Thread of aromatic polyamide and method of its manufacturing. RU patent 2505627.
 Method of producing ultra-high molecular weight polyamide fibres / 2493299Described is a method of producing ultra-high molecular weight polyamide fibres, particularly nylon, where the fibres have very high relative viscosity. The method involves a melt-phase polymerisation procedure which is optionally carried out in combination with a solid-phase polymerisation procedure. The procedures are carried out while observing selected controlled conditions, which enable to obtain polyamide fibres with denier from about 2 to about 100 (from about 2.2 dtex to about 111 dtex), having relative viscosity greater than about 200. |
 Method of producing high-strength high-modulus aramid threads (versions) / 2478143High-strength threads are obtained by a wet or dry-and-wet method of moulding an isotropic solution of an aromatic heterocyclic copolyamide in an organic solvent with leophilic salt additives, followed by washing, drying and heat treatment of the freshly moulded threads in a package under a vacuum and additional hot-stretching. Heat treatment is carried out in two steps: first under a vacuum of - 0.95 to -1.0 atm for 10-30 minutes, and the vacuum is reduced to - 0.75 to -0.9 atm and maintained until the end of the cycle; before hot-stretching, the threads are moistened to moisture content of 1.5-8.5%, said hot-stretching being carried out at temperature of 410-450°C. Heat treatment can also be carried out in a tubular heat chamber with gradient temperature distribution in the direction of movement of the thread from 30 to 500°C with a load of 0.05-0.5 cN/tex on the thread and oxygen content in the heat treatment zone of less than 1.5%. Air medium is fed by a stream which accompanies the movement of the thread at a speed which is at least twice as high as the speed of the thread. |
 Method of moulding and washing aramid fibre and regenerating sulphuric acid / 2473722Method employs a moulding apparatus and an apparatus for regenerating sulphuric acid. The method involves the following steps: a) moulding a (spinning) thread from aramid polymer from a spinning solution which contains sulphuric acid, and coagulating the thread in a coagulation bath having an inlet for water or diluted sulphuric acid and an outlet for water rich in sulphuric acid; b) washing the thread with water to obtain a washed thread and washing water containing 0.5-20.0 wt % sulphuric acid; c) reusing the water rich in sulphuric acid and, optionally, the washing water, which is fed into the apparatus for regenerating sulphuric acid; d) increasing content of sulphuric acid in the reused water which is rich in sulphuric acid and, optionally, in the washing water by evaporation to obtain sulphuric acid with concentration of 98% and water; e) mixing sulphuric acid with concentration of 98% with oleum to obtain sulphuric acid with concentration of 98-105%; f) reusing the sulphuric acid with concentration of 98-105% in the moulding apparatus as a spinning solution containing sulphuric acid. |
 Method and apparatus for manufacturing spinning solution for production of polymeric fiber / 2473721According to the method the polymer is mixed with a solvent, stirred, melted, homogenised and degassed, and then unloaded. Liquid sulfuric acid is used as a solvent, and at least stirring, homogenising and degassing is carried out in a single or twin screw kneading reactor, preferably of continuous operation. |
| Refined fibre / 2472879 Refined fibre has an average length of 2 mm to 4 mm, having the value of capacity for filler retention of at least 18% and the strength in the raw state of at least 1.8 mJ/mm2. The fibre is obtained by the method according to which the thread never exposed to drying or sliver having a length of at least 1 m are refined by performing at least the stage of feeding the thread or sliver and the liquid in the refiner which comprises refiner fillers comprising a housing that surrounds the central opening, and at least one inlet for the thread or sliver. The fibrillated fibre obtained in this way can be used for manufacture of friction materials, gaskets, brake pads or brake linings. |
 Particles consisting of para-aramid composite material and additional material / 2458191Invention relates to a method of producing particles from a polymer-additive composite material by: i) drawing a solution through a draw plate to obtain a fibre mass, fibril or a fibre product, wherein the solvent of the solution is selected from N-methyl-2-pyrrolidone, N,N'-dimethyl formamide, N,N'-dimethyl acetamide, tetramethyl urea, and 4-75 wt % composition consisting of 2-80 wt % para-aramid polymer and 20-98 wt % solid additional material to a total of 100 wt %, and where the aramid polymer is dissolved in the solvent, or ii) coagulation of the solution using a rotor-stator apparatus wherein the polymer solution is deposited through the stator onto the rotor such that the precipitated particle of the polymer-additive composite material is subject to shearing forces while in plastic deformation state. The aramid is preferably poly(para-phenylene terephthalamide) - PPTA. The additional material is selected from kaolin, talc, diatomite, zeolite, graphite, mineral fibre, calcium carbonate, barium sulphate, mica, dyes, pigments such as TiO2 and metal particles. The solution can be used to obtain particles such as fibre products, fibre mass and fibrils used in paper production. |
