CN113122952A - PBAT fiber and preparation method thereof - Google Patents
PBAT fiber and preparation method thereof Download PDFInfo
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- CN113122952A CN113122952A CN202110337999.9A CN202110337999A CN113122952A CN 113122952 A CN113122952 A CN 113122952A CN 202110337999 A CN202110337999 A CN 202110337999A CN 113122952 A CN113122952 A CN 113122952A
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
- D01F6/84—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products from copolyesters
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention 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, a butylene adipate chain segment and a butylene 5-sodium sulfonate isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 50-150% relative to the butylene terephthalate chain segment, and the molar content of the butylene 5-sodium sulfonate chain segment is 0.5-4% relative to the butylene terephthalate chain segment; the breaking strength of the PBAT fiber is 2.0-5.5 cN/dtex, the elongation at break is 15-60%, and the AA rate is more than or equal to 98%; the preparation method comprises the following steps: respectively esterifying terephthalic acid and adipic acid, respectively performing pre-polycondensation, then mixing the two obtained prepolymers, adding an m-phthalic acid-5-sodium sulfonate ester, performing final polycondensation, and finally preparing the PBAT fiber by a melt spinning method; according to the PBAT fiber, the balance relation between the crystallization capability and the performance of the PBAT is regulated and controlled through the length of the chain segment, and the performance of the fiber is improved by introducing SSIPA into the chain segment.
Description
Technical Field
The invention belongs to the technical field of polymer fiber preparation, and relates to a PBAT fiber and a preparation method thereof.
Background
Poly (butylene adipate-butylene terephthalate) (PBAT) is used as a novel biodegradable copolyester and is mainly prepared from 1, 4-Butanediol (BDO), Adipic Acid (AA) and terephthalic acid (PTA) as raw materials. The PBAT not only has good thermal stability and mechanical property of the PBT polyester, but also has good stretchability and ductility of the aliphatic polyester, and can be degraded into water and carbon dioxide under natural conditions. PBAT can be used in the fields of packaging, medical and agricultural films, etc.
As a degradable plastic with excellent performance, PBAT can be used in the field of textile and clothing as well. However, the PBAT is mainly prepared by a direct esterification or ester exchange method at present, the obtained high polymer is a random copolymer, the crystallinity is low, the glass transition temperature is below zero, the crystallization temperature is also low, and the speed is slow, so that the fiber bonding phenomenon is easy to occur in the spinning process, the winding and unwinding cannot be carried out, and meanwhile, the bonding also occurs at high temperature in the dyeing and finishing process, so that the hand feeling and the style of the fabric are different, and the wearability is reduced. In addition, in the case of a product which is not completely crystallized, the degree of crystallization is affected by the use environment during use, and the size, mechanical properties, etc. become unstable.
The factors influencing the crystallization of the polymer are various, the regularity of a molecular chain is a decisive factor influencing the crystallization performance of the polymer, and the better the regularity of the molecular chain is, the stronger the crystallization capacity of the polymer is; in addition, the crystallization of the polymer is controlled by nucleation and molecular chain movement, the crystallization speed is accelerated, and the crystallization temperature can be increased by introducing a nucleating agent. The patent 'a PBAT material with high crystallization speed and a preparation method thereof' (201810122762.7) provides a PBAT material with high crystallization speed and a preparation method thereof, which is realized by adding a nucleating agent of xylylene dialkyl urea, but the method does not change the crystallization performance of the polymer, does not help to improve the crystallinity of the polymer, and still cannot solve the problem of fiber adhesion in the processing and using process. So-called blocking, occurs mainly by interdiffusion due to the movement of segments when the fibers are in intimate contact with each other. The diffusion mainly occurs in the amorphous region, that is, the higher the proportion of the amorphous region, the more serious the blocking condition; in addition, the glass transition temperature of the high polymer is influenced by the high crystallinity, the crystallinity is high, and the glass transition temperature is also improved, namely, under the same temperature condition, the movement capability of molecular chains in the fiber with high crystallinity is weaker than that of the molecular chains in the fiber with low crystallinity, so that the generated diffusion phenomenon is reduced.
Based on the problems of the PBAT in the processing and forming and the basic principle of influencing the processing and forming, the invention provides the PBAT fiber and the preparation method thereof, which can continuously and stably produce the PBAT fiber and improve the stability of the product in the post-treatment and use processes. In consideration of a polymer crystallization mechanism, the crystallization performance of the PBAT can be improved by adjusting the chain segment length among the components, and the third component is introduced, so that the dyeing performance and the stain resistance of the PBAT product are further improved while the stability of the post-treatment performance of the PBAT product is improved.
Disclosure of Invention
The invention relates to a PBAT fiber and a preparation method thereof, which comprises the stages of esterification, pre-polycondensation, final polycondensation, spinning and the like. The crystallization performance of the PBAT is improved by adjusting the chain segment length among the components, and the third component is introduced, so that the dyeing performance and the stain resistance of the PBAT product are further improved while the post-treatment performance stability of the PBAT product is improved, finally, the PBAT fiber can be continuously and stably produced, and the stability of the PBAT fiber in the post-treatment and use processes is improved. The obtained product can be widely applied to the field of textile and clothing.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a molecular chain segment of the PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfoisophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 50-150% relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfoisophthalate chain segment is 0.5-4% relative to the butylene terephthalate chain segment. The design of the proportion needs to take the degradability and the thermal stability into consideration, if the content of the chain segment of the butylene terephthalate is too high, the degradability of the material is deteriorated, and if the content of the chain segment of the butylene adipate is too high, the thermal stability of the material is deteriorated, and meanwhile, the strength is also reduced; if the content of the segment of the isophthalic acid-5-sodium sulfonate butanediol ester is too high, the regularity of a molecular chain is greatly reduced, so that the crystallization performance is influenced, and the content is too low, so that the function of improving the dyeing performance of the PBAT product cannot be realized.
As a preferred technical scheme:
according to the PBAT fiber, the breaking strength of the PBAT fiber is 2.0-5.5 cN/dtex, the breaking elongation is 15-60%, and the AA rate is not less than 98% (the AA rate is an index for evaluating the spinning stability of the fiber, and the test standard of the AA rate is shown in FZ/T54003-2012, GB/T8960-2015, GB/T14460-2015 and the like).
