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CN-121991324-A - Polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer and preparation method thereof

CN121991324ACN 121991324 ACN121991324 ACN 121991324ACN-121991324-A

Abstract

The invention discloses a polycaprolactone-b-polybutadiene-b-polycaprolactone segmented copolymer and a preparation method thereof, wherein the copolymer has the following molecular structure: The elastic, ageing-resistant and low-temperature-resistant properties of the polyurethane are superior to those of conventional polycaprolactone, and the polyurethane contains double bonds and terminal hydroxyl groups, can be grafted with other alkenyl-containing polymers and can be crosslinked by ultraviolet light curing, and can be used as a raw material for toughening epoxy resin or synthesizing special polyurethane elastomer; the preparation method comprises the following steps: the double-end hydroxyl polybutadiene is used as an initiator to initiate epsilon-caprolactone to carry out ring-opening polymerization reaction, and the method is high in synthesis efficiency, low in cost and capable of being produced in a large scale.

Inventors

  • LI CHANGCUN
  • XIAO ZEWEI
  • LIU YONGJUN

Assignees

  • 中国石油化工股份有限公司
  • 中石化湖南石油化工有限公司

Dates

Publication Date
20260508
Application Date
20241107

Claims (7)

  1. 1. A polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer is characterized by having the following molecular structure: Wherein a, b and c are integers of 1 to 200, and m and n are integers of 1 to 1000.
  2. 2. The polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer according to claim 1, wherein a+b+c=10 to 100.
  3. 3. The method for preparing the polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer according to claim 1 or 2, wherein the method is characterized in that double-end hydroxyl polybutadiene is used as an initiator to initiate epsilon-caprolactone to carry out ring opening polymerization reaction.
  4. 4. A process for preparing a polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer according to claim 3, wherein the ring-opening polymerization reaction uses organotin as a catalyst.
  5. 5. The method for producing a polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer according to claim 4, wherein the organic tin comprises at least one of stannous isooctanoate, dibutyltin dilaurate, and butyl titanate.
  6. 6. The method for preparing the polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer according to any one of claims 3 to 5, wherein the ring-opening polymerization reaction is carried out at a temperature of 130 to 200 ℃ for 30 to 600 minutes.
  7. 7. The method for preparing a polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer according to claim 6, wherein the ring-opening polymerization reaction is carried out at a temperature of 150-165 ℃ for 100-200 min.

Description

Polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer and preparation method thereof Technical Field The invention relates to polyester, in particular to a polycaprolactone-b-polybutadiene-b-polycaprolactone segmented copolymer and a preparation method thereof, and belongs to the technical field of degradable polyester synthesis. Background Polycaprolactone (PCL) has the advantages of good biodegradability, biocompatibility, shape memory property and the like, and can be used as medical orthopedic splints, medical positioning films, absorbable surgical sutures, medical bone nails, in-vivo implantation stents, hot melt adhesives and the like. Polycaprolactone with a conventional structure has high crystallinity (the crystallinity is generally 50% -60%), poor elasticity, and cannot be subjected to grafting reaction with other compounds containing double bonds or directly subjected to ultraviolet light curing crosslinking. The application of polycaprolactone in the fields of modified SBS (styrene-butadiene-styrene block copolymer), toughened epoxy resin, ultraviolet light curing hot melt adhesive and paint is limited. Chinese patent (publication No. CN 101628971A) discloses a method for synthesizing polycaprolactone, which is completed by one-step reaction, namely, alkynyl poly (amide-amine) of 1 generation to 3 generation initiates the body ring-opening polymerization of caprolactone to prepare the end alkynyl linear or sector structure polycaprolactone. The polymerization temperature is 130 ℃, the reaction time is 24 hours, and the highest yield of polycaprolactone is 92.2%. The method requires longer reaction time and lower yield. Chinese patent (publication No. CN 105968036A) discloses a metal complex for the efficient controllable ring opening of epsilon-caprolactone, in particular to thiourea metal salt, which is suitable for the bulk polymerization and melt polymerization process of epsilon-caprolactone and is also suitable for the slow controllable polymerization in solution, but the cost of raw materials required for synthesizing the thiourea metal salt is higher. Chinese patent (publication No. CN 109336916A) discloses the synthesis of a beta-pyridine enamine bidentate aluminum complex and the catalysis of epsilon-caprolactone ring-opening polymerization. And (3) carrying out condensation reaction on the 2- (2-pyridyl) -acetophenone and aromatic amine containing different substituents to obtain a ligand containing two nitrogen atoms, and then coordinating with alkyl aluminum to synthesize the metal complex of beta-pyridine enamine bidentate aluminum. Can be used for catalyzing ring-opening polymerization of epsilon-caprolactone, wherein the polymerization temperature is 70-80 ℃ and the reaction time is 20-240 min. The method has more working procedures. Mary F. Mahon et al (Inorganic Chemistry; 2006, 45) 2282-2287.) report the synthesis of the novel compound titanium aryloxide, the X-ray structure and its use in epsilon-caprolactone ring-opening polymerization, a series of titanium catechol were prepared and characterized by single crystal X-ray diffraction studies, the electron and space effects of the ligands were studied, and the novel compound titanium aryloxide was used in epsilon-caprolactone ring-opening polymerization to give polycaprolactone with a maximum yield of 79% at room temperature. The polycaprolactone obtained by the method has lower yield. Disclosure of Invention Aiming at the defects of the conventional polycaprolactone in the prior art, the first aim of the invention is to provide a polycaprolactone-b-polybutadiene-b-polycaprolactone segmented copolymer which is superior to the conventional polycaprolactone in elasticity, ageing resistance and low temperature resistance, contains double bonds and hydroxyl ends, can be grafted with other alkenyl-containing polymers, can be crosslinked through ultraviolet light curing, can be used as a raw material for toughening epoxy resin or synthesizing special polyurethane elastomer, and can be widely applied to the fields of modified SBS, ultraviolet light curing hot melt adhesives, coatings and the like. The second aim of the invention is to provide a preparation method of the polycaprolactone-b-polybutadiene-b-polycaprolactone segmented copolymer, which has the advantages of mild reaction conditions, high catalyst efficiency, short reaction time, low cost and the like. In order to achieve the technical object, the present invention provides a polycaprolactone-b-polybutadiene-b-polycaprolactone block copolymer having the following molecular structure: Wherein a, b and c are integers of 1 to 200, and m and n are integers of 1 to 1000. The caprolactone-b-polybutadiene-b-polycaprolactone segmented copolymer has a special molecular structure, wherein the middle of the caprolactone-b-polybutadiene-b-polycaprolactone segmented copolymer is a polybutadiene random copolymerization block, and the two ends of the polycaprolactone-b-polyb