 Particle containing matrix and radical initiator / 2458081Invention pertains to a particle comprising a composition containing a matrix and a peroxide or azo radical initiator, as well as rubber-coated products, tyres, tyre treads and belts containing particle-elastomer systems. The particle is selected from aramid, polyester, polyamide, cellulose fibre and glass fibre. The matrix is selected from an extruded polymer, wax or mixture thereof. |
 Aromatic polyamide fibre based on heterocycle-containing aromatic polyamide, synthesis method thereof, fabric formed by fibre and fibre-reinforced composite material / 2452799Aromatic polyamide fibres, containing a heterocycle-containing aromatic polyamide, undergoes thermal treatment in conditions with oxygen content of 1 vol. % or less after stretching. The aromatic polyamide fibres are characterised by tensile strength of 20 cN/dtex or higher, initial modulus of 500 cN/dtex or higher, and the amount of substance dissolved in sulphuric acid equal to or less than 45%. |
 Method of producing nanofibres from aliphatic copolyamides / 2447207Solution with 15-30 wt % concentration of polyhexamethylene adipine amide and polyhexamethylene sebacinamide copolymer with ratio 60:40 wt % in an alcohol-water mixture with 45-97 vol. % ethanol content is obtained. The solution is filtered and deaerated. The solution is fed through a die hole-electrode in an electric field with strength E=1.5 104-4.0 105 V/m and distance between electrodes of 0.1-0.5 m. Nanofibres are deposited on an oppositely charged electrode with diameter d=50-4500 nm. The fibres form material having high porosity, vapour- and water-permeability, high hydrophilic behaviour and bioinertness. |
| Synthetic yarn with ability of identification and method of its production / 2447205 Synthetic yarn for production of technical fabrics based on polyamide or polyester is declared, and the way of its production. The thread is prepared from a melt of polyamide or polyester with use of a supplement containing the phosphor with a melting point 150-265 °C, put into the melt of the said polymers with the addition of light- and / or heat stabiliser. As the phosphor the thread contains a colourless organic photoluminescent phosphor of a specified colour of glow in the ultraviolet range. A method of producing the thread involves melting of the granules of the said polymer, insertion of additives into it of a light- and / or heat stabiliser, mixing, punching the melt through a multi-channel spinneret followed by a stretching, forming an integrated thread and winding of it on the packing. At that into the polymer melt with the addition of light- and / or heat stabiliser additionally additive is entered that contains a phosphor with a melting point of 150-265 °C. |
 Composition for manufacturing polycaproamide thread / 2270280Invention relates to polymer composition based on granulated polycaproamide, which contains polycaproamide, oligomers, water, titanium dioxide, and, additionally, complex modifying additive constituted by 1,1,5-trihydroperfluoripentanol and N,N-bis(2,2,6,6-yrytamethyl-4-piperidiniyl) 1,3-benzenedicarbamide. |
 Method of manufacturing thread from aromatic heterocyclic polyamide / 2277139Invention relates to heat-resistant thread manufacture technology and can be utilized in manufacture of special materials for flak jackets, high-pressure containers, and in airplane construction. Thread is made from aromatic heterocyclic polyamide prepared via low-temperature polycondensation of a mixture composed of 25-70 mol % diamine of formula: , where X represents -NH, -S, -O, -N(CH3), and N(C2H5) and Z represents N or C, and 30-75 mol % of p-phenylenediamine with aromatic dicarboxylic acid chloride used in equimolar proportions in organic solvent and in presence of lithium or calcium chloride. Thus prepared solution is molded into water-dimethylacetamide precipitation bath. Thread is rinsed, dried, thermally treated for 10-30 min at 340-360°C, and then is drawn at 230-270°C at heating time 1-3 sec. |
| Thermoplastic monofilament for bristle / 2287030 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. |
 Fine fiber compositions, methods for preparation thereof, and a method of manufacturing fine-fiber material / 2300543Invention relates to manufacture of polymer materials and, in particular, micro- and nanofibers showing elevated strength and durability, which can be employed in a variety of technical fields, including their use in various filters. Composition of fine fiber having diameters between 0,001 and 2 μm contains addition or condensation polymer and aromatic-nature resinous additive with molecular weight 500 to 3000, which additive may be disposed on the surface of fiber. Preparation method comprises exposure of polymer solution to electric field to form accelerated solution strands. Subsequent vaporization of solvent provides formation of fine fiber. Fibers are collected on a substrate and subjected to heat treatment at temperature not superior to melting point of polymer. From thus obtained fiber, fine-fiber material is manufactured. |
