CN109763224B - Full-dull polyester-polyester composite yarn and preparation method thereof - Google Patents
Full-dull polyester-polyester composite yarn and preparation method thereof Download PDFInfo
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- CN109763224B CN109763224B CN201811613962.9A CN201811613962A CN109763224B CN 109763224 B CN109763224 B CN 109763224B CN 201811613962 A CN201811613962 A CN 201811613962A CN 109763224 B CN109763224 B CN 109763224B
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Abstract
The invention relates to a full-dull polyester composite filament and a preparation method thereof, which comprises the steps of carrying out esterification reaction and polycondensation reaction on raw materials mainly comprising terephthalic acid, ethylene glycol, dihydric alcohol with a silicon-containing main chain and solid base catalyst powder roasted at high temperature to respectively prepare full-dull modified polyester and super bright modified polyester, wherein the full-dull modified polyester is also dispersed with a flatting agent, the content of the flatting agent is more than or equal to 2.0 wt%, then preparing two POY filaments from the full-dull modified polyester and the super bright modified polyester respectively according to a POY process, doubling the two POY filaments, and then processing the two POY filaments according to a DTY process to prepare the full-dull polyester composite filament. The intrinsic viscosity of the prepared product is reduced by 13-18% after the product is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65%. The preparation method of the invention has simple process and low cost; the prepared product has high natural degradation rate and good application prospect.
Description
Technical Field
The invention belongs to the technical field of modified polyester fibers, and relates to a full-dull polyester composite yarn and a preparation method thereof.
Background
With the large-scale expansion of polyester productivity at home and abroad, the market competition of the polyester filament yarn is increasingly violent, the profit margin of products is smaller and smaller, and the production enterprises can only develop and produce products with high technical content and high added value through the great breakthrough innovation of production technology to improve the benefit and ensure the competitiveness of the enterprises in the market.
Because the conventional terylene has regular shape, smooth surface and certain transparency, the intensity of reflected light is very high under the irradiation of light, and the terylene has obvious reflection and scintillation phenomena, and the visual comfort of the fiber is not high. A small amount of substances with different refractive indexes are added into the fiber, so that light rays are subjected to diffuse reflection in different directions, the glossiness of the fiber is reduced, the visual comfort degree of the fiber is improved, and the extinction treatment of the fiber product is realized. The polyester fiber extinction products in the prior stage mainly comprise three major categories of bright, semi-extinction and full-extinction. The price difference of polyester fibers with different extinction grades is large, and the full-extinction product has certain ultraviolet resistance besides good light-shielding performance, and the price of the full-extinction product is far higher than that of other products.
Titanium dioxide is commonly called titanium white, has the advantages of low price, no toxicity, small particle size, large specific surface area, strong magnetism, high catalytic activity, good absorption performance, strong ultraviolet ray absorption capacity, large surface activity, good thermal conductivity, good dispersibility, good stability and the like, and is widely applied to manufacturing industrial products such as high-grade coatings, cosmetics, paints, foods, textiles and the like. The polyester extinction additive is applied to textiles, has the advantages of antistatic property, ultraviolet resistance, antibacterial property, extinction, infrared absorption, ageing resistance, self-cleaning property and the like, has high refractive index, can realize extinction by being added into polyester and utilizing the refractive index difference between the polyester and the polyester, and is an ideal polyester extinction additive. In addition, the ultraviolet light absorber is an ultraviolet light absorber and has certain ultraviolet resistance.
However, with the rapid development of the PET industry, although PET does not directly cause harm to the environment, the waste products after the PET is used are huge in number and have strong resistance to atmosphere and microbial reagents, so that the waste polyester fibers are not easy to treat, and indirectly cause harm to the environment. The prior treatment method of the polyester fiber waste mainly comprises the following steps: burying, burning and recycling. From the environmental point of view, landfill and incineration, although the simplest methods, have many drawbacks and cause some environmental pollution. The chemical degradation recovery is an effective and scientific way for treating the PET wastes, the main methods comprise alcoholysis, ammonolysis and the like, and products of chemical degradation such as alcohol, acid, ester and the like can also be reused as chemical raw materials. However, because the PET has a compact structure and high crystallinity, the natural degradation time is very long (the degradation period of the conventional polyester fiber can reach 16-48 years), which greatly limits the application of chemical degradation recovery in the field of PET waste treatment.
Therefore, the development of the full-dull polyester fiber with high natural degradation rate has practical significance.
Disclosure of Invention
The invention aims to overcome the defect of slow natural degradation rate in the prior art and provides a full-dull polyester fiber with high natural degradation rate and a preparation method thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the preparation method of full dull polyester composite filament, according to POY craft make two kinds of POY filament from full dull modified polyester and bright modified polyester separately, and then process the full dull polyester composite filament according to DTY craft after the two kinds of POY filaments are doubled;
the preparation method of the modified polyester comprises the following steps: carrying out esterification reaction and polycondensation reaction on raw materials mainly comprising terephthalic acid, ethylene glycol, dihydric alcohol with a silicon-containing main chain and solid base catalyst powder subjected to high-temperature roasting in sequence;
the dihydric alcohol with the silicon-containing main chain is dimethyl silicon glycol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane glycol;
the high-temperature roasting temperature is 400-700 ℃, and the solid base catalyst is MgO, BaO and SiO2More than one of-BaO, high-temperature roasting can remove volatile components and keep certain chemical composition, in addition, a certain crystal form, grain size, pore structure and specific surface can be obtained due to solid-state reaction in the high-temperature roasting process, the high-temperature roasting temperature can be adjusted within a proper range, but the high temperature is not easy to be too high or too low, effective substances are easy to volatilize, the low temperature is easy to cause crystal form transformation to be not capable of meeting the requirements, and simultaneously the volatile components are difficult to remove;
the full-dull modified polyester is also dispersed with a dulling agent, and the content of the dulling agent is more than or equal to 2.0 wt%.
According to the invention, terephthalic acid, ethylene glycol, the dihydric alcohol with the silicon-containing main chain and the solid base catalyst powder calcined at high temperature are uniformly mixed and then subjected to esterification reaction and polycondensation reaction in sequence, so that the dihydric alcohol chain segment with the silicon-containing main chain is introduced into the modified polyester, and the cavity free volume of the polyester is obviously improved. Because the free volume of the cavity formed by the macromolecular chain containing the silicon-oxygen bond is higher in efficiency than the free volume formed by the macromolecular chain only containing the carbon-oxygen bond, water and oxygen molecules can be more easily permeated into the modified polyester macromolecules, and the natural degradation rate is improved to a certain extent.
