CN114621426B - Catalyst for synthesizing degradable polyester, preparation method and application thereof - Google Patents

Catalyst for synthesizing degradable polyester, preparation method and application thereof Download PDF

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CN114621426B
CN114621426B CN202210386447.1A CN202210386447A CN114621426B CN 114621426 B CN114621426 B CN 114621426B CN 202210386447 A CN202210386447 A CN 202210386447A CN 114621426 B CN114621426 B CN 114621426B
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catalyst
reaction
acid
stirring
butanediol
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CN114621426A (en
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刘春信
冯智刚
王璇
焦淑元
张中超
张振国
张海瑜
王延刚
王厚福
翟立国
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Shandong Ruifeng Chemical Co ltd
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention belongs to the technical field of catalysts for polyester synthesis, and particularly relates to a catalyst for degradable polyester synthesis, a preparation method and application thereof. The catalyst for synthesizing the degradable polyester comprises the following components: the catalyst comprises a catalyst main body, a stabilizer, an acid regulator, a complexing agent, a diluent and a catalyst carrier according to the mass molar ratio of 1:0.2-0.5: 0.05-0.15:0.3-0.7: 0.2-1.0:1.0-4.0. The invention provides a catalyst for synthesizing degradable polyester, which has the advantages of simple preparation method, mild reaction conditions, high catalytic activity, difficult inactivation and high degradation degree after being applied to polyester synthesis.

Description

Catalyst for synthesizing degradable polyester, preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalysts for polyester synthesis, and particularly relates to a catalyst for degradable polyester synthesis, a preparation method and application thereof.
Background
At present, the catalyst containing tetrabutyl titanate adopted in the synthetic method of polyester has good catalytic effect, but has low catalytic efficiency, is easy to hydrolyze and partially deactivated, and the hydrolyzed catalyst is unstable, so that a large amount of catalyst needs to be added simultaneously due to catalytic activity, the cost of the treatment and dosage of the catalyst at the later stage is higher, side reactions are serious, the prepared product has poorer color, and the requirement on vacuum degree is higher in the later polycondensation reaction, generally the requirement on equipment is higher, the reaction condition is harsh, and the production efficiency is low. In the prior art, the catalyst for catalyzing and synthesizing the tetrabutyl titanate of the polyester is difficult to deactivate and improve the hue of the polyester in order to have good catalytic effect, and mostly adopts the catalyst which is compounded with heavy metal or noble metal, has high price and is rare in raw materials; or high temperature calcination during the manufacturing process, or other severe conditions.
CN202111649537.7 discloses a titanium composite catalyst for polyester synthesis and its preparation and application, the titanium composite catalyst is composed of phosphate and titanium silicon composite catalyst, the preparation method is that dicarboxylic acid or its derivative and dihydric alcohol are adopted to carry out esterification reaction, and the titanium composite catalyst for polyester synthesis is added before esterification reaction to obtain prepolymer; then, carrying out polycondensation reaction on the prepolymer to obtain polyester; the adding amount of the titanium composite catalyst for polyester synthesis is 1-10 ppm calculated by the equivalent weight of titanium in the catalyst; the titanium compound is one or more of tetraethyl titanate, tetrapropyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetraisooctyl titanate and titanium tetrachloride; although the activity of the catalyst is not easy to be deactivated, the catalyst needs to be loaded on biomass charcoal with a porous structure to control side reaction in the polyester reaction, the combination is unstable, solid particles exist, the catalyst cannot be stored for a long time, and the pressure of the polycondensation reaction still needs to be below 100 pa.
CN202110411978.7 discloses a preparation method and application of a titanium phosphorus catalyst for polyester synthesis, the titanium phosphorus catalyst is prepared from titanium compound, phosphorus compound and fatty alkyl trimethyl ammonium halide, the preparation method is to dissolve fatty alkyl trimethyl ammonium halide in water; the phosphorus compound and the titanium compound are dissolved in the mixed solution, continuously stirred and placed at a constant temperature for reaction for 1.0 to 48.0 hours, and then the solid filtered out of the mixed solution is roasted at a high temperature. Finally, filtering, washing, vacuum drying, crushing and grinding to obtain the titanium-phosphorus catalyst for polyester, and adjusting the proportion of the titanium-phosphorus catalyst to obtain the solid titanium-phosphorus catalyst, wherein the solid catalyst has poor dispersibility, low reaction activity and high reaction condition.
CN202110067903.1 discloses a catalyst for synthesizing biodegradable semi-aromatic polyester, a preparation method and application, the catalyst is a compound of aluminum element, titanium element and phosphorus element, wherein the molar ratio of aluminum element, titanium element and phosphorus element is 1:0.5-2:0.05-0.5, the prepared catalyst adopts the compound of three element catalysts, the hydrolysis problem of the catalyst cannot be solved, the reaction activity is low, and the pressure of polycondensation reaction still needs to be below 100 pa.
Disclosure of Invention
The technical problem to be solved by the invention is to provide the catalyst for synthesizing the degradable polyester, which has high catalytic activity and is not easy to deactivate; the preparation method is simple and convenient, and the reaction condition is mild; the degradation degree is high after the polyester is synthesized.
The invention relates to a catalyst for synthesizing degradable polyester, which comprises the following components: the catalyst comprises a catalyst main body, a stabilizer, an acid regulator, a complexing agent, a diluent and a catalyst carrier according to the mol ratio of 1:0.2-0.5: 0.05-0.15:0.3-0.7: 0.2-1.0:1.0-4.0.
The main body of the catalyst is one or more of tetrabutyl titanate, stannous chloride, isopropyl titanate and stannous octoate;
the catalyst carrier is one or more of 1, 4-butanediol, ethanol, ethylene glycol, propylene glycol and pentanediol.
The stabilizer is one or more of triphenyl phosphate, N' -diisopropylcarbodiimide, dicyclohexylcarbodiimide and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride.
The acidity regulator is one or more of phosphoric acid, citric acid, acetic acid, carbonic acid, hypochlorous acid, nitric acid, hydrochloric acid and sulfuric acid.
The complexing agent is one or more of monoethanolamine, diethanolamine, triethanolamine, maleic anhydride, acetylacetone, sodium nitrilotriacetate, ethylenediamine tetraacetate and diethylenetriamine pentacarboxylate.
The diluent is one or more of tetrahydrofuran, 1, 4-butanediol, triethyl phosphate, triethyl citrate, diisopropyl ether and butyl formate.
The preparation method of the catalyst for synthesizing the degradable polyester comprises the following steps: firstly, dehydrating a catalyst main body, a stabilizer, an acid regulator, a complexing agent, a diluent and a catalyst carrier; then adding a diluent into a reaction kettle, removing air, stirring, heating to 70-90 ℃, sequentially adding an acid regulator, a complexing agent and a stabilizer, stirring, adding a catalyst main body, and keeping the solution in a clear and transparent state for reaction for 0.5-1h to obtain a reaction solution; and finally, adding the catalyst carrier into a reaction kettle, stirring, heating to 50-80 ℃, adding the reaction solution of the previous step into the reaction kettle, and uniformly stirring to obtain the clear and transparent catalyst for synthesizing the degradable polyester.
The catalyst is applied to the synthesis of degradable polyester: the method comprises the following steps: firstly, carrying out esterification reaction on dihydric alcohol, dibasic acid and a catalyst at the absolute pressure of 60-80 kpa, then carrying out pre-polycondensation reaction at the absolute pressure of 4-6 kpa, and finally carrying out final polycondensation at the absolute pressure of less than or equal to 300pa to obtain degradable polyester; the catalyst is used in an amount of 0.1-0.8% of the total mass of the degradable polyester.
The dihydric alcohol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 3-butanediol, 1, 4-butanediol, pentanediol, hexanediol, heptanediol, octanediol, and diethylene glycol.
The dibasic acid is C8-C14 aromatic dibasic acid or/and C2-C10 aliphatic dibasic acid.
Preferably, the mole ratio of the dihydric alcohol to the dibasic acid is 1 (1-1.8);
preferably, the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is 1 (0.65 to 1.5).
Aromatic dibasic acid: the aromatic dibasic acid is C8-C14 and is one or more of terephthalic acid, phthalic acid or isophthalic acid;
aliphatic dibasic acid: the aliphatic dibasic acid is C2-C10 and is one or more of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid and suberic acid.
Specifically, the preparation method of the catalyst for synthesizing the degradable polyester comprises the following steps: firstly, dehydrating a catalyst main body, a stabilizer, an acid regulator, a complexing agent, a diluent and a catalyst carrier; then, introducing nitrogen into a diluent container to replace air in a kettle, stirring for 30-120 r/min, heating to 70-90 ℃, sequentially adding an acid regulator, a complexing agent and a stabilizer, uniformly stirring, slowly adding a catalyst main body, keeping the solution in a clear and transparent state for reaction, and continuing stirring for 0.5-1h after the catalyst main body is added to ensure that the reaction is complete, thus obtaining a reaction solution; adding the catalyst carrier into a reaction kettle, stirring for 30-120 r/min, heating to 50-80 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain the clear and transparent degradable polyester catalyst.
Specifically, the catalyst is applied to the synthesis of degradable polyester: the method comprises the following steps: firstly, mixing dihydric alcohol, dibasic acid and a catalyst, heating to 230-235 ℃, vacuumizing to 60-80 kpa absolute pressure for esterification reaction, continuously heating to 235-240 ℃ after the esterification reaction is finished, vacuumizing to 4-6 kpa absolute pressure for pre-polycondensation reaction for 1-2h, continuously heating to 240-245 ℃, vacuumizing to less than or equal to 300pa absolute pressure for final polycondensation for 1-2h, and obtaining degradable polyester; the catalyst is used in an amount of 0.1-0.8% of the total mass of the degradable polyester.
The catalyst for synthesizing the degradable polyester prepared by the invention reacts with the complexing agent under the conditions of solvent and acidity to form a uniform catalyst complex, has extremely high stability, is not easy to hydrolyze, can stably exist even in the later period of the reaction, ensures the stability in the complexing reaction and the uniformity of the generated complex, and improves the dispersibility of the catalyst in the reaction by selecting the catalyst carrier according to the raw materials of the polyester reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst for synthesizing the degradable polyester has hydrolysis resistance and high reaction efficiency;
(2) The catalyst for synthesizing the degradable polyester has the advantages of easily available raw materials, low price, simple synthesis method, strong operability and strong popularization;
(3) The method for preparing polyester by adopting the catalyst disclosed by the invention has the advantages of mild reaction conditions, no chromatic aberration of the prepared polyester product and suitability for market application.
Detailed Description
The invention will be further illustrated with reference to specific examples.
Example 1
Preparation of a catalyst for synthesizing degradable polyester: dehydrating tetrabutyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol; adding triethyl phosphate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 80r/min, heating to 90 ℃, sequentially adding acetic acid, acetylacetone and triphenyl phosphate, uniformly stirring, slowly adding tetrabutyl titanate, and keeping the solution in a clear and transparent state for reacting for 0.5h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 60r/min, heating to 70 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol is 1.0:0.3:0.15:0.4:1.0:4.0;
synthesis of degradable polyesters: adding 288g of 1, 4-butanediol, 150g of terephthalic acid, 160g of adipic acid and 2.52g of a synthetic catalyst into a reaction kettle in sequence, stirring and heating to 235 ℃, vacuumizing to 80kpa absolute pressure for esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 6kpa absolute pressure for pre-polycondensation reaction for 1.5 hours, heating to 245 ℃, vacuumizing to 260-300 pa, and carrying out final polycondensation reaction for 1.5 hours to obtain the degradable polyester, namely polybutylene adipate terephthalate (PBAT).
Example 2
Preparation of a catalyst for synthesizing degradable polyester: dehydrating tetrabutyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol; adding triethyl phosphate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 120r/min, heating to 70 ℃, sequentially adding acetic acid, acetylacetone and triphenyl phosphate, uniformly stirring, slowly adding tetrabutyl titanate, and keeping the solution in a clear and transparent state for reaction for 1h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 60 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol is 1.0:0.4:0.15:0.6:0.3:1.0;
synthesis of degradable polyesters: 306g of 1, 4-butanediol, 159g of terephthalic acid, 154g of adipic acid and 1.26g of synthetic catalyst are sequentially added into a reaction kettle, stirring and heating to 235 ℃, vacuumizing to 70kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 4kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing to 80-100 pa, and carrying out final polycondensation reaction for 1.5h to obtain the degradable polyester, namely polybutylene adipate terephthalate (PBAT).
Example 3
Preparation of a catalyst for synthesizing degradable polyester: dehydrating tetrabutyl titanate, isopropyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol; adding triethyl phosphate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 120r/min, heating to 70 ℃, sequentially adding acetic acid, acetylacetone and triphenyl phosphate, uniformly stirring, slowly adding tetrabutyl titanate and isopropyl titanate, and keeping the solution in a clear and transparent state for reacting for 1h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 60 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, isopropyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol is 0.6:0.4:0.3:0.15:0.4:1.0:3.4;
synthesis of degradable polyesters: 216g of 1, 4-butanediol, 150g of terephthalic acid, 160g of adipic acid and 2.7g of synthetic catalyst are sequentially added into a reaction kettle, stirring and heating are carried out to 235 ℃, vacuumizing is carried out to 80kpa absolute pressure, esterification reaction is carried out, after the esterification reaction is finished, heating is carried out to 240 ℃, vacuumizing is carried out to 5kpa absolute pressure, pre-polycondensation reaction is carried out for 1.5h, then heating is carried out to 245 ℃, vacuumizing is carried out for 250-300 pa, and final polycondensation reaction is carried out for 1.5h, so that the degradable polyester, namely polybutylene adipate terephthalate (PBAT) is obtained.
Example 4
Preparation of a catalyst for synthesizing degradable polyester: carrying out dehydration treatment on stannous octoate, tetrabutyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate, tetrahydrofuran and 1, 4-butanediol; adding triethyl phosphate and tetrahydrofuran into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 110r/min, heating to 85 ℃, sequentially adding acetic acid, acetylacetone and triphenyl phosphate, uniformly stirring, slowly adding stannous octoate and tetrabutyl titanate, and keeping the solution in a clear and transparent state for reacting for 1h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 80 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and uniformly stirring to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of stannous octoate, tetrabutyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate, tetrahydrofuran and 1, 4-butanediol is 0.4:0.6:0.3:0.1:0.7:0.7:0.3:4.0;
synthesis of degradable polyesters: 324g of 1, 4-butanediol, 157g of terephthalic acid, 153g of adipic acid and 3.02g of synthetic catalyst are sequentially added into a reaction kettle, stirring and heating to 235 ℃, vacuumizing to 70kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 5kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing to 240-280 pa, and carrying out final polycondensation reaction for 1.5h to obtain the degradable polyester, namely polybutylene adipate terephthalate (PBAT).
Comparative example 1
Preparation of a catalyst for polyester synthesis: carrying out dehydration treatment on tetrabutyl titanate, triethyl phosphate and 1, 4-butanediol; adding triethyl phosphate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 120r/min, heating to 70 ℃, uniformly stirring, slowly adding tetrabutyl titanate, and keeping the solution in a clear and transparent state for reaction for 0.5h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 60 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate to triethyl phosphate to 1, 4-butanediol is 1:1:4.5;
synthesis of polyester: 28g of 1, 4-butanediol, 150g of terephthalic acid, 160g of adipic acid and 2.52g of synthetic catalyst are sequentially added into a reaction kettle, stirring and heating are carried out to 235 ℃, vacuumizing is carried out to 80kpa absolute pressure, esterification reaction is carried out, after the esterification reaction is finished, heating is carried out to 240 ℃, vacuumizing is carried out to 6kpa absolute pressure, pre-polycondensation reaction is carried out for 1.5h, then heating is carried out to 245 ℃, vacuumizing is carried out for 250-300 pa, and final polycondensation reaction is carried out for 1.5h.
Comparative example 2
Synthesis of polyester: 28g of 1, 4-butanediol, 150g of terephthalic acid, 160g of adipic acid and 0.84g of tetrabutyl titanate are sequentially added into a reaction kettle, stirring and heating to 235 ℃, vacuumizing to 80kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 6kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing to 250-300 pa, and carrying out final polycondensation reaction for 1.5h.
Comparative example 3
The preparation method of the catalyst for polyester synthesis comprises the following steps: carrying out dehydration treatment on tetrabutyl titanate, triethyl phosphate and 1, 4-butanediol; adding triethyl phosphate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 80r/min, heating to 90 ℃, uniformly stirring, slowly adding tetrabutyl titanate, and reacting for 1h while keeping the solution in a clear and transparent state to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 60r/min, heating to 70 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate to triethyl phosphate to 1, 4-butanediol is 1:1:2;
synthesis of polyester: 306g of 1, 4-butanediol, 159g of terephthalic acid, 154g of adipic acid and 1.26g of synthetic catalyst are sequentially added into a reaction kettle, stirring and heating are carried out to 235 ℃, vacuumizing is carried out to 70kpa absolute pressure, esterification reaction is carried out, after the esterification reaction is finished, heating is continued to 240 ℃, vacuumizing is carried out to 4kpa absolute pressure, pre-polycondensation reaction is carried out for 1.5h, then heating is carried out to 245 ℃, vacuumizing is carried out for 80-100 pa, and final polycondensation reaction is carried out for 1.5h, thus obtaining polybutylene adipate terephthalate (PBAT).
Comparative example 4
Synthesis of polyester: 306g of 1, 4-butanediol, 159g of terephthalic acid, 154g of adipic acid and 0.63g of tetrabutyl titanate are sequentially added into a reaction kettle, stirring and heating to 235 ℃, vacuumizing to 70kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 4kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing to 80-100 pa, and carrying out final polycondensation reaction for 1.5h to obtain polybutylene adipate terephthalate (PBAT).
Comparative example 5
Preparation of a catalyst for polyester synthesis: tetrabutyl titanate, isopropyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol are not dehydrated; adding tetrabutyl titanate and isopropyl titanate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 120r/min, heating to 70 ℃, adding triethyl phosphate, adding acetic acid, acetylacetone and triphenyl phosphate, and reacting for 1h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 60 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, isopropyl titanate, triphenyl phosphate, acetic acid, acetylacetone, triethyl phosphate and 1, 4-butanediol is 0.6:0.4:0.3:0.15:0.4:1.0:3.4;
synthesis of polyester: 216g of 1, 4-butanediol, 150g of terephthalic acid, 160g of adipic acid and 2.7g of synthetic catalyst are sequentially added into a reaction kettle, stirring and heating are carried out to 235 ℃, vacuumizing is carried out to 80kpa absolute pressure, esterification reaction is carried out, after the esterification reaction is finished, heating is continued to 240 ℃, vacuumizing is carried out to 5kpa absolute pressure, pre-polycondensation reaction is carried out for 1.5h, then heating is carried out to 245 ℃, vacuumizing is carried out for 250-300 pa, and final polycondensation reaction is carried out for 1.5h.
Example 5
Preparation of a catalyst for synthesizing degradable polyester: tetrabutyl titanate, triphenyl phosphate, phosphoric acid, ethylenediamine tetraacetic acid, tetrahydrofuran and 1, 4-butanediol are dehydrated; adding tetrahydrofuran into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 80r/min, heating to 95 ℃, sequentially adding phosphoric acid, ethylenediamine tetraacetic acid and triphenyl phosphate, uniformly stirring, slowly adding tetrabutyl titanate, and keeping the solution in a clear and transparent state for reaction for 0.5h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 60r/min, heating to 75 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, triphenyl phosphate, phosphoric acid, ethylenediamine tetraacetic acid, tetrahydrofuran and 1, 4-butanediol is 1.0:0.45:0.15:0.3:1.0:4.0;
synthesis of degradable polyesters: adding 288g of 1, 4-butanediol, 236g of succinic acid and 2.04g of a synthetic catalyst into a reaction kettle in sequence, stirring and heating to 235 ℃, vacuumizing to 80kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 6kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing to 220-260 pa, and carrying out final polycondensation reaction for 1.5h to obtain the degradable polyester, namely polybutylene succinate (PBS).
Example 6
Preparation of a catalyst for synthesizing degradable polyester: tetrabutyl titanate, triphenyl phosphate, phosphoric acid, ethylenediamine tetraacetic acid, tetrahydrofuran and 1, 4-butanediol are dehydrated; adding tetrahydrofuran into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 120r/min, heating to 75 ℃, sequentially adding phosphoric acid, ethylenediamine tetraacetic acid and triphenyl phosphate, uniformly stirring, slowly adding tetrabutyl titanate, and keeping the solution in a clear and transparent state for reaction for 1h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 65 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, triphenyl phosphate, phosphoric acid, ethylenediamine tetraacetic acid, tetrahydrofuran and 1, 4-butanediol is 1.0:0.35:0.15:0.3:0.5:1.0;
synthesis of degradable polyesters: 252g of 1, 4-butanediol, 236g of succinic acid and 1.02g of synthetic catalyst are sequentially added into a reaction kettle, stirring and heating are carried out to 235 ℃, vacuumizing is carried out to 60kpa absolute pressure, esterification reaction is carried out, after the esterification reaction is finished, heating is carried out to 240 ℃, vacuumizing is carried out to 4kpa absolute pressure, pre-polycondensation reaction is carried out for 1.5h, then heating is carried out to 245 ℃, vacuumizing is carried out for 80-100 pa, and final polycondensation reaction is carried out for 1.5h, so that degradable polyester, namely polybutylene succinate (PBS) is obtained.
Example 7
Preparation of a catalyst for synthesizing degradable polyester: carrying out dehydration treatment on stannous octoate, triphenyl phosphate, phosphoric acid, acetylacetone, triethyl citrate and 1, 4-butanediol; adding triethyl citrate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 100r/min, heating to 90 ℃, sequentially adding phosphoric acid, acetylacetone and triphenyl phosphate, uniformly stirring, slowly adding stannous octoate, and keeping the solution in a clear and transparent state for reacting for 1h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 90r/min, heating to 80 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of stannous octoate, triphenyl phosphate, phosphoric acid, acetylacetone, triethyl citrate and 1, 4-butanediol is 1.0:0.5:0.05:0.3:0.9:4.0;
synthesis of degradable polyesters: sequentially adding 306g of 1, 4-butanediol, 236g of succinic acid and 3.06g of synthetic catalyst into a reaction kettle, stirring and heating to 235 ℃, vacuumizing to 80kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 6kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing for 200-250 pa, and carrying out final polycondensation reaction for 1.5h to obtain the degradable polyester, namely the polybutylene succinate (PBS).
Example 8
Preparation of a catalyst for synthesizing degradable polyester: carrying out dehydration treatment on stannous octoate, triphenyl phosphate, phosphoric acid, acetylacetone, triethyl citrate and 1, 4-butanediol; adding triethyl citrate into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 110r/min, heating to 85 ℃, sequentially adding phosphoric acid, acetylacetone and triphenyl phosphate, uniformly stirring, slowly adding stannous octoate, and keeping the solution in a clear and transparent state for reacting for 1h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 80 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and uniformly stirring to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of stannous octoate, triphenyl phosphate, phosphoric acid, acetylacetone, triethyl citrate and 1, 4-butanediol is 1.0:0.2:0.1:0.7:0.6:1;
synthesis of degradable polyesters: sequentially adding 288g of 1, 4-butanediol, 236g of succinic acid and 1.36g of a synthetic catalyst into a reaction kettle, stirring and heating to 235 ℃, vacuumizing to 60kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 4kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing to 70-90 pa, and carrying out final polycondensation reaction for 1.5h to obtain the degradable polyester, namely the polybutylene succinate (PBS).
Example 9
Preparation of a catalyst for synthesizing degradable polyester: dehydrating tetrabutyl titanate, stannous chloride, triphenyl phosphate, phosphoric acid, ethylenediamine tetraacetic acid, tetrahydrofuran, triethyl citrate and 1, 4-butanediol; adding tetrahydrofuran into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 120r/min, heating to 75 ℃, sequentially adding phosphoric acid, ethylenediamine tetraacetic acid and triphenyl phosphate, uniformly stirring, slowly adding tetrabutyl titanate and stannous chloride, and reacting for 1h while keeping the solution in a clear and transparent state to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 100r/min, heating to 65 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a clear and transparent synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, stannous chloride, triphenyl phosphate, phosphoric acid, ethylenediamine tetraacetic acid, tetrahydrofuran, triethyl citrate and 1, 4-butanediol is 0.7:0.3:0.3:0.1:0.4:0.2:0.6:2
Synthesis of degradable polyesters: adding 360g of 1, 4-butanediol, 236g of succinic acid and 2.33g of synthetic catalyst into a reaction kettle in sequence, stirring and heating to 235 ℃, vacuumizing to 70kpa absolute pressure, carrying out esterification reaction, continuously heating to 240 ℃ after the esterification reaction is finished, vacuumizing to 5kpa absolute pressure, carrying out pre-polycondensation reaction for 1.5h, heating to 245 ℃, vacuumizing for 230-280 pa, and carrying out final polycondensation reaction for 1.5h to obtain degradable polyester, namely polybutylene succinate (PBS).
Comparative example 6
Preparation of a catalyst for polyester synthesis: tetrabutyl titanate, triphenyl phosphate, ethylenediamine tetraacetic acid, tetrahydrofuran and 1, 4-butanediol are subjected to dehydration treatment; then adding tetrahydrofuran into a reaction kettle, introducing nitrogen to replace air in the kettle, introducing a proper amount of nitrogen in the reaction process, stirring for 80r/min, heating to 95 ℃, sequentially adding ethylenediamine tetraacetic acid and triphenyl phosphate, uniformly stirring, slowly adding tetrabutyl titanate, and reacting for 0.5h to obtain a reaction solution; adding 1, 4-butanediol into a reaction kettle, stirring for 60r/min, heating to 75 ℃, slowly adding the reaction solution of the previous step into the reaction kettle, and stirring uniformly to obtain a synthetic catalyst;
wherein the molar ratio of tetrabutyl titanate, triphenyl phosphate, ethylenediamine tetraacetic acid, tetrahydrofuran and 1, 4-butanediol is 1.0:0.45:0.3:1.0:4.0;
synthesis of polyester: 288g of 1, 4-butanediol, 236g of succinic acid and 2.04g of synthetic catalyst are sequentially added into a reaction kettle, the mixture is stirred and heated to 235 ℃, the mixture is vacuumized to 80kpa absolute pressure, the esterification reaction is carried out, after the esterification reaction is finished, the mixture is continuously heated to 240 ℃, the mixture is vacuumized to 6kpa absolute pressure, the pre-polycondensation reaction is carried out for 1.5h, the mixture is heated to 245 ℃, and the mixture is vacuumized for 220-260 pa, and the final polycondensation reaction is carried out for 1.5h.
Comparative example 7
Synthesis of polyester: 252g of 1, 4-butanediol, 236g of succinic acid and 0.51g of tetrabutyl titanate are sequentially added into a reaction kettle, stirred and heated to 235 ℃, vacuumized to 60kpa absolute pressure, subjected to esterification reaction, continuously heated to 240 ℃ after the esterification reaction is finished, vacuumized to 4kpa absolute pressure, subjected to pre-polycondensation reaction for 1.5h, heated to 245 ℃, vacuumized to 80-100 pa, and subjected to final polycondensation reaction for 1.5h to obtain the polybutylene succinate.
Performance detection
1. The Polyesters (PBAT) prepared in examples 1 to 4 and comparative examples 3 to 4 were tested for melt Mass Flow Rate (MFR), color value, carboxyl group content, tensile strength at break, tensile strain at break performance parameters according to the standards GB/T32366-2015, GB/T30294-2013, and the test results are shown in Table 1;
TABLE 1 Polyester (PBAT) detection results
Figure BDA0003589333960000091
Figure BDA0003589333960000101
The procedure for the Polyesters (PBAT) prepared from examples 1-4 and comparative examples 1-5 above, and the results in Table 1, show that comparative example 1, although the main catalyst component tetrabutyl titanate is the same as example 1, does not give a conventionally acceptable product at a higher absolute pressure of the final polycondensation without adding an acidic regulator, a stabilizer and a complexing agent, and the detected performance parameter is not measured, or the parameter difference is far from comparable; when the catalyst added in the comparison document 2 is pure tetrabutyl titanate, qualified products still cannot be prepared under the requirement of a scheme, so the comparison document is not comparable; comparative example 5 in the case of the same kind of catalyst as in example 3, but in the preparation, when the order of the catalyst main body, the diluent, the complexing agent, etc. is changed, a qualified product still cannot be prepared due to severe hydrolysis of the catalyst main body; the absolute pressure of the final polycondensation of comparative example 3 and example 2 is smaller, and no mixture, stabilizer or complexing agent is added, so that although the product can be obtained, the solution mass flow rate is higher, the tensile strength at break is smaller, and the performance is poorer; comparative example 4 when the absolute pressure of the final polycondensation is smaller than that of example 2, only tetrabutyl titanate catalyst is selected, the product can be obtained, but the solution mass flow rate is still higher, and the product performance is poor; and the L values of the products of comparative example 3 and comparative example 4 were low, indicating poor color.
2. The Polyesters (PBS) prepared in examples 5 to 9 and comparative example 7 were tested for melt Mass Flow Rate (MFR), color value, carboxyl content, tensile strength at break, tensile strain at break, and intrinsic viscosity performance parameters according to the standards GB/T32366-2015 and GB/T30294-2013, and the test results are shown in Table 2;
TABLE 2 Polyester (PBS) detection results
Figure BDA0003589333960000102
The procedure for the preparation of Polyesters (PBAT) from examples 5-9 and comparative examples 6-7 above, and the results in table 2 show that comparative example 6 is identical to the catalyst starting material prepared in example 5, but when no acidic modifier is added, the catalyst produced a small amount of flocculent precipitate during the synthesis, the hydrolysis was severe, the catalytic performance was severely destroyed, so that no conventional acceptable product could be obtained, the detected performance parameters were also undetectable, or the parameter differences were far from comparable; comparative example 7 has the same parameters as the synthesis of the polyester of example 6, but comparative example 7 uses pure tetrabutyl titanate for the synthesis of the polyester, and the product has poor color, high solution mass flow rate, low viscosity and adverse effect on the processability of the product although the product can be obtained.
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.

Claims (4)

1. A catalyst for synthesizing degradable polyester, which is characterized in that: the catalyst comprises a catalyst main body, a stabilizer, an acid regulator, a complexing agent, a diluent and a catalyst carrier according to the molar ratio of 1:0.2-0.5: 0.05-0.15:0.3-0.7: 0.2-1.0:1.0-4.0;
the main body of the catalyst is one or more of tetrabutyl titanate, stannous chloride, isopropyl titanate and stannous octoate; the catalyst carrier is one or more of 1, 4-butanediol, ethanol, ethylene glycol, propylene glycol and pentanediol;
the stabilizer is triphenyl phosphate; the acid regulator is phosphoric acid or acetic acid;
the complexing agent is acetylacetone or ethylenediamine tetraacetate;
the diluent is one or more of tetrahydrofuran, triethyl phosphate and triethyl citrate;
the preparation method of the catalyst for synthesizing the degradable polyester comprises the following steps: firstly, dehydrating a catalyst main body, a stabilizer, an acid regulator, a complexing agent, a diluent and a catalyst carrier; then adding a diluent into a container, removing air, stirring, heating to 70-90 ℃, sequentially adding an acid regulator, a complexing agent and a stabilizer, stirring, adding a catalyst main body, and keeping the solution in a clear and transparent state for reaction for 0.5-1h to obtain a reaction solution; and finally, adding the catalyst carrier into a reaction kettle, stirring, heating to 50-80 ℃, adding the reaction solution of the previous step into the reaction kettle, and uniformly stirring to obtain the clear and transparent catalyst for synthesizing the degradable polyester.
2. Use of the catalyst of claim 1 in the synthesis of a degradable polyester, characterized in that: the method comprises the following steps: firstly, carrying out esterification reaction on dihydric alcohol, dibasic acid and a catalyst at the absolute pressure of 60-80 kpa, then carrying out pre-polycondensation reaction at the absolute pressure of 4-6 kpa, and finally carrying out final polycondensation at the absolute pressure of less than or equal to 300pa to obtain degradable polyester; the catalyst is used in an amount of 0.1-0.8% of the total mass of the degradable polyester.
3. Use of the catalyst according to claim 2 in the synthesis of degradable polyesters, characterized in that: the dihydric alcohol is one or more of ethylene glycol, 1, 3-propylene glycol, 1, 2-propylene glycol, 1, 3-butanediol, 1, 4-butanediol, pentanediol, hexanediol, heptanediol, octanediol, and diethylene glycol.
4. Use of the catalyst according to claim 2 in the synthesis of degradable polyesters, characterized in that: the dibasic acid is C8-C14 aromatic dibasic acid or/and C2-C10 aliphatic dibasic acid.
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