| Articles possessing antibacterial and antifungal activity / 2321690 Invention relates to using zinc sulfide in articles possessing N antibacterial and antifungal activity. In particular, it can be used in preparing any product able to interact with microorganisms and/or fungi, such as dress, carpets, curtains, bed affiliations and textile materials used for medicinal aims. |
| Method of production of thermally-light-stabilised polycaproamide thread / 2330131 Invention is related to technology of production of polycaproamide fibers and may be used in production of cord and technical threads for their stabilisation. Method of production of thermally-light-stabilised polycaproamide thread includes melting of polycaproamide granulated material and thread spinning. Prior to spinning via polymer concentrate multi-component thermal light stabiliser is introduced, which is taken in the following ratio: granulated material "ПА"-6 - 90-92%, multi-component thermal light-stabiliser - 8-10%. The latter consists of the following: - univalent copper salt 0.6-0.7%, potassium halogenide 2.4-5.6%), auxiliary additive: organic component from triazols class, plasticisers on the basis of stearates, phenol anti-oxidant 3.7-5%, optical bleach from class of benzoxazole 0-0.05%. |
| Nonfibrous polymer solution para-aramide with high relative viscosity / 2342474 Invention concerns receiving technology of para-aramide fibers, films, paper. Particularly it concerns receiving of polymer solutions for its manufacturing. Nonfibrous polymer solutions contains from 1 till 8 % wt of para-aramide at least, 50 % mol. aromatic remains of which are unreplaced; polar amide solvent, chosen from N- methyl -2- pyrrolidone, N,N'- dimethyl formamide, N,N'- dimethyl acetamide, tetra methyl urea and its mixtures; from 0.5% wt of chloride of alkaline or alkali-earth metal and till 7.5 % wt chloride of alkaline or alkali-earth metal, and till 5% wt of water. At least 50 % wt of formed hydrochloric acid is neutralised with receiving of solution, allowing dynamic viscosity, which is at least three times less than dynamic viscosity of polymer solution without neutralisation. |
 Lightproof and heat-resistant composition / 2351621Invention refers to lightproof and/or heat-resistant composition, method of production, to threads, fibres and/or filaments, as well as to textile product. The composition contains the following components: polyamide matrix, at least, one lightproof and/or heat-resistance stabilising agent containing, at least, one hindered functional amino group, titanium dioxide and manganese salt. Method of producing the composition consists that, at least, one lightproof and/or heat-resistance agent, titanium dioxide and manganese salt are introduced to polyamide base monomers before or with polymerisation. Threads, fibres and/or filaments are made of cast composition. Textile product contains, at least, threads, fibres and/or filaments made of above-stated composition. |
 Aramid fibrils / 2363780Invention concerns obtainment of para-aramid fibrils, as well as paper based on the claimed fibrils. In humid phase poly(para-phenylethylene terephthalamide) fibrils show drainage rate by Canada Standard under 100 ml, specific surface area after drying under 7 m2/g and weight-average particle length under 1.2 mm, defined respective of weight for particles over >250 mcm long (WL0.25). Method of fibril obtainment involves polymerisation of aromatic diamine and aromatic dicarboxylic acid haloid up to para-aramide polymer stage in the mix of N-methylpyrrolidone or dimethylacetamide and calcium or lithium chloride to obtain spinning solution. Concentration of polymer dissolved in the mix is 2-6 wt %. Obtained spinning solution is transformed into fibrils by spinning nozzle in gas flow, and fibril coagulation is performed by coagulation jet. Paper is made of components where at least 2 wt % corresponds to the claimed para-aramide fibrils. |
 Para-aramide fibrid film / 2366670Film is featured with para-orentation of at least 95% polymer bonds. The method for film making includes polymerisation of para-oriented aromatic diamine and para-oriented aromatic dicarbon acid haloid in the mixture of solvents consisting of N-methylpyrrolidone or dimethylacetamyde and calcium chloride or lithium with obtaining of aramide polymer containing only para-oriented bounds. Then the spinning solution is obtained by solution of the polymer in solvent mixture up to concentration 2 - 6 wt %. The spinning solution is transformed to para-aramide fibrid film with usual known methods used for meta-aramide fibrids production. |
FIELD: textiles, paper.
