CN115216862A - Preparation method of creep-resistant polyester industrial yarn - Google Patents
Preparation method of creep-resistant polyester industrial yarn Download PDFInfo
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- CN115216862A CN115216862A CN202211119353.4A CN202211119353A CN115216862A CN 115216862 A CN115216862 A CN 115216862A CN 202211119353 A CN202211119353 A CN 202211119353A CN 115216862 A CN115216862 A CN 115216862A
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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
- D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
- D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
- D01F8/14—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyester as constituent
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/088—Cooling filaments, threads or the like, leaving the spinnerettes
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
- D01D5/16—Stretch-spinning methods using rollers, or like mechanical devices, e.g. snubbing pins
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
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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
- D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
- D01F11/04—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers
- D01F11/08—Chemical after-treatment of artificial filaments or the like during manufacture of synthetic polymers of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention relates to a preparation method of creep-resistant polyester industrial yarn, which comprises the steps of carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups, and obtaining the creep-resistant polyester industrial yarn through electron beam irradiation after the spinning is formed; creep test is carried out on the creep-resistant polyester industry under the conditions that the temperature is 25 ℃, the relative humidity is 65%, the applied load is 30% of the breaking strength and the time is 24 hours, and the creep elongation of the creep-resistant polyester industrial yarn is 0.5-0.7%; the dry heat shrinkage rate of the polyester industrial yarn is less than or equal to 1.2 percent when the temperature is 177 ℃ and the pretension is 0.05 cN/dtex. The method has simple process and low cost, and is easier to popularize on a large scale; the creep resistance and the thermal stability of the prepared creep-resistant polyester industrial yarn are obviously improved.
Description
Technical Field
The invention belongs to the technical field of polyester industrial yarns, and relates to a preparation method of a creep-resistant polyester industrial yarn.
Background
The polyester industrial yarn has the characteristics of high strength, modulus, dimensional stability, impact resistance and the like, and is widely applied to the fields of tire cords, safety belts, safety airbags, geotechnical materials and the like. Like all high polymer materials, the polyester industrial yarn can creep under the action of stress load in the post-processing and using processes, so that the dimensional stability of the polyester industrial yarn in the application process is reduced, and the safe service life of the polyester industrial yarn is seriously influenced. Therefore, improving the creep resistance of the polyester industrial yarn is one of the important ways to improve the quality of the polyester industrial yarn.
The macromolecular structure of the polyester industrial yarn is a linear macromolecule containing benzene rings and ester group structures, and has a branched chain-free structure, and strong interaction does not exist among molecular chains, so that the molecular chains in an amorphous area in the fiber are easy to slide under the action of external load, which is a main factor of the creep phenomenon of the fiber. Therefore, increasing the interaction force between the molecular chains in the amorphous region and limiting the slippage are the main ideas for improving the creep resistance of the polyester industrial yarn. Chinese patent CN201310480196.4 and patent CN201310478959.1 end-capping partial macromolecular chains of polyester with fluorine-containing epoxy compounds to prepare creep-resistant polyester industrial yarns, and utilize fluorine atoms with strong electronegativity to form hydrogen bonds among polyester molecular chains, so that intermolecular force is increased, and creep-resistant effect is improved; however, for the polyester industrial yarn, the molecular weight is large, the number of hydrogen bonds which can be formed between the macromolecule end groups is limited, and compared with covalent bonds, the acting force of the hydrogen bonds is relatively weaker and is easily damaged by external conditions such as temperature, so that the creep resistance is improved limitedly, and the dry heat shrinkage rate of the fiber is 8.0 to 10.0% under the test conditions of 177 ℃ and 0.05 cN/dtex. Chinese patent CN202110889948.7 designs a thermoreversibly crosslinked polyester industrial yarn, covalent