CN109137130B - Preparation method of mould-proof high-strength polyester yarn - Google Patents
Preparation method of mould-proof high-strength polyester yarn Download PDFInfo
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- CN109137130B CN109137130B CN201810981704.XA CN201810981704A CN109137130B CN 109137130 B CN109137130 B CN 109137130B CN 201810981704 A CN201810981704 A CN 201810981704A CN 109137130 B CN109137130 B CN 109137130B
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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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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/547—Hydroxy compounds containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/52—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
- C08G63/54—Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation the acids or hydroxy compounds containing carbocyclic rings
- C08G63/553—Acids or hydroxy compounds containing cycloaliphatic rings, e.g. Diels-Alder adducts
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/78—Preparation processes
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Abstract
The invention discloses a preparation method of mildew-proof polyester high-strength yarn, which specifically comprises the following steps: s1, synthesizing dipentene-4-methyl succinate; s2, synthesizing isopentenol formate; s3, synthesizing bisabolol derivatives through methyl dipentene-4-succinate and prenol formate; s4, synthesizing mildew-proof polyester: carrying out esterification polycondensation on the bisabolol derivative and terephthalyl alcohol to obtain mildew-proof polyester; s5, preparing the mildew-proof polyester high-strength yarn: adding the mildew-proof polyester, a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, then performing melt filtration, liquid phase tackifying, extrusion through a spinneret orifice to form trickle, side-blowing cooling, oiling of strand silk, and winding forming to obtain the mildew-proof polyester high-strength yarn; the method is scientific and reasonable, and the prepared mildew-proof polyester fabric has excellent mildew-proof and bacteriostatic effects, good air permeability and moisturizing performance, good skin touch and soft hand feeling, and improves the wearing comfort.
Description
Technical Field
The invention belongs to the technical field of fabrics, and particularly relates to a preparation method of mildew-proof high-strength polyester yarns.
Background
The textile can absorb various nutrient substances in the air, under the environment of proper temperature and humidity, microorganisms inhabiting the textile can propagate and spread in a large quantity, secretion is generated, odor substances such as ammonia and the like are brought, or bacterial plaque is generated on the textile, the mildew and rot of the textile are serious, most bacteria can secrete various pigments, so that the textile is stained with various color spots such as red, blue, purple, black and the like, and the after-finishing effect and the quality of finished products are seriously influenced. Harmful microorganisms can rapidly reproduce under proper environmental conditions, spread diseases and affect the physical health of people. The textiles are easy to become brittle and even age after being mildewed. With the development of socioeconomic and the improvement of living standard, new market demands are generated, and consumers expect that textiles have the antibacterial and mildewproof functions so as to meet the needs of civilized, clean and comfortable environmental life.
The basic component of terylene is polyethylene glycol terephthalate with molecular formula HO-H2C-H2C-O[-OC-Ph-COOCH2CH2O-]n, polyester fiber (PET) because of the existence of a large number of ester groups on the molecular chain, the chemical structural formula of the long chain molecule is H (OCH)2CCOCO)NOCH2CH2OH, the relative molecular weight of polyester used for fibers is generally about 18000-25000, the molecular weight of the wool-like polyester is lower, and the molecular weight of the industrial polyester is higher. In practice, small amounts of monomers and oligomers are also present. These oligomers have a relatively low degree of polymerization and are present in cyclic form. The polyethylene terephthalate may be prepared from terephthalic acid (PTA) and Ethylene Glycol (EG)) Ethylene terephthalate 9BHET) is prepared by a direct esterification method and then condensed.
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, easiness in washing, quick drying and the like in the clothes making performance, but has the defects of hard hand feeling, poor touch feeling, soft luster, poor air permeability, poor moisture absorption and the like.
The organic antibacterial agent mainly comprises quaternary ammonium salts, biguanides, alcohols, phenols, aldehydes, organic acids, esters, peroxides, halogens, imidazoles, thiazoles, pyridines and the like. At present, quaternary ammonium salt organic bactericides are most widely used internationally and can be introduced into terylene in a blending mode, but in most cases, quaternary ammonium salt-containing solution is used for carrying out post-treatment such as impregnation and the like on terylene fabrics to endow the terylene fabrics with antibacterial performance, but the impregnated quaternary ammonium salt antibacterial mildewcide has poor washing fastness, and after multiple times of washing, the mildewproof and antibacterial performance of the terylene fabrics gradually deteriorates along with the loss of the quaternary ammonium salt antibacterial mildewcide, and finally, the antibacterial and mildewproof performance in the market is achieved.