SUBSTANCE: thread consists entirely of aromatic polyamide. The thread has a narrow range of polydispersity index (PDI) and lower paracrystalline parameter g11, which leads to decrease of defects of the crystal itself.
EFFECT: creation of a thread which has increased strength and value of elasticity modulus.
4 cl, 2 dwg, 1 tbl, 2 ex
AREA OF TECHNICAL USE
The present invention relates to a thread that is composed entirely of aromatic polyamide, and to a method of manufacturing of such threads, and more particularly to a method of making a new thread, completely composed of aromatic polyamide, has physical properties, including high strength and high value of the module.
ANALOGUES AND PROTOTYPE
As disclosed previously known documents, for example, patents of USA № 3869429 and № 3869430, yarn, consisting entirely of aromatic polyamide, and were using a number of processes including: process receipt of the polymer consists entirely of aromatic polyamide, by the polymerization of aromatic diamine and aromatic chloride in solvent containing N-methyl-2-pyrrolidone; the cooking process of the spinning solution obtained by dissolving polyamide in solvent - concentrated sulfuric acid; shaping process threads by extruding the spinning solution through a die and pass spinning material through a layer of a fluid medium, does not cause coagulation, in a tub of coagulant; and the process of cleaning obtained as a result of threads by washing, drying and heat treatment.
In Fig. 1 schematically illustrates the method of obtaining a thread that is composed entirely of aromatic polyamide, using the normal «dry-wet moulding.
By the usual method of manufacturing of threads, completely composed of aromatic polyamide, there is a problem, which consists in the fact that the polymer monomers, served in a reactor 20, not mixed with each other quite well and, thus, not polymerize evenly or homogeneity in the whole space of the reactor.
For this reason, the usual method has a drawback, namely increased deviation in the degree of polymerization upon receipt of the polymer consists entirely of aromatic polyamide, thus causing a problem, which consists in the fact that the physical properties, especially the strength and value of the modulus threads, completely composed of aromatic polyamide, are reduced.
In result of research performed by the author of the invention for the solution of the problems mentioned above, established the present invention, in which it was proposed to obtain a new thread that is composed entirely of aromatic polyamide, has the increased durability and higher value of the modulus.
DETAILED DESCRIPTION OF THE INVENTION
TECHNICAL TASK
Thus, the objective of this invention is to increase strength and modulus, the thread that is composed entirely of aromatic polyamide, as the finished product, by ensuring the implementation of uniform and homogeneous monomer polymerization in the whole space polymerization reactor 20, therefore, the minimization of the deviations in the degree of polymerization (below this phenomenon abbreviated called «deviation») received as a result of the polymer.
Another aim of the present invention is to create a thread that is composed entirely of aromatic polyamide, with a narrow range of distribution of molecular mass, called «polydispersity index» (designated as «SDI»), and reduced parameter (marked as «g II »), which determine the defects of the crystal, obtained as a result of minimal deviation of the polymer, and thanks to that thread has improved values of strength and modulus.
