CN111019106A - Titanium-based phosphorus-containing copolyester and preparation method thereof - Google Patents
Titanium-based phosphorus-containing copolyester and preparation method thereof Download PDFInfo
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- CN111019106A CN111019106A CN201911413968.6A CN201911413968A CN111019106A CN 111019106 A CN111019106 A CN 111019106A CN 201911413968 A CN201911413968 A CN 201911413968A CN 111019106 A CN111019106 A CN 111019106A
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- 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
- C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
- C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6926—Dicarboxylic acids and dihydroxy compounds
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- 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
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- 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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Abstract
The invention relates to a titanium-based phosphorus-containing copolyester and a preparation method thereof, wherein the preparation method comprises the following steps: synthesizing an esterification product by using a PTA, EG and polyester titanium catalyst composite material system as a main raw material, mixing the esterification product with a phosphorus-containing flame retardant monomer, and performing polycondensation to obtain titanium-based phosphorus-containing copolyester; the prepared titanium-based phosphorus-containing copolyester mainly comprises copolyester molecular chains and titanium catalysts dispersed among the molecular chains, wherein the copolyester molecular chains mainly comprise PTA chain segments, EG chain segments and phosphorus-containing flame retardant monomer chain segments, the LOI of the titanium-based phosphorus-containing copolyester is 34-36.6%, the SDR is 10-13, the UL-94 grade is V-0, and the sum of the fire extinguishing time and the smoke extinguishing time is 2-15 s. The preparation method of the titanium-based phosphorus-containing copolyester has the advantages of simple process, low cost and good application prospect; the titanium-based phosphorus-containing copolyester prepared by the preparation method has excellent flame retardant property.
Description
Technical Field
The invention belongs to the technical field of polyester, and relates to titanium-based phosphorus-containing copolyester and a preparation method thereof.
Background
Polyester, particularly polyethylene terephthalate (PET), has a wide range of applications due to its various excellent properties, and polyester fibers are the largest variety of synthetic fibers and have been leading the chemical fiber market, and therefore, without specific mention, the polyester fibers are mostly PET fibers. Due to the structural characteristics of textiles, textiles are the main materials causing fire, and therefore, the flame retardant performance of textile garments (such as evening wear, carpets, curtains, mattresses and the like) is more and more valued by people. In order to ensure the requirements of life and property safety of people, related technical laws and standards are established in many countries, requirements are made on the flame retardant performance of textiles such as evening wear, carpets, curtains and mattresses, and the textiles are tested according to the test method specified in the laws and regulations, so that commodities which do not meet the specified requirements are prohibited from being imported and sold.
At present, the titanium catalyst is applied to the direct esterification and continuous polycondensation polyester process, has the advantages of environmental protection, safety and high efficiency, greatly reduces the temperature in the synthesis and spinning process, reduces the energy consumption, simultaneously ensures that the physical and mechanical properties of the fiber are more uniform, improves the stability in the production process, and improves the utilization rate of materials.
Commercially available titanium-based catalysts include two main 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, methods such as surface modification are adopted, so that the process is complex and the cost is high; thirdly, it undergoes a large degree of hydrolysis reaction at the high temperature of the synthesis of polyester to destroy the catalytic activity of the catalyst.
Phosphorus flame retardants are often used for polyester flame retardant modification due to excellent flame retardant performance, and a common method is to introduce the phosphorus flame retardants into a polyester molecular chain as reaction monomers in an in-situ polymerization manner, but when the phosphorus flame retardants are introduced into a polyester polymerization reaction system, the phosphorus flame retardants have adverse effects on the activity of a titanium catalyst, so that in order to ensure the catalytic effect, the use amount of the titanium catalyst needs to be greatly increased, and the production cost is increased.
Therefore, a method for maintaining high dispersibility, high stability and high activity of the catalyst in the synthesis process of the titanium-based phosphorus-containing copolyester is urgently needed to be researched.
Disclosure of Invention
The invention aims to solve the problems of poor dispersity, poor stability and reduced activity of a titanium catalyst in the synthesis process of titanium-based phosphorus-containing copolyester in the prior art, and provides titanium-based phosphorus-containing copolyester and a preparation method thereof. According to the invention, the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 3-50, and the polyester prepolymer is only melted at a higher temperature to release the titanium catalyst, so that the hydrolysis reaction of the titanium catalyst which may occur can be reduced or even avoided, and the polyester prepolymer and an intermediate system of a synthesized polyester chip have intrinsic good compatibility, so that the agglomeration of the polyester prepolymer is avoided, and the high dispersibility and high activity of the polyester catalyst are ensured.
