CN113185682B - Modified copolyester and preparation method thereof - Google Patents
Modified copolyester and preparation method thereof Download PDFInfo
- Publication number
- CN113185682B CN113185682B CN202110458977.8A CN202110458977A CN113185682B CN 113185682 B CN113185682 B CN 113185682B CN 202110458977 A CN202110458977 A CN 202110458977A CN 113185682 B CN113185682 B CN 113185682B
- Authority
- CN
- China
- Prior art keywords
- titanium
- reaction
- tetrakis
- esterification
- isosorbide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- 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
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention discloses modified copolyester and a preparation method thereof, belonging to the field of high polymers. Mixing alcohols with terephthalic acid and/or 1, 4-cyclohexanedicarboxylic acid, and then carrying out esterification reaction, wherein when the esterification rate or the ester exchange rate reaches 90% or more, the esterification reaction step is completed; then, the polycondensation reaction step is carried out under the conditions of high temperature and low vacuum. The copolyester prepared by the invention has the characteristics of high reaction conversion rate of isosorbide components, high production efficiency and excellent heat resistance, and can be used for food packaging materials, shells of household appliances, cosmetic bottles and vehicle-mounted products.
Description
Technical Field
The invention relates to the field of macromolecules, in particular to modified copolyester and a preparation method thereof.
Background
Polyethylene terephthalate (PET) is excellent in mechanical, chemical, and other properties, and is widely used in the fields of fibers, films, bottles, and the like. However, the glass transition temperature of PET resin is low, the heat resistance of PET resin is poor, and the product of the PET resin deforms at 70-80 ℃, so that the application of PET in the field of heat resistance is limited.
People introduce a rigid chain segment into a PET molecular chain by a copolymerization modification method so as to achieve the aim of improving the heat resistance of the PET resin. The nuclear magnetic test data of the literature Synthesis and Characteristics of a Biobased High-Tg Terpolyer of Isosorb, Ethylene Glycol, and 1,4-Cyclohexane Dimethanol: Effect of Ethylene Glycol as a chain Linker on Polymerization, Macromolecules,2013,46, 7219-H7231 on page 7220 (characteristic of ternary copolyesters prepared with different amounts of Isosorbide) shows that the higher the content of Isosorbide component in the copolyester, the higher the glass transition temperature Tg, the more excellent the heat resistance, and indicates that the higher the Tg of the copolyester is directly positively correlated with the higher the Isosorbide content in the copolyester.
In recent years, polymerization methods have been disclosed in which isosorbide is used to impart a new function to a polyester resin to improve the heat resistance of the polyester. The diol reactivity of the polyester synthesis raw material decreases in the order of primary diol > secondary diol > tertiary diol, so that the reaction time is greatly prolonged or the reaction product yield is reduced once a polyester resin is synthesized using secondary or tertiary alcohols. Isosorbide is a secondary alcohol, polymerization reactivity is low, and according to the known polymerization method, when the isosorbide content of the diol portion exceeds 25 mol%, part of isosorbide does not participate in the polymerization reaction, resulting in insufficient polymerization degree of polyester, resulting in lowering of impact resistance, lowering of durability and excessively poor appearance of the polyester resin.
Disclosure of Invention
The invention provides modified copolyester and a preparation method thereof aiming at the technical problems.
The purpose of the invention can be realized by the following technical scheme:
a method for preparing modified copolyester, said method comprises carrying on the esterification reaction after mixing alcohols and terephthalic acid and/or 1,4-cyclohexane dicarboxylic acid, when the esterification rate or ester exchange rate reaches 90% or above, finish the esterification reaction step; after the esterification reaction is finished, carrying out polycondensation reaction to obtain polyester resin;
wherein: adding a catalyst of titanium hydroxy alkoxide in the esterification reaction and/or the polycondensation reaction, wherein the structural formula of the titanium hydroxy alkoxide is shown as a formula I:
wherein: a. the 1 、A 2 、A 3 And A 4 Each independently is an alkyl substituent with 2-6 carbon atoms, and n is 1 or 2.
The technical scheme of the invention is as follows: the conditions of the esterification reaction step are that the temperature is 230-260 ℃, the gauge pressure is 0.20-0.40MPa, and the time is 1-5 h; the conditions of the polycondensation reaction step are that the reaction temperature is 255-275 ℃, the absolute pressure is less than or equal to 70Pa, and the time is 1-5 h;
preferably: the conditions of the esterification reaction step are that the temperature is 240-260 ℃, the gauge pressure is 0.20-0.30MPa, and the time is 1-3 h; the conditions of the polycondensation reaction step are that the reaction temperature is 265-275 ℃, the absolute pressure is less than or equal to 70Pa, and the time is 2-3 h.
