CN114479023B - Novel bio-based degradable thermoplastic elastomer and preparation method thereof - Google Patents
Novel bio-based degradable thermoplastic elastomer and preparation method thereof Download PDFInfo
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Abstract
The invention provides a polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer and a preparation method thereof. The prepared triblock copolymer has the property of thermoplastic elastomer. The method provided by the invention has the following advantages: 1) The raw materials used are nontoxic and harmless and are biomass sources, and the prepared triblock copolymer can be completely degraded under natural conditions; 2) The catalytic system has high catalytic activity and high monomer conversion rate, the conversion rate of delta-caprolactone can reach about 85 percent, and the conversion rate of lactide is more than 95 percent; 3) The reaction condition is mild, the reaction time is short, and the energy consumption is greatly reduced.
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 bio-based degradable thermoplastic elastomer.
Background
The thermoplastic elastomer has the characteristics of good elasticity, reworkability and the like, and is widely applied to the fields of hot-melt pressure-sensitive adhesives, automobile parts, medical appliances and the like. Commercially available thermoplastic elastomers which are currently common are polystyrene-b-polybutadiene-b-polystyrene, polystyrene-b-polyisoprene-b-polystyrene, and the like. Although these materials are widely used, they rely on non-renewable raw materials and cannot degrade in the natural environment after disposal.
The preparation of sustainable bio-based thermoplastic elastomers using safe, non-toxic biomass-derived raw materials is of increasing interest. L-lactide is derived from plants such as sugarcane, and polylactic acid obtained by ring-opening polymerization of the L-lactide is a completely biodegradable polyester material. Hillmyer et al report the synthesis of polylactic acid-b-poly (beta-methyl-delta-valerolactone) -b-polylactic acid triblock copolymers, and the obtained triblock copolymers exhibit the properties of thermoplastic elastomers and have higher mechanical strength and elongation at break. However, β -methyl- δ -valerolactone as a synthetic raw material is not a commercial monomer, and the synthetic procedure is complicated and difficult to mass-produce industrially (Proceedings of the National Academy of Sciences of the United States of America,2014,111 (23), 8357). Delta-caprolactone (δCL) is a delta-methyl substituted six-membered ring lactone, naturally occurring in fruits and hot milk, and can also be produced from biomass-derived 5-hydroxymethylfurfural, which has been commercialized and is commonly used as a food additive. Poly (delta-caprolactone) (P delta CL) has a low glass transition temperature and exhibits a rubbery state at room temperature, and is expected to be useful as a soft segment of thermoplastic elastomers. By selecting a proper catalytic system, the sequential ring-opening polymerization of delta-caprolactone and lactide is realized, and the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid (PLA-b-P delta CL-b-PLA) triblock copolymer with a definite structure can be prepared. It is expected that thermoplastic elastomer materials having excellent properties can be obtained by adjusting the composition and proportion of the triblock copolymer. However, no related literature or data report about the synthesis and property study of PLA-b-P delta CL-b-PLA triblock copolymer.
In view of the above, the invention provides a binary catalytic system composed of strong alkali and biurea, and a method for preparing polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer with definite structure by realizing sequential ring-opening polymerization of delta-caprolactone and lactide. The prepared triblock copolymer has the property of thermoplastic elastomer. The method provided by the invention has the following advantages: 1) The raw materials used are nontoxic and harmless and are biomass sources, and the prepared triblock copolymer can be completely degraded under natural conditions; 2) The catalytic system has high catalytic activity and high monomer conversion rate, the conversion rate of delta-caprolactone can reach about 85 percent, and the conversion rate of lactide is more than 95 percent; 3) The reaction condition is mild, the reaction time is short, and the energy consumption is greatly reduced.
Disclosure of Invention
The invention aims to provide a novel bio-based degradable thermoplastic elastomer and a preparation method thereof.
The invention provides a polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer shown in a formula (I),
characterized in that m is a natural number of 200 or more, n is a natural number of 100 or more, R 1 Is an alkylene or arylalkylene group.
In the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer described above, the alkylene or arylalkylene group has a structure of one of the following:
the invention also provides a preparation method of the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer, which comprises the following steps:
(1) Dissolving an initiator, strong base and biurea in an organic solvent, and stirring for 1-10 min at room temperature;
(2) Delta-caprolactone is added into the mixed solution and reacts for 0.1 to 1 hour at the temperature of-20 to 40 ℃;
(3) Dissolving lactide in an organic solvent, adding the reaction system, continuously reacting for 0.1-1 h at the temperature of-20-40 ℃, adding an acidic substance to terminate the reaction, and adding the reaction mixture into methanol to precipitate to obtain the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer.