In addition, the solid base catalyst is introduced into the polyester, so that the attack capability of the nucleophilic reagent is enhanced, and the degradation rate of the polyester is improved. The solid alkali selected by the invention is MgO, BaO or SiO roasted at high temperature2BaO, MgO or BaO is mainly alkalescent hydroxyl at low temperature, but after high-temperature roasting, lattice defects such as points, lines, surfaces and the like can be generated on the surface, oxygen on the crystal surface can be enriched at the tip, when the solid base catalyst is charged, the charge is distributed on the surface, the charge density at the tip is the largest, so that the MgO or BaO surface has different strong alkaline sites, and OH is more easily ionized when the solid base catalyst is combined with water-，OH-Relative to H2O has stronger nucleophilic ability, so that the difficulty of nucleophilic addition reaction is reduced after the solid base catalyst is introduced into the polyester, and the degradation rate of the polyester is further improved. Furthermore, SiO2Alkali metal supported on BaO, which also increases the SiO content of the support relative to BaO2SiO as carrier2The framework as the active component plays the roles of dispersing BaO and increasing the strength of BaO, and can also change the crystal structure of BaO, form defects and cavities, increase the specific surface area and the pore diameter of BaO, thereby increasing the alkalinity of BaO and strengthening the reinforcing effect of the attack capability of BaO on nucleophilic reagents.
The diol with silicon-containing main chain and the solid base catalyst introduced into the polyester molecular chain can play a synergistic role, the solid base catalyst enhances the attack capability of a nucleophilic reagent and is beneficial to the proceeding of degradation reaction, and the diol with silicon-containing main chain can increase the cavity free volume of the polyester, thereby being beneficial to the permeation of oxygen and water, being convenient for increasing nucleophilic ions and further promoting the proceeding of nucleophilic addition reaction, thereby further improving the degradation rate.
As a preferable scheme:
the preparation method of the full-dull polyester-polyester composite filament, SiO2The content of BaO in the-BaO is 40-80 wt%; the high-temperature roasting process comprises the following steps: firstly, heating to 400 ℃, then preserving heat for 2-3 h, then heating to 700 ℃, preserving heat for 1-2 h, and finally cooling in the air; the solid alkali catalyst is roasted at high temperature and then crushed to obtain powder with the average grain diameter of less than 0.5 micron.
The preparation method of the full-dull polyester-polyester composite yarn is basically the same as the preparation methods of the full-dull modified polyester and the large light-modified polyester, and is different in that the addition amount of the flatting agent is 2.0-3.0 wt% and 0 wt% of the addition amount of the terephthalic acid when the full-dull modified polyester and the large light-modified polyester are prepared.
The preparation method of the full-dull polyester-polyester composite yarn comprises the following steps of:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and dihydric alcohol with a silicon-containing main chain into slurry, adding solid base catalyst powder subjected to high-temperature roasting, a polyester polymerization catalyst, a flatting agent and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction end point is determined when the water distillate in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
and after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the low vacuum stage from normal pressure to below 500Pa in 30-50 min at the reaction temperature of 250-260 ℃ for 30-50 min, then continuously pumping the vacuum to perform the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to below 100Pa, the reaction temperature is 270-275 ℃, and the reaction time is 50-90 min.
According to the preparation method of the full-dull polyester composite filament, the molar ratio of the terephthalic acid to the glycol with the silicon-containing main chain is 1: 1.2-2.0: 0.03-0.05, and the addition amounts of the solid base catalyst powder subjected to high-temperature roasting, the polyester polymerization catalyst and the stabilizer are respectively 0.03-0.05 wt%, 0.03-0.05 wt% and 0.01-0.05 wt% (mass percentage) of the addition amount of the terephthalic acid. The preferable range of the addition amount of the dihydric alcohol with the silicon-containing main chain can ensure that the modified fiber has good mechanical property and crystallinity, and can also obviously improve the dyeing property of the fiber, thereby being beneficial to the production and application of the fiber. The degradation catalysis of the solid base catalyst on the polyester is a long-term process, the addition amount mainly considers the influence on the technical indexes of the polyester fiber, the retention time of the mechanical property of the fiber, the degradation period and the like, the addition amount of the solid base catalyst can be adjusted according to practical application, but the adjustment range is not too large, the addition amount of the solid base catalyst powder is too large, the performance (mechanical property) of the fiber can be influenced, the application of the fiber is influenced, the addition amount of the solid base catalyst powder is too small, the influence on the degradation property of the fiber is too small, and the natural degradation rate of the fiber is difficult to obviously improve.
According to the preparation method of the full-dull polyester composite filament, the polyester polymerization catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, the flatting agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
The full-dull polyester composite filament has the modified polyester with the number average molecular weight of 25000-30000 and the molecular weight distribution index of 1.8-2.2.
The preparation method of the full-dull polyester-polyester composite yarn comprises the following steps: metering, spinneret plate extrusion, cooling, oiling and winding;
the parameters of the POY process are as follows: the spinning temperature is 280-285 ℃, the cooling temperature is 17-20 ℃, and the winding speed is 3200-3600 m/min;
the DTY process comprises the following steps: guide wire, plying, network, heating and stretching, false twisting, heat setting and winding;
the DTY process has the following parameters: the spinning speed is 500-800 m/min, the setting overfeed rate is 3.5-5.5%, the winding overfeed rate is 3.0-5.5%, the temperature of a first hot box is 180-200 ℃, the temperature of a second hot box is 150-180 ℃, and the draw ratio is 1.6-1.8.
The invention also provides the full-dull polyester composite yarn prepared by the preparation method of the full-dull polyester composite yarn, which is a DTY yarn mainly formed by compounding the yarn A and the yarn B, wherein the yarn A and the yarn B are respectively made of full-dull modified polyester and super bright modified polyester;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a dihydric alcohol chain segment with a silicon-containing main chain;
the solid base catalyst powder roasted at high temperature is dispersed in the full-dull modified polyester and the large-gloss modified polyester, and the flatting agent is also dispersed in the full-dull modified polyester, and the content of the flatting agent is more than or equal to 2.0 wt%.
As a preferable scheme:
the single-filament fineness of the filament A and the filament B of the full-dull polyester-polyester composite filament is 0.7-3.0 dtex, and the fineness ratio of the filament A to the filament B in the full-dull polyester-polyester composite filament is 1-2: 1-2;
the titer of the full-dull polyester composite filament is 100-200 dtex, the crimp shrinkage is 10.0 +/-1.0%, the crimp stability is more than or equal to 72%, the linear density deviation rate is less than or equal to 1.4%, the breaking strength is 3.0 +/-0.35 cN/dtex, the breaking strength CV value is less than or equal to 4.0%, the elongation at break is 30.0 +/-3.0%, the elongation at break CV value is less than or equal to 8.0%, the crimp shrinkage variation coefficient CV value is less than or equal to 9.0%, the boiling water shrinkage is 5.0 +/-0.5%, the oil content is 2-3 wt%, and the glossiness is less than 30%, the addition amount of the dihydric alcohol containing silicon in the main chain and the solid base catalyst is small, the influence on the processing and mechanical properties of the polyester composite filament is small, and the processing performance and the mechanical properties of the full-dull polyester composite filament are equivalent to those of the common polyester composite filament (the dihydric alcohol containing silicon in the main chain is not added and the solid;
the intrinsic viscosity of the full-dull polyester composite filament is reduced by 13-18% after the full-dull polyester composite filament is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65%, the intrinsic viscosity of a skin layer and the intrinsic viscosity of a core layer are only reduced by less than 5% under the same condition of the conventional polyester composite filament (no main chain silicon-containing dihydric alcohol and solid base catalyst are added).
