CN114369232B - Renewable degradable thermoplastic elastomer and preparation method thereof - Google Patents
Renewable degradable thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a novel renewable and degradable thermoplastic elastomer and a preparation method thereof. Compared with the prior reported method, the method provided by the invention has the following advantages: 1) The commercialized biomass monomer is adopted, so that the monomer sources are wide, simple and easy to obtain; 2) The thermoplastic elastomer prepared by the invention is expected to be applied to the field of biological medicine; 3) The properties of the thermoplastic elastomer provided by the invention can be regulated and controlled by changing the proportion of two monomers in the soft segment.
Description
Technical Field
The invention relates to the fields of high polymer materials and chemistry and chemical engineering, in particular to a preparation method of a novel renewable degradable thermoplastic elastomer.
Background
Thermoplastic elastomers, which are one of the polymer materials, have been widely used in electronic devices, packaging materials, automobile parts, medical devices, tires, sports equipment, footwear, pressure-sensitive adhesives, and the like because of their high elasticity, hot workability, and recyclability. Thermoplastic elastomers with high heat resistance, high elasticity and high ductility can also be used as electrolyte materials, nanoporous films, photolithographic films, stretchable optical fibers and memory materials. The thermoplastic elastomer commonly used in commerce is derived from non-renewable resources such as fossil fuel, cannot be degraded after use or is recycled by a chemical method, does not meet the requirement of recycling economy, and the greenhouse effect of the thermoplastic elastomer after use can be increased due to improper treatment and the like. In order to reduce the dependence on non-renewable resources and the adverse effect on the environment, the preparation of the bio-based degradable thermoplastic elastomer by using renewable biological resources meets the requirement of sustainable development and has important significance.
As one of thermoplastic elastomers, ABA type thermoplastic elastomers consist of hard and soft segments that are thermodynamically incompatible. Hard segments are generally substances with glass transition temperature or melting point higher than room temperature, and the molecular chains of the hard segments can form reversible physical crosslinking points to provide rigidity and hardness for the material by virtue of non-chemical bonding actions such as van der Waals force and the like or winding between chain segments. The soft segment is mainly a rubber segment with higher flexibility or a polyether or polyester segment with glass transition temperature lower than room temperature, and provides elasticity for the elastomer. The most common ABA thermoplastic elastomers are polystyrene-b-polybutadiene-b-polystyrene thermoplastic elastomer (SBS) and polystyrene-b-polyisoprene-b-polystyrene thermoplastic elastomer (SIS). However, the raw materials are derived from non-renewable petroleum resources, cannot be degraded under natural conditions after being abandoned, and are easy to destroy the ecological environment. The preparation of bio-based thermoplastic elastomer by renewable resources is one of the hot spot directions of the current research, but the problems of complex monomer synthesis process, undegraded final product and the like are also existed.
In view of this, the present invention provides a method for preparing a novel renewable and degradable thermoplastic elastomer by using commercialized biomass monomers such as gamma-butyrolactone (gamma-BL), alpha-methylene-gamma-butyrolactone (MBL), epsilon-caprolactone (epsilon-CL), delta-valerolactone (delta-VL), lactide (LA) and the like as raw materials and adopting a binary catalytic system composed of strong base and a cocatalyst. Compared with the prior reported method, the method provided by the invention has the following advantages: 1) The commercialized biomass monomer is adopted, so that the monomer sources are wide, simple and easy to obtain; 2) The used catalyst and cocatalyst have low toxicity, are easy to remove from products, and the prepared renewable degradable thermoplastic elastomer is expected to be applied to the field of biological medicine; 3) The copolymer is used as a soft segment, the properties of the soft segment can be regulated and controlled by regulating the proportion of two monomers in the soft segment, the properties of the prepared thermoplastic elastomer can be further regulated, and when PMBL-co-PCL or PMBL-co-PVL is used as the soft segment, a modifiable chemical site can be provided for the prepared thermoplastic elastomer due to the fact that the copolymer contains unsaturated double bonds, and the application range of the thermoplastic elastomer is further widened by regulating the physicochemical properties of the thermoplastic elastomer through post modification; 4) The prepared triblock copolymer has the property of thermoplastic elastomer, is degradable, reduces environmental pollution and meets the requirement of circular economy.
Disclosure of Invention
The invention aims to provide a novel renewable and degradable thermoplastic elastomer and a preparation method thereof.
The invention provides an ABA triblock copolymer, wherein a block A has a repeating structural unit shown as a formula (I):
the block B has a repeating structural unit represented by the formula (II) or (III):
according to an embodiment of the present invention, the ABA type triblock copolymer has one of structures represented by formulas (IV), (V), (VI), (VII),
characterized in that m is 1 or 2, x, y and z are natural numbers greater than or equal to 50, R 1 Is an alkylene or arylalkylene group.
In the above ABA type triblock copolymer, the alkylene or arylalkylene group has a structure of one of the following:
the invention also provides a preparation method of the ABA type triblock copolymer, which comprises the following steps:
(1) Dissolving an initiator, strong base and urea in an organic solvent, and stirring for 10-30 min at the temperature of-70 to-20 ℃;
(2) Adding five-membered ring lactone and other ring lactone monomers into the mixed solution, and reacting for 0.5-24 h at the temperature of-70 to-20 ℃;
(3) Dissolving lactide in an organic solvent, adding the reaction system, continuously reacting for 0.5-2 h at the temperature of-20-40 ℃, adding an acidic substance to terminate the reaction, adding the reaction mixture into methanol to settle, and centrifugally drying to obtain the ABA type triblock copolymer.
In the above preparation method, the urea has a structure of one of the following:
in the preparation method, the initiator is a difunctional initiator, and can be concretely ethylene glycol or 1, 2-propyleneDiols, 1, 2-butanediol, 1, 4-cyclohexanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 2-benzenedimethanol, 1, 3-benzenedimethanol, 1, 4-benzenedimethanol; the strong base may be alkali metal, alkali metal compound or organic phosphazene base catalyst, and specifically sodium, potassium hydride, sodium hydride, hexa [ tri (dimethyl amine) phosphazene]Triphosphazene ({ [ (NMe) 2 ) 3 P＝N] 2 P＝N} 3 ) P4-tert-butyl ([ (NMe) phosphazene ligand 2 ) 3 P＝N] 3 P＝NtBu，tert-Bu-P 4 ) P2-tert-butyl ([ (NMe) phosphazene ligand 2 ) 3 P＝N](NMe 2 ) 2 P＝NtBu，tert-Bu-P 2 ) The method comprises the steps of carrying out a first treatment on the surface of the The mol ratio of the strong alkali to the initiator is 1/1-10/1; the molar ratio of the alkali to the urea is 1/1-1/10.
In the above preparation method, the organic solvent in the step (1) may be toluene, tetrahydrofuran, dichloromethane, acetonitrile, N-dimethylformamide.
In the preparation method, in the step (2), the five-membered ring lactone is gamma-butyrolactone or alpha-methylene-gamma-butyrolactone, and the other ring lactones are epsilon-caprolactone or delta-valerolactone; the molar ratio of the five-membered ring lactone to other ring lactone monomers is 1/1-10/1; the molar ratio of the sum of the molar amounts of the five-membered ring lactone and other ring lactone monomers to the initiator is 100/1-1000/1; the sum of the molar concentration of the five-membered ring lactone monomer and other ring lactone monomers in the system is 1-8 mol/L.
In the above preparation method, the organic solvent in the step (3) may be toluene, tetrahydrofuran, dichloromethane, acetonitrile, N-dimethylformamide; the molar concentration of the lactide in the system is 0.1-3 mol/L; the lactide may be L-lactide, D-lactide, racemic lactide or meso-lactide; the molar ratio of the lactide to the five-membered ring lactone is 5/1-1/20.