bonds can be formed between the end groups of polyester macromolecules at low temperature, and the polyester macromolecules are dimerized at high temperature, the creep resistance of the fiber is enhanced, and the creep elongation of the fiber is 0.7 to 1.1 percent when the test is carried out at the temperature of 25 ℃, the relative humidity of 65 percent, the applied tension of 30 percent of the breaking strength and the time of 24 hours. Chinese patent CN202011607885.3 soaks the polyester industrial yarn in a water solution containing a coordination agent, a coordination bond is formed by utilizing the interaction of a metal and a ligand, the creep resistance of the fiber is enhanced, and the creep elongation of the fiber is 1.5 to 1.7% under the conditions that the temperature is 25 ℃, the relative humidity is 65%, the fixed tension is 2.00cN/dtex and the time is 10 min; however, the polyester industrial yarn itself has a dense structure with high crystallinity and high orientation, the complexing agent is difficult to diffuse into the fiber, the diffusion effect is improved by increasing the temperature of the impregnation liquid, and the molecular chain is disoriented, which causes strength loss. In addition, a photosensitizer or a radiosensitizer is added in the spinning process, the prepared fiber is initiated by ultraviolet light or electron beams to form chemical crosslinking in the fiber, the creep resistance of the fiber can be improved, however, for the polyester industrial yarn, the spinning temperature is over 300 ℃, the unsaturated photosensitizer or radiosensitizer structure is easy to damage, and the existence of low molecular substances can also influence the crystal orientation of the fiber, so that the improvement of the mechanical property of the fiber is restricted.
Therefore, the development of a preparation method of the creep-resistant polyester industrial yarn with excellent comprehensive performance is particularly important.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of creep-resistant polyester industrial yarn.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of creep-resistant polyester industrial yarn comprises the steps of carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups, and obtaining the creep-resistant polyester industrial yarn through electron beam irradiation after the spinning is formed;
creep test is carried out on the creep-resistant polyester industry under the conditions that the temperature is 25 ℃, the relative humidity is 65%, the applied load is 30% of the breaking strength, and the time is 24 hours, and the creep elongation of the creep-resistant polyester industrial yarn is measured to be 0.5-0.7%; the dry heat shrinkage of the creep-resistant polyester industrial yarn measured under the conditions of 177 ℃ and 0.05cN/dtex of pre-tension is less than or equal to 1.2% (the dry heat shrinkage is tested by referring to the GBT 16604-2017 standard, and the dry heat shrinkage is used for representing the dimensional stability at high temperature), which is much higher than the prior art.
In the prior art, the creep-resistant polyester industrial yarn builds coordinate bonds or hydrogen bonds in the fiber to increase the acting force among macromolecular chains and improve the creep resistance, but the acting force is far lower than the bonding force of covalent bonds. Or the creep resistance of the polyester industrial yarn can be improved by constructing the thermally reversible cross-linked covalent bond at normal temperature, but the thermally reversible covalent bond is subjected to deprimerization at high temperature, so that the creep resistance and the dimensional stability are obviously reduced. According to the invention, unsaturated functional groups are introduced into the chain ends of the linear native polyester macromolecules and the chain ends of the branched polyester macromolecules, so that the linear polyester in the prepared fiber can form a highly-crystalline and highly-oriented structure, and the branched polyester is dissociated in an amorphous region of the fiber. After electron beam irradiation, unsaturated bonds at chain ends of linear polyester macromolecules are opened, and cross-linking can be formed between the unsaturated bonds, so that slippage of molecular chains in a weak area inside the fiber is reduced; meanwhile, the branched polyester dissociated in the amorphous region can be crosslinked to form the effect similar to a molecular rope, the amorphous region subchain of the linear polyester is bound, the arrangement of the subchain is compact, the high-orientation structure is kept, and the creep resistance and the high-temperature dimensional stability of the fiber are obviously improved.
As a preferable technical scheme:
according to the preparation method of the creep-resistant polyester industrial yarn, the filament number of the creep-resistant polyester industrial yarn is 3-10dtex, the breaking strength is not less than 8.2cN/dtex, and the elongation at break is 10-18%.
