The solution for the formation of polyamide fibers

 

(57) Abstract:

Application: from the spinning solution get aromatic high-strength threads which is used to produce reinforced plastics, reinforced rubber product, in particular the cord for the reinforcement of tires, conveyor belts, high-strength woven sewing threads, cords, ropes, thermal insulation materials, high-strength fabrics and other products. The inventive solution for forming polyamide filaments contains statistical copolyamide structure 1 or 2, where l = 1 -9,5, m = 1 - 99, n - 98, NH-amino group is in position 5 or 6 benzimidazole cycle, and as the aliphatic polyamide-homopolyamide structure 3 or 4 or statistical copolyamide when the mass ratio of aliphatic to aromatic polyamide 2 : 98 to 20 : 80 and the following component (wt. %): a mixture of aromatic polyamide with aliphatic 11,0 - 22,0, concentrated sulphuric acid - the rest. table 2.

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The invention relates to the field of synthetic filaments, in particular, spun from sulfuric acid anisotropic solutions of rigid-rod aromatic polyamides with ingredients alipac get reinforced plastics, reinforced rubber products, in particular the cord for the reinforcement of tires, conveyor belts, high-strength woven sewing threads, cords, ropes, thermal insulation materials, high-strength fabrics, other products that require the combination of low density with high strength, high modulus of tensile elasticity, neprerekaemoi, high impact strength.

A known method of producing filaments from a mixture polyparaphenyleneterephtalamide (PFTA) aromatichyeskimi the copolyamids, for example, poly-4,41--terephthalylidene formula:

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which are taken in accordance to PFTA from 5 to 95 50 50 wt. As a result of processing 20-governmental sulfuric acid solutions PFTA with the addition of the specified aromatichyeskogo copolyamid taken to PFTA in the ratio of 15 to 85 wt. get after forming the thread with the highest tensile strength equal to 24 g/denier (220 CN/Tex). In the same conditions for forming filaments from PPTA receive the tensile strength of 19.2 g/denier (176 cH/Tex) [1]

The effect is more high strength filaments of the above-mentioned mixture of polymers is explained by the presence in the copolymer additive as aromatic part, with the same group Thurs and connecting adjacent crystallites of PPTA. The disadvantage of this method is the necessity to introduce in PFTA to 15 wt. aromatichyeskogo copolyamid, the synthesis of which is not easier than the synthesis of PPTA.

According to [2] to improve the adhesion to the rubber, cheaper cord material should enter in PFTA a small amount (1 to 7 wt.) aliphatic polyamides (polycaproamide or polyhexamethylenediamine). The addition of aliphatic polyamides produced by joint dilution with PPTA in sulfuric acid. When this is formed as in the case of PFTA optically anisotropic solutions. The application indicates that enter in the composition of PFTA not more than 7 wt. aliphatic polyamide (by weight of the mixture of polymers) due to a significant drop in the strength composite fibers, namely with 29 g/denier for PFTA up of 28.26 and 21 g/denier for 3.5 and 7-Noah supplements to PFTA aliphatic polyamides, i.e., the loss of strength is 3, 5, 10 and 28 on the strength of elementary fibers of PPTA (this strength in terms of complex thread of 213 CN/Tex for PPTA and 206, 191 and 154 cH/Tex for threads of a mixture of polymers).

Studies on mixtures of polymers unexpectedly showed that some of the aromatic copolyamids on the basis of PPTA in combination with alifaticheskie high tensile strength than the threads of PPTA and copolyamids on the basis of PFTA without the addition of aliphatic component. At a higher content of aliphatic additives copolyamid strength thread from a mixture of polymers is reduced, but to a much lesser extent than for PFTA mixed with polycaproamide and polyhexamethylenediamine.

The aim of the invention is the production of thread based on a mixture of polymers consisting of aromatic polyamide pair-structure and aliphatic polyamide, with high strength and fatigue properties. The objective is achieved due to the fact that the solution for forming polyamide filaments consisting of aromatic polyamide, aliphatic polyamide and concentrated sulfuric acid (99,8 Noi), according to the proposal it contains statistical copolyamide patterns:

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or

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where l 1 9,5; m 1 99; n to 98.