The invention mechanism is as follows:
the hydrolysis reaction of polyester is the reverse reaction of esterification reaction, and the essence is the breaking process of acyl-oxygen bond in ester bond, i.e. nucleophilic addition of nucleophilic reagent on carbonyl group to form tetrahedral intermediate and eliminate negative ion to complete hydrolysis. One important reason for the slow hydrolysis rate of conventional polyesters is that the nucleophile is predominantly H2O，H2The attack ability of O to the C atom of ester carbonyl RCOOR' is weak, nucleophilic addition reaction is not easy to occur, tetrahedral intermediate is difficult to form, and therefore the degradation rate of the polyester is slow.
According to the invention, the solid base catalyst is introduced into the polyester, so that the attack capability of the nucleophilic reagent is enhanced, and the degradation rate of the polyester is improved. The solid alkali selected by the invention is MgO, BaO or SiO roasted at high temperature2BaO, MgO or BaO is mainly alkalescent hydroxyl at low temperature, but after high-temperature roasting, lattice defects such as points, lines, surfaces and the like can be generated on the surface, oxygen on the crystal surface can be enriched at the tip, when the solid base catalyst is charged, the charge is distributed on the surface, the charge density at the tip is the largest, so that the MgO or BaO surface has different strong alkaline sites, and OH is more easily ionized when the solid base catalyst is combined with water-，OH-Relative to H2O has stronger nucleophilic ability, so that the difficulty of nucleophilic addition reaction is reduced after the solid base catalyst is introduced into the polyester, and the degradation rate of the polyester is further improved. Furthermore, SiO2Alkali metal supported on BaO, which also increases the SiO content of the support relative to BaO2SiO as carrier2The framework as the active component plays the roles of dispersing BaO and increasing the strength of BaO, and can also change the crystal structure of BaO, form defects and cavities, increase the specific surface area and the pore diameter of BaO, thereby increasing the alkalinity of BaO and strengthening the reinforcing effect of the attack capability of BaO on nucleophilic reagents.
According to the invention, the hollow free volume of the polyester is increased by adding the dihydric alcohol with a silicon-containing main chain, and the natural degradation rate of the polyester is further improved by matching with the solid base catalyst.
The dihydric alcohol with silicon-containing main chain is dimethyl silicon glycol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane glycol, and the structural formula is respectively as follows:
the rigidity of the high molecular chain is determined by the size of a rotation potential barrier in the molecular chain, the main chain structures are different, wherein the bond angles and bond lengths are different or the bonding modes are different, the rigidity is also different, after the diatomic alcohol with silicon in the main chain is introduced, the high molecular main chain contains-Si-O-Si-bonds, the silicon-oxygen bond gaps are larger, the internal rotation activation energy is lower, the free rotation of atoms is facilitated, and meanwhile, the Si atoms and-CH on the high molecular main chain3Is connected to-CH3Perpendicular to the plane of the Si-O-Si atom, the-CH results from the Si-C bond being longer than the C-C bond3Three of H are in a spread state, -CH3Three propped H atoms in the polymer material can freely rotate to increase the distance between adjacent Si-O molecular chain segments, and in addition, the inert methyl of the side chain blocks the approach of the high polymer, so that the high polymer material is very flexible, and the free volume of the cavity is obviously increased compared with the high polymer material without introducing the dihydric alcohol containing silicon in the main chain; when the Si atom on the main chain of the polymer is connected with the long branched chain substituent, the slit free volume is mainly increasedThe increase amplitude is small, the improvement effect on the permeability and diffusivity of small molecules is limited, meanwhile, long branched chain substituent groups are low in rigidity, molecular chains are easy to tangle, the increase of free volume is not facilitated, and the introduction of the dihydric alcohol with silicon in the main chain also enables the hollow free volume of the modified polyester to be increased.
The dihydric alcohol with the silicon-containing main chain and the solid base catalyst can play a synergistic role, the solid base catalyst enhances the attack capability of a nucleophilic reagent and is beneficial to the proceeding of degradation reaction, and the dihydric alcohol with the silicon-containing main chain can increase the cavity free volume of polyester, so that the permeation of oxygen and water is facilitated, the nucleophilic ions are convenient to increase, the proceeding of nucleophilic addition reaction is further promoted, and the degradation rate is further improved.
Has the advantages that:
(1) after the full-dull polyester-polyester composite yarn prepared by the method is placed for 60 months at the temperature of 25 ℃ and the relative humidity of 65%, the intrinsic viscosity is reduced by 13-18%, and the natural degradation rate is far higher than the prior art;
(2) the preparation method is simple and convenient to operate, only needs to modify the polyester, and simultaneously adds the solid base catalyst powder which is roasted at high temperature in the polyester synthesis process, thereby being easy to industrially popularize.
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
The preparation method of the full-dull polyester composite yarn comprises the following steps:
(1) preparing full-dull modified polyester;
(1.1) preparing MgO powder;
firstly, heating MgO to 400 ℃, preserving heat for 2h, then heating to 700 ℃, preserving heat for 1h, cooling in air, and finally crushing to obtain MgO powder with the average particle size of 0.49 micron;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and dimethyl silicon glycol into slurry, adding MgO powder, antimony trioxide, titanium dioxide and triphenyl phosphate, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 250 ℃, and the esterification reaction endpoint is when the distilled amount of water in the esterification reaction reaches 91% of a theoretical value, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the dimethyl silicon glycol is 1:1.2:0.03, and the adding amounts of the MgO powder, the antimony trioxide, the titanium dioxide and the triphenyl phosphate are respectively 0.05 wt%, 0.03 wt%, 0.20 wt% and 0.04 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to the absolute pressure of 500Pa within 30min, controlling the reaction temperature to be 255 ℃ and the reaction time to be 30min, then continuing to pump vacuum, and carrying out the polycondensation reaction in a high vacuum stage, so that the reaction pressure is further reduced to the absolute pressure of 100Pa, the reaction temperature is 270 ℃, the reaction time is 40min, and the number average molecular weight of the prepared modified polyester is 28000 and the molecular weight distribution index is 1.8;
(2) the method for preparing the super bright modified polyester is basically the same as the method for preparing the full dull modified polyester, and the difference is that the addition amount of the flatting agent during the esterification reaction is 0wt percent of the addition amount of the terephthalic acid;
(3) according to the POY process, the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn are respectively prepared from the full-dull modified polyester and the big bright modified polyester, the filament number of the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn is 1.5dtex, and the flow of the POY process is as follows: metering, spinneret plate extrusion, cooling, oiling and winding, wherein the parameters of the POY process are as follows: the spinning temperature is 280 ℃, the cooling temperature is 17 ℃, and the winding speed is 3400 m/min;
(4) the two POY yarns are doubled and then processed according to a DTY process to prepare the full-dull polyester-polyester composite yarn, wherein the DTY process comprises the following steps: the method comprises the following steps of yarn guiding, stranding, network, heating and stretching, false twisting, heat setting and winding, wherein the DTY process has the parameters as follows: the spinning speed is 500m/min, the setting overfeed rate is 3.5 percent, the winding overfeed rate is 4.0 percent, the temperature of the first hot box is 200 ℃, the temperature of the second hot box is 165 ℃, and the drawing ratio is 1.6.
