CN113668092A - Polyester fiber and method for producing same - Google Patents
Polyester fiber and method for producing same Download PDFInfo
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- CN113668092A CN113668092A CN202111237264.5A CN202111237264A CN113668092A CN 113668092 A CN113668092 A CN 113668092A CN 202111237264 A CN202111237264 A CN 202111237264A CN 113668092 A CN113668092 A CN 113668092A
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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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6954—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from polxycarboxylic acids and polyhydroxy compounds
- C08G63/6956—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
- C08G63/86—Germanium, antimony, or compounds thereof
- C08G63/866—Antimony or compounds thereof
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention relates to a polyester fiber and a preparation method thereof, wherein the preparation method comprises the following steps: blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; the preparation process of the functional master batch comprises the following steps: carrying out esterification reaction on dibasic acid, dihydric alcohol and acid anhydride to obtain an esterification product with a hydroxyl end group; mixing the esterification product with modified component slurry containing hydroxyl terminated polysiloxane, and then carrying out polycondensation reaction to obtain functional master batches; the prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester. The preparation method is simple, the prepared polyester fiber has excellent mechanical property and wear resistance, and little micro plastic is formed in the washing process.
Description
Technical Field
The invention belongs to the field of polyester preparation, and relates to a polyester fiber and a preparation method thereof.
Background
Polyester fibers are basic raw materials for textiles, wherein the polyester fibers are represented by PET (polyethylene terephthalate), and the yield of China in 2020 exceeds 5000 ten thousand tons, so that the polyester fibers are in an absolutely leading position. The polyester fiber is used as a basic raw material of textile, and plays an important role in national economy. However, with the increasing awareness of the environment protection of human beings in recent years, researches show that 60% of micro plastic in fresh water comes from laundry fiber. As we wash clothes, the microfibers fall off, they eventually enter wastewater treatment facilities, and from there into lakes and other large bodies of water. Natural materials also shed fibers in washing and drying machines, but microorganisms can digest them, which is not the case for fibers made of synthetic textiles. These are not biodegradable and may linger in the ecosystem for centuries. After entering nature, the micro plastic particles not only destroy the ecological environment, but also can be ingested by aquatic and marine organisms, causing physical harm to the organisms, and in addition, because the micro plastic is not easy to degrade, the micro plastic particles are easy to enrich in different organisms and can finally cause harmful effects on human health along with the transmission of food chains.
Plastics with a particle size of <5mm are generally defined as micro plastics, wherein the micro plastics of the source textile are generally referred to as fiber micro plastics. The fiber micro-plastic is an important existing form of the micro-plastic and belongs to the field of environmental pollutants. The total amount of micro-plastics discharged in the global ocean is 150 million tons per year, and reports indicate that the fibers shed from textile washing account for about 34.8%, i.e., 52 million tons per year. It is therefore an important development of how polyester fibers as textile base material can be achieved to reduce the formation of microplastics by shedding during the washing process. In view of the fact that China is a large textile country and has a great position in the textile and fiber processing industrial chain all over the world, the research on the fiber micro-plastic is helpful for promoting the healthy and sustainable development of the textile and chemical fiber industry in China.
To investigate the means and strategies for fiber microplastic cutting, it is necessary to clean the major source of fiber microplastic. It is currently believed that physical abrasion and wash maintenance processes during service of textiles are important causes of fiber micro-plastics production. The fiber product is abraded and broken under the action of multiple factors such as external heat, force and the like in the washing process to cause falling off, so that the fiber micro plastic is formed.
The low mechanical strength and insufficient wear resistance of the fiber are the root causes of the formation and the falling of fiber micro-plastic in the using process. From the perspective of fiber and textile functional design, designing and reinforcing the abrasion resistance of the fiber matrix by the textile structure is an important approach to reduce the amount of fiber micro-plastic produced. The journal of Carbohydrate Polymers reports a technology for solving the problems of surface abrasion and shedding of a large amount of fiber micro-plastics caused by the action of a washing machine by coating protection treatment on polyimide fabric, and the specific process comprises the following steps: firstly, pectin (a natural polysaccharide existing in plant cell walls) is modified by glycidyl methacrylate to reduce water solubility, so that the phenomenon that the coating layer is dissolved and loses protection when being washed is avoided, and then the modified pectin is grafted on the surface of the polyamide fabric through a crosslinking reaction. After multiple washings, the release of the fiber micro-plastic is obviously reduced. Although simple coating treatment achieves a certain degree of inhibition of the fiber micro-plastic, the coating gradually comes off as the number of washes increases.
From the above disclosure, it can be seen that no systematic solution has been developed to achieve a reduction in fiber micro-plastics. The biodegradable polyester fiber is developed, the micro plastic formed in the washing and dropping process is degraded as much as possible, so that the pollution to the environment is reduced, and although the fiber material used in certain specific fields can be biodegraded in specific environments after being discarded, the fiber micro plastic is easy to form due to the generally low mechanical property of the existing biodegradable polyester fiber, and the fiber micro plastic is difficult to be biodegraded in the true sense because the existing biodegradable polyester fiber does not have the condition of biological compost degradation when being discharged into a water system, particularly deep sea; the development of fiber materials or fiber products with high strength and good wear resistance can realize the improvement of the performance essentially.
For a large amount of polyester fibers, it would be of great interest to effectively achieve a reduction in the amount of fiber microplastics formed during the washing process.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a polyester fiber and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of polyester fiber comprises the steps of blending functional master batches and polyester, and then carrying out melt spinning to obtain the polyester fiber;
the preparation process of the functional master batch comprises the following steps: carrying out esterification reaction on dibasic acid, dihydric alcohol and acid anhydride to obtain an esterification product with a hydroxyl end group; the esterification product and the modified component slurry containing the hydroxyl terminated polysiloxane are mixed and then subjected to polycondensation reaction to prepare the functional master batch, in the process, the esterification product and the hydroxyl terminated polysiloxane are subjected to ester exchange reaction, and micromolecular dihydric alcohol (namely the esterified product terminated dihydric alcohol) is removed in a vacuum environment, so that the hydroxyl terminated polysiloxane is connected into a molecular chain of polyester.