The preparation method of the creep-resistant polyester industrial yarn comprises the following process parameters of melt blending spinning: the melt temperature is 310 to 335 ℃, the temperature of a post heater is 310 to 335 ℃, the cooling air blowing temperature is 0.5 to 0.8m/s, the air blowing temperature is 18 to 28 ℃, the one-roll speed is 600 to 1200m/min, and the hot-roll drawing magnification is 4.5 to 7 times.
According to the preparation method of the creep-resistant polyester industrial yarn, the irradiation dose of an electron beam is 5-15kGy, the irradiation dose rate is 0.1-5kGy/s, and the irradiation time is 3-30min. The parameters of the irradiation dose, the irradiation dose rate and the irradiation time of the electron beam are not easy to be too high or too low, the parameters are too low, the crosslinking degree of unsaturated end groups is too low, and the improvement of creep resistance is limited; too high, the polyester molecular weight is easily degraded and the loss of fiber strength is severe.
According to the preparation method of the creep-resistant polyester industrial yarn, the mass ratio of the linear polyester A containing unsaturated end groups to the branched polyester B containing unsaturated end groups is 19 to 19.9. The excessive dosage of the branched polyester B containing unsaturated end groups can influence the arrangement regularity of the linear polyester A, the orientation degree is reduced, and the improvement of the fiber strength is not facilitated; the branched polyester B containing unsaturated end groups has too little dosage, the crosslinking degree formed in the amorphous region of the fiber is too low, the constraint on the molecular chain of the amorphous region is weakened, and the improvement of the creep resistance is limited.
In the preparation method of the creep-resistant polyester industrial yarn, the linear polyester A containing unsaturated end groups is prepared by leading one end or two ends of macromolecular chains of linear primary polyester to be separated from each other
Obtained by end capping;
the chemical structural formula of the linear primary polyester is
In which E 1 And E 2 Each independently selected from hydroxy and carboxy, R 1 Is an aromatic ring, n is the polymerization degree, and the value range is 140 to 190.
The preparation method of the creep-resistant polyester industrial yarn comprises the linear polymerization of the unsaturated end groupThe preparation process of the ester A comprises the following steps: will be provided with
The polyester and linear primary polyester are subjected to reactive blending to prepare linear polyester A containing unsaturated end groups;
the temperature of the reactive blending is 275 to 290 ℃, the pressure is-0.03 to 0.05MPa, and the time is 10 to 20min.
The preparation method of the creep-resistant polyester industrial yarn comprises the step of preparing the branched polyester B containing the unsaturated end group from the tail end (including the main chain and the branch chain) of the branched polyester
And (3) blocking.
The preparation method of the creep-resistant polyester industrial yarn comprises the following steps of: will be provided with
Reactive blending with branched polyester to prepare branched polyester B containing unsaturated end groups;
the temperature of the reactive blending is 275-290 ℃, the pressure is-0.03-0.05MPa, and the time is 10-20min.
The preparation method of the creep-resistant polyester industrial yarn comprises the steps that the branched polyester is prepared by carrying out melt blending reaction on linear polyester and a polyfunctional branching agent;
the melting temperature is 265 to 280 ℃ and the time is 5 to 8min;
the mass ratio of the polyfunctional branching agent to the linear polyester is 5 to 10; the dosage of the polyfunctional branching agent is too small, the branching degree of the linear polyester is low, and the end groups capable of participating in the end sealing of the unsaturated monomer are few, so that the irradiation crosslinking degree is low, and the creep resistance effect is improved; the use amount of the polyfunctional branching agent is too much, and the branching degree of the linear polyester is too high, so that the orderliness of macromolecules of the linear polyester A can be influenced, and the strength of the fiber can not be maintained;
the polyfunctional branching agent is glycerol, pentaerythritol, trimellitic acid or pyromellitic acid;
the chemical structural formula of the linear polyester is
Wherein E is 3 And E 4 Each independently selected from hydroxy and carboxy, R 2 Is an aromatic ring, n is the polymerization degree, and the value range is 100 to 120.