TECHNICAL MEANS FOR SOLVING THE PROBLEM
To achieve the above objectives developed the method of the present invention the strands that is composed entirely of aromatic polyamide, including: the dissolution of the polymer consists entirely of aromatic polyamide, solvent - concentrated sulfuric acid, with the receipt of the spinning solution, in which the polymer consists entirely of aromatic polyamide, produced by polymerization of aromatic diamine and aromatic chloride in solvent containing N-methyl-2-pyrrolidone; and the transmission of spinning solution through a Spinneret with the receipt of the spinning material, characterized in that in the process of preparation the polymer consists entirely of aromatic polyamide, aromatic diamine, aromatic chloride and solvent, is fed into the reactor 20, stirred by mixing device, installed in the reactor 20, consisting of: (i) the rotor 3, driven by a motor 2 and containing many fingers 3a, and (ii) the stator 4, containing many fingers 4a, in which the speed of rotation the rotor 3 govern in such a way that it was in the range from 10 times to 100 times the speed of feeding the reactor aromatic chloride and aromatic diamine in solvent, and at the same time regulate the frequency of contacts between the fingers 3a and fingers 4a in the range from 100 Hz to 1000 Hz.
Thread, fully consisting of aromatic polyamide, according to the present invention wherein the SPD is in the range from 1.5 to 2.3, and parameter g II to heat treatment is ranging from 1.7% to 1.9%.
The present invention is described in more detail below, with links to enclosed drawings.
According to the present invention, the first obtained the polymer consists entirely of aromatic polyamide, polymerization aromatic diamine and aromatic chloride in solvent containing N-methyl-2-.
Aromatic diamine preferably contains n-phenylenediamine and aromatic chloride preferably contains .
Besides solvent preferably contains N-methyl-2-pyrrolidone containing dissolved chloride calcium.
Method for producing polymer that is composed entirely of aromatic polyamide, according to the present invention, as described above, aromatic diamine, aromatic chloride and solvent, submitted in the polymerization reactor, mix, using a mixing device, as shown in Fig. 2 installed in the reactor 20 and consisting of: (i) the rotor 3, driven by a motor 2 and containing many fingers 3a; and (ii) the stator 4, containing many fingers 4a, in which the speed of rotation the rotor 3 govern in such a way that it was in the range from 10 times to 100 times the speed of feeding the reactor aromatic chloride and aromatic diamine in solvent, and at the same time regulate the frequency of contacts between the fingers 3a and fingers 4a in the range from 100 Hz to 1000 Hz.
In Fig. 2 schematically shows a cross-section polymerization reactor 20, used in the present invention.
More specifically, the reactor 20 (see Fig. 2) according to the invention, provided with a mixing device, consisting of rotor 3, driven by a motor 2 and containing many fingers 3a, and stator 4, containing many fingers 4a,
According to the present invention, the passage of the polymerization process monomers and solvent, are fed into the reactor, shall be implemented by mixing.
The mixing device preferably use by adjusting the speed of rotation the rotor 3 so that she was in the range from 10 times to 100 times the speed of feeding the reactor 20 aromatic chloride and aromatic diamine in solvent, and at the same time regulate the frequency of contacts between the fingers 3a and fingers 4a in the range from 100 Hz to 1000 Hz.
If the rotor speed 3 below 10 times the speed of submission of monomer polymer or frequency of contacts between the fingers 3a and fingers 4a (reduced frequency of contacts») below 100 Hz, all monomers and solvent not mix well enough to achieve a homogeneous polymerization in the entire space of the reactor.
On the other hand, if the rotor speed 3 exceeds 100 times the feed rate, polymer monomer or frequency of contacts above 1000 Hz, may be generated ultra-high speed shift inside the reactor, leading to uneven polymerization.
Polymer, fully consisting of aromatic polyamide, has the characteristic viscosity constituting not less than 5.0, which preferred to increase the strength and modulus threads.
Conditions of polymerization mentioned above polymer are essentially the same as those previously known, for example, described in U.S. patent № 3869429 or similar document.
In a preferred embodiment, the method of receiving the polymer receive polymer in the form of ultra-fine powder due to the introduction of the solution, which can be prepared by dilution of 1 mole of n-phenylenediamine N-methyl-2- containing more than 1 mole of calcium chloride and 1 mol , in the polymerization reactor 20, provided with a mixing device, as shown in Fig. 2; mixing the mixture in the reactor for the formation of a polymer in the form of a gel; and crushing, washing and drying of the polymer in the form of gel with receiving, thus, polymer in the form of ultra-fine powder. can be injected into the reactor 20 half doses in two stages.
