CN111057227A - Polyester titanium catalyst composite material system and preparation method thereof - Google Patents
Polyester titanium catalyst composite material system and preparation method thereof Download PDFInfo
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- CN111057227A CN111057227A CN201911413994.9A CN201911413994A CN111057227A CN 111057227 A CN111057227 A CN 111057227A CN 201911413994 A CN201911413994 A CN 201911413994A CN 111057227 A CN111057227 A CN 111057227A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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Abstract
The invention relates to a polyester titanium catalyst composite material system and a preparation method thereof, wherein the preparation method comprises the following steps: (1) melting and blending a solid polyester prepolymer with the polymerization degree of 3-50 and an additive, and cooling; (2) adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 3-50, and then uniformly stirring and cooling; (3) before esterification reaction of a reaction system for synthesizing the polyester prepolymer, adding an additive or a dihydric alcohol dispersion liquid of the additive, and then performing esterification reaction, pre-polycondensation reaction and cooling, wherein the additive is a titanium catalyst, a stabilizer and a toner; the prepared polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 3-50 and a titanium catalyst dispersed in the polyester prepolymer. The method is simple and feasible, and the prepared product has good dispersibility and good stability.
Description
Technical Field
The invention belongs to the technical field of polyester catalysts, relates to a polyester catalyst composite material system and a preparation method thereof, and particularly relates to a polyester titanium catalyst composite material system and a preparation method thereof.
Background
Polyesters (PET and PBT, etc.) and their articles (resins, fibers, films and engineering plastics, etc.) are the largest, most widely used and fastest growing polymer products in the world. At present, the polyester material catalyst generally adopts an antimony catalyst, but the antimony is a heavy metal, is toxic and carcinogenic and is easy to migrate into a water body, so that the environment and the human health are endangered, and the research and the popularization of the high-quality antimony-free polyester resin catalyst are particularly important.
The catalyst which can be used for replacing antimony catalyst has the advantages and disadvantages as follows: the aluminum catalyst has poor stability and low activity, and is not easy to dissolve in ethylene glycol; the germanium catalyst has proper catalytic activity, but has small storage amount and high price; the tin catalyst is toxic and has poor product color value; the titanium catalyst has high activity, safety, environmental protection and feasible cost, the resin brightness, namely the chroma L value is high, the titanium catalyst is most feasible and most concerned in the aspect of replacing the antimony catalyst, but the problem that the hue of the resin is easy to be yellow needs to be solved, and the introduction of a phosphorus stabilizer or a toner is a main solution.
Commercial titanium-based catalysts include two broad classes: 1) the compound/dispersion liquid of the catalyst and the glycol is in a liquid state, such as: the catalyst has poor long-term stability and dispersion performance, so that the catalyst can generate agglomeration and particle enlargement phenomena in the transportation and storage processes, can influence the catalytic activity due to hydrolysis, is easy to deteriorate, and can generate hydrolysis reaction to a greater extent at the high temperature of the synthesized polyester to destroy the catalytic activity of the catalyst; 2) the solid powder of the catalyst is introduced into a polyester synthesis system by preparing an ethylene glycol dispersion liquid during application, the catalytic activity of titanium element is generally regulated by introducing a certain proportion of Si element, and the particle size is designed to be micron-sized so as to inhibit the agglomeration of particles, but the catalyst still has the following defects: firstly, because the particle size of the solid catalyst is further increased undoubtedly when compounds of other elements such as Si element are introduced, the particle size of the catalyst is larger, and the dispersibility is not good; secondly, in order to improve the dispersion effect of the solid catalyst, researchers often modify the solid catalyst by methods such as surface modification, and the like, so that the process is complex and the cost is high; thirdly, hydrolysis reaction can occur to a large extent at high temperature for synthesizing polyester, so that the catalytic activity of the catalyst is destroyed; fourthly, other substances containing heavy metals, such as cobalt substances, are often introduced when the chromaticity b value is regulated, so that the aim of synthesizing the heavy metal-free polyester cannot be achieved.
Therefore, the research on the polyester titanium catalyst with good dispersibility and stability is of great significance.