The above preparation containing unsaturation
When the end-capped linear polyester A and the branched polyester B are adopted, the values of the parameters should be set within a reasonable range, and the method is not suitable forIf the content of the terminal groups of the molecular chains of the linear polyester A and the branched polyester B participating in the reactive blending is too low, the covalent crosslinking degree in the fiber is low, the improvement of the creep resistance effect of the fiber is not facilitated, or excessive end-capping monomers are dispersed in the polyester in a free state, and the improvement of the fiber forming performance and the strength is influenced due to the existence of the low-molecular-weight substances.
The principle of the invention is as follows:
according to the invention, unsaturated functional groups are introduced into the linear primary polyester macromolecular chain end and the branched polyester macromolecular chain end, so that the linear polyester in the prepared fiber can form a high-crystalline high-orientation structure, and the branched polyester is dissociated in an amorphous region of the fiber. The molecular chain ends of the amorphous regions in the fiber are weak regions of the fiber. After fibers are formed into fibers, through electron beam irradiation, unsaturated bonds at chain ends of linear polyester macromolecules are opened, and cross-linking can be formed between the unsaturated bonds, so that slippage of molecular chains in a weak area inside the fibers is reduced; meanwhile, the branched polyester dissociated in the amorphous region can be crosslinked to form the effect similar to a molecular rope, so that the linear polyester amorphous region subchain is bound to be tightly arranged, a high-orientation structure is kept, and the creep resistance of the fiber and the improvement of the high-temperature dimensional stability are facilitated.
Has the advantages that:
(1) The preparation method of the creep-resistant polyester industrial yarn adopts reactive blending, melt blending spinning and irradiation crosslinking, has simple process, low cost, is easier to popularize on a large scale, and has good quality, durability and stability of fiber products and long safe service life;
(2) According to the creep-resistant polyester industrial yarn, after the fiber is subjected to electron beam radiation crosslinking, the amorphous region molecular chain ends of the fiber can form a crosslinking structure, so that the load resistance of a weak region of the fiber is effectively improved, the molecular rope bundling effect is formed by the crosslinking effect of the branched polyester, the interaction among the amorphous region molecular chains and the maintenance of an oriented structure are favorably increased, and the creep resistance and the thermal stability of the fiber are 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.
The test method adopted by the invention is as follows:
(1) Breaking strength: testing the breaking strength of the creep-resistant polyester industrial yarn by using GB/T16604-2017;
(2) Elongation at break: testing the elongation at break of the creep-resistant polyester industrial yarn by using GB/T16604-2017;
(3) Creep elongation: testing the creep elongation of the creep-resistant polyester industrial yarn under the conditions that the temperature is 25 ℃, the relative humidity is 65%, the applied load is 30% of the breaking strength, and the time is 24 hours, wherein the clamping distance of a sample is 500mm;
(4) Dry heat shrinkage: the creep-resistant polyester industrial yarn is tested for dry heat shrinkage with reference to the GBT 16604-2017 standard under the conditions of 177 ℃ of temperature and 0.05cN/dtex of pretension.
Example 1
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups;
will be provided with
And
(n = 140) carrying out reactive blending at 275 ℃ and 0.05MPa for 15min according to the mass ratio of 10;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) mixing Glycerol with
(n = 120) melt-blending at 280 ℃ for 5min at a mass ratio of 10;
(2.2) mixing
Carrying out reactive blending with the branched polyester prepared in the step (2.1) for 20min at 290 ℃ and-0.03 MPa according to the mass ratio of 40;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19.9;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 335 ℃, the temperature of a post heater is 335 ℃, the cooling blowing temperature is 0.8m/s, the blowing temperature is 18 ℃, the one-roll speed is 600m/min, and the hot-roll drafting magnification is 4.5 times;
the irradiation dose of the electron beam is 12kGy, the irradiation dose rate is 0.1kGy/s, and the irradiation time is 3min.