Then polymer, fully consisting of aromatic polyamide, prepared as described above, is dissolved in a solvent - concentrated sulfuric acid with the formation of the spinning solution. Then, as shown in Fig. 1, spinning solution is subjected to the process of forming, and passing it through the die 40 with the receipt of the spinning material, and then pass the spinning material through a layer of a fluid medium, does not cause coagulation, in a bath with 50 coagulant with the formation of threads. At the end of the thread, fully consisting of aromatic polyamide, according to the present invention, washed, dried and subjected to heat treatment. In Fig. 1 schematically illustrates the method of manufacturing of threads, completely composed of aromatic polyamide, utilizing the dry-wet moulding.
Concentrated sulphuric acid, which is used in the cooking of the spinning solution, preferably has a concentration ranging from 97% to 100% and can be replaced acid or acid.
If the concentration of the sulfuric acid less than 97%, the solubility of polymer decreases, and the solution cannot be easy to form a liquid-crystal structure. Thus, it is difficult to get the spinning solution constant viscosity and, in turn, manage the process of spinning, thus causing the deterioration of mechanical properties of finished textile product.
On the other hand, if the concentration of the sulfuric acid exceeds 100%, the content of the SO 3 becomes excessive in any steaming sulfuric acid containing overly group 3 SO ; therefore, it is undesirable to process and use sulfuric acid as an additive in the spinning solution, as it causes partial decomposition of the polymer. In addition, even if the fiber can be obtained by use of the spinning solution, it has a loose internal structure, essentially matte color, if to speak about appearance, and this decreases the speed of diffusion of a sulfuric acid in solution of coagulant, so that it can lead to the problem, consisting in the reduction of mechanical properties of fibers.
In the alternative case, the concentration of polymer in spinning solution is preferably within 10 wt.% up to 25 wt.%.
However, the concentration of sulfuric acid, and the concentration of polymer in spinning solution is not particularly limited.
A layer of fluid does not cause coagulation, may be, in General, air layer or a layer of inert gas.
Depth of the layer of a fluid medium, does not cause coagulation, i.e. the distance from the bottom dies 40 to the surface of the coagulant in the tub 50 with coagulant, preferably in the range from 0.1 cm to 15 cm, to improve spinning capacity or improve the physical properties of the thread.
Coagulant contained in the tub 50 with coagulant, you can serve with overflow, and it can contain (but its composition is not limited to the listed substances), for example, water, salt water or aqueous solution of sulfuric acid with a concentration of less than 70%.
Then preformed thread is washed, dried and subjected to heat treatment with obtaining a thread that is composed entirely of aromatic polyamide. The speed of the spinning and winding is in the range of 700 m/min up to 1500 m/min
The resulting thread, fully consisting of aromatic polyamide, according to the present invention has minimum deviation and, thus, has a narrow range of children's suffrage and reduced the g option II , which determine defects of the crystal, so it has very high strength before and after heat treatment, amounting to at least 26 g/denier, and a very high value of the module, amounting to a heat treatment is not less than 750 g/denier, and after thermal processing - not less than 950 g/denier.
More specifically, thread, fully consisting of aromatic polyamide, according to the present invention has an SDI in the range from 1.5 to 2.3, preferably from 1,5 to 2,0 and more preferably, 1.5 to 1.7, and the g option II to heat treatment ranging from 1.7% to 1.9%. Besides parameter g II after heat treatment at 300 C under tension 2% during 2 is in the range of 1.3% to 1.6%.
If children's suffrage and parameter g II exceed the limits above, there has been a slight increase in the value of the module. Conversely, if the DTI and parameter g II less than the above limits, while the value of the modulus increases, it is within a region that is difficult is achievable by the present invention.
In accordance with this, in comparison with common thread that is composed entirely of aromatic polyamide thread, fully consisting of aromatic polyamide, according to the present invention has a minimal variance in the degree of polymerization of polymer and, therefore, has a narrow meaning of children's suffrage and low parameter g II , which defines the defects in the crystal.
As a result of polymer, fully consisting of aromatic polyamide, has a very high strength and significantly improved the value of the modulus.
ADVANTAGES
As described above, this use of the present invention allows to provide the minimum deviation degree of polymerization by uniform promotion of polymerization of the monomer polymer in the whole space polymerization reactor 20.
In accordance with this thread, fully consisting of aromatic polyamide, made according to the present invention has a minimum deviation of the degree of polymerization and, thus, has a narrow meaning DTI and low the g option II , thus, reduced defects of the crystal, so it has a very high strength and significantly improved the value of the modulus.
BRIEF DESCRIPTION OF DRAWINGS
The above purpose, features and advantages of the present invention will become more obvious to a person skilled in the art when reading the following variants of carrying out the invention in conjunction with the accompanying drawings.
in Fig. 2 is a schematic cross-section of the polymerization reactor 20, used in the present invention.
Transcript of rooms positions of the main parts shown on the drawings:
2 - engine;
3 - rotor;
3a - finger firmly fixed in the rotor;
4 - stator;
4a - finger, rigidly mounted in the stator;
20 - polymerization reactor;
21 - inlet for submission of monomer and solvent;
22 - edition release of polymer;
30 - capacity storage spinning solution;
40 - die;
50 - bath with coagulant;
60 - washing device;
70 - drying unit;
80 - a device for thermal processing;
90 - device.
THE BEST WAY OF CARRYING OUT THE INVENTION
Distinctive features of the present invention described above, other benefits you can more fully understand when reading the following is not limiting the scope of the invention examples and comparative examples. However, it is clear for specialists in this area, that the present invention is not limited to specific content of the examples below.
EXAMPLE 1
1000 kg N-methyl-2- kept at a temperature of 80 C and connected with 80 kg of calcium chloride and 48,67 kg n-phenylenediamine, which then dissolved to obtain a solution of aromatic diamine.
After the introduction of the solution of aromatic diamine and molten in a molar dimension equal to the quantity of n-phenylenediamine, simultaneously in the polymerization reactor 20, provided with a mixing device, installed in the reactor 20 and consisting of rotor 3, containing many fingers 3a, and stator 4, containing many fingers 4a, both of these compounds mixed and received poly-n- with the characteristic viscosity of 7.0.
The rotor speed 3 installed such that it was approximately 30 times the speed of submission of monomer polymer, while the frequency of contacts between the fingers 3a and fingers 4a installed such that it was about 500 Hz.
The polymer continuously dissolved in concentrated sulfuric acid (99%) with the formation of an anisotropic optical spinning solution for spinning with the content of polymer 18%.
The resulting spinning solution is passed through the die of 40, as shown in Fig. 1, with the formation of the spinning material. After deletion of spinning material through the air layer thickness of 7 mm it was served in a tub of 50 with coagulant, contained water as a coagulant, thus getting the thread.
Then preformed thread inflicted water sprayed at a temperature of 25 C for washing thread, then the thread is passed through two-stage swivel drying unit with temperature of a surface of rollers 150 C, was reeled dried thread and received as a result of a string of poly-n- to heat processing.
Determined the various physical properties of the produced yarn of poly-n-, the results are presented in Table 1.
EXAMPLE 2
Thread of poly-n- obtained in Example 1, subjected to thermal treatment at the temperature of 300 C under tension 2% year 2 with the finished product, i.e. a thread of poly-n- after heat treatment.
Determined the various physical properties of the produced yarn of poly-n-, the results are presented in Table 1.
A COMPARATIVE EXAMPLE 1
Manufacturing of yarns of poly-n- to heat treatment was carried out, using the same procedure and maintaining the same conditions as in Example 1, except that the solution B aromatic diamine and melted cooked in Example 1, served in a normal reactor, equipped with only auger instead of mixing device, shown in Fig. 2.
Determined the various physical properties of the produced yarn of poly-n-, the results are presented in Table 1.
A COMPARATIVE EXAMPLE 2
Thread of poly-n-, resulting in a Comparative example 1, subjected to thermal treatment at 300 C under tension 2% year 2 with the finished product, i.e. a thread of poly-n- after heat treatment.
Determined the various physical properties of the produced yarn of poly-n-, the results are presented in Table 1.
TABLE 1Evaluation of physical properties of threads
Parameter
Example 1
Example 2
Compares. example 1
Compares. example 2
Index of polydispersity (SDIs)
1,6 1,5 2,7 2,6parameter (g II )
Before thermal processing
1,80% - 1,66% -After heat treatment at 300 C under tension 2% for 2
- 1,56% - 1,91%Strength (g/denier)
27 26 22 21Module (g/denier)
840 1080 740 930Listed above physical properties of threads according to the present invention, determined and/or evaluated using the following techniques:
Determination of strength (g/denier)
After measuring the strength of the (g)
at the precipice of a sample of complex thread on the device «» company Instron Engineering Corp. (, Kenton, PCs. Massachusetts, USA) at the length of the sample complex yarn 25 cm, the obtained value divided by (denier) sample of complex yarn for determination of strength. This strength value is the average value calculated according to the results of tests of five samples of complex yarn. In these tests the speed of movable clamp was 300 mm/min, and pre-load was determined by the formula: fineness (denier) x 1/30,
Module definition (g/denier)
Received curve of load-elongation» for a sample of complex yarn under the same conditions as for the definition of strength. The module is determined by the slope of the curve «load-elongation».
The definition of the characteristic viscosity
Prepared sample solution by dissolving 0,1250 g of the sample, i.e. polymer or the thread in 25.0 ml of sulfuric acid with a concentration of 98%, which was used as a solvent. Then, after measuring the time expires (time expires fluid, (C) each of the samples of the solution and the solvent (i.e. sulfuric acid) in a tub of water with constant temperature of 30 C, using capillary viscometer, called the Cannon Fenske viscometer type 300, calculated indicator of the relative viscosity η from by dividing the time expires sample solution on the time expires solvent. The calculated value of viscosity η from divided by the concentration of the sample solution to obtain the characteristic viscosity.
Definition of polydispersity index (SDI)
Using chromatography (indicated as «GPC»), were measured children's suffrage as follows:
(i) Synthesis derived polymer that is composed entirely of aromatic polyamide.
Thread composed entirely of aromatic polyamide, as a sample, and Ter-butoxide potassium added in dimethyl sulfoxide and dissolved at room temperature in a nitrogen atmosphere. Then, the solution was added for the preparation of polymer consists entirely of polyamide, with a substituted group (see ed. «Macromolecules» 2000, 33, 4390).
(ii) the Definition of children's suffrage
Cooked polymer consists entirely made of polyamide, was dissolved in CHCl 3 and determined IAP using GPC Shodex kit Waters for manual spraying at 35 C and flow rate of 10 ml/min, which is equipped with a detector of the refractive index.
Definition parameter g
IIUsed KMG and theory of diffraction Hosemann, based on the area of a single cell, determined parameter g II as follows:
(i) Preparation of sample
Samples of threads, completely composed of aromatic polyamide, of a thickness of about 1000 denier to 2000 denier and a length of 2-3 cm to carefully straightened, and then attached to the specimen.
(ii) the Procedure of measurements
- After attachment of prepared sample specimen, have established β position 0 degrees (the sample is attached to the specimen in the axial direction of the thread for installation β-position).
- Now the instrument of KMG prepared to definition of crystallinity (To) by a moderate increase in the supply voltage and current up to 50 kW and 180 mA, respectively, after heating device.
- Measured Meridian picture suitable for calculation parameter g II .
- The measurements were performed, in principle, as follows:
Used goniometer, continuous scan mode, scan within an angle from 10 degrees to 40 degrees, and the scanning speed of 0.5 [as the intensity of the peak is very small, it was specified duration of exposure beam at the time of scanning step, sufficient to increase the intensity of the peak to the 2000 CPS].
- Measured observed for 2 positions of peak (002 faces), to appear in a range between 10° and 15 of the profile in which produced the scan.
- Measured value profile injected in the following equation Hosemann to determine parameter g II :
whereδ S - degree of dispersion of the diffraction peak;
L - size crystal;
d - step lattice faces;
m is the order of the diffraction peak.
INDUSTRIAL APPLICATION
As described above, the present invention is useful for manufacturing of threads, completely composed of aromatic polyamide, with a very high durability and high value of the modulus.
1.Thread, fully consisting of aromatic polyamide, notable for its polydispersity index (SDI) is in the range from 1.5 to 2.3, and parameter g II to heat treatment is ranging from 1.7% to 1.9%.
2. Thread by p. 1, polydispersity index (SDI) is in the range from 1.5 to 2.0.
3. Thread by p. 1, polydispersity index (SDI) is in the range from 1.5 to 1.7.
4. Thread by p. 1, in which parameter g II after heat treatment at 300 C under tension 2% during 2 is in the range of 1.3% to 1.6%.