As a preferred technical scheme:
according to the preparation method of the polyester fiber, the modification component slurry containing the hydroxyl-terminated polysiloxane also contains an inorganic nano nucleating agent, a heat stabilizer and an antioxidant.
In the preparation method of the polyester fiber, the functional master batch is prepared by the following steps:
(1) performing esterification reaction;
carrying out esterification reaction on dibasic acid, dihydric alcohol, acid anhydride and a catalyst according to a certain molar ratio until a specified water yield is reached to obtain an esterification product;
(2) preparing modified component slurry;
mixing and pulping hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant to obtain modified component slurry; the heat stabilizer and the antioxidant have the functions of preventing side reactions of the polymer in a high-temperature environment, and the esterification reaction has higher temperature and is easier to generate the side reactions of the polymer compared with the polycondensation reaction; the inorganic nano nucleating agent is small-sized inorganic particles, needs to be dispersed, the hydroxyl-terminated polysiloxane modification component is added when the inorganic nano nucleating agent is added after esterification, the hydroxyl-terminated polysiloxane component has certain molecular weight and certain steric hindrance, and can prevent agglomeration among powder bodies, and the powder bodies indirectly play a role in dispersing in the mixing process;
(3) performing polycondensation reaction;
and mixing the esterification product and the modified component slurry according to a certain proportion, and then carrying out polycondensation reaction to obtain the functional master batch.
The preparation method of the polyester fiber comprises the following steps of (1), wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.1-2.0; the molar ratio of the acid anhydride to the dihydric alcohol is 0.05-0.2: 1 (the amount of the acid anhydride is strictly controlled within a certain range, in order to ensure that the acid anhydride is fully reacted and connected into a polyester main chain, the molar ratio of the acid anhydride to the dihydric alcohol is required to be controlled within a certain range to realize the full reaction of the acid anhydride, meanwhile, the amount of the acid anhydride cannot be too small, otherwise, the function improvement of the prepared functional master batch is limited, and the use requirement cannot be met, and the molar ratio of the acid anhydride to the dihydric alcohol is controlled to be 0.05-0.2: 1 based on the principle); the addition amount of the catalyst is 20-200 ppm of the mass of the dibasic acid;
the dibasic acid is more than one of terephthalic acid, isophthalic acid, succinic acid, adipic acid, suberic acid and sebacic acid; the dihydric alcohol is more than one of ethylene glycol, propylene glycol, butanediol and pentanediol; the acid anhydride is more than one of pyromellitic anhydride, cyclopentane tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, trimellitic anhydride and trimellitic dianhydride; the catalyst is more than one of ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, ethylene glycol titanium and tetraisopropyl titanate;
the temperature of the esterification reaction is 180-260 ℃, the pressure is 0.01-0.5 MPa, and the specified water yield is 90-98% of the theoretical water yield (namely, when the water yield of the esterification reaction reaches 90-98% of the theoretical water yield, the reaction is finished); the temperature of the esterification reaction is controlled to be 180-260 ℃, and is relatively low; the reaction activity of the introduced anhydride is high, and the anhydride is combined with water in the esterification reaction process to quickly form a multi-carboxyl functional group, and then the multi-carboxyl functional group and hydroxyl are subjected to esterification reaction; however, the temperature cannot be set very low, since the basic requirements of the reaction must be met; therefore, the reaction is controlled to be more than 180 ℃, although the increase of the reaction temperature can accelerate the esterification reaction, but the reaction is also accompanied with the generation of series side reactions, in the invention, when the esterification reaction is increased to be more than 260 ℃, the side reaction of self-polycondensation forming ether between the dihydric alcohol is increased, and the esterification mainly takes the side reaction; the water yield reflects the degree of esterification reaction, and the esterification rate is improved extremely limitedly by continuously prolonging the reaction time after the esterification reaction reaches a certain degree, and meanwhile, the side reaction becomes more and more dominant; thus, the esterification, i.e.the water output, is stopped after a certain degree of progress.
According to the preparation method of the polyester fiber, in the step (2), the addition amount of the inorganic nano nucleating agent is 0.1-2.0 wt% of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the heat stabilizer is 50-500 ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 50-500 ppm of the mass of the hydroxyl-terminated polysiloxane;
the number average molecular weight of the hydroxyl-terminated polysiloxane is 1000-8000 g/mol; the inorganic nano nucleating agent is barium sulfate powder, and the average particle size is 20-100 nm; the heat stabilizer is more than one of trimethyl phosphate, alkyl phosphodiester and tri (nonylphenyl) phosphite ester; the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616;
the stirring speed of mixing and pulping is 200-1000 r/min, and the temperature is 60-120 ℃.
According to the preparation method of the polyester fiber, in the step (3), the mass ratio of the esterification product to the modified component slurry is 8: 2-4: 6; the invention adopts esterification product and modified component slurry to react to prepare functional master batch; the content of the functional components in the master batch is relatively high, and if the content is too low, the effect of the master batch cannot be achieved; because the master batch is not directly subjected to spinning forming, the master batch needs to be diluted into a modified object according to a certain proportion, and the common polyester functional master batch is added into polyester according to the content within 10 percent for mixed spinning forming; the ideal master batch is that the higher the content of the functional component is, the better the content is, but the functional component can not be prepared into the master batch alone generally, and a certain polymer carrier is needed, on one hand, the mixing compatibility between the master batch and the polyester melt is improved by the carrier, and on the other hand, the master batch is combined with the carrier to realize certain thermal stability and the like, so that the functional component and the carrier are required to be combined according to a certain proportion; in the invention, esterification products and modified components are mixed and polycondensed according to a proportion to form functional master batches; the highest mixing proportion of the modified components is 60 percent, and the higher proportion can cause the content of the esterified product components in the functional master batch to be too small, the crystallization capacity of the prepared functional master batch is greatly reduced, the blending compatibility of the functional master batch and polyester is obviously reduced because the esterified product components in the functional master batch are too low, the phase separation is intensified and is not the microphase separation provided by the invention, and the spinning difficulty can be caused;
the polycondensation reaction is divided into two stages of pre-polycondensation reaction and final polycondensation reaction; the temperature of the pre-polycondensation reaction is 220-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, and the stirring speed is 5-15 rpm; the temperature of the final polycondensation reaction is 240-280 ℃, the pressure is 20-200 Pa, and the time is 1.0-5.0 h; the polycondensation reaction is a process for increasing the molecular weight, and certain reaction temperature, catalyst and reaction time are required for the polycondensation reaction; the polycondensation reaction temperature is above the melting point of the esterification product, so the temperature is higher than a certain temperature, the reaction activity is higher because the anhydride component is introduced, so the polycondensation temperature is slightly lower than that of the prior art, but the temperature is higher than 220 ℃, but the polycondensation reaction is always in an increased state when the polycondensation temperature is not higher, the polycondensation reaction is controlled within a certain range, otherwise the polyester is thermally decomposed; in the invention, the vacuum degree in the precondensation stage is less than that in the final polycondensation stage, and the residual oxygen content in the precondensation process is higher than that in the final polycondensation, so the temperature control is lower than that in the final polycondensation.