The technical scheme of the invention is as follows: the titanium hydroxyalkanoate is tetrakis (2-hydroxyethoxy) titanium, tetrakis (3-hydroxypropoxy) titanium, tetrakis (2, 3-dihydroxypropoxy) titanium, tetrakis (1, 3-dihydroxyisopropoxy) titanium, tetrakis (4-hydroxybutoxy) titanium, tetrakis (2, 3-dihydroxybutoxy) titanium, tetrakis (2, 4-dihydroxybutoxy) titanium, tetrakis (5-hydroxypentoxy) titanium, tetrakis (2, 5-dihydroxypentyloxy) titanium, tetrakis (6-hydroxyhexyloxy) titanium, tetrakis (2, 3-dihydroxyhexyloxy) titanium, tetrakis (2, 6-dihydroxyhexyloxy) titanium, bis (2-hydroxyethoxy) bis (3-hydroxypropoxy) titanium, bis (2-hydroxyethoxy) bis (2, 3-dihydroxypropoxy) titanium or bis (3-hydroxypropoxy) (2, 3-dihydroxypropoxy) (1, 3-dihydroxyisopropoxy) titanium.
The technical scheme of the invention is as follows: the hydroxyl alkoxyl titanium is tetra (2-hydroxyl ethoxyl) titanium, tetra (3-hydroxyl propoxyl) titanium or tetra (1, 3-dihydroxy isopropoxy) titanium.
The technical scheme of the invention is as follows: the preparation method of the hydroxyl alkoxy titanium comprises the following steps:
(1) dissolving alcohol substances in pyridine solution, adding acetic anhydride under the condition of stirring for acetylation reaction, and removing water after the reaction is finished to obtain an anhydrous product;
(2) slowly adding titanium tetrachloride into an anhydrous product under the protection of nitrogen for reaction, introducing ammonia gas in the reaction process to neutralize hydrochloric acid produced by the reaction until the pH value is neutral, and filtering ammonium chloride generated by the reaction after the reaction is finished to obtain acetylated titanium alkoxide; then the acetylated titanium alkoxide is subjected to a methanol decomposition reaction to remove an acetate protecting group, so as to obtain a polyhydroxy titanium alkoxide product;
wherein: the polyalcohol substances are one or more of ethylene glycol, 1, 3-propylene glycol, glycerol, 1, 4-butanediol, 1,2, 3-butanetriol, 1,2, 4-butanetriol, 1, 5-pentanediol, 1,2, 5-pentanetriol, 1, 6-hexanediol, 1,2, 3-hexanetriol or 1,2, 6-hexanetriol or alcohol derivatives thereof.
The technical scheme of the invention is as follows: the polyalcohol substance is ethylene glycol, 1, 3-propylene glycol or glycerol.
The technical scheme of the invention is as follows: the titanium atom content of the titanium oxyhydroxide is 5 to 100 [ mu ] g/g based on the total amount of the polyester resin.
The technical scheme of the invention is as follows: the phosphorus-containing stabilizer has a phosphorus atom content of 5 to 200. mu.g/g based on the total amount of the polyester resin.
The technical scheme of the invention is as follows: : the alcohols are isosorbide and other alcohols, and the other alcohols are ethylene glycol and/or 1, 4-cyclohexanedimethanol.
In some preferred embodiments: the alcohols are ethylene glycol, isosorbide and 1, 4-cyclohexanedimethanol, or the alcohols are ethylene glycol and isosorbide.
A modified copolyester is prepared by the following steps: mixing alcohols with terephthalic acid and/or 1, 4-cyclohexanedicarboxylic acid, and then carrying out esterification reaction, wherein when the esterification rate or the ester exchange rate reaches 90% or more, the esterification reaction step is completed; after the esterification reaction is finished, carrying out polycondensation reaction to obtain polyester resin;
wherein: adding a catalyst of titanium hydroxy alkoxide in the esterification reaction and/or the polycondensation reaction step, wherein the structural formula of the titanium hydroxy alkoxide is shown as a formula I:
wherein: a. the 1 、A 2 、A 3 And A 4 Each independently is an alkyl substituent with 2-6 carbon atoms, and n is 1 or 2.
The invention has the beneficial effects that:
in the method, the catalyst adopts polyhydroxy titanium alkoxide of tetravalent titanium element, so that the ester exchange reaction rate can be accelerated, the reaction conversion rate of isosorbide can be improved, and meanwhile, the catalyst has good compatibility with a reactant glycol component and high catalytic activity; in addition, the catalyst molecule has a plurality of hydroxyl functional groups, can play a role in chemical crosslinking, and can effectively promote the rapid increase of the polymerization degree of the polyester. And a phosphorus-containing stabilizer is added in the polymerization process to inhibit the degradation reaction activity of the polycondensation reaction. Compared with the disclosed method, the copolyester prepared by the invention has the characteristics of high reaction conversion rate of isosorbide components, high production efficiency and excellent heat resistance, and can be used for food packaging materials, shells of household appliances, cosmetic bottles and vehicle-mounted products.
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
the test method is as follows:
the polyester thermal performance test adopts a differential scanning calorimeter, and the method comprises the steps of firstly heating to 300 ℃ at a heating rate of 10 ℃/min for 5min under the nitrogen atmosphere, cooling to room temperature at a cooling rate of 400 ℃, and then carrying out second scanning at the heating rate of 10 ℃/min. Glass transition temperature T of polyester resin g Is the data after the thermal history is removed.
The intrinsic viscosity test method adopts a national standard GB/T14190-2018 fiber-grade polyester chip test method.
