CN115852520B - Preparation method of high-strength biodegradable polyester fiber - Google Patents
Preparation method of high-strength biodegradable polyester fiber Download PDFInfo
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Abstract
The invention relates to a preparation method of high-strength biodegradable polyester fiber, which comprises the steps of adding ionic copolyester into biodegradable polyester for melt spinning to obtain the high-strength biodegradable polyester fiber; the addition amount of the ionic copolyester is 1-10% of the mass of the biodegradable polyester; the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds; the nonionic polyester chain segment repeating unit is 4-10, and the sulfonate ionic polyester chain segment repeating unit is 2-8; the intrinsic viscosity of the ionic copolyester is 0.55-0.85 dl/g; the invention introduces the ionic copolyester into the biodegradable polyester, realizes continuous and stable fiber forming, and remarkably enhances the mechanical strength of the fiber.
Description
Technical Field
The invention belongs to the technical field of polyester, relates to preparation of biodegradable polyester fiber, and in particular relates to a preparation method of high-strength biodegradable polyester fiber.
Background
Fiber materials are basic raw materials in the textile industry. Technological innovation of fiber materials is continuously endowed with new vitality in textile industry. The conventional polyester fiber has stable chemical structure and excellent mechanical properties, and is widely applied to various fields such as home textiles, clothing, industry and the like. In the fields of disposable medical textiles and the like, the fiber materials cannot be recycled after being used, and the used fiber materials are required to have good biodegradability, so that the pollution to the environment is reduced.
Common biodegradable polyesters prepared from long carbon chain dibasic acids and dihydric alcohols include PBAT, PBST, PBS and the like. Wherein PBAT is a terpolymer of terephthalic acid, adipic acid and butanediol, is easy to process, has stronger toughness and good biodegradability, and is decomposed into carbon dioxide, biomass and water under the condition of soil or compost. Meanwhile, the PBAT fiber material has good biodegradability and soft hand feeling compared with fiber materials such as polylactic acid PLA, polyglycolic acid PGA and the like. However, because the synthesis process of PBAT adopts random copolymerization, the PBAT is not easy to crystallize, and the development of PBAT fiber preparation technology and the application of PBAT as a fiber material are restricted. Therefore, the PBAT is used as the raw material to prepare the degradable fiber which meets the requirements of environmental protection and sustainable development, can expand the application field of the fiber, and has important market significance.
The Chinese patent No. 100412242C discloses a preparation method of a poly (terephthalic acid) -co-butylene succinate fiber, which is characterized in that a copolyester is melted and extruded to form a primary yarn, and the primary yarn is subjected to constant temperature and constant humidity balance for 5-13 hours and then is subjected to drafting to prepare the biodegradable polyester fiber. The invention patent CN113201805A relates to a preparation method of PBAT fiber, when the PBAT fiber is spun, the processes of cooling, bundling, oiling, drafting and winding are sequentially carried out, the cooling adopts a mode of combining slow cooling and strong cooling, the cooling process of the PBAT fiber is optimized, namely, when the silk is cooled to the vicinity of the crystallization temperature, the temperature is set to be kept at the vicinity of the crystallization temperature by adopting the slow cooling mode, the sufficient crystallization time is given to the PBAT, the PBAT crystallization is perfected, the crystallinity of the PBAT is improved, the silk adhesion phenomenon of the PBAT fiber in the processes of bundling, winding and the like can be avoided, and the quality of the PBAT fiber is improved. CN103668540B relates to a PBAT fiber and a preparation method thereof, and when the molecular weight of the linear polyester is high and the distribution is uniform, the cooling distance is lengthened in the spinning process, so that the problems of difficult cooling and easy bonding in the spinning process of the PBAT are effectively improved. CN103668541B relates to a degradable fiber containing PBAT and a preparation method thereof, which is prepared from the following components in parts by weight: one or two of polyhydroxybutyrate, polyhydroxybutyrate-valerate, polybutylene succinate or polylactic acid is/are introduced into the poly (butylene adipate/terephthalate) (PBAT), and when the molecular weight of the linear polyester used for spinning is high and the distribution is uniform, the obtained fiber has better performance, and the cooling distance is prolonged in the spinning process, so that the problems of difficult cooling and easy bonding in the PBAT spinning process are effectively solved.
The Chinese patent No. 113122952A relates to a PBAT fiber and a preparation method thereof, wherein a molecular chain segment of the PBAT fiber comprises a butylene terephthalate chain segment, an adipic acid butylene ester chain segment and a isophthalic acid-5-sodium sulfonate butylene ester chain segment, the balance relation between the crystallization capability and the performance of the PBAT is regulated and controlled through the chain segment length, and SSIPA is introduced into the chain segment, so that the fiber performance is improved. CN112048058B relates to a method for preparing high-melting-point crystalline biodegradable copolyester, which comprises mixing isohexide polyester prepolymer, aliphatic polyester prepolymer and chain extender, and reacting to obtain the high-melting-point crystalline biodegradable copolyester. In order to obtain better comprehensive properties (thermal, mechanical and biodegradability), the terephthalic acid content in commercial PBAT and PBST aliphatic-aromatic copolyesters is generally 40-50 mol%. According to Δtm=Δhm/Δsm, the addition of the comonomer destroys the crystalline regularity of the PBS repeat structural units, decreases the segment crystallization enthalpy or increases the segment entropy, and thus the PBAT, PBST biodegradable polyesters have poor crystallization ability. In the block copolymer, when the chain segments of each component are long enough, the crystal regions can be formed, so that the copolymer has certain crystallinity.