The preparation method of the polyester fiber comprises the steps that the number average molecular weight (obtained by GPC test) of the functional master batch is 10000-40000 g/mol, the molecular weight distribution index (obtained by GPC test) is 2.0-4.0, and the dynamic viscosity (10-20 ℃ above the melting point of a tested polymer and the shear rate is 50s-1Measured under the conditions) is 50-100 Pa.s, the cooling crystallization temperature (measured by DSC (differential scanning calorimetry) is 100-200 ℃, and the semi-crystallization time t is1/2The crystal quality is characterized in that the crystal quality is 2-8 min (obtained by DSC (differential scanning calorimetry)) and 20-40J/g (obtained by DSC (differential scanning calorimetry)) and the crystallinity is 20-40% (obtained by DSC (differential scanning calorimetry)).
According to the preparation method of the polyester fiber, the content of the functional master batch in the blend is 2.0-10.0 wt% (namely the mass addition amount of the functional master batch is 2.0-10.0 wt% of the sum of the mass addition amounts of the functional master batch and the polyester); the products obtained by melt spinning can be POY (polyester pre-oriented yarn), FDY (fully drawn yarn), short fibers, non-woven fabrics and the like; compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 10-30%, the spinning temperature is reduced by 5-20 ℃, the melt spinning speed is improved by 10-30%, the fiber elongation at break is improved by 20-40%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added;
viscous flow activation energy is a physical quantity describing the viscosity-temperature dependence of a material, and is defined as the minimum energy required by a flow unit (i.e. a chain segment in the case of a high molecular material) to overcome a potential barrier and transition from an original position to a nearby "hole" during a flow process; viscous flow activation energy (E η) is a measure of the degree to which a polymer fluid is sensitive to temperature; the more flexible the polymer molecular chain, the lower E eta; when the molecular chain contains benzene rings, polar groups or larger side groups, the flexibility of the molecular chain is greatly reduced, and the E eta of the polymer is increased; the greater E eta, the greater the sensitivity of the viscosity of the polymer fluid to temperature, and the poorer the spinnability; in a smaller temperature range, the viscosity of the polymer fluid is related to temperature by the Arrheniuus equation, i.e., η = Aexp (E η/RT); wherein A is a constant; e eta is viscous flow activation energy, kJ/mol; eta is apparent viscosity, Pa · s; t is absolute temperature, K; r is a gas constant of 8.314J/(mol.K); drawing Ln eta and 1/T under different shear rates, and obtaining LnA (intercept of a straight line) and E eta/R (slope of the straight line) after linear fitting, thereby solving the viscous flow activation energy of the melt under different shear rates;
the spinning in the invention is melt spinning, which is realized by completely melting the polymer in a hot processing mode and then realizing the flow through a certain pressure, and the fluidity of the melt is influenced by the molecular structure of the melt and the external factors such as the melting temperature and the like play an important role; the flow of the melt is realized in a certain range, the resistance in the melt flow is increased when the temperature is lower, the fluidity is poor, and the quality of the melt is reduced (the molecular weight of the melt is reduced and the color is poor along with the prolonging of the time) when the melt stays in a pipeline for a long time; therefore, the melt must be controlled to spin above the minimum temperature; the spinning temperature is reduced by 5-20 ℃, which is a reduction value relative to the lowest spinning temperature of a reference sample (namely, the lower limit of the spinning temperature applicable to the reference sample under the condition of ensuring spinnability); similarly, the melt spinning speed is 10-30% higher than the highest spinning speed of the reference sample (i.e. the upper limit of the spinning speed suitable for the reference sample under the condition of ensuring spinnability).
The invention also provides the polyester fiber prepared by the preparation method, which has a skin-core structure, wherein the skin layer is the functional master batch, and the core layer is the polyester; the functional master batch has excellent flow characteristic and obvious shear thinning, and the fiber prepared by melt spinning after being blended with polyester forms a micro-phase structure, wherein the functional master batch is distributed on the skin layer of the fiber, and the polyester is distributed on the core layer of the fiber, so that the finally obtained fiber has a skin-core structure.