The fineness ratio of full-dull modified polyester POY yarns to large bright modified polyester POY yarns in the full-dull polyester composite yarns is 1: 1.2; the fineness of the full-dull polyester composite yarn is 200dtex, the crimp shrinkage is 9.0 percent, the crimp stability is 75 percent, the linear density deviation rate is 1.3 percent, the breaking strength is 3.0cN/dtex, the breaking strength CV value is 4.0 percent, the elongation at break is 29.0 percent, the elongation at break CV value is 7.8 percent, the crimp shrinkage variation coefficient CV value is 9.0 percent, the boiling water shrinkage is 5.0 percent, the oil content is 2.5 percent by weight, and the gloss is 28 percent;
the intrinsic viscosity of the full-dull polyester composite yarn is reduced by 16 percent after the full-dull polyester composite yarn is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65 percent.
Comparative example 1
The preparation method of the full-dull polyester-polyester composite filament is basically the same as that in the embodiment 1, except that dimethyl silicon glycol and MgO powder are not added in the step (1), namely, polyester is not modified, and the titer ratio of the full-dull polyester-polyester POY filament to the bright polyester POY filament in the prepared full-dull polyester-polyester composite filament is 1: 1.2; the fineness of the full-dull polyester composite yarn is 200dtex, the crimp shrinkage is 9.2%, the crimp stability is 76%, the linear density deviation rate is 1.2%, the breaking strength is 3.0cN/dtex, the breaking strength CV value is 4.0%, the elongation at break is 30.0%, the elongation at break CV value is 7.9%, the variation coefficient CV value of the crimp shrinkage is 9.0%, the boiling water shrinkage is 5.2%, the oil content is 2.5 wt%, the gloss is 27%, and the intrinsic viscosity is reduced by 4.5% after the full-dull polyester composite yarn is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65%. Compared with the example 1, the invention can find that the natural degradation rate of the fiber is obviously improved by modifying the polyester through the dimethyl silicon glycol and the solid base catalyst (MgO powder), and meanwhile, the addition of the solid base catalyst (MgO powder) and the dimethyl silicon glycol has little influence on other properties of the fiber and does not influence the processing property and the mechanical property of the fiber.
Comparative example 2
The preparation method of the full-dull polyester composite filament is basically the same as that in the embodiment 1, except that 1, 6-hexanediol is adopted to replace dimethyl silicon glycol in the step (1), and the titer ratio of the full-dull modified polyester POY filament to the large bright modified polyester POY filament in the prepared full-dull polyester composite filament is 1: 1.2; the full-dull polyester composite yarn has the fineness of 200dtex, the crimp shrinkage of 9.1 percent, the crimp stability of 73 percent, the linear density deviation rate of 1.4 percent, the breaking strength of 3.0cN/dtex, the breaking strength CV value of 4.1 percent, the elongation at break of 30.0 percent, the elongation at break CV value of 7.8 percent, the crimp shrinkage variation coefficient CV value of 9.0 percent, the boiling water shrinkage of 5.0 percent, the oil content of 2.5 percent by weight and the gloss of 28 percent, and the intrinsic viscosity of 10.4 percent after being placed for 60 months under the conditions of the temperature of 25 ℃ and the relative humidity of 65 percent.
Compared with example 1, it can be found that the dimethyl silicon glycol is more favorable for improving the natural degradation speed of the fiber compared with the 1, 6-hexanediol containing a long branched chain substituent, mainly because the more free volume of the dimethyl silicon glycol is the cavity free volume, the more free volume of the 1, 6-hexanediol is the slit free volume, and the rigidity of the dimethyl silicon glycol is greater than that of the 1, 6-hexanediol, the entanglement among molecular chains is reduced, so that the dimethyl silicon glycol has more free volumes in the molecular chain arrangement mode, and the natural degradation speed of the fiber is further favorable for improving.
Example 2
The preparation method of the full-dull polyester composite yarn comprises the following steps:
(1) preparing full-dull modified polyester;
(1.1) preparing BaO powder;
firstly heating BaO to 400 ℃, then preserving heat for 3h, then heating to 700 ℃, preserving heat for 2h, cooling in air, and finally crushing to obtain BaO powder with the average grain diameter of 0.45 micron;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and dimethyl diphenyl disiloxane glycol into slurry, adding BaO powder, antimony trioxide, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the esterification reaction temperature is 260 ℃, and the esterification reaction endpoint is determined when the distilled amount of water in the esterification reaction reaches 92% of a theoretical value, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the dimethyl diphenyl disiloxane glycol is 1:1.5:0.04, and the adding amounts of the BaO powder, the antimony trioxide to the titanium dioxide and the trimethyl phosphite are respectively 0.04 wt%, 0.25 wt% and 0.01 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to absolute pressure of 400Pa within 40min, controlling the reaction temperature to be 250 ℃ and the reaction time to be 40min, then continuing to pump vacuum, and carrying out the polycondensation reaction in a high vacuum stage to further reduce the reaction pressure to absolute pressure of 80Pa, control the reaction temperature to be 272 ℃ and control the reaction time to be 65min, wherein the number average molecular weight of the prepared modified polyester is 26000 and the molecular weight distribution index is 2.1;
(2) the method for preparing the super bright modified polyester is basically the same as the method for preparing the full dull modified polyester, and the difference is that the addition amount of the flatting agent during the esterification reaction is 0wt percent of the addition amount of the terephthalic acid;
(3) according to the POY process, the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn are respectively prepared from the full-dull modified polyester and the big bright modified polyester, the filament number of the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn is 0.8dtex, and the flow of the POY process is as follows: metering, spinneret plate extrusion, cooling, oiling and winding, wherein the parameters of the POY process are as follows: the spinning temperature is 280 ℃, the cooling temperature is 20 ℃, and the winding speed is 32000 m/min;
(4) the two POY yarns are doubled and then processed according to a DTY process to prepare the full-dull polyester-polyester composite yarn, wherein the DTY process comprises the following steps: the method comprises the following steps of yarn guiding, stranding, network, heating and stretching, false twisting, heat setting and winding, wherein the DTY process has the parameters as follows: the spinning speed is 500m/min, the setting overfeed rate is 5.5 percent, the winding overfeed rate is 3.0 percent, the first hot box temperature is 190 ℃, the second hot box temperature is 170 ℃, and the drawing ratio is 1.8.