In the preparation method, the acidic substance can be acetic acid, benzoic acid, hydrochloric acid, sulfuric acid and phosphoric acid, and the molar ratio of the acidic substance to the strong base is 1/1-10/1.
Drawings
FIG. 1 is a GPC chart of poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in comparative example.
FIG. 2 is a schematic diagram showing the polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 1 1 H NMR spectrum.
FIG. 3 is a GPC chart of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 1.
FIG. 4 is a drawing showing the stretching spectrum of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 1.
FIG. 5 is a drawing showing the stretching cycle spectrum of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 1.
FIG. 6 is a GPC chart of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 2.
FIG. 7 is a GPC chart of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 3.
FIG. 8 is a DSC chart of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid prepared in example 4 to example 6.
FIG. 9 is a drawing of the polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in examples 4 to 6.
FIG. 10 is a schematic diagram of polylactic acid-b-poly (α -methylene- γ -butyrolactone-co- ε -caprolactone) -b-polylactic acid obtained in example 7 1 HNMR spectra.
FIG. 11 is a GPC chart of polylactic acid-b-poly (α -methylene- γ -butyrolactone-co- ε -caprolactone) -b-polylactic acid obtained in example 7
FIG. 12 is a GPC chart of polylactic acid-b-poly (α -methylene- γ -butyrolactone-co- δ -valerolactone) -b-polylactic acid obtained in example 8.
FIG. 13 is a GPC chart of polylactic acid-b-poly (gamma-butyrolactone-co-delta-valerolactone) -b-polylactic acid obtained in example 9.
Detailed Description
The present invention will be specifically described with reference to the following examples, but the present invention is not limited to these examples.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Comparative examples
(0.05 mmol,5.4 mg) of benzyl alcohol, (0.05 mmol,59.9 mg) of hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15 mmol,37.9 mg) of 1-cyclohexyl-3- (4-chlorophenyl) urea was dissolved in 2.39mL of tetrahydrofuran, and the mixture was stirred at-50℃for 10 minutes in a low-temperature cold bath, and (9 mmol,0.69 mL) of gamma-butyrolactone and (6 mmol,0.67 mL) of epsilon-caprolactone were simultaneously added to the reaction tube, and after the reaction was carried out under nitrogen protection for 1 hour, (7.5 mmol,1080 mg) of lactide was dissolved in 5.11mL of tetrahydrofuran, and the reaction was continued for 1 hour under a nitrogen atmosphere at 25℃in the above reaction system, and then 10 drops of acetic acid were added to terminate the reaction. The reaction mixture was dissolved in 5mL of chloroform, poured into 50mL of methanol, and the precipitate was centrifuged to obtain a polymer, which had a number average molecular weight of 26.5kg/mol, a molecular weight distribution of 1.57, and a polymer was inelastic as determined by GPC.
Example 1
1, 4-phenyl-dimethanol (0.05 mmol,6.9 mg), hexa [ tris (dimethylamine) phosphazene ] triphosphazene (0.05 mmol,59.9 mg) and 1-cyclohexyl-3- (4-chlorophenyl) urea (0.15 mmol,37.9 mg) were dissolved in 2.39ml of tetrahydrofuran, and stirred at-50℃for 10 minutes in a low temperature cold bath, and then (9 mmol,0.69 mL) of gamma-butyrolactone and (6 mmol,0.67 mL) of epsilon-caprolactone were simultaneously added to the reaction tube. After the reaction was carried out under nitrogen atmosphere for 1 hour, L-lactide (7.5 mmol,1080 mg) was dissolved in 5.11mL of tetrahydrofuran and added to the above reaction system, and the reaction was continued under nitrogen atmosphere at 25℃for 1 hour, and 10 drops of acetic acid were added to terminate the reaction. The reaction mixture is dissolved in 5mL of chloroform, poured into 50mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, is successfully prepared by nuclear magnetic characterization. The nuclear magnetic hydrogen spectrum is shown in figure 2. CPC was found to have a number average molecular weight of 28.3kg/mol and a molecular weight distribution of 1.62, and GPC patterns are shown in FIG. 3. The tensile mechanical property test polymer has an elongation at break of about 1200%, a tensile strength of about 15MPa, and a tensile spectrum as shown in FIG. 4. The tensile elongation was 50% of the original length, the elastic recovery was about 90% and the residual strain was about 10% after 10 cycles, and the tensile cycle chart was shown in FIG. 5.
Example 2
1, 4-phenyl-dimethanol (0.05 mmol,6.9 mg), hexa [ tris (dimethylamine) phosphazene ] triphosphazene (0.05 mmol,59.9 mg) and 1-cyclohexyl-3- (4-chlorophenyl) urea (0.15 mmol,37.9 mg) were dissolved in 2.39mL of tetrahydrofuran, and stirred at-50℃for 10 minutes in a low temperature cold bath, and then (9 mmol,0.69 mL) of gamma-butyrolactone and (6 mmol,0.67 mL) of epsilon-caprolactone were simultaneously added to the reaction tube. After the reaction was performed under nitrogen protection for 1 hour, (7.5 mmol,1080 mg) rac-lactide was dissolved in 5.11mL tetrahydrofuran and added to the above reaction system, the reaction was continued under nitrogen atmosphere at 25℃for 10 minutes, and 10 drops of acetic acid were added to terminate the reaction. The reaction mixture is dissolved in 5mL of chloroform, poured into 50mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, is successfully prepared by nuclear magnetic characterization. CPC was found to have a number average molecular weight of 27.6kg/mol and a molecular weight distribution of 1.80, and GPC patterns are shown in FIG. 6. The elongation at break of the tensile mechanical property test polymer is about 600%, and the tensile strength is about 5MPa.
Example 3
(0.5 mmol,69 mg) 1, 4-phenyldimethanol, (0.5 mmol,599 mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (1.5 mmol,379 mg) 1-cyclohexyl-3- (4-chlorophenyl) urea was dissolved in 23.9mL tetrahydrofuran, stirred for 5min at-50℃in a low temperature cold bath, and (90 mmol,6.9 mL) gamma-butyrolactone and (60 mmol,6.7 mL) epsilon-caprolactone were simultaneously added to the reaction tube. After the reaction was carried out under nitrogen protection for 1 hour, (7.5 mmol,1080 mg) of L-lactide was dissolved in 51.1mL of tetrahydrofuran and added to the above reaction system, the reaction was continued under nitrogen atmosphere at 0℃for 5 minutes, and 30 drops of acetic acid were added to terminate the reaction. The reaction mixture was dissolved in 50mL of chloroform, poured into 100mL of methanol, and the precipitate was centrifuged to obtain a polymer. CPC was found to have a number average molecular weight of 32.7kg/mol and a molecular weight distribution of 1.56, and GPC patterns are shown in FIG. 7. The tensile mechanical property test polymer had an elongation at break of about 800% and a tensile strength of about 7.5MPa.
Example 4
1, 4-phenyldimethanol (0.05 mmol,6.9 mg), hexa [ tris (dimethylamine) phosphazene ] triphosphazene (0.05 mmol,59.9 mg) and 1-cyclohexyl-3- (trifluoromethylphenyl) urea (0.15 mmol,43 mg) were dissolved in 4.09mL of tetrahydrofuran, and stirred at-40℃for 30 minutes in a low temperature cold bath, and gamma-butyrolactone (12 mmol,0.92 mL) and epsilon-caprolactone (8 mmol,0.89 mL) were simultaneously added to the reaction tube. After the reaction was carried out under nitrogen atmosphere for 2 hours, 10mmol of (1440 mg) D-lactide was dissolved in 5.91mL of tetrahydrofuran and added to the above reaction system, the reaction was continued for 2 hours under nitrogen atmosphere at 0℃and 10 drops of acetic acid were added to terminate the reaction. The reaction mixture is dissolved in 4mL of chloroform, poured into 40mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, is successfully prepared by nuclear magnetic characterization. CPC was found to have a number average molecular weight of 30.9kg/mol and a molecular weight distribution of 1.70. The elongation at break of the tensile mechanical property test polymer is about 750%, and the tensile strength is about 5.5 MPa. The DSC spectrum is shown in FIG. 8, and the stretching spectrum is shown in FIG. 9.
Example 5
1, 4-phenyldimethanol (0.05 mmol,6.9 mg), hexa [ tris (dimethylamine) phosphazene ] triphosphazene (0.10 mmol,119.8 mg), 1-cyclohexyl-3-phenylurea (0.20 mmol,43.6 mg) were dissolved in 2.42mL of tetrahydrofuran, and stirred for 20 minutes at-50℃in a low temperature cold bath, and a mixed solution of (10 mmol,0.77 mL) of gamma-butyrolactone and (5 mmol,0.56 mL) of epsilon-caprolactone was added to the reaction tube. After the reaction was performed under nitrogen protection for 4 hours, (15 mmol,2160 mg) of lactide was dissolved in 5.08mL of tetrahydrofuran and added to the above reaction system, the reaction was continued under nitrogen atmosphere at 40℃for 20 minutes, and 10 drops of acetic acid were added to terminate the reaction. The reaction mixture is dissolved in 8mL of chloroform, poured into 60mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, is successfully prepared by nuclear magnetic characterization. CPC was found to have a number average molecular weight of 35.6kg/mol and a molecular weight distribution of 2.12. The DSC spectrum is shown in FIG. 8, and the stretching spectrum is shown in FIG. 9.
Example 6
(0.20 mol,27.6 g) of 1, 4-phenyldimethanol, (0.20 mol,4.8 g) of sodium hydride, (0.60 mol,168.15 g) of 1- (4-trifluoromethylphenyl) -3-phenylurea was dissolved in 2.36L of tetrahydrofuran, and the mixture was stirred under a low temperature bath at-70℃for 30 minutes, and (10 mol, 0.77L) of gamma-butyrolactone and (10 mol, 1.12L) of epsilon-caprolactone were simultaneously introduced into the reaction tube. After the reaction was performed under nitrogen protection for 10 hours, (40 mol,5760 g) of lactide was dissolved in 7.64L of tetrahydrofuran and added to the above reaction system, the reaction was continued for 2 hours under a nitrogen atmosphere at 40℃and 6L of acetic acid was added to terminate the reaction. The reaction mixture was dissolved in 12L of chloroform, poured into 80L of methanol, and the precipitate was centrifuged to obtain a polymer, CPC was found to have a number average molecular weight of 21.0kg/mol and a molecular weight distribution of 1.74. The DSC spectrum is shown in FIG. 8, and the stretching spectrum is shown in FIG. 9.
Example 7
1, 4-phenyldimethanol (0.05 mmol,6.9 mg), hexa [ tris (dimethylamine) phosphazene ] triphosphazene (0.05 mmol,59.9 mg), 1- (4-trifluoromethylphenyl) -3-phenylurea (0.15 mmol,42.04 mg) were dissolved in 5.94mL of tetrahydrofuran, stirred at-30℃under a low temperature cold bath for 20 minutes, and (5 mmol,0.44 mL) of α -methylene- γ -butyrolactone and (10 mmol,1.12 mL) of ε -caprolactone were simultaneously added to the reaction tube. After the reaction was performed under nitrogen protection for 1 hour, (5 mmol,720 mg) of lactide was dissolved in 4.06mL of tetrahydrofuran and added to the above reaction system, the reaction was continued under nitrogen atmosphere at 10℃for 10 minutes, and 10 drops of acetic acid were added to terminate the reaction. The reaction mixture is dissolved in 3mL of chloroform, poured into 45mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the nuclear magnetic characterization is successful to prepare the triblock thermoplastic elastomer, namely polylactic acid-b-poly (alpha-methylene-gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, and the nuclear magnetic spectrum diagram is shown in figure 10. CPC was found to have a number average molecular weight of 25.6kg/mol and a molecular weight distribution of 1.55, and GPC patterns are shown in FIG. 11. The tensile mechanical property test polymer has an elongation at break of about 1500% and a tensile strength of about 8.5MPa.
Example 8
1, 4-phenyl-dimethanol (0.05 mmol,6.90 mg), hexa [ tris (dimethylamine) phosphazene ] triphosphazene (0.05 mmol,59.9 mg) and 1-cyclohexyl-3- (4-chlorophenyl) urea were dissolved in 4.65mL of tetrahydrofuran, stirred for 30min at-40℃in a low temperature cold bath, and (5 mmol,0.44 mL) of alpha-methylene-gamma-butyrolactone and (10 mmol,0.91 mL) of epsilon-valerolactone were simultaneously added to the reaction tube. After the reaction was performed under nitrogen protection for 1 hour, (7.5 mmol,1080 mg) of lactide was dissolved in 4.06mL of tetrahydrofuran and added to the above reaction system, the reaction was continued under nitrogen atmosphere at 10℃for 1 hour, and 10 drops of acetic acid were added to terminate the reaction. The reaction mixture was dissolved in 4mL of chloroform, poured into 60mL of methanol, and the precipitate was centrifuged to obtain a polymer, CPC was found to have a number average molecular weight of 28.7kg/mol and a molecular weight distribution of 1.71, and the GPC chart was shown in FIG. 12. The tensile mechanical property test polymer has an elongation at break of about 900% and a tensile strength of about 6.5MPa.
Example 9
(0.05 mol,6.9 g) of 1, 4-phenyldimethanol, (0.05 mol,59.9 g) of hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15 mol,32.7 g) of 1-cyclohexyl-3-phenylurea was dissolved in 5.84L of toluene, and the mixture was stirred at-50℃under a low-temperature cold bath for 30 minutes, and (5 mol, 0.38L) of gamma-butyrolactone and (5 mol, 0.45L) of delta-valerolactone were simultaneously introduced into the reaction tube. After the reaction was performed under nitrogen protection for 3 hours, (5 mol,720 g) of lactide was dissolved in 4.16L of toluene and added to the above reaction system, the reaction was continued for 2 hours under nitrogen atmosphere at 20℃and 3L of acetic acid was added to terminate the reaction. The reaction mixture is dissolved in 6L of chloroform, poured into 40L of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-delta-valerolactone) -b-polylactic acid, is successfully prepared by nuclear magnetic characterization. CPC was found to have a number average molecular weight of 18.5kg/mol and a molecular weight distribution of 1.64, and GPC patterns are shown in FIG. 13. The tensile mechanical property test polymer had an elongation at break of about 460% and a tensile strength of about 3.5MPa.
Claims (8)
1. An ABA type triblock copolymer having one of the structures represented by the formulas (IV), (V), (VI), (VII),
wherein x, y and z are natural numbers greater than or equal to 50, R 1 Is an alkylene or arylalkylene group.
2. ABA triblock copolymer according to claim 1, characterized in that the alkylene or arylalkylene group has the structure of one of the following:
3. the method for preparing an ABA triblock copolymer according to claim 1, comprising the following steps:
(1) Dissolving an initiator, strong base and urea in an organic solvent, and stirring for 10-30 min at the temperature of-70 to-20 ℃;
(2) Adding five-membered ring lactone and other ring lactone monomers into the mixed solution, and reacting for 0.5-24 h at the temperature of-70 to-20 ℃;
(3) Dissolving lactide in an organic solvent, adding the reaction system, continuously reacting for 0.5-2 h at the temperature of-20-40 ℃, adding an acidic substance to terminate the reaction, adding the reaction mixture into methanol to settle, and centrifugally drying to obtain the ABA type triblock copolymer.
4. A method according to claim 3, wherein the urea has a structure of one of:
5. a process according to claim 3, wherein the initiator in step (1) is ethylene glycol, 1, 2-propanediol, 1, 2-butanediol, 1, 4-cyclohexanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 2-benzenedimethanol, 1, 3-benzenedimethanol, 1, 4-benzenedimethanol; the strong base is alkali metal, alkali metal compound or organic phosphazene base catalyst; the alkali metal is sodium or potassium; the alkali metal compound is potassium hydride or sodium hydride; the organic phosphazene base catalyst is hexa [ tri (dimethyl amine) phosphazene]Triphosphazene ({ [ (NMe) 2 ) 3 P＝N] 2 P＝N} 3 ) P4-tert-butyl ([ (NMe) phosphazene ligand 2 ) 3 P＝N] 3 P＝NtBu，tert-Bu-P 4 ) Or the phosphazene ligand P2-tert-butyl ([ (NMe) 2 ) 3 P＝N](NMe 2 ) 2 P＝NtBu，tert-Bu-P 2 ) The method comprises the steps of carrying out a first treatment on the surface of the The organic solvent is toluene, tetrahydrofuran, dichloromethane, acetonitrile or N, N-dimethylformamide.
6. A process according to claim 3 wherein in step (2) the five-membered ring lactone is gamma-butyrolactone or alpha-methylene-gamma-butyrolactone and the other ring lactone monomer is epsilon-caprolactone or delta-valerolactone; the sum of the molar concentration of the five-membered ring lactone and other ring lactone monomers in the system is 1-8 mol/L.
7. A process according to claim 3, wherein the organic solvent in step (3) is toluene, tetrahydrofuran, dichloromethane, acetonitrile or N, N-dimethylformamide; the molar concentration of the lactide in the system is 0.1-3 mol/L; the lactide is L-type lactide, D-type lactide, racemic lactide or meso-lactide; the acidic substance is acetic acid, benzoic acid, hydrochloric acid, sulfuric acid or phosphoric acid.
8. A method according to claim 3, characterized in that:
the mol ratio of the strong alkali to the initiator is 1/1-10/1; the molar ratio of the strong alkali to the urea is 1/1-1/10; the molar ratio of the five-membered ring lactone to other ring lactone monomers is 1/1-10/1; the molar ratio of the sum of the molar amounts of the five-membered ring lactone and other ring lactone monomers to the initiator is 50/1-1000/1; the molar ratio of the lactide to the five-membered ring lactone is 5/1-1/20; the molar ratio of the acidic substance to the strong base is 1/1-10/1.
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| JP2006183042A (en) * | 2004-11-30 | 2006-07-13 | Hiroshima Univ | New multiblock copolymer, method for producing the same, and its utilization |
| CN108250415A (en) * | 2018-02-09 | 2018-07-06 | 青岛科技大学 | A kind of poly- (gamma-butyrolacton)-b- polylactic-acid block copolymers and preparation method thereof |
| CN110305303A (en) * | 2019-07-24 | 2019-10-08 | 青岛科技大学 | A kind of preparation method of degradable biological base polyester of the side chain containing double bond functional group |
| CN110804163A (en) * | 2019-12-04 | 2020-02-18 | 青岛科技大学 | Preparation method of bio-based copolyester containing modifiable functional group |
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| JP2006183042A (en) * | 2004-11-30 | 2006-07-13 | Hiroshima Univ | New multiblock copolymer, method for producing the same, and its utilization |
| CN108250415A (en) * | 2018-02-09 | 2018-07-06 | 青岛科技大学 | A kind of poly- (gamma-butyrolacton)-b- polylactic-acid block copolymers and preparation method thereof |
| CN110305303A (en) * | 2019-07-24 | 2019-10-08 | 青岛科技大学 | A kind of preparation method of degradable biological base polyester of the side chain containing double bond functional group |
| CN110804163A (en) * | 2019-12-04 | 2020-02-18 | 青岛科技大学 | Preparation method of bio-based copolyester containing modifiable functional group |
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