CN111235677A - Preparation method of high-strength polyester yarn with impact resistance - Google Patents
Preparation method of high-strength polyester yarn with impact resistance Download PDFInfo
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
- C08G63/6854—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6856—Dicarboxylic acids and dihydroxy compounds
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
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Abstract
The invention discloses a preparation method of high-strength polyester yarns with impact resistance, which comprises the following steps: s1, synthesizing diamino methyl terephthalate; step S2, protecting amino functional groups to obtain modified monomers; step S3, taking furandicarboxylic acid, sebacic acid, modified monomer and ethylene glycol as raw materials, and preparing copolyester by adopting an in-situ polymerization method; step S4, obtaining polyester chips; and step S5, spinning the polyester chips and the flame retardant on a melt spinning machine to obtain the high-strength polyester yarn. The invention adopts copolyester as the raw material of the polyester yarn, and the polyester molecular chain not only has benzene ring, so that the fiber has good crease resistance and certain mechanical strength, but also has-NH2The fiber has certain hydrophilic capacity and flexibility by the aid of the polar functional groups, and the moisture absorption and hand feeling of the fiber are improved; at the same time in the fiberThe flame retardant is added in the fiber spinning process, so that the fiber has strong flame retardant performance, and has water washing resistance, so that the flame retardant performance is durable.
Description
Technical Field
The invention belongs to the technical field of fabrics, and particularly relates to a preparation method of high-strength polyester yarns with impact resistance.
Background
The basic component of the terylene is polyethylene terephthalate, which is called polyester fiber (PET) because of the existence of a large amount of ester groups on the molecular chain, the relative molecular weight of the polyester used for the fiber is generally about 18000-25000, the molecular weight of the wool-like terylene is lower, and the molecular weight of the industrial terylene is higher. From the view of the composition of terylene molecules, the terylene is composed of short aliphatic hydrocarbon chains, ester groups, benzene rings and terminal alcoholic hydroxyl groups. Except two terminal alcoholic hydroxyl groups, the terylene fibers have no other polar groups, so the hydrophilicity of the terylene fibers is very poor. The terylene molecule contains about 46 percent of ester groups, the ester groups can be hydrolyzed and thermally cracked at the temperature of more than 200 ℃, the ester groups can be saponified when meeting strong alkali, so that the polymerization degree is reduced, and the common detergent powder with the dosage of less than 100 ℃ has no influence on the terylene; the terylene molecules also contain aliphatic hydrocarbon chains, which can make the terylene molecules have certain flexibility, but because the terylene molecules also contain benzene rings which can not rotate, the terylene macromolecules are basically rigid molecules, and the molecular chains are easy to keep linear. Therefore, the polyester macromolecules are easy to form crystals under the condition, so that the crystallinity and the orientation of the polyester are high.
The high-strength polyester yarn has the characteristics of high strength, good wear resistance, good elasticity and the like, and is a special variety of industrial polyester yarn. The fabric woven by the common polyester filament has the advantages of good strength, smoothness, stiffness, easy washing, quick drying and the like in the clothing performance, but has the defect of poor hygroscopicity and can not meet the requirements of the field of the knitted fabric with the flame retardant function.
Disclosure of Invention
The invention aims to provide a preparation method of high-strength polyester yarn with impact resistance, which adopts copolyester as a raw material of the polyester yarn, wherein the copolyester comprises a modified monomer, furandicarboxylic acid and capric acid, and a polyester molecular chain obtained by blending not only has benzene rings, so that the fiber has good wrinkle resistance and certain mechanical strength, but also has-NH2The fiber has certain hydrophilic capacity and flexibility by the aid of the polar functional groups, and the moisture absorption and hand feeling of the fiber are improved; meanwhile, a flame retardant is added in the fiber spinning process, the flame retardant not only can act from a gas phase and a condensed phase to endow the fiber with stronger flame retardant property, but also has water washing resistance, so that the flame retardant property is durable; the obtained polyester high-strength yarn with impact resistance is suitable for spinning of functional fabrics.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of high-strength polyester yarns with impact resistance comprises the following steps:
step S1, accurately weighing 7.44g of 2, 5-diamino terephthalic acid, placing the 2, 5-diamino terephthalic acid in 60mL of methanol, placing the 2, 5-diamino terephthalic acid in a three-neck flask, slowly dropwise adding 12mL of thionyl chloride under the conditions of introducing nitrogen and ice bath, refluxing at room temperature for 12h, removing redundant methanol and thionyl chloride by rotary evaporation, and collecting the obtained solid;
s2, dissolving the solid obtained in the step S1 in 80mL of chloroform, adding 70mL of tetrahydrofuran solution, stirring uniformly under an ice bath condition, dropwise adding 8.8g of di-tert-butyl dicarbonate, heating to 25 ℃, stirring for 12 hours, removing the organic solvent by rotary evaporation, extracting the reactant with dichloromethane, collecting an organic layer, drying overnight with anhydrous sodium sulfate, filtering the drying agent, and removing the solvent to obtain a modified monomer;
step S3, taking furan dicarboxylic acid, sebacic acid, the modified monomer and ethylene glycol as raw materials, taking tetrabutyl titanate as a catalyst, and preparing copolyester in a polymerization reaction kettle by adopting an in-situ polymerization method;
step S4, according to the solid-liquid ratio of 1 g: 5mL of copolyester is dissolved in trichloromethane, after the copolyester is completely dissolved, trifluoroacetic acid is slowly dropped into the trichloromethane, the mixture is stirred at normal temperature for 30-35min, the solvent is removed by rotary evaporation, the product is dried in vacuum at 100 ℃ for 3h, then the temperature is raised to 120 ℃, and the vacuum drying is continued for 6h, so that dried polyester slices are obtained;
and step S5, spinning the polyester chips and the flame retardant on a melt spinning machine according to a certain mass ratio to obtain the high-strength polyester yarn.
Further, the mass ratio of the furandicarboxylic acid, the sebacic acid, the modified monomer, the ethylene glycol and the tetrabutyl titanate in the step S3 is 6-7:9-10:100:150-160: 1.
Further, the step S3 specifically comprises an esterification stage and a polycondensation stage, wherein the temperature in the reaction kettle is controlled to be 210-250 ℃, the pressure is 0.30-0.40MPa, the pressure is released when the water yield reaches 98% of the theoretical water yield, and the polycondensation stage is started after the pressure release is finished; controlling the temperature in the reaction kettle at 260-280 ℃ and the vacuum degree at 20-60Pa, and after the polycondensation process lasts for 3-4h, breaking the vacuum by nitrogen and discharging to obtain the copolyester.
Further, the dropping amount of trifluoroacetic acid in step S4 was 1/10 of the volume of chloroform.
Further, the mass ratio of the polyester chip to the flame retardant in the step S5 is 100: 2-3.
Further, the flame retardant is prepared by the following method:
(1) dissolving methyl phosphoric acid in deionized water to prepare a methyl phosphoric acid solution with the mass concentration of 20%;
(2) adding 29.2g of lysine into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 30-35g of deionized water, and stirring to dissolve the lysine;
(3) and slowly dripping 90-100mL of methylphosphonic acid aqueous solution into the system within 1h, keeping refluxing for 8h, performing rotary evaporation to remove solvent water, and performing vacuum drying to obtain the flame retardant.
The invention has the beneficial effects that:
the copolyester is used as a raw material of the polyester yarn, the copolyester contains a modified monomer, furan dicarboxylic acid and capric acid, and the furan dicarboxylic acid has a cyclic conjugated system, on one hand, an ether-oxygen bond on a furan ring carries lone pair electrons, so that the polyester yarn has the capability of accepting protons, and the static dissipation effect can be realized through the transfer of internal protons; on the other hand, an ether oxygen bond on the furan ring and water molecules in the air can form a hydrogen bond, so that a layer of water film is formed on the surface of the copolyester, the dissipation rate of surface charges can be accelerated, and the antistatic performance of the copolyester is further improved; in addition, a modified monomer is introduced into the polyester molecule, so that amino groups are further exposed on a molecular chain and have hydrophilicity; moreover, the introduction of the modified monomer also reduces the regularity of the molecular chain of the copolyester, which also enhances the hydrophilic capability of the copolyester; the addition of the long-chain sebacic acid greatly improves the flexibility of a copolyester molecular chain, further improves the impact resistance of the polyester, and can destroy the regularity and symmetry of the molecular chain, so that the amorphous region is increasedIn addition, the hydrophilic capacity of the copolyester is improved, the crystallinity of the polyester is reduced, and the degradability of the polyester is improved; the polyester molecular chain obtained by blending not only has benzene ring (with certain rigidity), so that the fiber has good wrinkle resistance and certain mechanical strength, but also has-NH2The fiber has certain hydrophilic capacity and flexibility by the aid of the polar functional groups, and the moisture absorption and hand feeling of the fiber are improved;
the invention adds the flame retardant in the fiber melt spinning process, and the-OH on the methyl phosphonic acid can be reacted with the-NH on the lysine2and-COOH and forming a polycondensate during continuous reflux, the polycondensate being a flame retardant; the synthesized flame retardant has good char-forming performance, a char layer formed during combustion covers the surface of the material to play a good role in blocking, and the methylphosphonic acid group in the flame retardant has a function of inhibiting flame in a gas phase; the synthesized flame retardant can play a flame retardant role in a gas phase and a condensed phase simultaneously, so that the polyester fiber is endowed with excellent flame retardant property; in addition, unreacted-OH in the flame retardant can react with exposed-NH on the molecular chain of the polyester2Interaction occurs, so that not only can the bonding fastness between the flame retardant and the polyester molecular chain be improved, the flame retardant components on the fiber can not gradually fall off along with washing, the washing resistance of the fiber is improved, but also the dispersion uniformity of the flame retardant on the fiber can be improved, and the flame retardant uniformity of the fiber is improved;
the polyester fibers are prepared by blending the copolyester containing the modified monomer, the furandicarboxylic acid and the capric acid with benzene rings, so that the fibers have good wrinkle resistance and certain mechanical strength, and have-NH2The fiber has certain hydrophilic capacity and flexibility by the aid of the polar functional groups, and the moisture absorption and hand feeling of the fiber are improved; meanwhile, a flame retardant is added in the fiber spinning process, the flame retardant not only can act from a gas phase and a condensed phase to endow the fiber with stronger flame retardant property, but also has water washing resistance, so that the flame retardant property is durable; the obtained polyester high-strength yarn with impact resistance is suitable for spinning of functional fabrics.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
A preparation method of high-strength polyester yarns with impact resistance comprises the following steps:
step S1, accurately weighing 7.44g of 2, 5-diamino terephthalic acid, placing the 2, 5-diamino terephthalic acid in 60mL of methanol, placing the 2, 5-diamino terephthalic acid in a three-neck flask, slowly dropwise adding 12mL of thionyl chloride under the conditions of introducing nitrogen and ice bath, refluxing at room temperature for 12h, removing redundant methanol and thionyl chloride by rotary evaporation, and collecting the obtained solid;
in the step, esterification reaction is carried out on-COOH on the 2, 5-diamino terephthalic acid and methanol under the catalytic action of thionyl chloride to obtain dimethyl diamino terephthalate;
s2, dissolving the solid obtained in the step S1 in 80mL of chloroform, adding 70mL of tetrahydrofuran solution, stirring uniformly under an ice bath condition, dropwise adding 8.8g of di-tert-butyl dicarbonate, heating to 25 ℃, stirring for 12 hours, removing the organic solvent by rotary evaporation, extracting the reactant with dichloromethane, collecting an organic layer, drying overnight with anhydrous sodium sulfate, filtering the drying agent, and removing the solvent to obtain a modified monomer;
in this step, di-tert-butyl dicarbonate is used to protect-NH on the dimethyl diamino terephthalate2Functional groups to obtain modified monomers;
s3, taking furandicarboxylic acid, sebacic acid, the modified monomer and ethylene glycol as raw materials, taking tetrabutyl titanate as a catalyst, preparing polyester in a polymerization reaction kettle by adopting an in-situ polymerization method, specifically comprising an esterification stage and a polycondensation stage, controlling the temperature in the reaction kettle to be 210-250 ℃, the pressure to be 0.30-0.40MPa, starting pressure relief when the water yield reaches 98% of the theoretical water yield, and entering the polycondensation stage after the pressure relief is finished; controlling the temperature in the reaction kettle to be 260-280 ℃, the vacuum degree to be 20-60Pa, breaking the vacuum by nitrogen after the polycondensation process lasts for 3-4h, and discharging to obtain copolyester;
the mass ratio of the furan dicarboxylic acid to the sebacic acid to the modified monomer to the ethylene glycol to the tetrabutyl titanate is 6-7:9-10:100:150-160: 1;
step S4, according to the solid-liquid ratio of 1 g: 5mL of copolyester is dissolved in trichloromethane, after the copolyester is completely dissolved, trifluoroacetic acid (the dropping amount of the trifluoroacetic acid is 1/10 of the volume of the trichloromethane) is slowly dropped, the mixture is stirred at normal temperature for 30-35min, then the solvent is removed by rotary evaporation, the product is dried in vacuum at 100 ℃ for 3h, then the temperature is raised to 120 ℃, and the vacuum drying is continued for 6h, so that dried polyester slices are obtained;
removing amino protecting groups by adopting trifluoroacetic acid;
step S5, spinning the polyester chips and the flame retardant on a melt spinning machine according to a certain mass ratio to obtain the high-strength polyester yarn;
the mass ratio of the polyester chip to the flame retardant is 100: 2-3;
furan dicarboxylic acid has a cyclic conjugated system, on one hand, ether-oxygen bonds on furan rings carry lone-pair electrons, so that the furan dicarboxylic acid has the capability of accepting protons, and the electrostatic dissipation effect can be realized through the transfer of internal protons; on the other hand, an ether oxygen bond on the furan ring and water molecules in the air can form a hydrogen bond, so that a layer of water film is formed on the surface of the copolyester, the dissipation rate of surface charges can be accelerated, and the antistatic performance of the copolyester is further improved; in addition, a modified monomer is introduced into the polyester molecule, so that amino groups are further exposed on a molecular chain and have hydrophilicity; moreover, the introduction of the modified monomer also reduces the regularity of the molecular chain of the copolyester, which also enhances the hydrophilic capability of the copolyester; the addition of the long-chain sebacic acid greatly improves the flexibility of a copolyester molecular chain, further improves the impact resistance of the polyester, can destroy the regularity and symmetry of the molecular chain, increases an amorphous region, improves the hydrophilic capability of the copolyester, reduces the crystallinity of the polyester, and improves the degradability of the polyester; the polyester molecular chain obtained by blending not only has benzene rings (has certain rigidity)) The fiber has good wrinkle resistance and certain mechanical strength, and has-NH2The fiber has certain hydrophilic capacity and flexibility by the aid of the polar functional groups, and the moisture absorption and hand feeling of the fiber are improved;
the flame retardant is prepared by the following method:
(1) dissolving methyl phosphoric acid in deionized water to prepare a methyl phosphoric acid solution with the mass concentration of 20%;
(2) adding 29.2g of lysine into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 30-35g of deionized water, and stirring to dissolve the lysine;
(3) slowly dripping 90-100mL of methylphosphonic acid aqueous solution into the system within 1h, keeping refluxing for 8h, performing rotary evaporation to remove solvent water, and performing vacuum drying to obtain the flame retardant;
the-OH group on methylphosphonic acid can react with the-NH group on lysine2and-COOH and forming a polycondensate during continuous reflux, the polycondensate being a flame retardant; the synthesized flame retardant has good char-forming performance, a char layer formed during combustion covers the surface of the material to play a good role in blocking, and the methylphosphonic acid group in the flame retardant has a function of inhibiting flame in a gas phase; the synthesized flame retardant can play a flame retardant role in a gas phase and a condensed phase simultaneously, so that the polyester fiber is endowed with excellent flame retardant property; in addition, unreacted-OH in the flame retardant can react with exposed-NH on the molecular chain of the polyester2The interaction occurs, so that not only can the bonding fastness between the flame retardant and the polyester molecular chain be improved, the flame retardant components on the fiber can not gradually fall off along with washing, the washing resistance of the fiber is improved, but also the dispersion uniformity of the flame retardant on the fiber can be improved, and the flame retardant uniformity of the fiber is improved.
Example 1
A preparation method of high-strength polyester yarns with impact resistance comprises the following steps:
step S1, accurately weighing 7.44g of 2, 5-diamino terephthalic acid, placing the 2, 5-diamino terephthalic acid in 60mL of methanol, placing the 2, 5-diamino terephthalic acid in a three-neck flask, slowly dropwise adding 12mL of thionyl chloride under the conditions of introducing nitrogen and ice bath, refluxing at room temperature for 12h, removing redundant methanol and thionyl chloride by rotary evaporation, and collecting the obtained solid;
s2, dissolving the solid obtained in the step S1 in 80mL of chloroform, adding 70mL of tetrahydrofuran solution, stirring uniformly under an ice bath condition, dropwise adding 8.8g of di-tert-butyl dicarbonate, heating to 25 ℃, stirring for 12 hours, removing the organic solvent by rotary evaporation, extracting the reactant with dichloromethane, collecting an organic layer, drying overnight with anhydrous sodium sulfate, filtering the drying agent, and removing the solvent to obtain a modified monomer;
s3, taking furandicarboxylic acid, sebacic acid, the modified monomer and ethylene glycol as raw materials, taking tetrabutyl titanate as a catalyst, preparing polyester in a polymerization reaction kettle by adopting an in-situ polymerization method, specifically comprising an esterification stage and a polycondensation stage, controlling the temperature in the reaction kettle to be 210 ℃ and the pressure to be 0.30MPa, starting pressure relief when the water yield reaches 98% of the theoretical water yield, and entering the polycondensation reaction stage after the pressure relief is finished; controlling the temperature in the reaction kettle at 260 ℃, the vacuum degree of 20Pa, breaking the vacuum by nitrogen and discharging after the polycondensation process lasts for 3 hours to obtain copolyester;
the mass ratio of furan dicarboxylic acid, sebacic acid, modified monomer, ethylene glycol and tetrabutyl titanate is 6:9:100: 150: 1;
step S4, according to the solid-liquid ratio of 1 g: 5mL of copolyester is dissolved in trichloromethane, after the copolyester is completely dissolved, trifluoroacetic acid (the dropping amount of the trifluoroacetic acid is 1/10 of the volume of the trichloromethane) is slowly dropped, the mixture is stirred at normal temperature for 30min, the solvent is removed by rotary evaporation, the product is dried in vacuum at 100 ℃ for 3h, then the temperature is raised to 120 ℃, and the vacuum drying is continued for 6h, so that dried polyester slices are obtained;
removing amino protecting groups by adopting trifluoroacetic acid;
and step S5, spinning the polyester chips and the flame retardant on a melt spinning machine according to a certain mass ratio to obtain the high-strength polyester yarn.
Example 2
A preparation method of high-strength polyester yarns with impact resistance comprises the following steps:
step S1, accurately weighing 7.44g of 2, 5-diamino terephthalic acid, placing the 2, 5-diamino terephthalic acid in 60mL of methanol, placing the 2, 5-diamino terephthalic acid in a three-neck flask, slowly dropwise adding 12mL of thionyl chloride under the conditions of introducing nitrogen and ice bath, refluxing at room temperature for 12h, removing redundant methanol and thionyl chloride by rotary evaporation, and collecting the obtained solid;
s2, dissolving the solid obtained in the step S1 in 80mL of chloroform, adding 70mL of tetrahydrofuran solution, stirring uniformly under an ice bath condition, dropwise adding 8.8g of di-tert-butyl dicarbonate, heating to 25 ℃, stirring for 12 hours, removing the organic solvent by rotary evaporation, extracting the reactant with dichloromethane, collecting an organic layer, drying overnight with anhydrous sodium sulfate, filtering the drying agent, and removing the solvent to obtain a modified monomer;
s3, taking furandicarboxylic acid, sebacic acid, the modified monomer and ethylene glycol as raw materials, taking tetrabutyl titanate as a catalyst, preparing polyester in a polymerization reaction kettle by adopting an in-situ polymerization method, specifically comprising an esterification stage and a polycondensation stage, controlling the temperature in the reaction kettle to be 230 ℃ and the pressure to be 0.35MPa, starting pressure relief when the water yield reaches 98% of the theoretical water yield, and entering the polycondensation reaction stage after the pressure relief is finished; controlling the temperature in the reaction kettle to be 270 ℃, the vacuum degree to be 40Pa, breaking the vacuum by nitrogen and discharging after the polycondensation process lasts for 3.5 hours to obtain copolyester;
the mass ratio of furan dicarboxylic acid, sebacic acid, modified monomer, ethylene glycol and tetrabutyl titanate is 6.5:9.5:100: 155: 1;
step S4, according to the solid-liquid ratio of 1 g: 5mL of copolyester is dissolved in trichloromethane, after the copolyester is completely dissolved, trifluoroacetic acid (the dropping amount of the trifluoroacetic acid is 1/10 of the volume of the trichloromethane) is slowly dropped, the mixture is stirred at normal temperature for 35min, the solvent is removed by rotary evaporation, the product is dried in vacuum at 100 ℃ for 3h, then the temperature is raised to 120 ℃, and the vacuum drying is continued for 6h, so that dried polyester slices are obtained;
removing amino protecting groups by adopting trifluoroacetic acid;
and step S5, spinning the polyester chips and the flame retardant on a melt spinning machine according to a certain mass ratio to obtain the high-strength polyester yarn.
Example 3
A preparation method of high-strength polyester yarns with impact resistance comprises the following steps:
step S1, accurately weighing 7.44g of 2, 5-diamino terephthalic acid, placing the 2, 5-diamino terephthalic acid in 60mL of methanol, placing the 2, 5-diamino terephthalic acid in a three-neck flask, slowly dropwise adding 12mL of thionyl chloride under the conditions of introducing nitrogen and ice bath, refluxing at room temperature for 12h, removing redundant methanol and thionyl chloride by rotary evaporation, and collecting the obtained solid;
s2, dissolving the solid obtained in the step S1 in 80mL of chloroform, adding 70mL of tetrahydrofuran solution, stirring uniformly under an ice bath condition, dropwise adding 8.8g of di-tert-butyl dicarbonate, heating to 25 ℃, stirring for 12 hours, removing the organic solvent by rotary evaporation, extracting the reactant with dichloromethane, collecting an organic layer, drying overnight with anhydrous sodium sulfate, filtering the drying agent, and removing the solvent to obtain a modified monomer;
s3, taking furan dicarboxylic acid, sebacic acid, the modified monomer and ethylene glycol as raw materials, taking tetrabutyl titanate as a catalyst, preparing polyester in a polymerization reaction kettle by adopting an in-situ polymerization method, specifically comprising an esterification stage and a polycondensation stage, controlling the temperature in the reaction kettle to be 250 ℃ and the pressure to be 0.40MPa, starting pressure relief when the water yield reaches 98% of the theoretical water yield, and entering the polycondensation reaction stage after the pressure relief is finished; controlling the temperature in the reaction kettle to be 280 ℃, the vacuum degree to be 60Pa, breaking the vacuum by nitrogen and discharging after the polycondensation process lasts for 4 hours to obtain copolyester;
the mass ratio of furan dicarboxylic acid, sebacic acid, modified monomer, ethylene glycol and tetrabutyl titanate is 7:10:100: 160: 1;
step S4, according to the solid-liquid ratio of 1 g: 5mL of copolyester is dissolved in trichloromethane, after the copolyester is completely dissolved, trifluoroacetic acid (the dropping amount of the trifluoroacetic acid is 1/10 of the volume of the trichloromethane) is slowly dropped, the mixture is stirred at normal temperature for 35min, the solvent is removed by rotary evaporation, the product is dried in vacuum at 100 ℃ for 3h, then the temperature is raised to 120 ℃, and the vacuum drying is continued for 6h, so that dried polyester slices are obtained;
removing amino protecting groups by adopting trifluoroacetic acid;
and step S5, spinning the polyester chips and the flame retardant on a melt spinning machine according to a certain mass ratio to obtain the high-strength polyester yarn.
Comparative example 1
The furan dicarboxylic acid raw material in the copolyester raw material of example 1 is removed, and the rest raw materials and the preparation process are unchanged.
Comparative example 2
The decanoic acid material in the copolyester raw material of example 1 was removed, and the rest of the raw materials and the preparation process were unchanged.
Comparative example 3
And spinning the polyethylene terephthalate and the flame retardant through a melt spinning machine to obtain the polyester yarn.
Comparative example 4
And spinning the polyethylene terephthalate by a melt spinning machine to obtain the polyester yarn.
Testing the mechanical property by referring to GB/T14344-2003; testing the antistatic performance by using a fiber specific resistance tester; testing the flame retardant property according to FZ/T50016-2011, and testing the water absorption rate according to GB/T21655.1-2008; the test results are given in the following table:
as can be seen from the above table, the breaking strength of the fiber prepared in the examples 1 to 3 is 2.5 to 2.6, and the impact strength is, which shows that the polyester fiber yarn prepared by the invention has high mechanical property, high impact resistance and high strength; the volume specific resistance of the fibers prepared in the examples 1 to 3 is 9.5 to 9.7, which shows that the fibers prepared by the invention have good antistatic property; the fibers prepared in the embodiments 1 to 3 have the limiting oxygen index LOI of 43 to 44 percent and the carbon residue at 450 ℃ of 35.9 to 36.7 percent, which shows that the polyester yarns prepared by the invention have higher flame retardant property, and the LOI value after 100 times of washing has small reduction amplitude (1 to 2), which shows that the flame retardant property of the fibers prepared by the invention has higher washing resistance; the water absorption of the polyester yarn prepared in the embodiments 1-3 is 120-122%, which shows that the polyester yarn prepared by the invention has certain moisture absorption performance; in comparison with comparative example 1, illustrating the participation of furandicarboxylic acid in the copolymerization of polyester, it can be mentionedThe antistatic property of the high polyester fiber; compared with comparative example 2, the flexibility of the polyester can be improved by the participation of the capric acid in the copolymerization of the polyester; comparison with comparative example 3 shows that the modified monomer of the present invention can provide hydrophilic-NH2The functional group improves the water absorption of the polyester yarn, and the flame retardant can react with-NH on the polyester molecule2And the water resistance of the flame retardant is improved through interaction.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (6)
1. The preparation method of the high-strength polyester yarn with impact resistance is characterized by comprising the following steps of:
step S1, accurately weighing 7.44g of 2, 5-diamino terephthalic acid, placing the 2, 5-diamino terephthalic acid in 60mL of methanol, placing the 2, 5-diamino terephthalic acid in a three-neck flask, slowly dropwise adding 12mL of thionyl chloride under the conditions of introducing nitrogen and ice bath, refluxing at room temperature for 12h, removing redundant methanol and thionyl chloride by rotary evaporation, and collecting the obtained solid;
s2, dissolving the solid obtained in the step S1 in 80mL of chloroform, adding 70mL of tetrahydrofuran solution, stirring uniformly under an ice bath condition, dropwise adding 8.8g of di-tert-butyl dicarbonate, heating to 25 ℃, stirring for 12 hours, removing the organic solvent by rotary evaporation, extracting the reactant with dichloromethane, collecting an organic layer, drying overnight with anhydrous sodium sulfate, filtering the drying agent, and removing the solvent to obtain a modified monomer;
step S3, taking furan dicarboxylic acid, sebacic acid, the modified monomer and ethylene glycol as raw materials, taking tetrabutyl titanate as a catalyst, and preparing copolyester in a polymerization reaction kettle by adopting an in-situ polymerization method;
step S4, according to the solid-liquid ratio of 1 g: 5mL of copolyester is dissolved in trichloromethane, after the copolyester is completely dissolved, trifluoroacetic acid is slowly dropped into the trichloromethane, the mixture is stirred at normal temperature for 30-35min, the solvent is removed by rotary evaporation, the product is dried in vacuum at 100 ℃ for 3h, then the temperature is raised to 120 ℃, and the vacuum drying is continued for 6h, so that dried polyester slices are obtained;
and step S5, spinning the polyester chips and the flame retardant on a melt spinning machine according to a certain mass ratio to obtain the high-strength polyester yarn.
2. The method as claimed in claim 1, wherein the mass ratio of the furandicarboxylic acid, the sebacic acid, the modified monomer, the ethylene glycol and the tetrabutyl titanate in the step S3 is 6-7:9-10:100:150-160: 1.
3. The method as claimed in claim 1, wherein the step S3 specifically includes an esterification step and a polycondensation step, the temperature in the reaction kettle is controlled to be 250 ℃ and the pressure is controlled to be 0.30-0.40MPa, the pressure is released when the water yield reaches 98% of the theoretical water yield, and the step S3 enters the polycondensation step after the pressure release; controlling the temperature in the reaction kettle at 260-280 ℃ and the vacuum degree at 20-60Pa, and after the polycondensation process lasts for 3-4h, breaking the vacuum by nitrogen and discharging to obtain the copolyester.
4. The method for preparing the high-tenacity polyester yarn with impact resistance according to claim 1, wherein the dropping amount of the trifluoroacetic acid in the step S4 is 1/10 of the volume of the trichloromethane.
5. The method for preparing the high-tenacity polyester yarn with impact resistance according to claim 1, wherein the mass ratio of the polyester chip to the flame retardant in the step S5 is 100: 2-3.
6. The method for preparing the high-tenacity polyester yarn with impact resistance according to claim 1, wherein the flame retardant is prepared by the following steps:
(1) dissolving methyl phosphoric acid in deionized water to prepare a methyl phosphoric acid solution with the mass concentration of 20%;
(2) adding 29.2g of lysine into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, adding 30-35g of deionized water, and stirring to dissolve the lysine;
(3) and slowly dripping 90-100mL of methylphosphonic acid aqueous solution into the system within 1h, keeping refluxing for 8h, performing rotary evaporation to remove solvent water, and performing vacuum drying to obtain the flame retardant.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114737384A (en) * | 2022-06-13 | 2022-07-12 | 江苏恒力化纤股份有限公司 | Preparation method of polyester simulated silk fabric with lasting flame retardance |
| CN115246924A (en) * | 2021-06-02 | 2022-10-28 | 四川大学 | Biodegradable furan group-containing copolyester and preparation and spinning methods thereof |
| CN116334840A (en) * | 2023-03-23 | 2023-06-27 | 扬州阿特兰新材料有限公司 | Double-layer composite fiber material and preparation method thereof |
-
2020
- 2020-03-20 CN CN202010202757.4A patent/CN111235677A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115246924A (en) * | 2021-06-02 | 2022-10-28 | 四川大学 | Biodegradable furan group-containing copolyester and preparation and spinning methods thereof |
| CN115246924B (en) * | 2021-06-02 | 2024-04-12 | 四川大学 | Biodegradable furan group-containing copolyester and preparation and spinning methods thereof |
| CN114737384A (en) * | 2022-06-13 | 2022-07-12 | 江苏恒力化纤股份有限公司 | Preparation method of polyester simulated silk fabric with lasting flame retardance |
| CN116334840A (en) * | 2023-03-23 | 2023-06-27 | 扬州阿特兰新材料有限公司 | Double-layer composite fiber material and preparation method thereof |
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