CN107955142B - Process for preparing isosorbide-containing polyesters - Google Patents
Process for preparing isosorbide-containing polyesters Download PDFInfo
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- CN107955142B CN107955142B CN201610902237.8A CN201610902237A CN107955142B CN 107955142 B CN107955142 B CN 107955142B CN 201610902237 A CN201610902237 A CN 201610902237A CN 107955142 B CN107955142 B CN 107955142B
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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
- C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
- C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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Abstract
The invention relates to a preparation method of polyester containing ethylene glycol, isosorbide and terephthalic acid, which mainly solves the problems that isosorbide is easy to decompose and has high loss rate in the polymerization process in the prior art. The preparation method of the isosorbide-containing polyester comprises the following steps: a) taking terephthalic acid and diol as raw materials, wherein the molar ratio of the diol to the terephthalic acid is 1.05: 1-1.3: 1, adding a catalyst, and carrying out esterification reaction at the esterification reaction temperature of 220-250 ℃ and the esterification reaction pressure of 10.4 KPa-0.5 MPa to obtain a prepolymer; b) the technical scheme of carrying out melt polycondensation on the obtained prepolymer under the vacuum condition that the melt polycondensation reaction temperature is 250-265 ℃ and the melt polycondensation reaction pressure is less than 150Pa to obtain a polymerization product better solves the problem and can be used for industrial production of polyester products containing isosorbide.
Description
Technical Field
The invention relates to a method for preparing polyester containing isosorbide by using an improved catalyst, which achieves the effects of reducing the reaction temperature, reducing the monomer decomposition and improving the retention ratio of isosorbide monomers which are difficult to participate in the reaction in the final polymer by changing the formula of the catalyst.
Background
1: 4; 3: 6-dianhydro-D-sorbitol, also known as isosorbide, is a polyester raw material that can be obtained by hydrogenation and acid-catalyzed dehydration of renewable resources such as sugar, starch, etc., and it can be polymerized with ethylene glycol and terephthalic acid to obtain polyethylene terephthalate co-isosorbide (PEIT). The polyester possesses a higher glass transition temperature (Tg) than conventional PET, which makes it useful in products such as bottles, heat-filled containers, films, thick sheets, fibers, wire, and optical articles. In these fields, the appearance is highly required, and isosorbide monomers are highly likely to form by-products with deteriorated color when reacted at high temperature, so that lowering the temperature for synthesizing PEIT is helpful to improve the product performance. Meanwhile, the isosorbide monomer is quite expensive relative to other polyester raw materials, and the behavior of forming a color-forming byproduct by heating in the synthesis process can cause extra loss of the isosorbide monomer, so that the proportion of isosorbide chain segments remained in the final polymer is far less than that of the input isosorbide, the extra cost is increased, and the economical efficiency of the polyester production is influenced.
CN99805312 reports a polyester production process using isosorbide as comonomer, and reports that a PEIT polymer having a logarithmic reduced viscosity of 0.65dl/g can be obtained by a direct synthesis process using an antimony, titanium or germanium catalyst for the synthesis of PEIT having a high reduced viscosity. The polycondensation reaction temperature of the polymerization is up to 275-285 ℃, and the retention rate of the isosorbide unit is lower than 60%.
CN03819324 reports a manufacturing method of a terephthalic acid-ethylene glycol-isosorbide copolyester polymer, which is characterized in that a light-colored PEIT polymer is prepared, a germanium dioxide catalyst is used, and cobalt acetate, Clariant @ RSB violet and the like are added for color mixing to obtain a product, namely the Hunter b value is less than 2. No mention is made in the patent of using a catalyst to lower the temperature required for the reaction, the retention of isosorbide units in the synthesized polymer being around 70%.
CN201110257448 reports a method for preparing PEIT by using a titanium catalyst, which is characterized in that an inner hydroxyl group and an outer hydroxyl group of isosorbide are respectively modified by using a halogenation reaction and p-toluenesulfonic acid chloride, the modified isosorbide can fully react with terephthalic acid, and the proportion of biologically-derived carbon in polyester can reach 33% -100%. The synthesis of the polyesters of the patent differs greatly from conventional polyesters and, although not mentioned herein, the yield and manufacturing cost of isosorbide must be affected by the use of multiple organic reactions for chemical modification of isosorbide. The process of this patent requires the use of solid state polymerization to achieve the target intrinsic viscosity.
