CN112979912A - Ultra-high-toughness polylactic acid-based polyurethane urea and preparation method thereof - Google Patents
Ultra-high-toughness polylactic acid-based polyurethane urea and preparation method thereof Download PDFInfo
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- CN112979912A CN112979912A CN202110212527.0A CN202110212527A CN112979912A CN 112979912 A CN112979912 A CN 112979912A CN 202110212527 A CN202110212527 A CN 202110212527A CN 112979912 A CN112979912 A CN 112979912A
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- polylactic acid
- polyurethane urea
- chain extender
- diisocyanate
- based polyurethane
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- 229920003226 polyurethane urea Polymers 0.000 title claims abstract description 81
- 239000004626 polylactic acid Substances 0.000 title claims abstract description 62
- 229920000747 poly(lactic acid) Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 33
- 239000004970 Chain extender Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000003077 polyols Chemical group 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 3
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 3
- 150000002009 diols Chemical class 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 9
- -1 small-molecule polyol Chemical class 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 230000001105 regulatory effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 125000003118 aryl group Chemical group 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- LCPNYLRZLNERIG-ZETCQYMHSA-N (2S)-6-amino-2-[2-(oxomethylidene)hydrazinyl]hexanoyl isocyanate Chemical group NCCCC[C@H](NN=C=O)C(=O)N=C=O LCPNYLRZLNERIG-ZETCQYMHSA-N 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000005058 Isophorone diisocyanate Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
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- 239000004416 thermosoftening plastic Substances 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
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- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
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- 230000002194 synthesizing effect Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000000930 thermomechanical effect Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920001244 Poly(D,L-lactide) Polymers 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920006030 multiblock copolymer Polymers 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920001434 poly(D-lactide) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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- 238000013268 sustained release Methods 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 150000004072 triols Chemical group 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 230000002792 vascular Effects 0.000 description 1
Images
Classifications
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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
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/428—Lactides
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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
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/06—Polyurethanes from polyesters
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- Chemical & Material Sciences (AREA)
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- Polymers & Plastics (AREA)
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Abstract
The invention relates to a polylactic acid polyurethane urea with super-strong toughness and a preparation method thereof, wherein the polylactic acid polyurethane urea comprises a polymerization unit of polylactic acid dihydric alcohol, at least two diisocyanates, a micromolecular polyol chain extender and water; wherein, the diisocyanate is at least two of diisocyanate containing aliphatic group, alicyclic group or aromatic group with 4-18 carbon atoms in the molecule, and the micromolecular polyalcohol chain extender is dihydric alcohol and/or trihydric alcohol with 2-12 carbon atoms in the molecule. The mechanical strength of the super-tough polyurethane urea material can be regulated and controlled by regulating the types and the proportion of the reaction raw materials. The PLA-based polyurethane urea has the characteristics of super toughness (the elongation at break is 15-55%, the tensile strength at break is 80-104MPa), low forming temperature (hot press forming can be carried out at 130 ℃), adjustable mechanical properties, good biocompatibility and degradability, and can be applied to the fields of biomedical materials and the like.
Description
Technical Field
The invention relates to the field of polymer synthesis, in particular to polylactic acid based polyurethane urea with super-strong toughness and a preparation method thereof.
Background
Polyurethanes (PU) and Polyurethaneureas (PUU) are a class of multiblock copolymers formed by the polycondensation of hydroxyl-terminated oligomeric diols, small molecule diols or diamines, and diisocyanates. The molecular chain is composed of soft segment and hard segment alternately, the soft segment is composed of polyether or polyester with low molecular weight, and the hard segment is composed of micromolecular chain extender and diisocyanate.
Polyurethane materials generally have higher toughness and elongation at break, better biocompatibility and degradability. Because of its good properties, polyurethane materials have been widely used in biomedical materials, such as drug sustained release carriers, sutures, artificial skin, vascular stents, etc., but their drawbacks are also very prominent, for example, their modulus and yield strength are low, and it is difficult to meet the requirements of hard tissue materials, especially bone tissue materials.
Polylactic acid (PLA) has good mechanical strength, degradability and biocompatibility, but its inherent brittleness greatly limits its applications. PLA-based polyurethanes/polyurethaneureas based on traditional synthetic methods are still brittle and are rarely reported in the literature. Therefore, when the PLA is used as the soft segment to synthesize the polyurethane at present, other flexible polyether or polyester diol is generally required to be added for copolymerization so as to improve the toughness of the obtained PU or PUU, but the tensile strength of the PU or PUU is still low (< 40MPa), and the PU or PUU cannot meet the requirements of a plurality of practical applications. At present, the super-tough PU or PUU material based on pure PLA is not reported in documents.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide the polylactic acid-based polyurethane urea with super-strong toughness and the preparation method thereof.
The invention claims a polylactic acid polyurethane urea, which comprises polymerized units of polylactic acid dihydric alcohol, at least two diisocyanates, a small molecule polyol chain extender and water; the molecular weight of the polylactic acid dihydric alcohol is 500-10000 g/mol, the diisocyanate is at least two of diisocyanate containing aliphatic group, alicyclic group or aromatic group with 4-18 carbon atoms in the molecule, and the micromolecular polyol chain extender is dihydric alcohol and/or trihydric alcohol with 2-12 carbon atoms in the molecule.
Further, the polylactic acid diol is one or more of dextrorotatory polylactic acid diol (PDLA diol), levorotatory polylactic acid diol (PLLA diol), racemic polylactic acid diol (PDLLA diol) and non-optical rotation polylactic acid diol (Meso-PLA diol).
Preferably, the polylactic acid diol is levorotatory polylactic acid diol.
Further, the small molecular polyol chain extender is dihydric alcohol, and the structural formula of the dihydric alcohol is selected from one or more of the following structural formulas:
preferably, the glycol chain extender is 1, 4-Butanediol (BDO).
When the small molecular polyol chain extender is only dihydric alcohol, the polylactic acid-based polyurethane urea is a linear molecule, has good mechanical property, low softening temperature and easy processing and forming, and simultaneously has degradability and good biocompatibility.
Further, the chain extender of the small molecular weight polyol comprises a trihydric alcohol besides the dihydric alcohol, and the structural formula of the trihydric alcohol is selected from one or more of the following structural formulas:
preferably, the triol is
When the small molecule polyol chain extender comprises a triol, the polylactic acid based polyurethaneurea is a partially crosslinked yet soluble, higher strength polyurethaneurea with thermoplasticity. Preferably, the small molecule polyol chain extender is a mixture of a diol and a triol.
Further, the structural formula of one diisocyanate A is selected from one or more of the following structural formulas:
the other diisocyanate B is selected from one or more of the following structural formulas:
preferably, the diisocyanate a is isophorone diisocyanate (IPDI).
Preferably, the diisocyanate B is L-Lysine Diisocyanate (LDI).
Further, the molar ratio of diisocyanate A to diisocyanate B is 5: 1 to 1: 5.
The polyurethane material synthesized by adopting the two diisocyanates has lower modulus and higher elongation at break than other polyurethane materials. The reason is that diisocyanate B has side groups, which destroys the regularity of a polymer chain and prevents strong hydrogen bonds from being formed between molecular chains, so that the interaction force between soft and hard segments and between hard and hard segments is weak, and no strong hard segment micro-region or soft and hard segment micro-phase separation exists, so that the obtained polyurethane urea material has low hardness and good toughness. Therefore, by incorporating such a diisocyanate in a PLA-based PUU, it is possible to flexibly adjust the mechanical properties thereof, thereby obtaining a PLA-based PUU material capable of having both high strength and toughness.
Further, the polylactic acid-based polyurethaneurea has an elongation at break of 15 to 55% and a tensile strength at break of 80 to 104 MPa.
According to the invention, from the perspective of molecular design, PLA diol with excellent performance is selected as a soft segment, and the strength of intermolecular hydrogen bonds is adjusted by introducing diisocyanate with bulky side groups into the system, so that the PLA-based polyurethane urea with high strength and toughness is obtained. The type of the chain extender in the system is adjusted, for example, a trihydric alcohol chain extender is added into the system, and a small amount of covalent bonds are introduced among molecular chains, so that the mechanical strength of the polyurethaneurea can be further improved, and the partially crosslinked thermoplastic super-tough PLA-based polyurethaneurea is obtained.
The linear polyurethane urea provided by the invention is a copolymer of oligomer diol, diisocyanate and a micromolecular polyol chain extender, can be dissolved in a plurality of organic solvents, has low softening temperature, can be formed by hot pressing at 130 ℃, and is greatly convenient for processing and application; at least two different diisocyanates are used in the synthesis, and the strength of intermolecular hydrogen bonds is adjusted by adjusting the ratio of the two diisocyanates, so that the mechanical properties of the material are controlled.
