Amorphous poly(m-phenyleneterephthalamide) fiber having antistatic properties, its production method and composition for antistatic finishing of this fiber
(57) Abstract:Describes amorphous poly(m-phenyleneterephthalamide) fiber having antistatic properties, containing from 5 to 15 wt.% anionic or cationic surfactants and having on the surface a coating of two components. The invention lies in the fact that one component of the coating is alkylphosphate potassium containing6-C18-alkyl, in an amount of from 65 to 90 wt.%, and another component of the coating is partially aminirovanie polyalkylene in the range from 10 to 3 wt.%, and partly aminirovanie polyalkylene has a residual amine number of from 200 to 800, and the coating is present in an amount of not less than about 0.5% by weight of the fiber. The combination of alkylphosphate potassium containing alkyl of 10 to 18 C atoms, and partially liderando polyalkylimide reduces the tendency is almost amorphous polietilentereftalatnogo fiber containing surfactant, accumulate static electricity. 3 S. and 1 C.p. f-crystals, 4 PL. Art
In U.S. patent 4668234 describes the production of practically oriented amorphous poly(m-phenyleneterephthalamide) fibers containing the of Oki tone. These fibers often have an open structure, facilitating the penetration of the dye into the fiber. This fiber is desirable for the application of conventional antistatic coatings, as the fiber over time and loses its protective effect against static electricity. It causes damage to the fibers in the process of scratching and pulling in the processing of staple fibers into yarn and fabric. Loss of the protective effect after a month or two months of storage makes it difficult or impossible time control of inventory and transportation to supply fiber, capable of processing without the occurrence of undesirable static electricity.In the author's evidence 1654397, A1, class D 01 6/74, 1991 described the use alkylphosphate surface-active substances for the treatment of poly(m-phenyleneterephthalamide) fibers in order to give them brightness. However, the concentration of surfactant in the fibers, as described in this author's evidence, too small to get a fiber capable of staining.The present invention aims to overcome to a considerable extent, these shortcomings.The invention
The present invention allows to obtain containing over the TEW accumulate static electricity and having on the surface a coating of two components, containing from 65 to 90 wt.% potassium salt of alkylphosphate containing alkyl 16-18 C atoms, and from 10 to 35 wt.% partially liderando polyalkylimide. This coating contained on the fiber in an amount of not less than 0.2% by weight of the fiber.Detailed description of the invention
Threads that handle according to the present invention, is described in U.S. patent N 4668234. In particular, they represent fibers of poly(m-phenylenedimaleimide) MPD-1, dried after application of 5 to 15 wt. % anionic surfactants, isopropylbenzenesulfonyl as described in example 1, part C of the upper column 8 of the patent.On the dried fiber MPD-1, described above, are coated with two active components. One component is partially aminirovanie polyalkylene with residual amine number of from 200 to 800, described in U.S. patent 3597265. It is produced by the interaction polyalkylimide with a molecular weight of from 800 to 5000 with fatty acid. In the following examples polyalkyleneglycol with an average molecular weight of 1200 is polyalkylene, partially aminirovanie fatty acid according to examples 1-4 above mentioned U.S. patent 3597265. Other active co is the alkyl 6-18 atoms C. Preferably, n-octylphosphine potassium.Both active components, namely partially aminirovanie polyalkylene and salts of phosphate, can be applied to the fiber at the same time in the form of an aqueous mixture or sequentially: first Imin, and then phosphate (with intermediate drying).The resulting coating should contain from 65 to 90 wt.% salt of phosphate and from 10-35 wt.% partially liderando polyalkylimide. An aqueous solution of the components is applied to the fiber in a quantity sufficient for the application of not less than 0.2 %and preferably not less than 0.4 wt.% active ingredients by weight of the fiber. Can be used to 0.9% of the mixture, but usually use the minimum effective amount for reasons of economy and to avoid contamination of equipment during use of excessive amounts. It is important to dry the fiber immediately after applying the antistatic coating, because the protective effect is reduced in the case of drying the fiber at ambient temperature.Especially preferred is the application of active components on the fiber in the mixture. When using partially liderando polyethylenimine in combination with n-existspath potassium or n-octylphosphine to="ptx2">The following examples except the control illustrate the invention without limiting it.Example 1