In order to achieve the purpose, the invention adopts the technical scheme that:
firstly, synthesizing an esterification product by using a PTA, EG and polyester titanium catalyst composite material system as a main raw material, mixing the esterification product with a phosphorus flame retardant monomer (containing a stabilizer, wherein the content of the stabilizer is 0.01-0.025 wt% of the esterification product), and then carrying out polycondensation reaction to obtain the titanium-based phosphorus-containing copolyester; 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 high, and the prepolymer is only melted at a high 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 the intermediate has good intrinsic 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;
when the traditional process is adopted to prepare the titanium-based phosphorus-containing copolyester, a stabilizer is generally required to be added, however, the existence of a phosphorus-containing flame retardant monomer and the stabilizer can cause the inactivation of a titanium catalyst, and in order to ensure the sufficient catalytic action, the dosage of the catalyst needs to be greatly increased, the phosphorus-containing flame retardant monomer and the stabilizer can not have adverse effects on the activity of the catalyst when the titanium-based phosphorus-containing copolyester is prepared by adopting the method disclosed by the invention, so that the dosage of the catalyst does not need to be greatly increased, the main reason for ensuring the activity of the catalyst under the condition of the phosphorus-containing flame retardant monomer and the stabilizer is that a polyester prepolymer with the polymerization degree of 3-50 is used for wrapping the catalyst, the polyester prepolymer can only be melted at a higher temperature to release the titanium catalyst, and thus the hydrolysis reaction of the titanium catalyst caused by water contained in the storage and transportation, the polyester prepolymer is an intermediate for preparing the polyester chip, and has intrinsic good compatibility with the intermediate system of the synthesized polyester chip, so that the agglomeration of the polyester prepolymer is avoided, and the high dispersibility and high activity of the polyester catalyst are ensured;
in addition, when the phosphorus-containing copolyester is prepared by adopting the traditional polymerization process, the catalyst is generally added into a pre-polycondensation kettle after the esterification reaction is finished, the main reason is that the catalyst is easy to hydrolyze under the action of high-temperature esterification reaction and water generated by the esterification reaction to reduce or even lose the catalytic activity, however, the catalyst also has the esterification catalytic action although mainly playing the polycondensation catalytic action, and the catalyst cannot play the esterification catalytic action and cannot fully play the effect of the catalyst after the esterification reaction is finished;
the catalyst can be added in the esterification reaction stage or after the esterification reaction, can play roles of esterification catalysis and polycondensation catalysis, and is mainly characterized in that the surface of the catalyst is wrapped by a polyester prepolymer with the polymerization degree of 5-30, and the prepolymer has a high melting point, so that the prepolymer can be melted only at the last stage of esterification and at the high temperature of pre-polycondensation to release a titanium catalyst in the polyester synthesis process, and cannot be released at the low temperature in the early stage of the esterification reaction stage, so that the catalyst activity reduction caused by hydrolysis reaction can be reduced or even avoided, the catalyst agglomeration can be avoided before the polymerization system is added, the problem of poor dispersibility is solved, and the prepolymer can be melted in the esterification reaction process to release the catalyst to enable the catalyst to have the esterification catalysis.
As a preferred technical scheme:
the preparation method of the titanium-based phosphorus-containing copolyester comprises the following specific steps:
(1) mixing PTA, EG and a polyester titanium catalyst composite material system, and then carrying out a first esterification reaction to obtain a first esterification product, wherein the first esterification reaction is carried out in a nitrogen atmosphere, the pressure is 150-400 KPa, the temperature is 180-210 ℃, and the time is 1-3 h;
(2) mixing the first esterification product and a phosphorus-containing flame retardant monomer, and then carrying out a second esterification reaction to obtain a second esterification product, wherein the pressure of the second esterification reaction is 150-400 KPa, the temperature is 180-210 ℃, and the time is 1-3 h;
(3) pre-polycondensation is carried out on the second esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 0.4-1.5 KPa, the temperature is 210-260 ℃, and the time is 1-3 h;
(4) and carrying out final polycondensation on the pre-polycondensation product to obtain the titanium-based phosphorus-containing copolyester, wherein the pressure of the final polycondensation reaction is 15-200 Pa, the temperature is 260-275 ℃, and the time is 1.5-5.5 h.
