Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
  • C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
  • C08L63/10—Epoxy resins modified by unsaturated compounds
• • 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
  • D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
  • D01F6/52—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of unsaturated carboxylic acids or unsaturated esters
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
  • C08J2363/10—Epoxy resins modified by unsaturated compounds

Definitions

• the invention relates to an oligomeric acrylates containing composition suitable for the production of endless objects without the use of carrier material.
• 'endless objects' are understood in the present specification objects that have a virtually infinite length in at least one direction, such as fibres, sheets and tubes.
• a 'carrier material' is understood material which potentially is infinitely long, such as filaments or films, and onto which the acrylates containing composition is applied and then cured. This could be a thermoplastic foil or fiber.
• a composition from ⁇ hich endless objects can be made without using carried material is described in JP-A-61262707.
• composition on the basis of acrylates which by a special treatment can be processed to endless objects, in particular to optical fibres.
• a set-up is built in which an acrylate mixture is pressed through i l tube, the acrylates being partially cured in the tube, after which the partially cured acrylates are spun and cured further.
• the aim of the invention is to provide a composition which does not have said drawbacks and from which therefor easily endless objects can be produced.
• thermoplastic polymer e.g. polyethylene terephthalate (PET), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrenethacrylate ethylene ethylene ethylene terephthalate (PEG 400000, polystyrenethacrylate (PS), polystyrenethacrylate (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polyst
• the composition can for instance be processed and formed in an extruder. Moreover, the composition can be stretched, either in one or in two directions. In this way fibres or sheets for instance can be produced.
• composition according to the invention need not be cured until after the spinning or the processing in the extruder, while the composition according to JP-A-61262707 is already partially cured before the spinning.
• the spinnability will be used as criterion of the continuous processability in the manner as set out here. If a composition is spinnable, it can presumably also be processed to other forms of endless objects besides fibers. The concept of spinnability is difficult to quantify, but in the present specification the definition as given by Ziabicki in 'Fundamentals of Fibre Formation', J. Wiley & Sons Ltd., London, 1976, will be used: 'A liquid is spinnable under the given conditions if a steady-state, continuous elongation of the fluid jet proceeds without a break of ariy kind'.
• the degree of change of the spinnability depends, among other factors, on the molecular weight of the thermoplast. The higher the molecular weight, the less material has to be added to cause the viscosity to be enhanced by a certain degree in order to make the composition spinnable.
• thermoplast is preferably at least partially solved in the acrylate monomers.
• thermoplast in general, it will be advantageous to add the thermoplast as little particles with a diameter of less then 0.5 mm, because this improves the speed of solvation of the thermoplast in the monomers. It is also possible to heat the thermoplastic before it is added to the composition. It has to be said that a fast solvation speed is not necessary for a successiveful application of a composition according to the invention.
• the composition preferably contains, relative to the composition as a whole, at least 0.1 wt.% thermoplastic polymer with an MW of more than 5,000,000 and up to about 50 wt.% with an MW of about 50,000.
• the composition more preferably contains, relative to the composition as a whole, at least .0,1 wt.% . .. thermoplastic polymer with a molecular weight of more than 5.000.000 and up to at least 2.5 wt.% of the thermoplastic polymer with a molecular weight of 900.000.
• thermoplast in general, of ther oplasts that are high viscous above their melting point, a lower quantity will be needed then of thermoplast that are low viscous above their melting point. For instance, in general a higher quantity of a branched thermoplast than of a linear thermoplast will be required. In general the desired properties of the composition will be determined by the average chain length of the thermoplastic polymer dissolved in it.
• thermoplast polyethylene oxide
• PEO polyethylene oxide
