CN111058122B - Method for preparing titanium-based extinction PBT fiber - Google Patents
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- CN111058122B CN111058122B CN201911407302.XA CN201911407302A CN111058122B CN 111058122 B CN111058122 B CN 111058122B CN 201911407302 A CN201911407302 A CN 201911407302A CN 111058122 B CN111058122 B CN 111058122B
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- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
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- C08G63/16—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention relates to a method for preparing titanium-based extinction PBT fiber, which comprises the following steps: the preparation method comprises the steps of synthesizing a titanium-based extinction PBT melt by using a PTA (pure terephthalic acid), BD (polybutylene terephthalate), PBT (polybutylene terephthalate) polyester titanium catalyst composite material system and titanium dioxide as main raw materials, and then slicing and spinning to obtain the titanium-based extinction PBT fiber, wherein the PBT polyester titanium catalyst composite material system mainly comprises a PBT polyester prepolymer with the polymerization degree of 3-50 and a titanium catalyst dispersed in the PBT polyester prepolymer. According to the method for preparing the titanium-based extinction PBT fiber, the PBT polyester prepolymer with the polymerization degree of 3-50 is used for wrapping the catalyst, so that the hydrolysis reaction of the catalyst caused by water contained in the storage and transportation process and generated by the esterification reaction of the PBT polyester can be reduced or even avoided, the high dispersibility and the high activity of the catalyst are ensured, more side reactions can be inhibited, and the chromaticity L value and the b value of the polyester are obviously improved.
Description
Technical Field
The invention belongs to the technical field of polyester fibers, and relates to a method for preparing titanium-based extinction PBT fibers.
Background
Polybutylene terephthalate (PBT) has excellent mechanical, electrical, chemical corrosion resistance, easy forming, low moisture absorption and other properties, and is a novel engineering plastic with excellent comprehensive properties. The PBT has good elasticity due to the molecular structure characteristics, so the PBT can be used for manufacturing fibers which have elasticity and extinction performance and are used for opaque white swimwear, training clothes, body building clothes, gymnastics clothes, tennis clothes, dancing tights, nurse clothes and the like, for example, extinction PBT polyester slices which have good extinction performance, reduce the phenomena of light reflection and flicker, and have good ultraviolet resistance and strong shielding performance.
The synthesis temperature of the PBT resin is 40-50 ℃ lower than that of the PET resin, and according to the characteristic, the catalyst of the PBT has high low-temperature activity and can inhibit side reaction for producing Tetrahydrofuran (THF). The commercial catalysts are mainly organic titanates and their derivatives. The titanate catalyst is effective in two stages of ester exchange and polycondensation, can be dissolved in a mixture of reactants, and has the advantages of high activity, small using amount, high reaction speed, high molecular weight of the obtained PBT resin, good color, low BG consumption and capability of reducing the production cost of the PBT resin. Titanates have many advantages over other catalysts for use in the synthesis of PBT resins. However, it also has some disadvantages because of its particularly sensitive hydrolyzability. In the production, the thermal cyclization of BG produces more or less tetrahydrofuran and water, and the produced water causes the hydrolysis of titanate, produces hydrolysate without catalytic activity, reduces the catalytic efficiency, and forms permanent precipitate in the reactor or production pipeline, which may seriously block the product outlet of the reaction kettle.
At present, a semi-dull polyester product is usually produced by adopting semi-dull polyester, titanium dioxide is added as a dulling agent to produce semi-dull polyester chips, and fabrics made of the produced polyester fibers are soft and glossy in hand feeling and good in dyeing property, so that the semi-dull polyester chips are widely used in the fields of clothing, automobiles and the like.
Therefore, a method capable of avoiding hydrolysis reaction of the polyester catalyst and ensuring high dispersibility and high activity of the polyester catalyst is urgently needed to be researched, and the method is further used for preparing the titanium-based delustering PBT fiber.
Disclosure of Invention
The invention aims to solve the problems that a PBT polyester catalyst is easy to hydrolyze and has poor dispersibility, and the activity of the catalyst is reduced by adding titanium dioxide, and provides a method for preparing the titanium-based delustering PBT fiber.