The copolyester composition test adopts a nuclear magnetic resonance spectrometer, and the relative integral area of glycol protons is utilized to determine the composition ratio. The test solvent was deuterated chloroform and the internal standard was tetramethylsilane.
The hydroxyl alkoxyl titanium is tetra (2-hydroxyl ethoxyl) titanium, tetra (3-hydroxyl propoxyl) titanium or tetra (1, 3-dihydroxy isopropoxy) titanium.
The preparation of tetrakis (2-hydroxyethoxy) titanium is as follows.
6.21g (0.10mol) of ethylene glycol were dissolved in 79.10g (1.00mol) of pyridine solution, and the solution was transferred to a flask. 12.25g (0.12mol) of acetic anhydride was added dropwise to the flask with stirring, and acetylation reaction was carried out at room temperature for 8 hours, followed by distillation under reduced pressure and removal of water with calcium oxide reflux stirring to obtain an anhydrous product. Slowly dripping 4.74g (0.025mol) of titanium tetrachloride into the vigorously stirred anhydrous product under the protection of nitrogen, introducing dry ammonia gas to neutralize hydrochloric acid generated by the reaction until the pH value is neutral, stirring for 30min, finishing the reaction, and filtering ammonium chloride generated by the reaction to obtain an acetylated titanium alkoxide solution. And then the product is subjected to methanolysis reaction to remove the acetate protecting group, and the final tetra (2-hydroxyethoxy) titanium is obtained. Tetrakis (2-hydroxyethoxy) titanium 1 H-NMR(CDCl 3 ,ppm):3.725,3.654,3.468。 13 C-NMR(CDCl 3 ,ppm):64.424,48.025。
The preparation of tetrakis (3-hydroxypropoxy) titanium is as follows.
7.61g (0.10mol) of 1, 3-propanediol were dissolved in 79.10g (1.00mol) of pyridine solution, and the solution was transferred to a flask. 12.25g (0.12mol) of acetic anhydride was added dropwise to the flask with stirring, and acetylation reaction was carried out at room temperature for 8 hours, followed by distillation under reduced pressure and removal of water with calcium oxide reflux stirring to obtain an anhydrous product. 4.74g (0.025mol) of titanium tetrachloride are slowly added dropwise under nitrogen to the vigorously stirred anhydrous product and dried by passing throughAnd (3) neutralizing hydrochloric acid generated in the reaction by ammonia gas until the pH value is neutral, stirring for 30min, finishing the reaction, and filtering ammonium chloride generated in the reaction to obtain an acetylated titanium alkoxide solution. And then the product is subjected to methanolysis reaction to remove the acetate protecting group, and the final tetra (3-hydroxypropoxy) titanium is obtained. Tetrakis (3-hydroxypropoxy) titanium 1 H-NMR(CDCl 3 ,ppm):3.655,3.532,3.501,1.792。 13 C-NMR(CDCl 3 ,ppm):58.852,41.032,35.162。
The preparation and synthesis route of the tetra (1, 3-dihydroxyisopropoxy) titanium is as follows.
9.21g (0.10mol) of glycerol were dissolved in 79.10g (1.00mol) of the pyridine solution, and the solution was transferred to a flask. 24.50g (0.24mol) of acetic anhydride was added dropwise to the flask with stirring, and acetylation reaction was carried out at room temperature for 8 hours, followed by distillation under reduced pressure and removal of water with calcium oxide reflux stirring to obtain an anhydrous product. Slowly dripping 4.74g (0.025mol) of titanium tetrachloride into the vigorously stirred anhydrous product under the protection of nitrogen, introducing dry ammonia gas to neutralize hydrochloric acid generated by the reaction until the pH value is neutral, stirring for 30min, finishing the reaction, and filtering ammonium chloride generated by the reaction to obtain the acetylated titanium alkoxide solution. And then the product is subjected to methanolysis reaction to remove the acetate protecting group, and the final tetra (1, 3-dihydroxyisopropoxy) titanium is obtained. Tetrakis (1, 3-dihydroxyisopropoxy) titanium 1 H-NMR(CDCl 3 ,ppm):3.652,3.395,3.507。 13 C-NMR(CDCl 3 ,ppm):62.702,60.851,58.824,34.256。
Comparative example 1:
the polyester resin synthesis reaction was carried out in a 20L polymerization reactor. 1458g (23.5mol) of ethylene glycol is weighed and heated to 70 ℃, 2441g (16.7mol) of isosorbide and 651g (4.5mol) of 1, 4-cyclohexanedimethanol are added into the ethylene glycol-isosorbide and the mixture and stirred to be melted to prepare an ethylene glycol-isosorbide-1, 4-cyclohexanedimethanol solution, and then the solution and 5000g (30.1mol) of terephthalic acid are mixed uniformly to complete the preparation step of the synthetic raw materials, and the molar ratio of the alcohol acid participating in the synthetic reaction is 1.5. Adding the synthetic raw materials and germanium dioxide of 250 mu g/g relative to the total amount of the polyester resin into a reaction kettle, and carrying out esterification reaction under the conditions of 0.25MPa (g) and 250 ℃. When the esterification water yield reaches 90 percent of the theoretical value, the esterification reaction step is completed. Then, 50. mu.g/g of bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium salt (CAS number 65140-91-2) was added to the reaction vessel, and polycondensation was carried out under 70Pa (absolute pressure) at 270 ℃. And when the stirring current of the motor of the reaction kettle reaches 1.0A, discharging and granulating to obtain the polyester resin. The esterification reaction time of the polyester is 146min, the esterification rate reaches 90 percent, the intrinsic viscosity of the polyester resin is 0.64dL/g, the ratio of isosorbide components in the resin is 18.0 percent, and the glass transition temperature of the polyester is 100 ℃ in the polycondensation reaction of 185 min.