The polyester such as the biodegradable PBAT, PBST, PBS has low crystallization capability, the fiber is bonded due to insufficient cooling and solidification in the spinning forming blowing cooling, continuous stable forming is not possible, and the mechanical strength of the fiber is low, so that the application is greatly limited by the factors. It can be seen from the above disclosed technology that, in order to solve the problem, after the biodegradable polyester is subjected to copolymerization modification, the bonding problem between fibers is improved by innovatively strengthening blowing cooling, prolonging blowing area and the like through a spinning process, and the technology reported in the prior art is to perform copolymerization of high-proportion modified components on the biodegradable polyester, improve heat resistance and crystallization performance of the biodegradable polyester, and optimize spinning to form fibers. However, the copolymerization modification of the high-proportion modifying component damages the original chemical sequence structure of the biodegradable polyester, and can have adverse effect on the biodegradability of the fiber. And the method for carrying out the spinning forming of the biodegradable polyester after the copolymerization modification is not flexible in terms of operation and does not have blending addition. Or the crystallization capacity is improved by regulating and controlling the length, sequence structure and introducing other chain segments in the synthesis stage of the biodegradable polyester, but the biodegradability of the synthesized copolyester is often changed, especially when the aromatic heterocycle in the introduced chain segments is added to seriously inhibit the biodegradability of the polyester, and the content is more than 50mol percent, the polymer is difficult to biodegrade.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of high-strength biodegradable polyester fiber. Aiming at the problems that the existing biodegradable PBAT, PBST, PBS and other polyesters cannot be cooled and solidified rapidly due to weak crystallization capability in melt spinning forming, and the fibers are bonded to each other, so that the application is impossible, the crystallization capability of the biodegradable polyester is obviously improved by introducing a certain amount of ionic copolyester into the biodegradable polyester, the continuous and stable forming of the fibers is realized, the fiber strength is greatly improved, and the application requirements are met.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the preparation method of the high-strength biodegradable polyester fiber comprises the steps of adding ionic copolyester into biodegradable polyester for melt spinning to obtain the high-strength biodegradable polyester fiber;
the addition amount of the ionic copolyester is 1-10% of the mass of the biodegradable polyester; most of the existing biodegradable polyesters (including PBAT, PBS, PBST and the like) cannot be sufficiently cooled and solidified in spinning forming blowing cooling, so that fibers are bonded, continuous stable forming cannot be realized, the mechanical strength of the fibers is low, and the application is greatly limited by the factors. The addition amount of the ionic copolyester has an important influence on the performance of the spun biodegradable polyester fiber. If the addition amount of the ionic copolyester is less than 1%, the content of the ionic copolyester in the biodegradable polyester is low, the melt of the biodegradable polyester cannot be effectively regulated and controlled, and the fiber is still extremely easy to generate bonding problem; if the amount of the ionic copolyester is more than 10%, the content of the ionic copolyester in the biodegradable polyester is higher, and although the spinnability of the fiber is greatly improved and the bonding problem does not occur, the biodegradability of the spun fiber is reduced. Therefore, the content of the ionic copolyester in the biodegradable polyester fiber needs to be strictly controlled;
The ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds;
the intrinsic viscosity of the ionic copolyester is 0.55-0.85 dl/g.
As a preferable technical scheme:
according to the preparation method of the high-strength biodegradable polyester fiber, the biodegradable polyester is poly (adipic acid)/butylene terephthalate (PBAT), poly (terephthalic acid)/butylene succinate (PBST), poly (butylene succinate) (PBS), poly (3-hydroxy alkanoate) (PHA) or poly (epsilon-caprolactone) (PCL), and the number average molecular weight of the biodegradable polyester is 50000-100000 g/mol.
The preparation method of the high-strength biodegradable polyester fiber comprises the following steps of: the spinning temperature is 220-280 ℃, the cooling blowing temperature is 15-20 ℃, the relative humidity is 60-85%, the air pressure is 20-80 kPa, the fiber oil content is 0.6-1.5%, the speed of the hot roller GR1 is 1000-1500 m/min, the temperature of the hot roller GR1 is 60-90 ℃, the speed of the hot roller GR2 is 2500-3500 m/min, and the temperature of the hot roller GR2 is 100-120 ℃.
According to the preparation method of the high-strength biodegradable polyester fiber, the nonionic polyester chain segment repeating units are 4-10, and the sulfonate ion polyester chain segment repeating units are 2-8. The number of repeating units of the nonionic polyester chain segment and the sulfonate ion polyester chain segment has important influence on the structure and the performance of the synthesized ionic copolyester, and the number of repeating units must be controlled within the range. When the number of the repeating units is lower than the set range, the two chain segment substances are polymerized according to a fixed mass ratio (namely, the mole numbers of the two chain segment substances are fixed), the synthesized ionic copolyester tends to be random copolyester, the crystallization performance is obviously reduced, and the bonding of the ionic copolyester in the drying process can not be used for spinning; when the number of the repeating units is higher than the set range, when the two chain segment substances are polymerized according to a fixed mass ratio (namely, the mole numbers of the two chain segment substances are fixed), the activity is reduced when the two chain segments are copolymerized due to the fact that the number of the repeating units is too large and the molecular weight is too large, so that the molecular weight of the ionic copolyester cannot meet the spinning requirement, and the ionic copolyester cannot be applied.
The preparation method of the high-strength biodegradable polyester fiber comprises the following steps of: firstly, respectively synthesizing nonionic polyester esterified substance and sulfonate ion polyester esterified substance through esterification reaction, and then carrying out polycondensation reaction on the nonionic polyester esterified substance and the sulfonate ion polyester esterified substance to obtain the ionic copolyester.
According to the preparation method of the high-strength biodegradable polyester fiber, the molar ratio of the nonionic polyester esterified substance to the sulfonate ionic polyester esterified substance is 2:8-8:2.
The nonionic polyester esterified substance is prepared from dibasic acid I and dihydric alcohol I through esterification reaction;
the molar ratio of the dibasic acid I to the dibasic alcohol I is 1:1.05-1.5;
the dibasic acid I is terephthalic acid, isophthalic acid or adipic acid;
the dihydric alcohol I is ethylene glycol, propylene glycol, butanediol or pentanediol.
According to the preparation method of the high-strength biodegradable polyester fiber, the catalyst for esterification reaction of the nonionic polyester esterified product is ethylene glycol titanium, tetrabutyl titanate, ethylene glycol antimony, antimony acetate or antimony oxide, and the dosage of the catalyst is 10-100 ppm of the mass of the dibasic acid I.
According to the preparation method of the high-strength biodegradable polyester fiber, the esterification reaction temperature of the nonionic polyester esterified substance is 150-250 ℃, the pressure is 0.01-0.5 MPa, and the time is 1.5-3.5 hours.
The sulfonate ion polyester esterified substance is prepared from dibasic acid II and dihydric alcohol II through a sectional esterification reaction;
The mole ratio of the carboxyl functional group number of the dibasic acid II to the hydroxyl functional group number of the dibasic alcohol II added in the first stage esterification reaction is 1.05-1.50; only adding dihydric alcohol II in the second-stage esterification reaction, wherein the addition amount is 10-60% of the molar amount of the dihydric acid II added in the first-stage esterification reaction;
dibasic acid II is isophthalic acid-5-sodium sulfonate or terephthalic acid-2-sodium sulfonate;
the dihydric alcohol II is 2, 5-dihydroxybenzene sulfonic acid potassium salt, 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-hydroxy propane sulfonic acid sodium salt.