• PVA polyvinyl acetate
• thermoplast should at least partially dissolve in the oligomeric acrylates.
• a molecular blend is obtained or a crystallisation or a phase separation takes place upon curing.
• the latter may give rise to favourable properties, such as improved toughness of the final product. This may be due to the glass transition temperature (Tg) of the thermoplast being lower than the service temperature. If such phenomenon is unwanted, the process conditions can be adapted such that it does not occur, e.g. by enhancing the spinning temperature.
• Low molecular thermoplasts may further be added to the composition to improve certain properties, such as the impact resistance.
• the usual additives may further be taken up in the composition, such as inhibitors, promoters, accelerators, flexibilizers, lubricants, release agents, antioxidants, pigments, surfactants, crosslinkers, fillers or fibre reinforcement agents.
• Initiation of the curing may be effected in all ways by which acrylates can be cured, such as thermally, with UV light, with other electromagnetic radiation or with electron or gamma radiation.
• the curing takes place under the influence of UV light, because then the curing can be effected simply.
• the time can be chosen freely then: during or after the shaping process or during the cooling stage.
• a possible mode of operation for a process for the manufacture of products is the following:
• thermoplast is suspended and dissolved in the acrylates. This may require heating of the composition to a suitable temperature, for instance between 50 and 200°C. Preferably the composition is not heated to a temperature at which one or more of the components start to boil. The mixture is then extruded or spun and then partially or fully cured.
• Additional steps in this mode of operation can be mixing in of strengthening fibres in the composition and stretching of the extruded or spun semimanufacture.
• strenthening fibers fibers that have properties that are such that they improve the properties of the product in which those fibers are incorporated.
• Strengthening fibers will normally not melt or otherwise loose their mechanical strength under the processing conditions. Examples are glass fibers and carbonfibers, but any other fiber can be used principally.
• the viscoelasticity of the composition can be set in dependence on the chosen method of processing. If spinning in a downward direction is opted for, a lower weight percentage or a lower molecular weight thermoplast will suffice than in the case of for instance film blowing in an upward direction. If it is intended to produce thin objects, it is recommendable to stretch the composition, before the curing.
• fibrous fillers have been added, which are required to be in oriented condition in the product, it is also recommendable to stretch the composition prior to curing. If anisotropy is wanted in the final product, it is recommendable to stretch after or during the curing. After curing the product consists of a threedimensional network, but can be stretched a little bit anyhow.
• the composition is stretched unaxially to a fiber with a thickness of less then 1 mm or biaxially to a sheet with a thickness of less then 1 mm.
• the viscoelasticity of the semimanufacture will decrease and the semimanufacture may be subjected to elongation, which may be undesirable, due to the effect of gravity among other things.
• This can be corrected by having the curing take place in a bath filled with a liquid that is inert during the curing reaction and has a specific gravity which is virtually equal to that of the composition. It is possible to have the reaction take place under the influence of a catalyst, which is in the inert liquid and from there diffuses into the composition.
• Products made from a composition according to the invention are, depending on the starting materials, suitable for applications in those areas where a good temperature resistance, a good fire resistance and/or a good corrosion and solvent resistance are required besides good mechanical properties.
• -Examples are cable sheathing, fireproof clothing, asbestos replacement, high temperature filters, aircraft interiors, precursors for carbon fibre, food packagings (for instance for use in a microwave oven), condenser films, optical fibre and filament winding products.
• the acrylate resin compositions according to the invention need not be processed at a high temperature, in contrast to thermoplasts with a high intrinsic temperature resistance because these thermoplasts usually have a high weakening point.
• the invention is notably advantageous where sheets, films, fibres, tubes or other endless objects are required with one or more of the above-mentioned properties.
