CN109575262B - Production method of semi-dull titanium polyester - Google Patents

Production method of semi-dull titanium polyester Download PDF

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CN109575262B
CN109575262B CN201710904408.5A CN201710904408A CN109575262B CN 109575262 B CN109575262 B CN 109575262B CN 201710904408 A CN201710904408 A CN 201710904408A CN 109575262 B CN109575262 B CN 109575262B
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titanium
acid
phosphate
compound
semi
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CN109575262A (en
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周芬
熊金根
周文乐
王睿
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a production method of semi-dull titanium polyester, which mainly solves the problems of low intrinsic viscosity and yellow color value of polyester caused by the inhibition effect of a titanium dioxide flatting agent on the activity of a titanium polyester catalyst when the titanium dioxide flatting agent and the titanium polyester catalyst are simultaneously added into a polymerization system in the prior art. The invention adopts the heat stabilizer for preparing the semi-dull titanium polyester, and is characterized in that the heat stabilizer is a technical scheme of a reaction product of at least one phosphorus compound and at least one alcohol with 2-10 carbon atoms, so that the problem is better solved, and the heat stabilizer can be used in the industrial production of the semi-dull titanium polyester.

Description

Production method of semi-dull titanium polyester
Technical Field
The invention relates to a production method of semi-dull polyester.
Background
Polyethylene terephthalate (hereinafter referred to as polyester) is the largest variety of synthetic fibers. With the increasing development of global economy and the increasing improvement of the living standard of people, the textile and clothing industry is rapidly developed. The semi-dull polyester chips are the main raw materials of the textile fibers due to the characteristics of excellent dyeing property, processability and the like. The catalyst for polyester synthesis involves almost all main and subgroup elements except halogen elements and inert elements. Currently, the polyester catalysts which are industrially applied and researched more are mainly three series of antimony, germanium and titanium catalysts.
The antimony catalyst (comprising antimony trioxide, antimony acetate, ethylene glycol antimony and the like) is the most commonly used polyester catalyst in polyester industrial devices, more than 90 percent of polyester in the world is produced by the antimony catalyst at present, and the antimony catalyst is mainly adopted in the polyester devices in China. The disadvantages of this catalyst are: the antimony catalyst contains heavy metals to pollute the environment; the polymer is grey. The germanium catalyst has good stability, causes less side reactions in the reaction process, and the prepared polyester has good color phase, but has low resource and high price. The titanium polyester catalyst has high activity, but the polyester prepared by the titanium polyester catalyst has the problems of poor stability, yellowing and turbidity of products, so that the titanium polyester catalyst is not used on a large scale.
Under the background of more and more attention on human living environment in the world, the development general trend of the polyester catalyst is towards the development of environmental protection, high efficiency, low toxicity and no toxicity, the production and the sale of green products are the development trend of the polyester in the future, developed countries represented by European Union increasingly use whether the green product standard can be reached as the condition for entering the market, and through the development of more than 10 years, the European Union ecological label (Eco-label) is gradually accepted by European Union consumers, and the popularity of products with attached ecological signs is gradually improved.
The titanium polyester catalyst does not contain heavy metal, so that the problem of environmental pollution is solved; the catalyst has high activity, and can shorten the reaction time and improve the unit productivity. The polyester produced by the titanium polyester catalyst has increased transparency and reduced gray scale, can be used for producing high-grade films and packaging bottles, has the residual metal content of only one tenth of that of antimony in the polyester, and is more favorable for spinning.