In order to achieve the purpose, the invention adopts the technical scheme that:
synthesizing a titanium-based extinction PBT melt by using a PTA, BD and PBT polyester titanium catalyst composite material system and titanium dioxide (containing dispersing agents of sodium silicate, sodium hexametaphosphate and DA1705, and the content is about 0.4-0.6 wt%) as main raw materials, and slicing and spinning to obtain the titanium-based extinction PBT fiber;
the PBT polyester titanium catalyst composite material system mainly comprises a PBT polyester prepolymer with the polymerization degree of 3-50 and a titanium catalyst dispersed in the PBT polyester prepolymer.
When the traditional process is adopted to prepare the delustering PBT polyester fiber, a dispersant is generally introduced, and the main reasons are as follows: the spinneret plate adopted in the fiber forming process has small aperture and large winding and drafting speed, the delustering agent (mostly adopting titanium dioxide) in a polymerization system can meet the requirements only by keeping the nanometer size, however, the commercial matting agent is subject to secondary agglomeration in the processes of drying, storage, transportation and the like, so that the secondary grinding and classification of a factory is often required before the PBT polyester synthesis system is introduced, but the secondary grinding and classification operation is more complicated, therefore, the method of directly adding the 1, 4-butanediol slurry of the flatting agent without secondary grinding is mainly adopted, because the grain diameter of the flatting agent in the 1, 4-butanediol sizing agent is uneven, the flatting agent is easy to agglomerate and block, the dispersibility is poor, and the flatting agent can not be directly used for flatting PBT polyester, a dispersing agent is required to be added, however, the introduction of the dispersant can deactivate the catalyst, and in order to ensure sufficient catalytic action, the dosage of the catalyst needs to be greatly increased;
when the method is used for preparing the extinction PBT polyester fiber, the dispersing agent does not have adverse effect on the activity of the catalyst, so that the dosage of the catalyst does not need to be greatly increased, and the main reason for ensuring the activity of the catalyst under the condition of the dispersing agent is that the PBT polyester prepolymer with the polymerization degree of 3-50 is used for wrapping the catalyst, and the polyester prepolymer only melts at a higher temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation process and generated by the esterification reaction of the PBT polyester can be reduced or even avoided, and the polyester prepolymer is an intermediate for preparing the polyester chips, has intrinsic good compatibility with an intermediate system of the synthesized polyester chips, so that the agglomeration of the polyester chips is avoided, and the high dispersibility and high activity of the PBT polyester catalyst are ensured.
As a preferred technical scheme:
the method for preparing the titanium-based delustering PBT fiber comprises the following specific steps:
(1) mixing a PTA, BD and PBT polyester titanium catalyst composite material system and titanium dioxide, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 30-40 KPa, the temperature is 200-240 ℃, and the time is 100-120 min;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 20-10 KPa, the temperature is 240-250 ℃, and the time is 40-50 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain a titanium-based extinction PBT melt, wherein the pressure of the final polycondensation reaction is 90-110 Pa, the temperature is 250-264 ℃, and the time is 160-180 min;
(4) and slicing and spinning the titanium-based extinction PBT melt to obtain the titanium-based extinction PBT fiber.