The fineness ratio of full-dull modified polyester POY yarns to large bright modified polyester POY yarns in the full-dull polyester composite yarns is 2: 1; the fineness of the full-dull polyester composite yarn is 160dtex, the crimp shrinkage is 10.0 percent, the crimp stability is 72 percent, the linear density deviation rate is 1.36 percent, the breaking strength is 2.65cN/dtex, the breaking strength CV value is 3.8 percent, the elongation at break is 30.0 percent, the elongation at break CV value is 7.6 percent, the crimp shrinkage variation coefficient CV value is 8.8 percent, the boiling water shrinkage is 5.5 percent, the oil content is 2.6 percent by weight, and the gloss is 27.2 percent;
the intrinsic viscosity of the full-dull polyester composite yarn is reduced by 13 percent after the full-dull polyester composite yarn is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65 percent.
Example 3
The preparation method of the full-dull polyester composite yarn comprises the following steps:
(1) preparing full-dull modified polyester;
(1.1) preparation of SiO2-BaO powder;
first heating SiO2Keeping the temperature of BaO at 400 ℃ for 2.5h, then heating to 700 ℃ and keeping the temperature for 1.5h, cooling in air, and finally crushing to obtain SiO with the average grain diameter of 0.48 micron2-BaO powder, SiO2The content of BaO in BaO is 40% by weight;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and tetramethyl disiloxane glycol into slurry, and adding SiO2After uniformly mixing the-BaO powder, the ethylene glycol antimony, the titanium dioxide and the triphenyl phosphate, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the temperature of the esterification reaction is 255 ℃, and the end point of the esterification reaction is when the distilled amount of water in the esterification reaction reaches 90% of the theoretical value, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the tetramethyl disiloxane glycol is 1:1.8:0.03, and SiO is2The addition amounts of-BaO powder, ethylene glycol antimony, titanium dioxide and triphenyl phosphate are 0.03 wt%, 0.04 wt%, 0.22 wt% and 0.05 wt% of the addition amount of terephthalic acid, respectively;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to absolute pressure of 450Pa within 45min, controlling the reaction temperature to be 256 ℃ and the reaction time to be 50min, then continuing to pump vacuum, and carrying out the polycondensation reaction in a high vacuum stage to further reduce the reaction pressure to absolute pressure of 100Pa, control the reaction temperature to be 275 ℃ and control the reaction time to be 60min, wherein the number average molecular weight of the prepared modified polyester is 25000 and the molecular weight distribution index is 2.2;
(2) the method for preparing the super bright modified polyester is basically the same as the method for preparing the full dull modified polyester, and the difference is that the addition amount of the flatting agent during the esterification reaction is 0wt percent of the addition amount of the terephthalic acid;
(3) according to the POY process, the full-dull modified polyester POY yarn and the large bright modified polyester POY yarn are respectively prepared from full-dull modified polyester and large bright modified polyester, the filament number of the full-dull modified polyester POY yarn and the filament number of the large bright modified polyester POY yarn are both 2.2dtex, and the flow of the POY process is as follows: metering, spinneret plate extrusion, cooling, oiling and winding, wherein the parameters of the POY process are as follows: the spinning temperature is 282 ℃, the cooling temperature is 17 ℃, and the winding speed is 3200 m/min;
(4) the two POY yarns are doubled and then processed according to a DTY process to prepare the full-dull polyester-polyester composite yarn, wherein the DTY process comprises the following steps: the method comprises the following steps of yarn guiding, stranding, network, heating and stretching, false twisting, heat setting and winding, wherein the DTY process has the parameters as follows: the spinning speed is 600m/min, the setting overfeed rate is 3.5 percent, the winding overfeed rate is 3.0 percent, the temperature of the first hot box is 180 ℃, the temperature of the second hot box is 180 ℃, and the drawing ratio is 1.7.
The fineness ratio of full-dull modified polyester POY yarns to large bright modified polyester POY yarns in the full-dull polyester composite yarns is 1: 1; the fineness of the full-dull polyester composite yarn is 100dtex, the crimp shrinkage is 11.0 percent, the crimp stability is 72 percent, the linear density deviation rate is 1.36 percent, the breaking strength is 3.35cN/dtex, the breaking strength CV value is 3.8 percent, the elongation at break is 33.0 percent, the elongation at break CV value is 7.6 percent, the crimp shrinkage variation coefficient CV value is 9.0 percent, the boiling water shrinkage is 4.5 percent, the oil content is 3 percent by weight, and the gloss is 26 percent;
the intrinsic viscosity of the full-dull polyester composite yarn is reduced by 13 percent after the full-dull polyester composite yarn is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65 percent.