Inorganic powder TiO2When added into polyester, the polyester has elegant luster and good extinction effect, and the fabric has the characteristics of deep dyeing, drapability and the like, and is widely applied to the field of clothing. But TiO 22Has a great inhibiting effect on the activity of the titanium catalyst. TiO 22The surface is rich in titanium hydroxyl Ti-OH to ensure that TiO2The surface is negatively charged, and the titanium active center is adsorbed by electrostatic attraction, so that the adsorption to TiO is limited2The activity range of the titanium active center on the surface makes the catalytic performance difficult to be fully exerted, so that the catalytic activity is reduced, the intrinsic viscosity of the polyester is low, and the color phase is yellow. Chinese patent CN102219894A believes that the addition of a sulfonic acid or sulfonate compound is effective in eliminating TiO2The flatting agent has the function of inhibiting the activity of the titanium polyester catalyst, but the sulfonic acid or sulfonate compound belongs to impurities in the polyester synthesis process and is not beneficial to post-processing such as polyester spinning, dyeing and the like. Chinese patent CN103539928A solves the problem of semi-dull titanium polyester productionThe hue of the polyester product is not shown when TiO is used2The specific implementation effect of the flatting agent and the titanium polyester catalyst are simultaneously added into the polymerization system, and the method for solving the problem of inhibiting the activity of the flatting agent on the titanium polyester catalyst is not mentioned.
Disclosure of Invention
One of the technical problems to be solved by the present invention is TiO existing in the prior art2TiO when the delustering agent and the titanium polyester catalyst are added into a polymerization system at the same time2The delustering agent has an inhibiting effect on the activity of a titanium polyester catalyst, so that the problems of low intrinsic viscosity and yellow color value of polyester are caused, and a novel heat stabilizer for preparing semi-dull titanium polyester is provided, and the heat stabilizer can effectively reduce TiO2The delustering agent has the inhibiting effect on the activity of the titanium polyester catalyst, and the prepared polyester has the advantages of high intrinsic viscosity and good color phase.
The second technical problem to be solved by the present invention is to provide a method for preparing a heat stabilizer for preparing a semi-dull titanium-based polyester, which solves the first technical problem.
The invention also provides a production method of the semi-dull titanium polyester, which is used for preparing the application method of the heat stabilizer of the semi-dull titanium polyester.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: the heat stabilizer for preparing the semi-dull titanium polyester is characterized by being a reaction product obtained by reacting at least one phosphorus compound with at least one alcohol with 2-10 carbon atoms.
In the above technical scheme, the alcohol having 2 to 10 carbon atoms is preferably a diol having 2 to 10 carbon atoms.
In the technical scheme, the molar ratio of the phosphorus compound to the alcohol is preferably 1 (1-10), and more preferably 1 (2-10).
In the above embodiment, the phosphorus compound is preferably at least one selected from the group consisting of an oxyacid of phosphorus, a salt of an oxyacid of phosphorus, and a phosphate ester.
In the above technical solution, the oxyacid of phosphorus is preferably at least one selected from phosphoric acid, pyrophosphoric acid, metaphosphoric acid and polyphosphoric acid; the salt of an oxyacid of phosphorus is preferably at least one selected from the group consisting of phosphate, pyrophosphate, metaphosphate, polyphosphate or acid salt of an oxyacid of phosphorus.
In the above technical solution, the oxyacid of phosphorus is preferably selected from phosphoric acid; the salt of the oxyacid of phosphorus is preferably at least one selected from the group consisting of sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, magnesium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, and zinc phosphate; the phosphate ester is preferably at least one selected from trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate and triphenyl phosphate.
In order to solve the second technical problem, the invention adopts the technical scheme that: the preparation method of the heat stabilizer comprises the following steps:
uniformly mixing a required amount of phosphorus compound with water, reacting the mixture with a required amount of dihydric alcohol containing 2-10 carbon atoms at the reaction temperature of 35-220 ℃ for 0.5-20 hours, and preparing a reaction product into a homogeneous alcohol-water mixed solution with the mass percent concentration of not less than 5% in terms of phosphorus element.
In the technical scheme, the reaction temperature is preferably 50-220 ℃.
In order to solve the third technical problem, the invention adopts the technical scheme that: a production method of semi-dull titanium polyester takes dicarboxylic acid and alkylene glycol as raw materials, a reaction product obtained by reacting a phosphorus compound with dihydric alcohol with 2-10 carbon atoms is added as a heat stabilizer at the beginning of esterification, esterification reaction is carried out at the reaction temperature of 230-280 ℃ and the reaction pressure of normal pressure to 0.5MPa to obtain an esterification product, and a titanium polyester catalyst and TiO are added2The flatting agent is subjected to polycondensation reaction at the reaction temperature of 250-320 ℃ and under the vacuum condition that the reaction pressure is less than 150Pa to obtain a polyester product, wherein the used titanium polyester catalyst comprises a reaction product obtained by reacting the following raw materials at the reaction temperature of 0-200 ℃ for 0.5-10 hours:
(A) a titanium compound having the general formula:
Ti(OR)4
r is selected from alkyl with 1-10 carbon atoms;
(B) selected from diols having 2 to 10 carbon atoms;
(C) at least one metal compound selected from IA of the periodic table;
(D) at least one metal compound selected from IIA, IB, IIB, VIIB and VIII in the periodic table of elements;
(E) at least one aliphatic organic acid selected from organic acids.
Wherein the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-8) to 1; the molar ratio of the metal compound (C) to the titanium compound (A) is (0.1-10) to 1; the molar ratio of the metal compound (D) to the titanium compound (A) is (0.1-20) to 1; the molar ratio of the aliphatic organic acid (E) to the titanium compound (A) is (1-20) to 1. The molar ratio of the heat stabilizer to the titanium compound (A) is preferably (0.1-10): 1.
in the technical scheme, the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is preferably (1-4) to 1; the molar ratio of the metal compound (C) to the titanium compound (A) is preferably (0.1-6) to 1; the molar ratio of the metal compound (D) to the titanium compound (A) is preferably (0.1-10) to 1; the molar ratio of the aliphatic organic acid (E) to the titanium compound (A) is preferably (1-15): 1. The molar ratio of the heat stabilizer to the titanium compound (A) is preferably (0.1-8): 1.
in the above technical solution, the dicarboxylic acid is at least one selected from terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and cyclohexanedicarboxylic acid; the alkylene glycol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol.
In the above technical solution, the titanium compound (a) is at least one compound selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; the dihydric alcohol (B) is at least one glycol selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol; the metal compound (C) is at least one of lithium, sodium or potassium compounds in IA in the periodic table of elements; the metal compound (D) is at least one selected from zinc, manganese, magnesium, calcium or cobalt compounds; the aliphatic organic acid (E) is at least one selected from citric acid, malic acid, tartaric acid, oxalic acid, succinic acid and lactic acid. The phosphorus compound as a reactant of the heat stabilizer is preferably at least one selected from phosphoric acid, sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, magnesium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate, zinc phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, and triphenyl phosphate; the reactant diol is preferably selected from diols having 2 to 10 carbon atoms. The catalyst is a homogeneous liquid catalyst and can be mutually soluble with ethylene glycol. The reaction temperature of the catalyst is preferably 10-180 ℃, and the reaction time is preferably 2-6 hours.
The preparation method of the heat stabilizer comprises the following steps:
the phosphorus compound is uniformly mixed with water, and then the mixture reacts with dihydric alcohol containing 2-10 carbon atoms at 35-220 ℃, preferably 50-220 ℃ for 0.5-20 hours, and the reaction product is prepared into homogeneous alcohol-water mixed solution with the mass percentage concentration of not less than 5% in terms of phosphorus element.
The preparation method of the liquid titanium catalyst comprises the following steps:
a) reacting a titanium compound with dihydric alcohol containing 2-10 carbon atoms to separate out a white precipitate, centrifugally separating a product after the reaction, washing the residue with distilled water, and drying the product in vacuum to obtain a white powdery substance;
b) adding at least one metal compound selected from IA in the periodic table of elements, at least one metal compound selected from IIA, IB, IIB, VIIB and VIII in the periodic table of elements and aliphatic organic acid into the white powdery substance obtained in the step a), and reacting to obtain the homogeneous liquid titanium catalyst.
The preparation method of the semi-dull polyester comprises the following steps:
can adopt the known polyester preparation method to prepare the dicarboxylic acidAcid and alkylene dihydric alcohol are used as raw materials, esterification reaction is carried out under the conditions that the reaction temperature is 230-280 ℃ and the reaction pressure is normal pressure-0.5 MPa to obtain prepolymer, and then polycondensation reaction is carried out under the vacuum condition that the reaction temperature is 250-320 ℃ and the reaction pressure is less than 100Pa to obtain the polyester product. A heat stabilizer is added before the esterification, a titanium polyester catalyst and TiO2The delustering agent is added into the polymerization kettle after the esterification and before the polycondensation reaction.