In transparent glass mixing vessel add sequentially 80,18 wt.h. demineralized water, 16,07 wt. including a 70% aqueous solution of n-octylphosphine potassium and 3.75 wt. including partially liderando polyethylenimine obtained according to examples 1-4 of U.S. patent 3597265 (amine number 340-420). The mixture is heated to 35-40oC and stirred for 15 min to obtain a clear 15%-aqueous solution. The solution has a pH 10,23.Example 2 (control)
In transparent mixing vessel successively added 85 including demineralized water and 15 wt. including partially liderando polyethylenimine similar to example 1. After stirring for about 15 min to get a clear solution. The solution is then diluted with demineralized water to a concentration of 0.25 wt.%.Example 3 (control)
In transparent mixing vessel successively added 80 wt. including demineralized water and 20 wt. including 75% solution of laurifolia potassium. The mixture is stirred for 15 min until a homogeneous opaque molokoobraznuyu 15% of the emulsion. An aliquot of this emulsion is then >In transparent mixing vessel add sequentially 78,6 wt.h. demineralized water and 21.4 wt.h. a 70% aqueous solution of n-octylphosphine potassium. The mixture is stirred for 15 min until a homogeneous molokoobraznuyu opaque 15% of the variance. Aliquots of this dispersion is then diluted to 0.75% and 1.0% concentration demineralized water.Example 5 (control)
In transparent mixing vessel add sequentially to 66.7 wt.h. demineralized water and 33 wt.h. 45% aqueous solution of n-hexylphosphonic potassium. The mixture is stirred for about 15 min until a clear solution is formed. Aliquots of this solution is then diluted with demineralized water to a concentration of 0.75% and 1.0%.Example 6
The coating solution obtained in example 1, diluted to 1% concentration demineralized water, and 5 g of this solution added to a beaker containing 5 g of aramid staple fibers (Type E-34 Nomex) of 1.5 denier, 1 1/2 inch, obtained in accordance with U.S. patent N 4668234. Staple fiber and the coating solution is stirred with a glass rod for about 5 min to distribute the solution of the coating on the fibers. Immediately after study is 7 (control)
The emulsion coating prepared according to example 5, applied to aramid staple fiber as in example 6.Example 8 (control)
Dispersion coating prepared according to example 4, applied to aramid staple fiber as in example 6.Example 9 (control)
The coating solution obtained in example 5, applied to aramid staple fiber as in example 6.Example 10
The coating solution according to example 2 is applied to aramid staple fiber by adding 5 g of a 0.25% aqueous solution of the coating to 5 g aramid staple fiber in a laboratory glass, stirring for 5 minutes and drying immediately after mixing for 10 minutes at 130oC. Then it is a staple fiber is placed in a Cup, add 5 g 0,75% emulsion coating according to example 3 is stirred for 5 min and dried at 130oC for 10 minutesExample 11
Treat the fiber as in example 10 using a 0.25% aqueous solution of the coating according to example 2 and 0.75% dispersion coating according to example 4.Example 12
Treat the fiber as in example 10 using a 0.25% aqueous solution of the coating according to example 2 and 0.75% RASTAM 6-14, processed into rovings short length through the Rotor Ring Model 580, manufacturer Spinlab. The electrical resistance of the samples is determined by the method described in the literature (Thomas J. Proffitt, Jr. "Surfactants as Textile Antistatic Agents", Proceedings of Session Lectures and Scientific Presentations on ISF-JOCS World Congress, vol. 11, p. 699, The Japan Oil Chemists Society, Tokyo). The results are presented in table 2 in the form of resistance, expressed as the index of log R. the Resistance log R measured at 47% relative humidity and repeat the measurement after keeping the samples.Example 14