Disclosure of Invention
The invention aims to overcome the problems in the prior art and provide a polyester titanium catalyst composite material system with good dispersibility and stability and a preparation method thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
the polyester titanium catalyst composite material system mainly comprises a polyester prepolymer with the polymerization degree of 3-50 and a titanium catalyst dispersed in the polyester prepolymer.
The polyester titanium catalyst in the prior art mainly comprises titanate, ethylene glycol titanium particles, silicon dioxide particles, a flaky titanium catalyst and the like, and has the problem of poor dispersibility in the polyester catalytic synthesis process, the catalyst is wrapped by the prepolymer with the polymerization degree of 3-50 as a carrier, the agglomeration is effectively avoided, the problem is solved, the melting point of the polyester prepolymer is higher, and the prepolymer is only melted at a higher temperature to release the catalyst in the polyester synthesis process, so that the secondary agglomeration phenomenon in the transportation or storage process can be avoided, meanwhile, the polyester prepolymer is an intermediate for preparing the polyester high polymer, and has intrinsic good compatibility with an intermediate system for synthesizing the high polymer, so the polyester prepolymer can present high dispersibility in the polyester synthesis process; in addition, the titanate and ethylene glycol titanium catalysts can influence the catalytic activity due to hydrolysis during the esterification reaction, particularly, the hydrolysis is easy to cause the catalytic activity to be reduced or even lost under the action of high-temperature esterification reaction and water generated by the esterification reaction, the prepolymer with higher polymerization degree is used as a carrier, and because the melting point of the prepolymer is higher, the prepolymer only melts at the last stage of esterification and the higher temperature of pre-polycondensation during the polyester synthesis process to release the titanium catalyst and does not release at the lower temperature in the early stage of the esterification reaction, the reduction of the hydrolytic activity of the titanium catalyst caused by the hydrolysis reaction can be reduced or even avoided, and the prepared polyester titanium catalyst composite material has high stability and high activity; the polymerization degree of the prepolymer used as the carrier is not suitable to be too small or too large, if the polymerization degree of the polyester prepolymer is too small, and the melting point of the whole composite material system is too low, water generated in the esterification reaction of the polyester can cause hydrolysis reaction of a titanium catalyst, so that negative effects are brought; if the polymerization degree is too high, the melting point is too high, and the polymer cannot be melted into the reaction system well even when the polycondensation reaction temperature is reached, and it is difficult to fully exert the function of the catalyst.
As a preferred technical scheme:
the polyester titanium catalyst composite material system further comprises a stabilizer and a toner, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%. The scope of the present invention includes, but is not limited to, stabilizers and toners that may not be included in the present invention.
The polyester titanium catalyst composite material system is prepared by mixing the titanium catalyst, the titanium dioxide particles, the ethylene glycol titanium particles or the sheet titanium catalyst with organic or inorganic components, and performing chemical or physical surface coating or doping modification on the particles, such as surface modification by using a general organic coupling agent, surface coating or composition hybridization of silicon dioxide or aluminum oxide, and doping of other metal elements;
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 that the temperature is 150-280 ℃ and the pressure is 0.01-0.4 MPa, specifically comprising the steps of controlling the temperature to react for 0.5-2.0 h under the condition that the temperature is 150-250 ℃, then heating to 200-280 ℃ to continue the reaction, stopping 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 ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol;
the stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl octyl phosphate, phosphoric acid and phosphorous acid, and can also be used in other conventional polyester synthesis processes;
the toner is a blueing agent (e.g., Issman chemical OB-1, Clainen, Germany, solvent blue 45, Ciba Irganox 1425, Ciba Irgamod 195, Germany) or a reddening agent (e.g., Prewan, Clariant, Germany, Red GFP), and may also be a toner used in other conventional polyester synthesis processes.
The invention also provides a method for preparing the polyester titanium catalyst composite material system, which is characterized in that the solid polyester prepolymer with the polymerization degree of 3-50 is melted, blended and cooled with the titanium catalyst, the stabilizer and the toner to prepare the solid polyester titanium catalyst composite material system.