In the present invention, the intrinsic viscosity and hue of the semi-dull polyester are measured by the following methods:
a) intrinsic viscosity: the mixture of phenol and tetrachloroethane is used as solvent, and the measurement is carried out at 25 ℃ by using an Ubbelohde viscometer.
b) Hue: lab color difference measurements were performed using a color-view automatic colorimeter from BYK Gardner. For the present invention, a high L value and a low b value are desired.
The invention adopts a product prepared by reacting a phosphorus compound with dihydric alcohol containing 2-10 carbon atoms as a heat stabilizer, and adds Ti (OR)4The method for preparing the liquid titanium polyester catalyst by the reaction of the titanium compound, dihydric alcohol, at least one metal compound selected from IA in the periodic table of elements, at least one metal compound selected from IIA, IB, IIB, VIIB and VIII in the periodic table of elements and aliphatic organic acid comprises the steps of enabling metal ions of the titanium polyester catalyst to be firstly absorbed by TiO through competitive adsorption2Adsorption, reduce TiO2The adsorption to the titanium active center ensures that the activity of the titanium active center is not affected, higher intrinsic viscosity can be obtained within the same polycondensation time, and the titanium active center has better polymerization speed and better hue.
By adopting the technical scheme of the invention, the product prepared by reacting the phosphorus compound with the dihydric alcohol containing 2-10 carbon atoms is used as the heat stabilizer, the titanium polyester catalyst is adopted, the intrinsic viscosity of the prepared polyester can reach 0.708dL/g, the L value can reach 88.0, and the b value can reach 3.08, and the good technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ COMPARATIVE EXAMPLE 1 ]
Preparation of liquid titanium catalyst A
In a reactor equipped with a stirrer, a condenser and a thermometer, 24.8 g (0.4 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery substance was put in a reactor equipped with a stirrer, a condenser and a thermometer, and 50 g of ethylene glycol, 16 g of a 25% aqueous sodium hydroxide solution (0.1 mol), 128 g of magnesium acetate tetrahydrate (0.6 mol) and 9 g of lactic acid (0.1 mol) were added and reacted at 150 ℃ for 2 hours to obtain a homogeneous liquid as catalyst a.
Preparation of semi-dull polyester
500 g of refined terephthalic acid and 243 g of ethylene glycol are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, and water generated by the reaction is discharged through a rectifying device. After the end of the esterification, catalyst A (5 mg/kg of titanium atoms by weight based on the mass of polymer formed) and 3.15 g of TiO were added2And (3) vacuumizing and decompressing a titanium dioxide/ethylene glycol suspension liquid with the content of 55% until the system pressure is lower than 100Pa, gradually raising the reaction temperature to 280 ℃ at the same time, starting polycondensation, stopping the reaction after the reaction time reaches 150 minutes, continuously extruding a reaction product from a casting belt at the bottom of a polymerization kettle, cooling, and pelletizing for performance test. The test results are shown in Table 1.
[ example 1 ]
Preparation of Heat stabilizer B
9.9 g (0.1 mol) of phosphoric acid was dissolved in 21.2 g of water, and the solution was charged into a reactor equipped with a stirrer, a condenser and a thermometer, and 30.9 g of ethylene glycol was dropped into the reactor to carry out a reaction at 70 ℃ for 4 hours, thereby obtaining a heat stabilizer B.
Preparation of semi-dull polyester
500 g of purified terephthalic acid, 243 g of ethylene glycol and a heat stabilizer B (the molar ratio of phosphorus atoms to added titanium atoms is 0.1: 1) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst A (based on the mass of the generated polymer, the weight of titanium atoms is 5mg/kg) and 3.15 g of titanium dioxide/ethylene glycol suspension with the titanium dioxide content of 55%, vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually raising the reaction temperature to 280 ℃, starting the polycondensation reaction, stopping the reaction after the reaction time reaches 150 minutes, continuously extruding the reaction product from a casting belt at the bottom of the polymerization kettle, cooling, and pelletizing for performance test. The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
Preparation of liquid titanium catalyst C
In a reactor equipped with a stirrer, a condenser and a thermometer, 12.4 g (0.2 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery substance was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 50 g of ethylene glycol, 134.4 g of a 25% potassium hydroxide aqueous solution (0.6 mol), 214.5 g (1 mol) of magnesium acetate tetrahydrate and 135 g (1.5 mol) of lactic acid were added and reacted at 150 ℃ for 2 hours to obtain a homogeneous liquid as catalyst C.
Preparation of semi-dull polyester
A semi-dull polyester was produced in the same manner as in comparative example 1, using a liquid titanium-based catalyst C as a catalyst (the weight of titanium atom was 5mg/kg based on the mass of the polymer produced). The test results are shown in Table 1. [ example 2 ]
Preparation of semi-dull polyester
A semi-matte polyester was produced in the same manner as in example 1, using a heat stabilizer B (molar ratio of phosphorus atoms to titanium atoms added: 3: 1) and a liquid titanium catalyst C as a catalyst (weight of titanium atoms was 5mg/kg based on the mass of the polymer produced). The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
Preparation of liquid titanium catalyst D
In a reactor equipped with a stirrer, a condenser and a thermometer, 49.6 g (0.8 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 50 g of ethylene glycol, 1.6 g of a 25% aqueous solution of sodium hydroxide (0.01 mol), 429 g (2 mol) of magnesium acetate tetrahydrate and 189 g (0.9 mol) of citric acid monohydrate were added and reacted at 150 ℃ for 2 hours to obtain a homogeneous liquid as catalyst D.
Preparation of semi-dull polyester
A semi-dull polyester was produced in the same manner as in comparative example 1, using a liquid titanium-based catalyst D as a catalyst (the weight of titanium atom was 5mg/kg based on the mass of the polymer produced). The test results are shown in Table 1.
[ example 3 ]
Preparation of Heat stabilizer E
Sodium dihydrogen phosphate (15.6 g, 0.1 mol) was dissolved in water (6.6 g), and the solution was charged into a reactor equipped with a stirrer, a condenser and a thermometer, and ethylene glycol (41.3 g) was added dropwise to the reactor to carry out a reaction at 170 ℃ for 3 hours, whereby a heat stabilizer E was obtained.
Preparation of semi-dull polyester
A semi-matte polyester was produced in the same manner as in example 1, using a heat stabilizer E (molar ratio of phosphorus atoms to titanium atoms added was 5: 1) and a liquid titanium catalyst D as a catalyst (weight of titanium atoms was 5mg/kg based on the mass of the polymer produced). The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 4 ]
Preparation of liquid titanium catalyst F
In a reactor equipped with a stirrer, a condenser and a thermometer, 12.4 g (0.2 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery substance was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 50 g of ethylene glycol, 44.8 g of a 25% aqueous solution (0.2 mol) of potassium hydroxide, 2.2 g (0.01 mol) of zinc acetate dihydrate and 27 g (0.3 mol) of lactic acid were added and reacted at 150 ℃ for 2 hours to obtain a homogeneous liquid as a catalyst F.
Preparation of semi-dull polyester
A semi-dull polyester was produced in the same manner as in comparative example 1, using a liquid titanium-based catalyst F as a catalyst (the weight of titanium atom was 5mg/kg based on the mass of the polymer produced). The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 5 ]
Preparation of semi-dull polyester
500 g of refined terephthalic acid, 243 g of ethylene glycol and trimethyl phosphate (the molar ratio of phosphorus atoms to added titanium atoms is 8: 1) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, and water generated by the reaction is discharged through a rectifying device. After the end of the esterification, catalyst F (5 mg/kg of titanium atoms by weight, based on the mass of polymer formed) and 3.15 g of TiO were added2And (3) vacuumizing and decompressing a titanium dioxide/ethylene glycol suspension liquid with the content of 55% until the system pressure is lower than 100Pa, gradually raising the reaction temperature to 280 ℃ at the same time, starting polycondensation, stopping the reaction after the reaction time reaches 150 minutes, continuously extruding a reaction product from a casting belt at the bottom of a polymerization kettle, cooling, and pelletizing for performance test. The test results are shown in Table 1.