According to the method for preparing the titanium-based delustering PBT fiber, in the step (1), the molar ratio of PTA to BD is 1: 1.1-2.5, in terms of the mass of a titanium element, the addition amount of a titanium catalyst contained in a PBT polyester titanium catalyst composite material system in the esterification reaction process is 50-150 ppm of the theoretical mass of a polymerization product of PTA and BD, in the traditional process, the addition amount of the titanium catalyst is about 160ppm of the theoretical mass of the polymerization product of PTA and BD due to the influence of a dispersing agent and the problem of no hydrolysis resistance, and the comparison shows that the addition amount of the catalyst is obviously reduced, the main reason is that a prepolymer used only melts at a high temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation process and generated in the esterification reaction of PBT polyester can be reduced or even avoided, meanwhile, the adverse effect of the dispersing agent on the catalyst is reduced, the adding amount of the titanium dioxide is 0.2-2.0 wt% of the theoretical mass of the polymerization products of PTA and BD, and when the adding amount of the titanium dioxide is 0.2-0.3 wt% of the theoretical mass of the polymerization products of PTA and BD, the titanium-based semi-dull PBT fiber is obtained; when the addition amount of the titanium dioxide is 0.6-2.0 wt% of the theoretical mass of the polymerization products of PTA and BD, the obtained titanium-based full-dull PBT fiber is obtained; the amount of the flatting agent required by the preparation of the flatting PBT fiber is less than that of the prior art, the main reason is that the prepolymer is used as a carrier, the melting point is higher, and the prepolymer can only melt at higher temperature to release functional materials in the synthesis process of the PBT polyester, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided;
in the step (3), the intrinsic viscosity of the titanium-based extinction PBT melt is 0.85-1.0 dL/g, the number of the agglomeration particles is 1.0-3.0/mg, the size of the agglomeration particles is 15-20 mu m, the chroma L value of the titanium-based extinction PBT resin obtained by sampling from the titanium-based extinction PBT melt is 80-90, and the b value is 4-7; the chromaticity L value of the PBT polyester prepared by the traditional process is generally 78-80, the b value is generally 1-3, and compared with the traditional process, the chromaticity L value and the b value of the PBT polyester are obviously improved, and the main reason is that the PBT polyester prepolymer is an intermediate for preparing the PBT polyester chip, and has intrinsic good compatibility with an intermediate system of the synthesized PBT polyester chip, so that the agglomeration of the PBT polyester prepolymer is avoided, the high dispersibility and the high activity of a PBT polyester catalyst are ensured, and more side reactions are inhibited;
in the step (4), the technological parameters of the slice spinning are as follows: the spinning temperature is 283-285 ℃, the spinning speed is 3500-3900 m/min, the side blowing temperature is 25-30 ℃, the side blowing wind speed is 0.2-0.4 m/s, and the drafting multiplying factor is 3.8-4.2.
According to the method for preparing the titanium-based delustering PBT fiber, the mass content of the titanium catalyst in the PBT polyester titanium catalyst composite material system is 0.5-20 wt%.
The method for preparing the titanium-based delustering PBT fiber comprises the steps of preparing a titanium-based catalyst, wherein the titanium-based catalyst is titanate, titanium dioxide particles subjected to or not subjected to hybridization treatment, titanium glycol particles subjected to or not subjected to hybridization treatment or a flaky titanium-based polyester catalyst subjected to or not subjected to hybridization treatment;
the sizes of the titanium dioxide particles, the ethylene glycol titanium particles and the sheet titanium polyester catalyst are in a nanometer or submicron level;
the titanium dioxide particles or the ethylene glycol titanium particles are porous particles or nonporous particles, and are spherical, ellipsoidal, flaky, rod-shaped or linear;
the structural general formula of the sheet titanium polyester catalyst is Tix(ORO)y(OOC6C4H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, the flaky titanium polyester catalyst is in a lamellar structure, and the thickness of the lamellar is 100-200 nm;
the preparation method of the sheet titanium polyester catalyst comprises the following steps: taking terephthalic acid or terephthalate, titanate and dihydric fatty alcohol as raw materials, carrying out reaction in stages under the conditions of temperature of 110-260 ℃ and pressure of 0.1-10 KPa, specifically comprising the steps of controlling the temperature to react for 0.5-2.0 h under the condition of temperature of 150-245 ℃, heating to 200-260 ℃ for continuous reaction, terminating the reaction when the degree of esterification or ester exchange reaches 70-90%, filtering while hot, and crushing and grinding the obtained solid product to prepare the sheet-shaped titanium polyester catalyst;
the terephthalic acid ester is dimethyl terephthalate, diethyl terephthalate, dihydroxyethyl terephthalate, dihydroxypropyl terephthalate or dihydroxybutyl terephthalate; the titanate is n-butyl titanate, tetraisopropyl titanate or ethyl titanate; the dihydric fatty alcohol is 1, 4-butanediol.