The single filament number of the prepared creep-resistant polyester industrial yarn is 10dtex, the breaking strength is 8.2cN/dtex, the elongation at break is 18%, the creep elongation is 0.7%, and the dry heat shrinkage rate is 1.2%.
Comparative example 1
A process for producing a polyester industrial yarn, which is substantially the same as that of example 1 except that the step (2.2) is omitted, and a branched polyester B having an unsaturated terminal group, which is not the branched polyester B having an unsaturated terminal group but the branched polyester produced in the step (2.1) is melt-blended and spun with the linear polyester A having an unsaturated terminal group in the step (3); the filament number of the finally prepared polyester industrial yarn is 10dtex, the breaking strength is 7.5cN/dtex, the elongation at break is 23%, the creep elongation is 2.8%, and the dry heat shrinkage rate is 3.0%. Comparing example 1 with comparative example 1, it can be seen that the creep elongation and the dry heat shrinkage rate of the polyester industrial yarn in example 1 are significantly lower than those in example 2, because the branched polyester containing unsaturated end groups in example 1 forms a cross-linked structure in the amorphous region of the fiber after irradiation, which has a binding effect on molecular chains in the amorphous region, and is beneficial to increasing the interaction between the molecular chains in the amorphous region and maintaining the oriented structure.
Example 2
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups;
will be provided with
And with
n = 190) according to the mass ratio of 15 to 1000, carrying out reactive blending for 20min at 290 ℃ and under the pressure of-0.03 MPa to prepare a linear polyester A containing unsaturated end groups;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) reacting pentaerythritol with
(n = 100) melt blending at 265 ℃ for 8min at a mass ratio of 5;
(2.2) mixing
Carrying out reactive blending with the branched polyester prepared in the step (2.1) for 15min at 275 ℃ and under the pressure of 0.05MPa according to the mass ratio of 15;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 310 ℃, the temperature of a post heater is 310 ℃, the cooling blowing temperature is 0.5m/s, the blowing temperature is 28 ℃, the one-roll speed is 1200m/min, and the hot roll drafting multiplying power is 7 times;
the irradiation dose of the electron beam is 15kGy, the irradiation dose rate is 5kGy/s, and the irradiation time is 30min.
The single filament number of the prepared creep-resistant polyester industrial yarn is 3dtex, the breaking strength is 8.35cN/dtex, the elongation at break is 10%, the creep elongation is 0.5%, and the dry heat shrinkage rate is 0.9%.
Example 3
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups;
will be provided with
And with
(n = 150) carrying out reactive blending at 280 ℃ and a pressure of 0.04MPa for 10min according to a mass ratio of 11;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) reacting trimellitic acid with
n = 105) melt blending at 270 ℃ for 5min according to a mass ratio of 6;
(2.2) mixing
Carrying out reactive blending with the branched polyester prepared in the step (2.1) for 10min at 285 ℃ and-0.02 MPa according to the mass ratio of 35;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19.2;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 315 ℃, the temperature of a post heater is 315 ℃, the cooling blowing temperature is 0.5m/s, the blowing temperature is 20 ℃, the one-roll speed is 700m/min, and the hot roll drafting multiplying power is 5 times;
the irradiation dose of the electron beam is 5kGy, the irradiation dose rate is 0.5kGy/s, and the irradiation time is 5min.
The single filament number of the prepared creep-resistant polyester industrial yarn is 8dtex, the breaking strength is 8.26cN/dtex, the elongation at break is 14%, the creep elongation is 0.53%, and the dry heat shrinkage rate is 0.95%.