The coating solution prepared by the method of example 1, applied to type 2 bundles of fibers with a thickness of 1.5 denier of MPD-1, i.e. harness, capable of staining without carrier fibers of aromatic polyamide NomexE-34 and harness, capable of printing without carrier fibers of aromatic polyamide Nomextype E-504 by passing strings in contact with the surfaces of the two applicators Baber (see U.S. patent N 3422796), which are located one above and the other below the bar wiring harness. Samples harnesses received when using the three velocities of flow of the coating solution for each of the resulting bundle.Then the sample is placed in the capacity to tow and immediately (~20 m with obtaining a staple length of 1 1/2 inch by Lummus cutter. The staple is directed to the carding machine of the cotton type with hopper feeder and receiver roller type. The level of electrostatic charging of the fibers was acceptable when the content of the coating on the fiber 0.2 wt.% by weight of the fiber and higher, and thus the cohesion of the fibers are improved. Content of the coating on the fiber over time, very little has changed, as shown in table 3, as well as electrostatic charge and the indicator log R, as shown in table 4. Cohesion determined by the tensile strength of wool ribbon in mg/denier, was changed from 2.46 to 3,84 the fiber-containing coating according to example 1, and Vice versa from 1,43 up to 1.83 for fibers containing a control coating of laurifolia potassium. The result is improved stability Cardin tape. 1. Amorphous poly(m-phenyleneterephthalamide) fiber having antistatic properties, containing from 5 to 15 wt.% anionic or cationic surfactants and having on the surface a coating of two components, wherein one component of the coating is alkylphosphate potassium containing alkyl of 6 to 18 C atoms, in an amount of from 65 to 90 wt.% and another component of the coating is partially aminirovanie the e amine number of from 200 to 800 and the coating is present in an amount of not less than about 0.2% by weight of the fiber.2. Fiber under item 1, characterized in that as alkylphosphate potassium it contains n-octylphosphine potassium.3. The method of obtaining fiber under item 1, by coating on the fiber coating, characterized in that the fiber is applied powder coating in the form of a mixture of both components or sequentially with intermediate drying after the application of each component.4. The composition for antistatic finish is able to be painted and containing surfactant poly(m-phenyleneterephthalamide) fibers, characterized in that it comprises an aqueous solution of n-hexylphosphonic potassium or n-octylphosphine potassium and partially aminirovanie polyalkylene at a ratio of from 65 to 90 wt.% phosphate and from 10 to 35 wt.% polyalkylimide, and partly aminirovanie polyalkylene has a residual amine number of from 200 to 800 and the surfactant is anionic or cationic surface-active agent is present in the fiber in an amount of 5 to 15 wt.%.
FIELD: optionally materials.
SUBSTANCE: invention 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.
EFFECT: improved performance characteristics of thread.
1 tbl, 7 ex
FIELD: polymer production.
SUBSTANCE: invention relates to technology of manufacturing threads and fibers from aromatic copolyamide and can be used in manufacture of special-destination composite materials and fabrics with elevated performance characteristics suitable to fabricate special protective clothing and the like. Method comprises three-step dissolution of 5(6)-amino-(p-aminophenyl)benzimidazole in aprotic organic solvent in presence of lithium salt. In the first step, crystalline 5(6)-amino-(p-aminophenyl)benzimidazole having melting point 239±1°C is completely dissolved, after which 40:60 to 60:40 mixture thereof with the same benzimidazole having melting point 215±5°C is added and, after complete dissolution of the mixture, crystal hydrate of 5(6)-amino-(p-aminophenyl)benzimidazole with melting point 140±10°C and content of water 2.0-2.7% is added. Thereafter, low-temperature polycondensation is carried out with participation of terephthalic acid dichloride and optional p-phenylenediamine. Resulting polycondensation solution is deaerated and molded into precipitation bath by wet manner. Gel-like threads obtained are stretched to 100%, washed, dried, and thermally treated at 340°C.
EFFECT: improved thermal and physico-mechanical properties of threads and fibers.
4 cl, 4 tbl, 7 ex
FIELD: polymer production.