The preparation method of the PBT polyester titanium catalyst composite material system comprises the following steps: and melting and blending the solid PBT polyester prepolymer with the polymerization degree of 3-50 with a titanium catalyst, and cooling to obtain the PBT polyester titanium catalyst composite material system, wherein the temperature of the melting and blending is 150-270 ℃, and the time is 1.5-6 h.
The method for preparing the titanium-based delustering PBT fiber comprises the following steps: adding a titanium catalyst or a dihydric alcohol dispersion liquid of the titanium catalyst into a PBT polyester prepolymer melt with the polymerization degree of 3-50, uniformly stirring and cooling to obtain a PBT polyester titanium catalyst composite material system, wherein the titanium catalyst can be directly added, can be added after being dispersed in dihydric alcohol, can be partially directly added, and can be partially added after being dispersed in the dihydric alcohol, the adding mode is within the protection range of the invention, and when the adding mode is carried out after being dispersed in the dihydric alcohol, when the mass ratio of the PBT polyester prepolymer to the dihydric alcohol is more than 1, the final product is in a solid state; when the mass ratio of the PBT polyester prepolymer to the dihydric alcohol is 0.5-1, the final product is in a slurry state; wherein the mass concentration of the dihydric alcohol dispersion liquid of the titanium catalyst is 30-70 wt%, and the dihydric alcohol is 1, 4-butanediol.
The method for preparing the titanium-based delustering PBT fiber comprises the following steps: a, B and C are uniformly mixed and then are subjected to esterification reaction, pre-polycondensation reaction and cooling to obtain a PBT polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is a titanium catalyst or a dihydric alcohol dispersion of the titanium catalyst, and all the dihydric alcohol is 1, 4-butanediol; the titanium catalyst can be directly added, or can be added after being dispersed in the dihydric alcohol to supplement the residual dihydric alcohol, or can be partially added directly, or partially added after being dispersed in the dihydric alcohol, and is within the protection scope of the invention. In the synthesis process of PBT polyester in the prior art, a titanium catalyst is added before esterification, and the titanium catalyst can undergo changes of system environments such as temperature, pressure and the like, and can possibly generate physical and chemical reactions with each other or with reaction monomers for preparing the PBT polyester, so that the catalytic activity of the titanium catalyst is changed. The titanium catalyst is introduced into the synthesis process of the prepolymer to prepare the PBT polyester titanium catalyst composite material system, and then the PBT polyester titanium catalyst composite material system is introduced into the reaction system of the PBT polyester; the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 0.1-9 KPa, the temperature is 160-260 ℃, and the time is 3-4 h; the pressure of the pre-polycondensation reaction is 105-7 KPa, the temperature is 260-265 ℃, and the time is 8-50 min.
In the method for preparing the titanium-based delustering PBT fiber, the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-2: 1, and the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-1.5, the final product is in a solid state; when the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is more than 1.5, the final product is in a slurry state; the dihydric alcohol in the dihydric alcohol dispersion liquid of the titanium catalyst is 1, 4-butanediol, the mass concentration of the dihydric alcohol dispersion liquid of the titanium catalyst is 35-70 wt%, and the mass of the titanium catalyst accounts for 10-20% of the sum of the masses of the dihydric alcohols in the component B and the component C.
A process for preparing titanium-based delustered PBT fiber as described above wherein the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalate and the dibasic acid ester is dimethyl terephthalate.
Has the advantages that:
(1) according to the method for preparing the titanium-based delustering PBT fiber, the PBT polyester prepolymer with the polymerization degree of 3-50 is adopted to wrap the catalyst, and the PBT polyester prepolymer can only melt at a higher temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation process and generated by the esterification reaction of the PBT polyester can be reduced or even avoided;
(2) according to the method for preparing the titanium-based extinction PBT fiber, the polyester prepolymer with the polymerization degree of 3-50 is adopted to wrap the catalyst, so that the influence of a dispersing agent in titanium dioxide on the catalyst is avoided, and the high activity of the catalyst is ensured;
(3) according to the method for preparing the titanium-based extinction PBT fiber, the polyester prepolymer with the polymerization degree of 3-50 is adopted to wrap the catalyst, so that the catalyst inhibits more side reactions, and the chromaticity L value and the b value of the polyester can be obviously improved.
Drawings
FIG. 1 is a WXRD pattern of a PBT polyester titanium catalyst composite system of example 7 of the invention.
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 a sheet titanium polyester catalyst comprises the steps of mixing terephthalic acid, ethylene glycol and n-butyl titanate with a molar ratio of 1:1.5:0.01, reacting for 0.5h at 150 ℃ and under 0.01MPa, heating to 200 ℃, continuing to react until the esterification degree reaches 70%, terminating the reaction, filtering while hot, and crushing and grinding to obtain the sheet titanium polyester catalyst with the average particle size of 0.5 mu m.
Examples 2 to 6
A process for preparing the flaky Ti-series polyester catalyst includes such steps as mixing BT, CT and DT in mole ratio AT, reacting GT AT ET and FT, heating to HT, reacting until the esterification degree reaches IT, filtering, and pulverizing.
Example 7
A preparation method of a PBT polyester titanium catalyst composite material system comprises the steps of firstly adding 1, 4-butanediol dispersion liquid of a sheet titanium polyester catalyst with the mass concentration of 30 wt% into a PBT polyester prepolymer melt with the polymerization degree of 3-8, and then uniformly stirring and cooling to obtain the PBT polyester titanium catalyst composite material system, wherein the sheet titanium polyester catalyst is prepared in example 1, and the mass content of the sheet titanium polyester catalyst in the PBT polyester titanium catalyst composite material system is 20 wt%; the PBT polyester titanium catalyst composite material system is subjected to a WXRD test, and the test result is shown in figure 1.
Examples 8 to 12
A preparation method of a PBT polyester titanium catalyst composite material system comprises the steps of firstly adding BN into a PBT polyester prepolymer melt with the polymerization degree of AN, uniformly stirring and cooling to obtain the PBT polyester titanium catalyst composite material system, wherein the BN is a titanium catalyst or a1, 4-butanediol dispersion liquid of the titanium catalyst, and the mass content of the titanium catalyst in the PBT polyester titanium catalyst composite material system is CN.
Example 13
A preparation method of a PBT polyester titanium catalyst composite material system comprises the steps of carrying out melt blending on a solid PBT polyester prepolymer with the polymerization degree of 25-35 and n-butyl titanate (catalyst) at the temperature of 150 ℃ for 2 hours, cooling and crushing to obtain the PBT polyester titanium catalyst composite material system, wherein the mass content of the n-butyl titanate in the PBT polyester titanium catalyst composite material system is 18 wt% respectively.
Examples 14 to 19
A preparation method of a PBT polyester titanium catalyst composite material system comprises the steps of carrying out melt blending on a solid PBT polyester prepolymer with polymerization degree of AS and a titanium catalyst at the temperature of BS (styrene-butadiene-styrene) for CS (styrene-butadiene-styrene), cooling and crushing to obtain the PBT polyester titanium catalyst composite material system, wherein the mass content of the titanium catalyst in the PBT polyester titanium catalyst composite material system is DS respectively.
Examples 20 to 24
A preparation method of a PBT polyester titanium catalyst composite material system comprises the steps of uniformly mixing A, B and C, and then carrying out esterification reaction, pre-polycondensation reaction and cooling to obtain the PBT polyester titanium catalyst composite material system, wherein A is dibasic acid (terephthalic acid, isophthalic acid or isophthalic acid-5-sodium sulfonate) or dibasic acid ester (dimethyl terephthalate), B is 1, 4-butanediol, C is a titanium catalyst or a1, 4-butanediol dispersion liquid of the titanium catalyst, the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-2: 1, the mass concentration of the 1, 4-butanediol dispersion liquid of the titanium catalyst is 35-70 wt%, the mass of the titanium catalyst accounts for 10-20% (D) of the sum of the mass of the dihydric alcohols in B and C, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 0.1-9 KPa, the temperature is 160-260 ℃ (the temperature is gradually increased), the time is 3-4 h, the pressure of the pre-polycondensation reaction is 105-7 KPa (the pressure is gradually reduced), the temperature is 260-265 ℃, the time is 8-50 min, and the mass content of the titanium catalyst in the PBT polyester titanium catalyst composite material system is 0.5-20 wt% (E).
Examples 25 to 42
The titanium-based delustering PBT fiber is prepared by adopting the polyester titanium catalyst composite material system prepared in the embodiment X, and the specific steps are as follows:
(1) mixing a PTA, BD and PBT polyester titanium catalyst composite material system and titanium dioxide, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure (P3) is 30-40 KPa, the temperature (T3) is 200-240 ℃, and the time (T3) is 100-120 min; wherein the molar ratio (molar ratio 1) of PTA to BD is 1: 1.1-2.5, the addition amount (addition amount 1) of the titanium catalyst contained in the PBT polyester titanium catalyst composite material system in the esterification reaction process is 50-150 ppm of the theoretical mass of the polymerization products of PTA and BD, and the addition amount (addition amount 2) of the titanium dioxide is 0.2-2.0 wt% of the theoretical mass of the polymerization products of PTA and BD;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure (P4) of the pre-polycondensation reaction is 10-20 KPa, the temperature (T4) is 240-250 ℃, and the time (T4) is 40-50 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain a titanium-based extinction PBT melt, wherein the pressure (P5) of the final polycondensation reaction is 90-110 Pa, the temperature (T5) is 250-264 ℃, and the time (T5) is 160-180 min; wherein the intrinsic viscosity (viscosity) of the titanium-based extinction PBT melt is 0.85-1.0 dL/g, the number of the agglomeration particles is 1.0-3.0/mg, the size of the agglomeration particles is 15-20 mu m, the chroma L value of the titanium-based extinction PBT resin is 80-90, and the b value is 4-7;
(4) slicing and spinning the titanium-based extinction PBT melt to obtain titanium-based extinction PBT fiber; wherein the technological parameters of the chip spinning are as follows: the spinning temperature (T6) is 283-285 ℃, the spinning speed (v1) is 3500-3900 m/min, the side blowing temperature (T7) is 25-30 ℃, the side blowing wind speed (v2) is 0.2-0.4 m/s, and the drafting multiplying power (a) is 3.8-4.2;
the parameters for examples 25 to 42 are specifically shown in Table 1-2.
Example 43
A process for preparing delustered titanium-based PBT fiber substantially the same as in example 25 except that the polyester titanium catalyst composite system and the amount thereof added in step (1) are changed to those added in step (2), and the specific parameters are shown in Table 2.
TABLE 1 parameters corresponding to examples 25 to 33
TABLE 2 parameters corresponding to examples 34 to 43
Comparative example 1
A method for preparing delustering titanium-based polyester fibers by melt direct spinning is basically the same as that in example 25, except that the catalyst used in the polyester synthesis process is the sheet-shaped titanium-based polyester catalyst prepared in example 1, but not the polyester titanium-based catalyst composite material system prepared in example 7, wherein the L value of the polyester melt prepared in the step (3) is reduced to 75, the intrinsic viscosity is reduced to 0.65, and the b value is increased to 7.3;
comparing example 25 with comparative example 1, it can be seen that, because the polyester prepolymer of the present invention is an intermediate for preparing a polyester melt, and has an intrinsically good compatibility with the intermediate system of the synthesized polyester melt, the polyester prepolymer of the present invention effectively prevents the sheet titanium polyester catalyst from agglomerating after being wrapped by the sheet titanium polyester catalyst, ensures the high dispersibility and high activity of the polyester catalyst, and accelerates the reaction process, the reaction efficiency of example 25 and comparative example 1 is higher under the same reaction conditions, and the viscosity and L value of the melt are higher.
Comparative example 2
The method for preparing delustered titanium-based polyester fiber by melt direct spinning is basically the same as that in example 30, except that the catalyst used in the polyester synthesis process is the n-butyl titanate used in example 13, but not the polyester titanium-based catalyst composite system prepared in example 13, the addition amount of the catalyst is 10ppm (by mass of titanium element) of the theoretical yield (mass) of ethylene terephthalate (namely, a polymerization product of terephthalic acid and ethylene glycol), the time of the polycondensation reaction is 110min, the L value of the prepared polyester chip is reduced to 73, the intrinsic viscosity is reduced to 0.60, and the b value is increased to 7.5.
Comparing example 30 with comparative example 2, it can be seen that, because the polyester titanium catalyst composite material of the present invention will only melt at the end of the esterification stage and at a higher temperature of the pre-polycondensation to release the titanium catalyst, the hydrolysis reaction of the titanium catalyst caused by the water contained in the storage and transportation process and generated by the polyester esterification reaction can be reduced or even avoided, and because the polyester prepolymer is an intermediate for preparing polyester chips, and has an intrinsically good compatibility with the intermediate system of the synthesized polyester chips, the agglomeration of the titanium catalyst is avoided, and the high dispersibility and high activity of the polyester catalyst are ensured, while the catalyst in comparative example 2 is not treated at all, is easily agglomerated, the catalyst in the interior can not contact with the reactants to play a role of catalysis, the catalytic efficiency is reduced, and the hydrolysis is easy to occur, so the reaction efficiency is inferior to example 30, this results in poorer luminance and chrominance of the slice compared to example 15.
Claims (10)
1. A method for preparing titanium-based delustering PBT fiber is characterized by comprising the following steps: synthesizing a titanium-based extinction PBT melt by using a PTA (pure terephthalic acid), BD (polybutylene terephthalate), PBT (polybutylene terephthalate) polyester titanium catalyst composite system and titanium dioxide as main raw materials, and slicing and spinning to obtain titanium-based extinction PBT fibers;
the PBT polyester titanium catalyst composite material system mainly comprises a PBT polyester prepolymer with the polymerization degree of 3-50 and a titanium catalyst dispersed in the PBT polyester prepolymer.
2. The method for preparing the titanium-based delustering PBT fiber is characterized by comprising the following specific steps of:
(1) mixing a PTA, BD and PBT polyester titanium catalyst composite material system and titanium dioxide, and then carrying out esterification reaction to obtain an esterification product, wherein the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 30-40 KPa, the temperature is 200-240 ℃, and the time is 100-120 min;
(2) carrying out pre-polycondensation reaction on the esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 20-10 KPa, the temperature is 240-250 ℃, and the time is 40-50 min;
(3) carrying out final polycondensation on the pre-polycondensation product to obtain a titanium-based extinction PBT melt, wherein the pressure of the final polycondensation reaction is 90-110 Pa, the temperature is 250-264 ℃, and the time is 160-180 min;
(4) and slicing and spinning the titanium-based extinction PBT melt to obtain the titanium-based extinction PBT fiber.
3. The method for preparing the titanium-based delustering PBT fiber as claimed in claim 2, wherein in the step (1), the molar ratio of PTA to BD is 1: 1.1-2.5, based on the mass of titanium element, the addition amount of the titanium catalyst contained in the PBT polyester titanium catalyst composite material system in the esterification reaction process is 50-150 ppm of the theoretical mass of the polymerization product of PTA and BD, and the addition amount of titanium dioxide is 0.2-2.0 wt% of the theoretical mass of the polymerization product of PTA and BD;
in the step (3), the intrinsic viscosity of the titanium-based extinction PBT melt is 0.85-1.0 dL/g, the number of the agglomeration particles is 1.0-3.0/mg, the chroma L value of the titanium-based extinction PBT resin is 80-90, and the b value is 4-7;
in the step (4), the technological parameters of the slice spinning are as follows: the spinning temperature is 283-285 ℃, the spinning speed is 3500-3900 m/min, the side blowing temperature is 25-30 ℃, the side blowing air speed is 0.2-0.4 m/s, and the drawing multiplying power is 3.8-4.2.
4. The method for preparing the titanium-based delustering PBT fiber as claimed in claim 1, wherein the mass content of the titanium catalyst in the PBT polyester titanium catalyst composite material system is 0.5-20 wt%.
5. The method for preparing the titanium-based delustering PBT fiber as claimed in claim 4, wherein the titanium-based catalyst is titanate, titanium dioxide particles treated or not hybridized, titanium glycol particles treated or not hybridized, or a sheet-shaped titanium-based polyester catalyst treated or not hybridized;
the sizes of the titanium dioxide particles, the ethylene glycol titanium particles and the sheet titanium polyester catalyst are in a nanometer or submicron level;
the titanium dioxide particles or the ethylene glycol titanium particles are porous particles or nonporous particles, and are spherical, ellipsoidal, flaky, rod-shaped or linear;
the structural general formula of the sheet titanium polyester catalyst is Tix(ORO)y(OOCC6H4COO)zH4Wherein R is C2～C4Z is more than or equal to 1, y + z is 2x +2, x is 4, and the flaky titanium polyester catalyst has a lamellar structure.
6. The method for preparing the titanium-based delustering PBT fiber as claimed in claim 5, wherein the preparation method of the PBT polyester titanium-based catalyst composite material system comprises the following steps: and melting and blending the solid PBT polyester prepolymer with the polymerization degree of 3-50 with a titanium catalyst, and cooling to obtain the PBT polyester titanium catalyst composite material system, wherein the temperature of the melting and blending is 150-270 ℃, and the time is 1.5-6 h.
7. The method for preparing the titanium-based delustering PBT fiber as claimed in claim 5, wherein the preparation method of the PBT polyester titanium-based catalyst composite material system comprises the following steps: adding a titanium catalyst or a dihydric alcohol dispersion liquid of the titanium catalyst into a PBT polyester prepolymer melt with the polymerization degree of 3-50, uniformly stirring and cooling to obtain the PBT polyester titanium catalyst composite material system, wherein the mass concentration of the dihydric alcohol dispersion liquid of the titanium catalyst is 30-70 wt%, and the dihydric alcohol is 1, 4-butanediol.
8. The method for preparing the titanium-based delustering PBT fiber as claimed in claim 5, wherein the preparation method of the PBT polyester titanium-based catalyst composite material system comprises the following steps: a, B and C are uniformly mixed and then are subjected to esterification reaction, pre-polycondensation reaction and cooling to obtain a PBT polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is a titanium catalyst or a dihydric alcohol dispersion of the titanium catalyst, and all the dihydric alcohol is 1, 4-butanediol; the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 0.1-9 KPa, the temperature is 160-260 ℃, and the time is 3-4 h; the pressure of the pre-polycondensation reaction is 105-7 KPa, the temperature is 260-265 ℃, and the time is 8-50 min.
9. The method for preparing the titanium-based delustering PBT fiber is characterized in that the molar ratio of the sum of the molar amounts of the dihydric alcohols in B and C to A is 1-2: 1, the dihydric alcohol in the dihydric alcohol dispersion liquid of the titanium-based catalyst is 1, 4-butanediol, the mass concentration of the dihydric alcohol dispersion liquid of the titanium-based catalyst is 35-70 wt%, and the mass of the titanium-based catalyst accounts for 10-20% of the sum of the mass amounts of the dihydric alcohols in B and C.
10. The method for preparing the titanium-based delustered PBT fiber as claimed in claim 8, wherein said dibasic acid is terephthalic acid, isophthalic acid or sodium 5-isophthalate, and said dibasic acid ester is dimethyl terephthalate.
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| US6437088B1 (en) * | 2001-08-14 | 2002-08-20 | E. I. Du Pont De Nemours And Company | Process for producing polyester with coated titanium dioxide |
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| CN104231238A (en) * | 2013-06-08 | 2014-12-24 | 中国石油化工股份有限公司 | Preparation method of PBT polyester for manufacturing delustering fibers |
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