CN109666135B - Preparation method of polyester resin with low acetaldehyde content - Google Patents
Preparation method of polyester resin with low acetaldehyde content Download PDFInfo
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- CN109666135B CN109666135B CN201710962753.4A CN201710962753A CN109666135B CN 109666135 B CN109666135 B CN 109666135B CN 201710962753 A CN201710962753 A CN 201710962753A CN 109666135 B CN109666135 B CN 109666135B
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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
- C08G63/183—Terephthalic acids
Abstract
The invention relates to a preparation method of polyester resin with low acetaldehyde content, which mainly solves the problem that the residual amount of acetaldehyde after injection molding of polyester products, especially bottle sheets, prepared by the prior titanium catalyst is high, and adopts a catalyst comprising the reaction product of the following raw material substances: 1) titanium compound a having the general formula: ti (OR)4(ii) a 2) Selected from diols B having 2 to 10 carbon atoms; 3) a metal compound C selected from group IA of the periodic Table of the elements; 4) at least one aliphatic organic acid D selected from organic acids; 5) at least one phosphate compound E selected from phosphorus compounds; 6) at least one metal compound F selected from IIA, IB, IIB, VIIB and VIII in the periodic table of elements; 7) the technical scheme of the nitrogen-containing compound G selected from organic amine or organic ammonium better solves the problem and can be used in the industrial production of the polyester resin with low acetaldehyde content.
Description
Technical Field
The invention relates to a preparation method of polyester resin with low acetaldehyde content.
Background
Polyethylene terephthalate is an important industrial raw material, and is widely used for materials such as fibers, films, sheets, bottles, and the like due to its excellent chemical and physical properties. It has excellent mechanical strength, chemical stability, gas barrier property, aroma retention property, hygienic degree, etc., is inexpensive and light in weight, and is particularly suitable for manufacturing beverage containers requiring heat sterilization filling.
At present, the polyester catalysts for industrial production and research are mainly antimony, germanium and titanium series catalysts, wherein the most common antimony catalysts used in polyester industrial devices (including antimony trioxide, antimony acetate, ethylene glycol antimony and the like) are more than 90% of the polyester produced by the antimony catalysts in the world at present, and the antimony catalysts are mainly adopted in the polyester devices in China. The metal antimony belongs to heavy metal elements, and when the resin produced by the catalyst is applied to the field of beverage containers, a problem can occur: the antimony based catalyst elutes from the container at high temperature, causing trace amounts of antimony to enter the beverage contained therein. 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 thermal stability, yellowing and turbidity of products, and acetaldehyde is easily decomposed under high temperature condition to generate acetaldehyde, so that the acetaldehyde enters the beverage filled in the beverage, and thus the titanium polyester catalyst is not used on a large scale.
Japanese patent laid-open No. 2000-143789 discloses a method of performing polymerization by adding a titanium compound and at least one compound selected from a magnesium compound, an aluminum compound, a barium compound and the like, but the above-disclosed method has a poor hue of the resulting polyester.
CN1328072 and CN1327985 disclose that a titanium ester and ethylene glycol react to form a granular titanium diol compound as a polyester catalyst, which may cause some application problems in the industrial production of polyester, and the acetaldehyde content of polyester prepared by using the catalyst is not reported in the patent.
CN101687984 discloses a solid phase polycondensation process for increasing the organic titanate catalyzed polyester with the addition of a hypophosphorous acid compound, wherein the polyester shows low acetaldehyde formation in melt processing, but there is no report on acetaldehyde content after solid phase polycondensation.
EP1013692 teaches that acetaldehyde is produced as a by-product during polycondensation and melt molding, and that titanium and certain metal compounds can be used as polycondensation catalysts to inhibit, while the specific amounts of titanium and metal atoms, such as magnesium, should be in a particular ratio.
CN1457343 teaches that polyesters with low acetaldehyde content can be prepared by adding titanium, magnesium, phosphorus containing compounds in the order phosphorus first followed by magnesium second followed by titanium, titanium and esterification followed by addition, which, according to the inventors' studies, provides a polyester with improved control of acetaldehyde formation, but has a significant drawback in polycondensation rate, especially in solid phase polycondensation rate.
CN1863839 teaches that polyesters with high solid phase polycondensation rates can be prepared using titanium, zinc, phosphorus and lactic acid as polycondensation catalysts, but no control of the acetaldehyde content of the resulting polyester is mentioned.
CN102002214A indicates that a low preform acetaldehyde can be obtained by adding a phosphorus-containing stabilizer and magnesium to a titanium-containing compound as a polycondensation catalyst, and simultaneously adding a certain phosphorus-and calcium-containing compound to increase the solid phase polycondensation rate.
CN101679620A teaches that titanium and phosphorus can be used as polycondensation catalysts, no acetaldehyde scavenger is added, and liquid phase polycondensation is used to obtain polyester suitable for producing bottled water, and free acetaldehyde in the polyester composition is low.
However, the products prepared by using the titanium catalyst of the above technology generally have the problems of yellow color and poor thermal stability after solid phase polycondensation, so that the acetaldehyde content of polyester products is high.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for preparing polyester resin with low acetaldehyde content, which solves the problem that the residual amount of acetaldehyde is high after the polyester prepared by the traditional titanium catalyst, particularly after injection molding. The method has the advantage of low residual acetaldehyde content.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a preparation method of polyester resin with low acetaldehyde content comprises the following steps:
a) using dicarboxylic acid and dihydric alcohol as raw materials, carrying out esterification reaction by adopting a titanium polyester catalyst under the conditions that the reaction temperature is 230-280 ℃ and the reaction pressure is normal pressure-0.5 MPa to obtain a prepolymer, and then carrying out melt polycondensation reaction under the vacuum condition that the reaction temperature is 250-320 ℃ and the reaction pressure is less than 150Pa to obtain a polyester product; the titanium polyester catalyst comprises the reaction product of the following raw materials which react for 0.5-10 hours at 0-200 ℃:
(1) titanium compound a having the general formula:
Ti(OR)4
r is selected from straight-chain or branched alkyl with 1-10 carbon atoms;
(2) selected from diols B having 2 to 10 carbon atoms;
(3) a metal compound C selected from group IA of the periodic Table of the elements;
(4) at least one aliphatic organic acid D selected from organic acids;
(5) at least one phosphate compound E selected from phosphorus compounds;
(6) at least one metal compound F selected from IIA, IB, IIB, VIIB and VIII in the periodic table of elements;
(7) a nitrogen-containing compound G selected from an organic amine or an organic ammonium;
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 is (0-10) to 1; the molar ratio of the aliphatic organic acid D to the titanium compound A is (1-20) to 1; the molar ratio of the phosphate compound E to the titanium compound A is (0-10) to 1; the molar ratio of the metal compound F to the titanium compound A is (0.1-20) to 1; the molar ratio of the nitrogen-containing compound G to the titanium compound A is (0.1-20) to 1;
b) after a polyester product obtained by melt polycondensation is subjected to pre-crystallization treatment, solid-phase polymerization is carried out at the reaction temperature of 200-250 ℃ in a nitrogen circulation state to obtain the polyester with the intrinsic viscosity of more than 0.8 deciliter/gram.
In the above technical scheme, the dicarboxylic acid is preferably at least one selected from terephthalic acid, phthalic acid, isophthalic acid, naphthalene dicarboxylic acid, biphenyl dicarboxylic acid, or cyclohexane dicarboxylic acid; the diol is preferably at least one selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, and 1, 4-cyclohexanedimethanol.
In the above technical scheme, the titanium compound a has a general formula shown in formula (I):
wherein R is1To R4Is independently selected from C1～C8A hydrocarbon group of (1). By way of example, the titanium compound A may be, for example, one selected from the group consisting of tetramethyl titanate, tetraethyl titanate, tetraethylhexyl titanate, tetrapropyl titanate, tetraisopropyl titanate or tetrabutyl titanate, tetraisooctyl titanateAt least one of them.
In the above technical solution, the diol B is preferably at least one selected from the group consisting of 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, ethylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, and diethylene glycol.
In the above technical solution, the group IA metal in the metal compound C is preferably at least one selected from lithium, sodium or potassium. The metal compound C is preferably a hydroxide, carbonate, bicarbonate or C2～C4Salts of carboxylic acids. More preferably, the metal compound C is selected from sodium hydroxide or potassium hydroxide.
In the above technical solution, the aliphatic organic acid D is preferably at least one selected from lactic acid, citric acid, malic acid, tartaric acid and oxalic acid.
In the above technical scheme, the phosphate ester compound E preferably has a general formula shown in formula (II):
wherein R is5、R6And R7Independently selected from H, C except that it cannot be H at the same time2～C6A hydrocarbon group of (1). For example, at least one selected from the group consisting of monomethyl phosphate, monoethyl phosphate, trimethyl phosphate, triethyl phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate and triphenyl phosphate may be used.
In the above technical solution, the metal compound F is preferably at least one selected from zinc, manganese, magnesium, calcium or cobalt compounds; such as at least one of magnesium acetate, zinc acetate, and cobalt acetate.
In the above technical solution, the nitrogen-containing compound G is preferably at least one selected from ammonium acetate, triethylamine, triammonium citrate and hexamethylenetetramine.
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 is preferably (1-10) to 1; the molar ratio of the aliphatic organic acid D to the titanium compound A is preferably (1-15): 1; the mol ratio of the phosphate ester phosphorus compound E to the titanium compound A is preferably (0-6) to 1; the molar ratio of the metal compound F to the titanium compound A is (0.1-20) to 1;
in the above technical solution, the molar ratio of the nitrogen-containing compound G to the titanium compound a is preferably (0.1 to 10) to 1.
In the technical scheme, the reaction temperature for preparing the titanium polyester catalyst is preferably 10-180 ℃, and the reaction time is preferably 2-6 hours. The amount of the catalyst added is preferably 1 to 20ppmw in terms of titanium atom based on the weight of the polyester product obtained by the melt polycondensation reaction.
The preparation method of the titanium polyester catalyst comprises the following steps:
adding a titanium compound into a required amount of 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 or VIII in the periodic table of elements, organic acid and phosphorus to react to obtain the homogeneous liquid titanium polyester catalyst.
The preparation method of the polyester comprises the following steps:
the method can adopt a known polyester preparation method, and comprises the first step of carrying out esterification reaction on dicarboxylic acid and dihydric alcohol to obtain a prepolymer, wherein the reaction temperature is 230-280 ℃, and the reaction pressure is normal pressure-0.5 MPa. And the second step is to carry out polycondensation reaction under high vacuum, wherein the reaction temperature is 250-320 ℃, and the reaction pressure is less than 150 Pa. The titanium polyester catalyst is added into the reaction system before the esterification reaction is started. And extruding and pelletizing after the reaction is finished.
Solid State Polymerization (SSP) method for polyester:
the polyester prepared by the method is further subjected to solid-phase polymerization to improve the viscosity. Before solid-phase polymerization, the polyester is pre-crystallized. And (3) heating the polyester particles prepared by the polyester preparation method in a vacuum environment at 80-130 ℃, preferably 90-120 ℃ for 1 minute-3 hours to dry. After drying, raising the temperature to 100-180 ℃, preferably 140-170 ℃ in an inert gas atmosphere or vacuum environment, and carrying out pre-crystallization for 1-10 hours, preferably 3-7 hours.
After the completion of the pre-crystallization, the pellets were fed to a solid phase polymerization apparatus and subjected to solid phase polymerization under a nitrogen flow. The reaction temperature is 200-250 ℃, preferably 210-230 ℃, and the nitrogen flow rate is 0-10L/min, preferably 1-5L/min. The equipment was warmed to the set value in 1 hour. The reaction time is 1 to 10 hours, preferably 3 to 8 hours.
In the present invention, the intrinsic viscosity, hue, acetaldehyde content (AA), and the like of the polyester are measured by the following methods:
(1) intrinsic viscosity: phenol-1, 1,2, 2-tetrachloroethane mixed solution (weight ratio 1: 1) was used as a solvent, and the measurement was carried out at 25 ℃ by using an Ubbelohde viscometer.
(2) Hue: the pellet samples were treated at 135 ℃ for 1 hour and measured for Hunter L value (lightness), a value (red-green hue) and b value (yellow-blue hue) using a color-view automatic color difference meter from BYK Gardner. Wherein, the higher the L value, the larger the brightness; when the value of b is high, the polyester chip is yellowish. For the present invention, a high L value and a low b value are desired.
(3) Acetaldehyde content (AA): after the polyester sample subjected to solid phase polycondensation was pulverized, 0.5g of the pulverized sample was accurately weighed and charged into a headspace bottle, and the air in the bottle was replaced with nitrogen and sealed. The headspace sampler furnace temperature was set at 150 ℃ and the equilibration time was 60 minutes. The acetaldehyde content of the samples was quantitatively analyzed by headspace sampling using a gas chromatograph (GC7890, Agilent).
