Method for producing of synthetic threads, fibers and filaments based on polyamide

FIELD: processes for manufacture of synthetic threads, fibers and filaments from polyamide.

SUBSTANCE: method involves mixing melts of two compounds, namely, linear polyamide and polyamide including macromolecular star-like or H-like chains comprising one or more nuclei, and at least three polyamide side chains or segments, which are bound with nucleus and produced from amino acid and/or lactam monomers, or multifunctional compounds with three similar acidic or amine functional groups; forming resultant melt mixture into threads, fibers or filaments and drawing if necessary.

EFFECT: increased effectiveness of process for producing of threads, fibers and filaments and improved elongation properties.

22 cl, 4 tbl, 6 ex

 

The present invention relates to a method for yarns, fibers and filaments, based on the polyamide, as well as yarns, fibers and filaments, which can be received by the specified method.

Yarns, fibers and filaments, based on the polyamide is obtained by forming filaments from a melt of polyamide or of compositions based on polyamide. Forming filaments from the melt is extruded polyamide or composition through a Spinneret and cooling at the exit of the nozzles. Get that through articles intended for use in various fields. As examples mnogoelementnyi yarn for the textile industry; fiber, designed for the production of them spinning mills woven products or for products of non-woven, cords, which are then cut, in order to obtain short fibers having a NAP; odnovremenno and mnogoelementnyi thread for special applications, in particular in industry.

Methods of obtaining yarns, fibers and filaments can vary significantly, in particular, depending on the speed range forming the threads. Depending on the selected method, the obtained products have different properties.

Thus, there are various ways to obtain yarns, fibres and filaments. As an example, you can call methods high speed recording motion is ostogo forming yarn POY (Partially Oriented Yarn - partially oriented yarn) (minimum speed of 3500 m/min), FEI (Filage-Etirage- joint molding - extrusion), sometimes also called FOY (Fully Oriented Yarn is fully oriented yarn), HOY (Highly Oriented Yarn - high-oriented thread) (speed not lower than 5500 m/min). You can also call methods of low-speed molding threads LOY (Low Oriented Yarn - nizkoreninova thread) (maximum speed of 3500 m/min). These methods and especially the way LOY include the stage of extrusion, to improve the mechanical properties of the above products. The specified stage hoods are also carried out to obtain odnoelementnykh threads. In addition, depending on use, the hood can be done for all types of yarns obtained according to the methods mentioned above. The threads obtained according to the methods POY, often also pull directly or after forming the threads (co-extrusion) or on a separate stage with the re-capture of the thread. These methods are well known in the art. They distinguish them from each other in the speed of forming the threads on the method of cooling at the die exit, the degree of drawing upon receipt of the threads. In addition, the products obtained can be subjected to various treatments, such as, for example, texturing, servicaixa, twisting fixation.

Used methods and PA is ometry these methods largely depend on the properties of polyamide or used composition based on polyamide. Thus, possible speed, temperature and pressure in forming the threads are set depending on the properties of the polymer or composition for molding, such as temperature and viscosity in the molten state.

Ongoing work to increase the productivity of these processes, that is, to obtain the greatest length of threads per unit of time. To increase the performance of these methods of forming filaments, in particular, to increase the speed of forming the threads, it has been suggested, for example, the rheological properties of the composition for molding by adding modifiers in the above composition.

Thus, in U.S. Patent US 5962131 to obtain pre-oriented yarns based on poly (ethylene terephthalate) describes the addition of immiscible copolymer in the form of a melt, which forms inclusions of small size in the original polymer.

In the French Patent FR 2677376 to obtain pre-oriented yarns of the polyamide type mineral particles with nanometric dimensions. The presence of these particles can increase the speed of forming the threads. However, it is difficult to obtain a good dispersion of the particles, therefore, the percentage of breakages during formation of the thread remains significant.

The purpose of this izaberete the Oia is a method of producing filaments, fibers and filaments based on polyamide compositions which have a molecular structure that allows them to increase the overall performance of the process of forming filaments, in particular, by improving the ability to extrude the obtained filaments, and thereby provides, for example, at a certain same speed molding filament is significantly greater length of fiber that can be obtained per unit of time after the drawing.

To this end, the invention proposes a method of production of synthetic yarns, fibers and filaments, based on the polyamide, which comprises the following stages:

i) mixing of melts of the following compounds a and b, where the compound a is a linear polyamide, and a connection selected from the group including polyamide or a composition based on polyamide containing:

- macromolecular chains of star-shaped or H-shaped form, containing one or more cores and at least 3 of the side link or 3rd polyamide segment associated with the specified kernel, which is derived from monomers of amino acids and/or lactams,

- if necessary linear polyamide macromolecular chains derived from monomers of amino acids and/or lactams, and the index of fusion melt of the polyamide or polyamide composition, measured in accordance with ISO 133 at a temperature of 275° With under a load of 100 g is more than 20 g for 10 min, and

multifunctional compound comprising at least 3 of the same acid or amino;

ii) forming from the molten mixture of yarns, fibers or filaments,

iii) and, if necessary, pulling receive one(CSOs) or more yarns, fibers or filaments.

The advantages of the invention are numerous and depend directly on the way of implementation. These benefits can be observed in the operation of forming the threads and, in particular, during subsequent operation of the pulling thread. These benefits allow you to increase the performance of the method or create the possibility of obtaining special products, such as filaments or fibers with a low titer.

