CN114369232A - Renewable degradable thermoplastic elastomer and preparation method thereof - Google Patents
Renewable degradable thermoplastic elastomer and preparation method thereof Download PDFInfo
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- CN114369232A CN114369232A CN202210094130.0A CN202210094130A CN114369232A CN 114369232 A CN114369232 A CN 114369232A CN 202210094130 A CN202210094130 A CN 202210094130A CN 114369232 A CN114369232 A CN 114369232A
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- lactide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920002725 thermoplastic elastomer Polymers 0.000 title abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 53
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 35
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 24
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims description 21
- -1 cyclic lactone Chemical class 0.000 claims description 18
- 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 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002585 base Substances 0.000 claims description 14
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011541 reaction mixture Substances 0.000 claims description 12
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 12
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 11
- 229920000428 triblock copolymer Polymers 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 10
- GSLDEZOOOSBFGP-UHFFFAOYSA-N alpha-methylene gamma-butyrolactone Chemical compound C=C1CCOC1=O GSLDEZOOOSBFGP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 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
- 239000003960 organic solvent Substances 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- 239000003446 ligand Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 3
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 3
- 239000012312 sodium hydride Substances 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
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-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
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound 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
- 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 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
- 238000001035 drying Methods 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims 1
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 3
- 229940079593 drug Drugs 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 22
- 229920000747 poly(lactic acid) Polymers 0.000 description 19
- 239000004626 polylactic acid Substances 0.000 description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 17
- 229960001701 chloroform Drugs 0.000 description 12
- 239000007983 Tris buffer Substances 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 6
- HMLXMYNUQCOEDG-UHFFFAOYSA-N 1-(4-chlorophenyl)-3-cyclohexylurea Chemical compound C1=CC(Cl)=CC=C1NC(=O)NC1CCCCC1 HMLXMYNUQCOEDG-UHFFFAOYSA-N 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WPLYTRWMCWBZEN-UHFFFAOYSA-N 1-cyclohexyl-3-phenylurea Chemical compound C=1C=CC=CC=1NC(=O)NC1CCCCC1 WPLYTRWMCWBZEN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 206010036711 Primary mediastinal large B-cell lymphomas Diseases 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- GKOUEWHYLFOVFG-UHFFFAOYSA-N 1-cyclohexyl-3-[2-(trifluoromethyl)phenyl]urea Chemical compound FC(F)(F)C1=CC=CC=C1NC(=O)NC1CCCCC1 GKOUEWHYLFOVFG-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229920006392 biobased thermoplastic Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 239000002699 waste material Substances 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
- C08G2230/00—Compositions for preparing biodegradable polymers
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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 novel renewable degradable thermoplastic elastomer and a preparation method thereof. Compared with the methods reported in the prior art, the method provided by the invention has the following advantages: 1) the commercialized biomass monomer is adopted, and the monomer source is wide, simple and easy to obtain; 2) the thermoplastic elastomer prepared by the invention is expected to be applied to the field of biological medicines; 3) the properties of the thermoplastic elastomer provided by the invention can be regulated and controlled by changing the ratio of the two monomers in the soft segment.
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 renewable degradable thermoplastic elastomer.
Background
Thermoplastic elastomers, which are one of 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 which is commercially available is derived from non-renewable resources such as fossil fuel, cannot be degraded or recycled by chemical methods after use, does not meet the requirement of recycling economy, and the greenhouse effect is aggravated by improper treatment of the used thermoplastic elastomer. 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 type of thermoplastic elastomer, ABA type thermoplastic elastomers are composed of hard and soft segments that are thermodynamically incompatible. The hard segment is generally a substance with a glass transition temperature or a melting point higher than room temperature, and reversible physical cross-linking points can be formed between the molecular chains of the hard segment by virtue of non-chemical bonding effects such as van der waals force or winding among the chain segments to provide rigidity and hardness for the material. The soft segment is mainly a rubber segment with higher flexibility or a polyether or polyester segment with the glass transition temperature lower than room temperature, and provides elasticity for the elastomer. The most common ABA-type 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, and the waste materials cannot be degraded under natural conditions, so that the ecological environment is easily damaged. The preparation of the bio-based thermoplastic elastomer by adopting renewable resources is one of the hot directions of the current research, but the problems of complex monomer synthesis process, nondegradable final product and the like exist.