The invention also provides a preparation method of the PBAT fiber, wherein terephthalic acid and adipic acid are respectively esterified, then are respectively subjected to pre-polycondensation, then the obtained two prepolymers are mixed, and are added with isophthalic acid-5-sodium sulfonate ester, then are subjected to final polycondensation, and finally the PBAT fiber is prepared by a melt spinning method.
As a preferred technical scheme:
the preparation method of the PBAT fiber comprises the following specific steps:
first step, terephthalic acid (PTA) esterification: uniformly mixing terephthalic acid, Butanediol (BDO), a catalyst I and an antioxidant I according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance;
second step, adipate esterification: uniformly mixing adipic acid, butanediol, a catalyst II and an antioxidant II according to a certain proportion, and then carrying out esterification reaction to obtain an adipate;
thirdly, esterifying isophthalic acid-5-Sodium Sulfonate (SSIPA): mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III and an antioxidant III uniformly according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate esterified substance;
fourthly, pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the first step to obtain a PBT prepolymer;
fifthly, pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the second step to obtain a PBA prepolymer;
sixth, final polycondensation: performing final polycondensation on the product obtained in the third to fifth steps to obtain a PBAT slice;
and seventhly, carrying out melt spinning on the PBAT slices obtained in the sixth step to obtain the PBAT fibers.
In the first step, the catalyst I is more than one of tetrabutyl titanate and ethylene glycol titanium, and the addition amount of the catalyst I is 5-100 ppm (mass concentration) relative to terephthalic acid;
the antioxidant I is more than one of triphenyl phosphate, antioxidant 300 and antioxidant 164, and the addition amount of the antioxidant I is 100-500 ppm (mass concentration) relative to the terephthalic acid;
the molar ratio of the terephthalic acid to the butanediol is 1: 1.1-1.4;
the temperature of the esterification reaction is 180-240 ℃, the absolute pressure is 100 Pa-0.6 MPa, and the esterification time is 90-300 min; when the water yield is more than or equal to 98 percent of the theoretical water yield, the esterification is considered to be finished;
the polymerization degree of the obtained terephthalic acid ester is 2-10.
In the second step, the catalyst II is more than one of tetrabutyl titanate and ethylene glycol titanium, and the addition amount of the catalyst II is 5-100 ppm (mass concentration) relative to adipic acid;
the antioxidant II is more than one of triphenyl phosphate, antioxidant 300 and antioxidant 164, and the addition amount of the antioxidant II is 100-500 ppm (mass concentration) relative to the adipic acid;
the molar ratio of the adipic acid to the butanediol is 1: 1.1-1.4;
the temperature of the esterification reaction is 140-200 ℃, the absolute pressure is 100 Pa-0.5 MPa, the esterification time is 90-280 min, and the esterification is considered to be finished when the water yield is more than or equal to 98% of the theoretical water yield;
the degree of polymerization of the obtained adipate is 2-10.
In the third step, the catalyst III is more than one of tetrabutyl titanate and ethylene glycol titanium, and the addition amount of the catalyst III is 5-100 ppm (mass concentration) relative to 5-sodium sulfoisophthalate;
the antioxidant III is more than one of triphenyl phosphate, antioxidant 300 and antioxidant 164, and the addition amount of the antioxidant III is 100-500 ppm (mass concentration) relative to the isophthalic acid-5-sodium sulfonate;
the mol ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2-2.1;
the temperature of the esterification reaction is 210-240 ℃, the absolute pressure is 100 Pa-0.6 MPa, the esterification time is 100-300 min, and the esterification is considered to be finished when the water yield is more than or equal to 98% of the theoretical water yield;
the polymerization degree of the obtained isophthalic acid-5-sodium sulfonate ester is 1-2, the polymerization degree of an isophthalic acid-5-sodium sulfonate chain segment is not too high, the polymerization degree is high, and the concentration phenomenon of sulfonic acid group distribution can be caused, so that the uniformity of subsequent dyeing is influenced.
In the fourth step, the temperature of the pre-polycondensation reaction is 240-260 ℃, the absolute pressure is 10-300 Pa, and the pre-polycondensation time is 30-90 min;
the polymerization degree of the obtained PBT prepolymer is 20-30, and the PBT prepolymer is too high, so that an obvious phase separation condition can occur, the mechanical property of a product is reduced, the polymerization degree is too low, the crystallization capacity of a PBT chain segment is reduced, and the crystallization performance of a PBAT material is influenced.
In the fifth step, the temperature of the pre-polycondensation reaction is 230-250 ℃, the absolute pressure is 10-300 Pa, and the pre-polycondensation time is 40-100 min;
the polymerization degree of the obtained PBA prepolymer is 20-30, the PBA prepolymer is too high, obvious phase separation can occur, the mechanical property of the product is reduced, the service life of the product is prolonged (the mechanical property is reduced due to too fast degradation in the using process), the polymerization degree is too low, the crystallization capability of a PBA chain segment is reduced, and the crystallization property of the PBAT material is influenced.
In the sixth step, the temperature of final polycondensation reaction is 240-260 ℃, the absolute pressure is 0-200 Pa, and the final polycondensation time is 60-180 min;
the intrinsic viscosity of the PBAT slice is 0.8-1.3 dL/g;
in the PBAT slice, the molar content of adipic acid is 50-150% relative to terephthalic acid, and the molar content of 5-sodium sulfoisophthalate is 0.5-4% relative to terephthalic acid.
In the seventh step of the preparation method of the PBAT fiber, the spinning temperature is 210-260 ℃, the spinning speed is 800-5000 m/min, and the draw ratio is 1.5-5 times.
