CN112794997B - Porous composite catalyst, preparation method thereof and preparation method of polybutylene terephthalate adipate - Google Patents
Porous composite catalyst, preparation method thereof and preparation method of polybutylene terephthalate adipate Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
- C08G63/183—Terephthalic acids
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Abstract
The invention provides a preparation method of a porous composite catalyst, which comprises the following steps: A) mixing calcium salt, carbonate and an additive in water, and reacting to obtain a first reaction solution; B) adding an alcoholic solution of a titanium source into the first reaction solution, and reacting to obtain an intermediate; C) and calcining the intermediate to obtain the porous composite catalyst. The carrier used by the nano-porous composite catalyst prepared by the method is porous calcium carbonate, and the porous structure can enhance the adsorption effect of calcium carbonate on metal ions on one hand, and can enlarge the contact area of a reaction substrate and the catalyst on the other hand to improve the catalytic efficiency; meanwhile, the calcium carbonate used as a carrier material can improve the mechanical property of PBAT. Experimental results show that the porous composite catalyst can effectively improve the catalytic efficiency of the reaction and the conversion rate of reaction substrates.
Description
Technical Field
The invention belongs to the technical field of organic polymer material preparation, and particularly relates to a porous composite catalyst, a preparation method of the porous composite catalyst and a preparation method of polybutylene terephthalate adipate.
Background
Polybutylene terephthalate adipate (PBAT) is a thermoplastic biodegradable polyester material. The molecular chain of the polymer contains aromatic chain segments and aliphatic chain segments. Thus, PBAT combines the stability and toughness of aromatic segments and the rigidity and degradability of aliphatic segments. The structural formula is as follows:
PBAT has excellent processability except complete degradability, and can be compared favorably with low-density polyethylene, so that the PBAT is industrially processed into degradable mulching films, express packaging bags, environment-friendly shopping bags and the like. There are many companies that realize the industrial production of PBAT in the world, among which BASF in germany, Eastman in the united states, dupont, etc. are large-scale companies.
The technical route of PBAT is mainly an esterification-polycondensation method. The method comprises the steps of firstly carrying out esterification reaction on carboxylic acid and excessive alcohol under the action of a catalyst to generate corresponding esterified substances, and then carrying out polycondensation reaction under a vacuum condition to obtain a final PBAT product. In the whole synthesis process, the catalyst plays a key role, can effectively promote the esterification reaction, and improves the conversion rate of reaction substrates and the yield of products. At present, germanium, antimony and titanium catalysts are used for synthesizing polyester in industry. Among them, the germanium catalyst has good catalytic performance and few side reactions, but is expensive, which limits its large-scale use. The antimony catalyst has less side reaction, the raw material is cheap but the activity is low, and the antimony belongs to heavy metal and can cause serious pollution to the environment, and the color of the produced product is dark.
Patent 110591058A discloses a catalytic polycondensation method for a degradable packaging material, which comprises heating the degradable packaging material, butanediol adipate and butanediol terephthalate in a salt bath, and adding tetrabutyl titanate into the heated degradable packaging material as a catalyst to perform catalytic reaction to obtain a PBAT product. However, the esterification reaction of PBAT generates water as a by-product, whereas tetrabutyl titanate is not resistant to hydrolysis and the activity is not effectively controlled in the whole catalytic reaction, resulting in poor stability, resulting in yellow or turbid product.
Patent CN103483522A discloses a high molecular weight aliphatic-aromatic copolyester and a preparation method thereof, wherein an aromatic monomer, 1, 4-butanediol, adipic acid and a catalyst are added into a reaction kettle for esterification under the protection of inert gas. And then vacuumizing for polycondensation reaction, wherein the polycondensation reaction time is 4-10 hours. The catalyst in the process is one of tetrabutyl titanate, antimony trioxide, antimony acetate, germanium trioxide, sodium germanate or trimethyl phosphate. The obtained PBAT product has low number average molecular weight, long reaction time and low catalytic efficiency of the catalyst.
Although the catalyst has a certain effect on improving the polyester synthesis rate, the catalyst has certain defects in consideration of comprehensive factors such as catalytic efficiency, byproducts, product color, product tensile strength, product molecular weight and the like, and the problems of dark product color, low molecular weight, more byproducts and the like are shown in the production of PBAT. Therefore, the development of a high-efficiency, stable and cheap catalyst has wide application prospect.
