EP0233667B1 (de) 1986-02-10 1987-02-03 Verfahren zur Herstellung einer Synthesefaser und einer orientierten Synthesefaser sowie nach diesem Verfahren hergestellte orientierte Synthesefaser

Country Status (5)

Country Link
EP (1) EP0233667B1 (de)
JP (1) JP2511929B2 (de)
DE (1) DE3765651D1 (de)
GR (1) GR3001070T3 (de)
NL (1) NL8600307A (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5073294A (en) * 1990-03-07 1991-12-17 Hercules Incorporated Process of preparing compositions having multiple oriented mesogens
WO2010046750A2 (en) * 2008-10-21 2010-04-29 Fein-Elast Italia Spa Plant and method for making continuous elastic yarns made of silicon material and continuous elastic yarn made of silicon material thus obtained
US7939578B2 (en) 2007-02-23 2011-05-10 3M Innovative Properties Company Polymeric fibers and methods of making
US8513322B2 (en) 2007-05-31 2013-08-20 3M Innovative Properties Company Polymeric beads and methods of making polymeric beads
EP2710050A1 (de) * 2011-05-18 2014-03-26 Palchik, Oleg Wärmeformbare und wärmehärtbare fasern sowie ihre herstellung durch uv-härtung

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6619353B1 (en) 1999-08-20 2003-09-16 Jong Gil Kim Chain for tire
US8318282B2 (en) 2007-12-12 2012-11-27 3M Innovative Properties Company Microstructured antimicrobial film

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2080737A1 (en) * 1970-02-24 1971-11-19 Schwarza Chemiefaser Mfg synthetic fibres or foils in a single step

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5361727A (en) * 1976-11-09 1978-06-02 Esu Booiden Jiyunia Jiyon Flexible elastic material hardened upon radiation of wave energy
JPS6088112A (ja) * 1983-10-19 1985-05-17 Matsushita Electric Ind Co Ltd メカノケミカル繊維の製造方法
JPS60215808A (ja) * 1984-04-04 1985-10-29 Hitachi Ltd 紡糸装置

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2080737A1 (en) * 1970-02-24 1971-11-19 Schwarza Chemiefaser Mfg synthetic fibres or foils in a single step

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 8, no. 138 (C-231)[1575], 27th June 1984; & JP-A-59 47 411 (TEIJIN K.K.) 17-03-1984 *
PATENT ABSTRACTS OF JAPAN, vol. 9, no. 228 (C-303)[1951], 13th September 1985; & JP-A-60 88 112 (MATSUSHITA DENKI SANGYO K.K.) 17-05-1985 *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5073294A (en) * 1990-03-07 1991-12-17 Hercules Incorporated Process of preparing compositions having multiple oriented mesogens
US7939578B2 (en) 2007-02-23 2011-05-10 3M Innovative Properties Company Polymeric fibers and methods of making
US8513322B2 (en) 2007-05-31 2013-08-20 3M Innovative Properties Company Polymeric beads and methods of making polymeric beads
WO2010046750A2 (en) * 2008-10-21 2010-04-29 Fein-Elast Italia Spa Plant and method for making continuous elastic yarns made of silicon material and continuous elastic yarn made of silicon material thus obtained
WO2010046750A3 (en) * 2008-10-21 2010-06-17 Fein-Elast Italia Spa Plant and method for making continuous elastic yarns made of silicon material and continuous elastic yarn made of silicon material thus obtained
AU2009306069B2 (en) * 2008-10-21 2015-10-29 Lemur S.P.A. Plant and method for making continuous elastic yarns made of silicon material and continuous elastic yarn made of silicon material thus obtained
US9481113B2 (en) 2008-10-21 2016-11-01 Lemur S.P.A. Plant for making continuous elastic yarns made of silicone material
US10099416B2 (en) 2008-10-21 2018-10-16 Lemur S.R.L. A Socio Unico Plant and method for making continuous elastic yarns made of silicone material and continuous elastic yarn made of silicone material thus obtained
EP2710050A1 (de) * 2011-05-18 2014-03-26 Palchik, Oleg Wärmeformbare und wärmehärtbare fasern sowie ihre herstellung durch uv-härtung
EP2710050A4 (de) * 2011-05-18 2015-02-18 Ltd Intellisiv Wärmeformbare und wärmehärtbare fasern sowie ihre herstellung durch uv-härtung

Also Published As

Publication number Publication date
EP0233667B1 (de) 1990-10-24
JP2511929B2 (ja) 1996-07-03
JPS62191506A (ja) 1987-08-21
NL8600307A (nl) 1987-09-01
GR3001070T3 (en) 1992-03-20
DE3765651D1 (de) 1990-11-29

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