The inventor surprisingly finds that the polyester prepared by the method has lower acetaldehyde content after solid-phase polymerization, the acetaldehyde content can be lower than 1ppmw, and better technical effect is achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Preparation of catalyst A
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 material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 50 g of ethylene glycol, 48 g of a 25 wt% aqueous sodium hydroxide solution (0.3 mol), 42.8 g (0.2 mol) of magnesium acetate, 42 g (0.2 mol) of citric acid monohydrate, 42 g (0.3 mol) of trimethyl phosphate and 15.4 g (0.2 mol) of ammonium acetate were added and reacted at a reaction temperature of 150 ℃ for 2 hours to obtain a nearly colorless homogeneous liquid as catalyst a.
Preparation of polyesters
600 g of terephthalic acid, 316 g of ethylene glycol and a catalyst A (based on the amount of the generated polyester, the weight of titanium atoms is 5ppmw) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the pressure is 0.25MPa, and water generated by the reaction is discharged through a rectifying device. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
Solid state polymerization of polyesters
Drying polyester particles obtained by liquid phase polycondensation under the conditions of a vacuum environment and 100 ℃, and raising the temperature to 160 ℃ after drying to perform pre-crystallization treatment for 6 hours. The treated particles were placed in a solid phase polymerization reaction apparatus and subjected to a solid phase polycondensation reaction of polyester at a nitrogen flow rate of 4L/min at 220 ℃ for 10 hours. And taking out after cooling.
And (3) carrying out injection molding on the granules in an HAAKE MINI JET injection molding machine under the conditions that the cavity temperature is 280 ℃, the mold temperature is 120 ℃, the injection molding pressure is 500bar and the holding pressure is 50 bar.
The test results are shown in Table 1.
[ example 2 ]
Polyester production and polyester solid-phase polymerization were carried out in the same manner as in example 1 except that the amount of ammonium acetate was changed to 38.5 g (0.5 mol).
The test results are shown in Table 1.
[ example 3 ]
Polyester production and polyester solid-phase polymerization were carried out in the same manner as in example 1 except that the amount of ammonium acetate was changed to 61.6 g (0.8 mol).
The test results are shown in Table 1.
[ example 4 ]
Polyester production and polyester solid-phase polymerization were carried out in the same manner as in example 1 except that the amount of ammonium acetate was changed to 77 g (1 mol).
The test results are shown in Table 1.
[ example 5 ]
Preparation of catalyst B
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, 32 g of a 25 wt% aqueous sodium hydroxide solution (0.2 mol), 42.8 g (0.2 mol) of magnesium acetate, 28 g (0.2 mol) of trimethyl phosphate, 63 g (0.3 mol) of citric acid monohydrate and 20.2 g (0.2 mol) of triethylamine were added and reacted at a reaction temperature of 150 ℃ for 2 hours to obtain a nearly colorless homogeneous liquid as catalyst B.
The polyester production and the solid-phase polymerization reaction of the polyester were carried out in the same manner as in example 1.
The test results are shown in Table 1.
[ example 6 ]
Preparation of 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, 48 g of a 35 wt% aqueous potassium hydroxide solution (0.2 mol), 42.8 g (0.2 mol) of magnesium acetate, 28 g (0.2 mol) of trimethyl phosphate, 63 g (0.3 mol) of citric acid monohydrate, 48.6(0.2 mol) of triammonium citrate were added and reacted at a reaction temperature of 150 ℃ for 2 hours to obtain a nearly colorless homogeneous liquid as catalyst C.
The polyester production and the solid-phase polymerization reaction of the polyester were carried out in the same manner as in example 1.
The test results are shown in Table 1.
[ example 7 ]
Preparation of catalyst D
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, 48 g of a 35 wt% potassium hydroxide aqueous solution (0.2 mol), 42.8 g of magnesium acetate (0.2 mol), 28 g of trimethyl phosphate (0.2 mol), 63 g of citric acid monohydrate (0.3 mol) and 28(0.2 mol) of hexamethylenetetramine were added and reacted at a reaction temperature of 150 ℃ for 2 hours to obtain a nearly colorless homogeneous liquid as a catalyst C.
The polyester production and the solid-phase polymerization reaction of the polyester were carried out in the same manner as in example 1.
The test results are shown in Table 1.
[ example 8 ]
Preparation of polyesters
600 g of terephthalic acid and 316 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 ℃, the pressure is 0.25MPa, and water generated by the reaction is discharged through a rectifying device. After the esterification is finished, reducing the pressure to normal pressure, adding a catalyst C (based on the amount of the generated polyester, the weight of titanium atoms is 5ppmw), stirring for 5min, vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, and then continuously extruding the reaction product from the bottom of a polymerization kettle in a strip shape, cooling and pelletizing.
The polyester pellets were subjected to solid-phase polymerization in the same manner as in example 1.
The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 1 ]
Preparation of catalyst E
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 material was placed in a reactor equipped with a stirrer, a condenser and a thermometer, and 50 g of ethylene glycol, 48 g of a 25 wt% aqueous sodium hydroxide solution (0.3 mol), 42.8 g (0.2 mol) of magnesium acetate, 42 g (0.2 mol) of citric acid monohydrate, and 42 g (0.3 mol) of trimethyl phosphate were added and reacted at a reaction temperature of 150 ℃ for 2 hours to obtain a nearly colorless homogeneous liquid as catalyst E.
Preparation of polyesters
600 g of terephthalic acid, 316 g of ethylene glycol and a catalyst E (based on the amount of the generated polyester, the weight of titanium atoms is 5ppmw) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the pressure is 0.25MPa, and water generated by the reaction is discharged through a rectifying device. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
Solid state polymerization of polyesters
Drying polyester particles obtained by liquid phase polycondensation under the conditions of a vacuum environment and 100 ℃, and raising the temperature to 160 ℃ after drying to perform pre-crystallization treatment for 6 hours. The treated particles were placed in a solid phase polymerization reaction apparatus and subjected to a solid phase polycondensation reaction of polyester at a nitrogen flow rate of 4L/min at 220 ℃ for 10 hours. And taking out after cooling.
And (3) carrying out injection molding on the granules in an HAAKE MINI JET injection molding machine under the conditions that the cavity temperature is 280 ℃, the mold temperature is 120 ℃, the injection molding pressure is 500bar and the holding pressure is 50 bar.
The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 2 ]
Preparation of polyesters
Mixing 600 g of terephthalic acid, 316 g of ethylene glycol, a catalyst E (based on the amount of the generated polyester, the weight of titanium atoms is 5ppmw), ammonium acetate (based on the mass number of 2 times of the molar amount of the titanium atoms), preparing into slurry, adding the slurry into a polymerization kettle, carrying out esterification reaction at the esterification temperature of 230-255 ℃ and the pressure of 0.25MPa, and discharging water generated by the reaction through a rectifying device. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
Solid state polymerization of polyesters
Drying polyester particles obtained by liquid phase polycondensation under the conditions of a vacuum environment and 100 ℃, and raising the temperature to 160 ℃ after drying to perform pre-crystallization treatment for 6 hours. The treated particles were placed in a solid phase polymerization reaction apparatus and subjected to a solid phase polycondensation reaction of polyester at a nitrogen flow rate of 4L/min at 220 ℃ for 10 hours. And taking out after cooling.
And (3) carrying out injection molding on the granules in an HAAKE MINI JET injection molding machine under the conditions that the cavity temperature is 280 ℃, the mold temperature is 120 ℃, the injection molding pressure is 500bar and the holding pressure is 50 bar.
The test results are shown in Table 1.
[ COMPARATIVE EXAMPLE 3 ]
Preparation of polyesters
600 g of terephthalic acid, 316 g of ethylene glycol and a catalyst E (based on the amount of the generated polyester, the weight of titanium atoms is 5ppmw) are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification temperature is 230-255 ℃, the pressure is 0.25MPa, and water generated by the reaction is discharged through a rectifying device. And after the esterification is finished, reducing the pressure to normal pressure, vacuumizing and reducing the pressure until the system pressure is lower than 100Pa, gradually increasing the reaction temperature to 280 ℃, stopping the reaction when the system reaction reaches 150min, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
Solid state polymerization of polyesters
Drying polyester particles obtained by liquid phase polycondensation under the conditions of a vacuum environment and 100 ℃, and raising the temperature to 160 ℃ after drying to perform pre-crystallization treatment for 6 hours. The treated pellets were mixed with ammonium acetate (mass number based on 2 times the molar weight of titanium atom), placed in a solid-phase polymerization apparatus, and subjected to a solid-phase polycondensation reaction of polyester at 220 ℃ under a nitrogen flow rate of 4L/min for 10 hours. And taking out after cooling.
And (3) carrying out injection molding on the granules in an HAAKE MINI JET injection molding machine under the conditions that the cavity temperature is 280 ℃, the mold temperature is 120 ℃, the injection molding pressure is 500bar and the holding pressure is 50 bar.
The test results are shown in Table 1.
TABLE 1
Claims (4)
1. A preparation method of polyester resin with low acetaldehyde content comprises the following steps:
a) using dicarboxylic acid and dihydric alcohol as raw materials, carrying out esterification reaction by adopting a titanium polyester catalyst to obtain a prepolymer, and then carrying out melt polycondensation reaction to obtain a polyester product; the titanium polyester catalyst comprises a reaction product obtained by reacting the following raw materials at 70-180 ℃ for 0.5-10 hours:
(1) a titanium compound A having the general formula shown below by formula (I):
wherein R is1To R4Is independently selected from C1~C8A hydrocarbon group of (a);
(2) a diol B selected from at least one of 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, ethylene glycol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, and diethylene glycol;
(3) a metal compound C selected from group IA of the periodic Table of the elements; wherein the group IA metal is selected from at least one of lithium, sodium or potassium;
(4) at least one aliphatic organic acid D selected from organic acids; the aliphatic organic acid D is at least one of lactic acid, citric acid, malic acid, tartaric acid or oxalic acid;
(5) at least one phosphate compound E selected from phosphorus compounds having a general formula shown in formula (II):
wherein R is5、R6And R7Independently selected from H, C except that it cannot be H at the same time2～C6A hydrocarbon group of (a);
(6) at least one metal compound F selected from IIA, IB, IIB, VIIB and VIII in the periodic table of elements; the metal compound F is at least one of zinc, manganese, magnesium, calcium or cobalt compounds;
(7) a nitrogen-containing compound G selected from an organic amine or an organic ammonium; the nitrogen-containing compound G is selected from at least one of ammonium acetate, triethylamine, triammonium citrate and hexamethylenetetramine;
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 is (0-10) to 1; the molar ratio of the aliphatic organic acid D to the titanium compound A is (1-20) to 1; the molar ratio of the phosphate compound E to the titanium compound A is (0-10) to 1; the molar ratio of the metal compound F to the titanium compound A is (0.1-20) to 1; the molar ratio of the nitrogen-containing compound G to the titanium compound A is (0.1-20) to 1;
b) performing solid phase polymerization on a polyester product obtained by melt polycondensation after pre-crystallization treatment to obtain the polyester resin with low acetaldehyde content, wherein the intrinsic viscosity of the polyester resin is more than 0.8 deciliter per gram;
the amount of the catalyst added is preferably 1 to 20ppmw in terms of titanium atom based on the weight of the polyester product obtained by the melt polycondensation reaction.
2. The method for preparing polyester resin with low acetaldehyde content according to claim 1, wherein the esterification reaction conditions are as follows: the reaction temperature is 230-280 ℃, and the reaction pressure is normal pressure-0.5 MPa; the conditions of the melt polycondensation reaction are as follows: the reaction temperature is 250-320 ℃, and the reaction pressure is less than 150 Pa; the solid-phase polymerization conditions are as follows: the reaction temperature is 200-250 ℃, and the reaction is carried out under the flow of inert gas.
3. The method for producing a polyester resin with a low acetaldehyde content as claimed in 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 dihydric alcohol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 4-cyclohexanedimethanol.
4. The method for preparing polyester resin with low acetaldehyde content as claimed in claim 1, wherein the metal compound F is at least one selected from magnesium acetate, zinc acetate, and cobalt acetate.
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| CN1457343A (en) * | 2001-02-06 | 2003-11-19 | 三菱化学株式会社 | Polyester resin and method for prodution thereof |
| CN1640932A (en) * | 2004-01-15 | 2005-07-20 | 远东纺织股份有限公司 | Polyester composition with low aldehyde content and its preparation method |
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| CN104558575A (en) * | 2013-10-28 | 2015-04-29 | 中国石油化工股份有限公司 | Production method of low-acetaldehyde titanium system polyester |
| CN106589340A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Method for producing low-acetaldehyde polyester product |
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| EP1818352A4 (en) * | 2004-11-30 | 2011-12-21 | Asahi Kasei Chemicals Corp | Polyester resin, molded object thereof, and processes for producing these |
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| CN1344754A (en) * | 2000-09-15 | 2002-04-17 | 因文塔-费希尔股份有限两合公司 | Process for production polyester with low content of free aldehyde |
| CN1457343A (en) * | 2001-02-06 | 2003-11-19 | 三菱化学株式会社 | Polyester resin and method for prodution thereof |
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