According to the preparation method of the high-strength biodegradable polyester fiber, the catalyst for the segmented esterification reaction of the sulfonate ion polyester ester is benzenesulfonic acid, and the catalyst is added in the first esterification reaction, wherein the dosage of the catalyst is 10-1000 ppm of the mass of the dibasic acid II.
According to the preparation method of the high-strength biodegradable polyester fiber, 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 h;
the temperature of the second stage esterification reaction is 240-260 ℃, the pressure is 0.1-0.5 MPa, and the time is 0.5-1.0 h.
The preparation method of the high-strength biodegradable polyester fiber comprises the steps of carrying out polycondensation reaction on nonionic polyester esterified substances and sulfonate ionic polyester esterified substances, wherein the polycondensation reaction is divided into a pre-polycondensation reaction and a final polycondensation reaction;
The pre-polycondensation reaction temperature is 240-260 ℃, the reaction time is 0.1-1.0 h, and the pressure is 500-1000 Pa;
the final polycondensation reaction temperature is 260-285 ℃, the reaction time is 1.5-3.0 h, and the pressure is 0-100 Pa.
According to the preparation method of the high-strength biodegradable polyester fiber, the polycondensation catalyst is tetrabutyl titanate, titanium glycol, antimony trioxide, antimony glycol or antimony acetate, and the addition amount is 50-500 ppm of the total mass of sulfonate ion polyester ester and nonionic polyester ester.
According to the preparation method of the high-strength biodegradable polyester fiber, the crystallization temperature of the ionic copolyester modified biodegradable polyester is 50-150 ℃, and the semi-crystallization time is t 1/2 1.0 to 3.0min, and the crystallization enthalpy is 10 to 50J/g.
According to the preparation method of the high-strength biodegradable polyester fiber, the single filament number of the high-strength biodegradable polyester fiber is 1.5-5.0 dtex, the number average molecular weight of the oil-free filaments is reduced to 500-2000 g/mol, the breaking strength of the fiber is more than or equal to 2.50cN/dtex, the breaking elongation is 15.0-35.0%, and the elastic recovery rate is more than or equal to 90% under 2-10% tensile deformation; the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is more than or equal to 60 percent, and the disintegration degree is more than or equal to 90 percent.
Principle of the invention
The PBAT fiber material has good biodegradability and soft hand feeling compared with fiber materials such as polylactic acid PLA, polyglycolic acid PGA and the like. However, the polyester such as the biodegradable PBAT, PBST, PBS has low crystallization capability, and the fiber are bonded due to insufficient cooling and solidification in the spinning forming blowing cooling, so that continuous stable forming is not possible, the mechanical strength of the fiber is low, and the application is greatly limited by the factors. The prior art improves the bonding problem between fibers by innovatively strengthening blowing cooling, prolonging blowing areas and the like through a spinning process, or improves crystallization capability by regulating and controlling the length, sequence structure and introducing other chain segments in the synthesis stage of biodegradable polyester, but the biodegradability of the synthesized copolyester is often changed, especially when aromatic heterocycle in the introduced chain segments is added to seriously inhibit the biodegradability of the polyester, and the content is more than 50mol percent, the polymer is difficult to biodegrade.
The invention introduces the ionic copolyester into the biodegradable polyester, the ionic copolyester is composed of sulfonate ionic polyester chain segments and nonionic polyester chain segments, and the nonionic polyester chain segments and the biodegradable polyester chain segments have good thermodynamic compatibility characteristics, so that the ionic copolyester can be uniformly dispersed in spinning melt. In the process of extruding and cooling the biodegradable polyester melt, the ionic copolyester plays a role of heterogeneous nucleating agent in the biodegradable polyester melt, promotes the melt to crystallize rapidly under the cooling condition, and simultaneously, under the conditions of high-speed spinning and high-power stretching, the melt is subjected to obvious orientation process, the orientation is further subjected to 'induced' crystallization, and when the fiber tows with a certain crystallinity are obviously reduced in bonding phenomenon, the continuous stable forming of fibers is realized.
The invention adopts a copolymerization method to prepare the ionic copolyester, and the copolyester consists of a nonionic chain segment and an ionic chain segment. The two chain segments are first hydroxyl terminated oligomer with certain low polymerization degree and formed through esterification reaction, and the two chain segments are then polycondensed to form copolyester with ordered block structure. The nonionic chain segment is obtained by esterification reaction of dihydric alcohol and dibasic acid, and the molar ratio of the dihydric alcohol is controlled to ensure that the dihydric alcohol is excessive, so that the oligomer is blocked by the dihydric alcohol after the esterification reaction is finished. The invention is designed for staged esterification. The first stage of esterification is to ensure that the alcohol monomer containing sulfonate ion groups fully reacts completely by excessively increasing the number of carboxyl functional groups of dibasic acid containing sulfonate ion groups. At the end of the first esterification reaction, the product is capped with a dibasic acid due to the excess carboxyl groups. And introducing excessive end capped glycol to fully react with the first-stage esterification product during the second-stage esterification reaction to form an ionic chain segment. The nonionic chain segment and the ionic chain segment are diol end-capped oligomers, and the final product is prepared through polycondensation reaction. The polycondensation reaction is divided into pre-polycondensation reaction and final polycondensation reaction, wherein the pre-polycondensation reaction is carried out under a lower vacuum degree, and mainly the relative molecular weight of a nonionic chain segment and an ionic chain segment is lower at the moment, if the high vacuum is directly pumped out of a reaction system, stable copolymerization cannot be realized. When the pre-polycondensation reaction is finished, the molecular weight of the product in the system is increased, and the product can not be pumped out of the reaction system by high vacuum in the final polycondensation reaction, so that stable polymerization can be realized.
The ionic copolyester introduced by the biodegradable polyester generally has better mechanical property and thermal stability than the matrix polymer. The ionic copolyester contains rich sulfonate ionic bonds, and because of the existence of multiple ion pairs and ion clusters in the ionomer, the aggregates can form physical crosslinking points to enhance the interaction between molecular chains, and the mechanical strength of the fiber can be remarkably enhanced when the ionic copolyester is introduced into the fiber material. The improvement of the mechanical property is reflected in the improvement of the breaking strength of the fiber in the stretching process and the improvement of the rebound resilience in a certain deformation range. At the same time, the crosslinking is reversible crosslinking, can be dissociated under a certain shearing force, and ensures thermoplastic processability.