In the above preparation method, the biuret has a structure of one of the following:
in the preparation method, the initiator is a difunctional initiator, and can be concretely ethylene glycol, 1, 2-propylene glycol, 1, 2-butanediol, 1, 4-cyclohexanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 2-benzenedimethanol, 1, 3-benzenedimethanol and 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 ) Phosphorus (P)Nitrile ligand P4-tert-butyl ([ (NMe) 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 1/1-20/1; the molar ratio of the strong base to the biurea 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, the molar concentration of delta-caprolactone in the system in the step (2) is 4-9 mol/L; the mol ratio of delta-caprolactone to the initiator is 200/1-3000/1.
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 delta-caprolactone is 1/1-1/20.
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 schematic diagram of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid obtained in example 1 1 H NMR spectrum.
FIG. 2 is a GPC chart of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid obtained in example 1 to example 3.
FIG. 3 is a DSC chart of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 1 at a scanning rate of 10℃per minute.
FIG. 4 is a DSC chart of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 2 at a scanning rate of 10℃per minute.
FIG. 5 is a DSC chart of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 3 at a scan rate of 10℃per minute.
FIG. 6 is a schematic diagram of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid obtained in example 4 1 H NMR spectrum.
FIG. 7 is a schematic diagram of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid obtained in example 5 1 H NMR spectrum.
FIG. 8 is a schematic diagram of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid obtained in example 6 1 H NMR spectrum.
FIG. 9 is a schematic diagram of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid obtained in example 7 1 H NMR spectrum.
Fig. 10 is a uniaxial stretching spectrum of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 5 to example 7.
FIG. 11 is a drawing showing the tensile cycle spectrum of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid obtained in example 7.
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 example 1
(0.08 mmol,11.05 mg) 1, 4-benzenedimethanol, (0.08 mmol,95.84 mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene was dissolved in 1.3mL tetrahydrofuran and stirred at room temperature for 10min, and (24 mmol,2.7 mL) delta-caprolactone was added to the reaction tube and the reaction was carried out under nitrogen protection at 30℃for 30min. Then (16 mmol,2.3 g) lactide was dissolved in 10.67mL tetrahydrofuran and the system was added and reacted for 10min under nitrogen protection at 25℃and 10mg benzoic acid was added to terminate the reaction. The reaction mixture is dissolved in 10mL of tetrahydrofuran, poured into 60mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the nuclear magnetic characterization polymer is a mixture of polylactic acid and poly (delta-caprolactone) and has poor mechanical property.
Comparative example 2
(0.08 mmol,11.05 mg) 1, 4-benzenedimethanol, (0.08 mmol,95.84 mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.24 mmol,68.72 mg) 1-cyclohexyl-3- (4-trifluoromethylphenyl) urea was dissolved in 1.3mL tetrahydrofuran, stirred at room temperature for 10min, and (24 mmol,2.7 mL) delta-caprolactone was added to the reaction tube and the reaction was carried out under nitrogen protection at 30℃for 30min. Then (16 mmol,2.3 g) lactide was dissolved in 10.67mL tetrahydrofuran and the system was added and reacted for 10min under nitrogen protection at 25℃and 10mg benzoic acid was added to terminate the reaction. The reaction mixture is dissolved in 10mL of tetrahydrofuran, poured into 60mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the nuclear magnetic characterization polymer is a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid. GPC showed that the number average molecular weight was 29.4kg/mol, the molecular weight distribution was 1.27, and the polymer molecular weight was low and inelastic.
Comparative example 3
(0.08 mmol,11.05 mg) 1, 4-benzenedimethanol, (0.08 mmol,95.84 mg) hexa [ tris (dimethylamine) phosphazene]Trimeric phosphazene, (0.24 mmol,84.96 mg) 1,1' - (hexylidene-1, 6-diacyl) bis (3-phenylurea)Dissolved in 1.3mL of tetrahydrofuran, stirred at room temperature for 10min, delta-caprolactone (24 mmol,2.7 mL) was added to the reaction tube and the reaction was carried out at 30℃under nitrogen for 30min. Then (16 mmol,2.3 g) lactide was dissolved in 10.67mL tetrahydrofuran and the system was added and reacted for 10min under nitrogen protection at 25℃and 10mg benzoic acid was added to terminate the reaction. The reaction system was heterogeneous and contained a large amount of insoluble matter, and the intended triblock copolymer was not obtained.
Example 1
(0.08 mmol,11.05 mg) 1, 4-benzenedimethanol, (0.08 mmol,95.84 mg) hexa [ tris (dimethylamine) phosphazene]Trimeric phosphazenes, (0.24 mmol,136.8 mg) 1,1' - (ethylene) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)Dissolved in 1.3mL of tetrahydrofuran, stirred at room temperature for 10min, delta-caprolactone (24 mmol,2.7 mL) was added to the reaction tube and the reaction was carried out at 30℃under nitrogen for 30min. Next, (16 mmol,2.3 g) lactide was dissolved in 10.67mL tetrahydrofuran and the system was added to the above, atThe reaction was stopped by adding 10mg of benzoic acid at 25℃under nitrogen blanket for 10 min. The reaction mixture is dissolved in 10mL of tetrahydrofuran, poured into 60mL of methanol, and the polymer is obtained by centrifugal separation and precipitation, and the nuclear magnetic resonance characterization polymer is a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, and the nuclear magnetic resonance hydrogen spectrum of the triblock copolymer is shown in figure 1. GPC showed that the number average molecular weight was 43.0kg/mol, the molecular weight distribution was 1.37, the GPC chart was shown in FIG. 2, and the DSC chart was shown in FIG. 3. The tensile mechanical property test polymer has an elongation at break of 200% and a tensile strength of about 3.5MPa. The elastic recovery was measured to be about 73% and the residual strain was about 18% when stretched to 100% of the original length and cycled 10 times.
Example 2
(0.05 mmol,6.91 mg) 1, 4-benzenedimethanol, (0.05 mmol,31.7 mg) phosphazene ligand P4-t-butyl catalyst, (0.1 mmol,61.4 mg) 1,1' - (oxybis (ethylene)) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)Dissolved in 1.35mL of tetrahydrofuran, stirred at room temperature for 5min, delta-caprolactone (25 mmol,2.82 mL) was added to the reaction tube, the reaction was performed under nitrogen protection at 25℃for 15min, then lactide (15 mmol,2.16 g) was dissolved in 10mL of tetrahydrofuran, and the above system was added, and the reaction was stopped by adding 10 drops of acetic acid at 25℃for 5min under nitrogen protection. The reaction mixture was dissolved in 5mL of chloroform, poured into 40mL of methanol, and the polymer was obtained by centrifugal separation and precipitation, and the nuclear magnetic resonance characterization polymer was a triblock copolymer, namely polylactic acid-b- (poly delta-caprolactone) -b-polylactic acid, and GPC gave a number average molecular weight of 73.2kg/mol, a molecular weight distribution of 1.20, a GPC spectrum shown in FIG. 2, and a DSC spectrum shown in FIG. 4. The tensile mechanical property test polymer has an elongation at break of 657% and a tensile strength of about 16.7MPa. The elastic recovery was measured to be about 87% and the residual strain was about 12% when stretched to 100% of the original length and cycled 10 times.
Example 3
(0.1 mmol,5.58 mL) ethylene glycol, (0.1 mmol,36.75 mg) phosphazene ligand P2-tert-butyl, (0.15 mmol,89.7 mg) 1,1' - (butylene) bis (3- (3, 5 bis (trifluoromethyl) phenyl) urea)And 3.78mL of tetrahydrofuran were added to the reaction tube, stirred at room temperature for 10min, delta-caprolactone (70 mmol,7.89 mL) was added to the reaction tube, and the reaction was carried out under nitrogen at 29℃for 20min. Then (30 mmol,4.32 g) lactide was dissolved in 20mL tetrahydrofuran and the system was added and reacted for 10min at 40℃under nitrogen protection, and 2mL of dilute sulfuric acid was added to terminate the reaction. The reaction mixture was dissolved in 30mL of tetrahydrofuran, poured into 200mL of methanol, and the polymer was obtained by centrifugal separation and precipitation, and the nuclear magnetic resonance characterization polymer was a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, and GPC gave a number average molecular weight of 121.7kg/mol, a molecular weight distribution of 1.25, a GPC spectrum shown in FIG. 2, and a DSC spectrum shown in FIG. 5. The tensile mechanical property test polymer has an elongation at break of 865% and a tensile strength of about 29.7MPa. The elastic recovery was measured to be about 90% and the residual strain was about 8% when stretched to 100% of the original length and cycled 10 times.
Example 4
(0.05 mmol,2.79 mL) ethylene glycol, (0.05 mmol,2 mg) potassium hydride, (0.15 mmol,93.9 mg) 1,1' - (hexylene) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)And 2.06mL of tetrahydrofuran were added to the reaction tube, stirred at room temperature for 10min, delta-caprolactone (15 mmol,1.69 mL) was added to the reaction tube, and the reaction was carried out under nitrogen at 19℃for 25min. Then (10 mmol,1.44 g) of lactide was dissolved in 10mL of tetrahydrofuran, and the above system was added, and the reaction was stopped by adding 1mL of hydrochloric acid at 40℃under nitrogen protection for 5min. The reaction mixture was dissolved in 50mL of methylene chloride, poured into 150mL of methanol, and the polymer was obtained by centrifugal separation and precipitation, and the nuclear magnetic resonance characterization polymer was a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, and GPC gave a number average molecular weight of 42.3kg/mol and a molecular weight distribution of 1.19, and the nuclear magnetic resonance hydrogen spectrum thereof was shown in FIG. 6. The tensile mechanical property test polymer has an elongation at break of 508% and a tensile strength of about 5.6MPa. Stretched to 100% of the original length, cycled 10 times, and measured for elastic recoveryThe rate was about 83% and the residual strain was about 12%.
Example 5
(0.06 mmol,3.35 mL) ethylene glycol, (0.06 mmol,22.05 mg) phosphazene ligand P2-tert-butyl, (0.06 mmol,35.04 mg) 1,1' - (propylene) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)And 0.97mL of tetrahydrofuran were added to the reaction tube, stirred at room temperature for 2min, delta-caprolactone (18 mmol,2.03 mL) was added to the reaction tube, and the reaction was carried out under nitrogen at 20℃for 35min. Then (12 mmol,1.73 g) of lactide was dissolved in 12mL of tetrahydrofuran, and the above system was added, and the reaction was terminated by adding 12 drops of dilute sulfuric acid under nitrogen protection at 30℃for 10 min. The reaction mixture was dissolved in 20mL of tetrahydrofuran, poured into 100mL of methanol, and the polymer was obtained by centrifugal separation and precipitation, and the nuclear magnetic resonance characterization polymer was a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, and GPC gave a number average molecular weight of 45.1kg/mol and a molecular weight distribution of 1.12, and the nuclear magnetic hydrogen spectrum thereof was shown in FIG. 7. The tensile mechanical property test polymer has an elongation at break of 762% and a tensile strength of about 7.5MPa, and a tensile spectrum is shown in FIG. 10. The elastic recovery was measured to be about 90% and the residual strain was about 11% when stretched to 100% of the original length and cycled 10 times.
Example 6
(0.04 mol,5.53 g) 1, 4-benzenedimethanol, (0.04 mol,25.36 g) phosphazene ligand P4-t-butyl catalyst, (0.06 mol,42.6 g) 1,1' - (hexylidene) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)Dissolved in 2.75L of tetrahydrofuran, stirred at room temperature for 10min, and (20 mol, 2.25L) of delta-caprolactone was added to the reaction tube and the reaction was carried out under nitrogen protection at 25℃for 60min. Then (8 mol,1150 g) of lactide was dissolved in 8L of tetrahydrofuran, and the above system was added, and the reaction was terminated by adding 1L of phosphoric acid at 30℃under nitrogen protection for 30 minutes. Dissolving the reaction mixture in 10L chloroform, pouring into 50L methanol, centrifuging to obtain polymer, and making the polymer into triblock copolymer by nuclear magnetic resonanceThe polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, which has a number average molecular weight of 80.1kg/mol and a molecular weight distribution of 1.30, was measured by GPC, and the nuclear magnetic hydrogen spectrum thereof is shown in FIG. 8. Tensile mechanical properties the polymer had an elongation at break of 627% and a tensile strength of about 18.2MPa, and the tensile spectrum is shown in FIG. 10. The elastic recovery was measured to be about 92% and the residual strain was about 9% when stretched to 100% of the original length and cycled 10 times.