Comparative example 2:
the difference from comparative example 1 is that 300. mu.g/g of ethylene glycol antimony with respect to the total amount of polyester was added in the esterification reaction step. The polyester resin prepared by the method has the esterification reaction time of 142min and the esterification rate of 90 percent, the intrinsic viscosity of the polyester resin is 0.64dL/g after the polycondensation reaction of 193min, the ratio of isosorbide in the resin is 17.0 percent, and the glass transition temperature reaches 99 ℃.
Comparative example 3:
the difference from comparative example 1 is that tetrabutyl titanate was added in the polycondensation step in an amount of 200. mu.g/g relative to the total amount of polyester. The polyester resin prepared by the method has the esterification reaction time of 145min and the esterification rate of 90 percent, the intrinsic viscosity of the polyester resin is 0.65dL/g and the ratio of isosorbide in the resin is 17.8 percent in the polycondensation reaction of 172min, and the glass transition temperature reaches 100 ℃.
Example 1:
in contrast to comparative example 1, the esterification step was conducted by adding tetrakis (1, 3-dihydroxyisopropoxy) titanium having an elemental titanium content of 100. mu.g/g. According to the polyester resin prepared by the method, after the esterification reaction lasts for 110min, the esterification rate reaches 93%, the intrinsic viscosity of the polyester resin is 0.65dL/g after the polycondensation reaction lasts for 140min, the ratio of an isosorbide component in the resin is 23.0%, and the glass transition temperature reaches 106 ℃.
Example 2:
the difference from comparative example 1 is that tetrakis (2-hydroxyethoxy) titanium having a titanium element content of 100. mu.g/g was added in the esterification reaction step. The polyester resin prepared by the method has the advantages that the esterification rate reaches 92% after the esterification reaction lasts for 115min, the intrinsic viscosity of the polyester resin reaches 0.65dL/g after the polycondensation reaction lasts for 143min, the ratio of an isosorbide component in the resin reaches 22.8%, and the glass transition temperature reaches 106 ℃.
Example 3:
the difference from comparative example 1 is that tetrakis (3-hydroxypropoxy) titanium having a titanium element content of 100. mu.g/g was added in the esterification reaction step. According to the polyester resin prepared by the method, after the esterification reaction lasts for 115min, the esterification rate reaches 93%, the intrinsic viscosity of the polyester resin is 0.65dL/g after the polycondensation reaction lasts for 150min, the ratio of isosorbide in the resin is 22.8%, and the glass transition temperature reaches 106 ℃.
Example 4:
the difference from comparative example 3 is that in the polycondensation step, tetrakis (1, 3-dihydroxyisopropoxy) titanium having a titanium element content of 100. mu.g/g was added. According to the polyester resin prepared by the method, after the esterification reaction lasts for 142min, the esterification rate reaches 94%, the intrinsic viscosity of the polyester resin is 0.65dL/g after the polycondensation reaction lasts for 144min, the ratio of an isosorbide component in the resin is 22.8%, and the glass transition temperature reaches 106 ℃.
Example 5:
the difference from comparative example 3 is that tetrakis (2-hydroxyethoxy) titanium having a titanium element content of 100. mu.g/g was added in the polycondensation step. According to the polyester resin prepared by the method, after the esterification reaction lasts for 146min, the esterification rate reaches 93%, the intrinsic viscosity of the polyester resin is 0.65dL/g after the polycondensation reaction lasts for 155min, the ratio of an isosorbide component in the resin is 22.7%, and the glass transition temperature reaches 106 ℃.
Example 6:
the difference from comparative example 3 is that tetrakis (3-hydroxypropoxy) titanium having a titanium element content of 100. mu.g/g was added in the polycondensation step. The polyester resin prepared by the method has the esterification rate of 93 percent after the esterification reaction lasts for 145min, the intrinsic viscosity of the polyester resin is 0.64dL/g after the polycondensation reaction lasts for 162min, the ratio of isosorbide in the resin is 22.8 percent, and the glass transition temperature reaches 106 ℃.
Example 7:
the difference from comparative example 2 was that tetrakis (1, 3-dihydroxyisopropoxy) titanium having a titanium element content of 50. mu.g/g was added in the esterification reaction step, and tetrakis (2-hydroxyethoxy) titanium having a titanium element content of 50. mu.g/g was added again in the polycondensation reaction step. According to the polyester resin prepared by the method, after the esterification reaction lasts for 132min, the esterification rate reaches 94%, the intrinsic viscosity of the polyester resin after the polycondensation reaction lasts for 138min is 0.65dL/g, the ratio of an isosorbide component in the resin is 23.8%, and the glass transition temperature reaches 107 ℃.