Example 4
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups;
will be provided with
And
(n = 160) according to the mass ratio of 12 to 1000, carrying out reactive blending for 12min at 282 ℃ and under the pressure of 0.03MPa to prepare a linear polyester A containing unsaturated end groups;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) reacting pyromellitic acid with
(n = 110) melt blending at 270 ℃ for 6min according to a mass ratio of 7;
(2.2) mixing
Carrying out reactive blending with the branched polyester prepared in the step (2.1) for 12min at the temperature of 280 ℃ and the pressure of 0.01MPa according to the mass ratio of 30;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19.4;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 320 ℃, the temperature of a post heater is 320 ℃, the cooling blowing temperature is 0.6m/s, the blowing temperature is 22 ℃, the one-roll speed is 800m/min, and the hot roll drafting multiplying power is 5 times;
the irradiation dose of the electron beam is 10kGy, the irradiation dose rate is 1kGy/s, and the irradiation time is 10min.
The single filament number of the prepared creep-resistant polyester industrial yarn is 7dtex, the breaking strength is 8.31cN/dtex, the elongation at break is 15%, the creep elongation is 0.57%, and the dry heat shrinkage rate is 1%.
Example 5
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups;
will be provided with
And
(n = 170) reactive blending was carried out at 285 ℃ and-0.01 MPa for 15min at a mass ratio of 13 to 1000 to obtain a linear polyester a containing unsaturated end groups;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) mixing Glycerol with
n = 112) was melt-blended at 275 ℃ for 7min at a mass ratio of 9;
(2.2) mixing
Carrying out reactive blending with the branched polyester prepared in the step (2.1) for 15min at 280 ℃ and-0.01 MPa according to the mass ratio of 25;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19.5;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 325 ℃, the temperature of a post heater is 325 ℃, the cooling blowing temperature is 0.7m/s, the blowing temperature is 25 ℃, the one-roll speed is 900m/min, and the hot-roll drafting magnification is 5.5 times;
the irradiation dose of the electron beam is 8kGy, the irradiation dose rate is 2kGy/s, and the irradiation time is 25min.
The single-filament fineness of the prepared creep-resistant polyester industrial yarn is 6dtex, the breaking strength is 8.4cN/dtex, the elongation at break is 13%, the creep elongation is 0.61%, and the dry-heat shrinkage rate is 1.03%.
Example 6
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups;
will be provided with
And
(n = 185) reactive blending was carried out at 288 ℃ and a pressure of-0.02 MPa for 18min at a mass ratio of 14 to 1000 to obtain a linear polyester a containing unsaturated end groups;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) reacting pentaerythritol with
(n = 115) melt-blending at 275 ℃ for 7min at a mass ratio of 8;
(2.2) mixing
Carrying out reactive blending with the branched polyester prepared in the step (2.1) for 18min at 285 ℃ and under the pressure of 0MPa according to the mass ratio of 20;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19.8;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 330 ℃, the temperature of a post heater is 330 ℃, the cooling blowing temperature is 0.8m/s, the blowing temperature is 26 ℃, the one-roll speed is 1000m/min, and the hot-roll drafting multiplying power is 6.5 times;
the irradiation dose of the electron beam is 8kGy, the irradiation dose rate is 4kGy/s, and the irradiation time is 18min.
The filament number of the prepared creep-resistant polyester industrial yarn is 4dtex, the breaking strength is 8.29cN/dtex, the elongation at break is 16%, the creep elongation is 0.68%, and the dry heat shrinkage rate is 1.15%.
Example 7
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups;
will be provided with
And
n = 175) according to the mass ratio of 12 to 1000, at 282 ℃ and under the pressure of 0.01MPa, carrying out reactive blending for 15min to obtain a linear polyester A containing unsaturated end groups;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) reacting isophthalic acid with
n = 105) was melt-blended at 270 ℃ for 6min at a mass ratio of 6;
(2.2) mixing
And the branched polyester prepared in the step (2.1) according to the mass ratio of 25 to 1000, at 280 ℃ and under pressureReactive blending is carried out for 13min under the pressure of 0.01MPa, and branched polyester B containing unsaturated end groups is prepared;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19.5;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 323 ℃, the temperature of a rear heater is 323 ℃, the cooling and blowing temperature is 0.7m/s, the blowing temperature is 23 ℃, the one-roll speed is 750m/min, and the hot-roll drafting multiplying power is 6 times;
the irradiation dose of the electron beam is 10kGy, the irradiation dose rate is 3.5kGy/s, and the irradiation time is 15min.
The single filament number of the prepared creep-resistant polyester industrial yarn is 8dtex, the breaking strength is 8.35cN/dtex, the elongation at break is 15%, the creep elongation is 0.62%, and the dry heat shrinkage rate is 1.05%.
Example 8
A preparation method of creep-resistant polyester industrial yarn comprises the following specific steps:
(1) Preparing linear polyester A containing unsaturated end groups; will be provided with
And with
(n = 180) by mass ratio 13 to 1000, at 285 ℃ and under a pressure of 0.02MPa, a linear polyester a containing unsaturated end groups was obtained by reactive blending for 15 min;
(2) Preparing a branched polyester B containing unsaturated end groups;
(2.1) reacting pyromellitic acid with
(n = 115) melt-blending at 275 ℃ for 7min at a mass ratio of 8;
(2.2) mixing
Carrying out reactive blending with the branched polyester prepared in the step (2.1) for 15min at 283 ℃ and 0.01MPa according to the mass ratio of 30;
(3) Carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups according to the mass ratio of 19.6;
wherein the technological parameters of the melt blending spinning are as follows: the melt temperature is 328 ℃, the temperature of a post heater is 328 ℃, the cooling blowing temperature is 0.7m/s, the blowing temperature is 25 ℃, the one-roll speed is 1100m/min, and the hot-roll drafting multiplying power is 6 times;
the irradiation dose of the electron beam is 12kGy, the irradiation dose rate is 3kGy/s, and the irradiation time is 20min.
The single filament number of the prepared creep-resistant polyester industrial yarn is 3.5dtex, the breaking strength is 8.45cN/dtex, the elongation at break is 13%, the creep elongation is 0.63%, and the dry heat shrinkage rate is 1.1%.
Claims (10)
1. A preparation method of creep-resistant polyester industrial yarn is characterized by comprising the following steps: carrying out melt blending spinning on linear polyester A containing unsaturated end groups and branched polyester B containing unsaturated end groups, and carrying out electron beam irradiation after spinning forming to prepare creep-resistant polyester industrial yarns;
creep test is carried out on the creep-resistant polyester industry under the conditions that the temperature is 25 ℃, the relative humidity is 65%, the applied load is 30% of the breaking strength, and the time is 24 hours, and the creep elongation of the creep-resistant polyester industrial yarn is measured to be 0.5-0.7%; the dry heat shrinkage of the creep-resistant polyester industrial yarn is less than or equal to 1.2 percent under the conditions that the temperature is 177 ℃ and the pretension is 0.05 cN/dtex.
2. The method for preparing the creep-resistant polyester industrial yarn as claimed in claim 1, wherein the creep-resistant polyester industrial yarn has a filament fineness of 3 to 10dtex, a breaking strength of not less than 8.2cN/dtex, and an elongation at break of 10 to 18%.
3. The method for preparing the creep-resistant polyester industrial yarn according to claim 1, wherein the process parameters of the melt blending spinning are as follows: the melt temperature is 310 to 335 ℃, the temperature of a post heater is 310 to 335 ℃, the cooling air blowing temperature is 0.5 to 0.8m/s, the air blowing temperature is 18 to 28 ℃, the one-roll speed is 600 to 1200m/min, and the hot-roll drawing magnification is 4.5 to 7 times.
4. The method for preparing the creep-resistant polyester industrial yarn according to claim 1, wherein the irradiation dose of electron beams is 5 to 15kGy, the irradiation dose rate is 0.1 to 5kGy/s, and the irradiation time is 3 to 30min.
5. The method for preparing the creep-resistant polyester industrial yarn according to claim 1, wherein the mass ratio of the linear polyester A containing unsaturated end groups to the branched polyester B containing unsaturated end groups is 19 to 19.9.
6. The method for preparing creep-resistant polyester industrial yarn according to claim 1, wherein the linear polyester A containing unsaturated end group is prepared by polymerizing one or both ends of macromolecular chain of linear raw polyester
Obtained by end capping;
the chemical structural formula of the linear primary polyester is
In which E 1 And E 2 Each independently selected from hydroxy and carboxy, R 1 Is an aromatic ring, and n is 140 to 190.
7. The method for preparing creep-resistant polyester industrial yarn according to claim 6, wherein the linear polyester A containing unsaturated end group is prepared by the following steps: will be provided with
Carrying out reactive blending with linear primary polyester to prepare linear polyester A containing unsaturated end groups;
the mass ratio of the polyester to the linear primary polyester is 10 to 15;
the temperature of the reactive blending is 275 to 290 ℃, the pressure is-0.03 to 0.05MPa, and the time is 10 to 20min.
8. The method for preparing creep-resistant polyester industrial yarn as claimed in claim 1, wherein the branched polyester B containing unsaturated end group is prepared by branching polyester with end group
And (3) end capping.
9. The method for preparing the creep-resistant polyester industrial yarn as claimed in claim 8, wherein the branched polyester B containing unsaturated end groups is prepared by the following steps: will be provided with
Reactive blending with branched polyester to prepare branched polyester B containing unsaturated end groups;
the mass ratio of the branched polyester to the branched polyester is 15 to 40;
the temperature of the reactive blending is 275 to 290 ℃, the pressure is-0.03 to 0.05MPa, and the time is 10 to 20min.
10. The method of claim 9, wherein the branched polyester is prepared by melt blending a linear polyester with a polyfunctional branching agent;
the melting temperature is 265 to 280 ℃, and the time is 5 to 8min;
the mass ratio of the polyfunctional branching agent to the linear polyester is 5 to 10;
the polyfunctional branching agent is glycerol, pentaerythritol, trimellitic acid or pyromellitic acid;
the chemical structural formula of the linear polyester is
Wherein, E 3 And E 4 Each independently selected from hydroxy and carboxy, R 2 Is an aromatic ring, and n is 100 to 120.
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| CN1541290A (en) * | 2001-08-10 | 2004-10-27 | ��Ļ���Ű˾ | Branched poly (etylene terephthalate) monofilaments |
| CN101098908A (en) * | 2004-11-17 | 2008-01-02 | Jvs-聚合物公司 | Crosslinkable biopolymer |
| JP2008260804A (en) * | 2007-04-10 | 2008-10-30 | Toyobo Co Ltd | Heat-resistant crosslinkable polyester composition, and polyester fiber material |
| CN109553936A (en) * | 2018-11-30 | 2019-04-02 | 复旦大学 | A kind of method of quick adjusting PET melt intensity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1541290A (en) * | 2001-08-10 | 2004-10-27 | ��Ļ���Ű˾ | Branched poly (etylene terephthalate) monofilaments |
| CN101098908A (en) * | 2004-11-17 | 2008-01-02 | Jvs-聚合物公司 | Crosslinkable biopolymer |
| JP2008260804A (en) * | 2007-04-10 | 2008-10-30 | Toyobo Co Ltd | Heat-resistant crosslinkable polyester composition, and polyester fiber material |
| CN109553936A (en) * | 2018-11-30 | 2019-04-02 | 复旦大学 | A kind of method of quick adjusting PET melt intensity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117107394A (en) * | 2023-10-19 | 2023-11-24 | 江苏恒力化纤股份有限公司 | Preparation method of polyester/polyester amide parallel composite elastic fiber |
| CN117107394B (en) * | 2023-10-19 | 2024-03-19 | 江苏恒力化纤股份有限公司 | Preparation method of polyester/polyester amide parallel composite elastic fiber |
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