In the preparation method of the titanium-based phosphorus-containing copolyester, in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of a titanium catalyst contained in a polyester titanium catalyst composite material system in the first esterification reaction process is 10-20 ppm of the theoretical mass of a polymerization product of PTA and EG; in the traditional process, the titanium catalyst has the problems of phosphorus-containing flame retardant monomer, stabilizer and non-hydrolysis resistance, and the addition amount is about 20ppm of the theoretical mass of the PTA and EG polymerization products, and the comparison shows that the invention obviously reduces the addition amount of the catalyst, and the main reason is that the used prepolymer is only melted 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 polyester esterification reaction can be reduced or even avoided, and the adverse effect of the phosphorus-containing flame retardant monomer and the stabilizer on the catalyst is reduced;
in the step (2), the addition amount of the phosphorus-containing flame retardant monomer is 20-40 wt% of the theoretical mass of the polymerization product of PTA and EG, and the phosphorus-containing flame retardant monomer is CEPPA or DOPO-based flame retardant (DDP, DOPO-PHBA, TDCA-DOPO or TDCAA-DOPO);
in the step (4), the intrinsic viscosity of the titanium-based phosphorus-containing copolyester melt is 0.60-0.65 dL/g, the chroma L value of the titanium-based phosphorus-containing copolyester resin is 80-90, and the b value is 3.6-6.7; the chroma L value of the titanium-based phosphorus-containing copolyester prepared by the traditional process is generally 78-84, and the b value is generally 1-5, compared with the traditional process, the invention obviously improves the chroma L value and the b value of a polyester melt, and the main reason is that the polyester prepolymer is an intermediate for preparing polyester chips, and has intrinsic good compatibility with an intermediate system of the synthesized polyester chips, so that the agglomeration of the polyester prepolymer is avoided, the high dispersibility and the high activity of a polyester catalyst are ensured, and more side reactions are inhibited.
According to the preparation method of the titanium-based phosphorus-containing copolyester, the polyester prepolymer also contains a stabilizer and a toner, and the mass contents of the titanium-based catalyst, the stabilizer and the toner in the polyester titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%.
The preparation method of the titanium-based phosphorus-containing copolyester 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, ethylene glycol titanium particles subjected to or not subjected to hybridization treatment or a sheet-shaped 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 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;
the toner is a bluing 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., Poulvan OnColoredgeglo, Clariant, Germany, Red GFP).
The preparation method of the titanium-based phosphorus-containing copolyester comprises the following steps: 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 a solid polyester titanium catalyst composite material system, wherein the melting and blending temperature is 100-270 ℃, and the time is 1.5-6 h.
The preparation method of the titanium-based phosphorus-containing copolyester comprises the following steps: 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, can also be added after being dispersed in dihydric alcohol, can also be partially added directly, and can be partially added after being dispersed in the dihydric alcohol, the adding modes are all within the protection range of the invention, when the adding mode is adopted after being dispersed in the dihydric alcohol, 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; the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
The preparation method of the titanium-based phosphorus-containing copolyester comprises the following steps: a, B and C are mixed evenly and then are processed by esterification, pre-polycondensation and cooling to obtain a solid or slurry polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is additive or dihydric alcohol dispersion liquid of the additive, and the additive is titanium catalyst, stabilizer and toner; the titanium-based catalyst, the stabilizer and the toner may be added directly, or may be added after being dispersed in the glycol and then the remaining glycol is replenished, or may be added partially directly or partially after being dispersed in the glycol, and the above addition is within the scope of the present 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 in the synthesis process of the prepolymer to prepare a polyester titanium catalyst composite material system, and then introduces the polyester titanium catalyst composite material system into a polyester reaction system, and as the synthesis process of the prepolymer is similar to the esterification and polycondensation reaction of 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 a polyester catalyst; 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 2-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-50 min.
In the preparation method of the titanium-based phosphorus-containing copolyester, when 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, and 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; 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 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.
The invention also provides the titanium-based phosphorus-containing copolyester prepared by the preparation method of the titanium-based phosphorus-containing copolyester, which mainly comprises copolyester molecular chains and titanium catalysts dispersed among the molecular chains, wherein the copolyester molecular chains mainly comprise PTA chain segments, EG chain segments and phosphorus-containing flame retardant monomer chain segments, the LOI of the titanium-based phosphorus-containing copolyester is 34-36.6%, the SDR (smoke density rating) is 10-13, the UL-94 rating is V-0, and the sum of the fire extinguishing time and the smoke extinguishing time is 2-15 s.
Has the advantages that:
(1) according to the preparation method of the titanium-based phosphorus-containing copolyester, the catalyst is wrapped by the polyester prepolymer with the polymerization degree of 3-50, so that agglomeration is effectively avoided;
(2) according to the preparation method of the titanium-based phosphorus-containing copolyester, the phosphorus-containing flame retardant monomer and the stabilizer do not have adverse effect on the activity of the catalyst, so that the dosage of the catalyst is reduced;
(3) the preparation method of the titanium-based phosphorus-containing copolyester has the advantages of simple process, low cost and good application prospect;
(4) the titanium-based phosphorus-containing copolyester prepared by the preparation method has excellent flame retardant property.
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.
Examples 8 to 12
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 13
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 150 ℃ 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%.
Examples 14 to 19
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 20 to 24
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).
Examples 25 to 42
The titanium-based phosphorus-containing copolyester 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 PTA, EG and a polyester titanium catalyst composite material system, and then carrying out a first esterification reaction to obtain a first esterification product, wherein the first esterification reaction is carried out under a nitrogen atmosphere, the pressure (P3) is 150-400 KPa, the temperature (T3) is 180-210 ℃, and the time (T3) is 1-3 h; wherein the molar ratio (molar ratio 2) of PTA to EG is 1: 1.1-1.6, and the addition amount of the titanium catalyst contained in the polyester titanium catalyst composite material system in the first esterification reaction process is 10-20 ppm of the theoretical mass (titanium content) of the polymerization product of PTA and EG in terms of the mass of titanium element;
(2) mixing the first esterification product and the phosphorus-containing flame retardant monomer (A), and then carrying out a second esterification reaction to obtain a second esterification product, wherein the pressure (P4) of the second esterification reaction is 150-400 KPa, the temperature (T4) is 180-210 ℃, and the time (T4) is 1-3 h; wherein the addition amount of the phosphorus-containing flame retardant monomer is 20-40 wt% of the theoretical mass (addition amount 1) of the PTA and EG;
(3) pre-polycondensation is carried out on the second esterification product to obtain a pre-polycondensation product, wherein the pressure (P5) of the pre-polycondensation reaction is 1.5-0.4 KPa, the temperature (T5) is 210-260 ℃, and the time (T5) is 1-3 h;
(4) carrying out final polycondensation on the pre-polycondensation product to obtain titanium-based phosphorus-containing copolyester, wherein the pressure (P6) of the final polycondensation reaction is 15-200 Pa, the temperature (T6) is 260-275 ℃, and the time (T6) is 1.5-5.5 h; wherein the intrinsic viscosity of the titanium-based phosphorus-containing copolyester melt is 0.60-0.65 dL/g, the chroma L value of the titanium-based phosphorus-containing copolyester resin is 80-90, and the b value is 3.6-6.7.
The LOI of the prepared titanium-based phosphorus-containing copolyester is 34-36.6%, the SDR is 10-13, the UL-94 grade is V-0, and the sum of the fire extinguishing time and the smoke extinguishing time (t7) is 2-15 s;
the parameters of examples 25 to 42 are shown in Table 1-2 below.
Example 43
The procedure of titanium-based phosphorus-containing copolyester and the preparation method thereof were substantially the same as in example 25, except that the polyester titanium-based catalyst composite system and the amount thereof added in step (1) were changed to those in step (2), and the specific parameters thereof are shown in Table 2.
Example 44
The procedure of titanium-based phosphorus-containing copolyester and the preparation method thereof were substantially the same as in example 25, except that the polyester titanium-based catalyst composite system and the amount thereof added in step (1) were changed to those in step (3), and the specific parameters thereof are shown in Table 2.
Table 1 parameters corresponding to examples 25 to 34
Table 2 parameters corresponding to examples 35 to 44
Claims (10)
1. The preparation method of the titanium-based phosphorus-containing copolyester is characterized by comprising the following steps: synthesizing an esterification product by using a PTA, EG and polyester titanium catalyst composite material system as a main raw material, mixing the esterification product with a phosphorus-containing flame retardant monomer, and performing polycondensation to obtain titanium-based phosphorus-containing copolyester;
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.
2. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in claim 1, which comprises the following steps:
(1) mixing PTA, EG and a polyester titanium catalyst composite material system, and then carrying out a first esterification reaction to obtain a first esterification product, wherein the first esterification reaction is carried out in a nitrogen atmosphere, the pressure is 150-400 KPa, the temperature is 180-210 ℃, and the time is 1-3 h;
(2) mixing the first esterification product and a phosphorus-containing flame retardant monomer, and then carrying out a second esterification reaction to obtain a second esterification product, wherein the pressure of the second esterification reaction is 150-400 KPa, the temperature is 180-210 ℃, and the time is 1-3 h;
(3) pre-polycondensation is carried out on the second esterification product to obtain a pre-polycondensation product, wherein the pressure of the pre-polycondensation reaction is 1.5-0.4 KPa, the temperature is 220-260210-260 ℃, and the time is 1-3 h;
(4) and carrying out final polycondensation on the pre-polycondensation product to obtain the titanium-based phosphorus-containing copolyester, wherein the pressure of the final polycondensation reaction is 15-200 Pa, the temperature is 260-275 ℃, and the time is 1.5-5.5 h.
3. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in claim 2, wherein in the step (1), the molar ratio of PTA to EG is 1: 1.1-1.6, and the addition amount of the titanium-based catalyst contained in the polyester titanium-based catalyst composite material system in the first esterification reaction process is 10-20 ppm of the theoretical mass of the polymerization product of PTA and EG;
in the step (2), the adding amount of the phosphorus-containing flame retardant monomer is 20-40 wt% of the theoretical mass of the polymerization product of PTA and EG, and the phosphorus-containing flame retardant monomer is CEPPA or DOPO based flame retardant;
in the step (4), the intrinsic viscosity of the titanium-based phosphorus-containing copolyester melt is 0.60-0.65 dL/g, the chroma L value of the titanium-based phosphorus-containing copolyester resin is 80-90, and the b value is 3.6-6.7.
4. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in claim 1, wherein the polyester prepolymer further contains a stabilizer and a toner, and the mass contents of the titanium-based catalyst, the stabilizer and the toner in the polyester titanium-based catalyst composite material system are respectively 0.5-20 wt%, 5-15 wt% and 0.5-8 wt%.
5. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in claim 4, wherein the titanium catalyst is titanate, titanium dioxide particles treated or not hybridized, ethylene glycol titanium particles treated or not hybridized, or sheet titanium 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(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.
6. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in claim 5, wherein the preparation method of the polyester titanium-based catalyst composite material system comprises the following steps: 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 a polyester titanium catalyst composite material system, wherein the temperature of melting and blending is 100-270 ℃, and the time is 1.5-6 h.
7. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in claim 5, wherein the preparation method of the polyester titanium-based catalyst composite material system comprises the following steps: 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 polyester titanium catalyst composite material system, wherein the additive is a titanium catalyst, a stabilizer and a toner, the mass concentration of the dihydric alcohol dispersion liquid of the additive is 30-70 wt%, and the dihydric alcohol is ethylene glycol, 1, 3-propylene glycol or 1, 4-butanediol.
8. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in claim 5, wherein the preparation method of the polyester titanium-based catalyst composite material system comprises the following steps: a, B and C are mixed evenly and then are subjected to esterification reaction, pre-polycondensation reaction and cooling to prepare a polyester titanium catalyst composite material system, wherein A is dibasic acid or dibasic acid ester, B is dihydric alcohol, C is an additive or a dihydric alcohol dispersion liquid of the additive, and the additive is a titanium catalyst, a stabilizer and a toner; 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 2-2.5 h; the pressure of the pre-polycondensation reaction is 100-10 KPa, the temperature is 260-270 ℃, and the time is 10-50 min.
9. The preparation method of the titanium-based phosphorus-containing copolyester as claimed in 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 catalyst accounts for 10-20% of the sum of the mass amounts of the diols in B and C; 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.
10. The titanium-based phosphorus-containing copolyester prepared by the preparation method of the titanium-based phosphorus-containing copolyester as claimed in any one of claims 1 to 9 is characterized in that: the flame-retardant polyester mainly comprises a copolyester molecular chain and a titanium catalyst dispersed among the molecular chains, wherein the copolyester molecular chain mainly comprises a PTA chain segment, an EG chain segment and a phosphorus-containing flame retardant monomer chain segment, the LOI of the titanium-based phosphorus-containing copolyester is 34-36.6%, the SDR is 10-13, the UL-94 grade is V-0, and the sum of the fire extinguishing time and the smoke extinguishing time is 2-15 s.
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| US6013756A (en) * | 1995-05-23 | 2000-01-11 | Karl Fischer Industrieanlagen Gmbh | Process for producing polyesters using titanium-containing catalyst-inhibitor combinations |
| CN101121777A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Titanium series polyester catalyst |
| CN101235049A (en) * | 2008-03-03 | 2008-08-06 | 东华大学 | Titanium series organic compound material and its preparation and application |
| CN106700042A (en) * | 2016-12-14 | 2017-05-24 | 浙江恒逸高新材料有限公司 | Antimony-free environment-friendly flame retardant polyester chip and preparation method thereof |
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