TABLE 1 comparison of resin compositions and test results for comparative examples 1-3 and examples 1-7
Note: the stabilizer is bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium salt
Compared with comparative examples 1-3, the polyester resins of examples 1-7 using the titanium oxyhydroxide catalyst had relatively shorter reaction time and relatively higher esterification rate; the molar composition of isosorbide in the resin is 22.7 to 23.8, which is higher than 18.0% of that in comparative examples 1-3; the reaction conversion rate of isosorbide is improved from about 70 percent to 91 to 95 percent; while the glass transition temperature T of the polyester resin g Also improves the temperature by 6-8 ℃.
Example 8:
the difference from comparative example 1 is that the esterification step was conducted to add tetrakis (1, 3-dihydroxyisopropoxy) titanium having an elemental titanium content of 50. mu.g/g. According to the polyester resin prepared by the method, after the esterification reaction lasts for 108min, the esterification rate reaches 94%, the intrinsic viscosity of the polyester resin reaches 0.64dL/g after the polycondensation reaction lasts for 131min, the ratio of an isosorbide component in the resin reaches 23.0%, and the glass transition temperature reaches 106 ℃.
Example 9:
the difference from comparative example 1 was that in the esterification step, tetrakis (1, 3-dihydroxyisopropoxy) titanium having a titanium element content of 10. mu.g/g was added, and in the polycondensation step, tetrakis (1, 3-dihydroxyisopropoxy) titanium having a titanium element content of 40. mu.g/g was added. After the esterification reaction of the polyester resin prepared by the method lasts for 136min, the esterification rate reaches 93 percent, the intrinsic viscosity of the polyester resin is 0.66dL/g after the esterification reaction lasts for 124min, the ratio of an isosorbide component in the resin is 24.5 percent, and the glass transition temperature reaches 108 ℃.
Example 10:
the difference from comparative example 1 was that in the esterification step, tetrakis (2-dihydroxyethoxy) titanium having a titanium element content of 20. mu.g/g was added, and in the polycondensation step, tetrakis (2-dihydroxyethoxy) titanium having a titanium element content of 30. mu.g/g was added. According to the polyester resin prepared by the method, after the esterification reaction lasts for 120min, the esterification rate reaches 93%, the intrinsic viscosity of the polyester resin is 0.66dL/g after the polycondensation reaction lasts for 135min, the ratio of an isosorbide component in the resin is 23.8%, and the glass transition temperature reaches 107 ℃.
Example 11:
the difference from comparative example 1 was that in the esterification step, tetrakis (3-hydroxypropoxy) titanium having a titanium element content of 20. mu.g/g was added, and in the polycondensation step, tetrakis (3-hydroxypropoxy) titanium having a titanium element content of 50. mu.g/g was added. According to the polyester resin prepared by the method, after the esterification reaction lasts for 131min, the esterification rate reaches 94%, the intrinsic viscosity of the polyester resin is 0.66dL/g after the polycondensation reaction lasts for 130min, the ratio of an isosorbide component in the resin is 24.5%, and the glass transition temperature reaches 108 ℃.
TABLE 2 resin composition and test results for comparative example 1 and examples 8-11
Note: the stabilizer is bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium salt
Compared with comparative example 1In the esterification step or the polycondensation step, the reaction time of the embodiment 8-11 supplemented with the hydroxy alkoxy titanium catalyst is shortened, the esterification rate is improved by 3-4 percent, the molar composition of the isosorbide in the resin is 23.0-24.5, which is higher than that in the comparative example 18.0 percent; the reaction conversion rate of the isosorbide is improved by 20 to 26 percent; simultaneous resin T g Also improves the temperature by 6-8 ℃.
Comparative example 4:
the polyester resin synthesis reaction was carried out in a 20L polymerization reactor. Weighing 1522g (24.5mol) of ethylene glycol, heating to 70 ℃, adding 660g (4.5mol) of isosorbide, stirring and melting to prepare an ethylene glycol-isosorbide solution, uniformly mixing the solution with 5000g (30.1mol) of terephthalic acid and 1000g (16.1mol) of glycol, wherein the molar ratio of the participating reaction alcohol acid is 1.5, and finishing the preparation step of the synthetic raw materials. Adding the synthetic raw materials and tetrabutyl titanate with the titanium element content of 100 mu g/g into a reaction kettle, and carrying out esterification reaction under the conditions of 0.25MPa (g) and 255 ℃. And finishing the esterification reaction when the esterification water yield reaches 89 percent of a theoretical value. In the polycondensation reaction step, adding 100 mug/g of calcium salt of bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) with phosphorus element content, and carrying out polycondensation reaction under the conditions of less than or equal to 70Pa (a) and 275 ℃. And when the stirring current of the motor of the reaction kettle reaches 1.0A, discharging and granulating to obtain the polyester resin. The esterification reaction time of the polyester is 125min, the esterification rate is 89%, the intrinsic viscosity of the polyester resin is 0.64dL/g, the ratio of isosorbide in the resin is 7.0% and the glass transition temperature of the polyester is 86 ℃ in the polycondensation reaction of 155 min.
Example 12:
the difference from comparative example 4 is that tetrakis (1, 3-dihydroxyisopropoxy) titanium having an elemental titanium content of 50. mu.g/g was added in the esterification reaction step. The polyester resin prepared by the method has the esterification reaction time of 98min and the esterification rate of 94 percent, the intrinsic viscosity of the polyester resin of 0.65dL/g in the polycondensation reaction of 123min, the ratio of an isosorbide component in the resin of 9.7 percent and the glass transition temperature of 90 ℃.
Example 13:
the difference from comparative example 4 is that 2363g (38.1mol) of ethylene glycol is weighed and heated to 70 ℃, 880g (6.0mol) of isosorbide is added and stirred to melt, thus obtaining ethylene glycol-isosorbide solution, and then the solution is evenly mixed with 5000g (30.1mol) of terephthalic acid and 1000g (16.1mol) of glycol, the molar ratio of the alcohol acid participating in the reaction is 2.0, thus completing the preparation step of the synthetic raw material. In the esterification step, tetrakis (1, 3-dihydroxyisopropoxy) titanium with the titanium element content of 100 mu g/g is added, and in the polycondensation step, bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium salt with the phosphorus element content of 200 mu g/g is added. The polyester resin prepared by the method has the esterification reaction time of 95min and the esterification rate of 94 percent, the intrinsic viscosity of the polyester resin is 0.65dL/g after the polycondensation reaction of 136min, the ratio of an isosorbide component in the resin is 9.8 percent, and the glass transition temperature reaches 89 ℃.
Example 14:
the difference from comparative example 4 is that 849g (13.7mol) of ethylene glycol was weighed and heated to 70 ℃, 483g (3.3mol) of isosorbide was added thereto and stirred to melt, and an ethylene glycol-isosorbide solution was prepared, and this solution was mixed with 5000g (30.1mol) of terephthalic acid and 1000g (16.1mol) of ethylene glycol in a molar ratio of 1.1 to participate in the reaction, thereby completing the synthesis raw material preparation step. In the esterification reaction step, 5 mu g/g of titanium element content is added in tetra (1, 3-dihydroxyisopropoxy) titanium, and in the polycondensation reaction step, 10 mu g/g of bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium salt is added. The polyester resin prepared by the method has esterification reaction time of 105min and esterification rate of 94 percent, polycondensation reaction of 165min and intrinsic viscosity of 0.65dL/g, the ratio of isosorbide in the resin of 9.9 percent and glass transition temperature of 90 ℃.
Example 15:
the difference from comparative example 4 is that in the raw material compounding step, 2242g (36.1mol) of ethylene glycol is weighed and heated to 70 ℃, 2639g (18.1mol) of isosorbide and 869g (6.0mol) of 1, 4-cyclohexanedimethanol are added and stirred to melt to prepare an ethylene glycol-isosorbide-1, 4-cyclohexanedimethanol solution, and the solution and 5000g (30.1mol) of terephthalic acid are mixed uniformly, the molar ratio of the participating alcohol acids is 1.5, and the synthetic raw material compounding step is completed. In the esterification step, titanium tetrakis (1, 3-dihydroxyisopropoxy) with the titanium element content of 60 mu g/g is added, and in the polycondensation step, bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium salt with the phosphorus element content of 60 mu g/g is added. The polyester resin prepared by the method has the advantages of esterification reaction time of 120min and esterification rate of 93 percent, polycondensation reaction of 158min, intrinsic viscosity of 0.64dL/g, isosorbide component ratio of 28.5 percent in the resin and glass transition temperature of 114 ℃.
Example 16:
the difference from example 15 is that a synthetic raw material was prepared by uniformly mixing an ethylene glycol-isosorbide-1, 4-cyclohexanedimethanolic solution with 4750g (28.6mol) of terephthalic acid and 259g (1.5mol) of 1, 4-cyclohexanedicarboxylic acid. The polyester resin prepared by the method has the esterification reaction time of 122min and the esterification rate of 93 percent, the intrinsic viscosity of the polyester resin is 0.64dL/g after the polycondensation reaction for 165min, the ratio of an isosorbide component in the resin is 28.8 percent, and the glass transition temperature reaches 115 ℃.
Example 17:
the difference from comparative example 4 is that 1121g (18.1mol) of ethylene glycol is weighed and heated to 70 ℃, 4398g (30.1mol) of isosorbide and 1736g (12.0mol) of 1, 4-cyclohexanedimethanol are added and stirred to melt to prepare an ethylene glycol-isosorbide-1, 4-cyclohexanedimethanol solution, and the solution and 5000g (30.1mol) of terephthalic acid are mixed uniformly, the molar ratio of the participating alcohol acids is 1.5, and the preparation step of the synthetic raw materials is completed. In the esterification step, titanium tetrakis (1, 3-dihydroxyisopropoxy) with the content of titanium element of 80 mu g/g is added, and in the polycondensation step, calcium bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonate monoethyl ester) with the content of phosphorus element of 60 mu g/g is added. The polyester resin prepared by the method has the advantages of esterification reaction time of 130min and esterification rate of 93 percent, polycondensation reaction time of 181min, intrinsic viscosity of the polyester resin of 0.63dL/g, isosorbide component ratio of 46.0 percent in the resin and glass transition temperature of 136 ℃.
TABLE 3 resin composition and test results for comparative example 4 and examples 12-17
Note: the stabilizer is bis (3, 5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester) calcium salt
Compared with the comparative example 1, the esterification rate of the example 12-17 adopting tetra (1, 3-dihydroxyisopropoxy) titanium in the esterification step is generally increased by 4-5%, and the reaction conversion rate of isosorbide is increased by 22-29%.
Claims (11)
1. A preparation method of modified copolyester is characterized by comprising the following steps: mixing alcohols with terephthalic acid and/or 1, 4-cyclohexanedicarboxylic acid, and then carrying out esterification reaction, wherein when the esterification rate or the ester exchange rate reaches 90% or more, the esterification reaction step is completed; after the esterification reaction is finished, carrying out polycondensation reaction to obtain polyester resin;
wherein: adding a catalyst of titanium hydroxy alkoxide in the esterification reaction and/or the polycondensation reaction, wherein the structural formula of the titanium hydroxy alkoxide is shown as a formula I:
formula I;
wherein: a. the 1 、A 2 、A 3 And A 4 Each independently is an alkyl substituent with 2-6 carbon atoms, and n is 1 or 2;
the alcohols in the esterification reaction are isosorbide and other alcohols, and the other alcohols are ethylene glycol and/or 1, 4-cyclohexanedimethanol;
the preparation method of the hydroxyl alkoxy titanium comprises the following steps:
(1) dissolving alcohol substances in pyridine solution, adding acetic anhydride under the condition of stirring for acetylation reaction, and removing water after the reaction is finished to obtain an anhydrous product;
(2) slowly adding titanium tetrachloride into an anhydrous product under the protection of nitrogen for reaction, introducing ammonia gas in the reaction process to neutralize hydrochloric acid produced by the reaction until the pH value is neutral, and filtering ammonium chloride generated by the reaction after the reaction is finished to obtain acetylated titanium alkoxide; and then the acetylated titanium alkoxide is subjected to a methanolysis reaction to remove the acetate protecting group, so as to obtain a polyhydroxy titanium alkoxide product.
2. The process for preparing modified copolyester according to claim 1, wherein: the conditions of the esterification reaction step are that the temperature is 230-260 ℃, the gauge pressure is 0.20-0.40MPa, and the time is 1-5 h; the conditions of the polycondensation reaction step are that the reaction temperature is 255-275 ℃, the absolute pressure is less than or equal to 70Pa, and the time is 1-5 h.
3. The process for preparing modified copolyester according to claim 1, wherein: the conditions of the esterification reaction step are that the temperature is 240-260 ℃, the gauge pressure is 0.20-0.30MPa, and the time is 1-3 h; the conditions of the polycondensation reaction step are that the reaction temperature is 265-275 ℃, the absolute pressure is less than or equal to 70Pa, and the time is 2-3 h.
4. The process for preparing modified copolyester according to claim 1, wherein: the titanium hydroxyalkanoate is tetrakis (2-hydroxyethoxy) titanium, tetrakis (3-hydroxypropoxy) titanium, tetrakis (2, 3-dihydroxypropoxy) titanium, tetrakis (1, 3-dihydroxyisopropoxy) titanium, tetrakis (4-hydroxybutoxy) titanium, tetrakis (2, 3-dihydroxybutoxy) titanium, tetrakis (2, 4-dihydroxybutoxy) titanium, tetrakis (5-hydroxypentoxy) titanium, tetrakis (2, 5-dihydroxypentyloxy) titanium, tetrakis (6-hydroxyhexyloxy) titanium, tetrakis (2, 3-dihydroxyhexyloxy) titanium, tetrakis (2, 6-dihydroxyhexyloxy) titanium, bis (2-hydroxyethoxy) bis (3-hydroxypropoxy) titanium, bis (2-hydroxyethoxy) bis (2, 3-dihydroxypropoxy) titanium or bis (3-hydroxypropoxy) (2, 3-dihydroxypropoxy) (1, 3-dihydroxyisopropoxy) titanium.
5. The process for preparing modified copolyester according to claim 4, wherein: the hydroxyl alkoxyl titanium is tetra (2-hydroxyl ethoxyl) titanium, tetra (3-hydroxyl propoxyl) titanium or tetra (1, 3-dihydroxy isopropoxy) titanium.
6. The process for preparing modified copolyester according to claim 1, wherein: in the preparation method of the hydroxyl alkoxy titanium, the alcohol substance is one or more of ethylene glycol, 1, 3-propylene glycol, glycerol, 1, 4-butanediol, 1,2, 3-butanetriol, 1,2, 4-butanetriol, 1, 5-pentanediol, 1,2, 5-pentanetriol, 1, 6-hexanediol, 1,2, 3-hexanetriol or 1,2, 6-hexanetriol or alcohol derivatives thereof.
7. The process of claim 6, wherein: the alcohol substance is ethylene glycol, 1, 3-propylene glycol or glycerol.
8. The process for preparing modified copolyester according to claim 1, wherein: the titanium atom content of the titanium oxyhydroxide is 5 to 100 [ mu ] g/g based on the total amount of the polyester resin.
9. The process for preparing modified copolyester according to claim 1, wherein: a phosphorus-containing stabilizer is added during the polymerization, wherein the content of phosphorus atoms in the phosphorus-containing stabilizer is 5 to 200 mu g/g based on the total amount of the polyester resin.
10. The process for preparing modified copolyester according to claim 1, wherein: the alcohols in the esterification reaction are ethylene glycol, isosorbide and 1, 4-cyclohexanedimethanol, or the alcohols are ethylene glycol and isosorbide.
11. A modified copolyester is characterized in that: the modified copolyester is prepared by the method of any one of claims 1 to 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110458977.8A CN113185682B (en) | 2021-04-27 | 2021-04-27 | Modified copolyester and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110458977.8A CN113185682B (en) | 2021-04-27 | 2021-04-27 | Modified copolyester and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113185682A CN113185682A (en) | 2021-07-30 |
| CN113185682B true CN113185682B (en) | 2022-08-12 |
Family
ID=76979352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110458977.8A Active CN113185682B (en) | 2021-04-27 | 2021-04-27 | Modified copolyester and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113185682B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114605623B (en) * | 2022-03-14 | 2023-08-11 | 华润化学材料科技股份有限公司 | Flexible PET-based copolyester and bead foam prepared from same |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3047515A (en) * | 1956-07-09 | 1962-07-31 | Goodyear Tire & Rubber | Preparation of polyesters using titanium-containing catalysts |
| JP4107699B2 (en) * | 1997-09-02 | 2008-06-25 | 三井化学株式会社 | Reaction liquid of titanium halide and ethylene glycol, preparation method thereof, polyester production catalyst, production method of polyester |
| US6451959B1 (en) * | 1998-12-25 | 2002-09-17 | Mitsui Chemicals, Inc. | Catalyst for polyester production, process for producing polyester using the catalyst, polyester obtained by the process, and uses of the polyester |
| CN1403464A (en) * | 2002-10-15 | 2003-03-19 | 上海交通大学 | Prepn of dibasic alkoxide of titanium |
| CN100386361C (en) * | 2005-12-06 | 2008-05-07 | 中国石油天然气股份有限公司 | Method for synthesizing non-fiber modified copolyester by catalysis of ethylene glycol titanium |
| CN107955142B (en) * | 2016-10-18 | 2020-02-07 | 中国石油化工股份有限公司 | Process for preparing isosorbide-containing polyesters |
| CN109897171A (en) * | 2019-03-29 | 2019-06-18 | 新凤鸣集团股份有限公司 | A kind of method that ecological efficient compounding polycondensation catalyst prepares polyester |
-
2021
- 2021-04-27 CN CN202110458977.8A patent/CN113185682B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113185682A (en) | 2021-07-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI618730B (en) | Preparation method of polyester resin | |
| JP2564463B2 (en) | Biodegradable aliphatic polyester and method for producing the same | |
| US5681918A (en) | Process for preparing copolyesters of terephthalic acid ethylene glycol and 1 4-cyclohexanedimethanol exhibiting a neutral hue high clarity and increased brightness | |
| JP3438072B2 (en) | Method for producing copolyester resin using titanium dioxide / silicon dioxide coprecipitate catalyst in suspension in glycol | |
| JP5711667B2 (en) | Method for producing polyester resin copolymerized with isosorbide | |
| CN109134834B (en) | Preparation method of isosorbide copolyester | |
| CN102558519A (en) | Aromatic-aliphatic copolyester and synthetic method thereof | |
| US4066627A (en) | Production of polyesters | |
| CN107955142B (en) | Process for preparing isosorbide-containing polyesters | |
| CN114835886A (en) | Solid-state bimetallic titanium polyester catalyst and preparation method and application thereof | |
| CN113185682B (en) | Modified copolyester and preparation method thereof | |
| CN111087583B (en) | Preparation method of low-end carboxyl PBT resin | |
| CN116574247B (en) | A preparation method of butanediol polyester | |
| KR20100079504A (en) | Method for preparing polyester resin copolymerized with neopentyl glycol | |
| CN111269404B (en) | Composite catalyst suitable for synthesizing polytrimethylene terephthalate and preparation method of polytrimethylene terephthalate | |
| CN115785409A (en) | Titanium catalyst and preparation method thereof | |
| JPH0563506B2 (en) | ||
| CN115612075B (en) | A highly transparent and light-colored PCT-based random copolyester resin and its preparation method | |
| JP2011174012A (en) | Method for producing copolyester | |
| CN114685853A (en) | Auxiliary agent for effectively improving hue of polyester and preparation method thereof | |
| CN117624567A (en) | Thermoplastic polyester, and preparation method and application thereof | |
| KR900001375B1 (en) | Method for preparing polybutylene terephthalate | |
| CN117567733A (en) | PETG copolyester and synthetic method for improving transparency of PETG copolyester | |
| CN119119440A (en) | Isosorbide-modified polyethylene terephthalate-1,4-cyclohexanedimethanol ester and preparation method thereof | |
| KR20250047507A (en) | Polyester resin with excellent mechanical properties and biodegradability and method for preparing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |