[go: up one dir, main page]

CN114957201A - Preparation method of low-cyclic by-product poly (butylene succinate) polyester - Google Patents

Preparation method of low-cyclic by-product poly (butylene succinate) polyester Download PDF

Info

Publication number
CN114957201A
CN114957201A CN202210678580.4A CN202210678580A CN114957201A CN 114957201 A CN114957201 A CN 114957201A CN 202210678580 A CN202210678580 A CN 202210678580A CN 114957201 A CN114957201 A CN 114957201A
Authority
CN
China
Prior art keywords
solvent
reaction
schiff base
cyclic
amino acid
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.)
Granted
Application number
CN202210678580.4A
Other languages
Chinese (zh)
Other versions
CN114957201B (en
Inventor
方文娟
胡江林
陈建旭
王喜蒙
高梦云
王雨龙
王磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wanhua Chemical Group Co Ltd
Original Assignee
Wanhua Chemical Group Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Wanhua Chemical Group Co Ltd filed Critical Wanhua Chemical Group Co Ltd
Priority to CN202210678580.4A priority Critical patent/CN114957201B/en
Publication of CN114957201A publication Critical patent/CN114957201A/en
Application granted granted Critical
Publication of CN114957201B publication Critical patent/CN114957201B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
    • B01J2231/49—Esterification or transesterification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
    • B01J2531/46—Titanium
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The invention relates to a preparation method of poly (butylene succinate) (PBS) with low cyclic by-products. The method comprises the following steps: mixing a catalyst Schiff base titanium complex, an auxiliary agent quaternary phosphonium salt, succinic acid and excessive 1, 4-butanediol for esterification reaction, vacuumizing for constant-temperature reaction, and granulating the obtained polymer melt to obtain the poly (butylene succinate) polymer. The content of the PBS cyclic byproduct is less than or equal to 1wt%, and the PBS cyclic byproduct has excellent mechanical properties.

Description

Preparation method of low-cyclic by-product poly (butylene succinate) polyester
Technical Field
The invention belongs to the field of biodegradable polymer materials, and particularly relates to a preparation method of a low-cyclic by-product poly (butylene succinate).
Background
Poly (butylene succinate) (PBS) and copolyester thereof are aliphatic polyesters with good biodegradability and comprehensive performance, and are generally prepared by direct esterification and polycondensation of succinic acid and 1, 4-butanediol, and the PBS has strong application potential in the field of food contact materials such as disposable lunch boxes, straws and the like due to excellent biodegradability and mechanical properties. However, there are strict legal and regulatory requirements for food contact materials, which not only have excellent yellowing resistance, but also require control of the total migration in food contact materials and products, but there are few studies related thereto.
"characterization and control methods for oligomers in polyesters" study (academic paper, university of east China, Wenweiang, 2015) describes the formation and control of cyclic by-products in PET, which are believed to be formed mainly by ring opening due to cleavage of ester groups by the attack of macromolecular chain ends, and summarizes current methods for addressing cyclic by-products in PET. Among them, Japanese patent No. 12-219731 discloses addition of S0 at the polycondensation stage 3 The sulfite compound of X is effective to reduce cyclic by-products in the polyester. Japanese patent No. 12-219729 discloses that the content of cyclic by-products can be effectively controlled by controlling the molar ratio of antimony element to phosphoric acid.
The art of PET polyesters has studied how to effectively control the formation of cyclic by-products, but research on reducing cyclic by-products in PBS has focused primarily on post-processing.
EP-A2623540 discloses a process for purifying aliphatic polyesters such as PBS, in which the cyclic by-products are removed by solvent extraction, but the extraction process has the disadvantage that degradation of the polyester occurs, the molecular weight is not controllable and the mechanical properties are poor.
CN111372972 discloses a process for purifying aliphatic polyesters in a degassing apparatus, the cyclic by-products being removed by means of an entrainer, preferably water, which likewise causes degradation of the polyester and is complicated to operate.
In conclusion, a method for preparing poly (butylene succinate) with low cyclic by-products by using a high-efficiency and easily-realized industrialized method is urgently needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of polybutylene succinate (PBS). The method can effectively reduce the generation of cyclic byproducts in the synthesis process, and the obtained PBS can be directly used for food contact materials, so that the PBS post-treatment step is omitted.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a low-cyclic by-product poly (butylene succinate) (PBS) comprises the steps of mixing a catalyst Schiff base titanium complex, an auxiliary agent quaternary phosphonium salt, succinic acid and 1, 4-butanediol for esterification, vacuumizing, and continuing constant-temperature polycondensation reaction to obtain a poly (butylene succinate) polymer.
In the field of PBS preparation, polyester obtained by the reaction of dibasic acid and dihydric alcohol inevitably generates cyclic byproducts, and researches suggest that the cyclic byproducts can be the interchange of ester groups between adjacent macromolecules, or the inner cyclization of macromolecules, or the end group cyclization of macromolecules, or carboxyl groups formed in thermal degradation to generate cyclic oligomers, or the closed-loop condensation of monomer oligomers, wherein the possibility of the chain ends of the macromolecules to form the cyclic oligomers by attacking the cracking of the ester groups is the greatest, and the following formula is the generation process of one cyclic trimer:
Figure BDA0003695558850000021
different from the traditional titanate catalyst, the Schiff base titanium complex changes the electron distribution around the titanium of the catalytic active center due to the steric hindrance effect of the Schiff base ligand and the synergistic effect of the Schiff base titanium complex and the auxiliary agent quaternary phosphonium salt, and has a stabilizing effect on polyester, so that the generation of cyclic byproducts can be inhibited under high-temperature melting, the hydrolysis resistance of the catalyst is improved, and the catalyst can be stored for a long time.
In the invention, the Schiff base titanium complex is an amino acid Schiff base titanium complex, preferably an alpha-amino acid Schiff base titanium complex, and more preferably glycine; preferably, the addition amount of the Schiff base titanium complex is 0.02-2% of the mass of the succinic acid, and preferably 0.2-1%.
In the present invention, the quaternary phosphonium salt is R 1 R 2 3 PX 1 Wherein R is 1 Is 1-16 carbon alkyl, R 2 Is 1-6 carbon alkyl or phenyl, X 1 Is Cl - 、Br - 、I - 、NO 3 - 、CH 3 COO - Preferably, the quaternary phosphonium salt is one or more of butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide and methyltriphenylphosphonium iodide, and more preferably, the quaternary phosphonium salt is butyltriphenylphosphonium bromide; preferably, the addition amount of the quaternary phosphonium salt is 0.01-1%, preferably 0.1-0.5% of the mass of the succinic acid.
In the invention, 1, 4-butanediol excessive relative to succinic acid is added, and the preferred molar ratio of the succinic acid to the 1, 4-butanediol is 1: 1.1-1: 1.3.
In the invention, the esterification reaction is carried out at 180-250 ℃.
In the invention, the polycondensation reaction is vacuumized twice, the first vacuumization is carried out until 1000-30,000 PaA, and the duration is 10-60 min; vacuumizing for the second time to less than 100PaA, and reacting for 60-200 min at constant temperature of 220-270 ℃.
It is another object of the present invention to provide a process for preparing a Schiff base titanium complex.
A preparation method of Schiff base titanium complex, which is the Schiff base titanium complex, comprises the following steps:
s1: dissolving amino acid and inorganic base in a solvent, and heating and refluxing until the solid is completely dissolved;
s2: dissolving an active carbonyl compound in a solvent, dropwise adding the solution into S1, and carrying out reflux reaction;
s3: dissolving a titanium compound in a solvent, dropwise adding the solution into S2, and carrying out reflux reaction;
s4: the solvent in S3 was evaporated to give a precipitate, which was washed and dried.
In the present invention, the amino acid in S1 is one or more of glycine, lysine, aspartic acid, valine, alanine, tryptophan and cysteine, and glycine is preferred.
In the invention, the inorganic base of S1 is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and calcium carbonate, preferably potassium hydroxide; preferably, the molar ratio of the amino acid described in S1 to the inorganic base is 1 (2-5), preferably 1 (3-4).
In the invention, the solvent S1 is one or more of C1-C6 small molecular alcohol, chloroform, N-Dimethylformamide (DMF) and dimethyl sulfoxide, and methanol is preferred.
In the invention, S1 reacts in a nitrogen environment, and the reaction temperature is 5-10 ℃ higher than the boiling point of the solvent.
In the invention, the active carbonyl compound S2 is one or more of salicylaldehyde, vanillin, 5-chlorosalicylaldehyde, 5-bromosalicylaldehyde and o-vanillin, preferably salicylaldehyde; preferably, the molar ratio of the active carbonyl compound to the amino acid is (2-5): 1, preferably (3-4): 1.
In the present invention, the solvent used in S1 is S2.
In the invention, S2 is reacted in a nitrogen environment at a temperature higher than the boiling point of the solvent by 5-10 ℃ for 5-24 h, preferably 8-12 h.
In the invention, the titanium compound of S3 is titanium tetrachloride; preferably, the molar ratio of the titanium compound to the amino acid is (1-3): 1, preferably (1.5-2): 1.
In the present invention, the solvent used in S1 is S3.
In the invention, S3 is reacted in a nitrogen environment at a temperature higher than the boiling point of the solvent by 5-10 ℃ for 5-24 h, preferably 8-12 h.
In the present invention, the washing solvent in S4 is an alcohol solvent, preferably ethanol.
In the invention, the drying temperature of S4 is 100-300 ℃, preferably 150-200 ℃, and the drying time is 24-56 hours, preferably 40-50 hours.
It is another object of the present invention to provide polybutylene succinate (PBS).
The poly (butylene succinate) (PBS) is prepared by the preparation method or is prepared by catalysis of the catalyst prepared by the catalyst preparation method, wherein the content of poly (butylene succinate) cyclic byproducts in the poly (butylene succinate) is less than or equal to 1wt%, preferably less than or equal to 0.5 wt%, based on the total mass of the poly (butylene succinate); wherein the poly butylene succinate cyclic byproduct has the following structure:
Figure BDA0003695558850000051
wherein n is a positive integer less than 10.
Compared with the prior art, the technical scheme of the invention has the advantages that:
(1) the generation of cyclic byproducts is effectively reduced through the synergistic effect of the Schiff base titanium complex and the quaternary phosphonium salt, and the catalyst has better hydrolysis resistance, so that the utilization rate of the catalyst is greatly improved;
(2) the method effectively controls the generation of cyclic byproducts in the synthesis process, reduces the steps of PBS post-treatment, effectively controls the molecular weight distribution and has excellent mechanical properties.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as limiting the scope of the invention.
Raw materials:
succinic acid, superior products, Shandong Feiyang chemical Co., Ltd;
1, 4-Butanediol (BDO), technical grade, Xinjiang Makei chemical industries, Inc.;
glycine, food grade, Shandong Youso chemical science and technology, Inc.;
alanine, food grade, Shandong Youso chemical science and technology Co., Ltd;
lysine, food grade, Shandong Youso chemical science and technology, Inc.;
potassium hydroxide, analytical grade, alatin reagent ltd;
methanol, analytical grade, alatin reagent ltd;
salicylaldehyde, 5-chlorosalicylaldehyde, analytically pure, Tianjin, maozhi chemical reagent plant;
titanium tetrachloride, 99%, alatin reagent, inc;
ethanol, analytical grade, alatin reagent ltd;
butyltriphenylphosphonium bromide, methyltriphenylphosphonium iodide, 98%, sigma aldrich trade ltd.
The apparatus and methods used in the present invention are those commonly used in the art, except where specifically indicated. Wherein the molecular weight of the sample was measured by using a Gel Permeation Chromatography (GPC) instrument of model 1515-.
The mechanical properties were tested by the following methods: tensile properties were measured using a mechanical tester (Instron 5960) at a tensile rate of 50 mm/min.
The cyclic by-products were characterized by a zemer fly TSQ 8000Evo gas chromatography-mass spectrometry combination (GC-MS).
Schiff base titanium complex preparation
Example 1
1mmol of alanine and 2mmol of potassium hydroxide were weighed into a flask, 40mL of methanol were added and heated to 70 ℃ under nitrogen reflux until all the solids were dissolved. Then 10mL of methanol solution containing 2mmol of 5-chlorosalicylaldehyde was added dropwise to the flask, and after the addition was completed, refluxing was continued for 5 h. A10 mL methanol solution containing 1mmol of titanium tetrachloride was added dropwise to the reaction system, and the mixture was heated under reflux for 5 hours under a nitrogen atmosphere. After the reaction is finished, removing the solvent to obtain solid precipitate, washing the solid precipitate with 100mL of ethanol for three times, and drying the solid precipitate for 24 hours at 100 ℃ to obtain the Schiff base complex A.
Example 2
Weigh 1mmol of lysine and 5mmol of potassium hydroxide and transfer to a flask, add 40mL of methanol, heat to 75 ℃ under nitrogen and reflux until all the solids are dissolved. Then 10mL of methanol solution containing 5mmol of salicylaldehyde was added dropwise to the flask, and after the addition was completed, reflux was continued for 24 h. A10 mL methanol solution containing 3mmol of titanium tetrachloride was added dropwise to the reaction system, and the mixture was heated under reflux for 24 hours under a nitrogen atmosphere. After the reaction is finished, removing the solvent to obtain solid precipitate, washing the solid precipitate with 100mL of ethanol for three times, and drying the solid precipitate for 56 hours at 300 ℃ to obtain the Schiff base complex B.
Example 3
Weigh 1mmol of glycine and 3mmol of potassium hydroxide and transfer to a flask, add 40mL of methanol, heat to 73 ℃ under nitrogen and reflux until all the solids are dissolved. Then, 10mL of a methanol solution containing 4mmol of salicylaldehyde was added dropwise to the flask, and the mixture was refluxed for 10 hours after the addition. A10 mL methanol solution containing 2mmol of titanium tetrachloride was added dropwise to the reaction system, and the mixture was heated under reflux for 10 hours under a nitrogen atmosphere. And after the reaction is finished, removing the solvent to obtain solid precipitate, washing the solid precipitate by using 100mL of ethanol for three times, and drying the solid precipitate for 45 hours at 180 ℃ to obtain the Schiff base complex C.
Preparing polyester:
example 4
Adding 10mol of succinic acid, 13mol of butanediol, 0.236g of Schiff base complex A and 0.118g of butyltriphenyl phosphonium bromide into a 5L polyester kettle, keeping normal pressure in the kettle, stirring at a constant speed of 100rpm, heating to 150 ℃, starting reaction, gradually heating to 250 ℃ within 1h, finishing the esterification process when the amount of distilled by-product water in the reaction kettle reaches 95% of theoretical water yield, gradually vacuumizing the reaction kettle to 20,000PaA for 30min, then gradually vacuumizing to 90PaA, heating to 220 ℃ and keeping, carrying out polycondensation reaction, reacting for 200min, obtaining polymer melt, and carrying out water cooling and pelletizing to obtain the product.
Example 5
Adding 10mol of succinic acid, 11mol of butanediol, 23.6g of Schiff base complex B and 11.8g of butyltriphenyl phosphonium bromide into a 5L polyester kettle, keeping normal pressure in the kettle, stirring at a constant speed, heating to 150 ℃, starting reaction, gradually heating to 180 ℃ within 1h, finishing the esterification process when the amount of distilled by-product water in the kettle reaches 95% of theoretical water yield, gradually vacuumizing the reaction kettle to 1000PaA for 20min, then gradually vacuumizing to 90PaA, heating to 270 ℃ and keeping for polycondensation reaction for 100min to obtain polymer melt, and water-cooling and granulating to obtain the product.
Example 6
Adding 10mol of succinic acid, 12mol of butanediol, 5.9g of Schiff base complex C and 3.54 g of methyl triphenyl phosphorus iodide into a 5L polyester kettle, keeping normal pressure in the kettle, stirring at a constant speed, heating to 150 ℃, starting reaction, gradually heating to 220 ℃ within 1h, finishing the esterification process when the amount of distilled by-product water in the kettle reaches 95% of theoretical water yield, gradually vacuumizing the reaction kettle to 2000PaA for 50min, then gradually vacuumizing to 90PaA, heating to 240 ℃ and keeping for polycondensation reaction for 150min to obtain polymer melt, and water-cooling and granulating to obtain the product.
Comparative example 1
No quaternary phosphonium salt was added to this comparative example.
Adding 10mol of succinic acid, 12mol of butanediol and 5.9g of Schiff base complex C into a 5L polyester kettle, keeping the normal pressure in the kettle, stirring at a constant speed, heating to 150 ℃, starting the reaction, gradually heating to 220 ℃ within 1h, and finishing the esterification process when the amount of distilled by-product water in the reaction kettle reaches 95% of theoretical water yield. Gradually vacuumizing the reaction kettle to 2000PaA for 50min, then gradually vacuumizing to 90PaA, heating to 240 ℃ and keeping for polycondensation reaction for 150min to obtain a polymer melt, and water-cooling and granulating to obtain the product.
Comparative example 2
In this comparative example, phthalate was used without the addition of Schiff base complex.
Adding 10mol of succinic acid, 12mol of butanediol, 5.9g of tetrabutyl titanate and 3.54 g of butyltriphenyl phosphonium bromide into a 5L polyester kettle, keeping normal pressure in the kettle, stirring at a constant speed, heating to 150 ℃, starting reaction, gradually heating to 220 ℃ within 1h, finishing the esterification process when the amount of distilled by-product water in the kettle reaches 95% of theoretical water yield, gradually vacuumizing the reaction kettle to 2000PaA for 50min, then gradually vacuumizing to 90PaA, heating to 240 ℃ and keeping, carrying out polycondensation reaction for 150min, obtaining polymer melt, and carrying out water cooling and pelletizing to obtain the product.
TABLE 1PBS Properties
Figure BDA0003695558850000091
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (9)

1. A preparation method of a low-cyclic by-product poly (butylene succinate) (PBS) is characterized in that a catalyst Schiff base titanium complex, an auxiliary agent quaternary phosphonium salt, succinic acid and 1, 4-butanediol are mixed for esterification reaction, and then the mixture is vacuumized and continuously subjected to constant-temperature polycondensation reaction to obtain a poly (butylene succinate) polymer.
2. The method for preparing according to claim 1, wherein the Schiff base titanium complex is an amino acid Schiff base titanium complex, preferably an α -amino acid Schiff base titanium complex, more preferably glycine;
preferably, the addition amount of the Schiff base titanium complex is 0.02-2% of the mass of the succinic acid, and preferably 0.2-1%;
and/or the quaternary phosphonium salt is R 1 R 2 3 PX 1 Wherein R is 1 Is 1-16 carbon alkyl, R 2 Is 1-6 carbon alkyl or phenyl, X 1 Is Cl - 、Br - 、I - 、NO 3 - 、CH 3 COO - Preferably, the quaternary phosphonium salt is one or more of butyltriphenylphosphonium bromide, butyltriphenylphosphonium iodide, butyltriphenylphosphonium chloride, ethyltriphenylphosphonium bromide and methyltriphenylphosphonium iodide, and more preferably, the quaternary phosphonium salt is butyltriphenylphosphonium bromide;
preferably, the addition amount of the quaternary phosphonium salt is 0.01-1%, preferably 0.1-0.5% of the mass of the succinic acid;
and/or adding excessive 1, 4-butanediol relative to the succinic acid, wherein the molar ratio of the succinic acid to the 1, 4-butanediol is preferably 1: 1.1-1: 1.3.
3. The production method according to claim 1 or 2, wherein the esterification reaction is carried out at 180 to 250 ℃;
and/or, carrying out twice vacuum pumping on the polycondensation reaction, wherein the first vacuum pumping is carried out until the vacuum pressure is 1000-30,000 PaA, and the vacuum pressure lasts for 10-60 min; vacuumizing for the second time to less than 100PaA, and reacting for 60-200 min at constant temperature of 220-270 ℃.
4. A method for preparing a schiff base titanium complex, which is the schiff base titanium complex according to any one of claims 1 to 3, comprising the steps of:
s1: dissolving amino acid and inorganic base in a solvent, and heating and refluxing until the solid is completely dissolved;
s2: dissolving an active carbonyl compound in a solvent, dropwise adding the solution into S1, and carrying out reflux reaction;
s3: dissolving a titanium compound in a solvent, dropwise adding the solution into S2, and carrying out reflux reaction;
s4: the solvent in S3 was evaporated to give a precipitate, which was washed and dried.
5. The method according to claim 3, wherein the amino acid at S1 is one or more selected from glycine, lysine, aspartic acid, valine, alanine, tryptophan and cysteine, preferably glycine;
and/or, the inorganic base in S1 is one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and calcium carbonate, and potassium hydroxide is preferred;
preferably, the molar ratio of the amino acid S1 to the inorganic base is 1 (2-5), preferably 1 (3-4);
and/or, the solvent of S1 is one or more of C1-C6 small molecular alcohol, chloroform, N-Dimethylformamide (DMF) and dimethyl sulfoxide, preferably methanol;
and/or reacting S1 in a nitrogen environment, wherein the reaction temperature is 5-10 ℃ higher than the boiling point of the solvent.
6. The preparation method according to claim 4, wherein the active carbonyl compound S2 is one or more of salicylaldehyde, vanillin, 5-chlorosalicylaldehyde, 5-bromosalicylaldehyde and o-vanillin, preferably salicylaldehyde;
preferably, the molar ratio of the active carbonyl compound to the amino acid is (2-5): 1, preferably (3-4): 1;
and/or, the solvent of S2 is the solvent used in S1;
and/or reacting S2 in a nitrogen environment, wherein the reaction temperature is 5-10 ℃ higher than the boiling point of the solvent, and the reaction time is 5-24 hours, preferably 8-12 hours.
7. The production method according to claim 4, wherein the titanium compound is titanium tetrachloride in S3;
preferably, the molar ratio of the titanium compound to the amino acid is (1-3) to 1, preferably (1.5-2) to 1;
and/or, the solvent of S3 is the solvent used in S1;
and/or reacting S3 in a nitrogen environment at the temperature of 5-10 ℃ higher than the boiling point of the solvent for 5-24 h, preferably 8-12 h.
8. The method according to claim 4, wherein the washing solvent of S4 is an alcohol solvent, preferably ethanol;
and/or the drying temperature of S4 is 100-300 ℃, preferably 150-200 ℃, and the drying time is 24-56 hours, preferably 40-50 hours.
9. A polybutylene succinate (PBS) prepared by the preparation method of any one of claims 1 to 3 or catalyzed by the catalyst prepared by the catalyst preparation method of any one of claims 4 to 8, wherein the content of cyclic side products of the polybutylene succinate in the polybutylene succinate is less than or equal to 1wt%, preferably less than or equal to 0.5 wt%, based on the total mass of the polybutylene succinate;
wherein the poly butylene succinate cyclic byproduct has the following structure:
Figure FDA0003695558840000031
wherein n is a positive integer less than 10.
CN202210678580.4A 2022-06-15 2022-06-15 Preparation method of low-cyclic byproduct polybutylene succinate polyester Active CN114957201B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210678580.4A CN114957201B (en) 2022-06-15 2022-06-15 Preparation method of low-cyclic byproduct polybutylene succinate polyester

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210678580.4A CN114957201B (en) 2022-06-15 2022-06-15 Preparation method of low-cyclic byproduct polybutylene succinate polyester

Publications (2)

Publication Number Publication Date
CN114957201A true CN114957201A (en) 2022-08-30
CN114957201B CN114957201B (en) 2023-10-20

Family

ID=82964004

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210678580.4A Active CN114957201B (en) 2022-06-15 2022-06-15 Preparation method of low-cyclic byproduct polybutylene succinate polyester

Country Status (1)

Country Link
CN (1) CN114957201B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536824A (en) * 2022-09-27 2022-12-30 万华化学集团股份有限公司 Preparation method of low-cyclic by-product poly (butylene succinate) polyester

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012092310A (en) * 2010-09-27 2012-05-17 Mitsubishi Chemicals Corp Method for producing polyester
CN104693428A (en) * 2015-03-17 2015-06-10 江苏钟腾化工有限公司 Preparation method of high-molecular weight poly(butylene succinate)
CN106366296A (en) * 2016-11-02 2017-02-01 安庆和兴化工有限责任公司 Preparation method of poly (butylene succinate-co-butylene adipate)
CN111372972A (en) * 2017-11-20 2020-07-03 巴斯夫欧洲公司 Process for purifying aliphatic polyesters
CN112280011A (en) * 2020-11-13 2021-01-29 营口康辉石化有限公司 A kind of preparation method of low melting index polybutylene succinate
CN114437321A (en) * 2021-12-30 2022-05-06 康辉新材料科技有限公司 A kind of polybutylene succinate and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012092310A (en) * 2010-09-27 2012-05-17 Mitsubishi Chemicals Corp Method for producing polyester
CN103124761A (en) * 2010-09-27 2013-05-29 三菱化学株式会社 Process for producing polyester
EP2623540A1 (en) * 2010-09-27 2013-08-07 Mitsubishi Chemical Corporation Process for producing polyester
CN104693428A (en) * 2015-03-17 2015-06-10 江苏钟腾化工有限公司 Preparation method of high-molecular weight poly(butylene succinate)
CN106366296A (en) * 2016-11-02 2017-02-01 安庆和兴化工有限责任公司 Preparation method of poly (butylene succinate-co-butylene adipate)
CN111372972A (en) * 2017-11-20 2020-07-03 巴斯夫欧洲公司 Process for purifying aliphatic polyesters
CN112280011A (en) * 2020-11-13 2021-01-29 营口康辉石化有限公司 A kind of preparation method of low melting index polybutylene succinate
CN114437321A (en) * 2021-12-30 2022-05-06 康辉新材料科技有限公司 A kind of polybutylene succinate and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王中仁等: "钛酸正四丁酯一磷酸铝催化合成聚丁二酸丁二醇酯的研究", 《石油化工》, vol. 42, no. 11, pages 1278 - 1281 *
黄关葆: "聚丁二酸丁二醇酯的研究与产业化现状", 《纺织学报》, vol. 35, no. 8, pages 156 - 162 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115536824A (en) * 2022-09-27 2022-12-30 万华化学集团股份有限公司 Preparation method of low-cyclic by-product poly (butylene succinate) polyester
CN115536824B (en) * 2022-09-27 2024-06-25 万华化学集团股份有限公司 Preparation method of low-cyclic byproduct polybutylene succinate polyester

Also Published As

Publication number Publication date
CN114957201B (en) 2023-10-20

Similar Documents

Publication Publication Date Title
US9765183B2 (en) Process for preparing a polymer having a 2,5-furandicarboxylate moiety within the polymer backbone and such (co)polymers
JP6505917B6 (en) Process for preparing cyclic oligomers, and cyclic oligomers obtained thereby
CN101935391B (en) Preparation method of high-molecular-weight aliphatic polyester
CN114957201A (en) Preparation method of low-cyclic by-product poly (butylene succinate) polyester
CN107964092B (en) Catalyst for producing polytrimethylene terephthalate and preparation method and application thereof
CN114507338A (en) Preparation method of poly (butylene succinate) with low cyclic by-product
CN108219121A (en) A kind of biology base high barrier polyester material and its synthetic method
CN112390940A (en) Catalyst for polyester synthesis
CN113896876B (en) Multifunctional composite catalyst and preparation method and application thereof
JP4693419B2 (en) Complex catalysts for catalyzing esterification and transesterification reactions and esterification / transesterification processes using them
CN115536824B (en) Preparation method of low-cyclic byproduct polybutylene succinate polyester
CN117024725A (en) Phosphorus-containing bimetallic titanium polyester catalyst, preparation method and application
CN116535632A (en) A kind of liquid titanium series catalyst, preparation method and application thereof
CN115785423B (en) Polyester and copolyester polycondensation catalyst and preparation method and application thereof
CN107955148B (en) Catalyst for producing polytrimethylene terephthalate and preparation method and application thereof
CN115505108A (en) Hydrolysis-resistant titanium catalyst and preparation method and application thereof
CN108003183B (en) A kind of method for catalyzing caprolactone polymerization using four-dentate nitrogen-oxygen-coordinated aluminum compound
US6054552A (en) Process for preparing ester amides and polyesteramides
CN115947934B (en) A catalyst for preparing polyester by ring-opening polymerization and a method for preparing polyester
KR0122003B1 (en) Production method of polyester
CN119318993A (en) Composite catalyst for polycondensation of carbon dioxide and aliphatic dihydric alcohol and method for preparing oligocarbonate by using composite catalyst
JP2004099531A (en) Method for producing polyethylene isophthalate cyclic dimer
CN116535626A (en) Bio-based polyester and preparation method thereof
CN108641094A (en) A kind of preparation method of modified lignin resin base biphenol monomer
Velmathi Low cost and less toxic p-Toluene sulfonic acid catalysed ecofriendly and extremely rapid synthesis of aliphatic poly esters

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