Bisabolol (Bisabolol), also called Bisabolol and ledebouriella seselol, is one of the more sesquiterpene compounds existing in nature; the bisabolol has the efficacies of diminishing inflammation, preventing mildew and sterilizing, healing ulcer, dissolving gallstone and the like, has light and pleasant fragrance, and is also a fixative with better stability.
Bisabolol can protect and heal the skin, prevent the skin from being affected by daily tension, accelerate the healing process of the skin, is particularly suitable for sensitive skin and body, is widely applied to the formulation of personal care (skin and body care solution, after-shave and after-sun care products), and has anti-inflammatory, natural and safe characteristics, so that the bisabolol becomes a common active ingredient for skin care. International annual demand for use on personal care products only reaches over 400 t. As demand increases, the amount of pure natural extract is just as unsatisfactory for the market.
Disclosure of Invention
The invention aims to provide a preparation method of the mould-proof high-strength polyester yarn, the prepared mould-proof high-strength polyester yarn has excellent mould-proof and bacteriostatic effects, and the prepared fabric has good air permeability and moisture retention performance, good skin touch feeling and soft hand feeling, reduces the uncomfortable feeling of sensitive skin and improves the wearing comfort.
The technical problems to be solved are as follows:
1. the mould-proof and bacteriostatic performance of the polyester fabric is enhanced, and the polyester fabric still has good mould-proof and bacteriostatic effects after being washed;
2. the existing terylene fabric has poor air permeability and hygroscopicity;
3. the existing polyester fabric has hard hand feeling, poor touch feeling and not soft luster.
The purpose of the invention can be realized by the following technical scheme:
the preparation method of the mould-proof polyester high-strength yarn specifically comprises the following steps:
s1 synthesis of methyl dipentene-4-succinate
Adding dipentene 1, dimethyl fumarate 2 and catalyst iodine into a high-pressure reaction kettle, introducing nitrogen to replace air in the high-pressure reaction kettle, heating in a closed manner, and preserving heat for 1h to obtain dipentene-4-methyl succinate 3;
the dipentene and the methyl succinate are used as raw materials, high-pressure reaction is adopted, the methyl succinate is introduced into the dipentene, the reaction time is shortened, and the reaction efficiency is improved;
s2, synthesis of prenyl 6 alcohol ester
Adding the prenol 4 and the formic acid 5 into a reaction bottle, and stirring and reacting for 5 hours at 40 ℃ to obtain prenol formate 6;
the mol ratio of the pentenol 4 to the formic acid 5 is 1:2-3, so that the amount of the formic acid is increased, the complete reaction of the isopentenol is facilitated, and the generation rate of the prenol formate can be increased;
s3 synthesis of bisabolol derivatives
Adding the dipentene-4-methyl succinate 3 prepared in the step S1 into the reaction bottle in the step S2, adding dichloromethane and sulfamic acid, stirring at 60-65 ℃, carrying out condensation reaction on the dipentene-4-methyl succinate 3 and isopentenol formate 6 for 4-5 hours to synthesize an intermediate 7, adding a small amount of water, continuing stirring at 80 ℃ for 1-2 hours, and carrying out hydrolysis reaction on the intermediate 7 in acid solution to obtain a bisabolol derivative 8;
under the action of sulfamic acid as an acid catalyst, dipentene-4-methyl succinate and isopentenol formate are subjected to condensation reaction to generate an intermediate 7, the intermediate 7 is hydrolyzed to obtain a bisabolol derivative, and the bisabolol derivative contains bisabolol active mildew-proof and bacteriostatic units, is a mild mildew-proof bacteriostatic agent and has excellent mildew-proof and bacteriostatic effects;
s4 synthetic mildew-proof polyester
Adding bisabolol derivative 8, terephthalyl alcohol 9 and catalyst ethylene glycol antimony into a stainless steel reaction kettle, introducing nitrogen for protection, heating to 245-class 255 ℃ under the pressure of 0.2MPa, heating to 268-class 275 ℃ until the esterification water yield is 98-100% of the theoretical water yield, slowly vacuumizing for pre-polycondensation, reducing the pressure to 60Pa within 25-30min, and continuing the polycondensation reaction for 1.5h to obtain the mildew-proof polyester 10;