By "forming threads" understand the operation of extrusion of the substance in the form of a melt through a Spinneret, followed by cooling between the die and at least the first stage of extraction of the product. Under "method of producing yarns, fibers and filaments," you see a set of steps leading to the yarns, fibres and filaments. The method includes, in particular, the operation of forming the threads. You can include other stage of the process after the operation of forming filaments, such as extrusion (continuous or periodic), allowing to improve the mechanical the e properties of the molded products and get for example, modulus, and residual elongation at break that is compatible with the known uses of these products and methods for their treatment. As ways of processing of molded products can be called such processing as relaxation, shirring thread, texturing, heat setting, dyeing.

The method according to the invention includes the operation of mixing the melt of at least two compounds, compound a and compound C. Both compounds are thermoplastic. The mixture can be obtained using the classical method of preparation of a mixture of two thermoplastic compounds, for example, using the device for the extrusion with single or double screw and/or screw with the blades. You can, for example, to enter granules connections in the connection And in the form of a melt or mix the granules connection and connection and melt the mixture of granules. In the mix you can enter other additives, such as pigments, fillers, matting additives, catalysts, heat and/or light stabilizers, antibacterial agents, antifungal agents. As matting additives include, for example, the product selected, for example, particles of titanium dioxide or zinc sulfide.

The mixture of the melt can then be subjected to hardening and pelleting. The solid mixture was then re-melted to conduct about which erali forming threads. After the blending operation melts mainly immediately perform the operation of forming the threads without intermediate solidification and granulation.

The mixture of compounds is formed in the form of a melt. This operation is performed by extrusion through a Spinneret at a temperature and pressure selected properly. You can use all of the known device for forming threads.

According to one feature of the invention, the compound a is a linear polyamide or a composition based on linear polyamide. As an example of acceptable polyamides can lead polyamides derived from lactams and/or amino acids, in particular, polyamides 6, 11, 12, mixtures and copolymers based on these polyamides. Linear polyamides may be used in mixtures in individual form or in the form of a composition, for example, with the above additives.

According to a preferred characteristic of the invention, the compound a is a linear polyamide or a composition based on linear polyamide obtained from a monomer decollate and diamine monomer. As examples of monomers of decislon can lead adipic acid, which is the preferred acid, dekanovu or sabotinova acid, dodekanisou acid, phthalic acid, such as terephthalic acid, isophthalic acid. the quality of monomers diamines can be called hexamethylenediamine were, methylpentylamine, 4,4'-diaminodicyclohexylmethane, butanediamine, meta xylylenediamine. Polyamides derived from these monomers are, in particular, polyamide 66 (polyadipates diamine), polyamide 46, polyamide 612. In accordance with the invention suitable linear polyamides are also copolyamids containing at least 90% mole. repeating units, which correspond to the above-described polyamides, other repeating units derived from monomers of decislon, diamines, amino acids or lactams. As copolyamids can be called, in particular, polyamide 66,6 containing less than 5% mole. parts of polyamide 6. Polyamides corresponding to the invention may also contain parts of the monofunctional monomer commonly used in the production of these polymers as a limiter circuits.

The connection according to the first variant embodiment of the invention is a polymer or polymer composition, comprising the macromolecular chains of star-shaped or H-shaped form and, if necessary, linear macromolecular chains. The polymers or polymer compositions containing such macromolecular chains of star-shaped or H-shaped, as described, for example, in French Patent FR 2743077, the French Patent FR 2779730, U.S. Patent US 5959069, European saveher 0632703, EP 0682057 and EP 0832149. These compounds are known that they have a better fluidity in comparison with linear polyamides. The flow index of the connection according to the invention, measured in accordance with ISO 1133 at a temperature of 275°under a load of 100 g is more than 20 g per 10 minutes

Macromolecular chain of star-shaped or H-shaped form derived from a multifunctional compound having at least three reactive groups, with all of the reactive groups are the same. The specified connection can be used as co monomer along with the other monomers in the polymerization method. This connection can also be added to the polyamide during the extrusion operation.

Macromolecular chain of star-shaped or H-shaped form the core and at least three side polyamide link. The side chains linked to the core by covalent linkage through an amide group or a group of different nature. The core is attached to the side links, is an organic or ORGANOMETALLIC compound, predominantly hydrocarbon compound containing, if necessary, the heteroatoms. The side parts are formed of polyamide chains. They may have branches; this applies in particular to the structure of the configuration N. Polyamide is chain forming a lateral links are mostly chains, obtained by polymerization of lactams or amino acids, for example, polyamide chains type of polyamide 6.

The connection contains, if necessary, in addition to chains of star-shaped or H-shaped, linear polyamide of the macromolecular chain. The weight ratio between the number of chains, star-shaped or H-shaped within the connection and the sum of the number of chains of star-shaped or H-shaped and linear chains is in the range from 0.1 to 1, including the boundaries of the interval. Mostly it ranges from 0.5 to 1.

According to the first variant of the method the connection is a star polyamide, i.e. a polyamide containing macromolecular star chain, and obtained by copolymerization of a mixture of monomers containing:

(a) a multifunctional compound having at least 3 reactive groups selected from amine, carboxyl groups and their derivatives, all of which reactive groups are the same,

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

C) if necessary, the monomers of the following General formula:

Z-R3-Z (III)

where Z is a group identical to those of the reactive groups, is the quiet contained in the multifunctional compound;

R2, R3the same or different from each other, represent aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, substituted or unsubstituted, which include from 2 to 20 carbon atoms and which may contain heteroatoms;

Y is a primary amino group, when X denotes a carboxylic radical, or

Y is a carboxyl group, when X is a primary amino group.

