Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/32—Phosphorus-containing 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
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/10—Other agents for modifying properties

Definitions

• the invention relates to a process for the manufacture of stabilized compositions based on polyamide, and to the compositions which can be obtained by the process.
• the compositions according to the invention can in particular be used for the manufacture of synthetic yarns, fibers and filaments.
• Polyamide is a synthetic polymer widely used for the manufacture of yarns, fibers and filaments. These fibers, threads and filaments are then used for the production of textile surfaces, and in particular of dyed textile surfaces.
• the polyamide can undergo degradation when it is subjected to external elements or conditions such as UV rays, heat, bad weather. Degradation can also be induced by the heat used during its manufacture and / or its shaping. This instability results in degradations, losses of mechanical properties, color changes. These problems can become critical for a number of applications.
• antioxidant antioxidant
• anti-UV UV absorbers
• Phosphites substituted by alkyl and / or aryl radicals are known for stabilization, for example tris- (2,4-di-tert-butylphenyl) phosphite.
• These stabilizers when they are introduced into the preparation medium for the polyamide, cause heavy foaming which risks damaging the installations and the products produced. This strong foaming occurs even in the presence of conventional anti-foaming agents.
• the document WO 9418364 teaches, for example, to introduce these stabilizers by mixing in the molten phase the polyamide and a masterbatch of the stabilizer in a polyamide matrix.
• Foaming problems can also be encountered with other stabilizing additives.
• the object of the invention is to propose a method for manufacturing a stabilized composition based on polyamide, comprising a phosphorus-based additive introduced into the synthesis.
• the invention provides a process for manufacturing a stabilized polyamide-based composition, comprising a phosphorus stabilization additive, characterized in that the phosphorus stabilization additive is chosen from phosphorous acid and hypophosphorous acid , and in that it is introduced into the polyamide polymerization medium, before or during the polymerization phase.
• the proportion by weight in the composition is preferably between 0.01% and 0.04%.
• the complementary additive is chosen from hindered phenolic antioxidants and light stabilizers having at least one hindered amine light stabilizer (H.A.L.S.). It is also possible to use a combination of these two additives with the phosphorus stabilizer. The presence of the phosphorus stabilizer chosen from phosphorous acid and hypophosphorous acid also makes it possible to reduce the foaming due to the only complementary additives.
• Light stabilizers having at least one hindered amino motif make it possible to improve the light stability of the polyamide, and to avoid a loss of brightness in the colors when the latter is dyed or contains colored pigments.
• the process for manufacturing the polyamide according to the invention can be chosen from all the known processes, provided that the phosphorus stabilizer, and if necessary the other stabilization additives, are introduced into the polymerization medium, before the polymerization phase did not start properly. It is possible that a product with a low degree of polycondensation is formed before the introduction of the additives.
• the light stabilizer having at least one hindered amine unit is preferably chosen from 4-amino-2,2,6,6-tetramethylpiperidine, 4-carboxy-2,2,6,6-tetramethylpiperidine, aromatic compounds of formula (I) comprising two or three carbonyl functions and comprising at least one group having a hindered amine unit, said unit being included in a group linked to one of the carbonyl functions.
• the carbonyl function can be included in an amide, ester or ester-amide group.
• R1 and R2 are identical or different groups, at least one of which has a hindered amine unit.
• the additive can have a chemical structure (II) or (III), defined as follows:
• R1 or R2 are the same or different groups, at least one pattern has a hindered amine, a group not comprising a sterically hindered amine pattern can be selected from alkoxy of Ci to C 18; aminoalkyl optionally substituted with hydrogen, the alkoxy of Ci to C 5 carbonyl groups, carbamoyl groups or alkoxycarbonyl groups; C 3 to C 5 epoxides; the group or groups comprising a sterically hindered amine unit which can be chosen from the following compounds of formula (IV): wherein R and R 'are independently selected from hydrogen, alkyl of C ⁇ to C 12 alkoxy C ⁇ -C 8 -COR3 structure groups, wherein R3 is selected from hydrogen, alkyl of d to C 6 ; phenyl; the group -COO (alkyl of C, to C 4); the group of structure NR5R6, where R5 and R6 are independently selected from hydrogen, alkyls from d to C 12 ,
• R " is chosen from alkyls from d to C 20 , aminoalkyls from Ci to C 2 o, substituted aminoalkyls from d to C 20 , hydroxyalkyls from Ci to C 20 , alkenes from d to C 20 , alkenes substituted from C- t to C 2 o, alkoxyalkyl groups, C ⁇ - 20 -oxy-N-C ⁇ - 20 -alkyl groups, -N-cycloalkyl groups from d to C 10 , - N-cycloalkyl groups from d to C 10 substituted by a group -COR4 where R4 is chosen from hydrogen, alkyls from d to C 6 , phenyl, groups C- ⁇ - 20 COO (H or Ci- 4 alkyl), and where R ' has the same meaning as for formula (IV)
• the light stabilizer is more preferably still the compound of formula (VI)
• This additive is for example provided by the company Clariant under the name Nylostab S-EED.
• the proportion in the composition of the light stabilization additive is advantageously between 0.15% and 0.5% by weight.
• the light stabilizer of formula (VI) is preferably introduced into the polymerization medium in the form of a suspension or a solution in water, caprolactam, or a mixture of water and caprolactam.
• the concentration by weight in the solution or in the suspension can for example be between 5% and 50%.
• a mixture of caprolactam and water is used comprising more caprolactam than water.
• the form of introduction, suspension or solution may depend in part on the temperature and pressure conditions during the introduction.
• the antioxidant is preferably chosen from alkyl monophenols, alkylated hydroxyquinones, alkylidenes bisphenols, alkyl-containing benzyl compounds, acylaminophenols, esters of propionic acid ⁇ - (3,5-di- tert- butyl-4-hydroxyphenyl).
• the proportion of the second additive in the composition is advantageously between 0.10% and 0.30% by weight.
• the stabilized polyamide-based composition may contain other additives, in addition to the additives already mentioned. These additives can be introduced by mixing into the polymerization medium or by mixing in the molten phase.
• additives By way of example of such additives, mention is made of pigments or matifiers, intended to give the compositions a mat and / or colored appearance, flame retardants and other stabilizers.
• the compositions comprise a mattifier, in the form of particles based on titanium dioxide or on zinc sulfide.
• concentration of particles in the composition can be between 0.01% and 3% by weight. It is advantageously greater than 1%.
• the matifier is preferably introduced into the polymerization medium, before or during the polymerization phase.
• the particles are advantageously introduced in the form of an aqueous suspension.
• Particles based on titanium are advantageously coated. It may for example be a coating based on silica with, if appropriate, alumina and / or a manganese oxide.
• the composition produced by the process according to the invention may be based on a polyamide of the type of those obtained by polymerization from a lactam and / or an amino acid, or based on a polyamide of the type of those obtained by polycondensation of a dicarboxylic acid and a diamine.
• the compositions are preferably based on polyamide 6, polyamide 66, blends and copolymers based on these polyamides. It may in particular be a polyamide-6,6 / 6 copolymer if a stabilizer of formula (VI) is used which is introduced into the polymerization medium in the form of a solution or of dispersion in a liquid comprising caprolactam.
• the composition is based on polyamide 6,6.
• An advantageous manufacturing process uses as raw material a hexamethylene diammonium adipate salt, preferably in the form of a solution at salt concentrations of between 50 and 70% by weight. This process, continuous or discontinuous, comprises a first phase of evaporation of the water, and a second phase of polymerization by polycondensation.
• compositions can be shaped into yarns, fibers and filaments, directly after the polymerization, without intermediate stages of solidification and reflow. They can also be shaped into granules, intended to undergo remelting for subsequent final shaping, for example for the manufacture of molded articles or for the manufacture of threads, fibers or filaments.
• the yarns, fibers and filaments formed from compositions obtained by the process according to the invention are produced by melt spinning: the composition is extruded in the molten state through dies comprising one or more orifices. All melt spinning methods can be used.
• the filaments can be drawn, in the form of a multifilament yarn or a wick, in a continuous step or in recovery, and undergo various treatments: sizing, texturing, fixing ...
• the filaments can for example be combined in the form of a wick or sheet, directly after spinning or in recovery, drawn, textured and cut.
• the fibers obtained can be used for the manufacture of nonwovens or yarns of fibers.
• the compositions can also be used for the manufacture of flock cable.
• the yarns, fibers and filaments, and the articles obtained from the yarns, fibers and filaments can be dyed. Mention is made in particular of the dyeing processes in bath or by jets.
• the preferred dyes are acid, metalliferous or non-metalliferous dyes.
• compositions according to the invention make it possible to obtain articles whose dye resistance to light is excellent. They also make it possible to obtain better resistance of the dye to washing.
• a polyamide 66-based copolymer is produced from 3590 kg of an aqueous solution of a hexamethylene diammonium adipate salt concentrated at 62% by weight, to which are added:
• the polyamide is manufactured according to a standard process, comprising a stage of concentration of the solution in an evaporator, a stage of polycondensation in a stirred autoclave reactor, with a phase of approximately 45 minutes of distillation under a pressure bearing at 1.85 MPa for which the final temperature is 245 ° C, a phase of approximately 35 minutes of decompression from 1.85 MPa to 0.1 MPa at final temperature of 260 ° C, and a finishing phase of approximately 30 minutes for which the final temperature is 270 ° C.
• a copolymer based on polyamide 6.6 is obtained comprising 2.0% by weight of units of polyamide 6 and 1.6% of titanium dioxide.
• the copolyamide is spun using an integrated spinning-stretching process. The winding speed is 4500 m / min.
• the titer of the threads obtained is 78 dtex for 68 filaments.
• the tenacity of the wire is 42 cN / tex and the elongation at break is 38%.
• a knitted surface is produced from the threads.
• the surface is washed at 60 ° C for 20 minutes in the presence of a detergency composition composed of 2g / l of
• Sandozine MRN sold by the company Clariant, 2 g / 1 of Sirrix AR, and 2 g / l of sodium carbonate. The surface is then thermofixed at 190 ° C for 45 seconds.
• the surface is dyed by quenching at 98 ° C, for 45 minutes, at pH 6, in the presence of the following agents: dyeing agents, sold by the company Ciba
• the light resistance of the surface was tested, using a Xenotest 450 device, according to DIN 75202, over 4 cycles (FAKRA test). After 4 cycles, the rating is 6-7.
• a copolyamide is produced according to the method of Example 1, without the phosphorous acid solution or the caprolactam + water + Nylostab + Irganox mixture.
• the rating is 5.
• compositions based on polyamide 6,6 are prepared in a 300 ml reactor, provided with a porthole allowing the observation of any foaming.
• the polyamide is prepared from a salt of hexamethylene diammonium adipate in solution, according to a process similar to that of Example 1.
• the decompression phase is carried out in 10 minutes, so that it is put used under conditions close to the conditions of Example 1 as regards the sensitivity to foaming.
• additives are added: - coated titanium dioxide particles (1.6% by weight relative to the composition obtained). The particles are added 5 minutes after the start of the plateau at 1.85 MPa.
• the amounts of additives are expressed by weight relative to the composition obtained.
• the level of foaming is evaluated by the height of foam in the reactor: 0 for zero foaming, 3 for very high foaming.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• General Chemical & Material Sciences (AREA)
• Textile Engineering (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Manufacturing & Machinery (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Polyamides (AREA)
• Artificial Filaments (AREA)
• Processes Of Treating Macromolecular Substances (AREA)
• Woven Fabrics (AREA)
• Knitting Of Fabric (AREA)

Applications Claiming Priority (3)

Publications (1)

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• 2000
  • 2000-12-29 FR FR0017260A patent/FR2818985B1/fr not_active Expired - Fee Related
• 2001
  • 2001-12-21 WO PCT/FR2001/004151 patent/WO2002053633A2/fr not_active Application Discontinuation
  • 2001-12-21 US US10/451,663 patent/US7074851B2/en not_active Expired - Fee Related
  • 2001-12-21 JP JP2002555151A patent/JP3887312B2/ja not_active Expired - Fee Related
  • 2001-12-21 MX MXPA03005385A patent/MXPA03005385A/es active IP Right Grant
  • 2001-12-21 RU RU2003123498/04A patent/RU2250242C1/ru not_active IP Right Cessation
  • 2001-12-21 BR BR0116754-5A patent/BR0116754A/pt not_active Application Discontinuation
  • 2001-12-21 EP EP01995754A patent/EP1358258A2/fr not_active Withdrawn
  • 2001-12-21 KR KR1020037008819A patent/KR100611547B1/ko not_active IP Right Cessation
  • 2001-12-21 CN CNA018215610A patent/CN1484670A/zh active Pending
  • 2001-12-21 IL IL15621901A patent/IL156219A0/xx unknown
  • 2001-12-21 AU AU2002226475A patent/AU2002226475A1/en not_active Abandoned
  • 2001-12-21 CA CA002432957A patent/CA2432957A1/fr not_active Abandoned
  • 2001-12-28 AR ARP010106095A patent/AR032216A1/es active IP Right Grant

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