None of the above reports report a preparation method in which a catalyst having a promoting effect on the reaction of isosorbide with terephthalic acid and an esterification product of terephthalic acid with a diol is used to obtain a desired molecular weight at a relatively low reaction temperature. The invention discloses a high-efficiency catalyst suitable for preparing isosorbide-containing polyester at a lower temperature and a method for preparing isosorbide-containing polyester by using the high-efficiency catalyst. Through the technical optimization of the invention, the polyethylene terephthalate co-isosorbide with isosorbide retention rate higher than 50% and intrinsic viscosity higher than 0.40dl/g can be prepared.
Disclosure of Invention
The invention aims to solve the technical problems of easy decomposition and high loss rate of isosorbide in the polymerization process in the prior art, and provides a preparation method of isosorbide-containing polyester, which has the advantages of effectively promoting the isosorbide to participate in polyesterification reaction at a lower reaction temperature, such as 250 ℃, reducing the loss of the isosorbide at a high temperature, and having the advantage of good isosorbide retention rate of the obtained polyester.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: a method for preparing isosorbide-containing polyester, comprising the steps of:
a) taking terephthalic acid and diol as raw materials, wherein the molar ratio of the diol to the terephthalic acid is 1.05: 1-1.3: 1, adding a catalyst, and carrying out esterification reaction at the esterification reaction temperature of 220-250 ℃ and the esterification reaction pressure of 10.4 KPa-0.5 MPa to obtain a prepolymer;
b) carrying out melt polycondensation on the obtained prepolymer under the vacuum condition that the melt polycondensation reaction temperature is 250-265 ℃ and the melt polycondensation reaction pressure is less than 150Pa to obtain a polymerization product;
wherein the diols comprise ethylene glycol and isosorbide.
In the above technical scheme, the polymerization product is polymerized in phenol-tetrachloroethane in a ratio of 60: 40 parts by weight of a solvent, and an intrinsic viscosity of not less than 0.50dl/g as measured at 25 ℃ with an Ubbelohde viscometer.
In the above scheme, the catalyst used is preferably a reaction product comprising:
a) an organic titanium compound,
b) a hydroxyl compound, a salt thereof or a mixture thereof,
c) a metal organic salt in which the metal element is at least one metal element selected from the group consisting of a group IA metal element, a group IIA metal element, aluminum, tin, zinc, zirconium, lanthanum or hafnium,
d) a phosphorus compound; preferably, the preparation method comprises the following steps:
reacting the organic titanium compound and a hydroxyl compound at 0-200 ℃ for 0.1-24 hours, adding the metal organic salt and the phosphorus compound into the product, reacting at 0-200 ℃ for 0.1-24 hours, and removing low-carbon alcohol and/or water in the system to obtain the catalyst for preparing the polyester.
In the above scheme, the organic titanium compound has a structure of general formula (I):
wherein R is1～R4Are independently selected from aliphatic groups with 1-10 carbon atoms, R1～R4Any two of them may form a ring.
In the above scheme, the hydroxy compound is one or more monohydric alcohols selected from ethanol, isopropanol, butanol; or a diol selected from ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, 1,4 butylene glycol; or a polyhydric alcohol selected from glycerol, pentaerythritol, sorbitol, mannitol; or a hydroxycarboxylic acid selected from lactic acid, citric acid, malic acid or tartaric acid.
In the above scheme, the phosphorus compound has a structure of general 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).
In the above scheme, the metal organic salt is a salt formed by an organic acid radical with an ionization constant greater than 4.0pKa in metal ions.
In the scheme, the amount of the added hydroxyl compound is (0.1-10) 1 by mole ratio of the total hydroxyl contained to the titanium element; the molar ratio of the metal organic salt to the titanium element in the titanium compound is (0.1-10) 1 in terms of the mole number of the contained metal; the molar ratio of the phosphorus compound to the titanium element in the titanium compound is (0.0001-10): 1, in terms of the number of moles of the phosphorus element contained.
In the scheme, the mass of the catalyst for preparing the polyester is 0.1-120mg/kg of terephthalic acid calculated by the mass of titanium element.
In the scheme, the molar ratio of the ethylene glycol to the isosorbide is preferably 1: 1-18: 1, and the molar ratio of the isosorbide remaining in the final polymer to the terephthalic acid segment is higher than 50% or more of the molar ratio of the isosorbide to the terephthalic acid segment in the initial stage of the reaction; it is further preferable that the molar ratio of ethylene glycol to isosorbide is 6:1 to 15:1, and in this case, the molar ratio of isosorbide remaining in the final polymer to the terephthalic acid segment is 80% or more higher than the molar ratio of isosorbide to the terephthalic acid segment at the initial stage of the reaction.
Conventional additives for polyesterification, such as color modifiers (cobalt compounds, pigments or dyes), stabilizers (hindered phenols, phosphites and thioethers), fillers, etc., may also be added to the polyester reaction mixture. These additives may be added at any stage of the polymerization reaction, preferably before the start of the polycondensation stage.
In the present invention, the intrinsic viscosity and hue of the polyester are tested by the methods described in GB/T14189-: intrinsic viscosity test phenol-tetrachloroethane was used as 60: 40 parts of the above-mentioned components were mixed as a solvent, and the mixture was measured at 25 ℃ with an Ubbelohde viscometer. The retention of isosorbide in the polyester was calculated from the results of H-NMR.
By adopting the method, because the catalyst for preparing the polyester and the lower melt polycondensation reaction temperature have the mutual synergistic effect, the method has the advantage of high isosorbide retention rate at the lower melt polycondensation reaction temperature, such as lower than 260 ℃ and further such as 250 ℃, and is particularly suitable for the production of isosorbide-containing polyester products which need to reduce the isosorbide loss and have certain requirements on the appearance of polymers, the intrinsic viscosity index is greater than 0.50dl/g, the isosorbide retention rate can reach more than 88 percent, and the method obtains better technical effects.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
142g of tetraisopropyl titanate, 46g of ethanol and 90g of lactic acid were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, and 36g of magnesium acetate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.625dl/g, the molar ratio of isosorbide to terephthalic acid segments was 8.4%, and the retention was 84%.
[ example 2 ]
142g of tetraisopropyl titanate, 46g of ethanol and 192g of citric acid were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, and 36g of magnesium acetate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.651dl/g, the molar ratio of isosorbide to terephthalic acid segment was 8.8%, and the retention was 88%.
[ example 3 ]
142g of tetraisopropyl titanate, 46g of ethanol and 192g of citric acid were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, 61g of zinc lactate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.674dl/g, the molar ratio of isosorbide to terephthalic acid segments was 8.2%, and the retention was 82%.
[ example 4 ]
84g of titanium glycol (Ti (OCH)2CH2O)2) Mixed with 46g of ethanol and 192g of citric acid, reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, and 36g of magnesium acetate and 91g of triethyl phosphate were added to the reaction mixture, and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. And (3) putting the reaction product into a reactor with a fractionating device, distilling off ethanol, and preparing the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.587dl/g, the molar ratio of isosorbide to terephthalic acid segments was 8.2%, and the retention was 82%.
[ example 5 ]
84g of titanium glycol (Ti (OCH)2CH2O)2) Mixed with 90g of lactic acid, reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, and 36g of magnesium acetate and 91g of triethyl phosphate were added to the reaction mixture, and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. And (3) putting the reaction product into a reactor with a fractionating device, distilling off ethanol, and preparing the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.613dl/g, the molar ratio of isosorbide to terephthalic acid segments was 8.4%, and the retention was 84%.
[ example 6 ]
142g of tetraisopropyl titanate, 46g of ethanol and 90g of lactic acid were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, and 82g of zirconium acetate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.581dl/g, the molar ratio of isosorbide to terephthalic acid segments was 9.0%, and the retention was 90%.
[ example 7 ]
142g of tetraisopropyl titanate, 46g of ethanol and 182g of sorbitol were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, and 36g of magnesium acetate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.610dl/g, the molar ratio of isosorbide to terephthalic acid segments was 8.4%, and the retention was 84%.
[ example 8 ]
142g of tetraisopropyl titanate, 46g of ethanol and 192g of citric acid were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, 61g of zinc lactate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 260 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 260 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.713dl/g, the molar ratio of isosorbide to terephthalic acid segments was 8.0%, and the retention was 80%.
[ example 9 ]
142g of tetraisopropyl titanate, 46g of ethanol and 192g of citric acid were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, 61g of zinc lactate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 202g of ethylene glycol, 106g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.615dl/g, the molar ratio of isosorbide to terephthalic acid segments was 15.6%, and the retention was 78%.
[ COMPARATIVE EXAMPLE 1 ]
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 0.35g of tetraisopropyl titanate are mixed to prepare a slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.363dl/g, the molar ratio of isosorbide to terephthalic acid segments was 6.4% and the retention was 64%.
[ COMPARATIVE EXAMPLE 2 ]
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 0.21g of antimony trioxide are mixed to prepare a slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 250 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.543dl/g, the molar ratio of isosorbide to terephthalic acid segment was 6.2%, and the retention was 62%.
[ COMPARATIVE EXAMPLE 3 ]
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 0.16g of germanium dioxide are mixed to prepare a slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 260 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 250 ℃, stopping the reaction when the system reacts for 3 hours, and continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.492dl/g, the molar ratio of isosorbide to terephthalic acid segments was 6.8%, and the retention was 68%.
[ COMPARATIVE EXAMPLE 4 ]
142g of tetraisopropyl titanate, 46g of ethanol and 192g of citric acid were mixed and reacted at a temperature of 100 ℃ for 4 hours in a reactor with stirring, 61g of zinc lactate and 91g of triethyl phosphate were added to the reaction mixture and reacted at a temperature of 120 ℃ for 4 hours in a reactor with stirring. The reaction product is placed in a reactor with a fractionating device, and ethanol and isopropanol are distilled off to prepare the catalyst. The catalyst was mixed with ethylene glycol, wherein the mass fraction of titanium atoms was 4%.
600g of terephthalic acid, 224g of ethylene glycol, 53g of isosorbide and 1.8g of catalyst are mixed to prepare slurry, the slurry is added into a polymerization kettle for esterification reaction, the esterification starting temperature is 220 ℃, the pressure is 0.25MPa, water generated by the reaction is discharged through a rectifying device, the reaction temperature is gradually increased to 230-250 ℃ after 1 hour of reaction, the reaction pressure is adjusted according to the temperature at the top end of the rectifying device, the top temperature is kept above the boiling point of water under the current pressure by 10-20 ℃, if the top temperature is lower than the temperature, the pressure is reduced, otherwise, the pressure is kept unchanged. And (3) reducing the pressure to normal pressure after the esterification is finished, starting to enter a polycondensation stage, vacuumizing to keep the reaction pressure at 0.5KPa and the liquid temperature at 280 ℃ for one hour, vacuumizing to reduce the pressure of the system to be lower than 130Pa and the reaction temperature at 280 ℃, stopping the reaction when the system reacts for 3 hours, and then continuously extruding the reaction product from the bottom of the polymerization kettle in a strip shape, cooling and pelletizing.
The PEIT intrinsic viscosity was 0.719dl/g, the molar ratio of isosorbide to terephthalic acid segments was 4.8%, and the retention was 48%.
TABLE 1
Claims (10)
1. A process for the preparation of isosorbide-containing polyesters comprising the steps of:
a) taking terephthalic acid and diol as raw materials, wherein the molar ratio of the diol to the terephthalic acid is 1.05: 1-1.3: 1, adding a catalyst, and carrying out esterification reaction at the esterification reaction temperature of 220-250 ℃ and the esterification reaction pressure of 10.4 KPa-0.5 MPa to obtain a prepolymer;
b) carrying out melt polycondensation on the obtained prepolymer under the vacuum condition that the melt polycondensation reaction temperature is 250-265 ℃ and the melt polycondensation reaction pressure is less than 150Pa to obtain a polymerization product;
wherein the diols comprise ethylene glycol and isosorbide;
the catalyst used was a reaction product comprising the following components:
a) an organic titanium compound,
b) a hydroxyl compound, a salt thereof or a mixture thereof,
c) a metal organic salt in which the metal element is at least one metal element selected from the group consisting of a group IA metal element, a group IIA metal element, aluminum, tin, zinc, zirconium, lanthanum or hafnium,
d) a phosphorus compound.
2. The process for preparing isosorbide-containing polyester according to claim 1, characterized in that the catalyst is prepared by the following method:
reacting the organic titanium compound and a hydroxyl compound at 0-200 ℃ for 0.1-24 hours, adding the metal organic salt and the phosphorus compound into the product, reacting at 0-200 ℃ for 0.1-24 hours, and removing low-carbon alcohol and/or water in the system to obtain the catalyst for preparing the polyester.
3. The process for preparing isosorbide-containing polyester according to claim 1, wherein the organotitanium compound has the structure of the general formula (i):
wherein R is1～R4Are independently selected from aliphatic groups with 1-10 carbon atoms, R1～R4Any two of them may form a ring.
4. The process for preparing isosorbide-containing polyester according to claim 1, wherein the hydroxyl compound is one or more monohydric alcohols selected from the group consisting of ethanol, isopropanol, butanol; or a diol selected from ethylene glycol, 1,2 propylene glycol, 1,3 propylene glycol, 1,4 butylene glycol; or a polyhydric alcohol selected from glycerol, pentaerythritol, sorbitol, mannitol; or a hydroxycarboxylic acid selected from lactic acid, citric acid, malic acid or tartaric acid.
5. The process for preparing isosorbide-containing polyester according to claim 1, wherein the phosphorus compound has the general 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).
6. The process for preparing isosorbide-containing polyester according to claim 1, wherein the metal organic salt is a salt of an organic acid having an ionization constant of more than 4.0pKa among metal ions.
7. The process for producing isosorbide-containing polyester according to claim 1, wherein the amount of the hydroxyl compound added is such that the molar ratio of the total hydroxyl groups contained to the titanium element is (0.1-10): 1; the molar ratio of the metal organic salt to the titanium element in the titanium compound is (0.1-10) 1 in terms of the mole number of the contained metal; the molar ratio of the phosphorus compound to the titanium element in the titanium compound is (0.0001-10): 1, in terms of the number of moles of the phosphorus element contained.
8. The process for producing isosorbide-containing polyester according to claim 1, wherein the mass of the catalyst added for polyester production is 0.1 to 120mg/kg of terephthalic acid in terms of the mass of titanium element.
9. The method for preparing isosorbide-containing polyester according to claim 1, wherein the molar ratio of ethylene glycol to isosorbide is 1:1 to 18:1, and the molar ratio of isosorbide remaining in the final polymer to the terephthalic acid segment is higher than 50% of the molar ratio of isosorbide to terephthalic acid at the initial stage of the reaction.
10. The method for preparing isosorbide-containing polyester according to claim 9, wherein the molar ratio of ethylene glycol to isosorbide is 6:1 to 15:1, and the molar ratio of isosorbide remaining in the final polymer to the terephthalic acid segments is higher than 80% of the molar ratio of isosorbide to terephthalic acid at the initial stage of the reaction.
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| CN112851919B (en) * | 2019-11-12 | 2022-08-26 | 中国科学院化学研究所 | 1,4, 3, 6-diglycidyl hexaol modified PET polyester and semi-continuous preparation method thereof |
| CN113185682B (en) * | 2021-04-27 | 2022-08-12 | 中国石油化工股份有限公司 | Modified copolyester and preparation method thereof |
| CN114276363B (en) * | 2021-12-30 | 2023-12-29 | 国科温州研究院(温州生物材料与工程研究所) | Method for purifying isosorbide by adopting dihydric alcohol recrystallization |
| CN117659368A (en) * | 2022-08-31 | 2024-03-08 | 科泽新材料股份有限公司 | Method for preparing PEIT copolyester |
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| CN102264794A (en) * | 2008-12-31 | 2011-11-30 | Sk化学株式会社 | Method for preparing a polyester resin in which isosorbide is copolymerized |
| CN102477151A (en) * | 2010-11-25 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Catalyst for preparation of polyester, its preparation method, and production method of polyester |
| CN105273176A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Catalyst used for preparation of polyester, preparation method and application thereof |
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| CN102264794A (en) * | 2008-12-31 | 2011-11-30 | Sk化学株式会社 | Method for preparing a polyester resin in which isosorbide is copolymerized |
| CN102477151A (en) * | 2010-11-25 | 2012-05-30 | 东丽纤维研究所（中国）有限公司 | Catalyst for preparation of polyester, its preparation method, and production method of polyester |
| CN105273176A (en) * | 2014-07-03 | 2016-01-27 | 中国石油化工股份有限公司 | Catalyst used for preparation of polyester, preparation method and application thereof |
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