Such methods of polymerization are described in Patents FR France 2743077 and FR 2779730.

In the case when use comonomer C), the reaction of polymerization (polycondensation) is carried out until reaching thermodynamic equilibrium.

The mixture of monomers may contain other compounds, such as limiting circuit, catalysts, additives.

The method leads to the formation of the macromolecular chains of star-shaped and, if necessary, linear macromolecular chains. The percentage of PS in the number of macromolecular chains of star-shaped with respect to the total number of chains is determined by the following formulas:

when the multifunctional compound has 4 reactive groups

where

if reactive groups are acid groups

if reactive groups are amino groups

T0denotes the number of moles multi-function compounds;

N0denotes the initial number of moles of monomer of formula (IIa) or (IIb);

R0denotes the initial number of moles of monomer of formula (III)in the case where the multifunctional compound has 3 reactive group

where

if reactive groups are acid groups

if reactive groups are amino groups

T0denotes the number of moles multi-function compounds;

N0denotes the initial number of moles of monomer of formula (IIa) or (IIb);

R0denotes the initial number of moles of monomer of formula (III).

According to the second variant embodiment of the invention the compound is a polyamide configuration N, that is, the polyamide containing macromolecular chain N-shaped and obtained by copolymerization of a mixture of monomers containing:

a) from 1 to 50 micromol per gram matrix of multifunctional compounds containing at least three reactive group chosen from amino groups, carboxyl groups and their derivatives, while re is clanspeople groups are the same,

C) lactam and/or amino acids,

C) difunctional compound which is chosen from dicarboxylic acids or diamines,

d) a monofunctional compound, the functional group selected from amino groups, carboxyl groups and their derivatives,

moreover, the functional groups of the compounds (C) and (d) are amino groups, if the functional groups of the compounds (a) are carboxyl,

and the functional group of compounds (C) and (d) are carboxyl, if the functional groups of the compounds (a) are amino groups,

the ratio in equivalents of functional groups of the compounds (a) to the amount of functional groups of the compounds (C) and (d) is in the range from 1.5 to 0.66, while the ratio in equivalents of functional groups of the compound (C) to the functional groups of the compound (d) is in the range from 0.17 to 1.5.

Such a method and such polymers are described in U.S. Patent US 5959069.

According to the third variant of the method the connection is obtained by mixing in the molten state, for example, using the device for the extrusion of polyamide, which is obtained by polymerization of lactams and/or amino acids, and multifunctional compounds containing at least three identical reactive groups which are selected from amino or carboxyl group. Polyamideimide, for example, polyamide 6.

Such methods of obtaining described in European applications EP 0682070 and EP 0672703.

According to another variant of the invention, the connection is a multifunctional compound similar to the compounds used as the core in the synthesis of polyamides star-shaped and/or polyamide configuration N described above and hereinafter. The specified connection type directly in the connection And in molten form is similar to the route of administration of compounds of the type polyamide star-shaped or polyamide configuration N.

Used multifunctional compounds may be selected from compounds having a tree-like or dendritic structure. They can also be selected from compounds represented by formula (I).

where R1is a hydrocarbon, linear or cyclic, aromatic or aliphatic radical containing at least two carbon atoms, which may also contain heteroatoms;

And denotes a covalent bond or an aliphatic hydrocarbon radical containing from 1 to 6 carbon atoms;

Z represents a primary amino group or carboxyl group;

m is an integer in the range from 3 to 8.

In a preferred method of carrying out the invention Radik is l R 1is a cycloaliphatic radical, such as tetravalent radical of cyclohexanone, or radical 1,1,1-tryprophan, 1,2,3-tryprophan.

In accordance with the invention as other radicals R1you can call trivalent radicals phenyl and cyclohexanol, substituted or unsubstituted, trivalent radicals diaminoalkylene with the number of methylene groups constituting mainly from 2 to 12, such as the radical derived from add (ethylenediaminetetraacetic acid), vosmiletnie radicals cyclohexanone or cyclohexadienyl, and radicals of the compounds obtained by the reaction of polyols, such as glycol, pentaerythritol, sorbitol or mannitol, with Acrylonitrile.

Radical And is preferably methylene or polymethene radical such as ethyl, propyl or butyl radical, or polyoxyalkylene radical, such as polyoxyethylene radical.

According to a preferred method of carrying out the invention, the number m is greater than 3 and preferably is in the range from 3 to 4.

Reactive group of the multifunctional compound represented by the symbol X-H, is a group that can form an amide group.

As examples of polyfunctional compounds of formula I can be called a 2,2,6,6-Tetra-(β-carboxyethyl)is yclohexanol, diaminopropane-N,N,N',N' -acetic acid of the following formula:

or compounds formed by the interaction of trimethylolpropane or glycerol with propylene oxide and aminating the end hydroxyl groups. These latter compounds are produced under the name JEFFAMINES T®the company HUNTSMAN and have the General formula

where - R1refers to 1,1,1-tailpipeby or 1,2,3-tailpipeby radical

- And means polyoxyethylene radical.

Examples of suitable multifunctional compounds can be found, in particular, in U.S. Patent US 5346984, in U.S. Patent US 5959069, in Patent WO 9635739, in European application EP 672703.

