CN115806660A - Preparation of ionic copolymerized flame-retardant polyester master batch and application of ionic copolymerized flame-retardant polyester master batch in fibers - Google Patents
Preparation of ionic copolymerized flame-retardant polyester master batch and application of ionic copolymerized flame-retardant polyester master batch in fibers Download PDFInfo
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Abstract
The invention relates to a preparation method of an ionic copolymerized flame-retardant polyester master batch and application thereof in fibers, wherein a phosphorus-containing polyester chain segment oligomer and a sulfonate-containing ionic bond chain segment oligomer are subjected to chain extension reaction by diisocyanate to generate the ionic copolymerized flame-retardant polyester master batch; the ionic copolymerized flame-retardant polyester master batch is a block copolymer with the total block number of 6 to 12; the ionic copolymerized flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 15 to 45 percent, and ester bonds are connected among different phosphorus-containing polyester chain segments, different sulfonate ionic bond chain segments and the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments; the application is as follows: adding the ionic copolymerized flame-retardant polyester master batch into a polyester melt for spinning to prepare the modified polyester fiber. The invention ensures good compatibility and spinnability with spinning polyester melt, and the prepared modified polyester fiber has excellent mechanical property and flame retardant property.
Description
Technical Field
The invention belongs to the technical field of polyester, and relates to preparation of an ionic copolymerized flame-retardant polyester master batch and application of the ionic copolymerized flame-retardant polyester master batch in fibers.
Background
The fiber material is a basic unit of textile, and the innovation development of the textile industry is inseparable with the technical upgrading of the fiber. Wherein the polyester fiber variety is the first major variety of fiber material. The polyester fiber material meets basic performances such as basic mechanical strength and the like and is continuously developed towards differentiation and functionalization directions. The polyester fiber material modifying technology includes polymerization modification, blending modification, post-treatment of fiber and other steps. The method for blending and spinning by introducing the functional master batches is the most common method at present, and has the advantages of flexibility, simplicity and convenience and the like. The functional master batch is usually formed by loading functional materials such as inorganic materials with antibacterial, delustering and far infrared functions, metal oxide materials, salts and the like in a thermoplastic polymer at a high content, and then mixing and granulating the mixture by combining with other auxiliaries such as a dispersing agent, a heat stabilizer and the like. The flame-retardant functional master batch in the functional master batch for the fiber is a modification method capable of remarkably improving the flame retardance of the polyester fiber material, wherein the use of a phosphorus flame retardant and other compounded auxiliary flame retardants becomes the main research direction of the flame-retardant master batch.
At present, the design and development of the flame-retardant master batch for surrounding the polyester fiber mainly develop towards two major directions: one is that multifunctional compounding is carried out on the basis of flame retardance, such as flame retardance, hydrophilicity, flame retardance, color and the like; and the other is how to further strengthen the melt drip resistance on the basis of the existing flame retardance, and the fiber prepared by blending and spinning has higher mechanical strength and the like. The preparation technology of the master batch is mainly divided into two types, one is to prepare the flame retardant and other auxiliary reagents in a blending mode to obtain blended flame-retardant polyester master batch, and the other is to prepare the master batch with high content of flame retardant in a polymerization mode.
In the melt direct spinning preparation method of the CN109252240A flame-retardant antibacterial polyester fiber, the flame-retardant antibacterial master batch is formed by mixing a flame retardant and a metal modified hyperbranched polymer, wherein the metal modified hyperbranched polymer is a network polymer formed by crosslinking a hyperbranched polymer with carboxyl at the end group and metal ions, and has the characteristics of insolubility and infusibility; the crosslinking is realized by connecting oxygen atoms on double bonds in the terminal group carboxyl-containing hyperbranched polymer molecules with metal ions through coordination bonds, and simultaneously connecting acid radical ions at the tail ends of the terminal group carboxyl-containing hyperbranched polymer molecules with the metal ions through ionic bonds. CN106498542B relates to a non-dyeing environment-friendly flame-retardant fiber and a preparation method thereof, wherein a pentaerythritol diphosphonate bis-dimethyl amino alcohol ester flame retardant, polybutylene terephthalate and a pigment are used as raw materials, and a double-screw extruder is adopted for melt blending extrusion to prepare the non-dyeing environment-friendly flame-retardant master batch. CN103590134B relates to an anti-ultraviolet, flame-retardant, anti-droplet, moisture-absorbing and sweat-releasing polyester monofilament and a preparation method thereof, wherein the flame-retardant and anti-droplet master batch is prepared by coating ammonium polyphosphate with a silane coupling agent, so that the compatibility of the ammonium polyphosphate and polyester is improved, and the anti-droplet performance of a flame retardant is also improved. CN103173888B discloses a halogen-free flame-retardant polyester material and a preparation method thereof, the flame-retardant master batch is prepared by the following raw materials by weight percentage: high molecular weight polyethylene glycol modified polyester is mixed with the phosphorus-containing flame retardant for granulation by adopting toluene diisocyanate, and the polyethylene glycol grafted on the polyester in the polyethylene glycol modified polyester is used for cooperating with the flame retardant component in the flame retardant for dehydration and carbonization, so that the thickness of a carbonized layer and the amount of residual carbon are increased, and the barrier effect is further enhanced. CN104292772B relates to a polytetrafluoroethylene molten drop-resistant master batch and a preparation method thereof. The polytetrafluoroethylene molten drop preventing master batch is composed of polytetrafluoroethylene powder irradiated by thermoplastic resin.
As described above, the blending method is to blend and granulate the flame retardant, the auxiliary agent and the carrier resin directly, but various requirements are made on the heat resistance, dispersibility and the like of the flame retardant for spinning, and although the blended masterbatch is easy to manufacture, the low molecular weight or incompatible flame retardant or flame retardant of inorganic materials may cause a decrease in spinnability.
The invention Chinese patent CN104451937B discloses an antifouling flame-retardant anti-dripping multifunctional copolyester fiber and a preparation method thereof, wherein the copolyester master batch takes terephthalic acid, ethylene glycol and hexafluoropropylene oxide as raw materials, the hexafluoropropylene oxide is subjected to a ring-opening reaction and then is subjected to a low-temperature reaction with the terephthalic acid, and then a high-temperature esterification reaction is carried out to prepare the high-fluorine polyester master batch with the antifouling flame-retardant anti-dripping function. Chinese patent CN 11356698B discloses a reactive functional polyester master batch and a preparation method thereof, wherein a molecular chain of the reactive functional polyester master batch is composed of a dibasic acid and dihydric alcohol polymerization chain segment and a hydroxyl-terminated modified copolymerization component chain segment, and simultaneously, the components also contain a nano inorganic nucleating agent. The combined action of the two modification components is introduced to solve the problems of high proportion copolymerization effectiveness of the functional components and the crystallization of the master batch to meet the use requirement. The Chinese invention patent CN114000226A relates to a method for preparing cation dyeable flame-retardant high-strength polyester fiber, which comprises mixing oligomer A, oligomer B and ethylene terephthalate, and performing polycondensation reaction to obtain cation dyeable flame-retardant polyester master batch. The polycondensation reaction carried out after the oligomer A, the oligomer B and the ethylene terephthalate are mixed is essentially a transesterification reaction to prepare the block copolyester. However, the oligomer A, the oligomer B and the ethylene terephthalate are mixed in one step, the ester exchange reaction activity of different oligomers is different, and the order of the prepared copolyester master batch is difficult to control.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of ionic copolymerized flame-retardant polyester master batch and application of the ionic copolymerized flame-retardant polyester master batch in fibers. The copolymerization type flame-retardant master batch for the fiber can copolymerize a high-content flame retardant into a matrix polymer, and the master batch has good fluidity, but the copolymerization introduction of the high-proportion flame retardant leads to the reduction of the molecular arrangement regularity, so that the crystallinity of the master batch is reduced, and the processability is deteriorated; the invention designs and invents a preparation method of ionic copolymerization flame-retardant master batch, which has good spinnability when being applied to fiber forming, and the fiber has excellent mechanical property and flame retardant property.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of ionic copolymerized flame-retardant polyester master batch comprises the steps of carrying out diisocyanate chain extension reaction on phosphorus-containing polyester chain segment oligomer and sulfonate-containing ionic bond chain segment oligomer to generate ionic copolymerized flame-retardant polyester master batch; compared with the conventional polyester chain segment, the phosphorus polyester chain segment has reduced ester exchange reaction activity and heat-resistant stability, and if the direct polycondensation reaction is adopted, the long reaction time and high-temperature degradation side reaction are increased; the diisocyanate is adopted to directly carry out chain extension, so that the reaction rate is high, and the retention time is short;
the ionic copolymerized flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 6 to 12;
the ionic copolymerized flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 15-45%, and ester bonds are connected among different phosphorus-containing polyester chain segments, different sulfonate ionic bond chain segments and the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments.
As a preferred technical scheme:
the preparation method of the ionic copolymerized flame-retardant polyester master batch comprises the following steps of 2 to 10 of repeating units of the phosphorus-containing polyester chain segment and 2 to 4 of repeating units of the sulfonate-containing ionic bond chain segment.
According to the preparation method of the ionic copolymerized flame-retardant polyester master batch, the phosphorus-containing polyester chain segment oligomer is prepared by esterification reaction of mixed dibasic acid and dihydric alcohol I;
the molar ratio of the mixed dibasic acid to the diol I is 1.2 to 2.0;
the mixed dibasic acid consists of dibasic acid A (a phosphorus-containing flame retardant with carboxyl) and dibasic acid B, wherein the dibasic acid A is [ (6-oxygen-6H-dibenzo- (C, e) (1, 2) -oxyphosphate cyclohexane-6-ketone) -methyl ] -succinic acid (DDP), 2-carboxyethyl phenyl hypophosphorous acid (CEPPA) or bis (4-carboxyphenyl) phenyl phosphine oxide (BCPPO), and the dibasic acid B is one of C4-C10 aliphatic dibasic acids; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 20 to 60 percent;
the dihydric alcohol I is one of C2-C5 aliphatic dihydric alcohols.
In the preparation method of the ionic copolymerized flame-retardant polyester master batch, the catalyst for the esterification reaction is ethylene glycol titanium, antimony acetate or antimony oxide, and the dosage of the catalyst is 100 to 1000ppm of the mass of the mixed dibasic acid.
The preparation method of the ionic copolymerization flame-retardant polyester master batch has the advantages that the temperature of esterification reaction is 150 to 220 ℃, the pressure is 0.01 to 0.05MPa, and the time is 1.0 to 2.5 hours.
The preparation method of the ionic copolymerization flame-retardant polyester master batch comprises the steps of preparing a sulfonate-containing ionic bond chain segment oligomer by a segmented esterification reaction of dibasic acid C and dihydric alcohol II;
the molar ratio of the number of carboxyl functional groups of the dibasic acid C added in the first stage of esterification reaction to the number of hydroxyl functional groups of the dihydric alcohol II is 1.05 to 1.50; only adding dihydric alcohol II into the second stage of esterification reaction, wherein the addition amount is 10 to 60 percent of the molar amount of the dibasic acid C added into the first stage of esterification reaction;
the dibasic acid C is isophthalic acid-5-sodium sulfonate or terephthalic acid-2-sodium sulfonate;
the dihydric alcohol II is 2, 5-dihydroxy benzene sulfonic acid potassium, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt, 2- [ (tri (hydroxymethyl) methyl) amino ] -1-ethanesulfonic acid sodium salt or 3- [ N-tri (hydroxymethyl) methylamine ] -2-hydroxypropanesulfonic acid sodium salt.
In the preparation method of the ionic copolymerized flame-retardant polyester master batch, the catalyst of the segmented esterification reaction is benzenesulfonic acid, and the dosage of the benzenesulfonic acid is 1000 to 5000ppm of the mass of the dibasic acid C during the first esterification reaction.
The preparation method of the ionic copolymerization flame-retardant polyester master batch comprises the following steps that the temperature of the first-stage esterification reaction is 220-250 ℃, the pressure is 0.05-0.5 MPa, and the time is 3.0-5.0 hours;
the temperature of the second stage esterification reaction is 240 to 260 ℃, the pressure is 0.1 to 0.5MPa, and the time is 0.5 to 1.0h.
In the preparation method of the ionic copolymerization flame-retardant polyester master batch, the diisocyanate chain extension reaction is that firstly, diisocyanate is added into a phosphorus-containing polyester chain segment oligomer, the molar ratio of the diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.05 to 1.20, the reaction temperature is 150 to 250 ℃, the reaction time is 30 to 60min, then, a sulfonate-containing ionomer chain segment oligomer is added, the sulfonate-containing ionomer chain segment oligomer is 15 to 45 percent of the molar quantity of the phosphorus-containing polyester chain segment oligomer, the reaction temperature is 150 to 250 ℃, and the reaction time is 45 to 90min.
The preparation method of the ionic copolymerized flame-retardant polyester master batch is characterized in that the diisocyanate is 1, 6-hexamethylene diisocyanate, toluene diisocyanate or dicyclohexylmethane diisocyanate.
The preparation method of the ionic copolymerized flame-retardant polyester master batch comprises the steps that the melt index of the ionic copolymerized flame-retardant polyester master batch is 15 to 40g/10min, and the semi-crystallization time t 1/2 6 to 15min, 0.50 to 0.70dl/g of intrinsic viscosity, 32 to 36 percent of limiting oxygen index, no molten drop and less than or equal to 4 of b value.
The invention also provides the application of the ionic copolymerized flame-retardant polyester master batch prepared by the method, and the ionic copolymerized flame-retardant polyester master batch is added into the polyester melt for spinning to prepare modified polyester fiber;
the addition amount of the ionic copolymerized flame-retardant polyester master batch is 4 to 10 percent of the mass of the polyester melt; the breaking strength of the modified polyester fiber is more than or equal to 3.5cN/dtex, the limiting oxygen index is 28 to 32 percent, and the modified polyester fiber has no molten drop and can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
The method of adding functional master batches in the fiber differential functional modification technology is the most commonly used technology. The flame-retardant functional master batch in the functional master batch for the fiber is a modification method capable of remarkably improving the polyester fiber material, wherein the use of a phosphorus flame retardant and other compounded auxiliary flame retardants becomes the main research direction of the flame-retardant master batch. At present, the design and development of the flame-retardant master batch for surrounding the polyester fiber are mainly developed towards two major directions: one is that multifunctional compounding is carried out on the basis of flame retardance, such as flame retardance, hydrophilicity, flame retardance, color and the like; and the other is how to further strengthen the melt drip resistance on the basis of the existing flame retardance, and the fiber prepared by blending and spinning has higher mechanical strength and the like. The preparation technology of the master batch is mainly divided into two types, one is to prepare the blend type flame-retardant polyester master batch by blending the flame retardant and other auxiliary reagents, and the other is to prepare the master batch with high content of flame retardant by copolymerization in a polymerization mode. The blending method is to blend and granulate the flame retardant, the auxiliary agent and the carrier resin directly, but when the blend type masterbatch is used for spinning, various requirements are put on the heat resistance, the dispersibility and the like of the flame retardant, and although the blend type masterbatch is convenient to manufacture, the low molecular weight or incompatible flame retardant or the flame retardant of an inorganic material can cause the reduction of the spinnability. The copolymerization type flame-retardant master batch for the fiber can copolymerize a high-content flame retardant into a matrix polymer, and the master batch has good fluidity, but the copolymerization introduction of the high-proportion flame retardant leads to the reduction of the molecular arrangement regularity, so that the crystallinity of the master batch is reduced, and the processability is poor. The invention designs and develops a preparation method of an ionic copolymerization flame-retardant master batch, which has good spinnability when being applied to fiber forming, and the fiber has excellent mechanical property and flame retardant property.
The invention adopts a copolymerization method to prepare the copolyester master batch carrier with ionic groups. The copolyester master batch consists of a phosphorus-containing polyester chain segment and a sulfonate-containing ionic bond chain segment. Firstly, both chain segments are hydroxyl-terminated oligomers with a certain low degree of polymerization formed by esterification reaction, and then the two chain segments are subjected to chain extension reaction to form copolyester with a block ordered structure. The phosphorus-containing polyester chain segment is obtained by esterification reaction of mixed dibasic acid of dihydric alcohol and phosphorus-containing flame retardant, and the oligomer is terminated by the dihydric alcohol after the esterification reaction is finished by controlling the molar ratio of the alcohol acid and the excessive dihydric alcohol. The sulfonate ionic chain segment is designed into segmented esterification due to the reason that the steric hindrance of sulfonate is larger and the prepared oligomer has higher reactivity. The first stage of esterification is to make the number of the dibasic acid carboxyl functional groups containing the sulfonate ionic groups excessive so as to ensure that the alcohol monomer containing the sulfonate ionic groups fully reacts. At the end of the first stage esterification reaction, because the carboxyl is excessive, the product is terminated with dibasic acid. And excessive end-capped dihydric alcohol is introduced in the second stage of esterification reaction to fully react with the first stage of esterification product to form an ionic chain segment. The phosphorus-containing polyester chain segment and the ionic chain segment are both diol terminated oligomers, and the final product is prepared through chain extension reaction. Diisocyanate is used as a chain extender, and the chain extension reaction is gradually carried out. Firstly, diisocyanate is added into the phosphorus-containing polyester chain segment, the mole number of diisocyanate-NCO groups is excessive, hydroxyl-OH in the phosphorus-containing polyester chain segment can be completely reacted, the isocyanate is blocked, and then the sulfonate ionic bond chain segment is introduced for further reaction to prepare the copolyester master batch with the ordered block structure.
The phosphorus-containing polyester chain segment and the sulfonate ionic chain segment in the invention are oligomers with certain molecular weight, and the copolyester with a block type ordered structure is prepared by regulating and controlling the mixing ratio and the polymerization process. The prepared ionic flame-retardant polyester master batch has certain crystallizability due to the ordered macromolecular structure, and the problem that the crystallization performance of the conventional copolymerization master batch matrix is often regulated and controlled by introducing an inorganic nucleating agent and the like is solved. Chain segments in the prepared ionic flame-retardant polyester master batch are connected by ester bonds, contain a large number of ester bond functional groups, and ensure good compatibility with spinning polyester melt. The ionic flame-retardant polyester master batch has higher molecular weight, has the structural characteristic of alloy when being introduced into polyester melt for blending, and ensures the good mechanical property of the fiber.
Ionomers generally have better mechanical properties and thermal stability than their matrix polymers. The ionic flame-retardant polyester master batch prepared by the invention contains abundant sulfonate ionic bonds, and because multiple ion pairs and ion clusters exist in the ionomer, the aggregates can generate a crosslinking effect, so that the interaction between molecular chains is enhanced, and the mechanical strength of the fiber can be obviously enhanced when the aggregates are introduced into a fiber material. Meanwhile, the crosslinking is reversible crosslinking and can be dissociated under a certain shearing acting force, so that the thermoplasticity of the master batch is ensured. When the master batch is introduced into the fiber material, the introduction of the phosphorus-containing flame-retardant chain segment enhances the flame-retardant performance of the fiber, and sulfonate ionic bonds can rapidly form a cross-linked structure on the surface of the fiber material in combustion by virtue of the ionic cluster effect of the sulfonate ionic bonds, so that a compact carbon layer is formed, and the continuation of combustion is blocked. The cross-linked structure prevents the formation of molten drops and avoids secondary damage. The phosphorus-containing polyester chain segment and the sulfonate ionic bond chain segment play a role in synergistic flame retardance.
Advantageous effects
(1) The ionic flame-retardant polyester master batch disclosed by the invention is composed of a phosphorus-containing nonionic chain segment and a sulfonate ionic chain segment, the carrier prepared by controlling the lengths of the nonionic chain segment and the ionic chain segment, the material feeding ratio and the optimization of a copolymerization process is a copolyester with a block ordered structure, the copolyester has certain crystallizability, the chain segments are connected by ester bonds and contain a large number of ester bond functional groups, and the good compatibility and spinnability with a spinning polyester melt are ensured.
(2) The ionic flame-retardant polyester master batch contains abundant ionic groups, and due to the existence of multiple ion pairs and ion clusters in the ionomer, the aggregates can generate a crosslinking effect, so that the interaction between molecular chains is enhanced, and the mechanical strength of the fiber is obviously enhanced. The sulfonate ionic bond can rapidly form a cross-linking structure on the surface of the fiber material in combustion by virtue of the ionic cluster effect of the sulfonate ionic bond, so as to form a compact carbon layer and block the continuation of combustion. The cross-linked structure prevents the formation of molten drops and avoids secondary damage. The phosphorus-containing polyester chain segment and the sulfonate ionic bond chain segment play a role in synergistic flame retardance.
Detailed Description
The present invention will be further described with reference to the following embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention can be made by those skilled in the art after reading the teaching of the present invention, and these equivalents also fall within the scope of the claims appended to the present application.
The test method adopted by the invention is as follows:
(1) Melt index: according to the provisions of GB/T3682.1-2018, the melt index of the ionic type copolymerization flame-retardant polyester master batch is measured under the conditions that the temperature is 280 ℃ and the load is 2.16 kg;
(2) Semi-crystallization time t 1/2 : testing the sample by adopting a DSC model Q-20 of American TA company; before testing, the sample is dried for 24 hours at the temperature of 135 ℃ by vacuum pumping; nitrogen atmosphere, heating rate: 10 ℃/min, raising the test temperature from 25 ℃ to 300 ℃, keeping for 3min to eliminate the thermal history, and then reducing the temperature from 300 ℃ to 25 ℃; the peak appeared in the process of reducing the temperature from 300 ℃ to 25 ℃ is called as the cooling crystallization peak, and the temperature corresponding to the peak is the cooling crystallization temperature. The time required for the whole process from the beginning of crystallization to the completion of crystallization of the sample is the crystallization time, the semi-crystallization time t 1/2 Is the time corresponding to a crystallinity of 50%;
(3) Intrinsic viscosity: testing the intrinsic viscosity of the ionic type copolymerization flame-retardant polyester master batch according to GB/T14190-2017; in the following examples of the invention, the mass ratio of phenol to 1, 2-tetrachloroethane is 50 for testing;
(4) Limiting oxygen index: GB/T2406.2-2009 plastics use the oxygen index method to determine the limit oxygen index of the burning behavior test sample, the sample uses the vertical injection machine to inject the sample into the sample strip with the length of 100mm, the width of 10mm and the thickness of 4mm after vacuum drying for 24h at 120 ℃, and the intelligent oxygen index tester is used for testing;
(5) b value: testing the b value of a sample slice by a GB/T14190-2017 fiber-grade Polyester (PET) slice test method, placing the sample into a forced air drying box for crystallization before testing, taking out the sample, crushing, sieving, and testing the b value of the sample by an automatic color difference instrument (D65 light source, 10-degree visual angle, hunter Lab color system);
(6) Breaking strength: and (3) testing the dry fracture strength by using a test method for the tensile property of the chemical fiber filament GB/T14344-2008.
Example 1
A preparation method of ionic copolymerized flame-retardant polyester master batch comprises the following specific steps:
(1) Mixing the mixed dibasic acid with ethylene glycol according to a molar ratio of 1:1.2, and carrying out esterification reaction for 1h at 150 ℃ and under the pressure of 0.05MPa to prepare a phosphorus-containing polyester chain segment oligomer;
wherein the mixed dibasic acid consists of dibasic acid A and dibasic acid B, the dibasic acid A is DDP, and the dibasic acid B is 1, 4-succinic acid; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 20%; the catalyst for the esterification reaction is ethylene glycol titanium, and the dosage of the ethylene glycol titanium is 100ppm of the mass of the mixed dibasic acid;
(2) Carrying out segmented esterification reaction on 5-sodium m-phthalic acid and potassium 2, 5-dihydroxy benzene sulfonate to prepare a chain segment oligomer containing sulfonate ionic bonds;
wherein, the mole ratio of the carboxyl functional group number of the isophthalic acid-5-sodium sulfonate added in the first stage of esterification reaction to the hydroxyl functional group number of the 2, 5-dihydroxy benzene potassium sulfonate is 1.05; only adding 2, 5-dihydroxy benzene sulfonic acid potassium in the second stage of esterification reaction, wherein the adding amount is 10 percent of the molar amount of isophthalic acid-5-sodium sulfonate added in the first stage of esterification reaction;
the catalyst of the segmented esterification reaction is benzenesulfonic acid, and the dosage of the benzenesulfonic acid is 1000ppm of the mass of 5-sodium sulfoisophthalate during the first esterification reaction;
the temperature of the first stage of esterification reaction is 220 ℃, the pressure is 0.5MPa, and the time is 3h; the temperature of the second stage esterification reaction is 240 ℃, the pressure is 0.1MPa, and the time is 1h;
(3) Firstly, adding 1, 6-hexamethylene diisocyanate into the phosphorus-containing polyester chain segment oligomer obtained in the step (1), wherein the molar ratio of the 1, 6-hexamethylene diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.20, the reaction temperature is 150 ℃, the reaction time is 30min, then adding the sulfonate-containing ionic bond chain segment oligomer obtained in the step (2), the sulfonate-containing ionic bond chain segment oligomer is 15% of the molar amount of the phosphorus-containing polyester chain segment oligomer, the reaction temperature is 150 ℃, and the reaction time is 45min, and generating the ionic copolymerized flame-retardant polyester master batch.
The prepared ionic copolymerization flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 12; the ionic type copolymerized flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 15%, and different phosphorus-containing polyester chain segments, different sulfonate ionic bond chain segments and the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments are connected by ester bonds; the repeating unit of the phosphorus-containing polyester chain segment is 10, and the repeating unit of the sulfonate-containing ionic bond chain segment is 2;
the melt index of the ionic copolymerized flame-retardant polyester master batch is 40g/10min, and the semicrystallization time t 1/2 6min, the intrinsic viscosity is 0.50dl/g, the limiting oxygen index is 36.0 percent, no molten drop exists, and the b value is 3;
the ionic copolymerized flame-retardant polyester master batch is added into a polyester melt for spinning to prepare the modified polyester fiber, the addition amount of the ionic copolymerized flame-retardant polyester master batch is 5 percent of the mass of the polyester melt, the breaking strength of the modified polyester fiber is 3.5cN/dtex, the limiting oxygen index is 32.0 percent, and the ionic copolymerized flame-retardant polyester fiber is free of molten drops and can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
Example 2
A preparation method of ionic copolymerized flame-retardant polyester master batch comprises the following specific steps:
(1) Mixing the mixed dibasic acid and 1, 5-pentanediol according to the molar ratio of 1;
wherein the mixed dibasic acid consists of dibasic acid A and dibasic acid B, the dibasic acid A is CEPPA, and the dibasic acid B is 1, 10-sebacic acid; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 25 percent; the catalyst of the esterification reaction is ethylene glycol titanium, and the dosage of the ethylene glycol titanium is 110ppm of the mass of the mixed dibasic acid;
(2) Performing segmented esterification reaction on 5-sodium m-phthalate and N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt to prepare a sulfonate-containing ionic bond chain segment oligomer;
wherein, the mole ratio of the carboxyl functional group number of the isophthalic acid-5-sodium sulfonate added in the first stage of esterification reaction to the hydroxyl functional group number of the N, N-bis (2-hydroxyethyl) -2-aminoethanesodium sulfonate is 1.5; only adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt in the second stage of esterification reaction, wherein the adding amount is 60% of the molar amount of the m-phthalic acid-5-sodium sulfonate added in the first stage of esterification reaction;
the catalyst of the segmented esterification reaction is benzenesulfonic acid, and the dosage of benzenesulfonic acid is 5000ppm of the mass of 5-sodium sulfoisophthalate during the first esterification reaction;
the temperature of the first stage of esterification reaction is 250 ℃, the pressure is 0.05MPa, and the time is 5h; the temperature of the second stage esterification reaction is 260 ℃, the pressure is 0.5MPa, and the time is 0.5h;
(3) Firstly, adding 1, 6-hexamethylene diisocyanate into the phosphorus-containing polyester chain segment oligomer obtained in the step (1), wherein the molar ratio of the 1, 6-hexamethylene diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.05.
The prepared ionic copolymerization flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 6; the ionic type copolymerization flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 45 percent, and ester bonds are connected among different phosphorus-containing polyester chain segments, among different sulfonate ionic bond chain segments and between the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments; the repeating unit of the phosphorus-containing polyester chain segment is 2, and the repeating unit of the sulfonate-containing ionic bond chain segment is 2;
the melt index of the ionic copolymerized flame-retardant polyester master batch is 27g/10min, and the semicrystallization time t 1/2 9min, intrinsic viscosity of 0.61dl/g, limiting oxygen index of 32.0 percent, no molten drop and b value of 4;
the ionic copolymerized flame-retardant polyester master batch is added into a polyester melt to prepare the modified polyester fiber through spinning, the addition amount of the ionic copolymerized flame-retardant polyester master batch is 5% of the mass of the polyester melt, the breaking strength of the modified polyester fiber is 4.4cN/dtex, the limiting oxygen index is 28.0%, and the ionic copolymerized flame-retardant polyester master batch is free of molten drops and can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
Example 3
A preparation method of ionic copolymerized flame-retardant polyester master batch comprises the following specific steps:
(1) Mixing the mixed dibasic acid with ethylene glycol according to a molar ratio of 1;
wherein the mixed dibasic acid consists of dibasic acid A and dibasic acid B, the dibasic acid A is BCPPO, and the dibasic acid B is 1, 5-glutaric acid; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 30 percent; the catalyst of the esterification reaction is antimony acetate, and the dosage of the antimony acetate is 300ppm of the mass of the mixed dibasic acid;
(2) Performing segmented esterification reaction on 5-sodium sulfoisophthalate and 2- [ (tri (hydroxymethyl) methyl) amino ] -1-ethanesulfonic acid sodium salt to prepare a chain segment oligomer containing sulfonate ionic bonds;
wherein, the mole ratio of the carboxyl functional group number of the isophthalic acid-5-sodium sulfonate added in the first stage of esterification reaction to the hydroxyl functional group number of the 2- [ (tri (hydroxymethyl) methyl) amino ] -1-sodium ethanesulfonate is 1.1; only 2- [ (tri (hydroxymethyl) methyl) amino ] -1-ethanesulfonic acid sodium is added in the second stage of esterification reaction, and the addition amount is 20 percent of the molar amount of the isophthalic acid-5-sulfonic acid sodium added in the first stage of esterification reaction;
the catalyst of the segmented esterification reaction is benzenesulfonic acid, and the dosage of benzenesulfonic acid is 2000ppm of the mass of 5-sodium sulfoisophthalate during the first esterification reaction;
the temperature of the first stage of esterification reaction is 225 ℃, the pressure is 0.1MPa, and the time is 4h; the temperature of the second stage esterification reaction is 245 ℃, the pressure is 0.2MPa, and the time is 0.9h;
(3) Firstly, adding toluene diisocyanate into the phosphorus-containing polyester chain segment oligomer obtained in the step (1), wherein the molar ratio of toluene diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.1.
The prepared ionic copolymerized flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 10; the ionic type copolymerization flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 20 percent, and the different phosphorus-containing polyester chain segments, the different sulfonate ionic bond chain segments and the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments are connected by ester bonds; the repeating unit of the phosphorus-containing polyester chain segment is 8, and the repeating unit of the sulfonate-containing ionic bond chain segment is 3;
the melt index of the ionic copolymerized flame-retardant polyester master batch is 33g/10min, and the semicrystallization time t 1/2 13min, the intrinsic viscosity is 0.66dl/g, the limiting oxygen index is 35.3 percent, no molten drop exists, and the b value is 3;
the ionic copolymerized flame-retardant polyester master batch is added into a polyester melt to prepare the modified polyester fiber through spinning, the addition amount of the ionic copolymerized flame-retardant polyester master batch is 5% of the mass of the polyester melt, the breaking strength of the modified polyester fiber is 3.6cN/dtex, the limiting oxygen index is 31.2%, and the ionic copolymerized flame-retardant polyester master batch is free of molten drops and can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
Example 4
A preparation method of ionic copolymerized flame-retardant polyester master batch comprises the following specific steps:
(1) Mixing the mixed dibasic acid with 1, 4-butanediol according to a molar ratio of 1;
wherein the mixed dibasic acid consists of a dibasic acid A and a dibasic acid B, the dibasic acid A is DDP, and the dibasic acid B is 1, 8-suberic acid; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 40%; the catalyst of the esterification reaction is antimony acetate, and the dosage of the antimony acetate is 800ppm of the mass of the mixed dibasic acid;
(2) Preparing sulfonate ionic bond chain segment-containing oligomer by carrying out segmented esterification reaction on terephthalic acid-2-sodium sulfonate and 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxypropanesulfonic acid sodium;
wherein, the mole ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage of esterification reaction to the hydroxyl functional group number of the 3- [ N-tris (hydroxymethyl) methylamine ] -2-sodium hydroxypropanesulfonate is 1.4; only 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxypropanesulfonic acid sodium salt is added in the second stage of esterification reaction, and the addition amount is 50 percent of the molar amount of the terephthalic acid-2-sodium sulfonate added in the first stage of esterification reaction;
the catalyst of the segmented esterification reaction is benzenesulfonic acid, and the dosage of the benzenesulfonic acid is 4000ppm of the mass of the terephthalic acid-2-sodium sulfonate during the first esterification reaction;
the temperature of the first stage of esterification reaction is 240 ℃, the pressure is 0.4MPa, and the time is 3.5h; the temperature of the second stage of esterification reaction is 255 ℃, the pressure is 0.4MPa, and the time is 0.6h;
(3) Firstly, adding toluene diisocyanate into the phosphorus-containing polyester chain segment oligomer obtained in the step (1), wherein the molar ratio of the toluene diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.12, the reaction temperature is 220 ℃, and the reaction time is 50min, then adding the sulfonate-containing ionic bond chain segment oligomer obtained in the step (2), wherein the sulfonate-containing ionic bond chain segment oligomer is 40% of the molar weight of the phosphorus-containing polyester chain segment oligomer, the reaction temperature is 220 ℃, and the reaction time is 80min, and generating the ionic copolymerized flame-retardant polyester master batch.
The prepared ionic copolymerized flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 8; the ionic type copolymerization flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 40%, and different phosphorus-containing polyester chain segments, different sulfonate ionic bond chain segments and the phosphorus-containing polyester chain segments and sulfonate ionic bond chain segments are connected by ester bonds; the repeating unit of the phosphorus-containing polyester chain segment is 7, and the repeating unit of the chain segment containing sulfonate ionic bond is 4;
the melt index of the ionic copolymerized flame-retardant polyester master batch is 21g/10min, and the semicrystallization time t 1/2 8min, the intrinsic viscosity is 0.57dl/g, the limiting oxygen index is 33.1 percent, no molten drop exists, and the b value is 4;
the ionic copolymerized flame-retardant polyester master batch is added into a polyester melt to prepare the modified polyester fiber through spinning, the addition amount of the ionic copolymerized flame-retardant polyester master batch is 5% of the mass of the polyester melt, the breaking strength of the modified polyester fiber is 4.1cN/dtex, the limiting oxygen index is 29.3%, and the ionic copolymerized flame-retardant polyester master batch is free of molten drops and can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
Example 5
A preparation method of ionic copolymerized flame-retardant polyester master batch comprises the following specific steps:
(1) Mixing the mixed dibasic acid and 1, 3-propylene glycol according to a molar ratio of 1:1.6, and carrying out esterification reaction at 180 ℃ under the pressure of 0.03MPa for 1.5h to prepare a phosphorus-containing polyester chain segment oligomer;
wherein the mixed dibasic acid consists of a dibasic acid A and a dibasic acid B, the dibasic acid A is CEPPA, and the dibasic acid B is 1, 7-pimelic acid; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 50%; the catalyst of the esterification reaction is antimony oxide, and the dosage of the antimony oxide is 1000ppm of the mass of the mixed dibasic acid;
(2) Carrying out segmented esterification reaction on terephthalic acid-2-sodium sulfonate and 2, 5-dihydroxy benzene potassium sulfonate to prepare a sulfonate-containing ionic bond chain segment oligomer;
wherein, the mole ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage of esterification reaction to the hydroxyl functional group number of the 2, 5-dihydroxy benzene potassium sulfonate is 1.2; only adding 2, 5-dihydroxy benzene sulfonic acid potassium in the second stage of esterification reaction, wherein the adding amount is 40 percent of the molar amount of terephthalic acid-2-sodium sulfonate added in the first stage of esterification reaction;
the catalyst of the segmented esterification reaction is benzenesulfonic acid, and the dosage of the benzenesulfonic acid is 3000ppm of the mass of terephthalic acid-2-sodium sulfonate during the first esterification reaction;
the temperature of the first stage of esterification reaction is 230 ℃, the pressure is 0.2MPa, and the time is 4.5h; the temperature of the second stage esterification reaction is 250 ℃, the pressure is 0.3MPa, and the time is 0.8h;
(3) Firstly, adding dicyclohexylmethane diisocyanate into the phosphorus-containing polyester chain segment oligomer obtained in the step (1), wherein the molar ratio of dicyclohexylmethane diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.15, the reaction temperature is 200 ℃, the reaction time is 40min, then adding the sulfonate-containing ionic bond chain segment oligomer obtained in the step (2), the sulfonate-containing ionic bond chain segment oligomer is 30% of the molar amount of the phosphorus-containing polyester chain segment oligomer, the reaction temperature is 180 ℃, and the reaction time is 60min, so as to generate the ionic copolymerized flame-retardant polyester master batch.
The prepared ionic copolymerized flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 9; the ionic type copolymerized flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 30%, and different phosphorus-containing polyester chain segments, different sulfonate ionic bond chain segments and the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments are connected by ester bonds; the repeating unit of the phosphorus-containing polyester chain segment is 6, and the repeating unit of the chain segment containing sulfonate ionic bond is 4;
the melt index of the ionic copolymerized flame-retardant polyester master batch is 29g/10min, and the semicrystallization time t 1/2 11min, intrinsic viscosity of 0.63dl/g, limited oxygen index of 34.4 percent, no molten drop and b value of 3;
the ionic copolymerized flame-retardant polyester master batch is added into a polyester melt to prepare the modified polyester fiber through spinning, the addition amount of the ionic copolymerized flame-retardant polyester master batch is 5% of the mass of the polyester melt, the breaking strength of the modified polyester fiber is 3.8cN/dtex, the limiting oxygen index is 30.4%, and the modified polyester fiber is free of molten drops and can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
Example 6
A preparation method of ionic copolymerized flame-retardant polyester master batch comprises the following specific steps:
(1) Mixing the mixed dibasic acid with ethylene glycol according to a molar ratio of 1:1.4, and carrying out esterification reaction for 1.8h at 210 ℃ and under the pressure of 0.03MPa to obtain a phosphorus-containing polyester chain segment oligomer;
wherein the mixed dibasic acid consists of dibasic acid A and dibasic acid B, the dibasic acid A is BCPPO, and the dibasic acid B is 1.6-adipic acid; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 60%; the catalyst of the esterification reaction is antimony oxide, and the dosage of the antimony oxide is 600ppm of the mass of the mixed dibasic acid;
(2) Preparing sulfonate-containing ionic bond chain segment oligomer by carrying out segmented esterification reaction on terephthalic acid-2-sodium sulfonate and N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium;
wherein, the mole ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage of esterification reaction to the hydroxyl functional group number of the N, N-bis (2-hydroxyethyl) -2-aminoethanesodium sulfonate is 1.3; only adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium into the second stage of esterification reaction, wherein the adding amount is 40 percent of the molar amount of the terephthalic acid-2-sulfonic acid sodium added into the first stage of esterification reaction;
the catalyst of the segmented esterification reaction is benzenesulfonic acid, and the dosage of the benzenesulfonic acid is 2500ppm of the mass of the terephthalic acid-2-sodium sulfonate during the first esterification reaction;
the temperature of the first stage of esterification reaction is 235 ℃, the pressure is 0.3MPa, and the time is 4h; the temperature of the second stage esterification reaction is 250 ℃, the pressure is 0.2MPa, and the time is 0.7h;
(3) Firstly, adding dicyclohexylmethane diisocyanate into the phosphorus-containing polyester chain segment oligomer obtained in the step (1), wherein the molar ratio of the dicyclohexylmethane diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.18, the reaction temperature is 160 ℃, the reaction time is 45min, then adding the sulfonate-containing ionic bond chain segment oligomer obtained in the step (2), the sulfonate-containing ionic bond chain segment oligomer is 35% of the molar amount of the phosphorus-containing polyester chain segment oligomer, the reaction temperature is 200 ℃, and the reaction time is 70min, and generating the ionic copolymerized flame-retardant polyester master batch.
The prepared ionic copolymerized flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 7; the ionic type copolymerization flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 35 percent, and ester bonds are connected among different phosphorus-containing polyester chain segments, among different sulfonate ionic bond chain segments and between the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments; the repeating unit of the phosphorus-containing polyester chain segment is 4, and the repeating unit of the sulfonate-containing ionic bond chain segment is 3;
the melt index of the ionic copolymerized flame-retardant polyester master batch is 15g/10min, and the semicrystallization time t 1/2 15min, the intrinsic viscosity is 0.70dl/g, the limiting oxygen index is 33.8 percent, no molten drop exists, and the b value is 4;
the ionic copolymerized flame-retardant polyester master batch is added into a polyester melt to prepare the modified polyester fiber through spinning, the addition amount of the ionic copolymerized flame-retardant polyester master batch is 5% of the mass of the polyester melt, the breaking strength of the modified polyester fiber is 3.9cN/dtex, the limiting oxygen index is 29.9%, and the modified polyester fiber is free of molten drops and can be widely applied to the fields of home textiles, clothing, industrial textiles and the like.
Claims (12)
1. A preparation method of ionic copolymerized flame-retardant polyester master batch is characterized by comprising the following steps: carrying out chain extension reaction on the phosphorus-containing polyester chain segment oligomer and the sulfonate-containing ionic bond chain segment oligomer through diisocyanate to generate ionic copolymerized flame-retardant polyester master batches;
the ionic copolymerized flame-retardant polyester master batch is a block copolymer, and the total number of blocks of the block copolymer is 6 to 12;
the ionic copolymerized flame-retardant polyester master batch consists of phosphorus-containing polyester chain segments and sulfonate-containing ionic bond chain segments, the molar weight percentage of the sulfonate-containing ionic bond chain segments to the phosphorus-containing polyester chain segments is 15-45%, and ester bonds are connected among different phosphorus-containing polyester chain segments, different sulfonate ionic bond chain segments and the phosphorus-containing polyester chain segments and the sulfonate ionic bond chain segments.
2. The preparation method of the ionic copolymerization flame-retardant polyester master batch according to claim 1, wherein the repeating unit of the phosphorus-containing polyester chain segment is 2 to 10, and the repeating unit of the sulfonate-containing ionic bond chain segment is 2 to 4.
3. The preparation method of the ionic copolymerization flame-retardant polyester masterbatch according to claim 2, wherein the phosphorus-containing polyester chain segment oligomer is prepared by esterification reaction of mixed dibasic acid and dihydric alcohol I;
the molar ratio of the mixed dibasic acid to the diol I is 1.2 to 2.0;
the mixed dibasic acid consists of a dibasic acid A and a dibasic acid B, wherein the dibasic acid A is [ (6-oxygen-6H-dibenzo- (C, e) (1, 2) -oxyphosphatehexacyclo-6-one) -methyl ] -succinic acid, 2-carboxyethylphenylhypophosphorous acid or bis (4-carboxyphenyl) phenylphosphine oxide, and the dibasic acid B is one of C4-C10 aliphatic dibasic acids; the molar weight percentage of the dibasic acid A in the mixed dibasic acid is 20 to 60 percent;
the dihydric alcohol I is one of C2-C5 aliphatic dihydric alcohols.
4. The method for preparing ionic copolymerized flame-retardant polyester masterbatch according to claim 3, wherein the catalyst for esterification is ethylene glycol titanium, antimony acetate or antimony oxide, and the amount of the catalyst is 100 to 1000ppm of the mass of the mixed dibasic acid.
5. The method for preparing the ionic copolymerized flame-retardant polyester master batch according to claim 4, wherein the esterification reaction temperature is 150 to 220 ℃, the pressure is 0.01 to 0.05MPa, and the time is 1.0 to 2.5 hours.
6. The preparation method of the ionic copolymerized flame-retardant polyester masterbatch according to claim 2, wherein the sulfonate-containing ionic bond chain segment oligomer is prepared from dibasic acid C and dihydric alcohol II through segmented esterification reaction;
the molar ratio of the number of carboxyl functional groups of the dibasic acid C added in the first stage of esterification reaction to the number of hydroxyl functional groups of the dihydric alcohol II is 1.05 to 1.50; only adding dihydric alcohol II into the second stage of esterification reaction, wherein the addition amount is 10 to 60 percent of the molar amount of the dibasic acid C added into the first stage of esterification reaction;
the dibasic acid C is isophthalic acid-5-sodium sulfonate or terephthalic acid-2-sodium sulfonate;
the dihydric alcohol II is 2, 5-dihydroxy benzene sulfonic acid potassium, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt, 2- [ (tri (hydroxymethyl) methyl) amino ] -1-ethanesulfonic acid sodium salt or 3- [ N-tri (hydroxymethyl) methylamine ] -2-hydroxypropanesulfonic acid sodium salt.
7. The method for preparing the ionic copolymerization flame-retardant polyester master batch according to claim 6, wherein the catalyst for the staged esterification reaction is benzenesulfonic acid, and the dosage of the benzenesulfonic acid added in the first esterification reaction is 1000 to 5000ppm of the weight of the dibasic acid C.
8. The preparation method of the ionic copolymerization flame-retardant polyester master batch as claimed in claim 7, wherein the temperature of the first stage esterification reaction is 220 to 250 ℃, the pressure is 0.05 to 0.5MPa, and the time is 3.0 to 5.0 hours;
the temperature of the second stage esterification reaction is 240 to 260 ℃, the pressure is 0.1 to 0.5MPa, and the time is 0.5 to 1.0h.
9. The preparation method of the ionic copolymerization flame-retardant polyester master batch according to claim 2, wherein the diisocyanate chain extension reaction is that firstly, diisocyanate is added into the phosphorus-containing polyester chain segment oligomer, the molar ratio of the diisocyanate to the phosphorus-containing polyester chain segment oligomer is 1.05 to 1.20, the reaction temperature is 150 to 250 ℃, the reaction time is 30 to 60min, then, sulfonate-containing ionic bond chain segment oligomer is added, the sulfonate-containing ionic bond chain segment oligomer is 15 to 45 percent of the molar quantity of the phosphorus-containing polyester chain segment oligomer, the reaction temperature is 150 to 250 ℃, and the reaction time is 45 to 90min.
10. The method for preparing the ionic copolymerized flame-retardant polyester masterbatch according to claim 9, wherein the diisocyanate is 1, 6-hexamethylene diisocyanate, toluene diisocyanate or dicyclohexylmethane diisocyanate.
11. The preparation method of the ionic copolymerized flame-retardant polyester master batch as claimed in any one of claims 1 to 10, wherein the ionic copolymerized flame-retardant polyester master batch has a melt index of 15 to 40g/10min and a semicrystallization time t 1/2 6 to 15min, intrinsic viscosity of 0.50 to 0.70dl/g, limited oxygen index of 32 to 36 percent, no molten drop and b value of less than or equal to 4.
12. The application of the ionic copolymerized flame-retardant polyester master batch prepared by the method of any one of claims 1 to 11, wherein the ionic copolymerized flame-retardant polyester master batch is prepared by the following steps: adding the ionic copolymerized flame-retardant polyester master batch into a polyester melt for spinning to prepare modified polyester fiber; the addition amount of the ionic copolymerized flame-retardant polyester master batch is 4 to 10 percent of the mass of the polyester melt; the breaking strength of the modified polyester fiber is more than or equal to 3.5cN/dtex, the limiting oxygen index is 28 to 32 percent, and no molten drop exists.
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