EP0122836B1 - Verfahren zur Herstellung von Phenoplastfasern - Google Patents
Verfahren zur Herstellung von Phenoplastfasern Download PDFInfo
- Publication number
- EP0122836B1 EP0122836B1 EP84400583A EP84400583A EP0122836B1 EP 0122836 B1 EP0122836 B1 EP 0122836B1 EP 84400583 A EP84400583 A EP 84400583A EP 84400583 A EP84400583 A EP 84400583A EP 0122836 B1 EP0122836 B1 EP 0122836B1
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- Prior art keywords
- fibres
- fibers
- composition
- temperature
- die
- 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
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229920001568 phenolic resin Polymers 0.000 title description 9
- 239000000835 fiber Substances 0.000 claims abstract description 120
- 239000000203 mixture Substances 0.000 claims abstract description 84
- 229920005989 resin Polymers 0.000 claims abstract description 44
- 239000011347 resin Substances 0.000 claims abstract description 44
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009833 condensation Methods 0.000 claims abstract description 5
- 230000005494 condensation Effects 0.000 claims abstract description 5
- 229920003987 resole Polymers 0.000 claims abstract description 5
- 229960004279 formaldehyde Drugs 0.000 claims abstract 4
- 235000019256 formaldehyde Nutrition 0.000 claims abstract 4
- 150000002989 phenols Chemical class 0.000 claims abstract 2
- 238000004132 cross linking Methods 0.000 claims description 26
- 230000015572 biosynthetic process Effects 0.000 claims description 24
- 239000003054 catalyst Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 150000007513 acids Chemical class 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims 1
- 238000007669 thermal treatment Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 description 21
- 238000004519 manufacturing process Methods 0.000 description 12
- 229920003986 novolac Polymers 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000009434 installation Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000003431 cross linking reagent Substances 0.000 description 5
- 230000006641 stabilisation Effects 0.000 description 5
- 238000011105 stabilization Methods 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- 239000012943 hotmelt Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000002093 peripheral effect Effects 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 230000002028 premature Effects 0.000 description 2
- 230000000750 progressive effect Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- -1 cationic fatty alcohols Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 229960004011 methenamine Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Images
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
- D01D5/18—Formation of filaments, threads, or the like by means of rotating spinnerets
-
- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
Definitions
- the invention relates to a process for the production of fibers from phenoplast resins of the resol type.
- Phenoplast resins are obtained by polycondensation of a phenol and an aldehyde. Most commonly phenoplasts come from the condensation of phenol and formalin. In the following description, we will mainly refer to these phenol resins based on phenol and formaldehyde, but the characteristics of the invention mean that it can be applied to all phenoplast resins provided that they have the properties which will be discussed below.
- the novolaks are obtained by polycondensation of an excess of phenol relative to the amount of formalin used, in the presence of an acid catalyst.
- the prepared resin which is hot melt, is crosslinkable using a crosslinking agent such as hexamethylene tetramine or paraformaldehyde in the presence of an acid catalyst. Cross-linking is accelerated by a rise in temperature.
- the resols come from the polycondensation of an excess of formalin relative to the amount of phenol used, in the presence of a basic catalyst.
- the formation of the resin which is accelerated when the temperature rises is difficult to control. It results in very diverse products according to the operating conditions and in particular according to the duration of the reaction. If the reaction is not stopped it continues until the formation of a solid product which is infusible and therefore cannot be spinned. To maintain the resin in conditions under which it can be worked, the reaction should be blocked by lowering the temperature and / or neutralizing the mixture. A resin in solution is then obtained, the characteristics of which, in particular of viscosity, vary according to the degree of progress of the reaction.
- the resin is crosslinkable and crosslinking can be accelerated in the presence of an acid catalyst. The crosslinking is all the faster the higher the temperature.
- novolak fibers are traditionally obtained by melting the hot-melt resin followed by fiberizing and treatment in an aqueous or gaseous medium with the crosslinking agent and the catalyst.
- This treatment resulting in crosslinking is very long because of the need to diffuse the crosslinking agent and the catalyst in the solidified resin fiber. It can extend over several hours.
- the operation leading to the formation of the fibers is particularly delicate. Unlike the novolaks for which the cooling after passage of the molten mixture in the die leads to fibers in a way frozen and well individualized, even if the crosslinking is barely started, the fibering operated with a resol in a state suitable for spinning, c that is to say a resol whose evolution has been stopped at a degree of condensation such that the viscosity is satisfactory, leads to the production of unstabilized fibers which remain sticky.
- the invention proposes to provide a process for the production of fibers from resols.
- the resin used the nature and the proportions of the products possibly added, in particular a crosslinking catalyst, are chosen to constitute a mixture whose characteristics, in particular of viscosity, are suitable for the formation of fibers by passage in a sector.
- composition to be fiberized is immediately directed to a member acting as a die and which is consisting of a centrifuge.
- the composition introduced into the centrifuge covers the inner peripheral wall of the centrifuge. This wall is pierced with orifices through which the composition passes. The latter is projected out of the orifices in the form of thin filaments which stretch into fibers and the orifices are of dimensions such that each of them gives rise to a separate fiber.
- the conditions determining the maturation kinetics of the fibers formed, in particular the choice of the possible catalyst and of its proportions, and the temperature conditions of the surrounding atmosphere in which the fibers are projected, are chosen so that during their trajectory in this atmosphere until they are received, the fibers are sufficiently crosslinked and dried to keep a clean shape and do not stick to each other.
- the preparation of resolated fibers is subject to conflicting requirements.
- it may seem desirable to form a mixture capable of accelerating the evolution process and on the other hand when such a mixture is actually carried out, it is difficult to sufficiently control the evolution so as to maintain the mixing under conditions suitable for passing through a die and drawing the fibers.
- compositions used according to the invention To be able to fiberize the compositions used according to the invention and taking into account the fact that they evolve rapidly towards a state in which precisely they could no longer be used for the formation of fibers, it is necessary to ensure that the mixture formed is very quickly used .
- the mixture is therefore formed as it is used. Once the mixture has been formed, the means used to produce the fibers must retain this mixture for as short a time as possible.
- the amount of composition held in the centrifuge can be extremely small. It can correspond to the quantity passing in a few seconds, so that the average residence time is very short and that there is no risk of "freezing" the composition before it passes through the orifices.
- the fibers being projected out of the centrifuge they must be stabilized as quickly as possible.
- the time interval separating the appearance of the fibers at the outlet of the centrifuge from their deposition on the collecting member is necessarily limited by the dimensions of the installation used.
- the formation of these bubbles is not desirable.
- the bubbles break the homogeneity of the structure of the fibers and in particular harm their mechanical properties.
- the temperature of the fibers in the atmosphere surrounding the centrifuge is preferably kept below the boiling temperature of the water, or of the water / solvent mixture, present in the composition.
- the temperature not to be exceeded corresponds approximately to that of boiling water.
- the temperature of the fibers, at least in the region closest to the centrifuge does not exceed 80 ° C.
- the temperature of the atmosphere itself can be significantly higher than that of the fibers as a result of the cooling caused on them by evaporation. We will see in the examples that the gas temperature can reach and even exceed 200 ° C.
- the fibers are subjected to a temperature which increases when they move away from the centrifuge.
- the exchanges taking place very quickly due to the fineness of the fibers, the crosslinking progressing and the drying taking place, it is possible to reach in the areas remote from the centrifuge temperatures higher than the limit temperatures indicated above. above.
- the hot gas stream is preferably driven at a relatively low speed when it is directed transversely to the direction of projection of the fibers out of the centrifuge to avoid folding the fibers too early on each other when they are not yet perfectly stabilized.
- the resin or resin-catalyst mixture should have a viscosity suitable for the mode of fiber formation envisaged.
- a viscosity of the order of 500 to 30,000 mPas and preferably from 1,500 to 10,000 mPas is advantageously chosen.
- the resin or the mixture is neither too fluid, which would lead to premature rupture of the filaments generating droplets and / or products that are insufficiently drawn, or too viscous, which would require the use of relatively large orifices and the fibers obtained would not meet the characteristics of fineness ordinarily sought.
- the viscosity of the composition used is determined first of all by that of the resin, which itself depends on how the resin is prepared. It is thus necessary to take into consideration the reaction time and temperature, as well as the molar ratio of the formalin and the starting phenol. Condensation must be stopped when the viscosity suitable for spinning is reached.
- the viscosity of the resin can however be modified by the addition of solvents.
- the resin used preferably has a molecular mass of between 100 and 1000 and more particularly between 400 and 800.
- the resin is preferably prepared from phenol and formaldehyde introduced in a molar ratio of formaldehyde to phenol of between 1.3 and 1.7.
- a third solvent is advantageously used in as small a quantity as possible.
- a compound which is both miscible with water and with resin and which is capable of being easily removed during the subsequent treatment of the fibers is used as a third solvent.
- the third solvent is an alcohol, in particular methanol.
- the viscosity of the assembly added to the resin can also be adjusted to avoid that, at the time of mixing, a too strong modification of the viscosity is observed.
- thickening agents for example glycols, and preferably di- or triethylene glycol.
- these thickening agents are introduced which, while allowing a higher final viscosity to be reached, also promote the homogenization of the mixture.
- the crosslinking catalysts used are strong acids, mineral or organic, alone or as a mixture. Acids such as sulfuric acid, phosphoric acid or hydrochloric acid and their mixtures in aqueous solution are preferably used.
- the use of a catalyst in solution allows a good dispersion thereof within the resin provided that the miscibility has been ensured as we have indicated above.
- the dispersion of the catalyst in the resin is a determining factor for the way in which the crosslinking takes place. Good dispersion naturally favors rapid and homogeneous crosslinking, which is desirable under the conditions used according to the invention.
- the characteristics of the spun compositions used according to the invention can be further modified to improve the formation and drawing of the fibers.
- surfactant it is also usual in the processes of formation of fibers from synthetic resins to add small proportions of a surfactant, always to improve the characteristics during fiberizing, and in particular to avoid early hair breaks.
- these are nonionic surfactants, such as sorbitan or cationic fatty alcohols, which exhibit better stability in an acid medium.
- Preferred surfactants are those sold under the names “TWEEN” and “SPAN” (registered trademarks). They are introduced into the composition in an amount of 0.5 to 3% by weight.
- FIG. 1 The installation shown diagrammatically in FIG. 1 is particularly representative of those which can be used according to the invention. It performs the conditioning of the composition, the fiberizing of this composition and the stabilization of the fibers formed.
- the resin previously prepared and optionally containing the various fiberizing additives is placed in a tank 1 in which it is maintained at a temperature which allows its conservation.
- the resin in the liquid state taken from the tank 1 by means appropriate to its state: pump, screw, etc. is conducted in a determined quantity in a mixer 2.
- the mixer also optionally receives in metered quantities the catalyst originating from 'a tank as shown in 24.
- the mixing operation is very vigorous to obtain a composition that is as homogeneous as possible.
- the volume offered in the mixer is small so that the composition stays there as short as possible.
- the composition is then sent directly to the centrifuge device.
- the line 8 leading the composition to be fiberized in the centrifuge device is as short as possible.
- the mixer 2 is advantageously located near the centrifuge device.
- the device comprises a centrifuge 3 fixed on a shaft 4 which is rotated by an electric motor 5 by means of belts 6.
- the shaft 4 is mounted on bearings 7.
- the shaft 4 is hollow.
- Line 8 leading the composition to the centrifuge is housed in this tree.
- the centrifuge device itself comprises a basket 9 on the bottom of which the composition is poured.
- the basket is pierced on its peripheral wall 10 with regularly spaced holes 11.
- the composition reaches the inner face of the wall 10 and escapes through the orifices 11 in the form of large composition nets, which are projected onto the peripheral wall 12 of the centrifuge proper 3.
- the presence of the basket 9 allows a first equalization of the distribution of the composition on the inner peripheral wall of the centrifuge.
- the use of a basket is all the more advantageous when the centrifuge is larger.
- the "natural" distribution of the composition is more likely to be unbalanced. It is very important for the quality of the fibers to have at all points of the centrifuge the same "reserve", that is to say the same thickness of composition so that the centrifugation conditions are everywhere the same and therefore that the fibers are formed under the same conditions.
- composition which forms the reserve escapes from the centrifuge through the orifices 14 arranged at the periphery.
- the orifices 14 have dimensions such that each of them gives rise to a single fiber which is then projected into the surrounding atmosphere.
- the internal profile of the centrifuge is determined so as to facilitate the flow of the composition.
- the orifices are preceded by a part of triangular cross section 15 which leads the composition towards the orifices 14. This profile notably avoids the stagnation of composition in blind spots, stagnation which could lead to deposits of crosslinked resins.
- FIG. 2 shows a centrifuge comprising a single row of orifices 14. It is of course possible to use a centrifuge comprising several rows of orifices, as shown in FIG. 3. In this case, it is necessary to choose the distance between two successive rows so that the fibers formed do not risk re-sticking before being stabilized. The distance between two orifices in the same row is also chosen so as to prevent the fibers from sticking together.
- the profile of the centrifuge with several rows of orifices represented in FIG. 3 also includes grooves 26 on the internal face, the section of which decreases when approaching the orifices 14, which allow good circulation of the material to be fiberized to each row orifices.
- the amount of composition in the basket and the centrifuge is kept at the minimum necessary to continuously feed the orifices 14.
- the "reserve” must suitably cover the orifices 14. This reserve must however be small to shorten the residence time.
- the composition is sprayed out of the centrifuge in the form of filaments, the dimensions of which are determined by those of the orifices.
- the orifices ordinarily, taking into account the viscosities of the composition which have been indicated above and in order to obtain fine fibers of the order of 20 micrometers or less, the orifices have a diameter advantageously less than 1 mm and preferably between 0.2 and 0 , 8 mm. For larger diameters, and if the other conditions remain unchanged, the fibers produced are larger. To find finer fibers, it is then necessary to carry out a more violent centrifugation and / or to reduce the flow of composition per orifice.
- the fibers are projected and stretch substantially in the plane perpendicular to the axis of rotation of the centrifuge. They develop in spirals which can extend at relatively large distances from the centrifuge when the initial acceleration is high.
- the path of the fibers in the plane, which can reach a meter or more, is usually limited for reasons of the size of the receiving enclosure 19.
- the path of the fibers is limited by blowing a gas stream along the walls 16, sufficiently intense to fold the fibers before they reach these walls.
- the blowing can be carried out for example by means of a series of nozzles 18 disposed along a conduit 17 for supplying compressed air.
- the nozzles 18 are preferably close enough to each other so that the jets fuse very quickly and constitute a practically continuous gas layer which obstructs the passage of the fibers.
- the fibers from the start of their path towards the wall 16 of the receiving enclosure 19, are subjected to the heat treatment which makes it possible to substantially accelerate the kinetics of crosslinking of the mixture and promotes the elimination of water and / or solvents present in the fibers.
- This heat treatment is advantageously obtained by means of hot gas streams arranged on the path of the fibers between the outlet of the centrifuge and the point where they are folded down.
- the hot gaseous layers are directed on the path of the fibers with a speed and at a temperature such that the modification of the path can be limited as much as possible and, consequently, the risks of sticking of the fibers not yet stabilized.
- the speed of the gases is preferably kept below 20 m / s.
- Figure 1 shows a double supply of hot gases. These two supplies are made from chambers 20 and 21 arranged concentrically around the centrifuge.
- the chambers 20 and 21 are supplied by one or more gas burners by means of pipes not shown. They are separated from the receiving enclosure 19 by widely open grids 22 letting the gases pass at low speed.
- the installation shown comprises two hot gas emission chambers, it is of course possible to regulate the temperature of the gases of these two chambers independently of one another. It is also possible to provide a larger number of gas emission chambers to control even better the progress of the conditions for treating the fibers.
- centrifuge may be advantageous to protect the centrifuge against heat coming from the neighboring chamber 20 by interposing for example a coil 25 surrounding the shaft 4 and the top of the centrifuge, and in which cooling water circulates .
- the length of the path required before to gather the fibers is determined at the same time as the gas temperature conditions for each composition treated, it being understood that in all cases it is necessary to collect fibers sufficiently dried and crosslinked so that they do not risk sticking to each other.
- the distance separating the centrifuge from the receiving belt is such that the time taken by the fibers to travel this path is between 0.1 and 2 s.
- the fibers carried by the gases are deposited on a conveyor belt 23 where they constitute a felt of entangled fibers.
- the suction means consist of a box 26 disposed under the conveyor and a fan, not shown.
- the conditions set out above according to the invention make it possible to collect fibers in which the crosslinking process is very advanced and this in a very short time. If the complete residence time of the fibers in the receiving enclosure is very short, it may happen that the fibers have not reached a degree of maturation (or crosslinking) allowing them to be given the best possible properties. In this case, it is advantageous to complete the crosslinking by a very brief passage in an oven.
- the temperature during such a heat treatment is greater than 100 ° C., and preferably between 100 and 150 ° C.
- Example of fiber preparation in the presence of a catalyst Example of fiber preparation in the presence of a catalyst.
- the reaction is stopped by cooling when the desired viscosity is reached. This is measured by the flow tube method.
- the reaction is stopped by cooling to 25 ° C.
- the resin obtained has a viscosity of 1000 mPas at 25 ° C.
- the dry extract constitutes 70.5% of its mass.
- the resin is stored at a temperature of 5 to 7 ° C.
- the viscosity of the fiber premix is 13,000 mPas at 25 ° C.
- the catalyst is measured at 7 parts.
- the mixture used to form the fibers is, as the case may be, 100 parts by weight of resin premix for 5 to 10 parts of catalyst.
- This mixture is in a homogeneous form with a viscosity varying from 3500 to 5000 mPas at 25 ° C.
- the operation is carried out continuously in an enclosure with a square section, and with a height of approximately 2.5 m of the type shown in FIG. 1.
- the mixture obtained in 4 is led by a pipe of the mixer in the receiving basket.
- the centrifuge and the basket rotate at 3000 rpm.
- the basket is pierced with 40 holes of 1.2 mm in diameter and the centrifuge whose diameter is 200 mm has 150 holes of 0.5 mm in diameter.
- the fibers deploy in the air blown by 5 concentric chambers.
- the speed of the gas emitted by these chambers increases as one moves away from the centrifuge, ensuring progressive deflection of the fibers.
- the air is heated to a regulated temperature between 150 and 160 ° C.
- a certain amount of air at room temperature is introduced through the walls forming the sides of the enclosure.
- the air temperature is 80 ° C at the receiving conveyor.
- the fibers are deposited in a continuous sheet of approximately 50 cm in width, formed of long dried and largely crosslinked fibers.
- the regulation of the suction allows, by controlling the temperature at the bottom of the hood, to vary the degree of crosslinking.
- the fiber diameters are between 2 and 19 ⁇ m.
- the histogram of the diameters is of very tight Gaussian type with an average diameter of 7 micrometers.
- the average tensile strength is around 300 MPa.
- the density of the felt is approximately 20 kg / m 3 and its thermal conductivity on the order of 35 mW / m ° K for a thickness of 80 mm.
- the felt obtained previously can be completely crosslinked by passing through the oven for 5 minutes at 120 ° C.
- the felt which is not completely crosslinked has a certain thermoplasticity. This can be taken advantage of to constitute a self-bonding felt: For this purpose the felt obtained is subjected for 3 minutes to a temperature of the order of 220 ° C. by slightly compressing it.
- a felt is thus obtained having a cohesion which makes it easy to handle.
- the fibers are formed by rotating the system at 3800 rpm.
- the basket 9 is pierced with 6 holes of 2.5 mm in diameter and the centrifuge has 4 rows of 150 holes of 0.4 mm in diameter.
- a stabilized fiber flow rate is obtained which is greater than that obtained with a single row of orifices.
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Artificial Filaments (AREA)
Claims (19)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8304737 | 1983-03-23 | ||
FR8304737A FR2543169B1 (fr) | 1983-03-23 | 1983-03-23 | Procede de production de fibres phenoplastes |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0122836A1 EP0122836A1 (de) | 1984-10-24 |
EP0122836B1 true EP0122836B1 (de) | 1987-03-18 |
Family
ID=9287133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP84400583A Expired EP0122836B1 (de) | 1983-03-23 | 1984-03-22 | Verfahren zur Herstellung von Phenoplastfasern |
Country Status (5)
Country | Link |
---|---|
US (1) | US5055241A (de) |
EP (1) | EP0122836B1 (de) |
JP (1) | JPS59179811A (de) |
DE (1) | DE3462703D1 (de) |
FR (1) | FR2543169B1 (de) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2588255A1 (fr) * | 1985-10-09 | 1987-04-10 | Saint Gobain Isover | Composition pour l'encollage de fibres minerales et fibres minerales encollees |
JPH0735610B2 (ja) * | 1986-01-24 | 1995-04-19 | 三菱石油株式会社 | ピツチ系炭素繊維遠心紡糸装置 |
FR2695413B3 (fr) * | 1992-09-09 | 1994-12-16 | Saint Gobain Isover | Dispositif pour la formation de fibres phénoplastes. |
RU2144099C1 (ru) * | 1995-03-03 | 2000-01-10 | Акцо Нобель Н.В. | Способ прядения волокон или филаментов (варианты), волокна и филаменты (варианты), волокнистая масса |
US6001303A (en) * | 1997-12-19 | 1999-12-14 | Kimberly-Clark Worldwide, Inc. | Process of making fibers |
US6368533B1 (en) * | 1997-12-22 | 2002-04-09 | Kimberly-Clark Worldwide, Inc. | Process for forming films, fibers and base webs from thermoset polymers |
HUP0700795A2 (en) * | 2007-12-10 | 2009-04-28 | Miskolci Egyetem | Coextrusion centrifugal apparatus to fibre formation |
JP5458280B2 (ja) * | 2010-01-06 | 2014-04-02 | パナソニック株式会社 | ナノファイバ製造装置および製造方法 |
JP5322112B2 (ja) * | 2010-01-18 | 2013-10-23 | パナソニック株式会社 | ナノファイバ製造装置および製造方法 |
EP2900853B1 (de) | 2012-08-06 | 2020-04-08 | Fibrerio Technology Corporation | Vorrichtungen und verfahren zur herstellung von mikrofasern und nanofasern |
DE102019003795A1 (de) * | 2019-05-29 | 2020-12-03 | Bb Engineering Gmbh | Vorrichtung und Verfahren zur Herstellung eines Vlieses |
CN111910272B (zh) * | 2020-06-29 | 2023-01-24 | 太原理工大学 | 一种熔喷纺丝制备酚醛纤维的方法 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4947613A (de) * | 1971-09-08 | 1974-05-08 | ||
JPS5010408B2 (de) * | 1971-11-06 | 1975-04-21 | ||
JPS5029817A (de) * | 1973-07-19 | 1975-03-25 | ||
US4323524A (en) * | 1977-03-11 | 1982-04-06 | Imperial Chemical Industries Limited | Production of fibres |
GB1573116A (en) * | 1977-03-11 | 1980-08-13 | Ici Ltd | Production of formaldehyde resin fibres by centrifugal spining |
NZ187979A (en) * | 1977-07-29 | 1982-05-31 | Ici Ltd | Centrifugal spinning of fibres from liquid |
EP0017510B1 (de) * | 1979-04-09 | 1984-02-15 | Imperial Chemical Industries Plc | Spinnverfahren und -vorrichtung |
EP0019383B1 (de) * | 1979-05-15 | 1982-06-23 | Imperial Chemical Industries Plc | Spinnverfahren |
JPS55163212A (en) * | 1979-06-06 | 1980-12-19 | Mitsui Petrochem Ind Ltd | Production of phenolic resin fiber |
-
1983
- 1983-03-23 FR FR8304737A patent/FR2543169B1/fr not_active Expired
-
1984
- 1984-03-22 EP EP84400583A patent/EP0122836B1/de not_active Expired
- 1984-03-22 DE DE8484400583T patent/DE3462703D1/de not_active Expired
- 1984-03-23 JP JP59054617A patent/JPS59179811A/ja active Granted
-
1986
- 1986-04-01 US US06/846,488 patent/US5055241A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0122836A1 (de) | 1984-10-24 |
FR2543169B1 (fr) | 1986-03-28 |
US5055241A (en) | 1991-10-08 |
DE3462703D1 (en) | 1987-04-23 |
JPH059525B2 (de) | 1993-02-05 |
JPS59179811A (ja) | 1984-10-12 |
FR2543169A1 (fr) | 1984-09-28 |
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