CN114479023A - 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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- CN114479023A CN114479023A CN202210093119.2A CN202210093119A CN114479023A CN 114479023 A CN114479023 A CN 114479023A CN 202210093119 A CN202210093119 A CN 202210093119A CN 114479023 A CN114479023 A CN 114479023A
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- polylactic acid
- caprolactone
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 36
- 239000004626 polylactic acid Substances 0.000 claims abstract description 36
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 28
- RZTOWFMDBDPERY-UHFFFAOYSA-N Delta-Hexanolactone Chemical compound CC1CCCC(=O)O1 RZTOWFMDBDPERY-UHFFFAOYSA-N 0.000 claims abstract description 26
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 58
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 29
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011541 reaction mixture Substances 0.000 claims description 11
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 claims description 9
- 239000003999 initiator Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 239000007983 Tris buffer Substances 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical group C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 3
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 3
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 3
- JJTUDXZGHPGLLC-ZXZARUISSA-N (3r,6s)-3,6-dimethyl-1,4-dioxane-2,5-dione Chemical compound C[C@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-ZXZARUISSA-N 0.000 claims description 2
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- XMUZQOKACOLCSS-UHFFFAOYSA-N [2-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC=C1CO XMUZQOKACOLCSS-UHFFFAOYSA-N 0.000 claims description 2
- YWMLORGQOFONNT-UHFFFAOYSA-N [3-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=CC(CO)=C1 YWMLORGQOFONNT-UHFFFAOYSA-N 0.000 claims description 2
- 230000001588 bifunctional effect Effects 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- 125000001118 alkylidene group Chemical group 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- 231100000252 nontoxic Toxicity 0.000 abstract description 3
- 230000003000 nontoxic effect Effects 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 40
- 229920000642 polymer Polymers 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 15
- 239000002585 base Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 230000005311 nuclear magnetism Effects 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- LUBJCRLGQSPQNN-UHFFFAOYSA-N 1-Phenylurea Chemical compound NC(=O)NC1=CC=CC=C1 LUBJCRLGQSPQNN-UHFFFAOYSA-N 0.000 description 1
- SOTSKDZKNSOBBM-UHFFFAOYSA-N 1-cyclohexyl-3-[4-(trifluoromethyl)phenyl]urea Chemical compound C1=CC(C(F)(F)F)=CC=C1NC(=O)NC1CCCCC1 SOTSKDZKNSOBBM-UHFFFAOYSA-N 0.000 description 1
- YHTLGFCVBKENTE-UHFFFAOYSA-N 4-methyloxan-2-one Chemical compound CC1CCOC(=O)C1 YHTLGFCVBKENTE-UHFFFAOYSA-N 0.000 description 1
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229920006392 biobased thermoplastic Polymers 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 229920002627 poly(phosphazenes) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/83—Alkali metals, alkaline earth metals, beryllium, magnesium, copper, silver, gold, zinc, cadmium, mercury, manganese, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/87—Non-metals or inter-compounds thereof
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
The invention 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 a thermoplastic elastomer. The method provided by the invention has the following advantages: 1) the used raw materials 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 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 instruments and the like. Currently common commercial thermoplastic elastomers are polystyrene-b-polybutadiene-b-polystyrene and polystyrene-b-polyisoprene-b-polystyrene. Although these materials are widely used, they rely on non-renewable raw materials and are not degradable in the natural environment after disposal.
There is increasing interest in using safe, non-toxic biomass-derived feedstocks to produce sustainable bio-based thermoplastic elastomers. 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 reported the synthesis of polylactic acid-b-poly (. beta. -methyl-. delta. -valerolactone) -b-polylactic acid triblock copolymers, which exhibited the properties of thermoplastic elastomers and had high mechanical strength and elongation at break. However, β -methyl- δ -valerolactone, which is a raw material for synthesis, is not a commercial monomer, and the synthetic steps thereof are complicated and complicated, and it is difficult to industrially produce on a large scale (Proceedings of the National Academy of Sciences of the United States of America,2014,111(23), 8357). Delta-caprolactone (delta CL), which is a six-membered ring lactone substituted with a methyl group at the delta position, naturally occurs in fruits and hot milk, can also be produced from 5-hydroxymethylfurfural of biomass origin, is currently commercialized and 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 a thermoplastic elastomer. The sequential ring-opening polymerization of delta-caprolactone and lactide is realized by selecting a proper catalytic system, 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 the proportion of the triblock copolymer. However, no relevant literature and data report on the synthesis and property research of the PLA-b-PdeltaCL-b-PLA triblock copolymer.
In view of the above, the invention provides a binary catalytic system composed of a strong base and a binary urea, and a method for preparing a polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer with a definite structure by realizing sequential ring-opening polymerization of delta-caprolactone and lactide. The prepared triblock copolymer has the property of a thermoplastic elastomer. The method provided by the invention has the following advantages: 1) the used raw materials 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),
wherein m is a natural number of 200 or more, n is a natural number of 100 or more, and R is1Is alkylene or arylalkylene.
In the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer, the alkylene or aryl alkylene 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 binary urea in an organic solvent, and stirring for 1-10 min at room temperature;
(2) adding delta-caprolactone into the mixed solution, and reacting for 0.1-1 h at-20-40 ℃;
(3) dissolving lactide in an organic solvent, adding the lactide into 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 for precipitation to obtain the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer.
In the above preparation method, the divalent urea has a structure of one of the following:
in the above preparation method, the initiator is a bifunctional initiator, and specifically may be 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 can be alkali metal, alkali metal compound or organic phosphazene base catalyst, and specifically can be sodium, potassium hydride, sodium hydride, hexa [ tris (dimethylamine) phosphazene]Polyphosphazene ({ [ (NMe) s)2)3P＝N]2P＝N}3) Phosphazene ligand P4-tert-butyl ([ (NMe)2)3P＝N]3P＝NtBu，tert-Bu-P4) Phosphazene ligand P2-tert-butyl ([ (NMe)2)3P＝N](NMe2)2P＝NtBu，tert-Bu-P2) (ii) a The molar ratio of the strong base to the initiator is 1/1-20/1; the molar ratio of the strong base to the binary urea is 1/1-1/10.
In the above preparation method, the organic solvent in step (1) may be toluene, tetrahydrofuran, dichloromethane, acetonitrile, N-dimethylformamide.
In the preparation method, the molar concentration of the delta-caprolactone in the step (2) in a system is 4-9 mol/L; the molar ratio of the delta-caprolactone to the initiator is 200/1-3000/1.
In the preparation method, the organic solvent in the step (3) can be toluene, tetrahydrofuran, dichloromethane, acetonitrile, N-dimethylformamide; the molar concentration of the lactide in the system is 0.1-3 mol/L; the lactide can 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 shows the preparation of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 11H NMR spectrum.
FIG. 2 is a GPC chart of polylactic acid-b-poly (. delta. -caprolactone) -b-polylactic acid obtained in examples 1 to 3.
FIG. 3 is a DSC spectrum of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 1 at a scanning rate of 10 deg.C/min.
FIG. 4 is a DSC spectrum of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 2 at a scanning rate of 10 deg.C/min.
FIG. 5 is a DSC spectrum of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 3 at a scanning rate of 10 deg.C/min.
FIG. 6 shows the preparation of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 41H NMR spectrum.
FIG. 7 shows the preparation of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 51H NMR spectrum.
FIG. 8 shows the preparation of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 61H NMR spectrum.
FIG. 9 shows the preparation of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 71H NMR spectrum.
Fig. 10 is a uniaxial tensile spectrum of polylactic acid-b-poly (δ -caprolactone) -b-polylactic acid prepared in examples 5 to 7.
FIG. 11 is a drawing cycle chart of polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid prepared in example 7.
Detailed Description
The following embodiments specifically describe the present invention, but the present invention is not limited to these embodiments.
The materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Comparative example 1
(0.08mmol, 11.05mg)1, 4-benzenedimethanol, (0.08mmol, 95.84mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene dissolved in 1.3mL tetrahydrofuran, stirred at room temperature for 10min, added (24mmol, 2.7mL) delta-caprolactone to the reaction tube and reacted at 30 ℃ for 30min under nitrogen protection. Lactide (16mmol, 2.3g) was then dissolved in 10.67mL tetrahydrofuran and the system was added and the reaction was quenched with nitrogen at 25 ℃ for 10min and 10mg benzoic acid was added. Dissolving the reaction mixture in 10mL of tetrahydrofuran, pouring the mixture into 60mL of methanol, and performing centrifugal separation and precipitation to obtain a polymer, wherein the nuclear magnetism characterization polymer is a mixture of polylactic acid and poly (delta-caprolactone) and has poor mechanical property.
Comparative example 2
(0.08mmol, 11.05mg)1, 4-benzenedimethanol, (0.08mmol, 95.84mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.24mmol,68.72mg) 1-cyclohexyl-3- (4-trifluoromethylphenyl) urea was dissolved in 1.3mL tetrahydrofuran, stirred at room temperature for 10min, and (24mmol, 2.7mL) delta-caprolactone was added to the reaction tube and the reaction was carried out at 30 ℃ under nitrogen protection for 30 min. Lactide (16mmol, 2.3g) was then dissolved in 10.67mL tetrahydrofuran and the system was added and the reaction was quenched with nitrogen at 25 ℃ for 10min and 10mg benzoic acid was added. Dissolving the reaction mixture in 10mL of tetrahydrofuran, pouring the mixture into 60mL of methanol, and performing centrifugal separation and precipitation to obtain a polymer, wherein the nuclear magnetism characterization polymer is a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid. The number average molecular weight was 29.4kg/mol as determined by GPC, the molecular weight distribution was 1.27, the polymer molecular weight was low and was inelastic.
Comparative example 3
(0.08mmol, 11.05mg)1, 4-benzenedimethanol, (0.08mmol, 95.84mg) hexa [ tris (dimethylamine) phosphazene]Triphosphazene, (0.24mmol,84.96mg)1,1' - (hexylidene-1, 6-diacyl) bis (3-phenylurea)
Dissolved in 1.3mL tetrahydrofuran, stirred at room temperature for 10min, delta-caprolactone (24mmol, 2.7mL) was added to the reaction tube and the reaction was carried out at 30 ℃ for 30min under nitrogen. Lactide (16mmol, 2.3g) was then dissolved in 10.67mL tetrahydrofuran and the system was added and the reaction was quenched with nitrogen at 25 ℃ for 10min and 10mg benzoic acid was added. The reaction system was heterogeneous and contained a large amount of insolubles, and the expected triblock copolymer was not obtained.
Example 1
(0.08mmol, 11.05mg)1, 4-benzenedimethanol, (0).08mmol, 95.84mg) hexa [ tris (dimethylamine) phosphazene]Triphosphazene, (0.24mmol,136.8mg)1, 1' - (ethylidene) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)
Dissolved in 1.3mL tetrahydrofuran, stirred at room temperature for 10min, delta-caprolactone (24mmol, 2.7mL) was added to the reaction tube and the reaction was carried out at 30 ℃ for 30min under nitrogen. Lactide (16mmol, 2.3g) was then dissolved in 10.67mL tetrahydrofuran and the system was added and the reaction was quenched with nitrogen at 25 ℃ for 10min and 10mg benzoic acid was added. Dissolving the reaction mixture in 10mL of tetrahydrofuran, pouring the mixture into 60mL of methanol, and performing centrifugal separation and precipitation to obtain a polymer, wherein the nuclear magnetic spectrum of the polymer is shown in figure 1, and the nuclear magnetic spectrum of the polymer is characterized by a triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid. The number average molecular weight was 43.0kg/mol as determined by GPC, the molecular weight distribution was 1.37, the GPC spectrum is shown in FIG. 2, and the DSC spectrum is shown in FIG. 3. Tensile mechanical property test the elongation at break of the polymer is 200 percent, and the tensile strength is about 3.5 MPa. The elongation was 100% of the original length, and the cycle was 10 times, and the elastic recovery was about 73% and the residual strain was about 18%.
Example 2
(0.05mmol, 6.91mg)1, 4-benzenedimethanol, (0.05mmol, 31.7mg) phosphazene ligand P4-tert-butyl catalyst, (0.1mmol,61.4mg)1,1' - (oxybis (ethylene)) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)
Dissolved in 1.35mL tetrahydrofuran, stirred at room temperature for 5min, delta-caprolactone (25mmol, 2.82mL) was added to the reaction tube and the reaction was carried out at 25 ℃ for 15min under nitrogen protection, then lactide (15mmol, 2.16g) was dissolved in 10mL tetrahydrofuran and the above system was added and reacted at 25 ℃ for 5min under nitrogen protection and 10 drops of acetic acid was added to stop the reaction. Dissolving the reaction mixture in 5mL of chloroform, pouring into 40mL of methanol, centrifuging and precipitating to obtain a polymer, wherein the nuclear magnetism characterization polymer is a triblock copolymer, namely polylactic acid-b- (poly delta-caprolactone) -b-polylactic acid, the number average molecular weight is 73.2kg/mol and the molecular weight distribution is1.20, the GPC chart is shown in figure 2, and the DSC chart is shown in figure 4. Tensile mechanical property test the elongation at break of the polymer is 657 percent, and the tensile strength is about 16.7 MPa. The elongation was 100% of the original length, and the cycle was 10 times, and the elastic recovery was found to be about 87%, and the residual strain was about 12%.
Example 3
Ethylene glycol (0.1mmol, 5.58mL), (0.1mmol, 36.75mg) phosphazene ligand P2-tert-butyl, (0.15mmol, 89.7mg)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, and delta-caprolactone (70mmol, 7.89mL) was added to the reaction tube and the reaction was carried out at 29 ℃ for 20min under nitrogen. Lactide (30mmol, 4.32g) was then dissolved in 20mL tetrahydrofuran and the system was added and the reaction was quenched with nitrogen at 40 ℃ for 10min and 2mL dilute sulfuric acid added. Dissolving the reaction mixture in 30mL of tetrahydrofuran, pouring into 200mL of methanol, and centrifuging to obtain a precipitate, wherein the nuclear magnetism characterization polymer is triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, the number average molecular weight is 121.7kg/mol, the molecular weight distribution is 1.25 by GPC, the GPC spectrum is shown in FIG. 2, and the DSC spectrum is shown in FIG. 5. Tensile mechanical property test the elongation at break of the polymer is 865 percent, and the tensile strength is about 29.7 MPa. Stretching to 100% of the original length, 10 cycles, and a measured elastic recovery of about 90% and a residual strain of about 8%.
Example 4
Ethylene glycol (0.05mmol, 2.79mL), (0.05mmol, 2mg) potassium hydride, (0.15mmol, 93.9mg)1,1' - (hexylidene) 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, and delta-caprolactone (15mmol, 1.69mL) was added to the reaction tube and the reaction was carried out at 19 ℃ for 25min under nitrogen. Then (10mmol, 1.44g) lactide was dissolved in 10mL tetrahydrofuran and added to the system above, inThe reaction was carried out at 40 ℃ for 5min under nitrogen protection and quenched by addition of 1mL of hydrochloric acid. The reaction mixture was dissolved in 50mL of methylene chloride, poured into 150mL of methanol, and centrifuged to precipitate a polymer characterized by a nuclear magnetic resonance as a triblock copolymer, i.e., polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, having a number average molecular weight of 42.3kg/mol as measured by GPC, a molecular weight distribution of 1.19, and a nuclear magnetic resonance spectrum as shown in FIG. 6. Tensile mechanical property test the elongation at break of the polymer is 508 percent, and the tensile strength is about 5.6 MPa. Stretching to 100% of the original length, 10 cycles, and a measured elastic recovery of about 83% and a residual strain of about 12%.
Example 5
Ethylene glycol (0.06mmol, 3.35mL), (0.06mmol, 22.05mg) phosphazene ligand P2-tert-butyl, (0.06mmol,35.04mg)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, and delta-caprolactone (18mmol, 2.03mL) was added to the reaction tube and the reaction was carried out at 20 ℃ for 35min under nitrogen. Then (12mmol, 1.73g) lactide was dissolved in 12mL tetrahydrofuran and added to the system, reacted at 30 ℃ for 10min under nitrogen protection and quenched by adding 12 drops of dilute sulfuric acid. The reaction mixture was dissolved in 20mL of tetrahydrofuran, poured into 100mL of methanol, and centrifuged to precipitate a polymer characterized by a nuclear magnetic resonance as a triblock copolymer, i.e., polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, having a number average molecular weight of 45.1kg/mol as measured by GPC, a molecular weight distribution of 1.12, and a nuclear magnetic resonance spectrum as shown in FIG. 7. Tensile mechanical property test the elongation at break of the polymer was 762%, the tensile strength was about 7.5MPa, and the tensile spectrum was as shown in fig. 10. Stretching to 100% of the original length, 10 cycles, and a measured elastic recovery of about 90% and a residual strain of about 11%.
Example 6
(0.04mol, 5.53g)1, 4-benzenedimethanol, (0.04mol, 25.36g) phosphazene ligand P4-tert-butyl catalyst, (0.06mol,42.6g)1,1' - (hexylidene) bis (3- (3, 5-bis (trifluoromethyl) phenyl) urea)
Dissolved in 2.75L tetrahydrofuran, stirred at room temperature for 10min, added (20mol, 2.25L) delta-caprolactone to the reaction tube, and reacted at 25 ℃ for 60min under nitrogen protection. Then (8mol, 1150g) lactide was dissolved in 8L tetrahydrofuran and added to the above system, reacted at 30 ℃ for 30min under nitrogen protection and quenched by adding 1L phosphoric acid. Dissolving the reaction mixture in 10L chloroform, pouring into 50L methanol, centrifuging and precipitating to obtain polymer, wherein the nuclear magnetism characterization polymer is triblock copolymer, namely polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, the number average molecular weight is 80.1kg/mol, the molecular weight distribution is 1.30 by GPC, and the nuclear magnetism hydrogen spectrum is shown in figure 8. Tensile mechanical property test the elongation at break of the polymer is 627%, the tensile strength is about 18.2MPa, and the tensile spectrum is shown in figure 10. The elongation was 100% of the original length, and the cycle was 10 times, and the elastic recovery was about 92% and the residual strain was about 9%.
Example 7
(0.5mol, 69.12g)1, 4-benzenedimethanol, (0.5mol, 599g) hexa [ tris (dimethylamine) phosphazene]Triphosphazene, (0.5mol,285g)1, 1' - (ethylene) bis (3- (3,5 bis (trifluoromethyl) phenyl) urea)
Dissolved in 48.07L tetrahydrofuran, stirred at room temperature for 10min, and (350mol, 39.43L) delta-caprolactone was added into the reaction tube and the reaction was carried out at 0 ℃ for 60min under nitrogen protection. Then (150mol, 2.16kg) lactide was dissolved in 150L tetrahydrofuran and added to the above system, reacted at 25 ℃ for 30min under nitrogen protection and then quenched by adding 10L acetic acid. The reaction mixture was dissolved in 200L of chloroform, poured into 700L of methanol, and centrifuged to precipitate a polymer, which was characterized as a triblock copolymer, i.e., polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid, by Nuclear Magnetic Resonance (NMR) with a number average molecular weight of 134.6kg/mol and a molecular weight distribution of 1.28, and its NMR spectrum is shown in FIG. 9. Tensile mechanical property test the elongation at break of the polymer is 1133%, the tensile strength is about 33.5MPa, and the tensile spectrum is shown in figure 10. The elastic recovery rate of the product is about 93 after 10 times of cycle after stretching to 100 percent of the original length% residual strain was about 6%, and the tensile cycle spectrum thereof is shown in FIG. 11.
Claims (9)
1. A polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer shown in a formula (I),
m is a natural number of 200 or more, n is a natural number of 100 or more, R1Is alkylene or arylalkylene.
2. The polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer of claim 1,
the alkylidene group 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 an initiator, strong base and binary urea in an organic solvent, and stirring for 1-10 min at room temperature;
(2) adding delta-caprolactone into the mixed solution, and reacting for 0.1-1 h at-20-40 ℃;
(3) dissolving lactide in an organic solvent, adding the lactide into 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 for precipitation to obtain the polylactic acid-b-poly (delta-caprolactone) -b-polylactic acid triblock copolymer.
4. The method of claim 3, wherein:
the bifunctional 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 [ tris (dimethylamine) phosphazene]Phosphonitrile trimer ({ [ (NMe)2)3P＝N]2P＝N}3) Phosphazene ligand P4-tert-butyl ([ (NMe)2)3P＝N]3P＝NtBu，tert-Bu-P4) Phosphazene ligand P2-tert-butyl ([ (NMe)2)3P＝N](NMe2)2P＝NtBu，tert-Bu-P2) One of (1); the organic solvent is toluene, tetrahydrofuran, dichloromethane, acetonitrile or N, N-dimethylformamide.
5. The method of claim 3, wherein the binary urea has the structure of one of:
6. the method of claim 3, wherein:
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 binary urea is 1/1-1/10.
7. The method of claim 3, wherein:
in the step (2), the molar concentration of the delta-caprolactone in the system is 4-9 mol/L; the molar ratio of the delta-caprolactone to the initiator is 200/1-3000/1.
8. The method of claim 3, wherein:
the organic solvent in the 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-lactide, D-lactide, racemic lactide or meso-lactide; the molar ratio of lactide to 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.
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| CN115895593A (en) * | 2022-12-27 | 2023-04-04 | 普立思生物科技有限公司 | Biodegradable pressure-sensitive adhesive and preparation method thereof |
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| CN115725058A (en) * | 2022-12-26 | 2023-03-03 | 青岛科技大学 | Preparation method of degradable recyclable copolyester and application of degradable recyclable copolyester in aspect of pressure-sensitive adhesive |
| CN115850668A (en) * | 2022-12-26 | 2023-03-28 | 青岛科技大学 | Preparation method of bio-based degradable block copolyester and application of bio-based degradable block copolyester in aspect of pressure-sensitive adhesive |
| 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 |
| CN115895593A (en) * | 2022-12-27 | 2023-04-04 | 普立思生物科技有限公司 | Biodegradable pressure-sensitive adhesive and preparation method thereof |
| CN115895593B (en) * | 2022-12-27 | 2023-11-07 | 普立思生物科技有限公司 | Biodegradable pressure-sensitive adhesive and preparation method thereof |
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