As a preferred technical scheme:
according to the method, the temperature of melt blending is 100-270 ℃, the time is 1.5-6 hours, the temperature of melt blending mainly depends on the melting point of the solid polyester prepolymer, and the time of melt blending can be properly adjusted as long as uniform mixing is ensured.
The invention also provides another method for preparing the polyester titanium catalyst composite material system, which comprises the steps of adding an additive or a dihydric alcohol dispersion liquid of the additive into a polyester prepolymer melt with the polymerization degree of 3-50, uniformly stirring and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein the additive is a titanium catalyst, a stabilizer and a toner, the titanium catalyst, the stabilizer and the toner can be directly added, or can be added after being dispersed in dihydric alcohol, or can be partially added directly, or partially added after being dispersed in the dihydric alcohol, wherein the adding modes are all within the protection range of the invention, when the adding mode after being dispersed in the dihydric alcohol is adopted, when the mass ratio of the polyester prepolymer to the dihydric alcohol is more than 1, the final product is in a solid state; when the mass ratio of the polyester prepolymer to the dihydric alcohol is 0.5-1, the final product is in a slurry state.
As a preferred technical scheme:
according to the method, the mass concentration of the glycol dispersion liquid of the additive is 30-70 wt%; the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
The invention also provides a third method for preparing the polyester titanium catalyst composite material system, which comprises the steps of uniformly mixing A, B and C, and then carrying out esterification reaction, pre-polycondensation reaction and cooling to obtain a solid or slurry polyester titanium catalyst composite material system;
a is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is additive or dihydric alcohol dispersion of additive, additive is titanium catalyst, stabilizer and colour toner, titanium catalyst, stabilizer and colour toner can all adopt the way of adding directly, can all adopt and add the way of supplementing the remaining dihydric alcohol after dispersing in dihydric alcohol, can also partly adopt the way of adding directly, partly adopt and add the way after dispersing in dihydric alcohol, the above-mentioned modes of addition are all within the protective scope of the invention. In the polyester synthesis process in the prior art, a titanium catalyst, a stabilizer and a toner are added before esterification reaction, and the titanium catalyst, the stabilizer and the toner are subjected to system environment changes such as temperature, pressure and the like, and physical and chemical reactions may occur among each other or between the titanium catalyst, the stabilizer and a reaction monomer for preparing polyester, so that the catalytic activity of the titanium catalyst, the stabilizer and the toner is changed. The invention firstly introduces the titanium catalyst, the stabilizer and the toner into the synthesis process of the prepolymer to prepare the polyester titanium catalyst composite material system, and then introduces the polyester titanium catalyst composite material system into the polyester reaction system, and because the synthesis process of the prepolymer is similar to the esterification and polycondensation reaction of the polyester synthesis, after the esterification and pre-polycondensation reaction of the prepolymer, the catalytic activity and the efficiency of the polyester titanium catalyst composite material system can be further improved when the polyester titanium catalyst composite material system is used as the polyester catalyst.
As a preferred technical scheme:
in the method, the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-2: 1, when the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-1.5, the final product is in a solid state, and when the molar ratio of the sum of the molar amounts of the diols in B and C to A is more than 1.5, the final product is in a slurry state; b is the same as the dihydric alcohol in the dihydric alcohol dispersion liquid of the additive, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the titanium catalyst accounts for 10-20% of the mass sum of the dihydric alcohol in B and C;
the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2.0-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-50 min; the technological parameters of the esterification reaction and the pre-polycondensation reaction are not limited to the above, and the polymerization degree of the prepolymer is ensured to be 3-50.
In the method, the dibasic acid is terephthalic acid, isophthalic acid or sodium 5-sulfoisophthalate, the dibasic ester is dimethyl terephthalate, and the dihydric alcohol is ethylene glycol, 1, 3-propanediol or 1, 4-butanediol.