Advantageous effects
(1) The invention introduces the ionic copolyester into the biodegradable polyester, the ionic copolyester plays a role of heterogeneous nucleating agent in the biodegradable polyester melt in the extrusion cooling of the biodegradable polyester melt, and simultaneously, under the conditions of high-speed spinning and high-power stretching, the orientation further induces crystallization, and when the fiber tows reaching a certain crystallinity are obviously reduced in bonding phenomenon, the continuous stable forming of the fibers is realized. The chemical structure of the biodegradable polyester is not changed and new spinning equipment is not required to be additionally added.
(2) The ionic copolyester introduced into the biodegradable polyester contains rich sulfonate ionic bonds, and because multiple ion pairs and ion clusters exist in the ionomer, the aggregates can form the action of physical crosslinking points, the interaction between molecular chains is enhanced, and the mechanical strength of fibers can be remarkably enhanced when the ionic copolyester is introduced into fiber materials. The improvement of the mechanical property is reflected in the improvement of the breaking strength of the fiber in the stretching process and the improvement of the rebound resilience in a certain deformation range.
Detailed Description
The invention is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
The test method adopted by the invention is as follows:
(1) Semi-crystallization time t 1/2 : testing the sample by using DSC model Q-20 of the American TA company; vacuum drying the sample at 135 ℃ for 24 hours before testing; nitrogen atmosphere, rate of temperature increase: 10 ℃/min, the test temperature is raised from 25 ℃ to 300 ℃, the heat history is eliminated after 3min, and then the temperature is lowered from 300 ℃ to 25 ℃; the peak occurring during the cooling from 300 ℃ to 25 ℃ is called cooling crystallization peak, and the temperature corresponding to the peak is cooling crystallization temperature. The time required for the whole process from the start of crystallization to the completion of crystallization of the sample is the crystallization time, the semi-crystallization time t 1/2 The time corresponding to the crystallinity of 50%;
(2) Enthalpy of crystallization: testing the sample by using DSC model Q-20 of the American TA company; vacuum drying the sample at 135 ℃ for 24 hours before testing; nitrogen atmosphere, rate of temperature increase: 10 ℃/min, the test temperature is raised from 25 ℃ to 300 ℃, the heat history is eliminated after 3min, and then the temperature is lowered from 300 ℃ to 25 ℃; the peak occurring in the process of cooling from 300 ℃ to 25 ℃ is called a cooling crystallization peak, and the temperature corresponding to the peak is the cooling crystallization temperature; the cooling crystallization process is an exothermic process, and the total heat released from the whole process from the crystallization start to the crystallization end is the crystallization enthalpy corresponding to the sample with unit mass;
(3) Molecular weight without oil silk: the molecular weight (number average Mn) and molecular weight distribution (PDI) of the polyester were determined by an Agilent 1260 Infinity II gel permeation chromatograph using 1, 3-hexafluoro-2-propanol as eluent at a flow rate of 1mL/min. The sample is dried and dissolved in hexafluoroisopropanol to prepare a solution of 10mg/mL, and the sample is tested when the temperature of the chromatographic column reaches 35+/-1 ℃;
(4) Intrinsic viscosity: testing the intrinsic viscosity of the ionic copolyester according to GB/T14190-2017; in the following examples of the invention, the mass ratio of phenol to 1, 2-tetrachloroethane was 50:50 for the test;
(5) The molecular weights (number average Mn and weight average Mw) and molecular weight distribution (PDI) of the biodegradable polyesters were determined by an Agilent 1260 information II gel permeation chromatograph. 1, 3-hexafluoro-2-propanol was used as eluent at a flow rate of 1mL/min. The sample is dried and dissolved in hexafluoroisopropanol to prepare a solution of 10mg/mL, and the sample is tested when the temperature of the chromatographic column reaches 35+/-1 ℃;
(6) Breaking strength: adopting a dry breaking strength test in GB/T14344-2008 chemical fiber filament tensile property test method;
(7) Elongation at break: the dry state breaking elongation measurement test in GB/T14344-2008 chemical fiber filament tensile property test method is adopted;
(8) Composting biological decomposition rate: the method for measuring the final aerobic biological decomposition capacity of the material under the controlled composting condition of GB/T19277.1-2011 is adopted for testing;
(9) Degree of disintegration: the test was carried out using GB/T19811-2005, determination of the degree of disintegration of plastics materials under the conditions of the defined composting pilot plant.
Example 1
The preparation method of the high-strength biodegradable polyester fiber comprises the following specific steps:
(1) Mixing terephthalic acid and ethylene glycol according to a molar ratio of 1:1.05, and carrying out esterification reaction for 3.5 hours at 250 ℃ under the pressure condition of 0.05MPa to obtain nonionic polyester esterified product;
wherein, the catalyst of the esterification reaction is ethylene glycol titanium, and the dosage of the catalyst is 10ppm of the mass of terephthalic acid;
(2) Carrying out sectional esterification reaction on isophthalic acid-5-sodium sulfonate and 2, 5-dihydroxybenzene potassium sulfonate to obtain sulfonate ion polyester esterified product;
wherein, the mole ratio of the carboxyl functional group number of the isophthalic acid-5-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the 2, 5-dihydroxybenzene potassium sulfonate is 1.05; the second stage esterification reaction only adds 2, 5-dihydroxybenzene sulfonic acid potassium, the addition amount is 10% of the mole amount of isophthalic acid-5-sodium sulfonate added in the first stage esterification reaction;
the catalyst of the staged esterification reaction is benzenesulfonic acid, which is added in the first esterification reaction, and the dosage of the catalyst is 1000ppm of the mass of isophthalic acid-5-sodium sulfonate;
the temperature of the first stage esterification reaction is 220 ℃, the pressure is 0.05MPa, and the time is 3 hours; the temperature of the second stage esterification reaction is 240 ℃, the pressure is 0.1MPa, and the time is 0.5h;
(3) Mixing the nonionic polyester esterified material obtained in the step (1) with the sulfonate ionic polyester esterified material obtained in the step (2) according to a molar ratio of 2:8, performing a pre-polycondensation reaction for 0.1h at 240 ℃ and 1000Pa, and performing a final polycondensation reaction for 1.5h at 260 ℃ and 0Pa to generate the ionic copolyester;
Wherein the polycondensation catalyst is tetrabutyl titanate, and the addition amount is 50ppm of the total mass of sulfonate ion polyester esterified substance and nonionic polyester esterified substance;
the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds; the nonionic polyester chain segment repeating unit is 10, and the sulfonate ionic polyester chain segment repeating unit is 6;
the intrinsic viscosity of the ionic copolyester is 0.55dl/g;
(4) Adding the ionic copolyester obtained in the step (3) into PBAT (number average molecular weight of 100000 g/mol), uniformly mixing to obtain ionic copolyester modified biodegradable polyester, and carrying out melt spinning to obtain high-strength biodegradable polyester fiber;
wherein the addition amount of the ionic copolyester is 1% of the mass of the PBAT;
the technological parameters of melt spinning are as follows: spinning temperature 220 ℃, cooling blowing temperature 15 ℃, relative humidity 60%, air pressure 80kPa, fiber oil content 0.6%, speed 1000m/min of hot roller GR1, temperature 90 ℃ of hot roller GR1, speed 2500m/min of hot roller GR2, temperature 100 ℃ of hot roller GR 2;
The crystallization temperature of the ionic copolyester modified biodegradable polyester is 110 ℃, and the semi-crystallization time is t 1/2 The crystallization enthalpy was 45J/g for 1 min.
The single filament number of the prepared high-strength biodegradable polyester fiber is 1.5dtex, the number average molecular weight of the oil-free fiber is reduced to 2000g/mol, the breaking strength of the fiber is 2.50cN/dtex, the elongation at break is 35.0%, and the elastic recovery rate under 2-10% tensile deformation is 91%;
the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is 60 percent, and the disintegration degree is 90 percent.
Example 2
The preparation method of the high-strength biodegradable polyester fiber comprises the following specific steps:
(1) Mixing isophthalic acid and propylene glycol according to a molar ratio of 1:1.5, and carrying out esterification reaction for 1.5 hours under the conditions of 230 ℃ and 0.5MPa to obtain nonionic polyester esterified product;
wherein, the catalyst of the esterification reaction is tetrabutyl titanate, and the dosage of the tetrabutyl titanate is 20ppm of the mass of isophthalic acid;
(2) The sodium isophthalate-5-sulfonate and N, N-di (2-hydroxyethyl) -2-aminoethanesulfonate are subjected to a staged esterification reaction to prepare sulfonate ion polyester ester;
wherein, the mole ratio of the carboxyl functional group number of the isophthalic acid-5-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the N, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt is 1.5; the second stage esterification is carried out by adding N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium with the addition amount being 60 percent of the mole amount of isophthalic acid-5-sodium sulfonate added in the first stage esterification;
The catalyst of the staged esterification reaction is benzenesulfonic acid, which is added in the first esterification reaction, and the dosage of the catalyst is 10ppm of the mass of isophthalic acid-5-sodium sulfonate;
the temperature of the first stage esterification reaction is 250 ℃, the pressure is 0.5MPa, and the time is 4 hours; the temperature of the second stage esterification reaction is 250 ℃, the pressure is 0.2MPa, and the time is 0.8h;
(3) Mixing the nonionic polyester esterified material obtained in the step (1) with the sulfonate ionic polyester esterified material obtained in the step (2) according to a molar ratio of 8:2, performing pre-polycondensation reaction for 1h at 260 ℃ and 500Pa, and performing final polycondensation reaction for 3h at 285 ℃ and 100Pa to obtain the ionic copolyester;
wherein the polycondensation catalyst is ethylene glycol titanium, and the addition amount is 60ppm of the total mass of sulfonate ion polyester esterified substance and nonionic polyester esterified substance;
the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds; the nonionic polyester chain segment repeating unit is 8, and the sulfonate ionic polyester chain segment repeating unit is 4;
the intrinsic viscosity of the ionic copolyester is 0.85dl/g;
(4) Adding the ionic copolyester obtained in the step (3) into PBST (number average molecular weight of 750000 g/mol), uniformly mixing to obtain ionic copolyester modified biodegradable polyester, and performing melt spinning to obtain high-strength biodegradable polyester fiber;
wherein the addition amount of the ionic copolyester is 10% of the mass of PBST;
the technological parameters of melt spinning are as follows: the spinning temperature is 280 ℃, the cooling blowing temperature is 20 ℃, the relative humidity is 85%, the air pressure is 20kPa, the fiber oil content is 1.5%, the speed of a hot roller GR1 is 1500m/min, the temperature of the hot roller GR1 is 60 ℃, the speed of the hot roller GR2 is 3500m/min, and the temperature of the hot roller GR2 is 120 ℃;
the crystallization temperature of the ionic copolyester modified biodegradable polyester is 150 ℃ and the semi-crystallization time is t 1/2 The crystallization enthalpy was 50J/g for 2 min.
The single filament number of the prepared high-strength biodegradable polyester fiber is 2dtex, the number average molecular weight of the oil-free fiber is reduced to 1500g/mol, the breaking strength of the fiber is 2.71cN/dtex, the elongation at break is 29.6%, and the elastic recovery rate is 90% under 2-10% tensile deformation;
the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is 90 percent, and the disintegration degree is 95 percent.
