CN110878137B - Flame-retardant polyester material, preparation method thereof, granules and fiber product - Google Patents

Flame-retardant polyester material, preparation method thereof, granules and fiber product Download PDF

Info

Publication number
CN110878137B
CN110878137B CN201911259623.XA CN201911259623A CN110878137B CN 110878137 B CN110878137 B CN 110878137B CN 201911259623 A CN201911259623 A CN 201911259623A CN 110878137 B CN110878137 B CN 110878137B
Authority
CN
China
Prior art keywords
flame
retardant polyester
parts
steps
vacuum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911259623.XA
Other languages
Chinese (zh)
Other versions
CN110878137A (en
Inventor
查皓
查家华
谢旭鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dongguan Doher New Material Technology Co ltd
Original Assignee
Dongguan Doher New Material Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dongguan Doher New Material Technology Co ltd filed Critical Dongguan Doher New Material Technology Co ltd
Priority to CN201911259623.XA priority Critical patent/CN110878137B/en
Publication of CN110878137A publication Critical patent/CN110878137A/en
Application granted granted Critical
Publication of CN110878137B publication Critical patent/CN110878137B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C08G63/68—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
    • 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
    • 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
    • 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
    • D01F1/10—Other agents for modifying properties
    • D01F1/106—Radiation shielding agents, e.g. absorbing, reflecting agents
    • 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

Abstract

The invention discloses a flame-retardant polyester material and a preparation method thereof, granules and fiber products, wherein the flame-retardant polyester material adopts o-hydroxy benzophenone derivatives, anhydride, 2-hydroxyethyl isocyanurate, chlorohydrin, terephthalic acid and glycol as raw materials, so that the defect of flammability of the traditional polyester is overcome, and meanwhile, the reaction steps are simple and easy to operate; 2-hydroxyethyl isocyanurate is adopted as one of the raw materials, not only-OH but also-NH2The reaction activity is higher, the reaction flexibility is large, and the nitrogen content is higher, so that the material has outstanding effect on flame retardance; o-hydroxybenzophenone derivatives are used as one of the starting materials. Firstly, the o-hydroxy benzophenone derivative has the function of ultraviolet absorption and can be used as a light stabilizer; secondly, para-position hydroxyl in the structure can be used as a reaction point for esterification; finally, the structure containing benzene ring is similar to that of polyester, so that the polyester has good compatibility and is beneficial to wide popularization and application.