• the products further, can be produced as bundles of thin filaments or as single, thicker monofilaments.
• the products according to the invention can be reduced to products of smaller length by cutting, sawing, breaking or similar methods.
• Polyethylene oxide was obtained from Aldrich Chemie, W. Germany, with molecular weights of 200,000, 900,000 and 5,000,000 according to the manufacturer.
• the epoxy acrylate resin was Ebecryl 600 R from 5. Radcure Specialties, Belgium.
• PEO's of different molecular weight were suspended at room temperature in the epoxy acrylate resin with varying concentrations.
• the different molecular weights and concentrations are stated in tables 1 to 3.
• the PEO was 0 dissolved in the resin in a Brabender kneader at a temperature of 120°C.
• the solution was transferred to dishes, which were subsequently heated to three different temperatures: 23°C in example I, 60°C in example II and 120°C in example III. 5
• a glass rod it was attempted to pick up a thread of material from each dish and then to wind the thread around a small spindle positioned horizontally over the dish. Then the spindle was put in a slow rotating motion so that the thread was continuously drawn from the solution 0 and wound around the spindle.
• 'moderately spinnable' in the following tables is meant that only after several attempts and with very careful action was it possible to pick up such a thread from the solution, wind it around the spindle and rotate the spindle. 5
• thermoplast [% w/w] a 200,000 1 + 0 b 5 + c 10 ++ d 20 ++ e 900,000 0.1 + f 1.1 + 5 g 2.5 ++ h 5.0 ++ i 10.0 ++ j 5,000,000 0.1 ++ k 0.2 ++ ' 0 .1 0.5 ++ m ⁇ 1.0 ++
• concentration of the thermoplast is given as weight percentage relative to the total composition.
• the spinnability was measured according to the test method as described above; — means very poorly spinnable, - means poorly spinnable, + means moderately spinnable, + means well spinnable and ++ means very well spinnable.
• thermoplast [% w/w] a 200,000 1 b 5 c 10 + d 20 ++ e 900,000 0.1 f 1.1 g 2.5 + O h 5.0 + i 10.0 ++ j 5,000,000 0.1 + k 0.2 +
• thermoplast [ w/w] a 200,000 1 b 5 c 10 - d 20 +
• thermoplast with a higher molecular weight a lower percentage is required to make the solution spinnable than of thermoplast with a lower 25 molecular weight.
• the invention relates by preference to a 30 composition with such a high percentage of thermoplast of a certain molecular weight that at the composition's processing temperature the composition is spinnable. This means that with a desired processing temperature of 23°C the composition contains at least 1% w/w of a thermoplast with a 35 molecular weight of 200,000.
• the composition preferably contains 10% w/w of the thermoplast with a molecular weight of 200,000. • . -13-
• the composition preferably contains 20% w/w of the thermoplast with a molecular weight of 200,000.
• Example IV The procedure of example II was repeated, polyvinyl acetate (PVA, Mowilith 70 from Hoechst Aktiengesellschaft, W. Germany) being suspended and dissolved in epoxy acrylate.
• PVA polyvinyl acetate
• the molecular weight of PVA was 1*10 and the concentration 15%. It was examined whether the solution could be spun to a fibre. This was the case.
• example I was mixed with 3 wt.% UV initiator (Irganox 651 from Ciba-Geigy, France). The solution was transferred to a spinning vessel and spun at
• the fibre has an E-modulus of 2.4 GPa, a tensile strength of 60 MPa and an elongation at rupture of 5%.
• the mixture was heated in an oven to 80°C and kept at this temperature during 12 hours. A homogeneous solution was obtained. The solution was transferred to a spinning vessel and spun at room temperature.
• the fiber was cured under UV-light, under N 2 -atmosphere, and wound on a spool.
• E Young's modulus
• Ts tensile strength
• eab elongation at break
• Composition Vile contained 15 g of Irgacure 651 instead of the Darocure 1173 .

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Organic Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Manufacturing & Machinery (AREA)
• Textile Engineering (AREA)
• General Chemical & Material Sciences (AREA)
• Materials Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Artificial Filaments (AREA)
• Macromonomer-Based Addition Polymer (AREA)

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Cited By (4)

Citations (1)

• 1990
  • 1990-02-02 NL NL9000258A patent/NL9000258A/nl not_active Application Discontinuation
• 1991
  • 1991-02-01 WO PCT/NL1991/000014 patent/WO1991011489A1/en not_active Application Discontinuation
  • 1991-02-01 JP JP91503169A patent/JPH05505631A/ja active Pending
  • 1991-02-01 AU AU71471/91A patent/AU7147191A/en not_active Abandoned
  • 1991-02-01 EP EP19910902997 patent/EP0515401A1/en not_active Withdrawn

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