the bisabolol derivative is prepared by introducing two carboxylic acids on the basis of bisabolol, carrying out esterification and polycondensation with terephthalyl alcohol to form polyester, wherein active groups containing mildew-proof and antibacterial properties are connected inside the polyester in a chemical bond mode, so that the prepared polyester fabric is not easy to fall off when being cleaned, and the mildew-proof and antibacterial properties of the polyester fabric can be preserved for a long time;
as the conventional polyethylene terephthalate has no other polar groups except two terminal alcoholic hydroxyl groups and ester group-COO-with small polarity in polyester molecules, the polyester has extremely poor hydrophilicity, and although the polyester molecules contain aliphatic hydrocarbon chain-OCH with strong internal rotation capacity2CH2O-, enables the polyester molecules to have certain flexibility, but because the polyester macromolecules also contain rigid groups-OC-Ar-CO- (Ar represents benzene rings), the polyester macromolecules can only vibrate as a whole, so the polyester macromolecules are basically rigid molecules, molecular chains are easy to keep linear, and the defects of hard handfeel, poor touch feeling, soft luster, poor air permeability, poor hygroscopicity and the like of the polyester fabric are caused. The bisabolol mildew-proof antibacterial active group introduced into the mildew-proof polyester increases the aliphatic hydrocarbon chain and-OH polar group of the polyester, and increases the flexibility and hydrophilicity of the polyester, thereby increasing the air permeability and hygroscopicity of the mildew-proof polyester fabric; simultaneous mildewproof-OCH in polyester2-Ar-CH2OH keeps the rigidity of the terylene, the modified polyester still has good wrinkle resistance and certain mechanical strength, and the mildew-proof polyester does not contain a symmetrical structure, so that the linear form cannot be maintained, the rigidity of the terylene is reduced, and the flexibility of the mildew-proof polyester is increased, thereby increasing the rigidity of the mildew-proof polyesterThe hand feeling, the touch feeling and the luster of the moldy polyester fabric are soft;
s5 preparation of mould-proof polyester high-strength yarn
Adding the mildew-proof polyester 10, a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, then performing melt filtration, liquid phase tackifying, extrusion through a spinneret orifice to form trickle, side-blowing cooling, oiling on strand silk, and winding and forming to obtain the mildew-proof polyester high-strength yarn.
Further, in the synthesis of the dipentene-4-methyl succinate in the step S1, the molar ratio of the dipentene 1, the dimethyl fumarate 2 and the catalyst iodine is 1:1.0-1.2: 0.001-0.0015.
Further, the temperature rise in step S1 is carried out at a rate of 15 ℃/min to 250 ℃.
Further, in the step S2 of synthesizing the prenyl alcohol formate, the molar ratio of the prenyl alcohol 4 to the formic acid 5 is 1: 4-5.
Further, in the step S3 of synthesizing the bisabolol derivative, the molar ratio of the methyl dipentene-4-succinate 3 to the prenyl alcohol formate 6 is 1: 1.2-1.5.
Further, in the step S3 of synthesizing the bisabolol derivative, the amount of dichloromethane added is 1/3 to 2/3 of the total volume of the dipentene-4-succinic acid methyl ester 3 and the prenyl alcohol formate 6 described in the step S3; the addition amount of sulfamic acid is 6.2 to 6.8 of the total mass of the methyl dipentene-4-succinate 3 and the isopentenol formate 6 in the step S3; the addition of a small amount of water is 20-25% of the volume of the added dichloromethane.
Further, in the step S4 of synthesizing the mildew-proof polyester, the molar ratio of the bisabolol derivative, the terephthalic acid and the catalyst ethylene glycol antimony is 1:2.3-3: 0.001-0.0015.
Further, in the step S4 of synthesizing the mildew-proof polyester, the viscosity of the mildew-proof polyester 10 is 0.95 to 1.23 dl/g.
Further, in the step S4 of synthesizing the mildew-proof polyester, n in the mildew-proof polyester 10 is 110-135.
Further, in the step S5 preparation of the mould-proof polyester high-strength yarn, the mass ratio of the mould-proof polyester 10 to the dispersing agent to the defoaming agent to the softening agent is 100:2-3:0.5-1: 1-2.
The invention has the beneficial effects that:
(1) under the action of sulfamic acid as an acid catalyst, dipentene-4-methyl succinate and isopentenol formate are subjected to condensation reaction to generate an intermediate 7, the intermediate 7 is hydrolyzed to obtain a bisabolol derivative, and the bisabolol derivative contains bisabolol active mildew-proof and bacteriostatic units, is a mild mildew-proof bacteriostatic agent and has excellent mildew-proof and bacteriostatic effects; the bisabolol derivative is prepared by introducing two carboxylic acids on the basis of bisabolol, carrying out esterification and polycondensation with terephthalyl alcohol to form polyester, wherein active groups containing mildew-proof and antibacterial properties are connected inside the polyester in a chemical bond mode, so that the prepared polyester fabric is not easy to fall off when being cleaned, and the mildew-proof and antibacterial properties of the polyester fabric can be preserved for a long time; the problem that the conventional polyester fabric is poor in mould-proof and bacteriostatic effects after being cleaned is solved;
(2) the bisabolol mildew-proof antibacterial active group introduced into the mildew-proof polyester increases the aliphatic hydrocarbon chain and-OH polar group of the polyester, and increases the flexibility and hydrophilicity of the polyester, thereby increasing the air permeability and hygroscopicity of the mildew-proof polyester fabric; the defects of poor air permeability and poor moisture absorption of the existing polyester fabric are overcome;
(3) -OCH in mildew-resistant polyesters2-Ar-CH2OH keeps the rigidity of the polyester, the modified polyester still has good crease resistance and certain mechanical strength, and as the mildew-proof polyester does not contain a symmetrical structure, the linear shape cannot be maintained, so that the rigidity of the polyester is reduced, and the flexibility of the mildew-proof polyester is increased, thereby increasing the soft hand feeling, touch feeling and luster of the mildew-proof polyester fabric; the defects of hard hand feeling, poor touch feeling and soft luster of the conventional polyester fabric are overcome.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1
The preparation method of the mould-proof polyester high-strength yarn specifically comprises the following steps:
s1 synthesis of dipentene-4-methyl succinate 3
Adding 120mol of dipentene 1, 130mol of dimethyl fumarate 2 and 0.15mol of catalyst iodine into a high-pressure reaction kettle, introducing nitrogen to replace air in the high-pressure reaction kettle, heating in a closed manner to 250 ℃ at the speed of 15 ℃/min, and preserving heat for 1h to obtain dipentene-4-methyl succinate 3, wherein the yield is 98.7%;
s2, synthesis of prenyl 6 alcohol ester
Adding 150mol of isopentenol 4 and 600mol of formic acid 5 into a reaction bottle, and stirring and reacting for 4 hours at 45 ℃ to obtain isopentenol formate 6, wherein the yield is 98.9%; (ii) a
S3 synthesis of bisabolol derivative 8
Adding the dipentene-4-methyl succinate 3 prepared in the step S1 into the reaction bottle in the step S2, adding dichloromethane and sulfamic acid, stirring at 60 ℃, carrying out condensation reaction on the dipentene-4-methyl succinate 3 and isopentenol formate 6 for 4 hours to synthesize an intermediate 7, adding a small amount of water, continuing stirring at 80 ℃ for 1 hour, and carrying out hydrolysis reaction on the intermediate 7 in an acid solution to obtain a bisabolol derivative 8, wherein the yield is 93.5%; the adding amount of the dichloromethane is 2/3 of the total volume of the dipentene-4-methyl succinate 3 and the isopentenol formate 6; the addition amount of sulfamic acid is 6.5 of the total mass of the dipentene-4-methyl succinate 3 and the isopentenol formate 6; the addition of a small amount of water accounts for 20 percent of the volume of the added dichloromethane;
the mass spectrum result of the target product 8 is as follows: HRMS m/z (ESI)+)calcd for C19H30O5([M]+),338.213,found 338.2161。
S4 synthetic mildew-proof polyester
Adding 8 parts of bisabolol derivative, 300mol of terephthalyl alcohol 9 and 0.18mol of catalyst ethylene glycol antimony into a stainless steel reaction kettle, introducing nitrogen for protection, heating to 250 ℃ under the pressure of 0.2MPa, heating to 275 ℃ until the esterification water yield is 98% of the theoretical water yield, slowly vacuumizing for pre-polycondensation, reducing the pressure to 60Pa within 30min, continuing the polycondensation reaction for 1.5h, and obtaining the mildew-proof polyester 10, wherein the viscosity of the mildew-proof polyester 10 is 1.12dl/g, and n in the mildew-proof polyester 10 is 116;
s5 preparation of mould-proof polyester high-strength yarn
Adding the mildew-proof polyester 10 prepared in the step S4, a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, and then performing melt filtration, liquid phase tackifying, spinneret hole extrusion to form trickle, side blowing cooling, strand oiling, winding and forming to obtain mildew-proof polyester high-strength yarns; the mass ratio of the mildew-proof polyester 10 to the dispersing agent to the defoaming agent to the softening agent is 100:2:0.6: 1.
Example 2
The preparation method of the mould-proof polyester high-strength yarn specifically comprises the following steps:
s1 synthesis of dipentene-4-methyl succinate 3
Adding 120mol of dipentene 1, 130mol of dimethyl fumarate 2 and 0.16mol of catalyst iodine into a high-pressure reaction kettle, introducing nitrogen to replace air in the high-pressure reaction kettle, heating in a closed manner to 250 ℃ at the speed of 15 ℃/min, and preserving heat for 1h to obtain dipentene-4-methyl succinate 3, wherein the yield is 98.9%;
s2, synthesis of prenyl 6 alcohol ester
Adding 150mol of isopentenol 4 and 650mol of formic acid 5 into a reaction bottle, and stirring and reacting for 4 hours at 45 ℃ to obtain isopentenol formate 6 with the yield of 99.2%; (ii) a
S3 synthesis of bisabolol derivative 8
Adding the dipentene-4-methyl succinate 3 prepared in the step S1 into the reaction bottle in the step S2, adding dichloromethane and sulfamic acid, stirring at 65 ℃, carrying out condensation reaction on the dipentene-4-methyl succinate 3 and isopentenol formate 6 for 5 hours to synthesize an intermediate 7, adding a small amount of water, continuing stirring at 80 ℃ for 2 hours, and carrying out hydrolysis reaction on the intermediate 7 in an acid solution to obtain a bisabolol derivative 8, wherein the yield is 94.1%; the adding amount of the dichloromethane is 1/3 of the total volume of the dipentene-4-methyl succinate 3 and the isopentenol formate 6; the addition amount of sulfamic acid is 6.3 of the total mass of the dipentene-4-methyl succinate 3 and the isopentenol formate 6; the addition of a small amount of water accounts for 25 percent of the volume of the added dichloromethane;
the mass spectrum result of the target product 8 is as follows: HRMS m/z (ESI)+)calcd for C19H30O5([M]+),338.213,found 338.2161。
S4 synthetic mildew-proof polyester
Adding 8 parts of bisabolol derivative, 350mol of terephthalyl alcohol 9 and 0.17mol of catalyst ethylene glycol antimony into a stainless steel reaction kettle, introducing nitrogen for protection, heating to 250 ℃ under the pressure of 0.2MPa until the esterification water yield is 100% of the theoretical water yield, heating to 275 ℃, slowly vacuumizing for pre-polycondensation, reducing the pressure to 60Pa within 30min, continuing the polycondensation reaction for 1.5h to obtain the mildew-proof polyester 10, wherein the viscosity of the mildew-proof polyester 10 is 1.21dl/g, and n in the mildew-proof polyester 10 is 120;
s5 preparation of mould-proof polyester high-strength yarn
Adding the mildew-proof polyester 10 prepared in the step S4, a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, and then performing melt filtration, liquid phase tackifying, spinneret hole extrusion to form trickle, side blowing cooling, strand oiling, winding and forming to obtain mildew-proof polyester high-strength yarns; the mass ratio of the mildew-proof polyester 10 to the dispersing agent to the defoaming agent to the softening agent is 100:3:0.8: 2.
Example 3
The preparation method of the mould-proof polyester high-strength yarn specifically comprises the following steps:
s1 synthesis of dipentene-4-methyl succinate 3
Adding 120mol of dipentene 1, 140mol of dimethyl fumarate 2 and 0.18mol of catalyst iodine into a high-pressure reaction kettle, introducing nitrogen to replace air in the high-pressure reaction kettle, heating in a closed manner to 250 ℃ at the speed of 15 ℃/min, and preserving heat for 1h to obtain dipentene-4-methyl succinate 3, wherein the yield is 98.5%;
s2, synthesis of prenyl 6 alcohol ester
Adding 150mol of isopentenol 4 and 700mol of formic acid 5 into a reaction bottle, and stirring and reacting for 4 hours at 45 ℃ to obtain isopentenol formate 6 with the yield of 99.0%; (ii) a
S3 synthesis of bisabolol derivative 8
Adding the dipentene-4-methyl succinate 3 prepared in the step S1 into the reaction bottle in the step S2, adding dichloromethane and sulfamic acid, stirring at 62 ℃, carrying out condensation reaction on the dipentene-4-methyl succinate 3 and isopentenol formate 6 for 4 hours to synthesize an intermediate 7, adding a small amount of water, continuing stirring at 80 ℃ for 1.5 hours, and carrying out hydrolysis reaction on the intermediate 7 in an acid solution to obtain a bisabolol derivative 8, wherein the yield is 93.3%; the adding amount of the dichloromethane is 2/3 of the total volume of the dipentene-4-methyl succinate 3 and the isopentenol formate 6; the addition amount of sulfamic acid is 6.4 of the total mass of the dipentene-4-methyl succinate 3 and the isopentenol formate 6; the addition of a small amount of water accounts for 22 percent of the volume of the added dichloromethane;
the mass spectrum result of the target product 8 is as follows: HRMS m/z (ESI)+)calcd for C19H30O5([M]+),338.213,found 338.2161。
S4 synthetic mildew-proof polyester
Adding 8 parts of bisabolol derivative, 310mol of terephthalyl alcohol 9 and 0.16mol of catalyst ethylene glycol antimony into a stainless steel reaction kettle, introducing nitrogen for protection, heating to 250 ℃ under the pressure of 0.2MPa until the esterification water yield is 99% of the theoretical water yield, heating to 270 ℃, slowly vacuumizing for pre-polycondensation, reducing the pressure to 60Pa within 30min, continuing the polycondensation reaction for 1.5h to obtain the mildew-proof polyester 10, wherein the viscosity of the mildew-proof polyester 10 is 0.98dl/g, and n in the mildew-proof polyester 10 is 112;
s5 preparation of mould-proof polyester high-strength yarn
Adding the mildew-proof polyester 10 prepared in the step S4, a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, and then performing melt filtration, liquid phase tackifying, spinneret hole extrusion to form trickle, side blowing cooling, strand oiling, winding and forming to obtain mildew-proof polyester high-strength yarns; the mass ratio of the mildew-proof polyester 10 to the dispersing agent to the defoaming agent to the softening agent is 100:2.5:1: 1.
Comparative example 1
Adding polyethylene terephthalate (with average polymerization degree of 120), a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, then carrying out melt filtration, liquid phase tackifying, extrusion through a spinneret orifice to form a trickle, cooling by side blowing, oiling on strand silk, and winding and forming to obtain the high-strength polyester yarn; the mass ratio of the mildew-proof polyester 10 to the dispersing agent to the defoaming agent to the softening agent is 100:2.5:1: 1.
Comparative example 2
Adding polyethylene terephthalate (with average polymerization degree of 120), bisabolol, a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, then carrying out melt filtration, liquid phase tackifying, extrusion at a spinneret orifice to form trickle, side-blowing cooling, oiling on strand silk, and winding to form the mildew-proof terylene high-strength yarn; the mass ratio of the mildew-proof polyester 10 to the bisabolol to the dispersing agent to the defoaming agent to the softening agent is 100: 10: 2.5:1:1.
Respectively spinning the high-strength polyester yarns prepared in the examples 1-3 and the comparative examples 1-2 to prepare polyester fabrics, and performing performance test on the polyester fabrics:
(1) and (3) testing the mildew-proof antibacterial performance: the method adopts national standard GB/T24346-2009 to carry out mildew-proof test and GB/T20944.3-2008 to carry out bacteriostasis test, the washing method is carried out on a washing fastness tester, and the washing conditions are as follows: washing powder 4g/L, bath ratio (mass ratio of fabric to washing liquid is 1:30), temperature 35 deg.C, time 10min for one washing; the results are shown in tables 1 and 2;
TABLE 1 mildew resistance of polyester fabrics
TABLE 2 antibacterial Rate of Terylene face Fabric
As can be seen from tables 1 and 2, a, the polyester fabric made of the common polyethylene terephthalate has poor mildew-proof and bacteriostatic properties; b. the polyester fabric is prepared by adopting the polyethylene terephthalate and additionally adding the bisabolol, so that the mildew-proof and bacteriostatic performance of the polyester fabric is greatly improved, but after washing, the mildew-proof and bacteriostatic performance of the polyester fabric is greatly reduced along with the separation of the bisabolol; c. the method is characterized in that the bisabolol derivative is adopted, two carboxylic acids are introduced on the basis of the bisabolol, esterification and polycondensation are carried out on the two carboxylic acids and terephthalyl alcohol to form polyester, active groups containing mildew-proof and antibacterial properties are connected inside the polyester in a chemical bond mode, the active groups containing mildew-proof and antibacterial properties are not easy to fall off when the prepared polyester fabric is cleaned, and the mildew-proof and antibacterial properties of the polyester fabric can be preserved for a long time.
(2) Test of comprehensive Properties
Wherein the air permeability is tested according to the national standard GB/T5453;
the moisture permeability test is carried out according to the national standard GB/T12704-1991;
testing the water absorption rate and the evaporation rate according to the national standard GB/T21655.1-2008;
the test results are shown in Table 3
TABLE 3 comprehensive properties of the polyester fabrics
As can be seen from table 3, a, the polyester fabric made of common polyethylene terephthalate has poor moisture permeability, water absorption, evaporation rate and elongation at break, which results in the defects of hard hand feeling, poor touch feeling, soft gloss, poor air permeability, poor moisture absorption and the like; b. the mildew-proof polyester prepared by condensation polymerization of the bisabolol derivative and the terephthalyl alcohol increases the aliphatic hydrocarbon chain and-OH polar group of the terylene, and increases the flexibility and the hydrophilicity of the terylene, thereby increasing the air permeability and the hygroscopicity of the mildew-proof terylene fabric; in the simultaneously mould-proof polyester-OCH2-Ar-CH2OH keeps the rigidity of the polyester, the modified polyester still has good wrinkle resistance and certain mechanical strength, and as the mildew-proof polyester does not contain a symmetrical structure, the linear form cannot be maintained, the rigidity of the polyester is reduced, and the flexibility of the mildew-proof polyester is increased, so that the hand feeling, touch feeling and gloss softness of the mildew-proof polyester fabric are improved.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (10)
1. The preparation method of the mould-proof high-strength polyester yarn is characterized by comprising the following steps of: the method specifically comprises the following steps:
s1 synthesis of methyl dipentene-4-succinate
Adding dipentene 1, dimethyl fumarate 2 and catalyst iodine into a high-pressure reaction kettle, introducing nitrogen to replace air in the high-pressure reaction kettle, heating in a closed manner, and preserving heat for 1h to obtain dipentene-4-methyl succinate 3;
s2, synthesis of prenyl 6 alcohol ester
Adding the prenol 4 and the formic acid 5 into a reaction bottle, and stirring and reacting for 5 hours at 40 ℃ to obtain prenol formate 6;
s3 synthesis of bisabolol derivatives
Adding the dipentene-4-methyl succinate 3 prepared in the step S1 into the reaction bottle in the step S2, adding dichloromethane and sulfamic acid, stirring at 60-65 ℃, carrying out condensation reaction on the dipentene-4-methyl succinate 3 and isopentenol formate 6 for 4-5 hours to synthesize an intermediate 7, adding a small amount of water, continuing stirring at 80 ℃ for 1-2 hours, and carrying out hydrolysis reaction on the intermediate 7 in acid solution to obtain a bisabolol derivative 8;
s4 synthetic mildew-proof polyester
Adding bisabolol derivative 8, terephthalyl alcohol 9 and catalyst ethylene glycol antimony into a stainless steel reaction kettle, introducing nitrogen for protection, heating to 245-class 255 ℃ under the pressure of 0.2MPa, heating to 268-class 275 ℃ until the esterification water yield is 98-100% of the theoretical water yield, slowly vacuumizing for pre-polycondensation, reducing the pressure to 60Pa within 25-30min, and continuing the polycondensation reaction for 1.5h to obtain the mildew-proof polyester 10;
s5 preparation of mould-proof polyester high-strength yarn
Adding the mildew-proof polyester 10, a dispersing agent, a defoaming agent and a softening agent into a screw extruder for melt extrusion, then performing melt filtration, liquid phase tackifying, extrusion through a spinneret orifice to form trickle, side-blowing cooling, oiling on strand silk, and winding and forming to obtain the mildew-proof polyester high-strength yarn.
2. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S1 of synthesizing the dipentene-4-methyl succinate, the molar ratio of the dipentene 1, the dimethyl fumarate 2 and the catalyst iodine is 1:1.0-1.2: 0.001-0.0015.
3. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: the temperature rise in step S1 is a temperature rise to 250 ℃ at a rate of 15 ℃/min.
4. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S2 synthesis of the prenol formate, the mole ratio of prenol 4 to formic acid 5 is 1: 4-5.
5. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S3 of synthesizing the bisabolol derivative, the molar ratio of the dipentene-4-methyl succinate 3 to the prenol formate 6 is 1: 1.2-1.5.
6. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S3 of synthesizing the bisabolol derivative, the amount of the added dichloromethane is 1/3 to 2/3 of the total volume of the dipentene-4-succinic acid methyl ester 3 and the prenol formate 6 in the step S3; the addition amount of sulfamic acid is 6.2 to 6.8 of the total mass of the methyl dipentene-4-succinate 3 and the isopentenol formate 6 in the step S3; the addition of a small amount of water is 20-25% of the volume of the added dichloromethane.
7. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S4 of synthesizing the mould-proof polyester, the molar ratio of the bisabolol derivative, the terephthalic acid and the catalyst ethylene glycol antimony is 1:2.3-3: 0.001-0.0015.
8. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S4 of synthesizing the mildew-proof polyester, the viscosity of the mildew-proof polyester 10 is 0.95 to 1.23 dl/g.
9. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S4 of synthesizing the mildew-proof polyester, n in the mildew-proof polyester 10 is 110-135.
10. The preparation method of the mildewproof polyester high-strength yarn as claimed in claim 1, which is characterized in that: in the step S5 preparation of the mould-proof polyester high-strength yarn, the mass ratio of the mould-proof polyester 10 to the dispersing agent to the defoaming agent to the softening agent is 100:2-3:0.5-1: 1-2.
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| WO2013025893A1 (en) * | 2011-08-16 | 2013-02-21 | The Gillette Company | Personal care compositions comprising an anti-irritation agent |
| CN104497291A (en) * | 2014-12-12 | 2015-04-08 | 东华大学 | Antifouling and flame-retardant polyester fibres and preparation method thereof |
| CN104988601A (en) * | 2015-07-17 | 2015-10-21 | 安徽月娇家具有限公司 | Health mattress fabric for treating bedsores and dermatopathy, and making method thereof |
| CN105082693A (en) * | 2015-08-19 | 2015-11-25 | 树业环保科技股份有限公司 | Mildew-proof antibacterial polyester film and preparation method thereof |
| CN106831322A (en) * | 2017-01-10 | 2017-06-13 | 南宁辰康生物科技有限公司 | A kind of production method of α bisabolols |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2013025893A1 (en) * | 2011-08-16 | 2013-02-21 | The Gillette Company | Personal care compositions comprising an anti-irritation agent |
| CN104497291A (en) * | 2014-12-12 | 2015-04-08 | 东华大学 | Antifouling and flame-retardant polyester fibres and preparation method thereof |
| CN104988601A (en) * | 2015-07-17 | 2015-10-21 | 安徽月娇家具有限公司 | Health mattress fabric for treating bedsores and dermatopathy, and making method thereof |
| CN105082693A (en) * | 2015-08-19 | 2015-11-25 | 树业环保科技股份有限公司 | Mildew-proof antibacterial polyester film and preparation method thereof |
| CN106831322A (en) * | 2017-01-10 | 2017-06-13 | 南宁辰康生物科技有限公司 | A kind of production method of α bisabolols |
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