NH-amino group is in position 5 or 6 benzimidazole cycle, and as the aliphatic polyamide homopolyamide patterns

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or

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or their statistical copolyamide consisting of m mol. including links polycaproamide and n mol. including links polyhexamethylenediamine, when the mass ratio of aliphatic to aromatic polyamide 2 98 20 80 and the following component (wt.): a mixture of aromatic polyamide with aliphaticity by polycondensation in the environment amide-salt solvent in accordance with U.S. Pat. USA N 4.159.932, C 08 G 69/28, 69/32, 1979 as monomers take

5/6/-amino-2-/n-AMINOPHENYL/benzimidazole

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diaminobenzanilide

,

the dihydrochloride of paraphenylenediamine

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dichlorohydrin terephthalic acid

. The synthesized aromatic copolyamids pair structure had a logarithmic viscositylog.2,77 5,8 DL/g

Synthesis of aromatic copolyamids different compositions is carried out in the same conditions. As an example, presents a synthesis of copolyamid composition 2,5 l; m 7,5; n 90 mol

Dissolve in 5560 wt. hours of dry dimethylacetamide with the addition of 85 wt. h (1,5 ) LiCl and 354 wt. h (3,8 mol. h) dry-picoline in the reactor with stirring in a stream of inert gas (nitrogen) ceiling of 5.60 wt. h (0,025 mol. h) 2-(para-AMINOPHENYL)-5-amino-benzimidazole; 17,025 wt. h (0,075 mol. h) diaminobenzanilide and 162,00 wt. h (0,9 mol. h) dihydrochloride para-phenylenediamine. To obtain high molecular weight polymer, the water content in the reaction mixture should not exceed 0,02 a-picoline take equimolar amount of HCl in the para-phenylenediamine and released during the polycondensation reaction. The solvent with LiCl and a-picoline take based on the content of the polymer 4

The resulting solution is cooled for 10 to 30 minutes to 1H.) powder terephthaloylchloride. After 2 to 3 minutes after adding terephthaloylchloride viscosity of the reaction mass begins to grow rapidly. The reaction continued for a further 30 minutes with stirring and the temperature rises to room. Get a gel-like mass, the polymer of which are planted with water. The polymer was repeatedly washed with water, diluted (0,5-s') and soda solution, water and dried in vacuum at 80 100oC. Get 249,8 wt. h (1 mol. h) copolyamid. The polymer yield is quantitative.

Synthesis of copolyamids other chemical compounds differs from the above only by the fact that they take a different ratio of the diamines. Elemental analysis data of copolyamids, are shown in table 1, confirm their chemical structure.

The strength and modulus of elasticity tensile breaking elongation of the twisted multifilament yarn was determined by a standard method on a tensile testing machine Instron, shimonthebest measured on the corresponding device and characterized by the number of cycles of the double bends with bend angle 90oWith that endured by the filament to break when the load on the filament 12 kgf/mm2. The logarithmic viscosity of hlog.the copolyamids was determined from the relation:

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where the concentration of polymer clay is astora (equal to the ratio of the expiration time of the polymer solution to the expiration time of the solvent), determined in a capillary viscometer at 25oC.

Example 1.

Prepare 20,0 th solution of a mixture of polymers, for which I take to 48.6 g (18.0 wt. ) aromatic copolyamid composition: 2.5 l; m 7,5; n 90log.5,54 DL/g and 5.4 g (2.0 wt.) aliphatic copolyamid composition: 29 m; n 71 log.to 1.0 DL/g and mixed contribute to 216 g (118,0 ml) and 99.8 sulfuric acid (80 wt.). The mixture is stirred using a stirrer for 3 hours at 76 82oC, predominantly 76oS, after which the solution is filtered and obezvozhivani at a temperature of dissolution within 1.5 to 2 hours. From the thus obtained anisotropic 20,0-aqueous spinning solution at 76oWith molded threads by dry-wet method through a 5 mm layer of air in water with a temperature of 10oWith the speed of receiving the threads of 120 m/min at a multiplicity of extrusion jets in the air gap 6 and the use of nozzles with a number of holes 100 and the hole diameter of 0.08 mm Wet the thread take on a bobbin and bobbin washed from acid, neutralize acid residues in strands diluted alkali solution, then the thread is dried at room temperature and wind up to 150 turns/m

The linear density of the yarn, its mechanical properties: tensile strength, ri polymer filaments are shown in table 2 (example 1A). In the comparative example (example 1B) indicators of filaments obtained in the same conditions of 20 aqueous sulfuric acid anisotropic solution of aromatic polyamide without the addition of aliphatic polymer.

Example 2.

Preparation of 20.0-aqueous solution mixture of the polymers and molding the threads operate in the same way as described in example 1, except that take 51,30 g (19.0 wt.) aromatic copolyamid composition: l2,5; 7,5 m; n 90log.5,54 DL/g and 2.70 g (1.0 wt.) aliphatic copolyamid composition: 29 m; n 71log.to 1.0 DL/g and mixed contribute to 216 g (118,0 ml) and 99.8 sulfuric acid (80 wt.). Indicators filaments are shown in table 2.

Example 3.

Preparation of 20.0-aqueous solution mixture of the polymers and molding the threads operate in the same way as described in example 1, except that take 52,92 g (19,6 wt.) aromatic copolyamid composition: l 2,5; 2,5 m; n 95log.5,41 DL/g and 1.08 g (0.4 wt.) aliphatic copolyamid composition: 36,7 m; n 63,3log.to 1.3 DL/g and mixed contribute to 216 g (118,0 ml) 100,2 sulfuric acid (80 wt.). Indicators filaments are shown in table 2.