In view of the above, the invention provides a method for preparing a novel renewable 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 consisting of strong base and a cocatalyst. Compared with the methods reported in the prior art, the method provided by the invention has the following advantages: 1) the commercialized biomass monomer is adopted, and the monomer is wide in source, simple and easy to obtain; 2) the used catalyst and cocatalyst have low toxicity and are easy to remove from the product, and the prepared renewable degradable thermoplastic elastomer is expected to be applied to the field of biomedicine; 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, when PMBL-co-PCL or PMBL-co-PVL is used as the soft segment, as the soft segment contains unsaturated double bonds, modifiable chemical sites can be provided for the prepared thermoplastic elastomer, the physicochemical properties of the thermoplastic elastomer can be regulated by post-modification, and the application range of the thermoplastic elastomer can be further expanded; 4) the prepared triblock copolymer has the property of a thermoplastic elastomer, is degradable, reduces the pollution to the environment and meets the requirement of circular economy.
Disclosure of Invention
The invention aims to provide a novel renewable degradable thermoplastic elastomer and a preparation method thereof.
The invention provides an ABA type triblock copolymer, wherein a block A has a repeating structural unit shown as a formula (I):
the block B has a repeating structural unit shown as a formula (II) or a formula (III):
according to an embodiment of the present invention, said ABA type triblock copolymer has one of the structures represented by formula (IV), (V), (VI), (VII),
wherein m is 1 or 2, x, y, z are natural numbers of 50 or more, and R is1Is alkylene or arylalkylene.
In the above ABA type triblock copolymer, the alkylene or aryl alkylene 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-70 to-20 ℃;
(3) dissolving lactide in an organic solvent, adding the lactide into 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 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 1/1-10/1; the molar ratio of the strong base to the 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 five-membered cyclic lactone in the step (2) is gamma-butyrolactone or alpha-methylene-gamma-butyrolactone, and the other cyclic lactone is epsilon-caprolactone or delta-valerolactone; the molar ratio of the five-membered cyclic lactone to other cyclic lactone monomers is 1/1-10/1; the molar ratio of the sum of the molar weight of the five-membered cyclic lactone and other cyclic lactone monomers to the molar weight of the initiator is 100/1-1000/1; the sum of the molar concentrations of the five-membered cyclic lactone monomer and other cyclic lactone monomers in the system is 1-8 mol/L.
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 five-membered cyclic 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 (γ -butyrolactone-co- ε -caprolactone) -b-polylactic acid obtained in comparative example.
FIG. 2 shows the preparation of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 11H NMR spectrum.
FIG. 3 is a GPC chart of polylactic acid-b-poly (γ -butyrolactone-co- ε -caprolactone) -b-polylactic acid obtained in example 1.
FIG. 4 is a drawing chart of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 1.
FIG. 5 is a drawing cycle chart of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in example 1.
FIG. 6 shows a GPC chart of polylactic acid-b-poly (γ -butyrolactone-co- ε -caprolactone) -b-polylactic acid obtained in example 2.
FIG. 7 shows a GPC chart of polylactic acid-b-poly (γ -butyrolactone-co- ε -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 obtained in examples 4 to 6.
FIG. 9 is a drawing chart of polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid obtained in examples 4 to 6.
FIG. 10 shows the preparation of polylactic acid-b-poly (. alpha. -methylene-. gamma. -butyrolactone-co-. epsilon. -caprolactone) -b-polylactic acid obtained in example 71HNMR spectrogram.
FIG. 11 is a GPC chart of polylactic acid-b-poly (. alpha. -methylene-. gamma. -butyrolactone-co-. epsilon. -caprolactone) -b-polylactic acid obtained in example 7
FIG. 12 is a GPC chart of polylactic acid-b-poly (. alpha. -methylene-. gamma. -butyrolactone-co-. delta. -valerolactone) -b-polylactic acid obtained in example 8.
FIG. 13 is a GPC chart of polylactic acid-b-poly (γ -butyrolactone-co- δ -valerolactone) -b-polylactic acid obtained in example 9.
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 examples
Benzyl alcohol (0.05mmol, 5.4mg), hexa [ tris (dimethylamine) phosphazene ] polyphosphazene, (0.15mmol, 37.9mg) 1-cyclohexyl-3- (4-chlorophenyl) urea are dissolved in 2.39mL tetrahydrofuran, the solution is stirred for 10min at-50 ℃ in a low-temperature cold bath, gamma-butyrolactone (9mmol, 0.69mL) and epsilon-caprolactone (6mmol, 0.67mL) are added into a reaction tube at the same time, after the reaction is carried out for 1h under the protection of nitrogen, lactide (7.5mmol, 1080mg) is dissolved in 5.11mL tetrahydrofuran, the reaction is added into the reaction system, the reaction is continued for 1h under the nitrogen atmosphere at 25 ℃, and 10 drops of acetic acid are added to stop the reaction. The reaction mixture was dissolved in 5mL of chloroform, poured into 50mL of methanol, and centrifuged to precipitate a polymer having a number average molecular weight of 26.5kg/mol as measured by GPC, a molecular weight distribution of 1.57, and no elasticity.
Example 1
(0.05mmol, 6.9mg)1, 4-benzenedimethanol, (0.05mmol, 59.9mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15mmol, 37.9mg) 1-cyclohexyl-3- (4-chlorophenyl) urea was dissolved in 2.39mL tetrahydrofuran, stirred at-50 ℃ for 10min in a cold bath, and (9mmol, 0.69mL) γ -butyrolactone and (6mmol, 0.67mL) ε -caprolactone were added simultaneously to the reaction tube. After the reaction was carried out for 1 hour under the protection of nitrogen gas, (7.5mmol, 1080mg) L-lactide was dissolved in 5.11mL of tetrahydrofuran and added to the reaction system, the reaction was continued for 1 hour under the nitrogen atmosphere at 25 ℃, and 10 drops of acetic acid were added to terminate the reaction. Dissolving the reaction mixture in 5mL of trichloromethane, pouring the trichloromethane into 50mL of methanol, performing centrifugal separation and precipitation to obtain a polymer, and successfully preparing the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, by nuclear magnetic characterization. The nuclear magnetic hydrogen spectrum is shown in FIG. 2. CPC gave a number average molecular weight of 28.3kg/mol, a molecular weight distribution of 1.62 and a GPC chart as shown in FIG. 3. Tensile mechanical property test the elongation at break of the polymer is about 1200%, the tensile strength is about 15MPa, and the tensile spectrum is shown in figure 4. The stretching was performed 10 times to 50% of the original length, and the elastic recovery was about 90% and the residual strain was about 10%, and the stretching cycle spectrum thereof is shown in fig. 5.
Example 2
(0.05mmol, 6.9mg)1, 4-benzenedimethanol, (0.05mmol, 59.9mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15mmol, 37.9mg) 1-cyclohexyl-3- (4-chlorophenyl) urea was dissolved in 2.39mL tetrahydrofuran, stirred at-50 ℃ for 10min in a cold bath, and (9mmol, 0.69mL) γ -butyrolactone and (6mmol, 0.67mL) ε -caprolactone were added simultaneously to the reaction tube. After the reaction was carried out for 1h under nitrogen protection, (7.5mmol, 1080mg) rac-lactide was dissolved in 5.11mL tetrahydrofuran and added to the reaction system, the reaction was continued for 10min at 25 ℃ under nitrogen atmosphere, and 10 drops of acetic acid were added to terminate the reaction. Dissolving the reaction mixture in 5mL of chloroform, pouring the solution into 50mL of methanol, performing centrifugal separation and precipitation to obtain a polymer, and successfully preparing the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, by nuclear magnetic characterization. CPC gave a number average molecular weight of 27.6kg/mol, a molecular weight distribution of 1.80 and a GPC chart as shown in FIG. 6. Tensile mechanical property test the elongation at break of the polymer is about 600 percent, and the tensile strength is about 5 MPa.
Example 3
(0.5mmol, 69mg)1, 4-benzenedimethanol, (0.5mmol, 599mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (1.5mmol, 379mg) 1-cyclohexyl-3- (4-chlorophenyl) urea was dissolved in 23.9mL tetrahydrofuran, stirred at-50 ℃ for 5min in a low temperature cold bath, and (90mmol, 6.9mL) γ -butyrolactone and (60mmol, 6.7mL) ε -caprolactone were added simultaneously to the reaction tube. After the reaction was carried out for 1h under nitrogen protection, (7.5mmol, 1080mg) L-lactide was dissolved in 51.1mL tetrahydrofuran and added to the reaction system, the reaction was continued for 5min under nitrogen atmosphere at 0 ℃ 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 gave a number average molecular weight of 32.7kg/mol, a molecular weight distribution of 1.56 and a GPC chart as shown in FIG. 7. Tensile mechanical property test the breaking elongation of the polymer is about 800 percent, and the tensile strength is about 7.5 MPa.
Example 4
(0.05mmol, 6.9mg)1, 4-benzenedimethanol, (0.05mmol, 59.9mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15mmol, 43mg) 1-cyclohexyl-3- (trifluoromethylphenyl) urea was dissolved in 4.09mL tetrahydrofuran, stirred at-40 ℃ for 30min in a low temperature cold bath, and (12mmol, 0.92mL) γ -butyrolactone and (8mmol, 0.89mL) ε -caprolactone were added simultaneously to the reaction tube. After the reaction was carried out for 2 hours under the protection of nitrogen, (10mmol, 1440mg) D-lactide was dissolved in 5.91mL of tetrahydrofuran, added to the above reaction system, and reacted further for 2 hours at 0 ℃ under a nitrogen atmosphere, and 10 drops of acetic acid were added to terminate the reaction. Dissolving the reaction mixture in 4mL of chloroform, pouring the chloroform into 40mL of methanol, performing centrifugal separation and precipitation to obtain a polymer, and successfully preparing the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, by nuclear magnetic characterization. CPC gave a number-average molecular weight of 30.9kg/mol and a molecular weight distribution of 1.70. Tensile mechanical property test the breaking elongation of the polymer is about 750 percent, and the tensile strength is about 5.5 MPa. Its DSC spectrum is shown in figure 8, and its tensile spectrum is shown in figure 9.
Example 5
A mixed solution of (0.05mmol, 6.9mg)1, 4-benzenedimethanol, (0.10mmol, 119.8mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.20mmol, 43.6mg) 1-cyclohexyl-3-phenylurea was dissolved in 2.42mL tetrahydrofuran, and stirred at-50 ℃ for 20min in a low temperature cooling bath, and (10mmol, 0.77mL) γ -butyrolactone and (5mmol, 0.56mL) ε -caprolactone was added to the reaction tube. After 4 hours of reaction under the protection of nitrogen, dissolving (15mmol, 2160mg) lactide in 5.08mL tetrahydrofuran, adding into the reaction system, continuing to react for 20min at 40 ℃ in nitrogen atmosphere, and adding 10 drops of acetic acid to stop the reaction. Dissolving the reaction mixture in 8mL of chloroform, pouring the solution into 60mL of methanol, performing centrifugal separation and precipitation to obtain a polymer, and successfully preparing the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, by nuclear magnetic characterization. CPC gave a number average molecular weight of 35.6kg/mol and a molecular weight distribution of 2.12. Its DSC spectrum is shown in figure 8, and its tensile spectrum is shown in figure 9.
Example 6
(0.20mol, 27.6g)1, 4-benzenedimethanol, (0.20mol, 4.8g) sodium hydride, (0.60mol, 168.15g)1- (4-trifluoromethylphenyl) -3-phenylurea was dissolved in 2.36L tetrahydrofuran, and stirred at-70 ℃ for 30min in a low-temperature cold bath, and (10mol, 0.77L) γ -butyrolactone and (10mol, 1.12L) ε -caprolactone were simultaneously added to the reaction tube. After the reaction was carried out for 10 hours under nitrogen protection, (40mol, 5760g) lactide was dissolved in 7.64L tetrahydrofuran and added to the above reaction system, the reaction was continued for 2 hours at 40 ℃ under nitrogen atmosphere, and 6L acetic acid was added to terminate the reaction. The reaction mixture was dissolved in 12L of chloroform, poured into 80L of methanol, and centrifuged to precipitate to give a polymer having a number average molecular weight of 21.0kg/mol in terms of CPC and a molecular weight distribution of 1.74. Its DSC spectrum is shown in figure 8, and its tensile spectrum is shown in figure 9.
Example 7
(0.05mmol, 6.9mg)1, 4-benzenedimethanol, (0.05mmol, 59.9mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15mmol, 42.04mg)1- (4-trifluoromethylphenyl) -3-phenylurea was dissolved in 5.94mL tetrahydrofuran, stirred at-30 ℃ in a cold bath for 20min, and (5mmol, 0.44mL) α -methylene- γ -butyrolactone and (10mmol, 1.12mL) ε -caprolactone were added simultaneously to the reaction tube. After the reaction was carried out for 1 hour under the protection of nitrogen, (5mmol, 720mg) lactide was dissolved in 4.06mL tetrahydrofuran and added to the above reaction system, the reaction was continued for 10min at 10 ℃ under nitrogen atmosphere, and 10 drops of acetic acid were added to terminate the reaction. Dissolving the reaction mixture in 3mL of chloroform, pouring into 45mL of methanol, performing centrifugal separation and precipitation to obtain a polymer, and performing nuclear magnetic characterization to successfully prepare the triblock thermoplastic elastomer, namely polylactic acid-b-poly (alpha-methylene-gamma-butyrolactone-co-epsilon-caprolactone) -b-polylactic acid, wherein the nuclear magnetic spectrum is shown in FIG. 10. CPC gave a number average molecular weight of 25.6kg/mol, a molecular weight distribution of 1.55 and a GPC chart as shown in FIG. 11. Tensile mechanical property test the breaking elongation of the polymer is about 1500 percent, and the tensile strength is about 8.5 MPa.
Example 8
(0.05mmol, 6.90mg)1, 4-benzenedimethanol, (0.05mmol, 59.9mg) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15mmol, 37.9mg) 1-cyclohexyl-3- (4-chlorophenyl) urea was dissolved in 4.65mL tetrahydrofuran, stirred at-40 ℃ for 30min in a cold bath, and (5mmol, 0.44mL) α -methylene- γ -butyrolactone and (10mmol, 0.91mL) ε -valerolactone were added simultaneously to the reaction tube. After the reaction was carried out for 1 hour under the protection of nitrogen gas, (7.5mmol, 1080mg) lactide was dissolved in 4.06mL tetrahydrofuran and added to the reaction system, the reaction was continued for 1 hour under the nitrogen atmosphere at 10 ℃, 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 centrifuged to precipitate a polymer having a number average molecular weight of 28.7kg/mol in terms of CPC and a molecular weight distribution of 1.71 as shown in FIG. 12 by GPC spectroscopy. Tensile mechanical property test the elongation at break of the polymer is about 900 percent, and the tensile strength is about 6.5 MPa.
Example 9
(0.05mol, 6.9g)1, 4-phenyl dimethanol, (0.05mol, 59.9g) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (0.15mol, 32.7g) 1-cyclohexyl-3-phenylurea was dissolved in 5.84L toluene, stirred in a low temperature cooling bath at-50 ℃ for 30min, and (5mol, 0.38L) gamma-butyrolactone and (5mol, 0.45L) delta-valerolactone were added simultaneously to the reaction tube. After the reaction was carried out for 3 hours under nitrogen protection, (5mol, 720g) lactide was dissolved in 4.16L toluene and added to the above reaction system, the reaction was continued for 2 hours at 20 ℃ under nitrogen atmosphere, and 3L acetic acid was added to terminate the reaction. Dissolving the reaction mixture in 6L chloroform, pouring into 40L methanol, centrifuging and precipitating to obtain a polymer, and successfully preparing the triblock thermoplastic elastomer, namely polylactic acid-b-poly (gamma-butyrolactone-co-delta-valerolactone) -b-polylactic acid by nuclear magnetic characterization. CPC was found to have a number average molecular weight of 18.5kg/mol, a molecular weight distribution of 1.64, and a GPC chart as shown in FIG. 13. Tensile mechanical property test the elongation at break of the polymer is about 460%, and the tensile strength is about 3.5 MPa.
Claims (9)
1. An ABA triblock copolymer wherein blocks A have repeating structural units according to formula (I):
the block B has a repeating structural unit shown as a formula (II) or a formula (III):
wherein m is 1 or 2, x, y and z are natural numbers of 50 or more, R1Is alkylene or arylalkylene.
2. ABA triblock copolymer according to claim 1 having one of the structures shown in formulas (IV), (V), (VI), (VII),
wherein x, y and z are natural numbers of 50 or more, and R is1Is alkylene or arylalkylene.
3. An ABA triblock copolymer according to claim 1 or 2 wherein the alkylene or aryl alkylene has the structure of one of:
4. process for the preparation of an ABA triblock copolymer according to claim 1 or 2 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-70 to-20 ℃;
(3) dissolving lactide in an organic solvent, adding the lactide into 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.
5. The method of claim 4, wherein the urea has the structure of one of:
6. the method according to claim 4, wherein the initiator in the 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 an alkali metal, an alkali metal compound or an 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 (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) Or phosphonitrile ligand P2-tert-butyl ([ (NMe)2)3P＝N](NMe2)2P＝NtBu，tert-Bu-P2) (ii) a The organic solvent isToluene, tetrahydrofuran, dichloromethane, acetonitrile or N, N-dimethylformamide.
7. The method according to claim 4, wherein the five-membered cyclic lactone in the step (2) is gamma-butyrolactone or alpha-methylene-gamma-butyrolactone, and the other cyclic lactone monomer is epsilon-caprolactone or delta-valerolactone; the sum of the molar concentrations of the five-membered cyclic lactone and other cyclic lactone monomers in a system is 1-8 mol/L.
8. The method according to claim 4, 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-lactide, D-lactide, racemic lactide or meso-lactide; the acidic substance is acetic acid, benzoic acid, hydrochloric acid, sulfuric acid or phosphoric acid.
9. The method of claim 4, wherein:
the molar ratio of the strong base to the initiator is 1/1-10/1; the molar ratio of the strong base to the urea is 1/1-1/10; the molar ratio of the five-membered cyclic lactone to other cyclic lactone monomers is 1/1-10/1; the molar ratio of the sum of the molar weight of the five-membered cyclic lactone and other cyclic lactone monomers to the molar weight of the initiator is 50/1-1000/1; the molar ratio of the lactide to the five-membered cyclic 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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| 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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