Example 4
The preparation method of the full-dull polyester composite yarn comprises the following steps:
(1) preparing full-dull modified polyester;
(1.1) preparing MgO/BaO powder;
firstly, heating MgO/BaO (mixture with the mass ratio of 1: 1) to 400 ℃, then preserving heat for 2h, then heating to 700 ℃, preserving heat for 2h, cooling in air, and finally crushing to obtain MgO/BaO powder with the average grain diameter of 0.47 micron;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and dimethyl silicon glycol into slurry, adding MgO/BaO powder, ethylene glycol antimony, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.1MPa, the esterification reaction temperature is 250 ℃, and the esterification reaction endpoint is determined when the distilled amount of water in the esterification reaction reaches 90% of a theoretical value, wherein the molar ratio of the terephthalic acid to the ethylene glycol to the dimethyl silicon glycol is 1:1.3:0.05, and the adding amounts of the MgO/BaO powder, the ethylene glycol antimony, the titanium dioxide and the trimethyl phosphite are respectively 0.03 wt%, 0.05 wt%, 0.20 wt% and 0.03 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the stage from normal pressure to absolute pressure of 420Pa within 50min, controlling the reaction temperature to be 260 ℃ and the reaction time to be 35min, then continuously pumping the vacuum to perform the polycondensation reaction in the high vacuum stage, further reducing the reaction pressure to absolute pressure of 85Pa, controlling the reaction temperature to be 272 ℃ and the reaction time to be 40min, wherein the number average molecular weight of the prepared modified polyester is 29400 and the molecular weight distribution index is 1.8;
(2) the method for preparing the super bright modified polyester is basically the same as the method for preparing the full dull modified polyester, and the difference is that the addition amount of the flatting agent during the esterification reaction is 0wt percent of the addition amount of the terephthalic acid;
(3) according to the POY process, the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn are respectively prepared from the full-dull modified polyester and the big bright modified polyester, the filament number of the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn is 0.7dtex, and the flow of the POY process is as follows: metering, spinneret plate extrusion, cooling, oiling and winding, wherein the parameters of the POY process are as follows: the spinning temperature is 282 ℃, the cooling temperature is 19 ℃, and the winding speed is 3600 m/min;
(4) the two POY yarns are doubled and then processed according to a DTY process to prepare the full-dull polyester-polyester composite yarn, wherein the DTY process comprises the following steps: the method comprises the following steps of yarn guiding, stranding, network, heating and stretching, false twisting, heat setting and winding, wherein the DTY process has the parameters as follows: the spinning speed is 600m/min, the setting overfeed rate is 4.0 percent, the winding overfeed rate is 5.5 percent, the temperature of the first hot box is 180 ℃, the temperature of the second hot box is 150 ℃, and the drawing ratio is 1.65.
The fineness ratio of full-dull modified polyester POY yarns to large bright modified polyester POY yarns in the full-dull polyester composite yarns is 1.5: 2; the fineness of the full-dull polyester composite yarn is 100dtex, the crimp shrinkage is 11.0 percent, the crimp stability is 76 percent, the linear density deviation rate is 1.4 percent, the breaking strength is 3.2cN/dtex, the breaking strength CV value is 3.5 percent, the elongation at break is 27.0 percent, the elongation at break CV value is 7.8 percent, the crimp shrinkage variation coefficient CV value is 8.6 percent, the boiling water shrinkage is 5.0 percent, the oil content is 2.2 percent by weight, and the gloss is 25 percent;
the intrinsic viscosity of the full-dull polyester composite yarn is reduced by 13 percent after the full-dull polyester composite yarn is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65 percent.
Example 5
The preparation method of the full-dull polyester composite yarn comprises the following steps:
(1) preparing full-dull modified polyester;
(1.1) preparation of MgO/SiO2-BaO powder;
first heating MgO/SiO2heating-BaO (mixture with mass ratio of 1: 2) to 400 deg.C, holding for 2h, heating to 700 deg.C, holding for 2h, cooling in air, and pulverizing to obtain MgO/SiO with average particle size of 0.48 μm2-BaO powder, SiO2The content of BaO in-BaO was 80 wt%；
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and dimethyl diphenyl disiloxane glycol into slurry, and adding MgO/SiO2After uniformly mixing BaO powder, antimony acetate, titanium dioxide and trimethyl phosphate, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.3MPa, the temperature of the esterification reaction is 252 ℃, the end point of the esterification reaction is when the distilled amount of water in the esterification reaction reaches 90% of a theoretical value, the molar ratio of terephthalic acid, ethylene glycol and dimethyl diphenyl disiloxane glycol is 1:2.0:0.05, and MgO/SiO2The addition amounts of-BaO powder, antimony acetate, titanium dioxide and trimethyl phosphate were 0.05 wt%, 0.03 wt%, 0.24 wt% and 0.04 wt%, respectively, of the addition amount of terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to the absolute pressure of 500Pa within 30min, controlling the reaction temperature to be 256 ℃ and the reaction time to be 45min, then continuously pumping the vacuum to perform the polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to the absolute pressure of 88Pa, controlling the reaction temperature to be 272 ℃ and the reaction time to be 75min, wherein the number average molecular weight of the prepared modified polyester is 28800 and the molecular weight distribution index is 2.1;
(2) the method for preparing the super bright modified polyester is basically the same as the method for preparing the full dull modified polyester, and the difference is that the addition amount of the flatting agent during the esterification reaction is 0wt percent of the addition amount of the terephthalic acid;
(3) according to the POY process, the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn are respectively prepared from the full-dull modified polyester and the big bright modified polyester, the filament number of the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn is 2.0dtex, and the flow of the POY process is as follows: metering, spinneret plate extrusion, cooling, oiling and winding, wherein the parameters of the POY process are as follows: the spinning temperature is 285 ℃, the cooling temperature is 18 ℃, and the winding speed is 3500 m/min;
(4) the two POY yarns are doubled and then processed according to a DTY process to prepare the full-dull polyester-polyester composite yarn, wherein the DTY process comprises the following steps: the method comprises the following steps of yarn guiding, stranding, network, heating and stretching, false twisting, heat setting and winding, wherein the DTY process has the parameters as follows: the spinning speed is 800m/min, the setting overfeed rate is 4.5 percent, the winding overfeed rate is 5.0 percent, the temperature of the first hot box is 200 ℃, the temperature of the second hot box is 150 ℃, and the drawing ratio is 1.6.
The fineness ratio of full-dull modified polyester POY yarns to large bright modified polyester POY yarns in the full-dull polyester composite yarns is 1.6: 1.1; the fineness of the full-dull polyester composite yarn is 200dtex, the crimp shrinkage is 10.0 percent, the crimp stability is 73 percent, the linear density deviation rate is 1.33 percent, the breaking strength is 3.35cN/dtex, the breaking strength CV value is 4.0 percent, the elongation at break is 31.0 percent, the elongation at break CV value is 7.2 percent, the crimp shrinkage variation coefficient CV value is 8.7 percent, the boiling water shrinkage is 5.5 percent, the oil content is 3 percent by weight, and the gloss is 26 percent;
the intrinsic viscosity of the full-dull polyester composite yarn is reduced by 17 percent after the full-dull polyester composite yarn is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65 percent.