Example 3
The preparation method of the high-strength biodegradable polyester fiber comprises the following specific steps:
(1) Mixing adipic acid and butanediol according to a molar ratio of 1:1.15, and carrying out esterification reaction for 1.5 hours at 150 ℃ under the pressure condition of 0.01MPa to obtain nonionic polyester esterified product;
wherein, the catalyst of the esterification reaction is ethylene glycol antimony, and the dosage of the catalyst is 100ppm of the mass of adipic acid;
(2) Carrying out a staged esterification reaction on isophthalic acid-5-sodium sulfonate and 2- [ (tri (hydroxymethyl) methyl) amino ] -1-ethane sodium sulfonate to obtain sulfonate ion polyester ester;
wherein the mole ratio of the carboxyl functional group number of the isophthalic acid-5-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the 2- [ (tris (hydroxymethyl) methyl) amino ] -1-ethane sodium sulfonate is 1.1; the second stage esterification is carried out by adding 2- [ (tri (hydroxymethyl) methyl) amino ] -1-ethane sodium sulfonate with the addition amount being 20% of the mole amount of isophthalic acid-5-sodium sulfonate added in the first stage esterification;
the catalyst of the staged esterification reaction is benzenesulfonic acid, which is added in the first esterification reaction, and the dosage of the catalyst is 100ppm of the mass of isophthalic acid-5-sodium sulfonate;
the temperature of the first stage esterification reaction is 230 ℃, the pressure is 0.1MPa, and the time is 5 hours; the temperature of the second stage esterification reaction is 260 ℃, the pressure is 0.3MPa, and the time is 1h;
(3) Mixing the nonionic polyester esterified material obtained in the step (1) with the sulfonate ionic polyester esterified material obtained in the step (2) according to a molar ratio of 5:5, performing a pre-polycondensation reaction for 0.2h at the temperature of 250 ℃ and the pressure of 800Pa, and performing a final polycondensation reaction for 2h at the temperature of 265 ℃ and the pressure of 10Pa to generate the ionic copolyester;
wherein the polycondensation catalyst is antimony trioxide, and the addition amount is 500ppm of the total mass of sulfonate ion polyester ester and nonionic polyester ester;
the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds; the nonionic polyester chain segment repeating unit is 4, and the sulfonate ionic polyester chain segment repeating unit is 2;
the intrinsic viscosity of the ionic copolyester is 0.75dl/g;
(4) Adding the ionic copolyester obtained in the step (3) into PBS (with the number average molecular weight of 50000 g/mol), uniformly mixing to obtain the ionic copolyester modified biodegradable polyester, and carrying out melt spinning to obtain the high-strength biodegradable polyester fiber;
Wherein the addition amount of the ionic copolyester is 2% of the mass of PBS;
the technological parameters of melt spinning are as follows: spinning temperature 240 ℃, cooling blowing temperature 16 ℃, relative humidity 65%, air pressure 70kPa, fiber oil content 0.8%, speed 1200m/min of hot roller GR1, temperature 85 ℃ of hot roller GR1, speed 2800m/min of hot roller GR2, temperature 105 ℃ of hot roller GR 2;
the crystallization temperature of the ionic copolyester modified biodegradable polyester is 80 ℃ and the semi-crystallization time is t 1/2 The crystallization enthalpy was 10J/g for 3 min.
The single filament number of the prepared high-strength biodegradable polyester fiber is 2.5dtex, the number average molecular weight of the oil-free fiber is reduced to 1200g/mol, the breaking strength of the fiber is 2.83cN/dtex, the elongation at break is 27.7%, and the elastic recovery rate is 90.5% under 2-10% tensile deformation;
the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is 80 percent, and the disintegration degree is 92 percent.
Example 4
The preparation method of the high-strength biodegradable polyester fiber comprises the following specific steps:
(1) Mixing terephthalic acid and pentanediol according to a molar ratio of 1:1.25, and carrying out esterification reaction for 2.5 hours under the conditions of 220 ℃ and a pressure of 0.1MPa to obtain nonionic polyester esterified product;
Wherein, the catalyst of the esterification reaction is antimony acetate, and the dosage of the catalyst is 80ppm of the mass of terephthalic acid;
(2) Carrying out sectional esterification reaction on terephthalic acid-2-sodium sulfonate and 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxy propane sodium sulfonate to obtain sulfonate ion polyester esterified product;
wherein the mole ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxy propane sodium sulfonate is 1.2; the second stage of esterification is only added with 3- [ N-tris (hydroxymethyl) methylamine ] -2-hydroxy propane sodium sulfonate, the addition amount is 30% of the mole amount of terephthalic acid-2-sodium sulfonate added in the first stage of esterification;
the catalyst of the staged esterification reaction is benzenesulfonic acid, which is added in the first esterification reaction, and the dosage of the catalyst is 800ppm of the mass of terephthalic acid-2-sodium sulfonate;
the temperature of the first stage esterification reaction is 240 ℃, the pressure is 0.4MPa, and the time is 3 hours; the temperature of the second stage esterification reaction is 245 ℃, the pressure is 0.4MPa, and the time is 0.5h;
(3) Mixing the nonionic polyester esterified material obtained in the step (1) with the sulfonate ionic polyester esterified material obtained in the step (2) according to a molar ratio of 3:7, performing a pre-polycondensation reaction for 0.8h at 245 ℃ and 600Pa, and performing a final polycondensation reaction for 2.5h at 280 ℃ and 80Pa to generate the ionic copolyester;
Wherein the polycondensation catalyst is ethylene glycol antimony, and the addition amount is 400ppm of the total mass of sulfonate ion polyester ester and nonionic polyester ester;
the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds; the nonionic polyester chain segment repeating unit is 6, and the sulfonate ionic polyester chain segment repeating unit is 3;
the intrinsic viscosity of the ionic copolyester is 0.60dl/g;
(4) Adding the ionic copolyester obtained in the step (3) into PHA (number average molecular weight is 85000 g/mol), uniformly mixing to obtain ionic copolyester modified biodegradable polyester, and carrying out melt spinning to obtain high-strength biodegradable polyester fiber;
wherein the addition amount of the ionic copolyester is 8% of the PHA mass;
the technological parameters of melt spinning are as follows: the spinning temperature is 270 ℃, the cooling blowing temperature is 18 ℃, the relative humidity is 80%, the air pressure is 30kPa, the fiber oil content is 1.2%, the speed of a hot roller GR1 is 1400m/min, the temperature of the hot roller GR1 is 70 ℃, the speed of the hot roller GR2 is 3200m/min, and the temperature of the hot roller GR2 is 115 ℃;
The crystallization temperature of the ionic copolyester modified biodegradable polyester is 70 ℃ and the semi-crystallization time is t 1/2 The crystallization enthalpy was 35J/g for 2.5 min.
The single filament number of the prepared high-strength biodegradable polyester fiber is 3dtex, the number average molecular weight of the oil-free fiber is reduced to 1000g/mol, the breaking strength of the fiber is 2.92cN/dtex, the elongation at break is 20.3%, and the elastic recovery rate is 90.7% under 2-10% tensile deformation;
the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is 75%, and the disintegration degree is 93%.
Example 5
The preparation method of the high-strength biodegradable polyester fiber comprises the following specific steps:
(1) Mixing isophthalic acid and ethylene glycol according to a molar ratio of 1:1.35, and carrying out esterification reaction for 3 hours at 240 ℃ and under a pressure of 0.3MPa to obtain nonionic polyester esterified product;
wherein, the catalyst of the esterification reaction is antimony oxide, and the dosage of the catalyst is 90ppm of the mass of isophthalic acid;
(2) Carrying out sectional esterification reaction on terephthalic acid-2-sodium sulfonate and 2, 5-dihydroxybenzene potassium sulfonate to obtain sulfonate ion polyester esterified product;
wherein the mole ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the 2, 5-dihydroxybenzene potassium sulfonate is 1.3; the second stage esterification reaction only adds 2, 5-dihydroxybenzene sulfonic acid potassium, the addition amount is 40% of the mole amount of terephthalic acid-2-sodium sulfonate added in the first stage esterification reaction;
The catalyst of the staged esterification reaction is benzenesulfonic acid, which is added in the first esterification reaction, and the dosage of the catalyst is 300ppm of the mass of terephthalic acid-2-sodium sulfonate;
the temperature of the first stage esterification reaction is 235 ℃, the pressure is 0.2MPa, and the time is 4 hours; the temperature of the second stage esterification reaction is 255 ℃, the pressure is 0.35MPa, and the time is 0.8h;
(3) Mixing the nonionic polyester esterified material obtained in the step (1) with the sulfonate ionic polyester esterified material obtained in the step (2) according to a molar ratio of 4:6, performing a pre-polycondensation reaction for 0.5h at the temperature of 250 ℃ and the pressure of 900Pa, and performing a final polycondensation reaction for 2h at the temperature of 270 ℃ and the pressure of 30Pa to generate the ionic copolyester;
wherein, the polycondensation catalyst is antimony acetate, and the addition amount is 200ppm of the total mass of sulfonate ion polyester ester and nonionic polyester ester;
the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds; the nonionic polyester chain segment repeating unit is 9, and the sulfonate ionic polyester chain segment repeating unit is 8;
the intrinsic viscosity of the ionic copolyester is 0.72dl/g;
(4) Adding the ionic copolyester obtained in the step (3) into PCL (number average molecular weight of 90000 g/mol), uniformly mixing to obtain ionic copolyester modified biodegradable polyester, and performing melt spinning to obtain high-strength biodegradable polyester fiber;
wherein the addition amount of the ionic copolyester is 3% of the mass of PCL;
the technological parameters of melt spinning are as follows: the spinning temperature is 260 ℃, the cooling blowing temperature is 17 ℃, the relative humidity is 70%, the air pressure is 60kPa, the fiber oil content is 1%, the speed of a hot roller GR1 is 1200m/min, the temperature of the hot roller GR1 is 80 ℃, the speed of a hot roller GR2 is 2900m/min, and the temperature of the hot roller GR2 is 110 ℃;
the crystallization temperature of the ionic copolyester modified biodegradable polyester is 50 ℃, and the semi-crystallization time is t 1/2 The crystallization enthalpy was 30J/g for 2.8 min.
The single filament number of the prepared high-strength biodegradable polyester fiber is 4dtex, the number average molecular weight of the oil-free fiber is reduced to 500g/mol, the breaking strength of the fiber is 3.0cN/dtex, the elongation at break is 15.0%, and the elastic recovery rate is 90.6% under 2-10% tensile deformation;
the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is 70% and the disintegration degree is 91%.
Example 6
The preparation method of the high-strength biodegradable polyester fiber comprises the following specific steps:
(1) Mixing adipic acid and propylene glycol according to a molar ratio of 1:1.4, and carrying out esterification reaction for 2 hours at 180 ℃ under the pressure condition of 0.4MPa to obtain nonionic polyester esterified compound;
wherein, the catalyst of the esterification reaction is ethylene glycol titanium, and the dosage of the catalyst is 30ppm of adipic acid;
(2) Preparing sulfonate ion polyester esterified substance by sectional esterification reaction of terephthalic acid-2-sodium sulfonate and N, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt;
wherein, the mole ratio of the carboxyl functional group number of the terephthalic acid-2-sodium sulfonate added in the first stage esterification reaction to the hydroxyl functional group number of the N, N-di (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium salt is 1.4; the second stage of esterification is only added with N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonic acid sodium, the addition amount is 50 percent of the mole amount of terephthalic acid-2-sodium sulfonate added in the first stage of esterification;
the catalyst of the staged esterification reaction is benzenesulfonic acid, which is added in the first esterification reaction, and the dosage of the catalyst is 500ppm of the mass of terephthalic acid-2-sodium sulfonate;
the temperature of the first stage esterification reaction is 225 ℃, the pressure is 0.3MPa, and the time is 5 hours; the temperature of the second stage esterification reaction is 240 ℃, the pressure is 0.5MPa, and the time is 1h;
(3) Mixing the nonionic polyester esterified material obtained in the step (1) with the sulfonate ionic polyester esterified material obtained in the step (2) according to a molar ratio of 6:4, performing pre-polycondensation at 255 ℃ and 700Pa for 0.6h, and performing final polycondensation at 275 ℃ and 50Pa for 2.5h to generate the ionic copolyester;
Wherein the polycondensation catalyst is tetrabutyl titanate, and the addition amount is 80ppm of the total mass of sulfonate ion polyester ester and nonionic polyester ester;
the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds; the nonionic polyester chain segment repeating unit is 5, and the sulfonate ionic polyester chain segment repeating unit is 5;
the intrinsic viscosity of the ionic copolyester is 0.81dl/g;
(4) Adding the ionic copolyester obtained in the step (3) into PBAT (number average molecular weight of 95000 g/mol), uniformly mixing to obtain ionic copolyester modified biodegradable polyester, and performing melt spinning to obtain high-strength biodegradable polyester fiber;
wherein the addition amount of the ionic copolyester is 5% of the mass of the PBAT;
the technological parameters of melt spinning are as follows: spinning temperature is 250 ℃, cooling blowing temperature is 19 ℃, relative humidity is 75%, air pressure is 50kPa, fiber oil content is 0.9%, speed of a hot roller GR1 is 1300m/min, temperature of the hot roller GR1 is 75 ℃, speed of the hot roller GR2 is 3000m/min, and temperature of the hot roller GR2 is 108 ℃;
The crystallization temperature of the ionic copolyester modified biodegradable polyester is 100 ℃, and the semi-crystallization time is t 1/2 The crystallization enthalpy was 40J/g for 1.5 min.