The invention also discloses a preparation method of the polylactic acid based polyurethane urea, which comprises the following steps:
(1) carrying out prepolymerization reaction on polylactic acid dihydric alcohol, at least two diisocyanates and a micromolecular polyol chain extender in an organic solvent under the action of a catalyst to obtain a prepolymer after the reaction is completed;
(2) and carrying out polymerization reaction on the prepolymer and water, and obtaining the polylactic acid-based polyurethane urea after the reaction is completed.
Further, in the step (1), the molar ratio of the polylactic acid dihydric alcohol to the small molecular weight polyol chain extender to the diisocyanate is (2-20) to (1-10) to (3-30). The mechanical strength of the super-tough polyurethane urea material can be regulated and controlled by regulating the proportion of polylactic acid diol and diisocyanate, the proportion of different diisocyanates and the type and proportion of the micromolecular polyol chain extender.
Further, in the step (1), the reaction temperature is 20-100 ℃; the reaction time is 1-10 h.
Further, in the step (1), the adding amount of the catalyst is 0.01-0.1% of the total mass of the polylactic acid dihydric alcohol, the diisocyanate and the small molecular weight polyol chain extender.
Further, in the step (1), the organic solvent is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, acetone, dimethyl sulfoxide (DMSO), N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), and the like.
Further, in the step (1), the catalyst is one of tin 2-ethylhexanoate, dibutyltin dilaurate and an organic bismuth catalyst.
Further, in the step (2), the reaction temperature is 20-100 ℃, and the reaction time is 12-72 h.
Further, in the step (2), the reaction is completed, and then the step of precipitating the product with a precipitating agent, removing the solvent and drying to obtain the polylactic acid based polyurethane urea (PUU) is included.
Further, the precipitant is a poor solvent of PUU, and is selected from one or more of water, n-hexane, n-heptane, isohexane, isoheptane, cyclohexane, petroleum ether, diethyl ether and ethanol.
Further, in step (2), water is added as an indirect chain extender in a molar amount of n (water) ═ 2[ n (diisocyanate) -n (polylactic acid diol) -n (small molecule diol) ].
Further, when the polylactic acid based polyurethane urea is applied, the dried polyurethane urea can be dissolved in a certain amount of organic solvent, poured into a mold for molding, and after the solvent is volatilized and dried, the residual trace amount of the solvent is completely removed in a vacuum oven, so that the polyurethane urea film is obtained. Wherein the organic solvent is one or more of dichloromethane, chloroform, 1, 2-dichloroethane, acetone, dimethyl sulfoxide (DMSO), N, N-Dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), etc.
By the scheme, the invention at least has the following advantages:
the PLA-based polyurethane urea provided by the invention has the characteristics of super toughness (the elongation at break is 15-55%, the tensile strength at break is 80-104MPa), low forming temperature (hot press forming can be carried out at 130 ℃), adjustable mechanical properties, good biocompatibility and degradability, and can be applied to the fields of biomedical materials and the like.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is an infrared spectrum of a polyurethaneurea prepared in example 1 of the present invention;
FIG. 2 is a stress-strain diagram for a tensile test of three polyurethaneureas prepared in example 1 of the present invention;
FIG. 3 is a dynamic thermo-mechanical analysis curve of a polyurethaneurea prepared in example 1 of the present invention;
FIG. 4 is a stress-strain diagram for a tensile test of four polyurethaneureas prepared in example 2 of the present invention;
FIG. 5 is a stress-strain plot of tensile tests of four super tough polyurethaneureas prepared in example 3 of the present invention;
FIG. 6 is a thermogravimetric analysis of a super tough polyurethaneurea prepared in example 3 of the present invention;
FIG. 7 is a photograph of a hot-pressed film obtained at 130 ℃ from super tough polyurethaneurea prepared in example 5 of the present invention.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials and the like used in the following examples are commercially available.
Example 1
The embodiment provides three polyurethane ureas and a synthesis method, and the specific steps are as follows:
levorotatory polylactic acid diol (PLLA diol) with the molecular weight of 2000g/mol, 1, 4-Butanediol (BDO), isophorone diisocyanate (IPDI) and L-Lysine Diisocyanate (LDI) are dissolved in a DMAc solution, 10 mu L of catalyst dibutyltin dilaurate (DBTDL) is added, and the reaction is carried out for 4 hours at the temperature of 70 ℃. The molar ratio of the reactants, i.e. PLA: BDO, (IPDI + LDI) ═ 2mol:1mol: nmol, was controlled. In this example, the molar ratio of IPDI to LDI was fixed at 2:1, and the value of n was 12. After the reaction is finished, is decreasedWarming to 50 ℃, adding 2(n-3) mol of H2The O is continuously reacted for 48 hours. After the reaction, the reaction solution was slowly poured into ether to obtain a white cake-like precipitate. The precipitate was chopped, sonicated for 45min with diethyl ether (to fully displace the high boiling point DMAc), and then dried in a vacuum oven at 70 ℃ for 12h to give the product PUU. This PUU was named PLAU 12-1.
Two other PUUs were prepared as described above and by varying the values of n to 15 and 18 respectively, PLAU15-1 and PLAU18-1 were synthesized respectively.
FIG. 1 is an infrared spectrum of PLAU15-1 provided in the present embodiment; it can be seen that 2940cm-1: a methylene peak; 1743cm-1: a carbamate carbonyl group; 1663cm-1: a urea carbonyl group; 1558cm-1: amide II has a characteristic vibrational peak.
FIG. 2 is a stress-strain curve of PLAU12-1, PLAU15-1 and PLAU18-1 provided in the present example. As can be seen, the stress is 30 to 79MPa, and the strain is 15 to 443%. With the increase of the hard segment content, the tensile strength of the material is increased, and the elongation at break is reduced. The reason is that along with the increase of the content of the hard segment, the content of carbamate and carbamido on the molecular chain is increased, the intermolecular force is continuously increased, and the strength of the material is obviously improved. The macroscopic mechanical properties of the polyurethaneurea gradually change from close to elastomers to hard plastics, and an obvious yield phenomenon occurs.
Fig. 3 is a dynamic thermomechanical analysis image of PLAU15-1 provided in this example. As can be seen, the storage modulus of the polyurethaneurea begins to decrease near 50 deg.C, and decreases to near 0 when the temperature reaches 160 deg.C, indicating that the polyurethaneurea has a lower softening temperature and can be thermoformed at a lower temperature.
Example 2
The present embodiment provides four kinds of polyurethaneureas and a synthesis method thereof, which specifically comprises the following steps:
dissolving levorotatory polylactic acid diol (PLLA diol) with molecular weight of 2000g/mol, 1, 4-Butanediol (BDO), isophorone diisocyanate (IPDI) and L-Lysine Diisocyanate (LDI) in DMAc solution, and adding 10 mu L of catalyst dibutyltin dilaurate(DBTDL) and reacting for 4 hours at 70 ℃. The molar ratio of the reactants is controlled, i.e. PLA: BDO, (IPDI + LDI) ═ 2mol:1mol (x + y) mol. In this example, x represents the mole number of IPDI, y represents the mole number of LDI, and the sum of x and y is 15, where x: y is 2: 1. After the reaction is finished, the temperature is reduced to 50 ℃, and 24mol of H is added2The O is continuously reacted for 48 hours. After the reaction, the reaction solution was slowly poured into ether to obtain a white cake-like precipitate. Shearing the precipitate, ultrasonic treating with diethyl ether for 45min, and drying in vacuum oven at 70 deg.C for 12 hr to obtain PUU. This PUU was named PLAU 15-1.
Three additional PUUs were prepared as described above and PLAU15-2, PLAU15-3 and PLAU15-4 were synthesized by varying the ratio of x to y in the order of 1: 1, 1: 2 and 1: 3.
FIG. 4 is a stress-strain curve of PLAU15-1, PLAU15-2, PLAU15-3 and PLAU15-4 provided in this example. It can be seen that the stress is 34 to 61MPa and the strain is 52 to 432%. With the increase of the LDI content, the tensile strength of the material is reduced, and the breaking elongation is improved. This is because the LDI side group is large and strong hydrogen bonds cannot be formed between molecules, so that the interaction force between the hard and soft segments and between the hard and soft segments is low and there is no strong hard segment interval. With the increase of the content of the L-lysine diisocyanate, the proportion of weak hydrogen bonds among molecules is increased continuously, the intermolecular force is reduced continuously, the strength of the material is reduced, and the elongation at break, namely the toughness is improved greatly. The macroscopic mechanical properties of the polyurethaneurea are changed from hard plastics to elastomers, and the yield phenomenon is less and less obvious.
Example 3
The embodiment provides a method for synthesizing partially crosslinked thermoplastic super-strength and toughness polyurethane urea, which comprises the following specific steps:
1) weigh 4.000g (2mmol) of PLA (M)n2000g/mol) in a 250mL three-necked flask, which was placed in a vacuum oven at 80 ℃ to dry overnight while a small amount of phosphorus pentoxide was placed in the vacuum oven to remove water. After completion of the drying, the three-necked flask was taken out, placed in a room-temperature oil bath, 10mL of DMAc dried in advance with anhydrous sodium sulfate was added to the three-necked flask with a measuring cylinder,adding a magnetic stirring bar for stirring. Further, 0.046g (0.5mmol) of 1, 4-Butanediol (BDO), 0.031g (0.33mmol) of glycerol, 2.245g (10mmol) of isophorone diisocyanate (IPDI), 1.1907g (5mmol) of L-Lysine Diisocyanate (LDI) and 20. mu.L of dibutyltin dilaurate (catalyst) were added.
2) Heating the mixture to 70 ℃, heating and stirring for reaction for 4H, then cooling the reaction system to 50 ℃, and adding 432 mu L (24mmol) of H2And O, continuously stirring the reaction. After water is added, the solution viscosity is increased along with the reaction, DMAc (about 60-65mL) is continuously added in the reaction process to control the concentration of the solution and prevent the system from gelling, and after 24 hours of reaction, the reaction is stopped and the temperature is reduced.
3) After the reaction solution is cooled to room temperature, the reaction solution is slowly poured into ether with 10 times volume of the reaction solvent for precipitation to obtain a massive solid, the massive solid is cut up, and ether is replaced by ether for ultrasonic treatment for 45min (in order to fully replace the high-boiling point DMAc). The solid was then dried in a vacuum oven at 70 ℃ for 12 hours to obtain a PUU polymer.
The method is characterized in that 50% of micromolecular diol chain extender is replaced by micromolecular triol chain extender, so that the original linear polyurethane urea is changed into partially crosslinked polyurethane urea, and the tensile strength of the polyurethane urea is greatly improved on the premise of ensuring that the material is soluble and meltable. The polyurethaneurea prepared in the above procedure was named PLAU15-C1 according to the amount of chain extender added.
According to the above method, PLAU15-C2, PLAU18-C1 and PLAU18-C2 were synthesized by changing the mole number of each raw material according to Table 1.
Table 1: raw material dosage for synthesizing different polyurethane ureas
| BDO(mmol) | Glycerol (mmol) | IPDI(mmol) | LDI(mmol) | |
| PLAU15-C2 | 0.25 | 0.75 | 10 | 5 |
| PLAU18-C1 | 0.5 | 0.5 | 12 | 6 |
| PLAU18-C2 | 0.25 | 0.75 | 12 | 6 |
FIG. 5 is a stress-strain curve for PLAU15-C1, PLAU15-C2, PLAU18-C1, and PLAU18-C2 provided in this example. It can be seen that after a certain amount of chain extender is added, the strength of the polyurethane urea is greatly improved, the maximum stress is 81-104 MPa, and the elongation at break is 17-53%. With the increase of the content of the chain extender triol, the breaking strength of the polyurethaneurea increases and the breaking elongation decreases. The three-functionality micromolecule is introduced into the system to form a partial cross-linking structure, covalent bond bonding is formed between partial molecular chains, acting force between the molecular chains is greatly enhanced, breaking strength of the polymer is greatly improved, and breaking elongation is correspondingly reduced.
FIG. 6 is a thermogravimetric analysis image of the PLAU18-C1 polyurethaneurea provided in this example. It can be seen from the figure that the material begins to lose weight significantly when the temperature reaches 250 c. This indicates that the thermal stability of the polyurethaneurea is excellent and that the thermoforming does not have a significant effect on it.
Example 4
The embodiment provides a method for manufacturing a partially crosslinked thermoplastic super-tough polyurethane urea film based on the polyurethane urea, which comprises the following specific manufacturing steps:
4g of PLAU15-C1 is dissolved in 12mL of DMAc, the solution is poured into a polytetrafluoroethylene mold after being fully dissolved, the polytetrafluoroethylene mold is dried for 24 hours in a forced air drying oven at 70 ℃, then dried for 24 hours in a vacuum drying oven at 80 ℃, and after the solvent is volatilized and dried, the polyurethane urea film is obtained.
Example 5
The embodiment provides a method for manufacturing a partially crosslinked thermoplastic super-tough polyurethane urea film based on the polyurethane urea, which comprises the following specific manufacturing steps:
pouring 4g of PLAU18-C1 powder into a square mould of 40mm multiplied by 40mm, putting the mould into a hot press, and hot-pressing at 130 ℃ and a certain pressure for 10min to obtain the polyurethane urea hot-pressed film with the thickness of about 2 mm.
FIG. 7 is a digital photograph of a hot-pressed film of PCLAU18-C1 provided in this example. It can be seen that the film is completely transparent, indicating that the polyurethaneurea can be thermoplastically formed well at 130 ℃.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
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