CN106280293B - Polyester composition and preparation method and application thereof - Google Patents
Polyester composition and preparation method and application thereof Download PDFInfo
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- CN106280293B CN106280293B CN201510311508.8A CN201510311508A CN106280293B CN 106280293 B CN106280293 B CN 106280293B CN 201510311508 A CN201510311508 A CN 201510311508A CN 106280293 B CN106280293 B CN 106280293B
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Abstract
The invention discloses a polyester composition with low generation speed of cyclic trimer and good heat resistance and hydrolysis resistance and a preparation method thereof. The polyester composition contains 10-100 ppm of antimony element and 10-400 ppm of barium element relative to the total amount of the polyester composition, the content of a cyclic trimer in the polyester composition is 0.2-0.8 wt%, the generation speed of the cyclic trimer in the polyester composition is 0.001-0.015 wt%/min when the cyclic trimer is melted at 300 ℃ under nitrogen, the hydrolysis resistance index delta COOH of the polyester composition is less than or equal to 45eq/t, and the heat resistance index% BB of the polyester composition is less than or equal to 0.9%, and the polyester composition can be applied to polyester products such as films.
Description
Technical Field
The invention relates to a polyester composition, a preparation method and application thereof, in particular to a polyester composition with low cyclic trimer content and good hydrolysis resistance.
Background
Polyesters, particularly polyethylene terephthalate (PET), polypropylene terephthalate (PPT), and polybutylene terephthalate (PBT), are widely used in the fields of fibers, films, resins, and the like because of their excellent mechanical properties, chemical properties, dimensional stability, and transparency.
In general, by-product oligomers are inevitably produced during the polymerization of the polyester, and the amount thereof is generally about 2wt% based on the total amount of the polyester. The oligomer mainly refers to a polymeric monomer, a dimer, a cyclic trimer and the like, wherein the cyclic trimer accounts for the most part and accounts for about 1wt% of the total amount of the polyester. The oligomer can cause pollution to some components on equipment such as a die, an exhaust port and a spinneret plate in the process of preparing a film or spinning, so that the frequency of cleaning and replacing the equipment is high, and the production efficiency is reduced.
In addition, the by-product cyclic trimer can be precipitated on the surface of the formed polyester product such as film, sheet and bottle to form white foreign matter, which causes the problems of unqualified formed product and quality reduction. When these polyester products are used in food packaging materials, the cyclic trimer can enter the food in the package, contaminating the food.
Due to the above problems, the person skilled in the art has now proposed several methods for reducing the cyclic trimer content of polyesters. One of the methods, for example, chinese patent CN101747531 discloses a composition for reducing/suppressing the content of polyester oligomer and a polyester composition, which removes a part of cyclic trimer by kneading polyester with chelating agent, boron salt, and amine compound. However, the polyester obtained by this method is likely to precipitate chelating agent, boron salt, etc. during the post-treatment at high temperature, and the effect of suppressing the regeneration of the cyclic trimer of the specific oligomer is not significant. In the second method, the obtained polyester is subjected to solid-phase polymerization or heat treatment under inert gas to reduce the content of cyclic trimer in the polyester, but the method can only reduce the content of initial cyclic trimer in the polyester, and cannot solve the problem of regeneration in the subsequent high-temperature processing environment. Another method, for example, Chinese patent CN102421820A, discloses poly (trimethylene terephthalate) pellets with reduced oligomers, which are prepared by removing cyclic trimer by extraction from polyester with an organic solvent, and which subsequently require the recovery of a large amount of organic solvent, and which are costly, cumbersome to operate and difficult to perform industrially.
Disclosure of Invention
The invention aims to provide a polyester composition which has low content of cyclic trimer, good effect of inhibiting the fusion regeneration of the cyclic trimer, good hydrolysis resistance and good heat resistance, and a preparation method thereof.
The technical solution of the invention is as follows:
a polyester composition contains 10-400 ppm of barium element relative to the total amount of the polyester composition and 10-100 ppm of antimony element relative to the total amount of the polyester composition, wherein the content of cyclic trimer in the polyester composition is 0.2-0.8 wt%, the generation speed of the cyclic trimer in the polyester composition is 0.001-0.015 wt%/min when the cyclic trimer is melted at 300 ℃ under nitrogen, the hydrolysis resistance index delta COOH of the polyester composition is less than or equal to 45eq/t, and the heat resistance index BB of the polyester composition is less than or equal to 0.9%.
The content of antimony element in the polyester composition is preferably 30-80 ppm relative to the total amount of the polyester composition. Meanwhile, the polyester composition preferably contains 10 to 100ppm of phosphorus element relative to the total amount of the polyester composition.
The polyester composition is preferably polyethylene terephthalate, polybutylene terephthalate or polytrimethylene terephthalate.
The invention also discloses a preparation method of the polyester composition, which comprises the steps of reacting aromatic dicarboxylic acid or esterified derivatives thereof with aliphatic diol to obtain micromolecules, carrying out polycondensation reaction on micromolecule polymers to obtain polyester, and finally carrying out solid-phase polymerization on the polyester to obtain the polyester composition, and is characterized in that: and adding an antimony compound and a barium compound in the polycondensation reaction stage, wherein the addition amount of the antimony compound is 12-105 ppm of the polyester composition in terms of antimony element, and the addition amount of the barium compound is 10-400 ppm of the polyester composition in terms of barium element.
Preferably, a stabilizer phosphorus compound is added in the polycondensation stage, and the addition amount of the stabilizer phosphorus compound is 12-125 ppm of the polyester composition in terms of phosphorus element.
The polyester composition has low content of cyclic trimer, good regeneration inhibition effect of the cyclic trimer when the cyclic trimer is melted at 300 ℃ in nitrogen atmosphere, good hydrolysis resistance and heat resistance, simple manufacturing method industry, easy operation, low processing cost, excellent heat resistance of the obtained polyester composition, and can be used for preparing films.
Detailed Description
There is a reversible reaction between linear polymers and cyclic trimers, in the case of PET, where the cyclic trimer is formed from two monomers (diacid/diacid ester and diol) of the polyester starting material. At a certain temperature, the content of the cyclic trimer in the polyester can reach an equilibrium saturation value, and after the equilibrium saturation value is reached, the content of the cyclic trimer cannot be increased. And the higher the temperature, the greater this equilibrium saturation value, i.e.the greater the content of cyclic trimer.
Although the method of reducing the cyclic trimer content in the polyester can reduce the cyclic trimer content in the polyester a little after the initial treatment, as mentioned above, the reaction for forming the cyclic trimer is an endothermic reaction, and the temperature of the polyester for subsequent use such as formation into fibers, films, etc. is inevitably higher than the melting point of the polyester, and the reaction proceeds toward the formation of the cyclic trimer until the equilibrium is reached.
The generation speed of the cyclic trimer is 0.001-0.015 wt%/min when the polyester composition is melted at 300 ℃ in a nitrogen atmosphere, and the generation speed can be better controlled within the range of 0.002-0.010 wt%/min by controlling the content of barium element and antimony element in the polyester composition. That is, the present invention provides a polyester composition that solves the problem of cyclic trimer regeneration in subsequent high temperature processing environments.
Usually, a certain amount of catalyst such as antimony catalyst is added in the polymerization reaction to satisfy the reactivity required for the polymerization reaction, and in order to protect the film-forming property of the polyester, some co-catalyst such as magnesium compound, calcium compound, etc. having relatively high polymerization activity is added, and the addition of such co-catalyst results in high regeneration rate of cyclic trimer in the polyester and poor heat resistance and hydrolysis resistance, whereas if these co-catalyst such as magnesium compound, calcium compound, etc. is not added, the film-forming property of the polyester composition is poor. The addition of the barium compound can ensure the film-forming property of the polyester composition and reduce the content of the cyclic trimer in the polyester and the regeneration speed of the cyclic trimer in the polyester during post-processing.
The polyester composition of the present invention contains 10 to 400ppm of a barium element derived from a barium compound relative to the total amount of the polyester composition. Unlike calcium compounds and magnesium compounds, barium compounds have low reactivity, and can ensure film-forming properties of polyesters while reducing the content of cyclic trimer in polyesters and the rate of regeneration of cyclic trimer in polyesters at the time of post-processing. The barium compound may be a fatty acid barium salt such as barium acetate or barium oxalate, barium carbonate, barium chloride, barium acetylacetonate, or the like, and barium acetate, barium oxalate, or barium propionate is preferable.
The content of antimony in the polyester composition is 10-100 ppm relative to the total amount of the polyester composition, and the antimony comes from an antimony catalyst. When the antimony content in the polyester composition is less than 10ppm, the activity of solid-phase polymerization is insufficient, and the content of cyclic trimer in the polyester composition is high and is more than 0.8 wt%. If the content of antimony is more than 100ppm, the polymerization activity of antimony is high due to the large amount of antimony catalyst, and the rate of formation of cyclic trimer is high, so that the effect of the present invention is not achieved. Preferably, the polyester composition has a minimum antimony content of 30ppm and a maximum antimony content of 80 ppm.
The polyester composition of the invention also preferably contains phosphorus element, and the content of the phosphorus element is 10-100 ppm relative to the total amount of the polyester composition. The phosphorus element comes from a stabilizer phosphorus compound added in the polyester reaction, such as phosphoric acid, trimethyl phosphate, triphenyl phosphate and the like. Phosphorus can reduce the regeneration rate of the cyclic trimer in the polyester composition, and the higher the content of phosphorus, the more obvious the effect of reducing the regeneration rate of the cyclic trimer is, but if too high, the speed of reducing the cyclic trimer in the solid phase polymerization is small, and the amount of the cyclic trimer in the polymer is higher than 0.8 wt%.
The polyester composition of the present invention is preferably polyethylene terephthalate, polybutylene terephthalate or polytrimethylene terephthalate.
The invention also discloses a preparation method of the polyester composition, which comprises the steps of reacting aromatic dicarboxylic acid or esterified derivatives thereof with aliphatic diol to obtain micromolecules, carrying out polycondensation reaction on micromolecule polymers to obtain polyester, and finally carrying out solid-phase polymerization on the polyester to obtain the polyester composition, and is characterized in that: and adding an antimony compound and a barium compound in the polycondensation reaction stage, wherein the addition amount of the antimony compound is 12-105 ppm of the polyester composition in terms of antimony element, and the addition amount of the barium compound is 10-400 ppm of the polyester composition in terms of barium element.
The barium compound may be a fatty acid barium salt such as barium acetate or barium oxalate, barium carbonate, barium chloride, barium acetylacetonate, or the like, and barium acetate, barium oxalate, or barium propionate is preferable.
Preferably, a stabilizer phosphorus compound is added in the polycondensation stage, and the addition amount of the stabilizer phosphorus compound is 12-125 ppm of the polyester composition in terms of phosphorus element. The stabilizer phosphorus compound can be any phosphorus-containing stabilizer known in the art that can be used in polyester reactions, such as phosphoric acid, trimethyl phosphate, triphenyl phosphate, and the like.
The antimony compound is a catalyst antimony compound, which is not particularly limited in the present invention, and may be an inorganic antimony compound or an organic antimony compound, such as antimony trioxide, antimony pentoxide, ethylene glycol antimony, and the like, and among them, antimony trioxide and ethylene glycol antimony are most preferable.
In order to obtain a polyester composition having a low content of an initial cyclic trimer, the production method of the present invention comprises solid-phase polymerization, wherein the solid-phase polymerization is carried out by heating the polyester at 100 to 180 ℃ for 0.5 to 8 hours under dry conditions to pre-crystallize the polyester, and then carrying out solid-phase polymerization at 190 to 235 ℃ under nitrogen flow or under reduced pressure for 1 to 50 hours to obtain a polyester composition chip.
The content of the cyclic trimer in the polyester composition is 0.2-0.8 wt%, and when the cyclic trimer in the polyester composition is melted at 300 ℃ under nitrogen, the hydrolysis resistance index delta COOH of the polyester composition is less than or equal to 45 eq/t. The polyester composition has a heat resistance index% BB of not more than 0.9%.
The polyester composition has low content of cyclic trimer, and the content of the cyclic trimer is 0.2-0.8 wt%; the regeneration inhibition effect of the cyclic trimer is good when the cyclic trimer is melted at 300 ℃ in a nitrogen atmosphere, and the generation speed is only 0.001-0.015 wt%/min; the polyester composition has good hydrolysis resistance and heat resistance, the hydrolysis resistance index delta COOH is less than or equal to 45eq/t, and the heat resistance index percent BB is less than or equal to 0.9 percent. The preparation method of the polyester composition is simple in industry, easy to operate and low in treatment cost, and the obtained polyester composition is excellent in heat resistance and can be used for preparing films.
The measurement method and evaluation method of each index of the present invention will be described below.
(1) Determination of cyclic trimer
Accurately weighing 0.1000g of polyester composition by adopting a liquid chromatography internal standard method, adding o-chlorophenol at 150 ℃ until the polyester composition is completely dissolved, then cooling, adding an internal standard solution of terphenyl/dichloromethane, adding a methanol solution to precipitate the polyester, and taking the solution after centrifugal separation to measure the oligomer.
(2) Carboxyl group Content (COOH)
The polyester chip was dissolved in a mixture of o-cresol and chloroform (70: 30 by weight), added with a bromothymol blue indicator, and then titrated with a 0.05N ethanol solution of potassium hydroxide, as measured by an optical titration method.
(3) Intrinsic Viscosity (IV)
0.8g of the polyester chips were dissolved in 10ml of an o-chlorophenol solution and tested at 25 ℃ by an automatic viscosity measuring apparatus (VTS-032UC) available from Koch.
(4) Rate of formation of cyclic trimer
Taking a proper amount of polyester composition to test the content of cyclic trimer in the polyester composition to be C3(0) (wt.%) the polyester composition was then heat treated at 300 ℃ for 30min and tested for its cyclic trimer content C3(30) (wt%), rate of regeneration of cyclic trimer (wt%/min) ([ C)3(30)－C3(0)]/30。
(5) Determination of phosphorus element and Metal element
After 5g of the polyester composition was melted on a hot stage, it was pressed into a plate shape by a hydraulic press and then tested by a fluorescent X-ray element analyzer.
(6) Heat resistance% BB
A small test tube was placed with 8g of the cut piece, and the cut piece was heated at 300 ℃ with nitrogen gas flowing therethrough for 8 minutes, 8 hours and 8 minutes, and the "η 0" treatment for 8 minutes and the "η t" treatment for 8 hours and 8 minutes were compared, and the ratio of ester bonds cleaved by thermal decomposition was determined in terms of the change in the number average molecular weight,
%BB=0.27×（1/「ηt」4/3—1/[η0」4/3）。
(7) diethylene glycol (DEG) content determination
Monoethanolamine is used as a solvent, and is mixed with 1, 6-ethylene glycol/methanol and then heated to be dissolved, and then methanol is added to be washed for 10 minutes by an ultrasonic washer. Then, an acid was added thereto to neutralize the reaction solution, and the filtrate was measured by a gas chromatograph (GC-14B manufactured by Shimadzu corporation, Japan) after filtration.
(8) Hydrolysis resistance index Δ COOH
A certain amount of polyester granules are placed in a sealed hydrolysis-resistant treatment system, treated for 4 hours under the conditions of 155 ℃ and 0.46MPa of water vapor, then the COOH of the treated sample is measured, and the change of the COOH of the polyester slices before and after treatment is compared.
Δ COOH = COOH (after heat treatment) -COOH (before heat treatment)
(9) Film forming property
The film forming property was judged by observing the adhesion property to a cold drum drawn after the polymer was discharged during the film forming process, and when the polymer was adhered to the cold drum and no peeling occurred, the film forming property was good as indicated by "○", when the polymer was occasionally peeled after being adhered to the cold drum but the film forming was not affected, the film forming property was good as indicated by "△", and when the polymer was peeled more from the cold drum or even could not be adhered to the cold drum and the film could not be formed, the film forming property was poor as indicated by "x".
The advantages of the present invention will be described in detail below with reference to the examples and comparative examples. The present invention is not limited to the following examples.
Some of the compounds referred to in the examples are shown below:
(1) terephthalic Acid (PTA): the grade is high purity, winnowing;
(2) ethylene Glycol (EG): BASF corporation;
(3) antimony trioxide (AO): japan essence ltd;
(4) ethylene glycol Antimony (AG): yangtai chemical Co., Ltd, Yangzhou;
(5) phosphoric Acid (PA): shanghai Haoho chemical Co., Ltd;
(6) barium acetate: (ii) alatin;
(7) barium oxalate: (ii) alatin;
(8) barium propionate: (ii) alatin;
(9) barium butyrate: (ii) alatin;
(10) barium carbonate: (ii) alatin;
(11) barium acetylacetonate: and (3) performing Aladdin.
Example 1
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 60ppm of the weight of the polyester composition in terms of antimony element, a catalyst AO which is equivalent to 200ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 30ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 18 hours to obtain a polyester composition.
A film making step: vacuum drying the prepared polyester composition at 130 ℃ for 7 hours, and adding the polyester composition into a double-screw extruder for melting and plasticizing; sending the melt after melting and plasticizing into a molding casting belt die, and forming a cooled and solidified non-extension film through a cold drum with the surface temperature of 25 ℃ by adopting an electrostatic printing method; preheating an unextended film at the temperature of 80 ℃, longitudinally stretching the unextended film by 3.5 times at the temperature of 85 ℃ to obtain a longitudinally stretched film, preheating the longitudinally stretched film at the temperature of 80 ℃, and transversely stretching the longitudinally stretched film by 5 times at the temperature of 90 ℃; subjecting the obtained biaxially oriented film to heat treatment at 230 ℃ for 10 seconds in a heat treatment apparatus, and then subjecting the biaxially oriented film to relaxation treatment at 230 ℃ in a 4% transverse direction; and finally, uniformly cooling and curling to obtain the biaxially oriented polyester film. In the film forming process, peeling occasionally occurs after the polymer is bonded to a cold drum, but the film forming is not affected, and the film forming property is good. The physical properties are shown in the attached table.
Example 2
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 20ppm of the weight of the polyester composition in terms of antimony element, a catalyst AO which is equivalent to 200ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 30ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 25 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 3
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 80ppm of the weight of the polyester composition in terms of antimony element, barium acetate which is equivalent to 400ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 100ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 17 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 4
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 30ppm of the weight of the polyester composition in terms of antimony element, barium acetate which is equivalent to 100ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 10ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 230 ℃ for 22 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 5
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 40ppm of the weight of the polyester composition in terms of antimony element, barium acetate which is equivalent to 20ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 50ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 210 ℃ for 26 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 6
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 60ppm of the weight of the polyester composition in terms of antimony element, a barium oxalate which is equivalent to 100ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 30ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 19 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 7
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AG which is equivalent to 60ppm of the weight of the polyester composition in terms of antimony element, a barium propionate which is equivalent to 100ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 30ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 210 ℃ for 24 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 8
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 80ppm of the weight of the polyester composition in terms of antimony element, barium acetate which is equivalent to 100ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 60ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 18 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 9
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AG which is equivalent to 60ppm of the weight of the polyester composition in terms of antimony element, a barium carbonate which is equivalent to 200ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 150ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 26 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 10
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AG which is equivalent to 100ppm of the weight of the polyester composition in terms of antimony element, a catalyst AG which is equivalent to 200ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 150ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 24 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 11
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AG which is equivalent to 100ppm of the weight of the polyester composition in terms of antimony element, a catalyst AG which is equivalent to 200ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 150ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 26 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Example 12
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AG which is equivalent to 100ppm of the weight of the polyester composition in terms of antimony element, a barium butyrate which is equivalent to 400ppm of the weight of the polyester composition in terms of metal barium element, and a stabilizer PA which is equivalent to 150ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 24 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Comparative example 1
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 60ppm of the weight of the polyester composition in terms of antimony element and a stabilizer PA which is equivalent to 30ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 18 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Comparative example 2
At the temperature of 250 ℃, 166 parts by weight of PTA and 71.3 parts by weight of EG are added into an esterification reaction kettle, the esterification reaction is carried out under normal pressure, when the esterification reaction is finished, the temperature in the esterification reaction kettle is 250 ℃, and water is fractionated to obtain the micromolecule polymer.
Adding a catalyst AO which is equivalent to 60ppm of the weight of the polyester composition in terms of antimony element, calcium acetate which is equivalent to 400ppm of the weight of the polyester composition in terms of metal calcium element, and a stabilizer PA which is equivalent to 30ppm of the weight of the polyester composition in terms of phosphorus element into the obtained small molecular polymer, starting to reduce the pressure and raise the temperature after 5min, reducing the pressure to about 300Pa after 1 hour, and raising the temperature to 290 ℃ after 1.5 hours; when the polycondensation reaction is finished, the pressure in the reaction kettle is about 200 Pa. The obtained polymer was further subjected to solid-phase polymerization at 220 ℃ for 18 hours to obtain a polyester composition. The procedure for the preparation of the film was the same as in example 1. The physical properties are shown in the attached table.
Attached watch
Claims (8)
1. A polyester composition characterized by: the polyester composition contains 10-400 ppm of barium element relative to the total amount of the polyester composition, 10-100 ppm of antimony element relative to the total amount of the polyester composition, the content of cyclic trimer in the polyester composition is 0.2-0.8 wt%, the generation speed of the cyclic trimer in the polyester composition is 0.001-0.015 wt%/min when the cyclic trimer is melted at 300 ℃ under nitrogen, and the hydrolysis resistance index delta COOH of the polyester composition is less than or equal to 45 eq/t; the content of the phosphorus element in the polyester composition is 10-100 ppm relative to the total amount of the polyester composition; the barium element is derived from barium acetate, barium oxalate, barium propionate, barium carbonate, barium acetylacetonate or barium butyrate; the antimony element is derived from a catalyst antimony compound; the phosphorus element is derived from a stabilizer phosphorus compound.
2. The polyester composition according to claim 1, wherein: the heat resistance index BB percent of the polyester composition is less than or equal to 0.9 percent.
3. The polyester composition according to claim 1, wherein: the barium element is derived from barium acetate, barium oxalate or barium propionate.
4. The polyester composition according to claim 1, wherein: the content of antimony element in the polyester composition is 30-80 ppm relative to the total amount of the polyester composition.
5. The polyester composition according to claim 1, wherein: the polyester in the polyester composition is polyethylene terephthalate, polybutylene terephthalate or polytrimethylene terephthalate.
6. A method for preparing the polyester composition of claim 1, comprising the steps of reacting an aromatic dicarboxylic acid or an esterified derivative thereof with an aliphatic diol to obtain a small molecule, performing polycondensation reaction on the small molecule polymer to obtain a polyester, and performing solid-phase polymerization on the polyester to obtain the polyester composition, wherein the method comprises the following steps: adding catalyst antimony compound and barium compound in the polycondensation reaction stage, wherein the addition amount of the catalyst antimony compound is 10-100 ppm of the polyester composition in terms of antimony element, and the addition amount of the barium compound is 10-400 ppm of the polyester composition in terms of barium element; adding a stabilizer phosphorus compound in the polycondensation stage, wherein the adding amount of the stabilizer phosphorus compound is 10-100 ppm of the polyester composition in terms of phosphorus element; the barium compound is barium acetate, barium oxalate, barium propionate, barium carbonate, barium acetylacetonate or barium butyrate.
7. The process for producing a polyester composition according to claim 6, wherein: the barium compound is barium acetate, barium oxalate or barium propionate.
8. Use of the polyester composition of claim 1 in a film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB742811A (en) * | 1953-04-30 | 1956-01-04 | Ici Ltd | Improvements in the manufacture of highly polymeric polymethylene terephthalates |
| CN1502657A (en) * | 2002-09-17 | 2004-06-09 | ������ѧ��ʽ���� | Polyester-based resin composition |
| CN1659231A (en) * | 2002-06-03 | 2005-08-24 | 东洋纺织株式会社 | Polyester composition and packaging material comprising the same |
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| KR100895634B1 (en) * | 2004-11-30 | 2009-05-07 | 아사히 가세이 케미칼즈 가부시키가이샤 | Polyester resin, molded object thereof, and processes for producing these |
| TWI386429B (en) * | 2008-05-06 | 2013-02-21 | Nanya Plastics Corp | A method of using inorganic titanium - PET polyester synthetic magnesium catalyst particles and Its Application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB742811A (en) * | 1953-04-30 | 1956-01-04 | Ici Ltd | Improvements in the manufacture of highly polymeric polymethylene terephthalates |
| CN1659231A (en) * | 2002-06-03 | 2005-08-24 | 东洋纺织株式会社 | Polyester composition and packaging material comprising the same |
| CN1502657A (en) * | 2002-09-17 | 2004-06-09 | ������ѧ��ʽ���� | Polyester-based resin composition |
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