Description

Flame-retardant polyester material, preparation method thereof, granules and fiber product
Technical Field
The invention relates to the technical field of polyester materials, in particular to a flame-retardant polyester material, a preparation method thereof, granules and a fiber product.
Background
The conventional polyester fiber has single functionality and is inflammable, the requirements of domestic and foreign markets on product diversification and functionalization cannot be met, and the new function given to the conventional chemical fiber is one of the key points and hot spots in the research field of new chemical fiber materials. Flame retardancy of fibers is one of the hot spots that is currently of concern. The flame retardant property of the textile on the market at present is improved by adding an auxiliary agent. The product obtained by the treatment has the defects of no wear resistance and no washing resistance, and most of the used flame retardants are halogen flame retardants, so that the product has harm to human health and environment.
Meanwhile, most textile fibers work in an atmospheric environment and are directly exposed to sunlight, so that the textile fibers inevitably suffer from the radiation effect of ultraviolet rays in the sunlight, gradually lose good mechanical properties, have poor gloss and are yellow in color. The same problem is also inevitably encountered with polyester, which is one of the commonly used fiber raw materials.
It is well known that organic polymer materials are mostly flammable and many fire accidents have occurred due to polymer materials. Therefore, it is urgent to solve the problem of flame retardancy of polyester fiber.
Disclosure of Invention
In view of the above disadvantages, an object of the present invention is to provide a flame retardant polyester material that is reasonably modified, has an anti-uv property while improving flame retardancy, and effectively improves the property.
The second purpose of the invention is to provide a preparation method of the flame-retardant polyester material, which can rapidly prepare the flame-retardant polyester material.
The invention also aims to provide a preparation method of the flame-retardant polyester granules.
The fourth purpose of the invention is to provide a preparation method of the flame-retardant polyester fiber and a fiber product thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a flame-retardant polyester material has the following structural formula:
Figure BDA0002311267210000021
wherein: r1is-H or-OH; r2is-H, -OCH3、-OC2H5、-OC3H7Any one of the above; r3is-C2H4Or C6H4。
A method for preparing a flame retardant polyester material, comprising the following steps (all expressed as mole fractions of reactive functional groups):
(1) the carboxyl-terminated benzophenone derivative is prepared through an esterification reaction, and specifically, the step (1) specifically comprises the following steps: (1.1) mixing and stirring 1 part of 2, 4-dihydroxy benzophenone derivative, 1.0-1.2 parts of anhydride, 0.01-5% of catalyst and 50 parts of organic solvent a, and heating and refluxing for 10-15 hours to obtain a first solution; (1.2) standing the first solution, filtering, and distilling the organic phase under reduced pressure to obtain a carboxyl-terminated benzophenone derivative marked as A;
(2) the isocyanurate-modified benzophenone derivative is prepared through an esterification reaction, and specifically, the step (2) specifically comprises the following steps: (2.1) mixing and stirring 1 part of A, 1.0-1.2 parts of hydroxyethyl isocyanurate, 0.01-5% of catalyst and 60 parts of organic solvent a, and heating and refluxing for 10-20 hours to obtain a second solution; (2.2) standing the second solution, filtering, distilling the organic phase under reduced pressure, and drying in vacuum to obtain an isocyanurate modified benzophenone derivative, which is marked as B;
(3) the diol with the isocyanurate structure is prepared through a substitution reaction, and specifically, the step (3) specifically comprises the following steps: (3.1) dissolving 1 part of B and 1 part of sodium hydroxide in 80 parts of water, intensively stirring and heating the suspension to 90-95 ℃, and dripping a mixed cooling solution consisting of 40 parts of water, 2 parts of sodium hydroxide and 4 parts of chloroethanol in 6-8 hours; (3.2) standing the mixed cooling solution for 5-24 h, then carrying out vacuum concentration on the mixed cooling solution, enriching residual components, adding a boiling organic solvent b for dissolving, filtering, cooling, and carrying out rotary evaporation to obtain glycol with an isocyanurate structure, wherein the mark is C;
(4) the flame-retardant polyester material is prepared through esterification and polycondensation, and specifically, the step (4) specifically comprises the following steps: (4.1) stirring and mixing 0.01-0.1 part of C, 0.9-0.99 part of ethylene glycol, 1 part of terephthalic acid and 0.01-5% of catalyst, heating, raising the temperature, controlling the reaction temperature at 220-240 ℃, filling nitrogen, keeping the pressure at 0.1-0.2 MPa and the pressure at 0.28-0.32 MPa; (4.2) after the esterification reaction is finished, starting a vacuum pump to slowly vacuumize, and controlling the time from low vacuum to high vacuum to be 30-35 min; (4.3) after entering high vacuum, controlling the temperature to be 280-285 ℃, judging the degree of polymerization reaction by observing the current and torque change of a motor, introducing nitrogen until the pressure is 0.15-0.20 MPa after reaching the discharging condition, opening a discharging valve, and allowing the melt to flow out of a casting belt head to prepare the flame-retardant polyester material.
The preparation method of the flame-retardant polyester granules comprises the steps of introducing the flame-retardant polyester material into a granulator, and carrying out a granulation process to obtain the flame-retardant polyester granules.
A preparation method of flame-retardant polyester fiber comprises the following steps:
(1) preparing an antioxidant and the flame-retardant polyester granules, wherein the flame-retardant polyester granules and the antioxidant are prepared from the following components in parts by weight: 100: 0.05-0.1, wherein the antioxidant is 1010, trimethyl phosphate, 122 or 300;
(2) placing the flame-retardant polyester granules and the antioxidant at 80-120 ℃ for vacuum drying for 4-6 h, and then placing at 100-140 ℃ for vacuum drying for 12-30 h;
(3) and after drying, mixing the flame-retardant polyester granules with an antioxidant, adding the mixture into an extruder, adjusting the temperature of each zone of the extruder to 245-255 ℃, adjusting the feeding speed to 130g/min and the screw rotation speed to 100r/min, and extruding to obtain the flame-retardant polyester fiber. The extruder is preferably a twin screw extruder.
A flame-retardant polyester fiber product prepared by the preparation method of the flame-retardant polyester fiber.
The flame-retardant polyester material provided by the invention has the following reaction process:
Figure BDA0002311267210000041
the invention has the beneficial effects that: the invention adopts o-hydroxy benzophenone derivatives, anhydride, 2-hydroxyethyl isocyanurate, chlorohydrin, terephthalic acid and ethylene glycol as raw materials, gets rid of the defect of flammability of the traditional polyester, and has simple reaction steps and easy operation; 2-hydroxyethyl isocyanurate is adopted as one of the raw materials. On the one hand, 2-hydroxyethyl isocyanurate is used as a trifunctional raw material, -OH, -NH2The reaction activity is higher, and the reaction flexibility is high; on the other hand, the flame retardant has higher nitrogen content and has outstanding effect on the flame retardance of the material; o-hydroxybenzophenone derivatives are used as one of the starting materials. Firstly, the o-hydroxy benzophenone derivative has the function of ultraviolet absorption and can be used as a light stabilizer; secondly, para-position hydroxyl in the structure can be used as a reaction point for esterification; finally, the structure containing benzene ring is similar to that of polyester, so that the polyester has good compatibility and is beneficial to wide popularization and application.
The present invention will be further described with reference to the following examples.
Detailed Description
Example 1: the preparation method of the flame-retardant polyester pellet provided by the embodiment comprises the following steps:
(1) 1 part of 2, 4-dihydroxy benzophenone derivative (R)1：-H、R2: -H), 1.2 parts of succinic anhydride, 0.01% parts of 4-dimethylaminopyridine and 50 parts of tetrahydrofuran in a three-necked flask, mechanically stirring, heating and refluxing for 10 hours, standing, filtering, and distilling the organic phase under reduced pressure to obtain a carboxyl-terminated benzophenone derivative (IR: 3352cm-1: the phenol-OH is weakened; 3386cm-1: -OH formation; 1780cm-1: ring-C ═ O disappears; 1750cm-1: -C ═ O generation), denoted a;
(2) placing 1 part of A, 1.2 parts of hydroxyethyl isocyanurate, 0.01 percent of 4-dimethylamino pyridine and 60 parts of tetrahydrofuran in a three-neck flask, mechanically stirring, heating and refluxing for 10 hours, standing, filtering, distilling an organic phase under reduced pressure, and drying in vacuum to obtain the isocyanurate modified benzophenone derivative (IR: 3352 cm)-1: -OH is present; 3215cm-1: secondary-NH is present; 3386cm-1: -OH disappearance; 1761cm-1: ester-C ═ O present), noted B;
(3) dissolving 1 part of B and 1 part of sodium hydroxide in 80 parts of water, intensively stirring and heating the suspension to 90 ℃, dripping a mixed cooling solution consisting of 40 parts of water, 2 parts of sodium hydroxide and 4 parts of chloroethanol in 8 hours, standing overnight, concentrating the solution in vacuum, enriching residual components, adding boiling N, N-dimethylformamide for dissolving, filtering, cooling, and performing rotary evaporation to obtain dihydric alcohol with an isocyanurate structure (IR: 3523 cm)-1、3395cm-1: -OH is present; 1712cm-1: ester-C ═ O present), noted C;
(4) stirring 0.01 part of C, 0.99 part of ethylene glycol, 1 part of terephthalic acid and 0.01 percent of 4-dimethylamino pyridine, heating, and filling nitrogen to keep 0.15 MPa; the reaction temperature is controlled at 230 ℃ and the pressure is 0.32 MPa; recording the reaction temperature and pressure in the esterification process; after the esterification reaction is finished, starting a vacuum pump, slowly vacuumizing the reaction kettle, and adjusting through a vacuum buffer tank emptying valvePumping, wherein the time from low vacuum to high vacuum is controlled to be 30 min; after entering high vacuum, controlling the temperature to be 280 ℃; the polymerization degree was judged by observing the change in the current and torque of the motor, the discharge current was 1.0A, the stirring speed was 80%, the torque was 70 N.m, after reaching the discharge condition, nitrogen was introduced to a pressure of 0.20MPa to obtain a polyester (IR: 3523 cm)-1: -OH disappearance; 3395cm-1: phenol-OH is present; 1712cm-1: ester-C ═ O present), noted D; and opening a discharge valve to allow the melt to flow out of the casting strip head, cooling the casting strip through a cooling water tank, introducing the casting strip into a granulator, and granulating to obtain the flame-retardant polyester granules.
Example 2: the preparation method of the flame-retardant polyester pellet provided by the embodiment comprises the following steps:
(1) 1 part of 2, 4-dihydroxy benzophenone derivative (R)1：-H、R2：-OCH3) 1.0 part of phthalic anhydride, 5% of zinc acetate and 50 parts of acetone are placed in a three-neck flask, mechanically stirred, heated and refluxed for 15 hours, kept stand, filtered and the organic phase is distilled under reduced pressure to obtain a carboxyl-terminated benzophenone derivative (IR: 3352cm-1: the phenol-OH is weakened; 3386cm-1: -OH formation; 1780cm-1: ring-C ═ O disappears; 1750cm-1: -C ═ O generation), denoted a;
(2) placing 1 part of A, 1.0 part of hydroxyethyl isocyanurate, 5 percent of zinc acetate and 60 parts of acetone into a three-neck flask, mechanically stirring, heating and refluxing for 20 hours, standing, filtering, distilling an organic phase under reduced pressure, and drying in vacuum to obtain the isocyanurate modified benzophenone derivative (IR: 3352 cm)-1: -OH is present; 3215cm-1: secondary-NH is present; 3386cm-1: -OH disappearance; 1761cm-1: ester-C ═ O present), noted B;
(3) dissolving 1 part of B and 1 part of sodium hydroxide in 80 parts of water, intensively stirring and heating the suspension to 95 ℃, dripping a mixed cooling solution consisting of 40 parts of water, 2 parts of sodium hydroxide and 4 parts of chloroethanol in 6 hours, standing overnight, carrying out vacuum concentration on the solution, enriching residual components, adding boiling isopropanol to dissolve, filtering, cooling, and carrying out rotary evaporation to obtain the dihydric alcohol (I) with the isocyanurate structureR：3523cm-1、3395cm-1: -OH is present; 1712cm-1: ester-C ═ O present), noted C;
(4) stirring 0.1 part of C, 0.9 part of ethylene glycol, 1 part of terephthalic acid and 5% of zinc acetate, heating, raising the temperature, and filling nitrogen to keep 0.15 MPa; the reaction temperature is controlled at 220 ℃ and the pressure is 0.28 MPa; recording the reaction temperature and pressure in the esterification process; after the esterification reaction is finished, starting a vacuum pump, slowly vacuumizing the reaction kettle, adjusting the air extraction amount through an air release valve of a vacuum buffer tank, and controlling the time from low vacuum to high vacuum to be 35 min; after entering high vacuum, controlling the temperature to be 285 ℃; the polymerization degree was judged by observing the change in the current and torque of the motor, the discharge current was 1.0A, the stirring speed was 80%, the torque was 70 N.m, after reaching the discharge condition, nitrogen was introduced to a pressure of 0.15MPa to obtain a polyester (IR: 3523 cm)-1: -OH disappearance; 3395cm-1: phenol-OH is present; 1712cm-1: ester-C ═ O present), noted D; and opening a discharge valve to allow the melt to flow out of the casting strip head, cooling the casting strip through a cooling water tank, introducing the casting strip into a granulator, and granulating to obtain the flame-retardant polyester granules.
Example 3: the preparation method of the flame-retardant polyester pellet provided by the embodiment comprises the following steps:
(1) 1 part of 2, 4-dihydroxy benzophenone derivative (R)1：-OH、R2：-OC2H5) 1.1 parts of succinic anhydride, 1% of antimony trioxide and 50 parts of N, N-dimethylformamide are placed in a three-neck flask, mechanically stirred, heated and refluxed for 12 hours, and then the mixture is allowed to stand, filtered and distilled under reduced pressure to obtain a carboxyl-terminated benzophenone derivative (IR: 3352cm-1: the phenol-OH is weakened; 3386cm-1: -OH formation; 1780cm-1: ring-C ═ O disappears; 1750cm-1: -C ═ O generation), denoted a;
(2) placing 1 part of A, 1.1 part of hydroxyethyl isocyanurate, 1 percent of antimony trioxide and 60 parts of N, N-dimethylformamide into a three-neck flask, mechanically stirring, heating and refluxing for 15 hours, standing, filtering, distilling an organic phase under reduced pressure, and drying in vacuum to obtain the isocyanurate modified benzophenone derivative (IR: 3352 cm)-1: -OH is presentAt least one of the following steps; 3215cm-1: secondary-NH is present; 3386cm-1: -OH disappearance; 1761cm-1: ester-C ═ O present), noted B;
(3) dissolving 1 part of B and 1 part of sodium hydroxide in 80 parts of water, heating the suspension to 92 ℃ by intense stirring, dripping a mixed cooling solution consisting of 40 parts of water, 2 parts of sodium hydroxide and 4 parts of chloroethanol in 7h, standing overnight, concentrating the solution in vacuum, enriching residual components, adding boiling dioxane for dissolving, filtering, cooling, and performing rotary evaporation to obtain the dihydric alcohol with the isocyanurate structure (IR: 3523 cm)-1、3395cm-1: -OH is present; 1712cm-1: ester-C ═ O present), noted C;
(4) stirring 0.05 part of C, 0.95 part of ethylene glycol, 1 part of terephthalic acid and 1% of antimony trioxide, heating, raising the temperature, and filling nitrogen to keep 0.15 MPa; the reaction temperature is controlled at 240 ℃ and the pressure is 0.30 MPa; recording the reaction temperature and pressure in the esterification process; after the esterification reaction is finished, starting a vacuum pump, slowly vacuumizing the reaction kettle, adjusting the air extraction amount through an air release valve of a vacuum buffer tank, and controlling the time from low vacuum to high vacuum to be 33 min; after entering high vacuum, controlling the temperature to be 283 ℃; the polymerization degree was judged by observing the change in the current and torque of the motor, the discharge current was 1.0A, the stirring speed was 80%, the torque was 70 N.m, after reaching the discharge condition, nitrogen was introduced to a pressure of 0.18MPa to obtain a polyester (IR: 3523 cm)-1: -OH disappearance; 3395cm-1: phenol-OH is present; 1712cm-1: ester-C ═ O present), noted D; and opening a discharge valve to allow the melt to flow out of the casting strip head, cooling the casting strip through a cooling water tank, introducing the casting strip into a granulator, and granulating to obtain the flame-retardant polyester granules.
Example 4: the preparation method of the flame-retardant polyester pellet provided by the embodiment comprises the following steps:
(1) 1 part of 2, 4-dihydroxy benzophenone derivative (R)1：-OH、R2：-OC3H7) 1.0-1.2 parts of phthalic anhydride, 3 percent of stannous oxide and 50 parts of dioxane are placed in a three-neck flask, mechanically stirred, heated and refluxed for 15 hours, kept stand, filtered and distilled under reduced pressure of an organic phase to obtainCarboxyl-terminated benzophenone derivatives (IR: 3352 cm)-1: the phenol-OH is weakened; 3386cm-1: -OH formation; 1780cm-1: ring-C ═ O disappears; 1750cm-1: -C ═ O generation), denoted a;
(2) placing 1 part of A, 1.2 parts of hydroxyethyl isocyanurate, 3 percent of stannous oxide and 60 parts of dioxane into a three-neck flask, mechanically stirring, heating and refluxing for 15 hours, standing, filtering, distilling an organic phase under reduced pressure, and drying in vacuum to obtain the isocyanurate modified benzophenone derivative (IR: 3352 cm)-1: -OH is present; 3215cm-1: secondary-NH is present; 3386cm-1: -OH disappearance; 1761cm-1: ester-C ═ O present), noted B;
(3) dissolving 1 part of B and 1 part of sodium hydroxide in 80 parts of water, intensively stirring and heating the suspension to 95 ℃, dripping a mixed cooling solution consisting of 40 parts of water, 2 parts of sodium hydroxide and 4 parts of chloroethanol in 8 hours, standing overnight, concentrating the solution in vacuum, enriching residual components, adding boiling butanone for dissolving, filtering, cooling, and performing rotary evaporation to obtain the dihydric alcohol with the isocyanurate structure (IR: 3523 cm)-1、3395cm-1: -OH is present; 1712cm-1: ester-C ═ O present), noted C;
(4) stirring 0.03 part of C, 0.97 part of ethylene glycol, 1 part of terephthalic acid and 3% of stannous oxide, heating, raising the temperature, and filling nitrogen to keep 0.15 MPa; the reaction temperature is controlled at 230 ℃ and the pressure is 0.30 MPa; recording the reaction temperature and pressure in the esterification process; after the esterification reaction is finished, starting a vacuum pump, slowly vacuumizing the reaction kettle, adjusting the air extraction amount through an air release valve of a vacuum buffer tank, and controlling the time from low vacuum to high vacuum to be 35 min; after entering high vacuum, controlling the temperature to be 285 ℃; the polymerization degree was judged by observing the change in the current and torque of the motor, the discharge current was 1.0A, the stirring speed was 80%, the torque was 70 N.m, after reaching the discharge condition, nitrogen was introduced to a pressure of 0.20MPa to obtain a polyester (IR: 3523 cm)-1: -OH disappearance; 3395cm-1: phenol-OH is present; 1712cm-1: ester-C ═ O present), noted D; opening a discharge valve to allow the melt to flow out of the casting strip head, cooling the casting strip through a cooling water tank,and introducing a granulator, and granulating to obtain the flame-retardant polyester granules.
Application example 1: the preparation method of the flame-retardant polyester fiber provided by the embodiment comprises the following steps:
(1) preparing an antioxidant 1010 and the flame-retardant polyester granules prepared in example 1, wherein the weight part ratio of the flame-retardant polyester granules to the antioxidant 1010 is 100: 0.05;
(2) placing the polyester granules and the antioxidant 1010 at 80 ℃ for vacuum drying for 5h, and then placing at 140 ℃ for vacuum drying for 24 h; stirring at a high speed, uniformly mixing, placing in a double-screw extruder, and setting the temperature of each zone of the double-screw extruder to be 245/246/248/250/255 ℃, the rotating speed of a screw to be 100r/min and the feeding speed to be 130g/min respectively to obtain the flame-retardant polyester fiber.
Application example 2: the preparation method of the flame-retardant polyester fiber provided by the embodiment comprises the following steps:
(1) preparing trimethyl phosphate and the flame-retardant polyester granules prepared in the example 2, wherein the weight part ratio of the flame-retardant polyester granules to the trimethyl phosphate is 100: 0.06;
(2) placing the polyester granules and trimethyl phosphate at 120 ℃ for vacuum drying for 5h, and then placing at 100 ℃ for vacuum drying for 24 h; stirring at a high speed, uniformly mixing, placing in a double-screw extruder, and setting the temperature of each zone of the double-screw extruder to be 245/246/248/250/255 ℃, the rotating speed of a screw to be 100r/min and the feeding speed to be 130g/min respectively to obtain the flame-retardant polyester fiber.
Application example 3: the preparation method of the flame-retardant polyester fiber provided by the embodiment comprises the following steps:
(1) preparing an antioxidant 300 and the flame-retardant polyester granules prepared in example 3, wherein the weight part ratio of the flame-retardant polyester granules to the antioxidant 300 is 100: 0.06;
(2) placing the polyester granules and the antioxidant 300 at 100 ℃ for vacuum drying for 5h, and then placing at 120 ℃ for vacuum drying for 24 h; stirring at a high speed, uniformly mixing, placing in a double-screw extruder, and setting the temperature of each zone of the double-screw extruder to be 245/246/248/250/255 ℃, the rotating speed of a screw to be 100r/min and the feeding speed to be 130g/min respectively to obtain the flame-retardant polyester fiber.
Application example 4: the preparation method of the flame-retardant polyester fiber provided by the embodiment comprises the following steps:
(1) preparing an antioxidant 122 and the flame-retardant polyester granules prepared in example 4, wherein the weight part ratio of the flame-retardant polyester granules to the antioxidant 122 is 100: 0.08;
(2) placing the polyester granules and the antioxidant 122 at 120 ℃ for vacuum drying for 5h, and then placing at 140 ℃ for vacuum drying for 24 h; stirring at a high speed, uniformly mixing, placing in a double-screw extruder, and setting the temperature of each zone of the double-screw extruder to be 245/246/248/250/255 ℃, the rotating speed of a screw to be 100r/min and the feeding speed to be 130g/min respectively to obtain the flame-retardant polyester fiber.
Comparative example 1, a method for preparing a polyester fiber is provided, which comprises the steps of:
(1) preparing raw materials, wherein the raw materials comprise the following components in parts by weight: 100 parts of common polyester granules and 10100.05 parts of antioxidant.
(2) Placing common polyester granules and an antioxidant at 80 ℃ for vacuum drying for 5h, and vacuum drying at 140 ℃ for 24 h; stirring at high speed, uniformly mixing, and placing in a double-screw extruder, wherein the temperature of each zone of the double-screw extruder is 245/246/248/250/255 ℃, the rotating speed of a screw is 100r/min, and the feeding speed is 130g/min in sequence, so as to obtain the polyester fiber.
Comparative example 2, a method for preparing a polyester fiber is provided, which comprises the steps of:
(1) preparing raw materials, wherein the raw materials comprise the following components in parts by weight: 100 parts of common polyester granules, 10100.5 parts of antioxidant and 0.01 part of organic phosphorus flame retardant.
(2) Placing common polyester granules, an antioxidant 1010 and an organic phosphorus flame retardant into a vacuum drying machine at 80 ℃ for 5 hours, and vacuum drying at 140 ℃ for 24 hours; stirring at high speed, uniformly mixing, and placing in a double-screw extruder, wherein the temperature of each zone of the double-screw extruder is 245/246/248/250/255 ℃, the rotating speed of a screw is 100r/min, and the feeding speed is 130g/min in sequence, so as to obtain the polyester fiber.
Comparative example 3, a method for preparing a polyester fiber is provided, which comprises the following steps:
(1) preparing raw materials, wherein the raw materials comprise the following components in parts by weight: 100 parts of common polyester granules, 10100.5 parts of antioxidant, 0.01 part of organic phosphorus flame retardant and 0.01 part of ultraviolet absorbent.
(2) Placing common polyester granules, an antioxidant 1010, an organic phosphorus flame retardant and an ultraviolet absorbent in a vacuum drying machine at 80 ℃ for 5 hours, and in a vacuum drying machine at 140 ℃ for 24 hours; stirring at high speed, uniformly mixing, and placing in a double-screw extruder, wherein the temperature of each zone of the double-screw extruder is 245/246/248/250/255 ℃, the rotating speed of a screw is 100r/min, and the feeding speed is 130g/min in sequence, so as to obtain the polyester fiber.
The physical properties of the PET fibers prepared in application examples 1 to 4 and comparative examples 1 to 3 of the present invention were measured, and the results of comparing the flame retardancy and the antibacterial and antifungal properties are shown in table 1.
TABLE 1
Figure BDA0002311267210000121
As can be seen from table 1, the flame retardant polyester fiber of the present invention has significant advantages in flame retardancy and mechanical properties compared to the conventional polyester fiber. The results in Table 1 show that compared with polyester fibers added with auxiliary agents, the polyester fibers of the invention have excellent performance data and obvious comprehensive performance advantages due to the problem of dispersibility of the auxiliary agents added after the addition.
In sum, the flame-retardant polyester fiber has obvious advantages in flame retardance and has the advantages of weather resistance and ageing resistance. The test method comprises the following steps:
1) flame retardancy: the flame retardant effect was observed visually on open fire. Flame retardancy expression method: 5 is optimal and 1 is worst.
2) Mechanical property testing (elongation at break, tensile stress): the mechanical property of the polyester fiber sample adopts the mechanical testing function of a model Q800 DMA analyzer manufactured by American TA company, the length of the sample is 8mm, the temperature is 35 ℃, the pretension is 0.001N, and the load mode is 0.2N/min.
The above examples are only preferred embodiments of the present invention, and the present invention is not limited to all embodiments, and any technical solution using one of the above examples or equivalent changes made according to the above examples is within the scope of the present invention.
Variations and modifications to the above-described embodiments may occur to those skilled in the art, which fall within the scope and spirit of the above description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation. Other fibers and methods of making the same, using the same or similar methods and components, as described in the above examples of the invention, are within the scope of the invention.

Claims (5)

1. A preparation method of a flame-retardant polyester material is characterized by comprising the following steps: which comprises the following steps:
(1) preparing a carboxyl-terminated benzophenone derivative through esterification reaction, and marking as A;
(2) preparing an isocyanurate modified benzophenone derivative through esterification reaction, and marking as B;
(3) preparing dihydric alcohol with an isocyanurate structure through a substitution reaction, and marking as C;
(4) preparing a flame-retardant polyester material through esterification and polycondensation;
the step (2) specifically comprises the following steps:
(2.1) mixing and stirring 1 part of A, 1.0-1.2 parts of hydroxyethyl isocyanurate, 0.01-5% of catalyst and 60 parts of organic solvent a, and heating and refluxing for 10-20 hours to obtain a second solution;
(2.2) standing the second solution, filtering, distilling the organic phase under reduced pressure, and drying in vacuum to obtain the isocyanurate modified benzophenone derivative;
all expressed as mole fractions of reactive functional groups;
the step (1) specifically comprises the following steps:
(1.1) mixing and stirring 1 part of 2, 4-dihydroxy benzophenone derivative, 1.0-1.2 parts of anhydride, 0.01-5% of catalyst and 50 parts of organic solvent a, and heating and refluxing for 10-15 hours to obtain a first solution;
(1.2) standing the first solution, filtering, and distilling the organic phase under reduced pressure to obtain a carboxyl-terminated benzophenone derivative;
all expressed as mole fractions of reactive functional groups;
the step (3) specifically comprises the following steps:
(3.1) dissolving 1 part of B and 1 part of sodium hydroxide in 80 parts of water, intensively stirring and heating the suspension to 90-95 ℃, and dripping a mixed cooling solution consisting of 40 parts of water, 2 parts of sodium hydroxide and 4 parts of chloroethanol in 6-8 hours;
(3.2) standing the mixed cooling solution for 5-24 h, concentrating the mixed cooling solution in vacuum, enriching residual components, adding a boiling organic solvent b for dissolving, filtering, cooling, and performing rotary evaporation to obtain glycol with an isocyanurate structure;
all expressed as mole fractions of reactive functional groups;
the step (4) specifically comprises the following steps:
(4.1) stirring and mixing 0.01-0.1 part of C, 0.9-0.99 part of ethylene glycol, 1 part of terephthalic acid and 0.01-5% of catalyst, heating, raising the temperature, controlling the reaction temperature at 220-240 ℃, filling nitrogen, keeping the pressure at 0.1-0.2 MPa and the pressure at 0.28-0.32 MPa;
(4.2) after the esterification reaction is finished, starting a vacuum pump to slowly vacuumize, and controlling the time from low vacuum to high vacuum to be 30-35 min;
(4.3) after entering high vacuum, controlling the temperature to be 280-285 ℃, judging the degree of polymerization reaction by observing the current and torque change of a motor, introducing nitrogen until the pressure is 0.15-0.20 MPa after reaching the discharging condition, opening a discharging valve, and allowing the melt to flow out of a casting belt head to prepare the flame-retardant polyester material.
2. The flame-retardant polyester material is characterized by being prepared by the preparation method of the flame-retardant polyester material according to claim 1, and the structural formula of the flame-retardant polyester material is as follows:
Figure DEST_PATH_IMAGE001
wherein: r1is-H or-OH; r2is-H, -OCH3、-OC2H5、-OC3H7Any one of the above; r3is-C2H4Or C6H4。
3. A preparation method of flame-retardant polyester granules is characterized by comprising the following steps: introducing the flame-retardant polyester material prepared by the method for preparing the flame-retardant polyester material according to claim 1 or the flame-retardant polyester material according to claim 2 into a granulator, and performing a granulation process to obtain flame-retardant polyester granules.
4. A preparation method of flame-retardant polyester fiber is characterized by comprising the following steps: which comprises the following steps:
(1) preparing an antioxidant and the flame-retardant polyester granules as defined in claim 3, wherein the weight portion ratio of the flame-retardant polyester granules to the antioxidant is as follows: 100: 0.05-0.1, wherein the antioxidant is 1010 or 300;
(2) placing the flame-retardant polyester granules and the antioxidant at 80-120 ℃ for vacuum drying for 4-6 h, and then placing at 100-140 ℃ for vacuum drying for 12-30 h;
(3) and after drying, mixing the flame-retardant polyester granules with an antioxidant, adding the mixture into an extruder, adjusting the temperature of each zone of the extruder to 245-255 ℃, adjusting the feeding speed to 130g/min and the screw rotation speed to 100r/min, and extruding to obtain the flame-retardant polyester fiber.
5. A flame-retardant polyester fiber product prepared by the method for preparing the flame-retardant polyester fiber according to claim 4.
CN201911259623.XA 2019-12-10 2019-12-10 Flame-retardant polyester material, preparation method thereof, granules and fiber product Active CN110878137B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911259623.XA CN110878137B (en) 2019-12-10 2019-12-10 Flame-retardant polyester material, preparation method thereof, granules and fiber product