Example 7
(0.5 mol,69.12 g) 1, 4-benzenedimethanol, (0.5 mol,599 g) hexa [ tris (dimethylamine) phosphazene]Triphosphazene, (0.5 mol, 284 g) 1,1' - (ethylene) bis (3- (3, 5 bis (trifluoromethyl) phenyl) urea)Dissolved in 48.07L tetrahydrofuran, stirred at room temperature for 10min, and (350 mol, 39.43L) delta-caprolactone was added to the reaction tube and the reaction was carried out under nitrogen protection at 0℃for 60min. Then (150 mol,2.16 kg) of lactide was dissolved in 150L of tetrahydrofuran, and the above system was added, and the reaction was terminated by adding 10L of acetic acid under nitrogen protection at 25℃for 30 minutes. The reaction mixture was dissolved in 200L of chloroform, poured into 700L of methanol, and the polymer was obtained by centrifugal separation and precipitation, and the nuclear magnetic resonance characterization polymer was a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, and GPC gave a number average molecular weight of 134.6kg/mol, a molecular weight distribution of 1.28, and a nuclear magnetic resonance hydrogen spectrum thereof was shown in FIG. 9. The tensile mechanical property test polymer has an elongation at break of 1133% and a tensile strength of about 33.5MPa, and the tensile spectrum is shown in FIG. 10. The tensile elongation was 100% of the original length, the elastic recovery was about 93% and the residual strain was about 6% after 10 cycles, and the tensile cycle chart was shown in FIG. 11.
Claims (9)
1. Polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer shown in formula (I),
m is a natural number of 200 or moreThe number n is a natural number greater than or equal to 100, R 1 Is an alkylene or arylalkylene group.
2. The polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer according to claim 1,
the alkylene is one of a formula (II), a formula (III), a formula (IV), a formula (V), a formula (VI) and a formula (VII); the aryl alkylene is one of the formula (VIII), the formula (IX) and the formula (X).
3. The method for preparing the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer according to claim 1 or 2, comprising the steps of:
(1) Dissolving a difunctional initiator, strong base and biuret in an organic solvent, and stirring for 1-10 min at room temperature;
(2) Delta-caprolactone is added into the mixed solution and reacts for 0.1 to 1 hour at the temperature of-20 to 40 ℃;
(3) Dissolving lactide in an organic solvent, adding the reaction system, continuously reacting for 0.1-1 h at the temperature of-20-40 ℃, adding an acidic substance to terminate the reaction, and adding the reaction mixture into methanol to precipitate to obtain the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer.
4. A method according to claim 3, characterized in that:
the difunctional initiator in the step (1) is one of ethylene glycol, 1, 2-propylene glycol, 1, 2-butanediol, 1, 4-cyclohexanediol, 2-butyl-2-ethyl-1, 3-propanediol, 1, 2-benzenedimethanol, 1, 3-benzenedimethanol and 1, 4-benzenedimethanol; the strong base is 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 ) One of the following; the organic solvent is toluene, tetrahydrofuran, dichloromethane, acetonitrile or N, N-dimethylformamide.
5. A method according to claim 3, wherein the biurea has a structure of one of:
6. a method according to claim 3, characterized in that:
the molar ratio of the strong base to the initiator in the step (1) is 1/1-20/1; the molar ratio of the strong base to the biurea is 1/1-1/10.
7. A method according to claim 3, characterized in that:
the molar concentration of delta-caprolactone in the system in the step (2) is 4-9 mol/L; the mol ratio of delta-caprolactone to the initiator is 200/1-3000/1.
8. A method according to claim 3, characterized in that:
the organic solvent in the step (3) is toluene, tetrahydrofuran, methylene dichloride, 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 molar ratio of the lactide to the delta-caprolactone is 1/1-1/20; the acidic substance is acetic acid, benzoic acid, hydrochloric acid, sulfuric acid or phosphoric acid; the molar ratio of the acidic substance to the strong base is 1/1-10/1.
9. Use of the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer according to claim 1 in thermoplastic elastomers.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN202210093119.2A CN114479023B (en) | 2022-01-26 | 2022-01-26 | Novel bio-based degradable thermoplastic elastomer and preparation method thereof |
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| CN115725058B (en) * | 2022-12-26 | 2024-01-05 | 东莞市成铭胶粘剂有限公司 | Preparation method of degradable and recyclable copolyester and application of degradable and recyclable copolyester in pressure-sensitive adhesive |
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| 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 |
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| "Aliphatic Polyester Block Polymer Design";Deborah K. Schneiderman等;《Macromolecules》;第49卷(第7期);第2419-2428页 * |
| "Bisurea and Bisthiourea H‑Bonding Organocatalysts for Ring-Opening Polymerization: Cues for the Catalyst Design";Rukshika S. Hewawasam等;《Macromolecules》;第52卷(第23期);第9232-9237页 * |
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