The single filament number of the prepared high-strength biodegradable polyester fiber is 2dtex, the number average molecular weight of the oil-free fiber is reduced to 1800g/mol, the breaking strength of the fiber is 2.64cN/dtex, the elongation at break is 32.9%, and the elastic recovery rate is 90.2% under 2-10% tensile deformation;
the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is 85%, and the disintegration degree is 94%.
Claims (11)
1. A preparation method of high-strength biodegradable polyester fiber is characterized in that: adding ionic copolyester into biodegradable polyester for melt spinning to obtain high-strength biodegradable polyester fiber;
the biodegradable polyester is poly (adipic acid)/poly (butylene terephthalate), poly (terephthalic acid)/poly (butylene succinate), poly (3-hydroxy alkanoate) or poly (epsilon-caprolactone);
the addition amount of the ionic copolyester is 1-10% of the mass of the biodegradable polyester;
the ionic copolyester consists of nonionic polyester chain segments and sulfonate ionic polyester chain segments, and the nonionic polyester chain segments, the ionic polyester chain segments and the nonionic polyester chain segments are connected through ester bonds;
The intrinsic viscosity of the ionic copolyester is 0.55-0.85 dl/g;
the nonionic polyester chain segment repeating unit is 4-10, and the sulfonate ionic polyester chain segment repeating unit is 2-8;
the preparation method of the ionic copolyester comprises the following steps: firstly, respectively synthesizing nonionic polyester esterified substance and sulfonate ion polyester esterified substance through esterification reaction, and then carrying out polycondensation reaction on the nonionic polyester esterified substance and the sulfonate ion polyester esterified substance to generate the ionic copolyester;
the sulfonate ion polyester esterified substance is prepared from dibasic acid II and dihydric alcohol II through a segmented esterification reaction; the mole ratio of the carboxyl functional group number of the dibasic acid II to the hydroxyl functional group number of the dibasic alcohol II added in the first stage esterification reaction is 1.05-1.50; only adding dihydric alcohol II in the second-stage esterification reaction, wherein the addition amount is 10-60% of the molar amount of the dihydric acid II added in the first-stage esterification reaction; dibasic acid II is isophthalic acid-5-sodium sulfonate or terephthalic acid-2-sodium sulfonate; the dihydric alcohol II is 2, 5-dihydroxybenzene sulfonic acid potassium salt, 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-hydroxy propane sulfonic acid sodium salt;
the single filament number of the high-strength biodegradable polyester fiber is 1.5-5.0 dtex, the number average molecular weight of the oil-free fiber is reduced to 500-2000 g/mol, the breaking strength of the fiber is more than or equal to 2.50cN/dtex, the elongation at break is 15.0-35.0%, and the elastic recovery rate is more than or equal to 90% under 2-10% tensile deformation; the biodegradability of the high-strength biodegradable polyester fiber is as follows: the composting biological decomposition rate is more than or equal to 60 percent, and the disintegration degree is more than or equal to 90 percent.
2. The method for preparing the high-strength biodegradable polyester fiber according to claim 1, wherein the number average molecular weight of the biodegradable polyester is 50000-100000 g/mol.
3. The method for preparing the high-strength biodegradable polyester fiber according to claim 1, wherein the process parameters of melt spinning are as follows: the spinning temperature is 220-280 ℃, the cooling blowing temperature is 15-20 ℃, the relative humidity is 60-85%, the air pressure is 20-80 kPa, the fiber oil content is 0.6-1.5%, the speed of the hot roller GR1 is 1000-1500 m/min, the temperature of the hot roller GR1 is 60-90 ℃, the speed of the hot roller GR2 is 2500-3500 m/min, and the temperature of the hot roller GR2 is 100-120 ℃.
4. The method for preparing the high-strength biodegradable polyester fiber according to claim 1, wherein the molar ratio of the nonionic polyester esterified substance to the sulfonate ionic polyester esterified substance is 2:8-8:2.
5. The method for preparing the high-strength biodegradable polyester fiber according to claim 1, wherein the nonionic polyester esterified substance is prepared from dibasic acid I and dihydric alcohol I through esterification reaction;
the molar ratio of the dibasic acid I to the dibasic alcohol I is 1:1.05-1.5;
the dibasic acid I is terephthalic acid, isophthalic acid or adipic acid;
The dihydric alcohol I is ethylene glycol, propylene glycol, butanediol or pentanediol.
6. The method for preparing the high-strength biodegradable polyester fiber according to claim 5, wherein the catalyst for the esterification reaction of the nonionic polyester esterified product is ethylene glycol titanium, tetrabutyl titanate, ethylene glycol antimony, antimony acetate or antimony oxide, and the amount of the catalyst is 10-100 ppm of the mass of the dibasic acid I.
7. The method for preparing the high-strength biodegradable polyester fiber according to claim 5, wherein the esterification reaction temperature of the nonionic polyester esterified substance is 150-250 ℃, the pressure is 0.01-0.5 MPa, and the time is 1.5-3.5 h.
8. The method for preparing the high-strength biodegradable polyester fiber according to claim 1, wherein the catalyst for the segmented esterification reaction of the sulfonate ion polyester ester is benzenesulfonic acid, and the catalyst is added during the first esterification reaction, and the dosage of the catalyst is 10-1000 ppm of the mass of the dibasic acid II.
9. The method for preparing the high-strength biodegradable polyester fiber according to claim 1, wherein 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 h;
the temperature of the second stage esterification reaction is 240-260 ℃, the pressure is 0.1-0.5 MPa, and the time is 0.5-1.0 h.
10. The method for producing a high-strength biodegradable polyester fiber according to claim 1, wherein the polycondensation of the nonionic polyester esterified substance and the sulfonate ionic polyester esterified substance is classified into a pre-polycondensation and a final polycondensation;
the pre-polycondensation reaction temperature is 240-260 ℃, the reaction time is 0.1-1.0 h, and the pressure is 500-1000 Pa;
the final polycondensation reaction temperature is 260-285 ℃, the reaction time is 1.5-3.0 h, and the pressure is 0-100 Pa.
11. The method for preparing the high-strength biodegradable polyester fiber according to claim 10, wherein the polycondensation catalyst is tetrabutyl titanate, titanium glycol, antimony trioxide, antimony glycol or antimony acetate, and the addition amount is 50-500 ppm of the total mass of sulfonate ion polyester ester and nonionic polyester ester.
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