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911259623.XA CN110878137B (en) 2019-12-10 2019-12-10 Flame-retardant polyester material, preparation method thereof, granules and fiber product

Publications (2)

Publication Number Publication Date
CN110878137A CN110878137A (en) 2020-03-13
CN110878137B true CN110878137B (en) 2022-04-12

Family

ID=69731381

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911259623.XA Active CN110878137B (en) 2019-12-10 2019-12-10 Flame-retardant polyester material, preparation method thereof, granules and fiber product

Country Status (1)

Country Link
CN (1) CN110878137B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111826741A (en) * 2020-07-26 2020-10-27 向自嫒 Anion polyester fiber and fabric
CN115785626B (en) * 2022-11-15 2024-03-12 嘉禾伍丰(河北)包装科技有限公司 Modified plastic particle and preparation method thereof

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7220815B2 (en) * 2003-07-31 2007-05-22 E.I. Du Pont De Nemours And Company Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom
CN101580574A (en) * 2009-06-10 2009-11-18 苏州沃斯汀新材料有限公司 Method for preparing fire retardant thermoplastic polyurethane elastomer
CN103467727A (en) * 2013-08-13 2013-12-25 嘉兴市清河高力绝缘有限公司 Preparation method of water soluble polyester resin and its amino baking varnish
CN105482085A (en) * 2015-11-24 2016-04-13 清华大学 Anti-ultraviolet copolyester and preparation method thereof

Also Published As

Publication number Publication date
CN110878137A (en) 2020-03-13

Similar Documents

Publication Publication Date Title
CN110878137B (en) Flame-retardant polyester material, preparation method thereof, granules and fiber product
US5763538A (en) Process for making an oriented polyester article having improved hydrolytic stability
WO2011131057A1 (en) Method for preparing modified poly (1,3-propanediol terephthalate)
CN116574338B (en) High weather-resistant chlorinated polyethylene cable sheath material
CN114634691A (en) Full-biodegradable composite material and preparation method thereof
CN111100307A (en) Thermochromic low-melting-point polyester master batch and preparation method thereof
CN111100267A (en) Photochromic low-melting-point polyester master batch and preparation method thereof
CN106349469B (en) A kind of synthetic method of response type multifunctional copolyesters
CN111101233B (en) Photochromic low-melting-point polyester fiber and preparation method thereof
CN112266589B (en) Creep-resistant PBAT material and preparation method and application thereof
CN101130603A (en) Modified poly- p-benzene dicarboxylic acid trimethylene glycol ester and method for producing the same
CN111621008B (en) Preparation method of antibacterial high-temperature-resistant copolyester
CN109354797A (en) A kind of anti-aging plastics film and its preparation process
CN110903470B (en) PET material and preparation method thereof, and granular material and fiber product
CN109517147B (en) Preparation method of environment-friendly polyester
WO2024078009A1 (en) High-transparency cellulose acetate film capable of being processed at low temperature and preparation method therefor
CN111101234B (en) Thermochromic low-melting-point polyester fiber and preparation method thereof
CN110158185A (en) The technique of waste polyester bottle chip regeneration processing uvioresistant terylene short fiber
CN115433429A (en) Halogen-free flame-retardant PET/ASA alloy material and preparation method thereof
WO2023060560A1 (en) P-n-b flame-retardant pbs plastic and preparation method therefor
SU615866A3 (en) Method of obtaining polyesters
CN114539503B (en) Flame-retardant polyurethane resin for fabric coating and preparation method thereof
CN110845712B (en) Polyester and preparation method thereof
WO2020019227A1 (en) Production process of polyester staple fibers for clothing accessories
CN116376189B (en) High-durability composite decorative film and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant