FR2831189A1 - Production of polyamide yarns, fibers and filaments comprises spinning a molten mixture of a linear polyamide and either a star or H polyamide or a polyfunctional acid or amine - Google Patents

Abstract

Production of polyamide yarns, fibers and filaments comprises spinning a molten mixture of a linear polyamide and either: (a) a polyamide composition comprising star- or H-shaped macromolecules and optionally linear macromolecules, the composition having a melt flow index of more than 20 g/10 min (275 deg C, 100 g); or (b) a polyfunctional compound having at least three indentical acid or amine functions.

Description

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PROCESS FOR PRODUCING YARNS, FIBERS AND FILAMENTS

 The present invention relates to a process for producing polyamide-based yarns, fibers and filaments, as well as yarns, fibers and filaments obtained by the process.

 The polyamide-based yarns, fibers and filaments are made by melt spinning a polyamide, or a polyamide-based composition. The melt-spinning consists of extruding the polyamide or the composition through dies, followed by cooling at the outlet of dies and possibly drawing. Thus articles are manufactured for use in many fields. Examples are multifilament yarns for the textile industry, fibers intended to be worked in spinning, or for the manufacture of nonwoven articles, cables intended to be cut to form short fibers capable of being flocked. , monofilaments and multifilaments for particular industrial applications.

 The processes for producing the yarns, fibers and filaments can vary considerably, especially in the field of spinning speed. Depending on the type of process the products obtained have different properties.

 Various families of yarn, fiber and filament manufacturing processes are thus known. High-speed POY (Partially Oriented Yarn) spinning processes (speed greater than 3500 m / min), FEI (Integrated Spinning-Drawing) sometimes referred to as FOY (Fully Oriented Yarn), HOY (Highly Oriented Yarn) ( speed above 5500 m / min). Low speed yarn processes LOY (Low Oriented Yarn) are also mentioned (speed less than 3500 m / min). These methods, and more particularly the LOY process, comprise a drawing step making it possible to improve the mechanical properties of said products. This stretching step is also carried out for the manufacture of monofilaments. In addition, depending on the applications, stretching may be applied to all types of yarns obtained by the processes described above.

Thus, the yarns obtained by the POY processes are very often stretched either directly at the output of the spinning process (integrated stretching) or in a separate step comprising resumption of the son.

These methods are well known to those skilled in the art. They differ from each other, for example by the spinning speeds, the cooling mode at the outlet of the die, by the possible drawings made. In addition, the products obtained can undergo different special treatments such as texturing, over-stretching, twisting, fastenings, for example.

 The processes used, and the technical parameters of these processes, depend to a large extent on the properties of the polyamide, or the polyamide-based composition used. Thus the speeds, temperatures and spinning pressures that it is

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 Possible to use are determined with respect to the properties of the polymer or the composition to be spun, such as for example the thermal stability and the melt viscosity.

Continuous work is undertaken to improve the productivity of these processes, ie to produce the longest film of threads per unit of time.

To improve the productivity of these spinning processes, in particular by increasing the spinning speed, it has been proposed to modify, in particular, the rheological properties of the spinning composition by adding modifiers to said composition.

 Thus, for the manufacture of pre-oriented polyethylene terephthalate yarns, US 5962131 discloses the melt addition of an immiscible copolymer forming small inclusions in the base polymer.

 For the production of pre-oriented polyamide-based yarns, the document FR 2677376 describes the addition of nanometric mineral particles. The presence of these particles makes it possible to increase the spinning speeds. However, it is difficult to obtain a good dispersion of the particles, so that the rate of breakage during spinning can be significant.

 The object of the present invention is to propose a process for manufacturing yarns, fibers and filaments based on a polyamide composition having a molecular structure making it possible to improve the total productivity of the spinning process, in particular by improving the drawing capacity of the son son products allowing to have, for example, for an identical spinning speed a son of wire per unit of time produced after drawing much higher.

For this purpose, the invention provides a process for the production of polyamide-based synthetic yarns, fibers and filaments, comprising the following operations: Melt at least the following compounds A and B: compound A: a linear polyamide obtained from diacid monomers and monomers diamines' compound B selected from the group comprising: a polyamide or a polyamide composition comprising: - star or H macromolecular chains comprising one or more cores and at least three branches or three polyamide segments linked to said core obtained from amino acid and / or lactam monomers, optionally linear macromolecular polyamide chains obtained from amino acid and / or lactam monomers, and

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 a multifunctional compound comprising at least three identical acidic or amine functions, the weight concentration of compound B is less than or equal to 30% of the mixture of compounds A and B; ! ii) spinning the melt phase mixture (a1) and optionally stretching said one or more yarns, fibers or filaments obtained.

 The advantages of the invention are multiple and depend on the method precisely implemented. These advantages can be observed during the spinning operation, and especially during a subsequent operation such as stretching. These advantages make it possible to improve the productivity of the process or the possibility of manufacturing special products such as yarns or fibers of very low titre.

 By "spinning" is meant the operation of extruding the molten material through dies and then cooling it between the dies and at least a first driving point. By "process for manufacturing yarns, fibers and filaments" is meant all the steps leading to yarns, fibers and filaments. The method comprises in particular the spinning operation. It may comprise other operations after the spinning operation, including a drawing step (continuous or rework) to improve the mechanical properties of the spun products and obtain for example, a module and a residual elongation at break consistent with the methods of use of these products and the methods of treatment thereof. Treatment methods for spun products include relaxation, crimping, texturing, heat setting and dyeing processes.

 The process according to the invention comprises a melt blending operation of at least two compounds, a compound A and a compound B. The two compounds are thermoplastic. The mixture may be obtained by any means conventionally used for producing a mixture of two thermoplastic compounds, for example an extrusion device, single or double screw and / or barrier screw. Compound B granules can, for example, be added to compound A in molten form, or granules of compound A and compound B can be mixed and the mixture of granules melted. Other additives may be added to the mixture, such as pigments, delustrants, mattifying agents, catalysts, heat and / or light stabilizers, antibacterial agents, antifungal agents. It may for example be a matting agent, for example selected from titanium dioxide particles or zinc sulfide.

 The melt phase mixture can be followed by solidification and granulation. The solid mixture is then re-melted for the spinning operation. So

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 Advantageously, the melt mixing operation is directly followed by the spinning operation, without intermediate solidification and granulation.

 The mixture of compounds is melt spun. This operation is carried out by extrusion through dies, at a temperature and at a pressure suitably chosen. All known spinning devices can be used.

 According to one characteristic of the invention, compound A is a linear polyamide; or a composition based on a linear polyamide obtained from a diacid monomer and a diamine monomer. As examples of diacid monomers, there may be mentioned adipic acid which is the preferred acid, decanoic or sebaccic acid, dodecanoic acid, phthalic acids such as terephthalic acid, isophthalic acid. Diamine monomers that may be mentioned include hexamethylenediamine, methyl pentamethylenediamine, 4,4'-diaminodicyclohexylmethane, butane diamine and metaxylylenediamine. The polyamides obtained from these monomers are in particular polyamide 66 (hexamethylenediamine polyadipate), polyamide 46, polyamine 612. The linear polyamides that are suitable for the invention are also copolyamides comprising at least 90 mol% of units. corresponding recurring polyamides described above, other recurring units may be derived from diacid monomers, diamines, amino acids or lactams. Copolyamides that may be mentioned include, in particular, polyamide 66,6 containing less than 5 mol% of polyamide 6 unit. Suitable polyamides for the invention may also comprise a monofunctional monomer conventionally used in the production of these polymers as chain-limiting agents.

Compound B is, in a first embodiment, a polymer, or a polymer composition comprising star or H macromolecular chains, and optionally linear macromolecular chains. Polymers or polymer compositions comprising such star or H macromolecular chains are for example described in documents FR 2.743. 077, FR 2.779. 730, US 5,959. 069, EP 0.632. 703, EP 0.682. 057 and EP 0.832. 149.

These compounds are known to exhibit improved fluidity over linear polyamides.

The star or H macromolecular chains are obtained by using a multifunctional compound having at least three reactive functions, all the reactive functions being identical. This compound can be used as a comonomer in the presence of other monomers in a polymerization process. It can also be brought into contact with a polyamide during an extrusion operation.

The star or H macromolecular chains comprise a core and at least three polyamide branches. The branches are linked to the heart by a covalent bond, by

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 through an amide group or a group of another nature. The core is an organic or organometallic chemical compound, preferably a hydrocarbon compound optionally comprising heteroatoms and to which the branches are connected. The branches are polyamide chains. They may have branches, this is particularly the case for structures H. The polyamide chains constituting the branches are preferably of the type obtained by polymerization of lactams or amino acids, for example polyamide 6 type.

Compound B optionally comprises, in addition to the star or H chains, linear macromolecular polyamide chains. The weight ratio between the amount of star or H chains in compound B and the sum of the amounts of star or H chains and linear chains is between 0.1 and 1 inclusive. It is preferably between 0.5 and 1.

b) des monomères de formules générales (lia) et (lIb) suivantes :

0 il X-R-Y (IIa) ou P-C (IIb) \/ NH c) éventuellement des monomères de formule générale (III) suivante :

dans lesquelles : 'Z représente une fonction identique à celle des fonctions réactives du composé multifonctionnel * R, Rs identiques ou différents représentent des radicaux hydrocarbonés aliphatiques, cycloaliphatiques ou aromatiques, substitués ou non, comprenant de 2 à 20 atomes de carbone, et pouvant comprendre des hétéroatomes, 'Y est un radical amine primaire quand X représente un radical carboxylique, ou Y est un radical carboxylique quand X représente un radical amine primaire According to a first process, compound B is a star polyamide, that is to say comprising star macromolecular chains, obtained by copolymerization from a monomer mixture comprising: a) a multifunctional compound comprising at least three reactive functional groups chosen from the amines, the carboxylic acids, and their derivatives, all the reactive functions being identical,

b) monomers of the following general formulas (IIa) and (IIb):

XRY (IIa) or PC (IIb) n / c) optionally monomers of the following general formula (III):

in which: Z represents a function identical to that of the reactive functions of the multifunctional compound R, Rs, which may be identical or different, represent substituted or unsubstituted aliphatic, cycloaliphatic or aromatic hydrocarbon radicals comprising from 2 to 20 carbon atoms, and which may comprise heteroatoms, Y is a primary amine radical when X is a carboxylic radical, or Y is a carboxyl radical when X is a primary amine radical

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 Such methods of obtaining are described in the documents FR2.743. 077 and FR 2.779. 730.

In the case where a comonomer c) is used, the polymerization reaction (polycondensation) is advantageously carried out until the thermodynamic equilibrium is reached.

The monomer mixture may comprise other compounds, such as chain imitators, catalysts, additives.

Dans laquelle :

si les fonctions réactives sont des fonctions acides

si les fonctions réactives sont des fonctions amines To représente le nombre de moles de composé multifonctionnel No représente le nombre de moles initiales en monomère de formule (Na) ou (lib) Ro représente le nombre de moles initiales en monomère de formule (III) This process leads to the formation of star macromolecular chains, and possibly linear macromolecular chains. The PS percentage by number of star macromolecular chains with respect to the total number of chains is determined by the following formulas: in the case where the multifunctional compound has 4 reactive functions:

In which :

if the reactive functions are acid functions

if the reactive functional groups are amino functions To represents the number of moles of multifunctional compound No represents the number of initial moles of monomer of formula (Na) or (lib) Ro represents the number of initial moles of monomer of formula (III)

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* dans le cas où le composé multifonctionnel présente 3 fonctions réactives :

Dans laquelle :

si les fonctions réactives sont des fonctions acides

si les fonctions réactives sont des fonctions amines To représente le nombre de moles de composé multifonctionnel No représente le nombre de moles initiales en monomère de formule (lia) ou (llb) Ro représente le nombre de moles initiales en monomère de formule (111)
Selon un deuxième mode de réalisation du procédé, le composé B est un polyamide H, c'est à dire comprenant des chaînes macromoléculaires H, obtenu par copolymérisation à partir d'un mélange de monomères comprenant : a) 1 à 50 umso) par gramme de matrice d'un composé multifonctionnel comprenant au moins trois fonctions réactives choisies parmi les amines, les acides carboxyliques et leurs dérivés, les fonctions réactives étant identiques, b) des lactames et/ou amino-acides c) un composé difonctionnel choisi parmi les acides dicarboxyliques ou les diamines, d) un composé monofonctionnel dont la fonction est choisie parmi les amines, les acides carboxyliques et leurs dérivés, les fonctions de c) et d) étant des amines lorsque les fonctions de a) sont des acides, les fonctions de c) et d) étant des acides lorsque les fonctions de a) sont des amines, le rapport en équivalents entre les groupements fonctionnels de a) et la somme des groupements fonctionnels de c) et d) étant compris entre 1,5 et 0,66, le rapport en

in the case where the multifunctional compound has 3 reactive functions:

In which :

if the reactive functions are acid functions

if the reactive functions are amino functions To represents the number of moles of multifunctional compound No represents the number of initial moles of monomer of formula (IIa) or (IIb) Ro represents the number of initial moles of monomer of formula (III)
According to a second embodiment of the process, compound B is a polyamide H, that is to say comprising macromolecular chains H, obtained by copolymerization from a monomer mixture comprising: a) 1 to 50 μmso) per gram matrix of a multifunctional compound comprising at least three reactive functional groups chosen from amines, carboxylic acids and their derivatives, the reactive functions being identical, b) lactams and / or amino acids c) a difunctional compound chosen from the acids dicarboxylic or diamines, d) a monofunctional compound whose function is chosen from amines, carboxylic acids and their derivatives, the functions of c) and d) being amines when the functions of a) are acids, the functions of (c) and (d) being acids when the functions of (a) are amines, the ratio in equivalents between the functional groups of (a) and the sum of the functional groups of (c) and d) between 1.5 and 0.66, the ratio in

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 equivalents between the functional groups of c) and the functional groups of d) being between 0.17 and 1.5.

Such a process and such polymers are described in US 5959069 According to a third embodiment of the process of the invention, compound B is obtained by melt blending, for example using an extrusion device. , a polyamide of the type obtained by polymerization of lactams and / or amino acids, and a multifunctional compound comprising a core and at least three branches, all of whose branches have identical end functions, chosen from amines, carboxylic acids and their derivatives.

Such methods of obtaining are described in EP 0.682. 070 and EP 0.672. 703.

According to another embodiment of the invention, compound B is a multifunctional compound such as those used as a core for the synthesis of star polyamides and / or polyamide H described above and below. This compound is added directly to compound A in a molten medium analogously to the methods for introducing compounds of type polyamide star or polyamide H.

dans laquelle : 'R- est un radical hydrocarboné comprenant au moins deux atomes de carbone linéaire ou cyclique, aromatique ou aliphatique et pouvant comprendre des hétéroatomes, A est une liaison covalente ou un radical hydrocarboné aliphatique comprenant de 1 à 6 atomes de carbone, Z représente un radical amine primaire ou un groupement carboxylique, . m est un nombre entier compris entre 3 et 8. The multifunctional compounds used can be chosen from compounds having a tree or dendritic structure. They can also be chosen from the compounds represented by the formula (1).

in which: R 'is a hydrocarbon radical comprising at least two linear or cyclic, aromatic or aliphatic carbon atoms and which may comprise heteroatoms, A is a covalent bond or an aliphatic hydrocarbon radical comprising from 1 to 6 carbon atoms, Z represents a primary amine radical or a carboxylic group, m is an integer from 3 to 8.

According to a preferred characteristic, the radical R 1 is either a cycloaliphatic radical such as the tetravalent cyclohexanonyl radical, or a 1,1,1-triylpropane, 1,2,3-tripropyl-propane radical.

 Other radicals R.sub.1 suitable for the invention include, for example, the trivalent radicals of phenyl and cyclohexanyl, which may or may not be substituted, the tetravalent diaminopolymethylene radicals with a number of methylene groups.

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 advantageously between 2 and 12, such as the radical originating from EDTA (ethylene diamino tetracetic acid), the octovalent radicals of cyclohexanonyl or cyclohexadinonyl, and the radicals derived from compounds derived from the reaction of polyols such as glycol, pentaerythritol, sorbitol or mannitol with acrylonitrile.

 The radical A is preferably a methylene or polymethylene radical such as ethyl, propyl or butyl radicals, or a polyoxyalkylene radical such as the polyoxyethylene radical.

 According to a preferred embodiment of the invention, the number m is greater than or equal to 3 and advantageously equal to 3 or 4.

 The reactive function of the multifunctional compound represented by the symbol X-H is a function capable of forming an amide function.

ou les composés provenant de la réaction du triméthylol propane ou du glycérol avec l'oxyde de propylène et amination des groupes hydroxyles terminaux. Ces derniers composés sont commercialisés sous le nom commercial JEFFAMINES T ('par la société HUNTSMAN, et ont comme formule générale :

Dans laquelle : - R1 représente un radical 1,1, 1-triyle propane, ou 1,2, 3-triyle propane, - A représente un radical polyoxyéthylénique. By way of example of polyfunctional compounds of formula 1, there may be mentioned 2,2,6,6-tetra- ((3-carboxyethyl) cyclohexanone, diaminopropane-N, N, N ', N' tetraacetic acid of formula next :

or compounds derived from the reaction of trimethylol propane or glycerol with propylene oxide and amination of terminal hydroxyl groups. These latter compounds are marketed under the trade name JEFFAMINES T ('by the company HUNTSMAN, and have as general formula:

Wherein: R 1 represents a 1,1,1-triyl propane, or 1,2,3-triyl propane, A represents a polyoxyethylene radical.

Examples of multifunctional compounds that may be suitable are mentioned in documents US 5346984, US 5959069, 9635739 and EP 672703.

We quote more particularly:

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 Nitrilotrialkylamines, in particular nitrilotriethylamine, dialkylenetriamines, in particular diethylenetriamine, trialkylenetetramines and tetraalkylenepentamines, the alkylene preferably being ethylene, 4-aminoethyl-1,8, octanediamine.

dans laquelle 'R est un atome d'hydrogène ou un groupement - (CH2) n -NR12 où . R1 est un atome d'hydrogène ou un groupement - (CH2) n -NR22 où . R2 est un atome d'hydrogène ou un groupement- (CHz) n-NRSz où . R3 est un atome d'hydrogène ou un groupement- (CHz) n-NHz, n étant un entier compris entre 2 et 6 (bornes incluses) x étant un entier compris entre 2 et 14 (bornes incluses) n est de préférence un entier égal à 3 ou 4, en particulier 3, et x est de préférence un entier compris entre 2 et 6 (bornes incluses), de préférence égal à 2,3 ou 4, en particulier 2. Chaque radical R peut être choisi indépendamment des autres. Le radical R est de préférence un atome d'hydrogène ou un groupement- (CH2) n-NH2. Dendrimers of formula (II) are also mentioned

wherein R is a hydrogen atom or a - (CH 2) n -NR 12 group where. R1 is a hydrogen atom or a - (CH2) n -NR22 group where. R2 is a hydrogen atom or a group- (CHz) n-NRSz where. R3 is a hydrogen atom or a group-(CHz) n-NHz, n being an integer from 2 to 6 (inclusive) x being an integer from 2 to 14 (inclusive) n is preferably an integer equal to 3 or 4, in particular 3, and x is preferably an integer between 2 and 6 (limits included), preferably equal to 2.3 or 4, in particular 2. Each radical R may be chosen independently of the others . The radical R is preferably a hydrogen atom or a group - (CH2) n -NH2.

Multifunctional compounds having 3 to 10 carboxylic acid groups, preferably 3 or 4, are also mentioned. Among these, compounds having an aromatic and / or heterocyclic ring, for example benzyl, naphthyl, antracenyl or biphenyl radicals, are preferred. and triphenyl, or heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoline, phenanthrene, porphyrin, phthalocyanine and naphthalocyanine. Particularly preferred are 3,5,3 ', 5'-biphenyltetracarboxylic acid, acids derived from phthalocyanine and naphthalocyanine, 3,5,3', 5'-biphenyltetracarboxylic acid, 1,3-acid, , 5,7-naphthalenetetracarboxylic acid, 2,4,6-pyridinetricarboxylic acid, 3,5,3 ', 5'bipyridyltetracarboxylic acid, 3,5,3', 5'-benzophenonetetracarboxylic acid, 1-acid, 3, 6, 8-acridinetetracarboxylic, more particularly trimesic acid and 1,2,4,5-benzenetetracarboxylic acid.

Multifunctional compounds whose core is a heterocycle having a point of symmetry, such as 1,3,5-triazines, 1,4-diazines, melanin, compounds derived from 2,3,5,6 tetraethylpiperazine, 1,4-piperazines, tetrathiafulvalenes.

More particularly, 2,4,6-triaminocaproic acid-1,3,5-triazine (TACT) is mentioned.

 The proportion by weight of compound B relative to the weight of compounds A and B in the mixture is preferably less than 30%, more preferably

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 less than 15%. This characteristic does not take into account the possible presence of other additives.

par rapport au poids total des chaînes macromoléculaires étoiles ou H et linéaires est de préférence inférieure à 25%, plus préférablement encore inférieure à 15%
Le procédé selon l'invention peut plus particulièrement, dans un premier mode de réalisation, être employé dans le cadre d'un procédé de filage haute vitesse, par exemple à des vitesses supérieures à 3500 m/min, de type POY, HOY, au FEI, pour la fabrication de fils multifilamentaires ou dans le procédé LOY pour la fabrication de fibres. The yarns, fibers and filaments obtained from the mixture of compounds A and B comprise macromolecular polyamide star or H chains, and linear polyamide chains. The proportion by weight of the star or H macromolecular chains

relative to the total weight of the star or H and linear macromolecular chains is preferably less than 25%, more preferably less than 15%
The method according to the invention may more particularly, in a first embodiment, be used in the context of a high-speed spinning process, for example at speeds greater than 3500 m / min, of the POY, HOY, FEI, for the manufacture of multifilament yarns or in the LOY process for the manufacture of fibers.

 The yarns obtained surprisingly have a capacity of greater stretchability than that observed on the yarns obtained from linear polyamide conventionally used, such as polyamide 66 for comparable mechanical properties and compatible with the use of these products in different applications such as the textile industry. Indeed, the products obtained according to the process of the invention have a modulus and a residual elongation at break equivalent to those presented by the polyamide yarns 66.

 This improved stretchability thus makes it possible to improve the productivity of the yarn manufacturing process either by increasing the spinning speed, or by increasing the stretching ratio applied to the yarns obtained or by applying these two increases.

In other words, the process of the invention makes it possible to manufacture yarns, fibers or monofilaments with the application of an overall draw ratio, stretching ratio applied to the spinning process plus the stretching ratio applied during step d stretching, higher than that applicable on linear polyamide yarns, for the same level of modulus and elongation at break for the yarn thus obtained.

 The process of the invention also makes it possible to produce, by melt-spinning and stretching, fine-text threads, for example, less than 0.8 dtex, preferably less than 0.6 dtex. Indeed, it is possible to produce, according to the process of the invention, threads at the die exit having a fine title, in a manner analogous to that obtained with a linear polyamide, and with a similar device. However, since it is possible to apply to the son obtained by the method of the invention a higher draw ratio, it is easily understood that the final title of the yarn according to the invention is significantly lower for equivalent mechanical properties. . This possibility is particularly interesting for the manufacture of fibers, very low title.

 Other details or advantages of the invention will emerge more clearly in the light of the examples given below, for information only.

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The following compounds are used: Compound A: polyamide 66 with a viscosity number of 136 ml / g, measured at 250 ° C. at a concentration of 0.01 g / ml in a 90% formic acid solution, with a concentration of acid terminal functions (GTA) of 55 meq / g polymer and a terminal amine concentration (GTC) of 66 meq / g polymer.

Compound B: star polyamide, obtained by copolymerization from caprolactam in the presence of 0.5% by mole of 2,2,6,6-tetra (-carboxyethyl) cyclohexanone, according to a process described in document FR 2743077, comprising about 80 % of macromolecular star chains and 20% of linear macromolecular chains, with a viscosity number of 98.2 ml / g, measured according to the method described above, and a GTA of 13.9 meq / g and a GTC of 165.3 meq / g.

The properties of elongation rupture and stress breaking son are determined on an Erichsen traction machine placed in a room conditioned at 50% RH and 23 C after conditioning son for 72 hours under these conditions. The initial length of the wires is 50 mm and the traverse speed is 50 mm / min. These measurements are performed according to ISO 2062 or AFNOR 07-002.

EXAMPLES The compounds are mixed in the melt phase by means of a single-screw extruder and the molten mixture is then spun with a speed at the first point of call, also referred to as spinning speed, of 4200 m / min. to obtain a continuous yarn comprising 34 filaments of total title indicated in Table 1 below. The spinning conditions are summarized in Table 1 below, the properties of the yarns obtained being collated in Table II.

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Tableau 1

Table 1

<Tb>
<tb> EX <SEP> Composition <SEP> (% <SEP> Temperature <SEP> Pressure <SEP> Flow <SEP> of <SEP> Speed <SEP> of
<tb> weight) <SEP> of <SEP> die <SEP> of <SEP> spinning <SEP> polymer <SEP> in <SEP> spinning
<tb> (C) <SEP> (bar) <SEP> die <SEP> g / min <SEP> (m / min)
<tb> 1c <SEP> Compound <SEP> A <SEP>: <SEP> 100% <SEP> 276 <SEP> 230 <SEP> 1, <SEP> 23 <SEP> 4200
<tb> 2 <SEP> Compound <SEP> A <SEP>: <SEP> 90 <SEP>% <SEP> 276 <SEQ> 280 <SEP> 1, <SEP> 23 <SEP> 4200
<tb> Compound <SEP> B <SEP>: <SEP> 10 <SEP>%
<tb> 3 <SEP> Compound <SEP> A <SEP>: <SEP> 90 <SEP>% <SEP> 276 <SEQ> 280 <SEP> 1, <SEP> 23 <SEQ> 4800
<tb> Compound <SEP> B <SEP>: <SEP> 10 <SEP>%
<tb> 4 <SEP> Compound <SEP> A <SEP>: <SEP> 90 <SEP>% <SEP> 276 <SEQ> 280 <SEP> 1, <SEQ> 23 <SEQ> 5400
<tb> Compound <SEP> B <SEP>: <SEP> 10 <SEP>%
<Tb>
Table II

<Tb>
<tb> EX <SEP> Title <SEP> total <SEP> elongation <SEP> to <SEP> Module <SEP> to <SEP> 5 <SEP>%
<tb> (dtex) <SEP> the <SEP> elongation <SEP>
<tb> (%) <SEP> (cN / tex)
<tb> li <SEP> 100 <SEP> 70 <SEP> 109
<tb> 2 <SEP> 99 <SEP> 94, <SEP> 2 <SEP> 104
<tb> 3 <SEP> 86 <SEP> 86, <SEP> 6 <SEP> 116
<tb> 4 <SEP> 76, <SEP> 6 <SEP> 76, <SEP> 2 <SEP> 137
<Tb>

les fils obtenus à une vitesse de 4200 m/min ont été étirés sur un banc d'étirage, les propriétés des fils obtenus sont rassemblés dans le tableau eau))) ci-dessous.

the yarns obtained at a speed of 4200 m / min were drawn on a drawing bench, the properties of the son obtained are collected in the water table))) below.

Board !

<Tb>
<tb> EX <SEP> stretching rate <SEP><SEP><SEP> stretching <SEP> to <SEP><SEP><SEP><SEP> 5 <SEP>%
<tb> (dtex) <SEP> rupture <SEP> of elongation
<tb> (%) <SEP> (cN / tex)
<tb> lc <SEP> 1, <SEP> 312 <SEP> 81, <SEP> 2 <SEP> 36, <SEP> 9 <SEP> 257
<tb> 2 <SEP> 1, <SEQ> 437 <SEP> 71, <SEP> 4 <SEP> 44, <SEP> 6 <SEP> 257
<Tb>
These tests show that it is possible to apply a higher draw ratio on the yarns according to the invention while obtaining yarns having a 5% modulus identical to that obtained with a polyamide 66 yarn with residual elongation. higher. This last feature of high residual elongation makes it possible to improve the workability of the yarns.

Claims (17)

Melt-blending at least the following compounds A and B: Compound A: a linear polyamide obtained from monomeric diacid monomers and monomers compound B selected from the group consisting of: a polyamide or a polyamide composition comprising: macromolecular chains stars or H comprising one or more cores and at least three branches or three polyamide segments linked to said core, obtained from amino acid and / or lactam monomers, - where appropriate linear macromolecular polyamide chains obtained from amino acid monomers and / or lactams a multifunctional compound comprising at least three identical reactive amine or acidic functions, the weight concentration of compound B is less than or equal to 30% of the mixture of compounds A and B; spinning the mixture in the melt phase, and optionally, stretching the one or more son, fibers or filaments obtained. 1. A method of manufacturing synthetic yarns, fibers and filaments based on polyamide, comprising the following operations: 2. Method according to claim 1 characterized in that the weight ratio between the star or H macromolecular chains and the sum of star or H macromolecular chains and linear chains in compound B is between 0.1 and 1. 3. Method according to one of the preceding claims characterized in that the compound B is a star polyamide obtained by copolymerization from a monomer mixture comprising: a) a multifunctional compound comprising at least three reactive functions selected from amines, the carboxylic acids, and their derivatives, the reactive functions being identical,

 b) monomers of the following general formulas (IIa) and / or (IIb):

 0 he X-R, -Y (Ha) or R-C (IIb) \ / NH <Desc / Clms Page number 15>  in which: Z represents a function identical to that of the reactive functions of the multifunctional compound R, Rg represent aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, substituted or unsubstituted, identical or different, comprising from 2 to 20 carbon atoms, and heteroatoms, Y is a primary amine radical when X is a carboxylic radical, or Y is a carboxylic radical when X is a primary amine radical, 4. Method according to one of claims 1 or 2 characterized in that the compound B is a polyamide H obtained by copolymerization from a mixture of monomers comprising: a) 1 to 50 umo! per gram of polymer of compound B of a multifunctional compound comprising at least three reactive functions chosen from amines, carboxylic acids and their derivatives, the reactive functions being identical, b) lactams and / or amino acids c) a compound difunctional selected from dicarboxylic acids or diamines, d) a monofunctional compound whose function is selected from amines, carboxylic acids and their derivatives, the functions of c) and d) being amines when the functions of a) are acids, the functions of c) and d) being acids when the functions of a) are amines, the ratio in equivalents between the functional groups of a) and the sum of the functional groups of c) and d) being between 1 , 5 and 0.66, the ratio in equivalents between the functional groups of c) and the functional groups of d) being between 0.17 and 1.5.

 c) where appropriate, monomers of the following general formula (III): 5. Method according to one of claims 1 or 2 characterized in that the compound B is obtained by extrusion of a polyamide of the type obtained by polymerization of lactams and / or amino acids with a multifunctional compound comprising <Desc / Clms Page number 16>  at least three reactive functions chosen from amines, carboxylic acids and their derivatives, the reactive functions being identical. 6. Method according to one of claims 1 to 5 characterized in that the multifunctional compound has a tree or dendritic structure. 7. Method according to one of claims 1 to 5 characterized in that the multifunctional compound is represented by the formula (1)

 in which : . R1 is a hydrocarbon radical comprising at least two linear or cyclic, aromatic or aliphatic carbon atoms and which may comprise heteroatoms, A is a covalent bond or an aliphatic hydrocarbon radical comprising 1 to 6 carbon atoms, Z represents a primary amine radical or a carboxylic group. m is an integer from 3 to 8. 8. Process according to claim 7, characterized in that the multifunctional compound is chosen from 2,2,6,6-tetra (P-carboxyethyl) -cyclohexanone, trimesic acid, 2,4,6-tri- (aminocaproic acid) -1,3,5-triazine, 4-aminoethyl-1,8-octanediamine. 9. Method according to one of the preceding claims characterized in that the proportion by weight of compound B in the mixture relative to the total weight of compounds A and B is less than 20% 10. The method of claim 9 characterized in that the proportion by weight of compound B in the mixture relative to the total weight of compounds A and B is less than 15%. 11. Process according to one of the preceding claims, characterized in that the proportion by weight of star or H macromolecular chains of compound B in the mixture relative to the total weight of compounds A and B is less than 25%. <Desc / Clms Page number 17> 12. Process according to one of the preceding claims, characterized in that the proportion by weight of star or H macromolecular chains of compound B in the mixture relative to the total weight of compounds A and B is less than 15%. 13. Method according to one of the preceding claims characterized in that the compound A is a polyamide 66 obtained from adipic acid and hexamethylenediamine. 14. Method according to one of the preceding claims characterized in that the compound A is a copolyamide comprising at least 90 mol% of repeating units of hexamethylenediamine adipate. 15. Method according to one of the preceding claims, characterized in that the spinning is performed with a spinning speed greater than 3500 m / min. 16. Yarns, fibers and filaments obtained by the process according to one of the preceding claims. 17. Yarns, fibers and filaments obtained by the process according to one of the preceding claims, characterized in that the monofilament titre is less than 0.8 dtex, preferably less than 0.6 dtex.