Example 6
The preparation method of the full-dull polyester composite yarn comprises the following steps:
(1) preparing full-dull modified polyester;
(1.1) preparation of BaO/SiO2-BaO powder;
first heating BaO/SiO2Keeping the temperature of-BaO (mixture with the mass ratio of 1: 3) at 400 ℃ for 3h, then keeping the temperature at 700 ℃ for 1h, cooling in air, and finally crushing to obtain BaO/SiO with the average particle size of 0.44 micron2-BaO powder, SiO2The content of BaO in BaO is 60% by weight;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and tetramethyl disiloxane glycol into slurry, and adding BaO/SiO2After uniformly mixing BaO powder, antimony trioxide, titanium dioxide and triphenyl phosphate, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure, the esterification reaction temperature is 260 ℃, and the esterification reaction endpoint is when the distilled amount of water in the esterification reaction reaches 95% of a theoretical value, wherein the molar ratio of terephthalic acid, ethylene glycol and tetramethyldisiloxane glycol is 1:1.2:0.05, and BaO/SiO2The addition amounts of-BaO powder, antimony trioxide, titanium dioxide and triphenyl phosphate are 0.04 wt%, 0.05 wt%, 0.25 wt% and 0.05 wt% of the addition amount of terephthalic acid, respectively;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in a low vacuum stage under the condition of negative pressure, stably pumping the pressure in the stage from normal pressure to absolute pressure of 490Pa within 30min, controlling the reaction temperature to be 260 ℃ and the reaction time to be 50min, then continuously pumping vacuum to perform the polycondensation reaction in a high vacuum stage, further reducing the reaction pressure to absolute pressure of 90Pa, controlling the reaction temperature to be 270 ℃ and the reaction time to be 55min, wherein the number average molecular weight of the prepared modified polyester is 30000 and the molecular weight distribution index is 2.2;
(2) the method for preparing the super bright modified polyester is basically the same as the method for preparing the full dull modified polyester, and the difference is that the addition amount of the flatting agent during the esterification reaction is 0wt percent of the addition amount of the terephthalic acid;
(3) according to the POY process, the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn are respectively prepared from the full-dull modified polyester and the big bright modified polyester, the filament number of the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn is 3.0dtex, and the flow of the POY process is as follows: metering, spinneret plate extrusion, cooling, oiling and winding, wherein the parameters of the POY process are as follows: the spinning temperature is 285 ℃, the cooling temperature is 20 ℃, and the winding speed is 3600 m/min;
(4) the two POY yarns are doubled and then processed according to a DTY process to prepare the full-dull polyester-polyester composite yarn, wherein the DTY process comprises the following steps: the method comprises the following steps of yarn guiding, stranding, network, heating and stretching, false twisting, heat setting and winding, wherein the DTY process has the parameters as follows: the spinning speed is 800m/min, the setting overfeed rate is 5.5 percent, the winding overfeed rate is 5.5 percent, the temperature of the first hot box is 190 ℃, the temperature of the second hot box is 150 ℃, and the drawing ratio is 1.6.
The fineness ratio of full-dull modified polyester POY yarns to large bright modified polyester POY yarns in the full-dull polyester composite yarns is 2: 1; the fineness of the full-dull polyester composite yarn is 130dtex, the crimp shrinkage is 10.0 +/-1.0%, the crimp stability is 74%, the linear density deviation rate is 1.4%, the breaking strength is 3.0cN/dtex, the breaking strength CV value is 3.5%, the elongation at break is 33.0%, the elongation at break CV value is 7.9%, the crimp shrinkage variation coefficient CV value is 8.8%, the boiling water shrinkage is 5.5%, the oil content is 2 wt%, and the gloss is 28%;
the intrinsic viscosity of the full-dull polyester composite filament is reduced by 18 percent after the full-dull polyester composite filament is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65 percent.
Example 7
The preparation method of the full-dull polyester composite yarn comprises the following steps:
(1) preparing full-dull modified polyester;
(1.1) preparing MgO powder;
firstly, heating MgO to 400 ℃, preserving heat for 2h, then heating to 700 ℃, preserving heat for 1.2h, cooling in air, and finally crushing to obtain MgO powder with the average particle size of 0.48 micron;
(1.2) esterification reaction;
preparing terephthalic acid, ethylene glycol and tetramethyl disiloxane glycol into slurry, adding MgO powder, ethylene glycol antimony, titanium dioxide and trimethyl phosphite, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is 0.2MPa, the esterification reaction temperature is 250 ℃, and the esterification reaction endpoint is when the distilled amount of water in the esterification reaction reaches 92% of a theoretical value, wherein the molar ratio of the terephthalic acid, the ethylene glycol and the tetramethyl disiloxane glycol is 1:2.0:0.045, and the adding amounts of the MgO powder, the ethylene glycol antimony, the titanium dioxide and the trimethyl phosphite are respectively 0.05 wt%, 0.04 wt%, 0.22 wt% and 0.01 wt% of the adding amount of the terephthalic acid;
(1.3) a polycondensation reaction;
after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, smoothly pumping the pressure in the stage from normal pressure to absolute pressure of 440Pa within 40min, controlling the reaction temperature to be 260 ℃ and the reaction time to be 40min, then continuing to pump vacuum, and carrying out the polycondensation reaction in the high vacuum stage to further reduce the reaction pressure to absolute pressure of 95Pa, control the reaction temperature to be 274 ℃ and control the reaction time to be 50min, wherein the number average molecular weight of the prepared modified polyester is 27900 and the molecular weight distribution index is 1.9;
(2) the method for preparing the super bright modified polyester is basically the same as the method for preparing the full dull modified polyester, and the difference is that the addition amount of the flatting agent during the esterification reaction is 0wt percent of the addition amount of the terephthalic acid;
(3) according to the POY process, the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn are respectively prepared from the full-dull modified polyester and the big bright modified polyester, the filament number of the full-dull modified polyester POY yarn and the big bright modified polyester POY yarn is 1.2dtex, and the flow of the POY process is as follows: metering, spinneret plate extrusion, cooling, oiling and winding, wherein the parameters of the POY process are as follows: the spinning temperature is 283 ℃, the cooling temperature is 17 ℃, and the winding speed is 3300 m/min;
(4) the two POY yarns are doubled and then processed according to a DTY process to prepare the full-dull polyester-polyester composite yarn, wherein the DTY process comprises the following steps: the method comprises the following steps of yarn guiding, stranding, network, heating and stretching, false twisting, heat setting and winding, wherein the DTY process has the parameters as follows: the spinning speed is 650m/min, the setting overfeed rate is 3.5 percent, the winding overfeed rate is 3.5 percent, the temperature of the first hot box is 200 ℃, the temperature of the second hot box is 180 ℃, and the drawing ratio is 1.8.
The fineness ratio of full-dull modified polyester POY yarns to large bright modified polyester POY yarns in the full-dull polyester composite yarns is 1: 1.5; the fineness of the full-dull polyester composite yarn is 200dtex, the crimp shrinkage is 10.0 percent, the crimp stability is 72 percent, the linear density deviation rate is 1.33 percent, the breaking strength is 3.35cN/dtex, the breaking strength CV value is 4.0 percent, the elongation at break is 30.0 percent, the elongation at break CV value is 7.7 percent, the crimp shrinkage variation coefficient CV value is 9.0 percent, the boiling water shrinkage is 4.5 percent, the oil content is 2 weight percent, and the gloss is 28 percent;
the intrinsic viscosity of the full-dull polyester composite filament is reduced by 14 percent after the full-dull polyester composite filament is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65 percent.
Claims (10)
1. The preparation method of the full-dull polyester composite yarn is characterized by comprising the following steps of: preparing two POY yarns from full-dull modified polyester and super bright modified polyester respectively according to a POY process, doubling the two POY yarns, and processing according to a DTY process to prepare full-dull polyester-polyester composite yarn;
the preparation method of the modified polyester comprises the following steps: carrying out esterification reaction and polycondensation reaction on raw materials mainly comprising terephthalic acid, ethylene glycol, dihydric alcohol with a silicon-containing main chain and solid base catalyst powder subjected to high-temperature roasting in sequence;
the dihydric alcohol with the silicon-containing main chain is dimethyl silicon glycol, dimethyl diphenyl disiloxane glycol or tetramethyl disiloxane glycol;
the high-temperature roasting temperature is 400-700 ℃, and the high-temperature roasting process comprises the following steps: firstly heating to 400 ℃, then preserving heat for 2-3 h, then heating to 700 ℃, preserving heat for 1-2 h, and finally cooling in air, wherein solid base catalysts are MgO, BaO and SiO2-one or more of BaO;
the full-dull modified polyester is also dispersed with a dulling agent, and the content of the dulling agent is more than or equal to 2.0 wt%.
2. The method for preparing full dull polyester-polyester composite filament according to claim 1, wherein SiO is2The content of BaO in the-BaO is 40-80 wt%; the solid alkali catalyst is roasted at high temperature and then crushed to obtain powder with the average grain diameter of less than 0.5 micron.
3. The preparation method of the full-dull polyester composite yarn according to claim 2, wherein the preparation method of the full-dull modified polyester and the preparation method of the high gloss modified polyester are substantially the same, except that the addition amount of the matting agent is 2.0-3.0 wt% and 0 wt% of the addition amount of the terephthalic acid when the full-dull modified polyester and the high gloss modified polyester are prepared.
4. The preparation method of the full-dull polyester composite filament according to claim 3, wherein the full-dull modified polyester and the high gloss modified polyester are prepared by the following steps:
(1) performing esterification reaction;
preparing terephthalic acid, ethylene glycol and dihydric alcohol with a silicon-containing main chain into slurry, adding solid base catalyst powder subjected to high-temperature roasting, a polyester polymerization catalyst, a flatting agent and a stabilizer, uniformly mixing, pressurizing in a nitrogen atmosphere to perform esterification reaction, wherein the pressurizing pressure is normal pressure to 0.3MPa, the esterification reaction temperature is 250-260 ℃, and the esterification reaction end point is determined when the water distillate in the esterification reaction reaches more than 90% of a theoretical value;
(2) performing polycondensation reaction;
and after the esterification reaction is finished, starting the polycondensation reaction in the low vacuum stage under the negative pressure condition, stably pumping the pressure in the low vacuum stage from normal pressure to below 500Pa in 30-50 min at the reaction temperature of 250-260 ℃ for 30-50 min, then continuously pumping the vacuum to perform the polycondensation reaction in the high vacuum stage, so that the reaction pressure is further reduced to below 100Pa, the reaction temperature is 270-275 ℃, and the reaction time is 50-90 min.
5. The preparation method of the full dull polyester composite yarn according to claim 4, wherein the molar ratio of the terephthalic acid, the ethylene glycol and the diol having a silicon-containing main chain is 1: 1.2-2.0: 0.03-0.05, and the addition amounts of the solid base catalyst powder subjected to the high temperature calcination, the polyester polymerization catalyst and the stabilizer are 0.03-0.05 wt%, 0.03-0.05 wt% and 0.01-0.05 wt% of the addition amount of the terephthalic acid, respectively.
6. The method for preparing full dull polyester composite filament according to claim 5, wherein the polyester polymerization catalyst is antimony trioxide, ethylene glycol antimony or antimony acetate, the matting agent is titanium dioxide, and the stabilizer is triphenyl phosphate, trimethyl phosphate or trimethyl phosphite.
7. The preparation method of the full-dull polyester composite filament according to claim 6, wherein the modified polyester has a number average molecular weight of 25000 to 30000 and a molecular weight distribution index of 1.8 to 2.2.
8. The preparation method of the full dull polyester composite yarn according to claim 1, wherein the POY process comprises the following steps: metering, spinneret plate extrusion, cooling, oiling and winding;
the parameters of the POY process are as follows: the spinning temperature is 280-285 ℃, the cooling temperature is 17-20 ℃, and the winding speed is 3200-3600 m/min;
the DTY process comprises the following steps: guide wire, plying, network, heating and stretching, false twisting, heat setting and winding;
the DTY process has the following parameters: the spinning speed is 500-800 m/min, the setting overfeed rate is 3.5-5.5%, the winding overfeed rate is 3.0-5.5%, the temperature of a first hot box is 180-200 ℃, the temperature of a second hot box is 150-180 ℃, and the draw ratio is 1.6-1.8.
9. The full-dull polyester composite yarn prepared by the preparation method of the full-dull polyester composite yarn as claimed in any one of claims 1 to 8 is characterized in that: the DTY yarn is formed by compounding a yarn A and a yarn B, and the yarn A and the yarn B are respectively made of full-dull modified polyester and super bright modified polyester;
the molecular chain of the modified polyester comprises a terephthalic acid chain segment, an ethylene glycol chain segment and a dihydric alcohol chain segment with a silicon-containing main chain;
the solid base catalyst powder roasted at high temperature is dispersed in the full-dull modified polyester and the large light modified polyester, and the full-dull modified polyester is also dispersed with a flatting agent, wherein the content of the flatting agent is more than or equal to 2.0 wt%.
10. The full-dull polyester-polyester composite yarn according to claim 9, wherein the single-filament fineness of the yarn A and the single-filament fineness of the yarn B are both 0.7-3.0 dtex, and the fineness ratio of the yarn A to the yarn B in the full-dull polyester-polyester composite yarn is 1-2: 1-2;
the titer of the full-dull polyester composite yarn is 100-200 dtex, the crimp shrinkage is 10.0 +/-1.0%, the crimp stability is more than or equal to 72%, the linear density deviation rate is less than or equal to 1.4%, the breaking strength is 3.0 +/-0.35 cN/dtex, the breaking strength CV value is less than or equal to 4.0%, the breaking elongation is 30.0 +/-3.0%, the breaking elongation CV value is less than or equal to 8.0%, the crimp shrinkage variation coefficient CV value is less than or equal to 9.0%, the boiling water shrinkage is 5.0 +/-0.5%, the oil content is 2-3 wt%, and the gloss is less than 30%;
the intrinsic viscosity of the full-dull polyester composite yarn is reduced by 13-18% after the full-dull polyester composite yarn is placed for 60 months under the conditions that the temperature is 25 ℃ and the relative humidity is 65%.
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