Has the advantages that:
(1) according to the polyester titanium catalyst composite material system, titanium dioxide particles, ethylene glycol titanium particles or sheet titanium polyester catalysts can keep smaller size (nano scale), have high dispersibility, high stability and high activity, and overcome the defects of larger particle size, easiness in hydrolysis and poor dispersibility of the catalysts in the prior art;
(2) the polyester titanium catalyst composite material system overcomes the defects that the common liquid catalyst is easy to hydrolyze in the presence of a liquid system and the catalytic activity is damaged by physical or chemical reaction with a stabilizer, a toner and the like in the subsequent use process, and has good stability;
(3) according to the polyester titanium catalyst composite material system, the carrier is a prepolymer synthesized by polyester, after the corresponding polyester synthesis system is introduced, the carrier participates in polyester synthesis reaction and enters a polyester polymer chain, other impurities are not introduced into the polyester synthesis system, and the obtained polyester resin is high in purity and good in quality;
(4) the polyester titanium catalyst composite material system adopts the polyester prepolymer as a carrier, utilizes the higher melting point of the polyester prepolymer to melt at the higher temperature of the pre-polycondensation to release the titanium catalyst, reduces or even avoids the negative influence caused by the reduction of the hydrolytic activity of the titanium catalyst caused by the hydrolysis reaction, and the prepared product has good stability;
(5) the preparation method of the polyester titanium catalyst composite material system has the advantages of simple process, low cost and good application prospect.
Drawings
FIG. 1 is an infrared spectrum (FTIR spectrum) of a composite system of the polyester titanium based catalyst of example 7 of the present 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 polyester titanium catalyst composite material system comprises the steps of firstly adding ethylene glycol dispersion liquid of a sheet-shaped titanium polyester catalyst with the mass concentration of 30 wt% into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of 3-8, and then uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the sheet-shaped titanium polyester catalyst is prepared from example 1, and the mass content of the sheet-shaped titanium polyester catalyst in the polyester titanium catalyst composite material system is 20 wt%.
0.1g of the polyester titanium catalyst composite system is dispersed in 30mL of water, after the mixture is heated and stirred for 3 hours at 70 ℃, the residual solid is washed by absolute ethyl alcohol and dried, and then the sample is subjected to FTIR characterization, as shown in figure 1, the crystal structure and characteristic groups of the sample of the polyester titanium catalyst composite system in the invention are not changed too much after the sample is treated by hot water, and the FTIR graph is also shown at 2924cm-1、2854cm-1Left and right CH2The vibration peak disappears, which indicates that the sample has better stability in water, and meanwhile, no stabilizer or toner is added in the above embodiment, so that the polyester titanium catalyst composite material system composed of the polyester prepolymer with the polymerization degree of 3-8 and the sheet titanium polyester catalyst has excellent stability.
Example 8
A preparation method of polyester chips comprises the steps of uniformly mixing terephthalic acid, ethylene glycol and the polyester titanium catalyst composite material system prepared in the embodiment 7, and then carrying out esterification reaction and polycondensation reaction to prepare the polyester chips, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 5:3, the addition amount of the polyester titanium catalyst composite material system is 10ppm (by mass of titanium element) of the theoretical yield (mass) of the ethylene glycol terephthalate (namely the polymerization product of the terephthalic acid and the ethylene glycol), the esterification reaction time is 2h, the esterification reaction temperature is 230 ℃, the polycondensation reaction time is 75min, the polycondensation reaction temperature is 280 ℃, the intrinsic viscosity of the prepared polyester chips is 0.678dL/g, the chroma L value is 90, and the b value is 6.9.
Comparative example 1
A polyester chip preparation method is basically the same as that in example 8, except that a 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, the polycondensation reaction time is 110min, the L value of the prepared polyester chip is 84.3, the b value is 6.35, and the intrinsic viscosity is 0.619 dL/g.
Comparing the example 8 with the comparative example 1, it can be seen that the polyester prepolymer of the invention is an intermediate for preparing polyester chips, which has an intrinsic good compatibility with the intermediate system of the synthesized polyester chips, and the polyester prepolymer wraps the sheet titanium polyester catalyst to effectively avoid the agglomeration of the sheet titanium polyester catalyst, thereby ensuring the high dispersibility and high activity of the polyester catalyst, shortening the time of the polycondensation reaction in the example 8, and further enabling the brightness, chromaticity and mechanical properties of the polyester chips prepared in the example 8 to be higher than those of the comparative example 1.