[ example 4 ]
Preparation of Heat stabilizer G
18.2G (0.1 mol) of triethyl phosphate was dissolved in 12.7G of water, and the solution was charged into a reactor equipped with a stirrer, a condenser and a thermometer, and 31.0G of butanediol was dropped into the reactor to react at 200 ℃ for 3 hours, thereby obtaining a heat stabilizer G.
Preparation of semi-dull polyester
A semi-matte polyester was produced in the same manner as in example 1, using a heat stabilizer G (molar ratio of phosphorus atoms to titanium atoms added was 8: 1) and a liquid titanium catalyst F as a catalyst (weight of titanium atoms was 5mg/kg based on the mass of the polymer produced). The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 6 ]
Preparation of liquid titanium catalyst H
In a reactor equipped with a stirrer, a condenser and a thermometer, 49.6 g (0.8 mol) of ethylene glycol was added, 28.4 g (0.1 mol) of tetraisopropyl titanate was slowly dropped into the reactor to precipitate a white precipitate, the reaction was carried out at 70 ℃ for 2 hours, the product was centrifuged, and the residue was washed with distilled water 3 times, and the product was vacuum-dried at 70 ℃ to obtain a white powdery substance. The dried white powdery material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 50 g of ethylene glycol, 1.6 g of a 25% aqueous sodium hydroxide solution (0.01 mol), 429 g (2 mol) of magnesium acetate tetrahydrate, 189 g (0.9 mol) of citric acid monohydrate, and 78 g (0.5 mol) of sodium dihydrogen phosphate were added and reacted at 150 ℃ for 2 hours to obtain a homogeneous liquid as catalyst H.
Preparation of semi-dull polyester
A semi-matte polyester was produced in the same manner as in example 1, using a liquid titanium-based catalyst H as a catalyst (the weight of titanium atoms was 5mg/kg, based on the mass of the polymer produced). The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 7 ]
Preparation of a homogeneous liquid phosphorus Compound solution
Dissolving 9.9 g (0.1 mol) of phosphoric acid in 21.2 g of water, adding the solution into a reactor provided with a stirrer, a condenser and a thermometer, dripping 30.9 g of ethylene glycol into the reactor, and uniformly mixing the solution at room temperature (25-30 ℃) to obtain a homogeneous liquid solution of the phosphoric acid.
Preparation of semi-dull polyester
500 g of purified terephthalic acid, 243 g of homogeneous liquid solution of ethylene glycol and phosphoric acid (the molar ratio of phosphorus atoms to added titanium atoms is 0.1: 1) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, and water generated by the reaction is discharged through a rectifying device. After the esterification, adding a catalyst A (based on the mass of the generated polymer, the weight of titanium atoms is 5mg/kg) and 3.15 g of titanium dioxide/ethylene glycol suspension with the titanium dioxide content of 55%, vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually raising the reaction temperature to 280 ℃, starting the polycondensation reaction, stopping the reaction after the reaction time reaches 150 minutes, continuously extruding the reaction product from a casting belt at the bottom of the polymerization kettle, cooling, and pelletizing for performance test. The test results are shown in Table 1.
TABLE 1
Figure BDA0001423704840000111

Claims (8)

1. A production method of semi-dull titanium polyester is characterized in that dicarboxylic acid and alkylene glycol are used as raw materials, a heat stabilizer is added, esterification reaction is carried out at the reaction temperature of 230-280 ℃ and the reaction pressure of normal pressure-0.5 MPa to obtain an esterification product, a titanium polyester catalyst and a titanium dioxide delustering agent are added, polycondensation reaction is carried out at the reaction temperature of 250-320 ℃ and the reaction pressure of less than 150Pa to obtain a polyester product, wherein the used titanium polyester catalyst comprises the following raw material substances which react for 0.5-10 hours at the reaction temperature of 0-200 ℃:
(A) a titanium compound having the general formula:
Ti(OR)4
r is selected from alkyl with 1-10 carbon atoms;
(B) selected from diols having 2 to 10 carbon atoms;
(C) at least one metal compound selected from IA of the periodic table;
(D) at least one metal compound selected from IIA, IB, IIB, VIIB and VIII in the periodic table of elements;
(E) at least one aliphatic organic acid selected from organic acids;
the molar ratio of the dihydric alcohol (B) to the titanium compound (A) is (1-8) to 1; the molar ratio of the metal compound (C) to the titanium compound (A) is (0.1-10) to 1; the molar ratio of the metal compound (D) to the titanium compound (A) is (0.1-20) to 1; the molar ratio of the aliphatic organic acid (E) to the titanium compound (A) is (1-20) to 1; the molar ratio of the heat stabilizer to the titanium compound (A) is (0.1-10): 1;
the heat stabilizer is a reaction product of at least one phosphorus compound and at least one alcohol with 2-10 carbon atoms; the preparation method of the heat stabilizer comprises the following steps:
and (2) uniformly mixing the phosphorus compound with water, reacting the mixture with the dihydric alcohol with 2-10 carbon atoms at 50-220 ℃ for 0.5-20 hours, and preparing a reaction product into a homogeneous alcohol-water mixed solution with the mass percentage concentration of phosphorus element not less than 5% to obtain the heat stabilizer.
2. The method for producing a semi-dull titanium-based polyester according to claim 1, wherein in said heat stabilizer, said alcohol having 2 to 10 carbon atoms is a diol having 2 to 10 carbon atoms; the molar ratio of the phosphorus compound to the alcohol is 1 (1-10).
3. The process for producing a semi-dull titanium-based polyester according to claim 1, wherein said phosphorus compound is at least one selected from the group consisting of an oxyacid of phosphorus, a salt of an oxyacid of phosphorus, and a phosphate ester.
4. The process for producing a semi-dull titanium-based polyester according to claim 3, wherein said heat stabilizer is at least one member selected from the group consisting of phosphoric acid, pyrophosphoric acid, metaphosphoric acid and polyphosphoric acid; the salt of the oxyacid of phosphorus is selected from at least one of phosphate, pyrophosphate, metaphosphate, polyphosphate or acid salt of the oxyacid of phosphorus.
5. The process for producing a semi-dull titanium-based polyester according to claim 4, wherein in said heat stabilizer, said oxyacid of phosphorus is selected from the group consisting of phosphoric acid; the salt of the oxyacid of phosphorus is selected from at least one of sodium hydrogen phosphate, sodium dihydrogen phosphate, sodium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, potassium phosphate, magnesium hydrogen phosphate, magnesium dihydrogen phosphate, magnesium phosphate, calcium hydrogen phosphate, calcium dihydrogen phosphate and zinc phosphate; the phosphate ester is at least one selected from trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate and triphenyl phosphate.
6. The process for producing a semi-matte titanium-based polyester according to claim 1, wherein the dicarboxylic acid is at least one selected from the group consisting of terephthalic acid, phthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid and cyclohexanedicarboxylic acid; the alkylene glycol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol.
7. The process for producing a semi-dull titanium-based polyester according to claim 1, wherein the titanium compound (A) is at least one compound selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate and tetrabutyl titanate; the dihydric alcohol (B) is at least one glycol selected from ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol or 1, 6-hexanediol; the metal compound (C) is at least one of lithium, sodium or potassium compounds in IA in the periodic table of elements; the metal compound (D) is at least one selected from magnesium, calcium, copper, zinc, manganese, or cobalt compounds; the aliphatic organic acid (E) is at least one selected from citric acid, malic acid, tartaric acid, oxalic acid, succinic acid and lactic acid.
8. The process for producing a semi-dull titanium-based polyester according to claim 1, wherein the molar ratio of the diol (B) to the titanium compound (A) is (1 to 4): 1; the molar ratio of the metal compound (C) to the titanium compound (A) is (0.1-6) to 1; the molar ratio of the metal compound (D) to the titanium compound (A) is (0.1-10) to 1; the molar ratio of the aliphatic organic acid (E) to the titanium compound (A) is (1-15) to 1; the molar ratio of the heat stabilizer to the titanium compound (A) is (0.1-8): 1.
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