The mechanism of the invention is as follows:
the crystallization of the high polymer requires that the molecular chain of the high polymer has extremely high regularity and also has certain molecular weight, and because the crystal region of the high polymer is formed by regular arrangement of the molecular chain, the length of the molecular chain is not enough, regular arrangement cannot be realized, and the crystallinity is low or even cannot be crystallized. For the copolymer, in the random copolymer, the crystallinity is extremely low or even the random copolymer cannot be crystallized due to the poor regularity of the molecular chain, while in the block copolymer, when the chain segments of each component are long enough, crystal regions can be formed respectively to enable the copolymer to have a certain crystallinity, but when the chain segments of each component are too long, the situation of large-amplitude phase separation is easy to occur, the occurrence of the phase separation phenomenon has a great influence on the processing and forming of the copolymer, and the mechanical properties of the obtained product are also obviously reduced. The lengths of all chain segments (butylene terephthalate chain segments and butylene adipate chain segments) of the PBAT are in a reasonable range, so that the chain segments can independently form a crystal region, and the phenomenon of obvious phase separation cannot occur; furthermore, a third component SSIPA is introduced in the polymerization process, and the third component is a short chain segment, so that the heterogeneous nucleation effect is achieved, the crystallization temperature and the crystallization rate of the polymer are improved, and the good mechanical property and the good stability in the use process of the PBAT product are ensured.
Has the advantages that:
1. the balance relation between the crystallization capability and the performance of the PBAT is regulated and controlled through the chain segment length, the crystallization capability of the PBAT is improved through improving the chain segment length, the stability in the processing and using processes is improved, and the biodegradability of the PBAT is not influenced;
2. by introducing SSIPA into the chain segment, the method can play a role of heterogeneous nucleation, so that PBAT is crystallized at high temperature, and the crystallization speed is increased, thereby effectively avoiding the bonding phenomenon in the processing process;
3. by introducing SSIPA into the chain segment, the dyeing performance of the PBAT fiber can be improved, the dyeing temperature is greatly reduced, the fabric style change caused by the fiber bonding phenomenon in the post-treatment is avoided, and the color vividness is also greatly improved.
Detailed Description
The invention will be further illustrated with reference to specific 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 may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
A preparation method of PBAT fiber comprises the following steps:
(1) esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I (tetrabutyl titanate) and an antioxidant I (triphenyl phosphate) according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance with the polymerization degree of 2;
the amount of catalyst I added was 5ppm relative to terephthalic acid; the addition amount of the antioxidant I is 100ppm relative to the terephthalic acid; the molar ratio of terephthalic acid to butanediol is 1: 1.1;
the temperature of the esterification reaction is 180 ℃, the absolute pressure is 100Pa, and the esterification time is 300 min; when the water yield is equal to 98 percent of the theoretical water yield, the esterification is considered to be finished;
(2) esterification of adipate: uniformly mixing adipic acid, butanediol, a catalyst II (tetrabutyl titanate) and an antioxidant II (triphenyl phosphate) according to a certain proportion, and then carrying out esterification reaction to obtain an adipate with the polymerization degree of 2;
the addition amount of catalyst II was 5ppm relative to adipic acid; the addition amount of the antioxidant II is 100ppm relative to the adipic acid; the molar ratio of adipic acid to butanediol is 1: 1.1;
the temperature of the esterification reaction is 140 ℃, the absolute pressure is 100Pa, the esterification time is 280min, and the esterification is considered to be finished when the water yield is equal to 98 percent of the theoretical water yield;
(3) esterification of 5-sodium sulfoisophthalate: mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III (tetrabutyl titanate) and an antioxidant III (triphenyl phosphate) uniformly according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate with the polymerization degree of 1;
the addition amount of the catalyst III is 5ppm relative to the isophthalic acid-5-sodium sulfonate; the addition amount of the antioxidant III is 100ppm relative to the isophthalic acid-5-sodium sulfonate; the molar ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2;
the temperature of the esterification reaction is 180 ℃, the absolute pressure is 100Pa, the esterification time is 300min, and the esterification is considered to be finished when the water yield is equal to 98 percent of the theoretical water yield;
(4) pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the step (1) to obtain a PBT prepolymer with the polymerization degree of 20;
the temperature of the pre-polycondensation reaction is 240 ℃, the absolute pressure is 10Pa, and the pre-polycondensation time is 90 min;
(5) pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the step (2) to obtain a PBA prepolymer with the polymerization degree of 20;
the temperature of the pre-polycondensation reaction is 230 ℃, the absolute pressure is 10Pa, and the pre-polycondensation time is 100 min;
(6) final polycondensation: performing final polycondensation on the products obtained in the steps (3) to (5) to obtain PBAT slices with the intrinsic viscosity of 0.8 dL/g;
the temperature of the final polycondensation reaction is 240 ℃, the absolute pressure is 10Pa, and the final polycondensation time is 180 min;
in the PBAT chips, the molar content of adipic acid relative to terephthalic acid was 50%, and the molar content of 5-sodium sulfoisophthalate relative to terephthalic acid was 0.5%;
(7) carrying out melt spinning on the PBAT slices obtained in the step (6) to obtain PBAT fibers; the spinning temperature is 210 ℃, the spinning speed is 800m/min, and the draw ratio is 1.5 times.
The molecular chain segment of the prepared PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 50 percent relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 0.5 percent relative to the butylene terephthalate chain segment; the PBAT fiber had a breaking strength of 2cN/dtex, an elongation at break of 60% and an AA rate of 98%.
Example 2
A preparation method of PBAT fiber comprises the following steps:
(1) esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I (tetrabutyl titanate) and an antioxidant I (triphenyl phosphate) according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance with the polymerization degree of 4;
the addition amount of the catalyst I is 10ppm relative to the terephthalic acid; the addition amount of the antioxidant I is 150ppm relative to the terephthalic acid; the molar ratio of terephthalic acid to butanediol is 1: 1.1;
the temperature of the esterification reaction is 190 ℃, the absolute pressure is 0.1MPa, and the esterification time is 250 min; when the water yield is equal to 98 percent of the theoretical water yield, the esterification is considered to be finished;
(2) esterification of adipate: uniformly mixing adipic acid, butanediol, a catalyst II (tetrabutyl titanate) and an antioxidant II (triphenyl phosphate) according to a certain proportion, and then carrying out esterification reaction to obtain an adipate with the polymerization degree of 4;
the addition amount of catalyst II is 10ppm relative to the adipic acid; the amount of antioxidant II added was 150ppm based on adipic acid; the molar ratio of adipic acid to butanediol is 1: 1.1;
the temperature of the esterification reaction is 150 ℃, the absolute pressure is 0.1MPa, the esterification time is 250min, and the esterification is considered to be finished when the water yield is equal to 98 percent of the theoretical water yield;
(3) esterification of 5-sodium sulfoisophthalate: mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III (tetrabutyl titanate) and an antioxidant III (triphenyl phosphate) uniformly according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate with the polymerization degree of 1;
the addition amount of the catalyst III is 10ppm relative to the isophthalic acid-5-sodium sulfonate; the addition amount of the antioxidant III is 150ppm relative to the isophthalic acid-5-sodium sulfonate; the molar ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2;
the temperature of the esterification reaction is 190 ℃, the absolute pressure is 0.1MPa, the esterification time is 250min, and the esterification is considered to be finished when the water yield is equal to 98 percent of the theoretical water yield;
(4) pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the step (1) to obtain a PBT prepolymer with the polymerization degree of 22;
the temperature of the pre-polycondensation reaction is 245 ℃, the absolute pressure is 10Pa, and the pre-polycondensation time is 80 min;
(5) pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the step (2) to obtain a PBA prepolymer with the polymerization degree of 22;
the temperature of the pre-polycondensation reaction is 235 ℃, the absolute pressure is 10Pa, and the pre-polycondensation time is 90 min;
(6) final polycondensation: performing final polycondensation on the products obtained in the steps (3) to (5) to obtain PBAT slices with the intrinsic viscosity of 0.9 dL/g;
the temperature of the final polycondensation reaction is 245 ℃, the absolute pressure is 10Pa, and the final polycondensation time is 160 min;
in the PBAT chips, the molar content of adipic acid was 60% with respect to terephthalic acid and the molar content of 5-sodium sulfoisophthalate was 1% with respect to terephthalic acid;
(7) carrying out melt spinning on the PBAT slices obtained in the step (6) to obtain PBAT fibers; the spinning temperature is 215 ℃, the spinning speed is 1000m/min, and the draw ratio is 2 times.
The molecular chain segment of the prepared PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 60 percent relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 1 percent relative to the butylene terephthalate chain segment; the PBAT fiber had a breaking strength of 2.5cN/dtex, an elongation at break of 50% and an AA rate of 98%.
Example 3
A preparation method of PBAT fiber comprises the following steps:
(1) esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I (tetrabutyl titanate) and an antioxidant I (antioxidant 300) according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified product with the polymerization degree of 6;
the addition amount of the catalyst I is 20ppm relative to the terephthalic acid; the addition amount of the antioxidant I is 200ppm relative to the terephthalic acid; the molar ratio of terephthalic acid to butanediol is 1: 1.2;
the temperature of the esterification reaction is 200 ℃, the absolute pressure is 0.2MPa, and the esterification time is 200 min; when the water yield is equal to 98 percent of the theoretical water yield, the esterification is considered to be finished;
(2) esterification of adipate: uniformly mixing adipic acid, butanediol, a catalyst II (tetrabutyl titanate) and an antioxidant II (antioxidant 300) according to a certain proportion, and then carrying out esterification reaction to obtain an adipate with the polymerization degree of 6;
the addition amount of catalyst II was 20ppm relative to adipic acid; the amount of the antioxidant II added was 200ppm based on the amount of adipic acid; the molar ratio of adipic acid to butanediol is 1: 1.2;
the temperature of the esterification reaction is 160 ℃, the absolute pressure is 0.2MPa, the esterification time is 200min, and the esterification is considered to be finished when the water yield is equal to 98 percent of the theoretical water yield;
(3) esterification of 5-sodium sulfoisophthalate: mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III (tetrabutyl titanate) and an antioxidant III (antioxidant 300) uniformly according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate with polymerization degree of 1;
the addition amount of the catalyst III is 20ppm relative to the isophthalic acid-5-sodium sulfonate; the addition amount of the antioxidant III is 200ppm relative to the isophthalic acid-5-sodium sulfonate; the molar ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2;
the temperature of the esterification reaction is 200 ℃, the absolute pressure is 0.2MPa, the esterification time is 200min, and the esterification is considered to be finished when the water yield is equal to 98 percent of the theoretical water yield;
(4) pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the step (1) to obtain a PBT prepolymer with the polymerization degree of 24;
the temperature of the pre-polycondensation reaction is 250 ℃, the absolute pressure is 15Pa, and the pre-polycondensation time is 70 min;
(5) pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the step (2) to obtain a PBA prepolymer with the polymerization degree of 24;
the temperature of the pre-polycondensation reaction is 240 ℃, the absolute pressure is 15Pa, and the pre-polycondensation time is 80 min;
(6) final polycondensation: performing final polycondensation on the products obtained in the steps (3) to (5) to obtain PBAT slices with intrinsic viscosity of 1 dL/g;
the temperature of the final polycondensation reaction is 250 ℃, the absolute pressure is 15Pa, and the final polycondensation time is 140 min;
in the PBAT chips, the molar content of adipic acid with respect to terephthalic acid was 70%, and the molar content of 5-sodium sulfoisophthalate with respect to terephthalic acid was 1.5%;
(7) carrying out melt spinning on the PBAT slices obtained in the step (6) to obtain PBAT fibers; the spinning temperature was 220 ℃, the spinning speed was 2000m/min, and the draw ratio was 2.5 times.
The molecular chain segment of the prepared PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 70 percent relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 1.5 percent relative to the butylene terephthalate chain segment; the PBAT fiber had a breaking strength of 3cN/dtex, an elongation at break of 45% and an AA rate of 98%.
Example 4
A preparation method of PBAT fiber comprises the following steps:
(1) esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I (ethylene glycol titanium) and an antioxidant I (antioxidant 300) according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance with the polymerization degree of 7;
the amount of catalyst I added was 40ppm relative to terephthalic acid; the addition amount of the antioxidant I is 250ppm relative to the terephthalic acid; the molar ratio of terephthalic acid to butanediol is 1: 1.2;
the temperature of the esterification reaction is 210 ℃, the absolute pressure is 0.3MPa, and the esterification time is 180 min; when the water yield is equal to 99 percent of the theoretical water yield, the esterification is considered to be finished;
(2) esterification of adipate: uniformly mixing adipic acid, butanediol, a catalyst II (ethylene glycol titanium) and an antioxidant II (antioxidant 300) according to a certain proportion, and then carrying out esterification reaction to obtain an adipate with the polymerization degree of 7;
the addition amount of catalyst II was 40ppm relative to adipic acid; the amount of antioxidant II added was 250ppm based on adipic acid; the molar ratio of adipic acid to butanediol is 1: 1.2;
the temperature of the esterification reaction is 170 ℃, the absolute pressure is 0.25MPa, the esterification time is 180min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(3) esterification of 5-sodium sulfoisophthalate: mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III (ethylene glycol titanium) and an antioxidant III (antioxidant 300) uniformly according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate with the polymerization degree of 2;
the addition amount of the catalyst III is 40ppm relative to the isophthalic acid-5-sodium sulfonate; the addition amount of the antioxidant III is 250ppm relative to the isophthalic acid-5-sodium sulfonate; the molar ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2;
the temperature of the esterification reaction is 210 ℃, the absolute pressure is 0.3MPa, the esterification time is 180min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(4) pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the step (1) to obtain a PBT prepolymer with the polymerization degree of 26;
the temperature of the pre-polycondensation reaction is 252 ℃, the absolute pressure is 20Pa, and the pre-polycondensation time is 60 min;
(5) pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the step (2) to obtain a PBA prepolymer with the polymerization degree of 26;
the temperature of the pre-polycondensation reaction is 242 ℃, the absolute pressure is 20Pa, and the pre-polycondensation time is 70 min;
(6) final polycondensation: performing final polycondensation on the products obtained in the steps (3) to (5) to obtain PBAT slices with the intrinsic viscosity of 1.1 dL/g;
the temperature of the final polycondensation reaction is 255 ℃, the absolute pressure is 20Pa, and the final polycondensation time is 120 min;
in the PBAT chips, the molar content of adipic acid relative to terephthalic acid was 90%, and the molar content of 5-sodium sulfoisophthalate relative to terephthalic acid was 2%;
(7) carrying out melt spinning on the PBAT slices obtained in the step (6) to obtain PBAT fibers; the spinning temperature is 230 ℃, the spinning speed is 3000m/min, and the draw ratio is 3 times.
The molecular chain segment of the prepared PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 90 percent relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 2 percent relative to the butylene terephthalate chain segment; the PBAT fiber had a breaking strength of 3.5cN/dtex, an elongation at break of 40% and an AA rate of 99%.
Example 5
A preparation method of PBAT fiber comprises the following steps:
(1) esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I (ethylene glycol titanium) and an antioxidant I (antioxidant 164) according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance with the polymerization degree of 8;
the amount of catalyst I added was 60ppm relative to terephthalic acid; the addition amount of the antioxidant I is 300ppm relative to the terephthalic acid; the molar ratio of terephthalic acid to butanediol is 1: 1.3;
the temperature of the esterification reaction is 220 ℃, the absolute pressure is 0.4MPa, and the esterification time is 150 min; when the water yield is equal to 99 percent of the theoretical water yield, the esterification is considered to be finished;
(2) esterification of adipate: uniformly mixing adipic acid, butanediol, a catalyst II (ethylene glycol titanium) and an antioxidant II (antioxidant 164) according to a certain proportion, and then carrying out esterification reaction to obtain an adipate with the polymerization degree of 8;
the addition amount of catalyst II was 60ppm relative to adipic acid; the amount of the antioxidant II added was 300ppm based on the amount of adipic acid; the molar ratio of adipic acid to butanediol is 1: 1.3;
the temperature of the esterification reaction is 180 ℃, the absolute pressure is 0.3MPa, the esterification time is 150min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(3) esterification of 5-sodium sulfoisophthalate: uniformly mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III (ethylene glycol titanium) and an antioxidant III (antioxidant 164) according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate with the polymerization degree of 2;
the addition amount of the catalyst III is 60ppm relative to the isophthalic acid-5-sodium sulfonate; the addition amount of the antioxidant III is 300ppm relative to the isophthalic acid-5-sodium sulfonate; the molar ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2.1;
the temperature of the esterification reaction is 220 ℃, the absolute pressure is 0.4MPa, the esterification time is 150min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(4) pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the step (1) to obtain a PBT prepolymer with the polymerization degree of 28;
the temperature of the pre-polycondensation reaction is 254 ℃, the absolute pressure is 30Pa, and the pre-polycondensation time is 50 min;
(5) pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the step (2) to obtain a PBA prepolymer with the polymerization degree of 28;
the temperature of the pre-polycondensation reaction is 245 ℃, the absolute pressure is 30Pa, and the pre-polycondensation time is 60 min;
(6) final polycondensation: performing final polycondensation on the products obtained in the steps (3) to (5) to obtain PBAT slices with the intrinsic viscosity of 1.2 dL/g;
the temperature of the final polycondensation reaction is 257 ℃, the absolute pressure is 30Pa, and the final polycondensation time is 100 min;
in the PBAT chips, the molar content of adipic acid relative to terephthalic acid was 110%, and the molar content of 5-sodium sulfoisophthalate relative to terephthalic acid was 3%;
(7) carrying out melt spinning on the PBAT slices obtained in the step (6) to obtain PBAT fibers; the spinning temperature is 240 ℃, the spinning speed is 4000m/min, and the draw ratio is 3.5 times.
The molecular chain segment of the prepared PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 110 percent relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 3 percent relative to the butylene terephthalate chain segment; the PBAT fiber had a breaking strength of 4cN/dtex, an elongation at break of 35% and an AA rate of 99%.
Example 6
A preparation method of PBAT fiber comprises the following steps:
(1) esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I (ethylene glycol titanium) and an antioxidant I (antioxidant 164) according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance with the polymerization degree of 9;
the amount of catalyst I added was 80ppm relative to terephthalic acid; the addition amount of the antioxidant I is 400ppm relative to the terephthalic acid; the molar ratio of terephthalic acid to butanediol is 1: 1.3;
the temperature of the esterification reaction is 230 ℃, the absolute pressure is 0.5MPa, and the esterification time is 130 min; when the water yield is equal to 99 percent of the theoretical water yield, the esterification is considered to be finished;
(2) esterification of adipate: uniformly mixing adipic acid, butanediol, a catalyst II (ethylene glycol titanium) and an antioxidant II (antioxidant 164) according to a certain proportion, and then carrying out esterification reaction to obtain an adipate with the polymerization degree of 9;
the addition amount of catalyst II was 80ppm relative to adipic acid; the amount of antioxidant II added was 400ppm based on adipic acid; the molar ratio of adipic acid to butanediol is 1: 1.3;
the temperature of the esterification reaction is 190 ℃, the absolute pressure is 0.4MPa, the esterification time is 130min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(3) esterification of 5-sodium sulfoisophthalate: uniformly mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III (ethylene glycol titanium) and an antioxidant III (antioxidant 164) according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate with the polymerization degree of 2;
the addition amount of the catalyst III is 80ppm relative to the isophthalic acid-5-sodium sulfonate; the addition amount of the antioxidant III is 400ppm relative to the isophthalic acid-5-sodium sulfonate; the molar ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2.1;
the temperature of the esterification reaction is 230 ℃, the absolute pressure is 0.5MPa, the esterification time is 130min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(4) pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the step (1) to obtain a PBT prepolymer with polymerization degree of 29;
the temperature of the pre-polycondensation reaction is 257 ℃, the absolute pressure is 50Pa, and the pre-polycondensation time is 40 min;
(5) pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the step (2) to obtain a PBA prepolymer with the polymerization degree of 29;
the temperature of the pre-polycondensation reaction is 248 ℃, the absolute pressure is 50Pa, and the pre-polycondensation time is 50 min;
(6) final polycondensation: performing final polycondensation on the products obtained in the steps (3) to (5) to obtain PBAT slices with the intrinsic viscosity of 1.25 dL/g;
the temperature of the final polycondensation reaction is 258 ℃, the absolute pressure is 50Pa, and the final polycondensation time is 80 min;
in the PBAT chips, the molar content of adipic acid was 130% with respect to terephthalic acid and the molar content of 5-sodium sulfoisophthalate was 3.5% with respect to terephthalic acid;
(7) carrying out melt spinning on the PBAT slices obtained in the step (6) to obtain PBAT fibers; the spinning temperature is 250 ℃, the spinning speed is 4500m/min, and the draw ratio is 4 times.
The molecular chain segment of the prepared PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 130 percent relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 3.5 percent relative to the butylene terephthalate chain segment; the PBAT fiber had a breaking strength of 4.5cN/dtex, an elongation at break of 20% and an AA rate of 99%.
Example 7
A preparation method of PBAT fiber comprises the following steps:
(1) esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I (tetrabutyl titanate and ethylene glycol titanium with the molar ratio of 1:1) and an antioxidant I (triphenyl phosphate and an antioxidant 300 with the molar ratio of 1:1) according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance with the polymerization degree of 10;
the addition amount of the catalyst I is 100ppm relative to the terephthalic acid; the addition amount of the antioxidant I is 500ppm relative to the terephthalic acid; the molar ratio of terephthalic acid to butanediol is 1: 1.4;
the temperature of the esterification reaction is 240 ℃, the absolute pressure is 0.6MPa, and the esterification time is 90 min; when the water yield is equal to 99 percent of the theoretical water yield, the esterification is considered to be finished;
(2) esterification of adipate: uniformly mixing adipic acid, butanediol, a catalyst II (tetrabutyl titanate and ethylene glycol titanium with the molar ratio of 1:1) and an antioxidant II (triphenyl phosphate and an antioxidant 300 with the molar ratio of 1:1) according to a certain proportion, and then carrying out esterification reaction to obtain an adipate with the polymerization degree of 10;
the addition amount of the catalyst II is 100ppm relative to the adipic acid; the amount of the antioxidant II added was 500ppm based on the amount of adipic acid; the molar ratio of adipic acid to butanediol is 1: 1.4;
the temperature of the esterification reaction is 200 ℃, the absolute pressure is 0.5MPa, the esterification time is 90min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(3) esterification of 5-sodium sulfoisophthalate: uniformly mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III (tetrabutyl titanate and ethylene glycol titanium, and the molar ratio is 1:1) and an antioxidant III (triphenyl phosphate and an antioxidant 300, and the molar ratio is 1:1) according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate with the polymerization degree of 2;
the addition amount of the catalyst III is 100ppm relative to the isophthalic acid-5-sodium sulfonate; the addition amount of the antioxidant III is 500ppm relative to the isophthalic acid-5-sodium sulfonate; the molar ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2.1;
the temperature of the esterification reaction is 240 ℃, the absolute pressure is 0.6MPa, the esterification time is 100min, and the esterification is considered to be finished when the water yield is equal to 99 percent of the theoretical water yield;
(4) pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the step (1) to obtain a PBT prepolymer with the polymerization degree of 30;
the temperature of the pre-polycondensation reaction is 260 ℃, the absolute pressure is 300Pa, and the pre-polycondensation time is 30 min;
(5) pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the step (2) to obtain a PBA prepolymer with the polymerization degree of 30;
the temperature of the pre-polycondensation reaction is 250 ℃, the absolute pressure is 300Pa, and the pre-polycondensation time is 40 min;
(6) final polycondensation: performing final polycondensation on the products obtained in the steps (3) to (5) to obtain PBAT slices with the intrinsic viscosity of 1.3 dL/g;
the temperature of the final polycondensation reaction is 260 ℃, the absolute pressure is 200Pa, and the final polycondensation time is 60 min;
in the PBAT chips, the molar content of adipic acid relative to terephthalic acid was 150%, and the molar content of 5-sodium sulfoisophthalate relative to terephthalic acid was 4%;
(7) carrying out melt spinning on the PBAT slices obtained in the step (6) to obtain PBAT fibers; the spinning temperature is 260 ℃, the spinning speed is 5000m/min, and the draw ratio is 5 times.
The molecular chain segment of the prepared PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 150 percent relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 4 percent relative to the butylene terephthalate chain segment; the PBAT fiber had a breaking strength of 5.5cN/dtex, an elongation at break of 15% and an AA rate of 99%.
Claims (11)
1. A PBAT fiber characterized by: the molecular chain segment of the PBAT fiber comprises a butylene terephthalate chain segment, a butylene adipate chain segment and a 5-sodium sulfobutylene isophthalate chain segment, wherein the molar content of the butylene adipate chain segment is 50-150% relative to the butylene terephthalate chain segment, and the molar content of the 5-sodium sulfobutylene isophthalate chain segment is 0.5-4% relative to the butylene terephthalate chain segment.
2. The PBAT fiber of claim 1, wherein the PBAT fiber has a breaking strength of 2.0 to 5.5cN/dtex, an elongation at break of 15 to 60%, and an AA rate of 98% or more.
3. A method for preparing PBAT fiber is characterized in that: respectively esterifying terephthalic acid and adipic acid, respectively performing pre-polycondensation, then mixing the two obtained prepolymers, adding an isophthalic acid-5-sodium sulfonate ester, performing final polycondensation, and finally preparing the PBAT fiber by a melt spinning method.
4. The method of claim 3 for preparing PBAT fiber, characterized by the following steps:
first step, esterification of terephthalic acid: uniformly mixing terephthalic acid, butanediol, a catalyst I and an antioxidant I according to a certain proportion, and then carrying out esterification reaction to obtain a terephthalic acid esterified substance;
second step, adipate esterification: uniformly mixing adipic acid, butanediol, a catalyst II and an antioxidant II according to a certain proportion, and then carrying out esterification reaction to obtain an adipate;
step three, esterifying isophthalic acid-5-sodium sulfonate: mixing 5-sodium sulfoisophthalate, butanediol, a catalyst III and an antioxidant III uniformly according to a certain proportion, and then carrying out esterification reaction to obtain 5-sodium sulfoisophthalate esterified substance;
fourthly, pre-polycondensation of terephthalate: carrying out pre-polycondensation reaction on the terephthalic acid ester obtained in the first step to obtain a PBT prepolymer;
fifthly, pre-polycondensation of adipate: carrying out pre-polycondensation reaction on the adipate obtained in the second step to obtain a PBA prepolymer;
sixth, final polycondensation: performing final polycondensation on the product obtained in the third to fifth steps to obtain a PBAT slice;
and seventhly, carrying out melt spinning on the PBAT slices obtained in the sixth step to obtain the PBAT fibers.
5. The method for preparing PBAT fibers according to claim 4, wherein in the first step, the catalyst I is one or more of tetrabutyl titanate and titanium glycolate, and the addition amount of the catalyst I is 5-100 ppm relative to terephthalic acid;
the antioxidant I is more than one of triphenyl phosphate, antioxidant 300 and antioxidant 164, and the addition amount of the antioxidant I is 100-500 ppm relative to the terephthalic acid;
the molar ratio of the terephthalic acid to the butanediol is 1: 1.1-1.4;
the temperature of the esterification reaction is 180-240 ℃, the absolute pressure is 100 Pa-0.6 MPa, and the esterification time is 90-300 min; when the water yield is more than or equal to 98 percent of the theoretical water yield, the esterification is considered to be finished;
the polymerization degree of the obtained terephthalic acid ester is 2-10.
6. The method for preparing PBAT fiber according to claim 4, wherein in the second step, the catalyst II is more than one of tetrabutyl titanate and titanium glycol, and the addition amount of the catalyst II is 5-100 ppm relative to adipic acid;
the antioxidant II is more than one of triphenyl phosphate, antioxidant 300 and antioxidant 164, and the addition amount of the antioxidant II is 100-500 ppm relative to the adipic acid;
the molar ratio of the adipic acid to the butanediol is 1: 1.1-1.4;
the temperature of the esterification reaction is 140-200 ℃, the absolute pressure is 100 Pa-0.5 MPa, the esterification time is 90-280 min, and the esterification is considered to be finished when the water yield is more than or equal to 98% of the theoretical water yield;
the degree of polymerization of the obtained adipate is 2-10.
7. The method for preparing PBAT fiber according to claim 4, wherein in the third step, the catalyst III is one or more of tetrabutyl titanate and titanium glycolate, and the addition amount of the catalyst III is 5-100 ppm relative to 5-sodium sulfoisophthalate;
the antioxidant III is more than one of triphenyl phosphate, antioxidant 300 and antioxidant 164, and the addition amount of the antioxidant III is 100-500 ppm relative to the sodium 5-sulfoisophthalate;
the mol ratio of the isophthalic acid-5-sodium sulfonate to the butanediol is 1: 2-2.1;
the temperature of the esterification reaction is 210-240 ℃, the absolute pressure is 100 Pa-0.6 MPa, the esterification time is 100-300 min, and the esterification is considered to be finished when the water yield is more than or equal to 98% of the theoretical water yield;
the polymerization degree of the obtained isophthalic acid-5-sodium sulfonate ester is 1-2.
8. The method for preparing PBAT fiber according to claim 4, wherein in the fourth step, the temperature of the pre-polycondensation reaction is 240-260 ℃, the absolute pressure is 10-300 Pa, and the pre-polycondensation time is 30-90 min;
the polymerization degree of the obtained PBT prepolymer is 20-30.
9. The preparation method of the PBAT fiber according to claim 4, characterized in that in the fifth step, the temperature of the pre-polycondensation reaction is 230-250 ℃, the absolute pressure is 0-300 Pa, and the pre-polycondensation time is 40-100 min;
the polymerization degree of the obtained PBA prepolymer is 20-30.
10. The method for preparing PBAT fiber according to claim 4, wherein in the sixth step, the temperature of final polycondensation is 240-260 ℃, the absolute pressure is 10-200 Pa, and the final polycondensation time is 60-180 min;
the intrinsic viscosity of the PBAT slice is 0.8-1.3 dL/g;
in the PBAT slice, the molar content of adipic acid is 50-150% relative to terephthalic acid, and the molar content of 5-sodium sulfoisophthalate is 0.5-4% relative to terephthalic acid.
11. The method for preparing PBAT fiber according to claim 4, wherein in the seventh step, the spinning temperature is 210-260 ℃, the spinning speed is 800-5000 m/min, and the draw ratio is 1.5-5 times.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449059A (en) * | 2022-08-24 | 2022-12-09 | 中山市泓溢薄膜科技有限公司 | Preparation method and application of degradable polybutylene adipate terephthalate |
| CN115852520A (en) * | 2023-02-07 | 2023-03-28 | 江苏恒力化纤股份有限公司 | Preparation method of high-strength biodegradable polyester fiber |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1432600A (en) * | 1972-09-20 | 1976-04-22 | Du Pont | Acid dyeable polyesters |
| JPH07305229A (en) * | 1994-05-11 | 1995-11-21 | Mitsubishi Rayon Co Ltd | Method for producing modified polyester fiber |
| US6787245B1 (en) * | 2003-06-11 | 2004-09-07 | E. I. Du Pont De Nemours And Company | Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom |
| JP2005179431A (en) * | 2003-12-17 | 2005-07-07 | Toray Ind Inc | Polybutylene terephthalate, its preparation method and molded product comprising the same |
| US20060194047A1 (en) * | 2003-06-19 | 2006-08-31 | Gupta Rakesh K | Water-dispersible and multicomponent fibers from sulfopolyesters |
| JP2012177045A (en) * | 2011-02-28 | 2012-09-13 | Toray Ind Inc | Polylactic acid-based film |
| CN103814066A (en) * | 2011-09-12 | 2014-05-21 | 东丽株式会社 | Film |
| CN105063797A (en) * | 2015-07-16 | 2015-11-18 | 中国纺织科学研究院 | Method for preparing low-melting-point polyester composite fiber by adopting continuous polymerization and melt direct-spinning |
| CN106164349A (en) * | 2014-03-25 | 2016-11-23 | 东丽株式会社 | There is fiber and the manufacture method thereof of phase separation structure |
| WO2017207827A1 (en) * | 2016-05-30 | 2017-12-07 | Sociedad Anónima Minera Catalano-Aragonesa | Method for obtaining biodegradable polyesteretheramide |
| CN109456469A (en) * | 2018-10-14 | 2019-03-12 | 东华大学 | A kind of preparation method of the cation-modified copolyesters of high fluidity |
| CN110952161A (en) * | 2019-12-16 | 2020-04-03 | 扬州富威尔复合材料有限公司 | Low-melting-point elastic polyester fiber and preparation method thereof |
| CN111607202A (en) * | 2020-07-08 | 2020-09-01 | 浙江晟祺实业有限公司 | Methylated lignin PBAT biodegradable plastic and preparation method thereof |
| CN111733475A (en) * | 2020-06-30 | 2020-10-02 | 北京科方创业科技企业孵化器有限公司 | Biodegradable spinning material and preparation method and application thereof |
| CN111848937A (en) * | 2020-07-30 | 2020-10-30 | 浙江大学 | Biodegradable polyester with high gas barrier property and preparation method and application thereof |
-
2021
- 2021-03-30 CN CN202110337999.9A patent/CN113122952B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1432600A (en) * | 1972-09-20 | 1976-04-22 | Du Pont | Acid dyeable polyesters |
| JPH07305229A (en) * | 1994-05-11 | 1995-11-21 | Mitsubishi Rayon Co Ltd | Method for producing modified polyester fiber |
| US6787245B1 (en) * | 2003-06-11 | 2004-09-07 | E. I. Du Pont De Nemours And Company | Sulfonated aliphatic-aromatic copolyesters and shaped articles produced therefrom |
| US20060194047A1 (en) * | 2003-06-19 | 2006-08-31 | Gupta Rakesh K | Water-dispersible and multicomponent fibers from sulfopolyesters |
| JP2005179431A (en) * | 2003-12-17 | 2005-07-07 | Toray Ind Inc | Polybutylene terephthalate, its preparation method and molded product comprising the same |
| JP2012177045A (en) * | 2011-02-28 | 2012-09-13 | Toray Ind Inc | Polylactic acid-based film |
| CN103814066A (en) * | 2011-09-12 | 2014-05-21 | 东丽株式会社 | Film |
| CN106164349A (en) * | 2014-03-25 | 2016-11-23 | 东丽株式会社 | There is fiber and the manufacture method thereof of phase separation structure |
| CN105063797A (en) * | 2015-07-16 | 2015-11-18 | 中国纺织科学研究院 | Method for preparing low-melting-point polyester composite fiber by adopting continuous polymerization and melt direct-spinning |
| WO2017207827A1 (en) * | 2016-05-30 | 2017-12-07 | Sociedad Anónima Minera Catalano-Aragonesa | Method for obtaining biodegradable polyesteretheramide |
| US20190202986A1 (en) * | 2016-05-30 | 2019-07-04 | Sociedad Anonima Minera Catalano- Aragonesa | Method for obtaining biodegradable polyesteretheramide |
| CN109456469A (en) * | 2018-10-14 | 2019-03-12 | 东华大学 | A kind of preparation method of the cation-modified copolyesters of high fluidity |
| CN110952161A (en) * | 2019-12-16 | 2020-04-03 | 扬州富威尔复合材料有限公司 | Low-melting-point elastic polyester fiber and preparation method thereof |
| CN111733475A (en) * | 2020-06-30 | 2020-10-02 | 北京科方创业科技企业孵化器有限公司 | Biodegradable spinning material and preparation method and application thereof |
| CN111607202A (en) * | 2020-07-08 | 2020-09-01 | 浙江晟祺实业有限公司 | Methylated lignin PBAT biodegradable plastic and preparation method thereof |
| CN111848937A (en) * | 2020-07-30 | 2020-10-30 | 浙江大学 | Biodegradable polyester with high gas barrier property and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| FANGFANG HUANG等: "Sulfonated biodegradable PBAT copolyesters with improved gas barrier properties and excellent water dispersibility: From synthesis to structure-property", 《POLYMER DEGRADATION AND STABILITY》 * |
| 韩长青等: "分散染料易染聚酯纤维的改性技术", 《合成纤维工业》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115449059A (en) * | 2022-08-24 | 2022-12-09 | 中山市泓溢薄膜科技有限公司 | Preparation method and application of degradable polybutylene adipate terephthalate |
| CN115852520A (en) * | 2023-02-07 | 2023-03-28 | 江苏恒力化纤股份有限公司 | Preparation method of high-strength biodegradable polyester fiber |
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