Examples 9 to 13
A preparation method of a polyester titanium catalyst composite material system comprises the steps of firstly adding BN into a polyester prepolymer (ethylene terephthalate prepolymer) melt with the polymerization degree of AN, uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the BN contains additives, the additives comprise a titanium catalyst, a stabilizer and a toner, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are CN, DN and EN.
Example 14
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with the polymerization degree of 25-35, n-butyl titanate (catalyst), triisopropyl phosphate (stabilizer) and Germany Ciba Irganox 1425 (toner) at the temperature of 100 ℃ for 2 hours, cooling and crushing to obtain the polyester titanium catalyst composite material system, wherein the mass contents of the n-butyl titanate, the triisopropyl phosphate and the Germany Ciba Irganox 1425 in the polyester titanium catalyst composite material system are respectively 18 wt%, 5 wt% and 4 wt%.
Example 15
A preparation method of polyester chips comprises the steps of uniformly mixing terephthalic acid, ethylene glycol and the polyester titanium catalyst composite material system prepared in the embodiment 14, and then carrying out esterification reaction and polycondensation reaction to prepare the polyester chips, wherein the mass ratio of the terephthalic acid to the ethylene glycol is 5:3, the addition amount of the polyester titanium catalyst composite material system is 10ppm (by mass of titanium element) of the theoretical yield (mass) of the ethylene glycol terephthalate (namely the polymerization product of the terephthalic acid and the ethylene glycol), the esterification reaction time is 2h, the esterification reaction temperature is 230 ℃, the polycondensation reaction time is 90min, the polycondensation reaction temperature is 280 ℃, the intrinsic viscosity of the prepared polyester chips is 0.dL/g, the chroma L value is 87, and the b value is 7.4.
Comparative example 2
A polyester chip was prepared in substantially the same manner as in example 15 except that the catalyst used in the synthesis of the polyester was the phosphitylated n-butyl titanate used in example 14, instead of the titanium polyester catalyst composite system prepared in example 14, the amount of the catalyst added was 10ppm (in terms of the mass of titanium element) of the theoretical yield (mass) of ethylene terephthalate (i.e., a polymerization product of terephthalic acid and ethylene glycol), the polycondensation reaction time was 110min, and the polyester chip obtained had an L value of 84.3, a b value of 7.9 and an intrinsic viscosity of 0.619 dL/g.
Comparing example 15 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 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, which has an inherently good compatibility with the intermediate system of the synthesized polyester chips, the agglomeration of the titanium catalyst is avoided, the high dispersibility and high activity of the polyester catalyst are ensured, the time of the polycondensation reaction in example 15 is shortened, while the catalyst in comparative example 2 is not treated at all, the agglomeration is easy to occur, the agglomerated catalyst in the interior can not contact with the reactants to play a role of catalysis, and the catalytic efficiency is reduced, hydrolysis also occurred easily, and thus the reaction time was prolonged, which resulted in poorer brightness and chroma of the slice than in example 15.
Comparative example 3
A process for producing polyester chips, substantially the same as in example 15, except that in the polyester synthesis using a phosphitylated n-butyl titanate as used in example 14 instead of the polyester titanium catalyst composite system obtained in example 14, when the same polyester having an intrinsic viscosity of 0.643dL/g was obtained, the minimum amount of n-butyl titanate added was 20ppm (in terms of the mass of titanium element) relative to the theoretical yield (mass) of ethylene terephthalate (i.e., a polymerization product of terephthalic acid and ethylene glycol).
Comparing example 15 with comparative example 3, it can be seen that the catalyst in comparative example 3 is not coated, and it is agglomerated in the reaction system, after agglomeration, the catalyst inside can not contact with the reactant to play the catalytic role, and it is easy to be deactivated by hydrolysis, so when the same catalytic role is reached, the amount of the catalyst is increased greatly.
Examples 16 to 21
A preparation method of a polyester titanium catalyst composite material system comprises the steps of melting and blending a solid polyester prepolymer (ethylene terephthalate prepolymer) with polymerization degree of AS with a titanium catalyst, a stabilizer and a toner at the temperature of BS (styrene-butadiene-styrene) for CS, cooling and crushing to obtain the solid polyester titanium catalyst composite material system, wherein the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are DS, ES and FS respectively.
Examples 22 to 26
A preparation method of a 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 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 dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, the additive is a titanium catalyst, a stabilizer and a toner, the molar ratio of the sum of the molar amounts of the dihydric alcohol in the B and the dihydric alcohol in the C to the molar amount of the dihydric alcohol in the A is 1-2: 1, B is the same as the dihydric alcohol in the glycol dispersion liquid of the additive (specifically ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol), the mass concentration of the dihydric alcohol dispersion liquid of the additive is 35-70 wt%, and the mass of the titanium catalyst accounts for 10-20% (D) of the sum of the mass of the dihydric alcohol in the B and the dihydric alcohol in the C, the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, the time is 2.0-2.5 h, the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, the time is 10-50 min, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite material system are respectively 0.5-20 wt% (E), 5-15 wt% (F) and 0.5-8 wt% (G).
Claims (10)
1. The polyester titanium catalyst composite material system is characterized in that: mainly comprises a polyester prepolymer with the polymerization degree of 3-50 and a titanium catalyst dispersed in the polyester prepolymer.
2. The polyester titanium catalyst composite system according to claim 1, wherein the polyester prepolymer further contains a stabilizer and a toner, and the mass contents of the titanium catalyst, the stabilizer and the toner in the polyester titanium catalyst composite system are 0.5 to 20 wt%, 5 to 15 wt% and 0.5 to 8 wt%, respectively.
3. The polyester titanium catalyst composite system according to claim 2, wherein the titanium catalyst is titanate, titanium dioxide particles with or without hybrid treatment, titanium glycol particles with or without hybrid treatment, or a sheet-like titanium polyester catalyst with or without hybrid 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, and the flaky titanium polyester catalyst has a lamellar structure;
the stabilizer is more than one of trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, triphenyl phosphate, tripropyl octyl phosphate, phosphoric acid and phosphorous acid;
the toner is a bluing agent or a reddening agent.
4. A process for preparing a polyester titanium based catalyst composite system according to any one of claims 1 to 3, characterized in that: and melting and blending the solid polyester prepolymer with the polymerization degree of 3-50 with a titanium catalyst, a stabilizer and a toner, and cooling to obtain the polyester titanium catalyst composite material system.
5. The method of claim 4, wherein the melt blending is performed at a temperature of 100 to 270 ℃ for 1.5 to 6 hours.
6. A process for preparing a polyester titanium based catalyst composite system according to any one of claims 1 to 3, characterized in that: and adding an additive or a dihydric alcohol dispersion liquid of the additive into the polyester prepolymer melt with the polymerization degree of 3-50, uniformly stirring and cooling to obtain the polyester titanium catalyst composite material system, wherein the additive is a titanium catalyst, a stabilizer and a toner.
7. The method according to claim 6, wherein the glycol dispersion liquid of the additive has a mass concentration of 30 to 70 wt%; the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
8. A process for preparing a polyester titanium based catalyst composite system according to any one of claims 1 to 3, characterized in that: a, B and C are mixed evenly and then are processed by esterification reaction, pre-polycondensation reaction and cooling to obtain a polyester titanium catalyst composite material system;
a is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is additive or dihydric alcohol dispersion of additive, the additive is titanium catalyst, stabilizer and colour toner.
9. The method according to claim 8, wherein the molar ratio of the sum of the molar amounts of the diols in B and C to A is 1-2: 1, B is the same as the diol in the diol dispersion liquid of the additive, the mass concentration of the diol dispersion liquid of the additive 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 diols in B and C;
the esterification reaction is carried out in a nitrogen atmosphere, the pressure is 100-400 KPa, the temperature is 180-260 ℃, and the time is 2.0-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 60-270 ℃, and the time is 10-50 min.
10. The method of claim 8, wherein the dibasic acid is terephthalic acid, isophthalic acid, or sodium 5-sulfoisophthalate, the dibasic ester is dimethyl terephthalate, and the glycol is ethylene glycol, 1, 3-propanediol, or 1, 4-butanediol.
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