CN114133507A - One-pot preparation method of bio-based degradable polyurethane - Google Patents
One-pot preparation method of bio-based degradable polyurethane Download PDFInfo
- Publication number
- CN114133507A CN114133507A CN202111640179.3A CN202111640179A CN114133507A CN 114133507 A CN114133507 A CN 114133507A CN 202111640179 A CN202111640179 A CN 202111640179A CN 114133507 A CN114133507 A CN 114133507A
- Authority
- CN
- China
- Prior art keywords
- cocatalyst
- polyurethane
- butyrolactone
- gamma
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004814 polyurethane Substances 0.000 title claims abstract description 39
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 39
- 238000005580 one pot reaction Methods 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims description 15
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 239000012948 isocyanate Substances 0.000 claims abstract description 10
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 10
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 229920000728 polyester Polymers 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000007983 Tris buffer Substances 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 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
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 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
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-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
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical group CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000004806 packaging method and process Methods 0.000 abstract description 2
- 230000001988 toxicity Effects 0.000 abstract description 2
- 231100000419 toxicity Toxicity 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- BWVAOONFBYYRHY-UHFFFAOYSA-N [4-(hydroxymethyl)phenyl]methanol Chemical compound OCC1=CC=C(CO)C=C1 BWVAOONFBYYRHY-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- LOZAIRWAADCOHQ-UHFFFAOYSA-N triphosphazene Chemical compound PNP=NP LOZAIRWAADCOHQ-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000954 Polyglycolide Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000001727 in vivo Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 239000004633 polyglycolic acid Substances 0.000 description 2
- 239000004626 polylactic acid Substances 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- KAJICSGLHKRDLN-UHFFFAOYSA-N 1,3-dicyclohexylthiourea Chemical compound C1CCCCC1NC(=S)NC1CCCCC1 KAJICSGLHKRDLN-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 239000002473 artificial blood Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000000747 cardiac 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
- 235000005822 corn Nutrition 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- LMYQWQCDUHNQLF-UHFFFAOYSA-N hexylthiourea Chemical compound CCCCCCNC(N)=S LMYQWQCDUHNQLF-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical compound CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4684—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing phosphorus
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a method for preparing polyester polyurethane taking poly (gamma-butyrolactone) as a soft segment by using a one-pot method, which comprises the following steps: (1) dissolving a polyol initiator, a strong base and a cocatalyst a in an organic solvent, adding gamma-butyrolactone, and reacting for a period of time at a low temperature; (2) and adding the cocatalyst b into the reaction system, stirring for 5min, adding isocyanate, and reacting at a certain temperature for a period of time to obtain the polyurethane. Compared with the traditional method, the method provided by the invention has the following advantages: 1) the polyurethane is prepared by a one-pot method, so that the process is simple, and the cost is saved; 2) the used catalytic system is an organic catalytic system, has low biological toxicity and is easy to remove from the product; 3) the polyurethane has good biocompatibility and degradability, and has great application potential in the fields of packaging and biomedicine.
Description
Technical Field
The invention relates to the fields of high polymer materials and chemical engineering, in particular to a bio-based degradable polyurethane and a preparation method thereof.
Background
Polyurethane materials are widely used for medical devices and artificial organs which are implanted for a long time, such as cardiac pacemaker insulated wires, artificial blood vessels, interventional catheters and the like, due to their excellent mechanical strength, high elasticity, wear resistance, lubricity, fatigue resistance, biocompatibility, processability and the like. The biodegradable polyurethane material has good biocompatibility and biodegradability, and is particularly suitable for being used in the field of biomedicine. The biodegradable polyurethane is synthesized by mainly introducing degradable components such as polycaprolactone, polylactic acid, polyglycolic acid, glycolic acid-lactic acid copolymer, polyvinyl carbonate and the like into a soft segment. These segments are easily degraded under the action of in vivo enzymes, and are finally metabolized into small molecules such as carbon dioxide, water and the like to be discharged out of the body.
The gamma-butyrolactone is a bio-based monomer with wide source and low price, can be obtained from biomass raw materials, such as corn, wheat and other crops, and is a renewable raw material. Poly (gamma-butyrolactone), a homopolymer of gamma-butyrolactone, is an important aliphatic polyester, which has a suitable degradation rate in vivo, between polyglycolic acid and polylactic acid, and does not cause accumulation of acidic substances in tissues upon degradation, and is less likely to induce inflammation, compared to existing biomaterials. Compared with caprolactone and lactide, gamma-butyrolactone has a lower price and a cost advantage. Therefore, the poly (gamma-butyrolactone) is used as a soft segment to construct a novel bio-based degradable polyurethane material, and compared with the existing polyester polyurethane material, the novel bio-based degradable polyurethane material has lower price and better tissue compatibility. When the polyester polyurethane is prepared by using a conventional method, polyester polyol needs to be prepared first, and after repeated purification, the polyester polyol is subjected to chain extension reaction by using isocyanate. This method increases the process flow, and also increases the cost of using and recovering a large amount of solvent when purifying polyester polyol (CN 110527049A). On the other hand, the synthesis process of poly (gamma-butyrolactone) needs to use strong base as a catalyst, and the strong base can also catalyze the isocyanate reaction. In the conventional method, if poly (. gamma. -butyrolactone) obtained without purification is directly reacted with isocyanate, crosslinking easily occurs.
In view of the above, the present invention provides a new method for preparing biodegradable polyurethane by a one-pot method. Compared with the traditional method, the method provided by the invention has the following advantages: 1) the polyurethane is prepared by a one-pot method, so that the process is simple, and the cost is saved; 2) the used catalytic system is an organic catalytic system, has low biological toxicity and is easy to remove from the product; 3) the polyurethane has good biocompatibility and degradability, and has great application potential in the fields of packaging and biomedicine.
Disclosure of Invention
The invention aims to provide a method for preparing polyester polyurethane with poly (gamma-butyrolactone) as a soft segment by using a one-pot method, which comprises the following steps:
(1) dissolving a polyol initiator, a strong base and a cocatalyst a in an organic solvent, adding gamma-butyrolactone, and reacting for a period of time at a low temperature;
(2) and adding the cocatalyst b into the reaction system, stirring for 5min, adding isocyanate, and reacting at a certain temperature for a period of time to obtain the polyurethane.
The polyurethane has a repeating unit structure shown in a formula (I),
wherein m is a natural number of 5 or more, and n is a natural number of 5 or more.
In the formula, R1The structure can be as follows:
R2the structure can be as follows:
in the preparation method, the cocatalyst a is at least one of urea and has a structure of one of the following:
in the preparation method, the cocatalyst b is at least one of thiourea and has a structure of one of the following:
in the preparation method, the polyol initiator in the step (1) is ethylene glycol, propylene glycol, butanediol, 1, 4-cyclohexanediol, 1, 4-phenyl dimethanol, 2-butyl-2-ethyl-1, 3-propanediol, glycerol or pentaerythritol; the strong base can be sodium, potassium hydride, sodium hydroxide, potassium hydroxide, 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 organic solvent is toluene, tetrahydrofuran, dichloromethane, acetonitrile or N, N-dimethylformamide.
In the preparation method, the low temperature in the step (1) is-70 to-20 ℃; the reaction time is 0.5-48 h. The molar ratio of the strong base to the polyol initiator is 1/3-20/1; the molar ratio of the strong base to the catalyst a is 1/1-1/10; the molar ratio of the polyol initiator to the gamma-butyrolactone is 1/10-1/300; the molar concentration of the gamma-butyrolactone in the system is 4-13 mol/L.
In the preparation method, the isocyanate in the step (2) is toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or 1, 5-naphthalene diisocyanate.
In the preparation method, the molar ratio of the isocyanate to the polyol initiator in the step (2) is 1/1-2/1; the ratio of the cocatalyst b to the cocatalyst a is 1/1-3/1; in the preparation method, the reaction temperature in the step (2) is 25-150 ℃; the reaction time is 0.5-48 h.
Drawings
FIG. 1 shows the preparation of the polyurethane obtained in example 11H NMR spectrum.
FIG. 2 shows the preparation of the polyurethane obtained in example 21H NMR spectrum.
FIG. 3 is an IR spectrum of the polyurethane obtained in example 3.
FIG. 4 is an IR spectrum of the polyurethane obtained in example 4.
FIG. 5 is a GPC chart of the polyurethane obtained in example 1.
FIG. 6 is a graph showing the tensile curves of the polyurethanes obtained in examples 1 and 2, at a tensile rate of 50 mm/min.
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
(1mmol, 138.2mg)1, 4-benzenedimethanol, (1mmol, 1.2g) hexa [ tris (dimethylamine) phosphazene ] triphosphazene, (3mmol, 843.42mg) U1 was dissolved in 1.5mL tetrahydrofuran, stirred in a low temperature cold bath at-50 ℃ for 10min, and (20mmol, 1.72g) γ -butyrolactone was added to the reaction tube. The reaction was carried out at-50 ℃ under nitrogen protection for 1h, then (1.1mmol, 275mg) diphenylmethane diisocyanate was added and the reaction was carried out at 50 ℃ with rapid crosslinking of the system. The polyurethane obtained is insoluble and infusible, and cannot be tested and reprocessed.