Disclosure of Invention
The invention aims to provide a porous composite catalyst, a preparation method thereof and a preparation method of polybutylene terephthalate adipate.
The invention provides a preparation method of a porous composite catalyst, which comprises the following steps:
A) mixing calcium salt, carbonate and an additive in water, and reacting to obtain a first reaction solution;
B) adding an alcoholic solution of a titanium source into the first reaction solution, and reacting to obtain an intermediate;
C) and calcining the intermediate to obtain the porous composite catalyst.
Preferably, the calcium salt is one or more of calcium chloride, calcium acetate and calcium nitrate tetrahydrate;
the carbonate is one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate;
the molar ratio of the carbonate to the calcium salt is (1-4): 1.
preferably, the additive is one or more of polyethylene glycol, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and sodium dodecyl sulfate;
the molar ratio of the calcium salt to the additive is 1: (1.2-2).
Preferably, the reaction temperature of the step A) is 200-260 ℃; the reaction time in the step A) is 8-10 hours.
Preferably, the concentration of the alcoholic solution of the titanium source is 0.1-0.4 mol/L;
the titanium source is one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, tetramethyl titanate and diisopropyl titanate
The molar ratio of the titanium source to the calcium salt is (20-5): 1.
preferably, the reaction temperature in the step B) is 30-80 ℃; the reaction time in the step B) is 2-4 hours.
Preferably, the calcining temperature in the step C) is 400-600 ℃; the calcining heat preservation time is 2-5 hours;
the temperature rise rate of the calcination in the step C) is 50-200 ℃/h.
The present invention provides a porous composite catalyst prepared by the preparation method as described above, comprising porous calcium carbonate and titanium supported on the porous calcium carbonate;
the porous calcium carbonate has the aperture of 40-55 nm and the specific surface area of 20-35 m 2 /g。
The invention provides a preparation method of polybutylene terephthalate adipate, which comprises the following steps:
A) mixing the porous composite catalyst, terephthalic acid, adipic acid, 1, 4-butanediol and a primary sensitization auxiliary agent, and carrying out esterification reaction at 160-220 ℃ under normal pressure;
B) and reducing the reaction pressure to 1000-4000 Pa for 30-60 min, gradually reducing the pressure to below 50Pa, heating to 240-250 ℃, adding a heat stabilizer and the porous composite catalyst, and performing polycondensation reaction to obtain the polybutylene terephthalate adipate.
Preferably, in the esterification reaction, the adding amount of the porous composite catalyst accounts for 40-50 ppm of the total mass of the terephthalic acid and the adipic acid;
in the polycondensation reaction, the adding amount of the porous composite catalyst accounts for 150-200 ppm of the total mass of the terephthalic acid and the adipic acid.
The invention provides a preparation method of a porous composite catalyst, which comprises the following steps: A) mixing calcium salt, carbonate and an additive in water, and reacting to obtain a first reaction solution; B) adding an alcoholic solution of a titanium source into the first reaction solution, and reacting to obtain an intermediate; C) and calcining the intermediate to obtain the porous composite catalyst.
Compared with the prior art, the technical scheme of the invention has the following positive effects:
(1) the carrier used by the nano-porous composite catalyst prepared by the method is porous calcium carbonate, and the porous structure can enhance the adsorption effect of calcium carbonate on metal ions on one hand, and can enlarge the contact area of a reaction substrate and the catalyst on the other hand to improve the catalytic efficiency;
(2) the nano porous composite catalyst prepared by the method has the advantages that the catalytic active metal is titanium metal, no heavy metal is contained, the reaction activity is high, the toxicity is low, and the pollution is avoided;
(3) the nano porous composite catalyst carrier prepared by the method is nano calcium carbonate which is usually used as a reinforcing and toughening additive of plastics and can replace part of expensive fillers and auxiliary agents, so that the production cost of the product is reduced, and the market competitiveness is improved. Therefore, the composite catalyst prepared by the invention can improve the catalytic efficiency, and simultaneously, the calcium carbonate used as a carrier material can improve the mechanical property of PBAT;
(4) the nano-porous composite catalyst prepared by the method has the advantages of wide raw material source, low price and simple preparation process, and is suitable for industrial large-scale production and application;
(5) the porous composite catalyst prepared by the invention is white in color and does not influence the whiteness of the product.
Detailed Description
The invention provides a preparation method of a porous composite catalyst, which comprises the following steps:
A) mixing calcium salt, carbonate and an additive in water, and reacting to obtain a first reaction solution;
B) adding an alcoholic solution of a titanium source into the first reaction solution, and reacting to obtain an intermediate;
C) and calcining the intermediate to obtain the porous composite catalyst.
In the invention, the calcium salt is preferably one or more of calcium chloride, calcium acetate and calcium nitrate tetrahydrate, wherein the calcium chloride is preferably anhydrous calcium chloride; the carbonate is preferably one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate, wherein the sodium carbonate is preferably anhydrous sodium carbonate; the additive is a template agent, and preferably is one or more of polyethylene glycol, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and sodium dodecyl sulfate.
In the invention, the molar ratio of the carbonate to the calcium salt is preferably (1-4): 1, more preferably (2-3): 1, such as 1:1, 2:1, 3:1 or 4:1, preferably a range having any of the above values as upper or lower limits; the molar ratio of calcium salt to additive is preferably 1: (1.2-2), more preferably 1: (1.5 to 1.8) such as 1:1.2, 1:1.3, 1:1.4, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, preferably any of the above values is a range having an upper limit or a lower limit.
In the invention, the reaction temperature is preferably 200-260 ℃, more preferably 210-250 ℃, such as 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃ and 260 ℃, and preferably ranges with any value as the upper limit or the lower limit; the reaction time is preferably 8 to 10 hours, such as 8 hours, 9 hours or 10 hours.
In the present invention, it is preferable that the alcoholic solution of the titanium source is added dropwise to the first reaction, and the reaction is carried out, and after the reaction is completed, the temperature is lowered to room temperature, so that a white precipitate is obtained.
In the invention, the titanium source is preferably one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, tetramethyl titanate and diisopropyl titanate; the titanium source alcoholic solution is preferably a titanium source alcoholic solution, the concentration of the titanium source alcoholic solution is preferably 0.1-0.4 mol/L, more preferably 0.2-0.3 mol/L, such as 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/, and preferably a range value taking any value as an upper limit or a lower limit; the molar ratio of the titanium source to the calcium salt is preferably (20-5): 1, more preferably (18 to 10): 1, such as 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, preferably any of the above values is the upper or lower limit of the range.
In the invention, the reaction temperature is preferably 30-80 ℃, more preferably 40-70 ℃, such as 30 ℃, 35 ℃,40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ and 80 ℃, preferably in a range with any value as the upper limit or the lower limit; the reaction time is preferably 2 to 4 hours, and more preferably 3 hours.
The white precipitate is taken out by a solid-liquid separation method, washed to be neutral and dried to obtain white powder serving as an intermediate.
According to the invention, the white precipitate is dried preferably under a vacuum condition, and the drying temperature is preferably 60-80 ℃, more preferably 65-75 ℃; the drying time is preferably 12-24 hours, and more preferably 12-20 hours.
In the invention, the calcination can make the catalyst more stable, and the calcination temperature is preferably 400-600 ℃, more preferably 450-550 ℃, such as 400 ℃, 450 ℃, 500 ℃, 550 ℃ and 600 ℃, and is preferably a range value taking any value as an upper limit or a lower limit; the heat preservation time of the calcination is preferably 2-5 hours, and more preferably 3-4 hours; the heating rate of the calcination is preferably 50-200 ℃/h, and more preferably 100-150 ℃/h.
The invention also provides a porous composite catalyst prepared by the preparation method.
The porous composite catalyst comprises carrier porous calcium carbonate and titanium loaded on the porous calcium carbonate, and the nano porous calcium carbonate carrier prepared by the invention has certain adsorption capacity on metal ions, and substances adsorbed on the highly dispersed calcium carbonate cannot be desorbed in the later aggregation process, and the desorption can only occur when precipitates are recrystallized, so that the aim of loading the titanium is achieved.
The invention also provides a preparation method of polybutylene terephthalate adipate, which comprises the following steps:
A) mixing the porous composite catalyst, terephthalic acid, adipic acid, 1, 4-butanediol and a primary sensitization auxiliary agent, and carrying out esterification reaction at 160-220 ℃ under normal pressure;
B) and reducing the reaction pressure to 1000-4000 Pa for 30-60 min, gradually reducing the pressure to below 50Pa, heating to 240-250 ℃, adding a heat stabilizer and the porous composite catalyst, and performing polycondensation reaction to obtain the polybutylene terephthalate adipate.
In the invention, the primary sensitizer is preferably sodium acetate, and the amount of the primary sensitizer is preferably 0.1 to 5 wt%, more preferably 1 to 4 wt%, and most preferably 2 to 3 wt% of the mass of the polybutylene terephthalate by taking the mass of the polybutylene terephthalate obtained by the esterification reaction as a reference.
In the present invention, the molar ratio of terephthalic acid to adipic acid is preferably 1: (1.1 to 1.5), more preferably 1: (1.2 to 1.4), such as 1:1.1, 1:1.2, 1:1.3, 1:1.4 or 1:1.5, preferably any of the above values as an upper or lower limit, and the molar ratio of the total molar amount of terephthalic acid and adipic acid to 1, 4-butanediol is preferably 1: (1.5-2), more preferably 1: (1.6 to 1.9) such as 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2.0, and preferably ranges having any of the above values as upper or lower limits.
In the present invention, the amount of the catalyst used in the esterification reaction is 40 to 50ppm, such as 40ppm, 41ppm, 42ppm, 43ppm, 44ppm, 45ppm, 46ppm, 47ppm, 48ppm, 49ppm, 50ppm, based on the total mass of the terephthalic acid and the adipic acid, and any of the above values is preferably used as an upper limit or a lower limit.
In the invention, the temperature of the esterification reaction is preferably 160-220 ℃, more preferably 170-210 ℃, such as 160 ℃, 170 ℃, 180 ℃, 1, 190 ℃, 200 ℃, 210 ℃ and 220 ℃, preferably a range value taking any value as an upper limit or a lower limit; the time of the esterification reaction is preselected to be 3-4 hours. The esterification reaction is preferably carried out under normal pressure.
After the esterification reaction is finished, the reaction kettle is vacuumized to 1000-4000 Pa, preferably 1500-3500 Pa, such as 1000Pa, 1500Pa, 2000Pa, 2500Pa, 3000Pa, 3500Pa and 4000Pa, and preferably the range value taking any value as the upper limit or the lower limit; and maintaining the system after the esterification reaction for 30-60 min, preferably 40-50 min under the pressure of 1000-4000 Pa.
And then gradually vacuumizing to below 50Pa, raising the temperature to 240-250 ℃, adding the porous composite catalyst and the heat stabilizer, performing polycondensation reaction to obtain a polymer melt, and performing water-cooling granulation to obtain the granules of the polybutylene terephthalate adipate.
In the present invention, the amount of the porous composite catalyst added in the polycondensation reaction is preferably 150 to 200ppm, such as 150ppm, 160ppm, 170ppm, 180ppm, 190ppm or 200ppm, based on the total mass of the terephthalic acid and the adipic acid, and is preferably a range value in which any of the above values is an upper limit or a lower limit.
In the invention, the total adding amount of the porous composite catalyst is 20-800 ppm, preferably 100-700 ppm, more preferably 200-500 ppm, and most preferably 250-400 ppm.
The heat stabilizer is preferably maleic anhydride and/or epoxidized soybean oil, and the dosage of the heat stabilizer is preferably 0.1-5 wt%, more preferably 1-4 wt%, and most preferably 2-3 wt% of the mass of the polybutylene terephthalate adipate.
In the present invention, the time of the polycondensation reaction is preferably 2 to 3 hours.
The polybutylene terephthalate adipate obtained is prepared by using the catalyst in the invention.
The invention provides a preparation method of a porous composite catalyst, which comprises the following steps: A) mixing calcium salt, carbonate and an additive in water, and reacting to obtain a first reaction solution; B) adding an alcoholic solution of a titanium source into the first reaction solution, and reacting to obtain an intermediate; C) and calcining the intermediate to obtain the porous composite catalyst.
Compared with the prior art, the technical scheme of the invention has the following positive effects:
(1) the carrier used by the nano-porous composite catalyst prepared by the method is porous calcium carbonate, and the porous structure can enhance the adsorption effect of calcium carbonate on metal ions on one hand, and can enlarge the contact area of a reaction substrate and the catalyst on the other hand to improve the catalytic efficiency;
(2) the nano-porous composite catalyst prepared by the method has the catalytic active metal of titanium metal, does not contain heavy metal, has high reaction activity, low toxicity and no pollution;
(3) the nano porous composite catalyst carrier prepared by the method is nano calcium carbonate which is usually used as a reinforcing and toughening additive of plastics and can replace part of expensive fillers and auxiliary agents, so that the production cost of the product is reduced, and the market competitiveness is improved. Therefore, the composite catalyst prepared by the invention can improve the mechanical property of PBAT by using calcium carbonate as a carrier material while improving the catalytic efficiency;
(4) the nano-porous composite catalyst prepared by the method has the advantages of wide raw material source, low price and simple preparation process, and is suitable for industrial large-scale production and application;
(5) the porous composite catalyst prepared by the invention is white in color and does not influence the whiteness of the product.
In order to further illustrate the present invention, the following examples are provided to describe a porous composite catalyst, a method for preparing the same, and a method for preparing polybutylene terephthalate adipate in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 0.1mol of tetrabutyl titanate at room temperature, and diluting the tetrabutyl titanate to a certain volume by using ethanol to obtain a 0.1mol/L tetrabutyl titanate-ethanol solution.
Placing 1mol of anhydrous calcium chloride, 1mol of anhydrous sodium carbonate and 0.2mol of polyethylene glycol in water, stirring uniformly at room temperature, then placing the mixture in a stainless steel reaction kettle, and reacting for 8 hours at the temperature of 200 ℃. And dropwise adding tetrabutyl titanate-ethanol solution into the reaction system, finishing dropwise adding within 30min, and continuously reacting for 2 h. After the reaction is finished, cooling to room temperature, taking out white precipitate, washing the white precipitate to be neutral by acetone and clear water, and drying the white precipitate under the vacuum condition to obtain white powder. And finally, placing the obtained white powder in a tubular furnace, heating to 400 ℃ at the speed of 100 ℃/h, preserving the temperature for 2 hours, and naturally cooling to obtain the porous composite catalyst A.
Example 2
Weighing 0.1mol of tetrabutyl titanate at room temperature, and diluting the tetrabutyl titanate to a certain volume by using ethanol to obtain a 0.1mol/L tetrabutyl titanate-ethanol solution.
Placing 1mol of anhydrous calcium chloride, 2mol of anhydrous sodium carbonate and 0.2mol of polyethylene glycol in water, stirring uniformly at room temperature, then placing the mixture in a stainless steel reaction kettle, and reacting for 8 hours at 240 ℃. And dropwise adding tetrabutyl titanate-ethanol solution into the reaction system, completing dropwise adding for 30min, and continuously reacting for 2 h. After the reaction is finished, cooling to room temperature, taking out white precipitate, washing the white precipitate to be neutral by acetone and clear water, and drying the white precipitate under the vacuum condition to obtain white powder. And finally, placing the obtained white powder in a tubular furnace, heating to 400 ℃ at the speed of 100 ℃/h, preserving the temperature for 2 hours, and naturally cooling to obtain the porous composite catalyst B.
Example 3
Weighing 0.1mol of tetrabutyl titanate at room temperature, and diluting the tetrabutyl titanate to a certain volume by using ethanol to obtain a 0.1mol/L tetrabutyl titanate-ethanol solution.
Placing 1mol of anhydrous calcium chloride, 3mol of anhydrous sodium carbonate and 0.2mol of polyethylene glycol in water, stirring uniformly at room temperature, then placing the mixture in a stainless steel reaction kettle, and reacting for 8 hours at the temperature of 260 ℃. And dropwise adding tetrabutyl titanate-ethanol solution into the reaction system, finishing dropwise adding within 30min, and continuously reacting for 2 h. After the reaction is finished, cooling to room temperature, taking out white precipitate, washing the white precipitate to be neutral by acetone and clear water, and drying the white precipitate under the vacuum condition to obtain white powder. And finally, placing the obtained white powder in a tubular furnace, heating to 400 ℃ at the speed of 100 ℃/h, preserving the temperature for 2 hours, and naturally cooling to obtain the porous composite catalyst C.
Examples 4 to 6: properties of PBAT product synthesized by porous composite catalyst
10mol of terephthalic acid, 10mol of adipic acid, 30mol of butanediol and 40ppm of catalyst (accounting for the total mass of the terephthalic acid and the adipic acid) are added into a 10L polyester kettle in sequence according to the table 1, the temperature is raised to 160 ℃, the reaction time is 3 hours, and the esterification process is completed.
Vacuumizing the reaction kettle to 1000Pa for 30min, gradually vacuumizing to below 50Pa, heating to 250 ℃ and keeping, adding 150ppm of catalyst and 0.5 wt% of maleic anhydride for polycondensation reaction for 3 hours to obtain a polymer melt, and performing water cooling and pelletizing to obtain a PBAT product.
The PBAT products of examples 4-6 were tested and the properties are shown in Table 1,
TABLE 1 Properties of PBAT in examples 4-6
Note: determining the weight average molecular weight of the polymer product by adopting a GPC method; the tensile strength, the elongation at break and the color are measured according to the standard GB/T32366-; the intrinsic viscosity of the polymer product was measured using an Ubbelohde viscometer.
As can be seen from the data in Table 1, when PBAT is synthesized by using the porous composite catalyst, high molecular weight and tensile strength can be obtained, and the mechanical properties are excellent. The side reactions in the reaction are less, the reaction temperature is reduced, and the reaction time is shortened, which shows that the catalyst has high catalytic reaction efficiency, high conversion rate of reaction substrates, less amount of formed byproducts and high color and whiteness of products.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A preparation method of a porous composite catalyst comprises the following steps:
A) mixing calcium salt, carbonate and an additive in water, and reacting to obtain a first reaction solution;
the calcium salt is one or more of calcium chloride, calcium acetate and calcium nitrate tetrahydrate; the carbonate is one or more of sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate; the molar ratio of the carbonate to the calcium salt is (1-4): 1;
the additive is one or more of polyethylene glycol, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and sodium dodecyl sulfate; the molar ratio of the calcium salt to the additive is 1: (1.2-2);
B) adding an alcoholic solution of a titanium source into the first reaction solution, and reacting to obtain an intermediate;
the titanium source is one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, tetramethyl titanate and diisopropyl titanate;
C) and calcining the intermediate to obtain the porous composite catalyst.
2. The preparation method according to claim 1, wherein the temperature of the reaction in the step A) is 200-260 ℃; the reaction time in the step A) is 8-10 hours.
3. The method according to claim 1, wherein the concentration of the alcoholic solution of the titanium source is 0.1 to 0.4 mol/L;
the molar ratio of the titanium source to the calcium salt is (20-5): 1.
4. the preparation method according to claim 1, wherein the temperature of the reaction in the step B) is 30-80 ℃; the reaction time in the step B) is 2-4 hours.
5. The preparation method according to claim 1, wherein the temperature of the calcination in the step C) is 400-600 ℃; the calcining heat preservation time is 2-5 hours;
the temperature rise rate of the calcination in the step C) is 50-200 ℃/h.
6. The porous composite catalyst prepared by the preparation method of any one of claims 1 to 5, which comprises porous calcium carbonate and titanium loaded on the porous calcium carbonate;
the pore diameter of the porous calcium carbonate is 40-55 nm, and the specific surface area is 20-35 m 2 /g。
7. A preparation method of polybutylene terephthalate adipate comprises the following steps:
A) mixing the porous composite catalyst, terephthalic acid, adipic acid, 1, 4-butanediol and primary sensitization auxiliary agent in claim 6, and carrying out esterification reaction at 160-220 ℃ under normal pressure;
B) reducing the reaction pressure to 1000-4000 Pa for 30-60 min, gradually reducing the pressure to below 50Pa, heating to 240-250 ℃, adding a heat stabilizer and the porous composite catalyst in claim 6, and performing polycondensation reaction to obtain polybutylene terephthalate adipate.
8. The preparation method according to claim 7, wherein in the esterification reaction, the addition amount of the porous composite catalyst accounts for 40-50 ppm of the total mass of the terephthalic acid and the adipic acid;
in the polycondensation reaction, the adding amount of the porous composite catalyst accounts for 150-200 ppm of the total mass of the terephthalic acid and the adipic acid.
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