Include, in particular:

nitrosodialkylamines, in particular, nitrilotriacetates, dialkylanilines, in particular, Diethylenetriamine, trialkylamine and tetraalkylammonium, and alkylene preferably is ethylene and 4-amino-ethyl-1,8-octanediamine.

You can also call the dendrimers of formula (II)

(R2N-(CH2)n)2-N-( CH2)x-N-((CH2)n-NR2)2(II)

where R is a hydrogen atom or a group -( CH2)n-NR12,

where R1is a hydrogen atom or a group -( CH2)n-NR22,

where R2one is camping hydrogen atom or a group -( CH 2)n-NR32,

where R3is a hydrogen atom or a group -( CH2)n-NH2;

n is an integer in the range from 2 to 6;

x is an integer in the range from 2 to 14.

n is preferably an integer in the range from 3 to 4, in particular equal to 3, and x is preferably an integer in the range from 2 to 6 (including the boundaries of the interval), preferably equal to 2, 3 or 4, in particular equal to 2. Each radical R can be selected independently of the others. The radical R is preferably a hydrogen atom or a group -(CH2)n-NH2.

Are also multifunctional compounds having from 3 to 10 carboxyl groups, preferably from 3 to 4. Among these compounds, preferred compounds having one aromatic cycle and/or a heterocycle, for example, benzyl, nattily, Anthranilic, biphenylyl or thriftily radical, or heterocycles such as pyridine, bipyridine, pyrrole, indole, furan, thiophene, purine, quinoline, phenanthrene, porphyrin, phthalocyanine and naphthalocyanine. Especially preferred is 3,5,3',5'-biphenyltetracarboxylic acid, acid derivatives of phthalocyanine and naphthalocyanine, 3,5,3',5'-biphenyltetracarboxylic acid, 1,3,5,7-naphthalenemethanol acid, 2,4,6-pyridylcarbonyl acid, 3,5,3',5'-piperidineacetate the new acid, 3,5,3',5'-benzophenonetetracarboxylic acid, 1,3,6,8 - gridinteractive acid, and more preferred tremezzina acid and 1,2,4,5-benzylaminocarbonyl acid.

Specified a multi functional connections, the core of which is a heterocycle, having a point of symmetry, such as 1,3,5-triazine, 1,4-diazine, melamine, derivatives 2,3,5,6-tetramethylpyrazine, 1,4-piperazines, tetrathiafulvalenes. More specifically, indicated 2,4,6-three(aminocaproic acid)-1,3,5-triazine (TACT).

Weight fraction of connections in relation to the weight of the compounds a and b in the mixture is preferably less than 30%, preferably less than 20%, even more preferably less than 15%. When this feature is not taken into account the possible presence of other additives.

Yarns, fibers and filaments, obtained from a mixture of compounds a and b, include polyamide macromolecular chains of star-shaped or H-shaped and chain linear polyamide. Weight fraction of macromolecular chains of star-shaped or H-shaped with respect to the total weight of the macromolecular chains of star-shaped or H-shaped and linear chains is preferably less than 25%, even more preferably less than 15%.

The method according to the invention, in particular, performed in the first embodiment of the invention, can be used within the method wysokosc the speed of forming the threads, for example, at speeds above 3500 m/min, type POY, HOY, FEI to get mnogoelementnykh threads or in the way LOY to obtain fibers.

Unexpectedly it was found that the resulting filaments have a higher ability to extrude than that possessed by the filament obtained from the classically used linear polyamide such as polyamide 66, in particular, with comparable mechanical properties, compatible for all relevant applications of these products in various technical fields, such as textiles. Indeed, the products obtained according to the method of the invention, have the module and the permanent elongation at fracture equivalent to those possessed by the threads of polyamide 66.

This higher ability to extrude allows, therefore, to improve the performance of the method of producing threads or by increasing the speed of forming the threads, or by increasing the drawing ratio of the obtained filaments, or by combining these two techniques. In other words, the method according to the invention allows to obtain filaments, fibers and monofilament using the total drawing ratio, i.e. the drawing ratio in forming the threads plus the drawing ratio in the drawing process, greater than that applied to the threads of the linear polyamide having the same value for m is a module and the residual elongation at break for the given thread.

The method according to the invention also allows the threads very low titer, for example, below 0.8 dtex, mostly below 0.6 dtex, by forming filaments from the melt and pulling. Indeed, the method according to the invention allows to receive the threads on the exit from the die, having a low titer, just as they are obtained from a linear polyamide and similar equipment. However, since the filaments obtained in the method according to the invention, it is possible to use a higher drawing ratio, it becomes clear that the final title of the thread according to the invention is clearly lower at equivalent mechanical properties. This capability is particularly important for obtaining fibers with very low titer.

The method according to the invention in accordance with a second embodiment of implementation can be used to produce yarns, fibers and filaments of linear polyamide of high molecular weight. These polyamides are usually used to improve the mechanical properties and/or improved chemical resistance and heat resistance, such as resistance to abrasion. He, in particular, suitable for the production of fibres for felt for paper machines. The use of connection allows the molding at a lower temperature and/or under reduced pressure p is compared with the conditions which would have been necessary in the absence of this connection. Thus, it is possible to either obtain a yarn with the best resistance to abrasion, since the molecular weight of the polyamide is higher, or to obtain fibers with similar properties in a simple way. In a specific embodiment of the invention, the linear polyamide is polyamide 6, the relative viscosity of which, measured at a temperature of 25°at a concentration of 0.01 g/ml in 96%sulfuric acid, above a 3.5, mostly above 3,8.

In accordance with a specific embodiment of the invention during the mixing of the compounds and these compounds is administered in dry form, preferably with a moisture level of less than 0.3% and add a compound capable of catalyzing the polycondensation of the polyamide preferably with a weight concentration in the range of 0.005% to 5%. The specified connection can be selected from compounds containing phosphorus, for example, phosphoric acid, Tris(2,4-di-tert-butylphenyl)phosphite [manufactured by CIBA under the name Irgafos 168, or in a mixture with N,N-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate) under the name Irganox In 1171]. The specified connection can be added in the form of powder or concentrate in a matrix of polyamide (Royal mix). The mixture of different compounds is carried out in a device for ex is Rosie with single or double screw.

To obtain fibers intended for use in non-woven form, felts for paper machines, forming filaments is carried out in General at a moderate speed below 1000 m/min, followed by stretching.

Other details and advantages of the invention will become more apparent from the examples below for clarification.

Use the following connections:

Connection: polyamide 66 with viscosity index 136 ml/g, measured at a temperature of 25°at a concentration of 0.01 g/ml in 90%formic acid, with the concentration of acid end groups (GTA) 55 mEq per gram of polymer and a concentration of amine end groups (GTC) 66 mEq per gram of polymer.

Connection: polyamide star-shaped, obtained by copolymerization of caprolactam in the presence of 0.5% mole. 2,2,6,6-Tetra(β-carboxyethyl)cyclohexanone in the manner described in French Patent FR 2743077, and containing approximately 80% of the macromolecular chains of star-shaped and 20% linear macromolecular chains, the viscosity index, measured according to the method described above, is of 98.2 ml/g, GTA is 13.9 mEq/g and GTC is 165,3 mEq/g and a melt flow index, measured at a temperature of 275°under a load of 100 g, 55 g for 10 minutes

Connection: polyamide 6 with a relative viscosity, priblizitelen is equal to 3.8 and measured at a temperature of 25° With a concentration of 0.01 g/ml in 96%sulfuric acid, which is produced by the company BASF under the name W.

The magnitude of the elongation yarns at break and strength at break determined on the car stretching Eriksen, placed in a climate chamber with a relative humidity of 50% and a temperature of 23°and, after keeping the threads within 72 hours under specified conditions. The initial length of yarn is 50 mm, and the speed when the stretch is 50 mm/min the Above measurement is carried out in accordance with ISO 2062 or AFNOR 07-002.

Examples 1 to 4

Mixed compounds in the melt using a single device for the extrusion, and then shaped molten mixture with the speed of exit from the die also called speed molding of the thread, which is 4200 m/min, with continuous filaments, containing 34 filaments with a total titer indicated in the following Table I. Conditions for forming the thread below in Table I and the properties of the obtained yarns are presented in Table II.

Table I
ExampleComposition (% weight)Temperature of the die (°)Forming pressure (bar)The flow of polymer in filiere g/minThe rate of formation (m/min)
1CConnection: 100%2762301,234200
2Connection A: 90%

Connection: 10%
2762801,234200
3Connection A: 90%

Connection: 10%
2762801,234800
4Connection A: 90%

Connection: 10%
2762801,235400

Table II
ExampleThe total titer (dtex)Elongation at break (%)Module when the elongation of 5% (CN/Tex)
1C10070109
299a 94.2104
38686,6116
476,676,2137

The threads obtained at a speed of 4200 m/min, pulled at the facility for drawing; the properties of the obtained yarns are presented in Table III.

Table III
ExampleThe cylinder is UNT hoods Titer (dtex)Elongation at break (%)Module when the elongation of 5% (CN/Tex)
1C1,31281,236,9257
21,43771,444,6257

These tests show that for threads according to the invention it is possible to apply a higher drawing ratio, you get a thread with 5%module similar to the module, which receive the threads of polyamide 66 with higher residual elongation. This high residual elongation can improve the processability of threads.

Example 5

Mixed compounds in the melt, using the device for the extrusion with dual screw, is then formed molten mixture with the speed of exit from the die 3300 m/min, with continuous mnogopredmetnoy yarns with a titer of 55 dtex, consisting of 10 filaments. Temperature, pressure and exhaust ventilation, as well as the properties of the obtained yarns are presented in Table IV.

Comparative Example 6

Is formed into a filament in the same way as in Example 5, but only from the connection With. the Temperature, pressure and exhaust ventilation, as well as the properties of the obtained yarns are presented in Table IV.

Example 5
Table IV
Comparative Example 6
Connection80%100%
Connection20%
The temperature of the molding285°320°
Quality hoodsA small number of breakagesThe number of breakages very much
The pressure in filiere150 bar150 bar
Elongation at break (%)9595
Tensile strength (CN/Tex)2525

1. The method of production of synthetic yarns, fibers and filaments, based on the polyamide, which includes the following operations:

i) mixing of melts of compounds a and b, where the compound a is a linear polyamide, and a connection selected from a group comprising: polyamide or composition based on the polyamide, including:

macromolecular chain of star-shaped or H-shaped form, containing one or more cores and at least 3 polyamide side link or 3rd polyamide segment associated with the specified kernel, which is derived from monomers of amino acids and/or lactams,

if necessary linear polyamide macro is Molekulyarnye chain derived from monomers of amino acids and/or lactams, and the index of fusion melt of the polyamide or polyamide composition, measured in accordance with ISO 1133 at a temperature of 275°under a load of 100 g is more than 20 g for 10 min, and

multifunctional compound comprising at least 3 of the same acid or amine functional groups;

ii) forming from the molten mixture of yarns, fibers or filaments,

iii) and, if necessary, stretching the resulting filaments, fibers or filaments.

2. The method according to claim 1, characterized in that the weight ratio between the macromolecular chains of star-shaped or H-shaped form and amount of the macromolecular chains of star-shaped or H-shaped and linear chains within the connection is in the range from 0.1 to 1.

3. The method according to any one of claims 1 and 2, characterized in that the compound is a polyamide star-shaped, obtained by copolymerization of a mixture of monomers containing:

(a) a multifunctional compound having at least 3 reactive group chosen from amine, carboxyl groups and their derivatives, all of which reactive groups are the same,

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

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C) if necessary, the monomers of the following General formula:

Z-R3-Z (III)

where Z represents a group of identical reactive groups of the multifunctional compounds

R2, R3denote aliphatic, cycloaliphatic or aromatic hydrocarbon radicals, substituted or unsubstituted, identical or different, containing from 2 to 20 atoms and which may contain heteroatoms,

Y is a primary amino group when X represents a carboxyl radical, or

Y is a carboxyl group when X represents a primary amino group.

4. The method according to any of claim 1 or 2, characterized in that the compound is N-polyamide obtained by copolymerization of a mixture of monomers containing:

a) from 1 to 50 micromol per gram of polymer compounds In the multifunctional compound containing at least three reactive group chosen from amine, carboxyl groups and their derivatives, while the reactive groups are the same,

C) lactam and/or amino acids,

c) defunctionalize a compound selected from dicarboxylic acids or diamines,

d) a monofunctional compound, the functional group selected from amine, carb is xilinix groups and derivatives thereof,

when the functional group of compounds (C) and (d) are amine, if the functional groups of the compounds (a) are acid, and the functional group of compounds (C) and (d) are acidic, if the functional compounds of group a) are amine, and the ratio in equivalents of functional groups of the compounds (a) to the amount of functional groups of the compounds (C) and (d) is in the range from 1.5 to 0.66, while the ratio in equivalents of functional groups of the compound (C) to the functional groups of the compound (d) is in the range from 0.17 to 1.5.

5. The method according to any of claim 1 or 2, characterized in that the compound obtained In the extrusion of the polyamide of this type, which is obtained by polymerization of lactams and/or amino acids and multifunctional compounds containing at least three reactive group chosen from amine, carboxyl groups and their derivatives, while the reactive groups are the same.

6. The method according to any of PP-5, wherein the multifunctional compound is a tree-like or dendritic structure.

7. The method according to any of PP-5, characterized in that the multifunctional compound corresponds to the formula (I)

where R1is hydrocarbon of linear or cyclic, aromatic realitycheck radical, containing at least two carbon atoms, and which may also contain heteroatoms,

And denotes a covalent bond or an aliphatic hydrocarbon radical containing from 1 to 6 carbon atoms,

Z represents a primary amino group or carboxyl group,

m is an integer in the range from 3 to 8.

8. The method according to claim 7, characterized in that the multifunctional compound selected from 2,2,6,6-Tetra-(β-carboxyethyl)cyclohexanone, criminology acid, 2,4,6-tri-(aminocaproic acid)-1,3,5-triazine, 4-amino-ethyl-1,8-octanediamine.

9. The method according to any one of claims 1 to 8, characterized in that the weight fraction of compounds In the mixture relative to the total weight of compounds a and b is less than 30%.

10. The method according to claim 9, characterized in that the weight fraction of compounds In the mixture relative to the total weight of compounds a and b is less than 20%.

11. The method according to claim 10, characterized in that the weight fraction of compounds In the mixture relative to the total weight of compounds a and b is less than 15%.

12. The method according to any one of claims 1 to 11, characterized in that the weight proportion of the macromolecular chains of star-shaped or H-shaped connection in the mixture relative to the total weight of compounds a and b is less than 25%.

13. The method according to any one of claims 1 to 12, characterized in that the weight proportion of the macromolecular chains of stars is shaped or H-shaped connection in the mixture relative to the total weight of compounds a and b is less than 15%.

14. The method according to any one of claims 1 to 13, characterized in that the compound a is a polyamide selected from polyamide 6, polyamide 11, polyamide 12, mixtures of compounds and copolymers based on these polyamides.

15. The method according to any one of claims 1 to 14, characterized in that the compound a is a polyamide 6, a relative viscosity of which is not less than 3.5.

16. The method according to any one of claims 1 to 13, characterized in that the compound a is a linear polyamide obtained from monomers of decislon and diamines.

17. The method according to item 16, characterized in that the compound a is a polyamide 66, obtained from adipic acid and a diamine.

18. The method according to any of item 16 or 17, characterized in that the compound a is copolyamide containing at least 90 mol.% duplicate links of adipate diamine.

19. The method according to any of the preceding paragraphs, characterized in that the mixture entering the compound capable of catalyzing the polycondensation of polyamide, while the compounds a and b are present in a dry form.

20. The method according to any of the preceding items, wherein the forming of the thread carried out with a minimum speed of 3500 m/min

21. Products that represent threads, fibers or filaments obtained by the method according to any one of claims 1 to 20.

22. The product according to item 21, wherein the titer of monofilament is below 0.8 dtex, mostly below 0.6 dtex.

Priority points and features:

22.02.2001 according to claims 1, 2 to 9, 11-17, 19 and 21 of the formula when the connection is In the polyamide or polyamide composition;

23.10.2001 according to claims 1, 2 to 9, 11-17, 19 and 21 formula, when the connection is polyfunctionally connection and PP and 20;

21.02.2002 of claim 10.



 

Same patents:

The invention relates to a technology for obtaining molded products - fibers or films based on aromatic copolyamid with heterocycles in the chain and can be used in the chemical industry for the reinforcement of plastics, rubber products, as tire cord, for obtaining fabrics and other materials for technical purposes and for the manufacture of films and pulp

The invention relates to the production of high-quality fiber pulp

The invention relates to the field of synthetic fibers, particularly synthetic fibers, spun from anisotropic solutions in sulfuric acid of rigid-rod aromatic polyamides, mixed with aliphatic polyamides

The invention relates to the field of production of high strength fibers based on aromatic depolimerization (ABI) used, usually in organoplastic aerospace, defense, etc

The invention relates to the production of films and fibers of compositions containing polyvinyl chloride (PVC) and aromatic polyamide (PA)

The invention relates to the field of synthetic filaments, in particular, spun from sulfuric acid anisotropic solutions of rigid-rod aromatic polyamides with the addition of aliphatic polyamides

FIELD: processes for manufacture of synthetic threads, fibers and filaments from polyamide.

SUBSTANCE: method involves mixing melts of two compounds, namely, linear polyamide and polyamide including macromolecular star-like or H-like chains comprising one or more nuclei, and at least three polyamide side chains or segments, which are bound with nucleus and produced from amino acid and/or lactam monomers, or multifunctional compounds with three similar acidic or amine functional groups; forming resultant melt mixture into threads, fibers or filaments and drawing if necessary.

EFFECT: increased effectiveness of process for producing of threads, fibers and filaments and improved elongation properties.

22 cl, 4 tbl, 6 ex

FIELD: production of electric conducting pulp for manufacture of paper, reinforcing polymer materials and packaging films.

SUBSTANCE: pulp contains fibrous particles including 65-95 mass-% of para-amide and 5-35 mass-% of sulfonated polyaniline containing sulfur in the amount of 8.5-15 mass-% which is dispersed over entire para-amide partially covering the particles externally. Specific area of surface of fibrous particles exceeds 7.5 m2/g. Pulp may be mixed with 95 mass-% of pulp of other material including poly-n-phenylene terephthlamide. Paper made from this pulp reduces rate of electric charge lesser than 150 ml.

EFFECT: enhanced efficiency.

6 cl, 4 tbl, 1 ex

FIELD: polymer materials.

SUBSTANCE: invention relates to technology of manufacturing thermoplastic monofilaments and can be used in fabrication of bristle used under high humidity conditions. Monofilament is composed of polymer blend constituted by at least one polyamide and at least one thermoplastic polyester. Ratio of constituents in the blend is selected according to technical and functional properties determined, on one hand, by destination of bristle and, on the other hand, by environmental conditions in the bristle application location. Polyamide fraction ranges from 10 to 30% and that of polyester from 70 to 90%. Bristle completely meets functional and technical requirements as well as environmental conditions.

EFFECT: reduced manufacturing cost.

16 cl

FIELD: production of thermally- and fire-resistant textile materials, in particular, materials produced from mixture of thermally stable synthetic fiber and oxidized polyacrylonitrile fiber, which may be used for manufacture of protective clothing for rescuers, servicemen, firemen, oil industry workers, and gas industry workers, filtering fabrics for cleaning of hot gases from toxic dust in metallurgical, cement and other branches of industry, decorative materials, thermally-resistant isolation, and toxic asbestos substitutes.

SUBSTANCE: method involves mixing non-oxidized polyacrylonitrile fiber with thermally stable synthetic fiber in the ratio of from 30/70 to 80/20, respectively; subjecting resulting mixture in the form of yarn, tape, fabric to thermally oxidizing processing at temperature of 240-310 C during 10-180 min.

EFFECT: elimination of problems connected with textile processing of frangible oxidized polyacrylonitrile fibers owing to employment of elastic polyacrylonitrile fibers rather than such oxidized fibers.

2 cl, 7 tbl, 6 ex

FIELD: processes for producing of fibers, fibrids and articles from said fibers and fibrids, in particular, non-woven products, paper, and may be used for manufacture of electric insulation.

SUBSTANCE: articles are reinforced with fibers and/or fibrids produced from mixture of thermally stable polymers - aromatic polyamides, aromatic polyamide-imide resins or polyimide resins and thermoplastic polymers - polysulfides, polysulfones. Method involves reinforcing articles by thermal pressing at temperature exceeding glass transition temperature of thermoplastic polymer.

EFFECT: improved mechanical properties and air permeability and high processability.

23 cl, 2 dwg, 7 tbl, 20 ex

FIELD: process for producing of fully aromatic polyamide fibers comprising filler, in particular, aluminous mineral.

SUBSTANCE: fully aromatic polyamide fiber contains 100 weight parts of fully aromatic polyamide and from 0.05 to 20 weight parts of particles of aluminous mineral having laminated structure, such as hectorite, saponite, stevensite, beidellite, montmorillonite, and swelling mica.

EFFECT: improved mechanical properties of fibers, which may be provided with technological stability at fiber forming stage.

17 cl, 1 dwg, 3 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: method involves preparation of two solutions of a mixture of 5(6)-amino-2(para-aminophenyl)benzimidazole with 5(6)-amino-2(para-iminoquinone)benziimide in dimethylacetamide which contains lithium chloride, and then addition of paraphenylenediamine and an equimolar amount of terephthaloyl chloride to the first solution, and to the second solution - an equimolar amount of a dianhydride of pyromellitic acid. Said solutions are mixed at room temperature until formation of a spinning solution with dynamic viscosity of 300-600 P and concentratio of 3.5-4.0 wt %. The solution is filtered, vacuum treated and formed in a water-salt or water-alcohol settling bath, dried and thermally treated in free state. Industrial fireproof ballistic fabric is then produced from the obtained fibres. Threads obtained according to the invention have elementary fibre diametre higher than 10 mcm, rupture resistance not lower than 280 cN/tex and relative elongation of 3.8-4.5%.

EFFECT: invention enables to obtain fibres, threads, films with high elasticity while retaining good strength properties.

2 cl, 3 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: present invention relates to production of cross-linkable aramide copolymer compositions and articles made therefrom. The composition contains an aramide copolymer obtained from monomers containing 1,4-phenylenediamine and tetraphthaloyl dichloride, and having at least one arylene-carboxylic acid link and at least one hydroxyarylene link. Alternatively, the composition contains an aramide copolymer obtained from monomers containing 1,4-phenylenediamine and tetraphthaloyl dichloride, and having at least one arylene-carboxylic acid link or at least one hydroxyarylene link and a covalent cross-linking agent. The invention also relates to cross-linked copolymers obtained from said composition and moulded articles containing such cross-linked copolymers.

EFFECT: invention enables to obtain materials with improved operational properties.

15 cl, 9 ex

FIELD: process engineering.

SUBSTANCE: proposed invention may be used for protection against poison-gases and chemicals. Butyl rubber-based three-layer material comprises central reinforcing layer and outer cover layers arranged on its both sides. Said central layer is made up of fabric from polyester high-strength thread with liner density of 9-12 tex, specific breaking load of, at least, 160 mN/tex and number of turns of 180-220 t/m, or high-strength aramide thread with linear density of 6.3-14.3 tex, specific breaking load of 200 cN/tex, and number of turns of 90/130 t/m, or mix thereof. Said thread is two-component combine thread. First rod-shape component represents aramide and/or polyester complex thread or yarn, while second component represents rod shield with number of turns of 600-900 t/m made up of modified fire-resistant viscose thread or yarn with linear density of 10-30 tex. Said fabric represents calico, twill, momie or satin weave with identical thread base and weft characteristics and densities. Two outer cover layers are made from rubber composition based on butyl rubber containing cure accelerator, that is, zinc white and thiuram D, curing agent, that, technical sulfur, curing rate regulator, that is, 2-mercaptobenzothiazole, filler, that is, white carbon and technical carbon, plasticiser, that is, stearic acid, chlorinated paraffin wax, netoxol, fluid PMC-400 and zinc stearate, fire retardant, that is, antimony trioxide, chlorinated paraffin wax and melamine cyanurate, pigment, that is, titanium white, and adhesive, that is, paraffin. Barrier film material is applied on both sides on aforesaid material. Said barrier material consists of five consecutive layers with total thickness of 18-36 mcm. Adhesive layers are arranged on both sides of third barrier layer made form copolymer of ethylene with vinyl alcohol and maleic anhydride, or the like.

EFFECT: better protection, higher incombustibility and low surface density.

11 cl, 6 ex

FIELD: process engineering.

SUBSTANCE: proposed invention may be used for protection against poison-gases and chemicals. Butyl rubber-based three-layer material comprises central reinforcing layer and outer cover layers arranged on its both sides. Said central layer is made up of fabric from polyester high-strength thread with liner density of 9-12 tex, specific breaking load of, at least, 610 mN/tex and number of turns of 180-220 t/m, or high-strength aramide thread with linear density of 6.3-14.3 tex, specific breaking load of 200 cN/tex, and number of turns of 90-130 t/m, or mix thereof. Said thread is two-component combine thread. First rod-shape component represents aramide and/or polyester complex thread or yarn, while second component represents rod shield with number of turns of 600-900 t/m made up of modified fire-resistant viscose thread or yarn with linear density of 10-30 tex. Said fabric represents calico, twill, momie or satin weave with identical thread base and weft characteristics and densities. Two outer cover layers are made from rubber composition based on chloroprene rubber containing magnesium oxide, cure accelerator, that, guianide F, that is 1,3-diphenylduanidine, zinc white and thiuram D, curing agent, that is, technical sulfur, filler, that is, technical carbon, plasticiser, that is, stearic acid and chlorinated paraffin wax, fire retardant, that is, antimony trioxide and chlorinated paraffin wax. Barrier film material is applied on both sides on aforesaid material. Said barrier material consists of five consecutive layers with total thickness of 18-36 mcm or with total thickness of (co) polyolefins 35-70 mcm. Adhesive layers are arranged on both sides of third barrier layer made form (co)polyolefins. Adhesive layers are arranged on both sides of third barrier layer made form copolymer of ethylene with vinyl alcohol and maleic anhydride, or the like.

EFFECT: better protection, higher incombustibility and low surface density.

10 cl, 6 ex

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