As a preferred technical scheme:
the polyester fiber has the skin layer with the thickness of 0.5-2 μm and the core layer with the diameter of 10-20 μm; the oilless intrinsic viscosity of the polyester fiber is reduced by less than or equal to 0.01 dL/g; the static friction coefficient of the polyester fiber is less than or equal to 0.20, and the dynamic friction coefficient is less than or equal to 0.40; compared with a comparison sample, the quantity of the micro-plastic formed in the washing process of the polyester fiber is reduced by more than 80 percent, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added;
the 'no-oil-silk intrinsic viscosity reduction' refers to the fiber intrinsic viscosity at the stage of testing the no-oil-silk, and the method adopts an Ubbelohde viscometer to test;
the procedure for testing the amount of micro-plastic formed during the washing process was as follows:
(1) the fiber is sampled into the same fabric, the specifications of the fabric are consistent, the component information of the fabric is determined according to the infrared spectrum, and the structure of the fabric and the like are observed through SEM; the washing sample can be a whole piece of clothes or square cloth cut into 20cm x 20cm (the edge is sewn by using 0.5cm cotton threads);
(2) putting 1-3 kg of fabric into a Heier washing machine (model: G70758BX 12S), pouring 10-30G of laundry detergent and 0-20 ml of softener, wherein the washing procedure is mixed washing, the temperature of washing water is 30-60 ℃, the spin-drying speed is 600-1200 rpm, the rinsing frequency is 2 times, the water level is low, the washing time is 50-80 min, a 40L water storage barrel is arranged at a water outlet of the washing machine, and washing wastewater is collected;
(3) selecting a filter screen with the particle size of 25-50 mu m and the particle size of 300-500 mu m to carry out graded filtration on the washing wastewater; measuring the volume V0 (liter) of all collected water, uniformly stirring, taking 1 liter of water out of the water, and filtering; the filter screen is placed in a constant temperature and humidity box with the temperature of 25 ℃ and the RH of 65 percent until the weight is constant, the weight is recorded as m0, the filter screen is placed in a constant temperature and humidity box with the temperature of 25 ℃ and the RH of 65 percent until the weight is constant, the weight is recorded as m1 after the filtration, the mass m = (m 1-m 0) of the released micro plastic is V0, and the length and the diameter of the collected micro plastic are observed.
The principle of the invention is as follows:
the functional master batch is added in the polyester melt spinning process, the functional master batch is prepared by mixing an esterification product with a hydroxyl end group and modified component slurry containing hydroxyl end-capped polysiloxane and then carrying out polycondensation reaction, and the esterification product with the hydroxyl end group is generated by esterification reaction of dibasic acid, dihydric alcohol and acid anhydride;
the acid anhydride with a branched structure is added in the process of preparing the functional master batch, so that the acid anhydride component with a branched structure is introduced into a polyester molecular chain, the functional master batch has good fluidity, the functional master batch plays a role of plasticizing and promoting flow in melt blending with the polyester, the viscous flow activation energy of the polyester melt is obviously reduced, the polyester melt can realize the flow of the melt at a lower temperature, the temperature required by spinning forming is further reduced, the viscosity drop of the polyester melt is reduced, the plastic tensile property of the melt is improved, and the mechanical property of the fiber is improved. The fiber and the product thereof are formed into the micro plastic in the washing process because the fiber is broken and falls off, the strength of the fiber is improved through the melt quality, the breakage probability of the fiber with higher strength is reduced under the same washing condition, and the amount of the formed micro plastic is reduced.
Polysiloxane is added in the process of preparing the functional master batch, on one hand, the flow property of the polysiloxane is excellent, the melt spinning forming temperature of polyester is reduced after the polysiloxane is connected to a polyester molecular chain, the viscosity drop of polyester melt is reduced, the plastic tensile property of the melt is improved, the mechanical property of the fiber is improved, the breakage probability of the fiber with higher strength is reduced under the same washing condition, and the amount of formed micro-plastic is reduced; on the other hand, the polysiloxane has low surface energy and good lubricity, reduces the frictional resistance of the polyester fiber, improves the wear-resisting property of the polyester fiber, and the introduced polysiloxane reduces the friction coefficient of the fiber, which means that the fiber and the fiber, the fiber and a washing machine and the like are reduced in the damage probability of the fiber, and meanwhile, the polysiloxane component mainly on the surface of the fiber has good wear resistance and is less prone to being worn and broken under the same mechanical acting force; meanwhile, the polysiloxane also has a certain hydrophobic effect, so that the contact between the polyester fiber and water in the washing process is reduced, the hydrophobic effect slows down the combination of water molecules and ester bonds in the fiber, and the hydrolysis of the ester bonds is greatly reduced, so that the strength of the fiber is maintained, and the amount of micro-plastics formed in the washing process can be reduced.
Has the advantages that:
(1) the preparation method of the polyester fiber is simple, and the amount of the micro plastic formed in the washing process of the polyester fiber is obviously reduced;
(2) according to the preparation method of the polyester fiber, the added functional master batch can migrate to the outer layer of the melt under the shearing action force in the polyester blending extrusion process, and the functional components are distributed to the surface layer of the fiber, so that the maximum modification effect of the functional components is achieved, and meanwhile, the polysiloxane component in the functional master batch is connected to the polyester molecular chain due to the ester bond effect, so that the polyester fiber has certain similar compatibility with polyester;
(3) according to the polyester fiber, the functional master batch of the skin layer has good crystallization performance and does not have crystallization performance due to the introduction of a high proportion of copolymerization components (in the preparation of the functional master batch, hydroxyl-terminated polysiloxane, an inorganic nano nucleating agent, a heat stabilizer and an antioxidant are mixed and pulped to obtain modified component slurry, and then the modified component slurry and an esterified substance are subjected to polycondensation to prepare the modified component, wherein the modified component contains a certain proportion of the inorganic nano nucleating agent, does not participate in a reaction, but plays a role in promoting crystallization in the functional master batch to improve the crystallization capacity of the functional master batch), so that the actual application value is ensured, the use of the functional master batch can realize the adjustment of the fiber performance by regulating the addition amount, and the polyester fiber has the characteristics of simplicity and flexibility and is beneficial to popularization and application.
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 polyester fiber comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: terephthalic acid;
a dihydric alcohol: ethylene glycol;
acid anhydride: pyromellitic anhydride;
catalyst: ethylene glycol antimony;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 1000 g/mol;
inorganic nano nucleating agent: barium sulfate powder with average particle size of 20 nm;
thermal stabilizer: trimethyl phosphate;
antioxidant: an antioxidant 1010;
(2) performing esterification reaction;
mixing dibasic acid, dihydric alcohol, acid anhydride and a catalyst, and then carrying out esterification reaction at the temperature of 180 ℃ and the pressure of 0.5MPa until the water yield reaches 92% of the theoretical water yield to obtain an esterification product; wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.1; the molar ratio of anhydride to glycol is 0.05: 1; the addition amount of the catalyst is 20ppm of the mass of the dibasic acid;
(3) preparing modified component slurry;
hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant are mixed and pulped at the stirring speed of 1000r/min at the temperature of 60 ℃ to obtain modified component slurry; wherein the addition amount of the inorganic nano nucleating agent is 0.1wt% of the mass of the hydroxyl-terminated polysiloxane; the adding amount of the heat stabilizer is 50ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 50ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product and the modified component slurry according to a mass ratio of 8:2, performing a pre-polycondensation reaction for 2.5 hours under the conditions of a temperature of 220 ℃, a pressure of 1KPa and a stirring speed of 15rpm, and performing a final polycondensation reaction for 5 hours under the conditions of a temperature of 240 ℃ and a pressure of 200Pa to obtain a functional master batch;
the obtained functional master batch has number average molecular weight of 40000g/mol, molecular weight distribution index of 2, dynamic viscosity of 100 Pa.s, cooling crystallization temperature of 120 deg.C, and semi-crystallization time t1/27min, 22J/g of crystallization enthalpy and 24% of crystallinity;
(5) preparing polyester fibers;
blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%;
compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 10%, the spinning temperature is reduced by 6 ℃, the melt spinning speed is improved by 12%, the elongation at break of the fiber is improved by 24%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the thickness of the skin layer is 0.8 μm, and the diameter of the core layer is 18 μm; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.002dL/g, the static friction coefficient is 0.19, and the dynamic friction coefficient is 0.35; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 81% relative to the control.
Comparative example 1
A polyester fiber was produced substantially as in example 1 except that acid anhydride (pyromellitic anhydride) was not added in the esterification reaction in the step (2).
The obtained functional master batch has number average molecular weight of 20000g/mol, molecular weight distribution index of 1.5, dynamic viscosity of 1000 Pa.s, cooling crystallization temperature of 180 deg.C, and semi-crystallization time t1/23min, crystallization enthalpy 30J/g, crystallinity 32%.
Compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 5%, the spinning temperature is reduced by 2 ℃, the melt spinning speed is improved by 2%, the elongation at break of the fiber is improved by 5%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.005dL/g, the static friction coefficient is 0.25, and the dynamic friction coefficient is 0.45; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 30% relative to the control.
Comparing the example 1 with the comparative example 1, it can be seen that the introduction of the acid anhydride component with a branched structure into the polyester molecular chain can make the functional master batch have good fluidity, the functional master batch plays a role in plasticizing and promoting flow in melt blending with the polyester, the viscous flow activation energy of the polyester melt is obviously reduced, the polyester melt can realize the flow of the melt at a lower temperature, the temperature required by spinning forming is further reduced, the viscosity drop of the polyester melt is reduced, meanwhile, the plastic tensile property of the melt is improved, and the mechanical property of the fiber is improved.
Comparative example 2
A polyester fiber was produced substantially as in example 1 except that the hydroxyl-terminated polysiloxane in step (3) was replaced with a diol (ethylene glycol).
The obtained functional master batch has number average molecular weight of 35000g/mol, molecular weight distribution index of 1.8, dynamic viscosity of 500 Pa.s, cooling crystallization temperature of 100 deg.C, and semicrystallization time t1/210min, crystallization enthalpy 18J/g, crystallinity 20%.
Compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 6%, the spinning temperature is reduced by 3 ℃, the melt spinning speed is improved by 6%, the elongation at break of the fiber is improved by 8%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.008dL/g, the static friction coefficient is 0.30, and the dynamic friction coefficient is 0.50; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 10% relative to the control.
Comparing the example 1 with the comparative example 2, it can be seen that the introduction of the hydroxyl-terminated polysiloxane improves the flow property of the master batch, the melt spinning forming temperature of the polyester is reduced after the hydroxyl-terminated polysiloxane is grafted into a polyester molecular chain, the viscosity drop of the polyester melt is reduced, the plastic tensile property of the melt is improved, the mechanical property of the fiber is improved, the breakage probability of the fiber of the example 1 is reduced under the same washing condition, and the amount of the formed micro-plastic is reduced; on the other hand, the hydroxyl-terminated polysiloxane has low surface energy and good lubricity, reduces the frictional resistance of the polyester fiber, improves the wear resistance of the polyester fiber, and the introduced hydroxyl-terminated polysiloxane reduces the friction coefficient of the fiber, which means that the fiber damage probability is reduced under the conditions of fiber and fiber, fiber and washing machine, and the like, and meanwhile, the hydroxyl-terminated polysiloxane component on the surface of the fiber has good wear resistance and is less prone to being worn and broken under the same mechanical acting force; meanwhile, the hydroxyl-terminated polysiloxane also has a certain hydrophobic effect, so that the contact between polyester fibers and water in the washing process is reduced, the hydrophobic effect slows down the combination of water molecules and ester bonds in the fibers, and the hydrolysis of the ester bonds is greatly reduced, so that the strength of the fibers is maintained, and the amount of micro-plastics formed in the washing process can be reduced.
Example 2
A preparation method of polyester fiber comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: isophthalic acid;
a dihydric alcohol: propylene glycol;
acid anhydride: cyclopentane tetracarboxylic dianhydride;
catalyst: antimony trioxide;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 2000 g/mol;
inorganic nano nucleating agent: barium sulfate powder with average particle size of 40 nm;
thermal stabilizer: an alkyl phosphodiester;
antioxidant: an antioxidant 168;
(2) performing esterification reaction;
mixing dibasic acid, dihydric alcohol, acid anhydride and a catalyst, and then carrying out esterification reaction at the temperature of 190 ℃ and the pressure of 0.4MPa until the water yield reaches 93 percent of the theoretical water yield to obtain an esterification product; wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.2; the molar ratio of anhydride to glycol is 0.07: 1; the adding amount of the catalyst is 40ppm of the mass of the dibasic acid;
(3) preparing modified component slurry;
hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant are mixed and pulped at the temperature of 70 ℃ and the stirring speed of 900r/min to obtain modified component slurry; wherein the addition amount of the inorganic nano nucleating agent is 0.3wt% of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the heat stabilizer is 100ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 150ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product and the modified component slurry according to the mass ratio of 7:3, then carrying out pre-polycondensation reaction for 2 hours under the conditions of temperature of 225 ℃, pressure of 0.9KPa and stirring speed of 14rpm, and then carrying out final polycondensation reaction for 4.5 hours under the conditions of temperature of 250 ℃ and pressure of 170Pa to obtain functional master batches;
the obtained functional master batch has number average molecular weight of 35000g/mol, molecular weight distribution index of 3.2, dynamic viscosity of 75 Pa.s, cooling crystallization temperature of 140 deg.C, and semicrystallization time t1/26.5min, the crystallization enthalpy is 26J/g, and the crystallinity is 28%;
(5) preparing polyester fibers;
blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%;
compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 12%, the spinning temperature is reduced by 8 ℃, the melt spinning speed is improved by 13%, the elongation at break of the fiber is improved by 25%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the thickness of the skin layer is 0.9 μm, and the diameter of the core layer is 16 μm; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.004dL/g, the static friction coefficient is 0.18, and the dynamic friction coefficient is 0.36; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 82% relative to the control.
Example 3
A preparation method of polyester fiber comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: succinic acid;
a dihydric alcohol: butanediol;
acid anhydride: benzophenone tetracarboxylic dianhydride;
catalyst: antimony acetate;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 3000 g/mol;
inorganic nano nucleating agent: barium sulfate powder with average particle size of 50 nm;
thermal stabilizer: tris (nonylphenyl) phosphite;
antioxidant: an antioxidant 616;
(2) performing esterification reaction;
mixing dibasic acid, dihydric alcohol, acid anhydride and a catalyst, and then carrying out esterification reaction at the temperature of 200 ℃ and the pressure of 0.3MPa until the water yield reaches 95 percent of the theoretical water yield to obtain an esterification product; wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.3; the molar ratio of anhydride to glycol is 0.09: 1; the addition amount of the catalyst is 70ppm of the mass of the dibasic acid;
(3) preparing modified component slurry;
hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant are mixed and pulped at the temperature of 80 ℃ and the stirring speed of 800r/min to obtain modified component slurry; wherein the addition amount of the inorganic nano nucleating agent is 0.6wt% of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the heat stabilizer is 200ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 250ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product and the modified component slurry according to a mass ratio of 4:6, then carrying out a pre-polycondensation reaction for 1.6h under the conditions of a temperature of 230 ℃, a pressure of 0.8KPa and a stirring speed of 13rpm, and then carrying out a final polycondensation reaction for 4h under the conditions of a temperature of 260 ℃ and a pressure of 140Pa to obtain a functional master batch;
the obtained functional master batch has number average molecular weight of 30000g/mol, molecular weight distribution index of 3.5, dynamic viscosity of 50 Pa.s, cooling crystallization temperature of 160 deg.C, and semicrystallization time t1/26min, crystallization enthalpy of 28J/g and crystallinity of 30 percent;
(5) preparing polyester fibers;
blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%;
compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 14%, the spinning temperature is reduced by 7 ℃, the melt spinning speed is improved by 15%, the fiber elongation at break is improved by 26%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the thickness of the skin layer is 1.2 μm, and the diameter of the core layer is 14 μm; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.006dL/g, the static friction coefficient is 0.15, and the dynamic friction coefficient is 0.38; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 85% relative to the control.
Example 4
A preparation method of polyester fiber comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: adipic acid;
a dihydric alcohol: pentanediol;
acid anhydride: a mixture of trimellitic anhydride and trimellitic dianhydride in a mass ratio of 1: 1;
catalyst: tetrabutyl titanate;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 4000 g/mol;
inorganic nano nucleating agent: barium sulfate powder with average particle size of 70 nm;
thermal stabilizer: an alkyl phosphodiester;
antioxidant: an antioxidant 1010;
(2) performing esterification reaction;
mixing dibasic acid, dihydric alcohol, acid anhydride and a catalyst, and then carrying out esterification reaction at the temperature of 210 ℃ and the pressure of 0.2MPa until the water yield reaches 94 percent of the theoretical water yield to obtain an esterification product; wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.4; the molar ratio of anhydride to glycol is 0.11: 1; the adding amount of the catalyst is 100ppm of the mass of the dibasic acid;
(3) preparing modified component slurry;
hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant are mixed and pulped at the temperature of 90 ℃ and the stirring speed of 700r/min to obtain modified component slurry; wherein the addition amount of the inorganic nano nucleating agent is 1wt% of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the heat stabilizer is 300ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 300ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product and the modified component slurry according to a mass ratio of 8:2, then carrying out a pre-polycondensation reaction for 1.4h under the conditions of a temperature of 240 ℃, a pressure of 0.7KPa and a stirring speed of 12rpm, and then carrying out a final polycondensation reaction for 3.5h under the conditions of a temperature of 270 ℃ and a pressure of 80Pa to obtain a functional master batch;
the obtained functional master batch has number average molecular weight of 25000g/mol, molecular weight distribution index of 2.5, dynamic viscosity of 70 Pa.s, cooling crystallization temperature of 170 deg.C, and semicrystallization time t1/25min, crystallization enthalpy of 30J/g and crystallinity of 32 percent;
(5) preparing polyester fibers;
blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%;
compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 16%, the spinning temperature is reduced by 10 ℃, the melt spinning speed is improved by 14%, the elongation at break of the fiber is improved by 32%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the thickness of the skin layer is 1.4 μm, and the diameter of the core layer is 17 μm; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.005dL/g, the static friction coefficient is 0.16, and the dynamic friction coefficient is 0.35; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 90% relative to the control.
Example 5
A preparation method of polyester fiber comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: suberic acid;
a dihydric alcohol: ethylene glycol;
acid anhydride: the mixture of the pyromellitic dianhydride and the benzophenone tetracarboxylic dianhydride in the mass ratio of 1: 1;
catalyst: titanium ethylene glycol;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 6000 g/mol;
inorganic nano nucleating agent: barium sulfate powder with average particle size of 85 nm;
thermal stabilizer: tris (nonylphenyl) phosphite;
antioxidant: an antioxidant 168;
(2) performing esterification reaction;
mixing dibasic acid, dihydric alcohol, acid anhydride and a catalyst, and then carrying out esterification reaction at the temperature of 230 ℃ and the pressure of 0.1MPa until the water yield reaches 90 percent of the theoretical water yield to obtain an esterification product; wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.5; the molar ratio of anhydride to glycol is 0.14: 1; the adding amount of the catalyst is 140ppm of the mass of the dibasic acid;
(3) preparing modified component slurry;
hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant are mixed and pulped at the stirring speed of 600r/min at the temperature of 100 ℃ to obtain modified component slurry; wherein the addition amount of the inorganic nano nucleating agent is 1.4wt% of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the heat stabilizer is 400ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 350ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product and the modified component slurry according to the mass ratio of 7:3, then carrying out pre-polycondensation reaction for 1.2h under the conditions of the temperature of 245 ℃, the pressure of 0.6KPa and the stirring speed of 8rpm, and then carrying out final polycondensation reaction for 3h under the conditions of the temperature of 275 ℃ and the pressure of 50Pa to obtain the functional master batch;
the obtained functional master batch has number average molecular weight of 20000g/mol, molecular weight distribution index of 3.6, dynamic viscosity of 70 Pa.s, cooling crystallization temperature of 180 deg.C, and semi-crystallization time t1/24min, crystallization enthalpy of 32J/g and crystallinity of 33 percent;
(5) preparing polyester fibers;
blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%;
compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 20%, the spinning temperature is reduced by 12 ℃, the melt spinning speed is improved by 13%, the elongation at break of the fiber is improved by 30%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the thickness of the skin layer is 1.2 μm, and the diameter of the core layer is 16 μm; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.008dL/g, the static friction coefficient is 0.18, and the dynamic friction coefficient is 0.36; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 92% relative to the control.
Example 6
A preparation method of polyester fiber comprises the following specific steps:
(1) preparing raw materials;
dibasic acid: a mixture of terephthalic acid and sebacic acid in a mass ratio of 1: 1;
a dihydric alcohol: a mixture of ethylene glycol and propylene glycol in a mass ratio of 1: 1;
acid anhydride: a mixture of pyromellitic anhydride and trimellitic anhydride in a mass ratio of 1: 1;
catalyst: a mixture of ethylene glycol antimony and tetraisopropyl titanate in a mass ratio of 1: 1;
a hydroxyl-terminated polysiloxane having a number average molecular weight of 7000 g/mol;
inorganic nano nucleating agent: barium sulfate powder with average particle size of 100 nm;
thermal stabilizer: a mixture of trimethyl phosphate and alkyl diester phosphate in a mass ratio of 1: 1;
antioxidant: a mixture of antioxidant 1010 and antioxidant 168 in a mass ratio of 1: 1;
(2) performing esterification reaction;
mixing dibasic acid, dihydric alcohol, acid anhydride and a catalyst, and then carrying out esterification reaction at the temperature of 250 ℃ and the pressure of 0.05MPa until the water yield reaches 98 percent of the theoretical water yield to obtain an esterification product; wherein the molar ratio of the dibasic acid to the dihydric alcohol is 1: 1.8; the molar ratio of anhydride to glycol is 0.17: 1; the addition amount of the catalyst is 180ppm of the mass of the dibasic acid;
(3) preparing modified component slurry;
hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant are mixed and pulped at the temperature of 110 ℃ and the stirring speed of 400r/min to obtain modified component slurry; wherein the addition amount of the inorganic nano nucleating agent is 2wt% of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the heat stabilizer is 500ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 500ppm of the mass of the hydroxyl-terminated polysiloxane;
(4) performing polycondensation reaction;
mixing the esterification product and the modified component slurry according to a mass ratio of 4:6, then carrying out a pre-polycondensation reaction for 0.8h under the conditions of a temperature of 260 ℃, a pressure of 0.55KPa and a stirring speed of 6rpm, and then carrying out a final polycondensation reaction for 2h under the conditions of a temperature of 265 ℃ and a pressure of 120Pa to obtain a functional master batch;
the obtained functional master batch has number average molecular weight of 10000g/mol, molecular weight distribution index of 3.8, dynamic viscosity of 55 pas, cooling crystallization temperature of 200 deg.C, and semicrystallization time t1/23min, the crystallization enthalpy is 35J/g, and the crystallinity is 30 percent;
(5) preparing polyester fibers;
blending the functional master batch and polyester, and then carrying out melt spinning to obtain polyester fiber; wherein the content of the functional master batch in the blend is 6 wt%;
compared with a comparison sample, the viscous flow activation energy of the polyester fiber is reduced by 22%, the spinning temperature is reduced by 10 ℃, the melt spinning speed is improved by 12%, the fiber elongation at break is improved by 34%, and the preparation process of the comparison sample is basically the same as that of the polyester fiber, except that no functional master batch is added.
The prepared polyester fiber has a skin-core structure, wherein the skin layer is functional master batch, and the core layer is polyester; the thickness of the skin layer is 1.5 μm, and the diameter of the core layer is 14 μm; the oilless intrinsic viscosity of the polyester fiber is reduced to 0.007dL/g, the static friction coefficient is 0.16, and the dynamic friction coefficient is 0.38; the amount of micro-plastic formed during washing of the polyester fiber was reduced by 85% relative to the control.
Claims (10)
1. The preparation method of the polyester fiber is characterized in that the polyester fiber is prepared by blending the functional master batch and the polyester and then carrying out melt spinning;
the preparation process of the functional master batch comprises the following steps: carrying out esterification reaction on dibasic acid, dihydric alcohol and acid anhydride to obtain an esterification product with a hydroxyl end group; and mixing the esterification product with modified component slurry containing hydroxyl terminated polysiloxane, and performing polycondensation reaction to obtain the functional master batch.
2. The method for preparing polyester fiber according to claim 1, wherein the slurry of the modifying component containing hydroxyl-terminated polysiloxane further contains inorganic nano nucleating agent, heat stabilizer and antioxidant.
3. The preparation method of the polyester fiber according to claim 2, wherein the preparation steps of the functional masterbatch are as follows:
(1) performing esterification reaction;
carrying out esterification reaction on dibasic acid, dihydric alcohol, acid anhydride and a catalyst according to a certain molar ratio until a specified water yield is reached to obtain an esterification product;
(2) preparing modified component slurry;
mixing and pulping hydroxyl-terminated polysiloxane, inorganic nano nucleating agent, heat stabilizer and antioxidant to obtain modified component slurry;
(3) performing polycondensation reaction;
and mixing the esterification product and the modified component slurry according to a certain proportion, and then carrying out polycondensation reaction to obtain the functional master batch.
4. The method for preparing polyester fiber according to claim 3, wherein in the step (1), the molar ratio of the dibasic acid to the glycol is 1: 1.1-2.0; the molar ratio of the acid anhydride to the dihydric alcohol is 0.05-0.2: 1; the addition amount of the catalyst is 20-200 ppm of the mass of the dibasic acid;
the dibasic acid is more than one of terephthalic acid, isophthalic acid, succinic acid, adipic acid, suberic acid and sebacic acid; the dihydric alcohol is more than one of ethylene glycol, propylene glycol, butanediol and pentanediol; the acid anhydride is more than one of pyromellitic anhydride, cyclopentane tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, trimellitic anhydride and trimellitic dianhydride; the catalyst is more than one of ethylene glycol antimony, antimony trioxide, antimony acetate, tetrabutyl titanate, ethylene glycol titanium and tetraisopropyl titanate;
the temperature of the esterification reaction is 180-260 ℃, the pressure is 0.01-0.5 MPa, and the specified water yield is 90-98% of the theoretical water yield.
5. The preparation method of the polyester fiber according to claim 3, wherein in the step (2), the addition amount of the inorganic nano nucleating agent is 0.1-2.0 wt% of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the heat stabilizer is 50-500 ppm of the mass of the hydroxyl-terminated polysiloxane; the addition amount of the antioxidant is 50-500 ppm of the mass of the hydroxyl-terminated polysiloxane;
the number average molecular weight of the hydroxyl-terminated polysiloxane is 1000-8000 g/mol; the inorganic nano nucleating agent is barium sulfate powder, and the average particle size is 20-100 nm; the heat stabilizer is more than one of trimethyl phosphate, alkyl phosphodiester and tri (nonylphenyl) phosphite ester; the antioxidant is more than one of antioxidant 1010, antioxidant 168 and antioxidant 616;
the stirring speed of mixing and pulping is 200-1000 r/min, and the temperature is 60-120 ℃.
6. The preparation method of the polyester fiber according to claim 3, wherein in the step (3), the mass ratio of the esterification product to the modified component slurry is 8: 2-4: 6;
the polycondensation reaction is divided into two stages of pre-polycondensation reaction and final polycondensation reaction; the temperature of the pre-polycondensation reaction is 220-270 ℃, the pressure is 0.5-1.0 KPa, the time is 0.5-2.5 h, and the stirring speed is 5-15 rpm; the temperature of the final polycondensation reaction is 240-280 ℃, the pressure is 20-200 Pa, and the time is 1.0-5.0 h.
7. The method for preparing polyester fiber according to claim 3, wherein the functional masterbatch has a number average molecular weight of 10000-40000 g/mol, a molecular weight distribution index of 2.0-4.0, a kinematic viscosity of 50-100 Pa.s, a cooling crystallization temperature of 100-200 ℃, and a semi-crystallization time t1/22-8 min, 20-40J/g of crystallization enthalpy and 20-40% of crystallinity.
8. The preparation method of the polyester fiber according to claim 1, wherein the content of the functional masterbatch in the blend is 2.0-10.0 wt%.
9. The polyester fiber prepared by the preparation method according to any one of claims 1 to 8, wherein the polyester fiber has a sheath-core structure, the sheath layer is the functional master batch, and the core layer is the polyester.
10. The polyester fiber according to claim 9, wherein the skin layer has a thickness of 0.5 to 2 μm, and the core layer has a diameter of 10 to 20 μm; the oilless intrinsic viscosity of the polyester fiber is reduced by less than or equal to 0.01 dL/g; the static friction coefficient of the polyester fiber is less than or equal to 0.20, and the dynamic friction coefficient is less than or equal to 0.40.
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| CN113683762A (en) * | 2021-10-25 | 2021-11-23 | 苏州宝丽迪材料科技股份有限公司 | Functional master batch and preparation method and application thereof |
| CN114213815A (en) * | 2021-12-22 | 2022-03-22 | 上海翌璠工贸发展有限责任公司 | Functional master batch for reducing polyester melt spinning temperature and production method thereof |
| CN114351278A (en) * | 2021-12-22 | 2022-04-15 | 上海翌璠工贸发展有限责任公司 | Method for reducing polyester melt spinning temperature |
| CN115852519A (en) * | 2023-02-07 | 2023-03-28 | 江苏恒力化纤股份有限公司 | Preparation method of polyester fiber not prone to producing micro-plastics in use process |
| CN118065007A (en) * | 2024-04-18 | 2024-05-24 | 江苏恒力化纤股份有限公司 | Preparation method of high-flexibility wear-resistant polyester monofilament |
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| CN113683762A (en) * | 2021-10-25 | 2021-11-23 | 苏州宝丽迪材料科技股份有限公司 | Functional master batch and preparation method and application thereof |
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| CN114351278B (en) * | 2021-12-22 | 2024-03-15 | 上海依璠新材料有限公司 | Method for reducing polyester melt spinning temperature |
| CN115852519A (en) * | 2023-02-07 | 2023-03-28 | 江苏恒力化纤股份有限公司 | Preparation method of polyester fiber not prone to producing micro-plastics in use process |
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