SUBSTANCE: invention relates to technology of manufacturing heat-resistant threads from aromatic polyamides, in particular copolyamidobenzimidazole, and can be used in manufacture of filter cloth for treating hot gases to remove toxic dust, in textile industry for sewing protective clothing for life-servers, firemen, oil and gas industry workers, and other those working in extremal situations, as well as for manufacturing carpet coverings and decorative and finishing fabrics. Method comprises synthesis of copolymer from mixture of 25-30 mol % 5(6)-amino-2-(4-aminophenyl)benzimidazole, 10-30 mol % p-phenylenediamine, and 40-60 mol % m-phenylenediamine per 100% terephthaloyl chloride in aprotic organic solvent in presence of LiCl or CaCl2 until specific viscosity of copolymer in concentrated sulfuric acid achieves 1.2 to 2.0. p-Phenylenediamine is then added during cooling of resulting solution to 0-15°C. Thus obtained polycondensation solution is molded into water-organic bath to form thread, which is subjected to plasticizing stretching, rinsing, and drying.
EFFECT: simplified and reduced in price thread manufacturing process and reduced degree of shrinkage of thread.
5 cl, 1 tbl, 12 ex
FIELD: polymer production.
SUBSTANCE: invention relates to technology of manufacturing high-strength heat-resistant threads from aromatic copolyamide having heterocycles in the chain, in particular copolyamidobenzimidazole, and can be used to reinforce plastics, in manufacture of technical rubber articles, fiber optics cables, and other special-destination articles. Method comprises dissolving 5(6)-amino-2-(4-aminophenyl)benzimidazole in amide solvent in presence of LiCl or CaCl2 at 18-24°C. p-Phenylenediamine is then added during cooling of resulting solution to 0-15°C and two-step low-temperature polycondensation is effected by introducing 80-90 mol % terephthaloyl chloride until formation of oligomer, after which follows filtration of oligomer and reaction is continued to achieve required viscosity of copolymer. Molding is effected at 18-24°C. In second embodiment of industry, diamines are dissolved simultaneously, resulting polycondensation solution is heated to 25-35°C, and molding in water-organic bath is carried out at the same temperature. After plasticizing stretching, rinsing, and drying, thread is subjected to heat treatment at 350-360°C for 0.5 h and then to thermal stretching by 1.0-1.5% at 370-410°C.
EFFECT: improved mechanical properties of threads.
9 cl, 2 tbl, 34 ex
FIELD: polymer materials.
SUBSTANCE: invention relates to technology of producing synthetic fibers from aromatic polymers and may be employed to reinforce plastics, mechanical rubber goods, and fiber-optics cables as well as to create armor and the like materials. Copolyamidobenzimidazole solution is prepared by low-temperature polycondensation of 50-80 mol % 5(6)-amino-2-(p-aminophenyl)benzimidazole and 20-50 mol % p-phenylenediamine with 100 mol % terephthaloyl chloride in dimethylacetamide or N-methylpyrrolidone as solvent with lithium chloride or calcium chloride as additive. Hydrogen chloride released from polymer synthesis is partly neutralized with reagents such as LiOH, LiOH·H2O, Li2CO3, CaO, CaCO3 so that level of hydrogen chloride in solution would be 0.2-0.9, which corresponds to molar ratio of residual HCl to benzimidazole cycles of polymer from 0.5 to 2.0.
EFFECT: increased strength and modulus of fibers.
2 cl, 1 tbl, 3 ex
FIELD: production of high-strength high-modulus threads, in particular, copolyamidobenzimidazole-based threads which may be used for reinforcement of plastics, technical rubber articles, fiber optics cables, as well as for creating of shell-proof jackets or safety helmets and other articles.
SUBSTANCE: method involves carrying-out low-temperature polycondensation synthesis of mixture of aromatic diamines of 5(6)-amino-,2-(para-aminophenyl) benzimidazole and paraphenylene diamine with terephthaloil chloride in amide solvent medium with salt admixture; providing wet or dry-wet forming from 4.0-5.1%-polycondensation solutions containing hydrogen chloride as by-product of polymer synthesis in aqueous-amide settling bath; washing resultant thread with water to remove solvent and providing alkaline processing of thread for neutralization of hydrogen chloride chemically bound with polymer and removal of produced chloride and excessive alkaline; finally washing thread with water and carrying-out drying, thermal processing and thermal draught; obtaining threads with neutral pH of aqueous extract after boiling process. Said threads have strength of up to 260 sN/tex, microplastic strength of up to 520 kgf/mm2, modulus of elasticity of 15000-15300 kgf/mm2, relative elongation at break of 2.6-3.3%.
EFFECT: improved strength characteristics of threads and wider range of usage.
4 cl, 4 ex
FIELD: manufacture of high-strength fibers and films.
SUBSTANCE: proposed method of production of synthetic organic aromatic heterocyclic rod-shaped fibers or films includes the following stages: molding the fiber or film; loading the fiber or film in presence of technological additive at temperature below boiling point of this additive but higher than minus 50 C at tension equal to 10-95% of fiber or film rupture strength; removal of technological additive and/or heating at tension which is equal to 10-95% of fiber or film rupture strength. Proposed method also includes production of PIPD fiber at line density of monofilament within 0.1-500 dtex and average tensile strength exceeding 3200 mN/tex, as well as production of film whose modulus of elasticity is no less than 14 Gpa, 20 Gpa being preferable.
EFFECT: enhanced tensile strength and increased modulus of elasticity.
11 cl, 2 tbl
FIELD: process engineering.
SUBSTANCE: proposed method comprises preparing spinning solution during production of polymer consisting only of aromatic polyamide, aromatic diamine, aromatic diatomic chloride and polymerisation solution fed into reactor (20), mixing them by mixer arranged inside reactor (20). Said mixer consists of rotor (3) driven by motor (2) and comprising multiple pins (3a); and stator (4) with multiple pins (4a). Note that rotor rpm is adjusted to vary from 10-fold to 100-fold rate of feed of aromatic diatomic chloride and aromatic diamine in polymerisation solution into reactor (20). Uniform and homogeneous polymerisation are effected over the entire space of polymerisation reactor (20) that results in reduction of deviances in polymerisation degree, since polymer monomers are mixed together to produce their good interaction directly after introducing them into reactor (20). Now the solution is forced through spinnerets.
EFFECT: higher strength of thread and higher modulus.
4 cl, 2 dwg, 1 tbl, 4 ex
FIELD: machine building.
SUBSTANCE: spinning solution is produced with successive loading oleum at 10-40°C, with adding arylene-dicarbonic acid and hydrazine-sulphate containing 0.1-1.0% of sulphuric acid at weight ratio of free sulphuric anhydride in oleum, arylene-dicarbonic acid and hydrazine-sulphate 1.2-1.4:1.0:0.79-1.0 correspondingly. Total contents of sulphuric anhydride in oleum are not less, than 84.6%. Continuously stirred mixture is heated to 40-100°C and conditioned at this temperature till solution of oligomer of specific viscosity of 0.1-0.3 is obtained. Mixture is cooled to temperature not exceeding 40°C, oleum of 10-40°C temperature is additionally introduced, and ratio of free sulphuric anhydride in oleum to arylene-dicarbonic acid is 1.4-1.8:1. Further the procedure consists in mixing, in poly-condensation by holding at 80-160°C till specific viscosity 1.5-4.0 is achieved and in diluting poly-condensate solution with sulphuric acid. Successively solution is homogenised, filtered and degassed. Sedimentation is carried out at 25-80°C in a settling bath, where contents of total sulphuric anhydride are 25-50%. Additionally sodium sulphate, or ammonium, or zinc or their mixture at amount of from 0.5 g/l to 300 g/l is added into the bath. Further formed fibre or thread is stretched, pressed and washed. Formed fibre or thread is neutralised to pH 8.5-9.5 with water solution of sodium bicarbonate or potassium bicarbonate, or sodium carbonate or their mixture, or water solution of sodium hydroxide. Finally fibre or thread is heat-treated.
EFFECT: fibres or threads possess increased resistance to hydrolysis and fire, and upgraded elastic properties.
FIELD: machine building.
SUBSTANCE: procedure consists in poly-condensation of three aromatic diamines with dianhydride of tetra-carbonic acid in a-proton polar solvent of equimolar amount. 2,5-bis(aminophenyl)pyrimidine, and paraphenylendiamine are used as diamines, while the third aromatic diamine is chosen from a row containing meta-phenylendiamine, 2,4-bis(aminophenyl)pyrimidine at their molar ratio 50:49:1 - 50:35:15 correspondingly.
EFFECT: fibres produced by wet moulding and subjected to fibre thermal cyclisation possess high durability and thermal resistance.
2 tbl, 8 ex