Comparative example 2
(1mmol, 138.2mg)1, 4-benzenedimethanol, (1mmol, 1.2g) hexa [ tris (dimethylamine) phosphazene]Triphosphazene, (3mmol, 843.42mg) U1 was dissolved in 1.5mL tetrahydrofuran, stirred in a low temperature cold bath at-50 ℃ for 10min, and gamma-butyrolactone (20mmol, 1.72g) was added to the reaction tube. The reaction was carried out at-50 ℃ under nitrogen for 1h and 1, 3-dicyclohexylthiourea (3.3mmol, 792mg) was added
Adding into a reaction tube, stirring for 5min, adding (1.1mmol, 275mg) diphenylmethane diisocyanate, reacting at 50 deg.C, and rapidly crosslinking. The polyurethane obtained is insoluble and infusible, and cannot be tested and reprocessed.
Example 1
(1mmol, 138.2mg)1, 4-benzenedimethanol, (1mmol, 1.2g) hexa [ tris (dimethylamine) phosphazene]Triphosphazene, (3mmol, 843.4mg) U1 was dissolved in 1.5mL tetrahydrofuran, stirred in a low temperature cold bath at-50 ℃ for 10min, and gamma-butyrolactone (20mmol, 1.72g) was added to the reaction tube. The reaction was carried out at-50 ℃ under nitrogen for 1h, then TU1 (3.3mmol, 1.2g) was added to the reaction tube, stirred for 5min and then diphenylmethane diisocyanate (1.1mmol, 275mg) was added and reacted at 50 ℃ for 4h to obtain polyurethane. Number average molecular weight by GPC of 67.1kg/mol, molecular weight distribution of 1.80, of the obtained polyurethane1The H NMR spectrum is shown in FIG. 1, the GPC spectrum is shown in FIG. 5, and the stretching graph is shown in FIG. 6.
Example 2
(2.5mmol, 345.5mg)1, 4-phenyl dimethanol, (1mmol, 634mg) phosphazene ligand P4-tert-butyl catalyst, (3mmol, 740.1mg) U2 was dissolved in 1mL tetrahydrofuran, stirred in a low temperature cooling bath at-50 ℃ for 10min, and (50mmol, 4.30g) γ -butyrolactone was added to the reaction tube. After the reaction was carried out at-50 ℃ for 2h under nitrogen protection, TU1 (3.3mmol, 1.2g) was added to the reaction tube, and after stirring for 5min, isophorone diisocyanate (2.75mmol, 610.5mg) was added and reacted at 50 ℃ for 4h to obtain polyurethane. Number average molecular weight of 72.2kg/mol and molecular weight distribution of 1.76 as determined by GPC, of the obtained polyurethane1The H NMR spectrum is shown in FIG. 2, and the tensile diagram is shown in FIG. 6.
Example 3
Ethylene glycol (0.5mol, 31g), (potassium hydride (0.75mol, 30g), (2.25mol, 654.9g) U7 and 500mL of tetrahydrofuran were added to the reaction vessel, stirred in a cold bath at-40 ℃ for 10min, and gamma-butyrolactone (20mol, 1.72kg) was added to the reaction vessel. The reaction was carried out at-40 ℃ under nitrogen for 2h and then (2.5mmol, 743g) TU2 was added to the kettle and stirred for 5 min. Then adding (0.6mol, 157.4g) dicyclohexylmethane diisocyanate, heating to 120 ℃ and reacting for 12h to obtain polyurethane. The number average molecular weight was 120.5kg/mol and the molecular weight distribution was 2.12 as determined by GPC, and the IR spectrum of the resulting polyurethane is shown in FIG. 3.
Example 4
Glycerol (0.2mol, 18.4g), potassium hydroxide (0.6mol, 33.6g) and U5 (1.8mol, 454.9g) are added into a reaction kettle, vacuum pumping is carried out at 150 ℃ for 2h, 500mL of tetrahydrofuran is added after cooling to room temperature, the mixture is placed in a low-temperature cold bath at-50 ℃ and stirred for 10min, and gamma-butyrolactone (20mol, 1.72kg) is added into the reaction kettle. The reaction was carried out at-50 ℃ under nitrogen for 3h and then (2mmol, 594.4g) TU2 was added to the kettle and stirred for 5 min. Hexamethylene diisocyanate (0.3mol, 50.5g) was then added and reacted at 40 ℃ for 12h to give the polyurethane. The number average molecular weight was 130.2kg/mol and the molecular weight distribution was 2.20 by GPC, and the infrared spectrum of the resulting polyurethane is shown in FIG. 4.
Claims (8)
1. A method for preparing a polyester polyurethane having poly (gamma-butyrolactone) as a soft segment using a one-pot process, comprising the steps of:
(1) dissolving a polyol initiator, a strong base and a cocatalyst a in an organic solvent, adding gamma-butyrolactone, and reacting at-70 to-20 ℃ for 0.5 to 48 hours;
(2) and adding the cocatalyst b into the reaction system, stirring for 5min, adding isocyanate, and reacting at 25-150 ℃ for 0.5-48 h to obtain the polyurethane.
2. The method according to claim 1, wherein the polyurethane has a main chain structure represented by the formula (I),
the method is characterized in that m is a natural number which is more than or equal to 5, and n is a natural number which is more than or equal to 5;
in the formula, R1Is one of the following structures:
R2is one of the following structures:
3. the method of claim 1, wherein:
the cocatalyst a has a structure of one of the following:
4. the process of claim 1, said cocatalyst b having the structure of one of:
5. the method of claim 1, wherein:
the polyalcohol initiator is ethylene glycol, propylene glycol, butanediol, 1, 4-cyclohexanediol, 1, 4-phenyl dimethanol, 2-butyl-2-ethyl-1, 3-propanediol, glycerol and pentaerythritol; the strong base is selected from sodium, potassium hydride, sodium hydroxide, potassium hydroxide, 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) One of (1); the organic solvent is toluene, tetrahydrofuran, dichloromethane, acetonitrile or N, N-dimethylformamide.
6. The method of claim 1, wherein:
in the preparation method, the molar ratio of the strong base to the polyol initiator is 1/3-20/1; the molar ratio of the strong base to the cocatalyst a is 1/1-1/10; the molar ratio of the polyol initiator to the gamma-butyrolactone is 1/10-1/300; the molar concentration of the gamma-butyrolactone in the system is 4-13 mol/L.
7. The method of claim 1, wherein:
in the preparation method, the isocyanate is toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, and 1, 5-naphthalene diisocyanate.
8. The method of claim 1, wherein:
in the preparation method, the molar ratio of the isocyanate to the polyol initiator is 1/1-2/1; the ratio of the cocatalyst b to the cocatalyst a is 1/1-3/1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111640179.3A CN114133507B (en) | 2021-12-29 | 2021-12-29 | One-pot preparation method of bio-based degradable polyurethane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111640179.3A CN114133507B (en) | 2021-12-29 | 2021-12-29 | One-pot preparation method of bio-based degradable polyurethane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114133507A true CN114133507A (en) | 2022-03-04 |
| CN114133507B CN114133507B (en) | 2023-03-14 |
Family
ID=80383534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111640179.3A Active CN114133507B (en) | 2021-12-29 | 2021-12-29 | One-pot preparation method of bio-based degradable polyurethane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114133507B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116589659A (en) * | 2023-06-13 | 2023-08-15 | 安庆市索隆新材料有限公司 | Preparation method of self-repairing polyurethane elastomer |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009001705A (en) * | 2007-06-22 | 2009-01-08 | Tosoh Corp | Poly-3-hydroxybutyrate-based complex |
| US20100311917A1 (en) * | 2009-06-09 | 2010-12-09 | International Business Machines Corporation | Methods for making multi-branched polymers |
| CN109851765A (en) * | 2018-12-28 | 2019-06-07 | 中国科学院青岛生物能源与过程研究所 | A kind of organic concerted catalysis lactone ring opening polymerization without metal catalyst system |
| CN110527049A (en) * | 2019-07-29 | 2019-12-03 | 青岛科技大学 | A kind of degradable biological base polyester polyurethane and preparation method thereof |
| US20200010610A1 (en) * | 2018-07-06 | 2020-01-09 | International Business Machines Corporation | Ring-opening polymerizations using a flow reactor |
| CN110713582A (en) * | 2019-09-10 | 2020-01-21 | 华中科技大学 | Preparation method of copolyester polyurethane |
| CN110804163A (en) * | 2019-12-04 | 2020-02-18 | 青岛科技大学 | Preparation method of bio-based copolyester containing modifiable functional group |
| CN113045730A (en) * | 2019-12-26 | 2021-06-29 | 北京化工大学 | Mixing type polyurethane rubber based on bio-based and preparation method and application thereof |
-
2021
- 2021-12-29 CN CN202111640179.3A patent/CN114133507B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009001705A (en) * | 2007-06-22 | 2009-01-08 | Tosoh Corp | Poly-3-hydroxybutyrate-based complex |
| US20100311917A1 (en) * | 2009-06-09 | 2010-12-09 | International Business Machines Corporation | Methods for making multi-branched polymers |
| US20200010610A1 (en) * | 2018-07-06 | 2020-01-09 | International Business Machines Corporation | Ring-opening polymerizations using a flow reactor |
| CN109851765A (en) * | 2018-12-28 | 2019-06-07 | 中国科学院青岛生物能源与过程研究所 | A kind of organic concerted catalysis lactone ring opening polymerization without metal catalyst system |
| CN110527049A (en) * | 2019-07-29 | 2019-12-03 | 青岛科技大学 | A kind of degradable biological base polyester polyurethane and preparation method thereof |
| CN110713582A (en) * | 2019-09-10 | 2020-01-21 | 华中科技大学 | Preparation method of copolyester polyurethane |
| CN110804163A (en) * | 2019-12-04 | 2020-02-18 | 青岛科技大学 | Preparation method of bio-based copolyester containing modifiable functional group |
| CN113045730A (en) * | 2019-12-26 | 2021-06-29 | 北京化工大学 | Mixing type polyurethane rubber based on bio-based and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| ZHIBO LI ET AL.: "Chemically Recyclable Thermoplastic Polyurethane Elastomers via a Cascade Ring-Opening and Step-Growth Polymerization Strategy from Bio-renewable δ-Caprolactone", 《MACROMOLECULES》 * |
| 沈勇;李志波;: "有机磷腈碱催化环内酯开环聚合制备可降解聚酯研究进展" * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116589659A (en) * | 2023-06-13 | 2023-08-15 | 安庆市索隆新材料有限公司 | Preparation method of self-repairing polyurethane elastomer |
| CN116589659B (en) * | 2023-06-13 | 2023-11-10 | 安庆市索隆新材料有限公司 | Preparation method of self-repairing polyurethane elastomer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114133507B (en) | 2023-03-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6770717B2 (en) | Sequentially ordered biodegradable lactide (glycolide or lactide/glycolide)ε-caprolactone multi-block copolymer and process for the preparation thereof | |
| US6784273B1 (en) | Biomedical polyurethane, its preparation and use | |
| US5665831A (en) | Biocompatible block copolymer | |
| EP2184307B1 (en) | Producing method for polylactic acid-based copolymer | |
| US6861503B2 (en) | Interlinked solid polyethylene glycols and copolymers thereof | |
| US8362159B2 (en) | Degradable biocompatible block copolymer | |
| CN101684175A (en) | Biodegradable multi-block polyester copolymer and method for preparing same | |
| CN110527049A (en) | A kind of degradable biological base polyester polyurethane and preparation method thereof | |
| CN114133507B (en) | One-pot preparation method of bio-based degradable polyurethane | |
| AU2013297329A1 (en) | Method for manufacturing biodegradable copolymer by split-injecting aromatic dicarboxylic acid compound | |
| Wang et al. | Melt synthesis and characterization of poly (L-lactic acid) chain linked by multifunctional epoxy compound | |
| CN104629028A (en) | Polycaprolactone with reactive group on side chain and preparation method of polycaprolactone | |
| CN101519494B (en) | Preparation method of high molecular weight poly-morpholine-2,5-dione derivative and preparation method of the copolymer thereof | |
| EP2647656A2 (en) | Bioresorbable and biocompatible thermoplastic elastomer having a shape memory, particularly for biomedical applications and a process for their preparation | |
| CN114524913A (en) | High-flexibility high-elasticity degradable-controllable absorbable polyurethane elastomer, and preparation method and application thereof | |
| CN113024791A (en) | Preparation method of ultra-high molecular weight aliphatic polycarbonate | |
| CN101585828A (en) | Annular aliphatic carbonate monomer with three bond lateral group and preparation method | |
| JP3477824B2 (en) | Copolymer of polyurethane and aliphatic polyester and method for producing the same | |
| CA2100236A1 (en) | Amino acid terminated polyesters having predetermined monomeric sequence | |
| CN115197396B (en) | Preparation method of polysorbate modified polylactic acid polyurethane | |
| CN113881021B (en) | Terpolymer, suture and preparation method and application thereof | |
| CN114276512A (en) | Recyclable polyester polyurethane and preparation method thereof | |
| Liu | New biodegradable Polymers from renewable resources | |
| CN114262420A (en) | Preparation method of recyclable bio-based polyester polyurethane | |
| KR0132155B1 (en) | Preparation of biodegradable polyester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |