EP0488907A1 - Fasern aus mit Diisocyanaten vernetzten Polyvinylchlorid und Verfahren zu deren Herstellung - Google Patents

Fasern aus mit Diisocyanaten vernetzten Polyvinylchlorid und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0488907A1
EP0488907A1 EP91420380A EP91420380A EP0488907A1 EP 0488907 A1 EP0488907 A1 EP 0488907A1 EP 91420380 A EP91420380 A EP 91420380A EP 91420380 A EP91420380 A EP 91420380A EP 0488907 A1 EP0488907 A1 EP 0488907A1
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Prior art keywords
pvc
filaments
polymer
temperature
oxime
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EP91420380A
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English (en)
French (fr)
Inventor
Sophie Commereuc
Alain Michel
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Rhovyl SA
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Rhovyl SA
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    • 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
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/10—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polyvinyl chloride or polyvinylidene chloride

Definitions

  • the present invention relates to yarns based on polyvinyl chloride crosslinked by diisocyanate groups and to the process for obtaining them.
  • Polyvinyl chloride fibers are appreciated in the textile field because of certain special properties: non-flammability, resistance to light, chemical inertness and thermal, electrical and acoustic insulation power.
  • These new polymers with a more syndiotactic structure have a glass transition temperature (Tg) generally greater than 90 ° -100 ° C. giving the yarns and fibers obtained better thermal resistance and markedly improved properties compared to textile products obtained from polyvinyl chloride. ordinary.
  • Tg glass transition temperature
  • French application No. 2,161,084 published on 6.07.1973 illustrates fibers with good mechanical properties based on this type of polymer.
  • a low temperature polymerization process is an extremely expensive process which considerably increases the cost price of the fibers and takes away much interest from their industrial production.
  • PVC polyvinyl chloride
  • French patent No. 2,495,645 describes the production of yarns based on atactic PVC having improved properties, such as a residual shrinkage rate in boiling water. of the order of 1.5 to 35% and an elongation at break of the order of 75 to 80%.
  • Such wires still have insufficient thermal resistance.
  • French Patent No. 2 609 479 proposes obtaining articles based on chlorofibers made of PVC slightly crosslinked on the surface which do not shrink much and retain their fire behavior property.
  • articles have a yellow to brown coloration on the finished article and lose some of their flexibility due to the various treatments undergone. These latter phenomena strongly limit their textile use.
  • the present invention relates to crosslinked polyvinyl chloride (PVC) filaments, threads, fibers retaining their flexibility and a very light color and having limited shrinkage at temperatures equal to or greater than 100 ° C.
  • PVC polyvinyl chloride
  • the swelling rate of the crosslinked fibers is less than 25 and more generally between 6 and 15. The lowest values of the swelling rate correspond to the highest values of crosslinking density.
  • the crosslinking nodes are distributed regularly, which results in better regularity of the threads and therefore better subsequent properties, in particular shrinkage.
  • the yarns and fibers according to the invention have quite remarkable residual shrinkage characteristics: ⁇ 8%, preferably ⁇ 6%.
  • the shrinkage measurement at 130 ° C in air was carried out in a cylindrical oven, with a temperature rise of 2 ° C / min.
  • the sample of initial length (10) about 30 cm, is placed in a horizontal oven, one end is kept fixed, the other mobile with a lead weight at its end.
  • the lead weight, necessary for positioning the sample, is considered to be negligible (0.1 mg / dtex) and the recorded withdrawal is assimilated to a free withdrawal.
  • the nylon wire holding the lead weight is subjected to prior annealing, at 200 ° C., in order to overcome any phenomenon of parasitic shrinkage. Under these conditions, the shrinkage curves% are plotted as a function of the temperature for the control and the crosslinked wires. From these curves, the shrinkage at 130 ° C. is deduced therefrom.
  • FIG. 1 shows the shrinkage of the crosslinked fibers with temperature. Curve No. 1 represents commercial chlorofiber (homopolymer PVC). It is observed that the shrinkage increases rapidly to 130 ° C. and then less rapidly to a ceiling value of the order of 160-170 ° C.
  • the height dR dT (% / C °) is called specific shrinkage.
  • the specific shrinkage as a function of the temperature is represented in FIG. 2.
  • the curves in fact represent the derivative with respect to the temperature of the curves shown in FIG. 1.
  • the yarns and fibers according to the invention are prepared from a solution of hydroxylated PVC in the presence of a diisocyanate / oxime reaction product in a usual solvent mixture.
  • the diisocyanate can be represented by the formula: OCN-R-NCO, R can be an aliphatic, cyclo aliphatic, aromatic group, which can carry other non-reactive functions with respect to isocyanates.
  • R can be an aliphatic, cyclo aliphatic, aromatic group, which can carry other non-reactive functions with respect to isocyanates.
  • diisocyanates which can be used mention may be made of hexamethylene diisocyanate (HDI), but aromatic diisocyanates are preferred, for example diisocyanate 44 ′ diphenylmethane (MDI) and diisocyanate 44 ′ diphenylether (DIDE), phenylene diisocyanate (DPI).
  • R1 (R2) C N-OH in which R1 and R2 are aromatic or aliphatic groups having a low number of carbon atoms.
  • acetone and butanone oxime mention may be made of acetone and butanone oxime.
  • reaction product of diisocyanate and oxime is a compound (A) of formula: R, R1, R2 having the meanings indicated above.
  • the reaction between the oxime and the diisocyanate is carried out separately at a temperature between room temperature and 80 ° C, preferably between 55 and 65 ° C and generally in the presence of catalysts based on transition metals such as the compounds of l tin and in particular tin dibutyldilaurate (DBDLE) although other catalysts can also be used, for a period of at least 2 hours, preferably 2 hours 30 to 3 hours, depending on the reactivity of the diisocyanate with respect to l blocking agent.
  • the presence of the catalyst is not essential.
  • Compound A is obtained in the presence of a suitable solvent such as toluene.
  • the diisocyanate / oxime system precipitates from the reaction medium and is then filtered, washed and dried. It can be checked by IR that the reaction is complete by disappearance of the characteristic band of the free -NCO groups. It is also necessary to ensure the purity of the system obtained. In all cases (HDI, MDI, DIDE, PDI), a white powder is obtained which is soluble in the solvent mixture of carbon sulphide / acetone (50/50) which can be added directly to the solution of PVC OH in the solvent mixture.
  • the mixture-solvent system acetone / CS2
  • hydroxylated PVC hydroxylated PVC
  • compound A diisocyanate / oxime
  • they can be mixed using a mixer at 30-35 ° C before being sent to the spinning cells.
  • They can also be mixed directly above the spinning cell using a known static mixer at a temperature between 70 and 120 ° C.
  • the solutions thus obtained are spun in the usual way by spinning in solution according to a dry method, either according to a usual method, that is to say with heating of the solution to approximately 80 ° C. or according to the overdissolved method with heating to about 120 ° C as described in French patent N ° 2524475.
  • the most commercially used solvents are benzene / acetone and preferably carbon sulfide / acetone mixtures in appropriate proportions, preferably 50/50 by volume.
  • the solutions are filtered to remove any solid type impurities or gels likely to clog the orifices of the die.
  • the filaments are stretched to give them a molecular orientation and improve their mechanical characteristics at a rate between 3 and 6 X, in one or more stages at a temperature between 60 and 100 ° C, but preferably in the 'boiling water. It is generally preferred to gradually raise the temperature of the filaments, by preheating, pre-drawing in a bath, the water of which can be maintained between 75 and 95 ° C., then continuous drawing in boiling water to obtain an overall drawing rate of at least minus 4 X, preferably 4-6 X.
  • the filaments thus drawn are then subjected to stabilization under tension to limit shrinkage, for example in the presence of pressurized steam at a temperature between 105 and 130 ° C, preferably 110-120 ° C for 1 to 3 seconds.
  • the filaments are subjected, preferably continuously, to a free retraction which can be carried out in boiling water for a variable duration, for example at least 10 min in general 10-20 min or even more, in steam saturated water, for example by passing through a suitable nozzle (as described in the addition No. 83329 to French patent No. 1 289491).
  • the filaments must at any time after spinning be subjected to a treatment which causes the elimination of the blocking agent and the crosslinking of the fiber by condensation of the OH groups of the hydroxylated PVC on the diisocyanate groups.
  • the treatment is carried out batchwise or continuously, for example by passing through an appropriate enclosure such as an oven, at a crosslinking temperature of between 120 and 145 ° C., under stress, the crosslinking temperature being maintained at 2 min to 10 min depending on the diisocyanate and the oxime used.
  • a duration of 4 to 5 minutes is generally sufficient. The duration of treatment depends on the temperature: the lower the temperature, the lower the temperature.
  • the crosslinking treatment is carried out before the retraction phase, that is to say directly after stretching or stabilization.
  • the stabilization phase can also be included in the stress crosslinking phase.
  • Cross-linking is characterized by the insolubility of the fibers or the rate of swelling in THF as explained above.
  • the filaments and fibers thus obtained have better thermal resistance than that of yarns based on ordinary polyvinyl chloride obtained hitherto.
  • the process according to the invention makes it possible to obtain filaments at an attractive price capable of undergoing all the textile operations suitable for their finishing and of being used for the production of fabrics, knits, non-woven articles, etc. mixed with other yarns, which can undergo the usual washing and dry cleaning treatments under appropriate conditions without subsequent removal.
  • the polymers in solutions spun according to the present application may contain usual additives such as stabilizers, brighteners, pigments, dyes, plasticizers capable of improving some of their properties such as color, dye affinity, thermal stability, electrical resistivity, etc. in particular, they dye well with dispersed dyes.
  • additives such as stabilizers, brighteners, pigments, dyes, plasticizers capable of improving some of their properties such as color, dye affinity, thermal stability, electrical resistivity, etc. in particular, they dye well with dispersed dyes.
  • 84 g of product prepared above are introduced with 1200 g of hydroxylated PVC in 2800 g of solvent mixture CS2 / acetone (50/50), 7.2 g of tin thioglycolate as stabilizer, the concentration of the solution being 30% polymer.
  • the hydroxylated PVC consists of a vinyl chloride / hydroxyethyl acrylate copolymer (4.06% by weight), ie 0.035 mole OH per 100 g of polymer.
  • the solution is heated to 120 ° C. and then spun through a die comprising 80 holes of 0.06 mm diameter at a speed of 200 m / min.
  • the filaments are then drawn in boiling water at different rates: 3 X, 4 X and then all stabilized under the same conditions at 110 ° C in the presence of vapor under tension for 2 seconds.
  • the crosslinking reaction is then carried out on the dry filaments, under stress at a temperature of 145 ° C for 5 min. They were then shrunk in boiling water for 20 min.
  • the solution thus obtained is heated to 60 ° C. and maintained at this temperature for 4 hours.
  • a white precipitate is obtained which is filtered, washed and dried and then separated from the solvent.
  • the solution is heated to 80 ° C., then spun through a die comprising 80 holes of 0.06 mm diameter, at a speed of 200 m / min.
  • the filaments are then drawn into boiling water at a rate of 4 X, then stabilized at 110 ° C in the presence of water vapor under tension for 2 seconds.
  • the crosslinking reaction is carried out on the dry fibers under stress, at a temperature of 145 ° C. for 5 min. They are then retracted in boiling water for 20 minutes.
  • the filaments are then cut in the form of fibers.
  • the table below indicates the titer of the fibers as well as the toughness, elongation, shrinkage in boiling water and in oil at 115 ° C., this with respect to uncrosslinked PVC threads obtained according to French patent No. 2495645.
  • a blocking agent is prepared from acetone oxime and MDI as indicated in Example 1 and its purity is checked.
  • 84 g of this same product are introduced with 1200 g of hydroxylated PVC identical to that used in example 1 in 2800 g of solvent mixture CS2 / acetone (50/50) and 7.2 g of tin thioglycolate as stabilizer so as to obtain a polymer concentration of approximately 30%.
  • the solution is heated to 80 ° C. and then spun through a die comprising 80 holes of 0.06 mm diameter at a call speed of 200 m / min.
  • the filaments are then drawn, stabilized, crosslinked, retracted as indicated in Example 1.
  • the MDI / AO reaction product is prepared as indicated in Example 1. 120 g of MDI / AO reaction product and 1200 g of hydroxylated PVC are introduced into 3086 g of solvent mixture CS2 / acetone (50/50 by volume), 7.2 g of tin thioglycolate as stabilizer, the concentration of the solution thus obtained being approximately 28% of hydroxylated PVC.
  • This is a vinyl chloride / hydroxyethyl acrylate copolymer containing 0.05 mole OH per 100 g of polymer (11.6% by weight of acrylate).
  • the solution is then heated to 80 ° C. and then spun through a die comprising 80 holes of diameter 0.06 mm in diameter at a speed of 200 m / min.
  • the filaments are then drawn into boiling water at a rate of 4 X and then crosslinked under stress at a temperature of 145 ° C for 5 min, stabilization takes place during the crosslinking treatment.
  • the filaments are then retracted in boiling water for 20 minutes and then cut.
  • the table below indicates the values of tenacity, elongation, shrinkage at 115 ° C, 130 ° C as well as the insoluble and swelling rates.
  • the control wire is obtained according to the method of French patent N ° 2499648 from atactic PVC having undergone a stress stabilization steam treatment at a temperature of 120 ° C for 2 seconds.
  • Example 4 is repeated but using a PVC containing 0.1 mole of OH per 100 g of polymer and using 240 g of the reaction product MDI / AO with 1200 g of hydroxylated PVC and 2230 g of solvent CS2 / acetone (50/50 by volume) and 7.2 g of tin thioglycolate.
  • the concentration of the solution is approximately 35%.
  • the solution is spun and the threads treated as indicated in Example 4.
  • the yarns obtained have the following characteristics:
  • a blocking agent is prepared from acetone oxime and MDI as indicated in Example 1 and its purity is checked. 84 g of the reaction product MDI / AO are introduced with 1200 g of a mixture of atactic PVC polymer and PVC OH in a proportion of 70/30 in 3086 g of solvent mixture CS2 / acetone (50/50 by volume), 7, 2 g of tin thioglycolate as stabilizer, the concentration of the solution being 28%.
  • the PVC OH used contains, alone, 0.15 mol OH / 100 g so that the PVC / PVCOH mixture contains 0.050 mol OH per 100 g of polymer mixture.
  • the solution of the polymer obtained is heated to 80 ° C. and then spun through a die comprising 80 holes of 0.06 mm diameter at a speed of 200 m / min.
  • the filaments are then drawn into boiling water at a rate of 4 X.
  • the dry fibers are then crosslinked under stress at temperature 145 ° C for 5 min.
  • Cross-linking treatment takes the place of stabilization. Free retraction in boiling water is carried out on crosslinked wires for 20 min.
  • the threads are then cut in the usual way.
  • the characteristics of the wires relative to control wires based on atactic PVC obtained according to French patent No. 2499648 having undergone a steam stabilization treatment at 120 ° C. for 2 seconds, are given in the table below:
  • Example 6 is repeated, but using a polymer mixture containing 40% PVCOH with an OH content of 0.15 mol / 100 g so as to obtain a polymer mixture containing: 0.060 mol OH / 100 g of the polymer mixture.
  • the polymer solutions are obtained using 144 g of the reaction product MDI / acetone-oxime, 1200 g of polymer in 3086 g of solvent mixture in the presence of 7.2 g of tin thioglycolate at polymer concentration is 28% .
  • the solution is heated to 80 ° C., then spun through a die having 80 holes of 0.06 mm diameter at a speed of 200 m / min.
  • the filaments obtained are then drawn into boiling water at a rate of 4 X then crosslinked under stress at 140 ° C for 10 min, and retracted for 20 min in boiling water, the characteristics of the fibers obtained are as follows:

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Artificial Filaments (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
EP91420380A 1990-10-31 1991-10-24 Fasern aus mit Diisocyanaten vernetzten Polyvinylchlorid und Verfahren zu deren Herstellung Withdrawn EP0488907A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9013756A FR2668502B1 (fr) 1990-10-31 1990-10-31 Fils a base de polychlorure de vinyle reticule par des diisocyanates et leur procede d'obtention.
FR9013756 1990-10-31

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EP0488907A1 true EP0488907A1 (de) 1992-06-03

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102111089B1 (ko) * 2018-11-19 2020-05-15 영남대학교 산학협력단 저가 탄소 섬유, 저가 탄소 섬유용 전구체 섬유 및 그 제조 방법

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2923598A (en) * 1954-06-30 1960-02-02 Pittsburgh Plate Glass Co Method of forming filaments embodying polyurethane resins
GB853726A (en) * 1957-02-28 1960-11-09 Montedison Spa Process for the production of synthetic textile fibres

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2923598A (en) * 1954-06-30 1960-02-02 Pittsburgh Plate Glass Co Method of forming filaments embodying polyurethane resins
GB853726A (en) * 1957-02-28 1960-11-09 Montedison Spa Process for the production of synthetic textile fibres

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FR2668502A1 (fr) 1992-04-30
JPH04343706A (ja) 1992-11-30
FR2668502B1 (fr) 1993-02-19

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