Example 4.

In the reactor at 60 l prepare a 20-cent solution, which take 8,00 kg (16,0 wt. the ar is composition: 85 m; n 15 slog.to 1.0 DL/g and 40,08 kg (21,9 l) 99,8 sulfuric acid. At the initial stage of dissolution of the polymer, the temperature of the mixture rises from the exothermic reaction of their interaction with sulfuric acid of from 20 to 65 - 70oS, after which the temperature of the solution 75 80oWith support by supplying hot water in the jacket of the apparatus. The composition is stirred under vacuum of 50 mm RT.article during the whole time of preparation of the solution is 4 hours, mainly at a temperature of 75oC. Obtained 20,0 th solution withlog.mixtures of polymers 5,27 DL/g serves to filter and machine molding filament at a temperature of 75oC. Forming the thread carried through the air gap of 7 mm in an aqueous precipitation bath containing 2 sulfuric acid with a temperature of 8oWith the speed of receiving the threads of 85 m/min, filero with the number of holes 300 and a hole diameter of 0.08 mm at a multiplicity of extrusion jets in the space of 8.5. The thread on the molding machine under tension of 2.5 to 4.0 CN/Tex is washed from acid, neutralization of the residual acid and dried at 12 150oWith and accepted after the application of sizing to the cartridge receiving device without twist.log.mixtures of polymers into filaments of 4.7 DL/g Thread to determine LASS="ptx2">

Example 5.

Preparation 22,0-aqueous solution mixture of polymers and the formation of filaments is similar to that described in example 1, except that take 57,88 g (20,9 wt.) aromatic copolyamid composition: 9,5 l; m 90,5log.5,8 DL/g and 3.05 g (1.1 wt.) aliphatic copolyamid composition: 29 m; n 71log.to 1.0 DL/g and mixed contribute to 216 g (118,0 ml) and 99.8 sulfuric acid (78 wt.). Indicators filaments are shown in table 2.

Example 6.

Preparation 22,0-aqueous solution mixture of the polymers and molding the threads operate in the same way as described in example 1, except that take 54,83 g (of 19.8 wt.) aromatic copolyamid composition: l 1,0; 99,0 mlog.of 5.6 DL/g and 6,09 g (2.2 wt.) polyhexamethylenediaminelog.to 1.0 DL/g and mixed contribute to 216 g (118,0 ml) and 99.8 sulfuric acid (78 wt.). Get a 22-cent solution. Indicators filaments are shown in table 2.

Example 7.

Preparation 19,0-aqueous solution mixture of the polymers and molding the threads operate in the same way as described in example 1, except that take 46,93 g (17.6 wt.) aromatic copolyamid composition: l 1,0; 1,0 m; n 98log.5,54 DL/g and of 3.73 g (1.4 wt.) polycaproamidelog.to 1.4 DL/g imovane thread support level 85oC. Indicators of threads are given in table 2.

Example 8.

Prepare 11,0-s ' solution of a mixture of polymers, which take 25,36 g (10,45 wt. ) aromatic copolyamid composition: 2,5 l; m 7,5; n 90log.2,77 DL/g and of 1.33 g (of 0.55 wt.) aliphatic copolyamid composition: 29 m; n 71log.to 1.0 DL/g and mixed contribute to 216 g (118,0 ml) 98,0 sulfuric acid (89 wt.). The mixture is stirred using a stirrer for 3 hours at 45oC. Then the solution is filtered and obezvozhivani for 2 hours at 45oC. Of the thus obtained anisotropic 11,0-aqueous spinning solution at 45oWith molded threads on a wet method using a Spinneret with 100 holes with a hole diameter of 0.07 mm as a precipitation bath take a 15 aqueous solution of sulfuric acid at 40 - 45oC. a Multiplicity of spunbond extrusion jets in a precipitation bath of 2.25. Plastification pulling absent. The speed of receiving the threads on a perforated bobbin 20 m/min, the Yarn is washed with water, neutralized acid residues diluted alkali solution, dried at 100oC, rigged up to 150 turns/m Receive filament linear density of 33.4 Tex. mechanical properties of the filaments are shown in table 2.

The solution for forming the polyamide is consistent sulfuric acid, characterized in that the aromatic polyamide pair of patterns it contains statistical copolyamide patterns

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where l 1-9,5; m 1-99; n 98; NH of the amino group is in position 5 or 6-benzimidazole cycle, and as the aliphatic polyamide homopolyamide patterns

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or their statistical copolyamide when the mass ratio of aliphatic to aromatic polyamide 2:98-20:80 and the following content, wt.

A mixture of aromatic copolyamid with aliphatic 11,0-22,0

Concentrated sulphuric acid Rest

 

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