CN116023613A - Polyurethane elastomer for self-repairing blood environment and preparation method and application thereof - Google Patents
Polyurethane elastomer for self-repairing blood environment and preparation method and application thereof Download PDFInfo
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- CN116023613A CN116023613A CN202310086437.0A CN202310086437A CN116023613A CN 116023613 A CN116023613 A CN 116023613A CN 202310086437 A CN202310086437 A CN 202310086437A CN 116023613 A CN116023613 A CN 116023613A
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- 239000008280 blood Substances 0.000 title claims abstract description 65
- 210000004369 blood Anatomy 0.000 title claims abstract description 65
- 229920003225 polyurethane elastomer Polymers 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004970 Chain extender Substances 0.000 claims abstract description 36
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 17
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- -1 polyhexamethylene carbonate Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 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 15
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 13
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000376 reactant Substances 0.000 claims description 8
- YYYOQURZQWIILK-UHFFFAOYSA-N 2-[(2-aminophenyl)disulfanyl]aniline Chemical compound NC1=CC=CC=C1SSC1=CC=CC=C1N YYYOQURZQWIILK-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- ZPSUIVIDQHHIFH-UHFFFAOYSA-N 3-(trifluoromethyl)-4-[2-(trifluoromethyl)phenyl]benzene-1,2-diamine Chemical group FC(F)(F)C1=C(N)C(N)=CC=C1C1=CC=CC=C1C(F)(F)F ZPSUIVIDQHHIFH-UHFFFAOYSA-N 0.000 claims description 4
- XGKGITBBMXTKTE-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)disulfanyl]phenol Chemical compound C1=CC(O)=CC=C1SSC1=CC=C(O)C=C1 XGKGITBBMXTKTE-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002473 artificial blood Substances 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 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 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 239000011261 inert gas Substances 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
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 3
- UEVVKZOFWMPZAW-UHFFFAOYSA-N 1,1,2,2,3,3,4,4-octafluorohexane-1,6-diol Chemical compound OCCC(F)(F)C(F)(F)C(F)(F)C(O)(F)F UEVVKZOFWMPZAW-UHFFFAOYSA-N 0.000 claims description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 2
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 claims description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 2
- KYNFOMQIXZUKRK-UHFFFAOYSA-N 2,2'-dithiodiethanol Chemical compound OCCSSCCO KYNFOMQIXZUKRK-UHFFFAOYSA-N 0.000 claims description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
- GIMXWZYFIFOCBJ-UHFFFAOYSA-N 2-fluorobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(F)=C1 GIMXWZYFIFOCBJ-UHFFFAOYSA-N 0.000 claims description 2
- LKJWDWUXGCKFPN-UHFFFAOYSA-N 4-(1,1,1,3,3,3-hexafluoropropan-2-yl)phenol Chemical compound OC1=CC=C(C(C(F)(F)F)C(F)(F)F)C=C1 LKJWDWUXGCKFPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- RFAXLXKIAKIUDT-UHFFFAOYSA-N IPA-3 Chemical compound C1=CC=C2C(SSC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 RFAXLXKIAKIUDT-UHFFFAOYSA-N 0.000 claims description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 210000004204 blood vessel Anatomy 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- 210000003709 heart valve Anatomy 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 238000005829 trimerization reaction Methods 0.000 claims description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 8
- 230000035876 healing Effects 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 17
- 239000000806 elastomer Substances 0.000 description 17
- 239000000463 material Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 12
- 229920002635 polyurethane Polymers 0.000 description 12
- 239000004814 polyurethane Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 150000002540 isothiocyanates Chemical class 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- JPZRPCNEISCANI-UHFFFAOYSA-N 4-(4-aminophenyl)-3-(trifluoromethyl)aniline Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F JPZRPCNEISCANI-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
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- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of medical polymer materials, and discloses a polyurethane elastomer for self-repairing blood environment, and a preparation method and application thereof. The method comprises the following steps: mixing diisocyanate and a chain extender in an organic solvent, and reacting to obtain a low-molecular prepolymer solution; the chain extender is a chain extender containing dynamic disulfide bonds and a chain extender containing fluorine; and adding the active hydrogen end-capped oligomer and a catalyst, reacting to obtain polyurethane prepolymer, washing and drying to obtain the polyurethane elastomer for self-repairing the blood environment. The invention adopts an interfacial polymerization method, firstly reacts the hard segment with the chain extender to synthesize the prepolymer of the ultra-long hard segment, and finally obtains the polyurethane elastomer with high molecular weight, which has excellent hydrophobicity and mechanical strength and strong healing capacity in blood.
Description
Technical Field
The invention relates to the technical field of medical polymer materials, in particular to a polyurethane elastomer for self-repairing blood environment, and a preparation method and application thereof.
Background
Polyurethane elastomers are widely used in the fields of furniture, construction, commodity transportation, etc.; in the medical field, polyurethane materials are also hot spots for research by numerous researchers, have excellent properties such as biocompatibility, flexibility, strength, memory, processability and the like, and can be manufactured into medical devices or drug carriers such as surgical instruments and medical implants which are often in contact with human bodies. The existing polyurethane elastomer synthesis process adopts a one-step method and a prepolymer method, and the uniform solution formed by the reaction raw materials is required to ensure the sufficient contact and reaction among molecules. However, the material synthesized by the method has poor performance, such as low self-healing efficiency, weak tensile strength and the like, for special and mutually incompatible raw materials. For mutually incompatible raw materials, an interfacial polymerization method is often adopted, but in the polyurethane field, the interfacial polymerization method is used as a newer microencapsulation method, and the formed microcapsules are often used as fillers in film coatings. It becomes challenging to achieve synthesis of polyurethane elastomers with raw materials that are mutually incompatible.
CN115073687a discloses a self-healing polyurethane, which is prepared by reacting polytetrahydrofuran and isophorone diisocyanate to form polyurethane prepolymer, adding chain extender bis (4-hydroxyphenyl) -disulfide, reacting isocyanate bond with hydroxy of bis (4-hydroxyphenyl) -disulfide, and obtaining polyurethane with self-healing property.
Polyurethane elastomer materials have excellent self-healing properties in air, since dynamic bonds are typically affected by hydrogen bond saturation, metal cation coordination, or ion solvation in aqueous environments, development of self-healing polyurethane materials in blood environments has become a challenge. There are researches and reports that Polydimethylsiloxane (PDMS) with relatively strong hydrophobicity is used as a soft segment, and the multi-strength hydrogen bond of a hard segment provides a driving force for underwater self-healing, so that the self-healing of the material under various extreme conditions is realized. However, active hydrogen terminated Polydimethylsiloxanes (PDMS) are not compatible with hard segments, and thus it is challenging to prepare polyurethane elastomers with excellent properties using PDMS as a raw material.
At present, the polyurethane elastomer capable of self-healing in a blood environment is relatively less, and the early CN114957592A of the applicant discloses a preparation method of the polyurethane elastomer capable of self-healing in the blood environment. However, the material has low molecular weight, soft material, low hardness and poor mechanical properties, and is difficult to be used as an in-vivo material requiring mechanical support. And the addition of a crosslinking agent is required, which results in difficulty in employing a thermoplastic processing method in the later stages of polyurethane.
Disclosure of Invention
Aiming at the problems of low molecular weight and poor mechanical property of the polyurethane elastomer in the prior art, the invention provides a preparation method of the polyurethane elastomer with high molecular weight and excellent mechanical property, and the prepared elastomer can be self-repaired in a blood environment and has strong self-healing capability.
The method adopts an interfacial polymerization method to prepare the polyurethane elastomer integrating hydrophobicity, rapid self-healing and excellent mechanical properties.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of a polyurethane elastomer for self-repairing blood environment comprises the following steps:
and 2, adding the active hydrogen end-capped oligomer and the catalyst into the low-molecular prepolymer solution in the step 1, reacting to obtain a polyurethane prepolymer, and washing and drying to obtain the polyurethane elastomer for self-repairing the blood environment.
In the preparation of polyurethane elastomers, it is difficult to sufficiently react to synthesize high molecular weight polyurethane due to the difficulty in compatibility between the soft and hard segments. The preparation method comprises the steps of firstly reacting hard segment diisocyanate with a chain extender to obtain an ultra-long hard segment chain, which is favorable for forming a compact hydrogen bond network between hard segments to further enhance the tensile property of the material, and secondly dripping the soft segment of the active hydrogen end-capped oligomer into the hard segment solution in the step 1 in the step 2, wherein the hard segment solution in the step 1 is a high-polarity carbon-containing organic matter, the added active hydrogen end-capped oligomer is a low-polarity polymer, and uniformly dispersing the end-capped oligomer in the carbon-containing organic matter in small liquid drops for interfacial polymerization by mechanical stirring. The interface reaction is utilized to make the hard segment and the soft segment fully contact and react, so as to obtain the polyurethane elastomer with high molecular weight and excellent mechanical strength. The polyurethane elastomer has long hard segment chain length, high hard segment hydrogen bond density, high hard segment stacking stability and less damage to microphase area, and may be used in blood to heal fast and to show excellent mechanical strength after being soaked in blood, acid or alkali solution for long time.
And the chain extender is selected from a chain extender containing dynamic disulfide bonds and a chain extender containing fluorine, wherein the chain extender endows the elastomer with self-repairing capability, and the chain extender endows the elastomer with excellent hydrophobicity, and finally the hydrophobic self-repairing elastomer is obtained. The chain extender containing dynamic disulfide bonds provides chain exchange capability in a body temperature environment, and the chain extender containing fluorine provides hydrophobic effect, and particularly guarantees microscopic hydrophobic isolation of a hard phase region.
The diisocyanate comprises one or more of diphenylmethane-4, 4 '-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, 1, 3-dimethyl isocyanate cyclohexane, xylylene diisocyanate, 3' -dimethyl-4, 4 '-biphenyl diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate and p-phenylene diisocyanato;
preferably, the diisocyanate includes diphenylmethane-4, 4' -diisocyanate, 1, 5-naphthalene diisocyanate, 3' -dimethyl-4, 4' -biphenyl diisocyanate, etc., containing aromatic benzene rings and large pi bonds, thereby improving the regularity and binding force of hard segment stacking.
The chain extender containing dynamic disulfide bonds comprises one or more of bis (2-aminophenyl) disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-hydroxy-1-naphthyl) disulfide and bis (2-hydroxyethyl) disulfide;
the fluorine-containing chain extender comprises one or more of 2,2' -bis (trifluoromethyl) diaminobiphenyl, fluorohydroquinone, 2-bis (4-hydroxyphenyl) hexafluoropropane perfluoro bisphenol A and octafluoro-1, 6-hexanediol.
The active hydrogen terminated oligomer comprises a hydroxyl terminated oligomer and/or an amino terminated oligomer; and/or the molecular weight of the active hydrogen end-capped oligomer is 500-8000 g/mol. Preferably 3000-8000g/mol. If the molecular weight is too low, the polymer is difficult to mold, and if the molecular weight is too high, the ductility and self-healing properties of the polymer are deteriorated.
The hydroxyl-terminated oligomer comprises one or more of polyhexamethylene carbonate glycol, polytetrahydrofuran glycol, polycaprolactone glycol, polypropylene carbonate glycol, polyethylene glycol, polylactic acid glycol and polycarbonate glycol;
the amino-terminated oligomer comprises one or more of aminopropyl double-terminated polydimethylsiloxane, polyether amine and polyoxyethylene diamine.
The organic solvent comprises one or more of N, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide;
the catalyst comprises one or more of pentamethyldiethylenetriamine, dimethylcyclohexylamine, dimethylaminoethyl ether, dibutyltin dilaurate, organic bismuth, triazine trimerization catalyst, N-dimethylcyclohexylamine and N, N' -diethyl piperazine.
The molar ratio of the active groups of the chain extender containing dynamic disulfide bonds to isocyanate groups in diisocyanate is 0.2-0.4:1, the addition of the dynamic disulfide bonds can endow the material with self-repairing capability, and if the content of the dynamic disulfide bonds is too high, the use of the fluorine-containing chain extender is correspondingly reduced, so that the hydrophobic capability of the material is reduced;
the molar ratio of the active group of the fluorine-containing chain extender to the isocyanate group in the diisocyanate is 0.2-0.4:1; the addition of the fluorine-containing chain extender can reduce the surface energy of the material, reduce the adsorption effect of small molecules such as surface water and the like, prolong the service life of the material in blood, correspondingly reduce the use of dynamic disulfide bonds when the content of the weak fluorine-containing chain extender is too high, and reduce the self-repairing rate of the material;
the molar ratio of the active groups in the active hydrogen end-capped oligomer to the isocyanate groups in the diisocyanate is 0.2-0.6:1. If the diisocyanate content is too high, the hard segment ratio of the polymer is too high, which is detrimental to the tensile properties of the polymer, and if the diisocyanate content is too low, the polymer has poor mechanical strength and cannot be molded. Therefore, the content of the polyurethane elastomer is in the range, and the obtained polyurethane elastomer has good comprehensive mechanical properties.
The reaction temperature in the step 1 is room temperature, and the reaction time is 0.5-2h; the amino-terminated chain extender used is highly reactive with the diisocyanate at room temperature and is therefore chosen to react at room temperature in order to prevent crosslinking of the small molecules at higher temperatures.
The reaction temperature of the step 2 is 60-100 ℃ and the reaction time is 7-9h; the mass concentration of the reactant in the step 2 is 30-60%; the reactants comprise the low-molecular prepolymer in the step 1 and the active hydrogen end-capped oligomer added in the step 2, and the concentration is too high, the system viscosity is difficult to stir in the later period of reaction, and the reaction is further influenced; if the concentration is small, the collision probability between reactants is reduced, and the polymerization degree of the reaction is reduced.
Preferably, the entire reaction is carried out under inert gas protection; the inert gas comprises argon, nitrogen and the like; the isocyanate groups are very easy to react with water in the air, and because the relative molecular mass of water molecules is small, a small amount of water in the reaction system consumes a large amount of isocyanate groups to interfere with the occurrence of polymerization reaction and influence the performance of the obtained polyurethane elastomer.
The catalyst accounts for 0.1-1% of the mass of all reactants; all reactant amounts herein include the total mass of diisocyanate, chain extender and active hydrogen terminated oligomer.
Preferably, the washing in the third step means that the prepolymer is carried out in a solvent such as methanol, water, diethyl ether and the like; drying is carried out for 24-48 h at 50-80 ℃ under vacuum environment.
The invention also provides a polyurethane elastomer with the blood environment self-repairing function, which is prepared by the preparation method, and has the number average molecular weight of 2.5 multiplied by 10 4 -9×10 4 The method comprises the steps of carrying out a first treatment on the surface of the The highest polymerization degree can reach 21; the tensile strength is 2.5MPa-4.5MPa; the elastic modulus is 1.6MPa-5.0MPa;
the polymerization degree of the PDMS-based polyurethane elastomer prepared by the conventional method is about 10, and the polyurethane elastomer has high molecular weight, long hard segment, high hydrogen bond density, strong self-healing capability and high mechanical strength due to different preparation methods.
The polyurethane elastomer for self-repairing the blood environment can be used for preparing artificial blood vessels, heart stents and artificial heart valves.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention adopts an interfacial polymerization method, and the hard segment and the chain extender are reacted to synthesize the prepolymer of the ultra-long hard segment, and finally the polyurethane elastomer with high molecular weight is obtained, and the elastomer has excellent hydrophobicity and mechanical property and has strong healing capability in blood.
(2) The self-repairing polyurethane elastomer for the blood environment disclosed by the invention is synthesized by adopting an interfacial polymerization method, has the advantages of easily available raw materials, simple steps, contribution to industrial production popularization, capability of realizing the self-healing effect under various extreme environments of blood and high use value.
(3) According to the blood environment self-repairing polyurethane elastomer disclosed by the invention, the mechanical property of a polyurethane material can be improved and the tensile property is increased by preparing the polyurethane elastomer through an interfacial polymerization method, so that the excellent material property is realized.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a blood environment self-healing polyurethane elastomer prepared in example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of the blood environment self-healing polyurethane elastomer prepared in examples 2-5.
FIG. 3 is a Fourier infrared spectrum of the blood environment self-healing polyurethane elastomer prepared in examples 1-5.
FIG. 4 is a graph showing the water contact angle of the self-healing polyurethane elastomer in blood environment prepared in examples 1 to 5.
FIG. 5 is a graph of microscopic results of self-healing test in blood environment performed by self-healing polyurethane elasticity in water and blood environment prepared in example 4.
FIG. 6 is a graph showing the results of elastic mechanical properties of the blood environment self-healing polyurethane prepared in examples 1 to 5.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Modifications and equivalents will occur to those skilled in the art upon understanding the present teachings without departing from the spirit and scope of the present teachings.
The raw materials used in the following embodiments are all commercially available.
Example 1
the molar ratio of the active groups of the 2,2 '-bis (trifluoromethyl) diaminobiphenyl to the isocyanate groups in the diphenylmethane-4, 4' -diisocyanate is 0.27:1; the molar ratio of the active groups of the bis (2-aminophenyl) disulfide to the isocyanate groups of the diphenylmethane-4, 4' -diisocyanate is 0.27:1; the reaction temperature in the step 1 is room temperature, and the reaction time is 0.5h;
the molecular weight of the aminopropyl double-end-capped polydimethylsiloxane is 3000g/mol, and the mol ratio of the active group to the isocyanate group in the diphenylmethane-4, 4' -diisocyanate is 0.42:1; the mass concentration of the reactant in the step 2 is 36wt%; the reaction temperature in the step 2 is 70 ℃ and the reaction time is 8h. The prepolymer is washed by distilled water for several times, and is dried in vacuum for 24 hours to constant weight at 80 ℃ to obtain the self-healing polyurethane elastomer PU-1 in the blood environment.
PU-1 has Mn of 8.56X10 4 The nuclear magnetic resonance hydrogen spectrogram is shown in figure 1, the Fourier infrared spectrogram is shown in figure 3, the water contact angle is shown in figure 4, and the mechanical property is shown in figure 6.
Example 2
The preparation method of the blood environment self-repairing polyurethane elastomer PU-2 is the same as in example 1, except that diphenylmethane-4, 4' -diisocyanate is replaced by a mixture of diphenylmethane-4, 4' -diisocyanate and terephthalyl isothiocyanate, wherein the molar ratio of the diphenylmethane-4, 4' -diisocyanate to the terephthalyl isothiocyanate is 2.93:1.
PU-2 has Mn of 5.52X10 4 The nuclear magnetic resonance hydrogen spectrogram is shown in figure 2, the Fourier infrared spectrogram is shown in figure 3, the water contact angle is shown in figure 4, and the mechanical property is shown in figure 6.
Example 3
The preparation method of the blood environment self-repairing polyurethane elastomer PU-3 is the same as in example 2, except that the molar ratio of diphenylmethane-4, 4' -diisocyanate to terephthalyl isothiocyanate is 0.79:1.
PU-3 has a Mn of 5.36×10 4 The nuclear magnetic resonance hydrogen spectrogram is shown in figure 2The inner leaf infrared spectrogram is shown in figure 3, the water contact angle is shown in figure 4, and the mechanical properties are shown in figure 6.
Example 4
The preparation method of the blood environment self-repairing polyurethane elastomer PU-4 is the same as in example 2, except that the molar ratio of diphenylmethane-4, 4' -diisocyanate to terephthalyl isothiocyanate is 0.57:1.
PU-4 has Mn of 5.07×10 4 The nuclear magnetic resonance hydrogen spectrogram is shown in figure 2, the Fourier infrared spectrogram is shown in figure 3, the water contact angle is shown in figure 4, the self-healing performance in the blood environment is shown in figure 5, the self-healing performance in water is shown in figure 5, and the mechanical performance is shown in figure 6.
Example 5
The preparation method of the blood environment self-repairing polyurethane elastomer PU-5 is the same as in example 2, except that the molar ratio of diphenylmethane-4, 4' -diisocyanate to terephthalyl isothiocyanate is 0.33:1.
PU-5 has a Mn of 2.75X10 4 The nuclear magnetic resonance hydrogen spectrogram is shown in figure 2, the Fourier infrared spectrogram is shown in figure 3, the water contact angle is shown in figure 4, and the mechanical property is shown in figure 6.
Analysis of results
1. Nuclear magnetic resonance (1H NMR)
The sample of example 1 was tested at a concentration of 1-5wt% by 1HNMR spectroscopy on AVANCE III (600 MHz) using chloroform as an internal standard at normal temperature and pressure. As a result, as shown in FIG. 1, example 1 successfully synthesized the blood environment self-healing polyurethane elastomer, and hydrogen peaks of diphenylmethane-4, 4 '-diisocyanate, 2' -bis (trifluoromethyl) diaminobiphenyl, and bis (2-aminophenyl) disulfide, and hydrogen peaks of hydroxyl-terminated polydimethylsiloxane were present on the hydrogen spectrum. The sample of example 2 was tested at a concentration of 1-5wt%. As a result, as shown in FIG. 2, example 2 successfully synthesized the blood environment self-healing polyurethane elastomer, and hydrogen peaks of diphenylmethane-4, 4 '-diisocyanate, terephthalisothiocyanate, 2' -bis (trifluoromethyl) diaminobiphenyl, and bis (2-aminophenyl) disulfide, and hydrogen peaks of hydroxyl-terminated polydimethylsiloxane were present on the hydrogen spectrum.
2. Fourier infrared spectroscopy
The blood environment self-healing polyurethane elastomers prepared in examples 1 to 5 were tested at normal temperature and pressure using an attenuated total reflection fourier transform infrared (Nicolet IS 50) from Thermo Scientific american company to obtain fourier infrared spectrum data.
As shown in fig. 3, the appearance of the stretching vibration peak of-Si-O-in the hydroxyl-terminated polydimethylsiloxane, the-c=o characteristic peak on the polyurea linkage, and the stretching vibration peak of-NH 2-in the bis (2-aminophenyl) disulfide residue also demonstrates successful synthesis of the blood environment self-healing polyurethane.
3. Molecular weight test
Polyurethane molecular weight and molecular weight distribution (PDI) were analyzed using an Agilent PL-GPC50c, agilent Inc. of America, using a differential refractive index detector at 40℃and solvent flow rate was controlled to 1mL/min with chloroform (CHCl 3) as the mobile phase. The test results are shown in table 1.
TABLE 1 molecular weight of the elastomers prepared in examples 1-5
4. Water contact angle test
The blood environment self-healing polyurethane elastomers prepared in examples 1 to 5 were tested at normal temperature and pressure using a contact angle measuring instrument (DSA 25E) of KRUSS, germany, to obtain surface water contact angle data.
As shown in fig. 4, the water contact angles of the blood-environment self-healing polyurethane elastomers prepared in examples 1 to 5 are all greater than 100 °, and the blood-environment self-healing polyurethane elastomer prepared in example 3 has a water contact angle of 116 ° at the maximum.
5. Self-healing Performance test in blood Environment
The blood environment self-repairing polyurethane films prepared in examples 1 to 5 with a thickness of 300 μm were cut into small pieces, scratched in the middle with a knife, put in artificial blood, and the self-healing condition of scratches was observed by an optical microscope (Olympus/BX 51, japan) for various times.
As shown in FIG. 5, the self-healing polyurethane elastomer in the blood environment prepared in example 4 can realize self-healing in artificial blood at 35 ℃ for 24 hours, and can realize complete self-healing in water for 12 hours.
6. Mechanical property test
Mechanical property tests were carried out using a 1KN universal material tester from the Germany manufacturer Zwick Roell GmbH & Co. The 300 μm thick blood environment self-repairing polyurethane films prepared in examples 1-5 were cut into standard dumbbell-shaped bars according to BG/T528-2009 specifications.
As shown in FIG. 6, the elongation at break of the blood self-repairing elastomer PU-1 prepared in example 1 was 472%, the elongation at break of the blood self-repairing elastomer PU-2 prepared in example 2 was 442%, the elongation at break of the blood self-repairing elastomer PU-3 prepared in example 3 was 398%, the elongation at break of the blood self-repairing elastomer PU-4 prepared in example 4 was 588%, and the elongation at break of the blood self-repairing elastomer PU-5 prepared in example 5 was 207%.
The breaking strength of the blood self-repairing elastomer PU-2 prepared in the example 2 is 4.5MPa, the elastic modulus is 5.0MPa, the breaking strength of the blood self-repairing elastomer PU-1 prepared in the example 1 is 4.2MPa, the elastic modulus is 3.4MPa, the breaking strength of the blood self-repairing elastomer PU-3 prepared in the example 3 is 3.9MPa, the elastic modulus is 4.2MPa, the breaking strength of the blood self-repairing elastomer PU-4 prepared in the example 4 is 2.9MPa, the elastic modulus is 1.6MPa, the breaking strength of the blood self-repairing elastomer PU-5 prepared in the example 5 is 3.5MPa, and the elastic modulus is 2.5MPa.
The elastomer of example 1 had a stress of 0.06Mpa and a strain of 1280% relative to the previous study result CN114957592a of the subject group; the stress of example 2 was 0.9MPa and the strain was 506%; the stress of example 3 was 3.7MPa and the strain was 227%; the stress of example 4 was 0.1MPa and the strain was 735MPa; the stress of example 5 was 0.35MPa and the strain was 720MPa. Therefore, the polymerization method used in the research can effectively increase the mechanical properties of the material.
Claims (10)
1. The preparation method of the polyurethane elastomer for self-repairing the blood environment is characterized by comprising the following steps:
step 1, mixing diisocyanate and a chain extender in an organic solvent, and reacting to obtain a low-molecular prepolymer solution; the chain extender is a chain extender containing dynamic disulfide bonds and a chain extender containing fluorine;
and 2, adding the active hydrogen end-capped oligomer and the catalyst into the low-molecular prepolymer solution in the step 1, reacting to obtain a polyurethane prepolymer, and washing and drying to obtain the polyurethane elastomer for self-repairing the blood environment.
2. The method for preparing the polyurethane elastomer for self-repairing the blood environment according to claim 1, wherein the diisocyanate comprises one or more of diphenylmethane-4, 4 '-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, 1, 5-naphthalene diisocyanate, 1, 3-dimethylisocyanate cyclohexane, xylylene diisocyanate, 3' -dimethyl-4, 4 '-biphenyl diisocyanate, dicyclohexylmethane 4,4' -diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanato;
and/or the chain extender containing dynamic disulfide bonds comprises one or more of bis (2-aminophenyl) disulfide, bis (4-hydroxyphenyl) disulfide, bis (2-hydroxy-1-naphthyl) disulfide, and bis (2-hydroxyethyl) disulfide;
and/or the fluorine-containing chain extender comprises one or more of 2,2' -bis (trifluoromethyl) diaminobiphenyl, fluorohydroquinone, 2-bis (4-hydroxyphenyl) hexafluoropropane perfluoro-bis 35/35 phenol A and octafluoro-1, 6-hexanediol.
3. The method of preparing a blood environment self-repairing polyurethane elastomer according to claim 1, wherein the active hydrogen terminated oligomer comprises a hydroxyl terminated oligomer and/or an amino terminated oligomer; and/or the molecular weight of the active hydrogen end-capped oligomer is 500-8000 g/mol.
4. The method of preparing a blood environment self-repairing polyurethane elastomer according to claim 3, wherein the hydroxyl terminated oligomer comprises one or more of polyhexamethylene carbonate glycol, polytetrahydrofuran glycol, polycaprolactone glycol, polypropylene carbonate glycol, polyethylene glycol, polylactic acid glycol, polycarbonate glycol;
the amino-terminated oligomer comprises one or more of aminopropyl double-terminated polydimethylsiloxane, polyether amine and polyoxyethylene diamine.
5. The method for preparing the polyurethane elastomer for the self-repairing of the blood environment according to claim 1, wherein the organic solvent comprises one or more of N, N-dimethylformamide, tetrahydrofuran and dimethyl sulfoxide;
the catalyst comprises one or more of pentamethyldiethylenetriamine, dimethylcyclohexylamine, dimethylaminoethyl ether, dibutyltin dilaurate, organic bismuth, triazine trimerization catalyst, N-dimethylcyclohexylamine and N, N' -diethyl piperazine.
6. The method for preparing a polyurethane elastomer for self-repairing blood environment according to claim 1, wherein the molar ratio of the active group of the chain extender containing dynamic disulfide bonds to the isocyanate group in diisocyanate is 0.2-0.4:1;
the molar ratio of the active group of the fluorine-containing chain extender to the isocyanate group in the diisocyanate is 0.2-0.4:1;
and/or the molar ratio of the active groups in the active hydrogen end-capped oligomer to the isocyanate groups in the diisocyanate is 0.2-0.6:1.
7. The method for preparing the polyurethane elastomer for self-repairing the blood environment according to claim 1, wherein the reaction temperature in the step 1 is room temperature, and the reaction time is 0.5-2h; the reaction temperature of the step 2 is 60-100 ℃ and the reaction time is 7-9h; the mass concentration of the reactant in the step 2 is 30-60%.
8. The method for preparing a polyurethane elastomer for self-repairing a blood environment according to claim 1, wherein the whole reaction is carried out under inert gas protection and anhydrous conditions; the catalyst accounts for 0.1-1% of the mass of all reactants.
9. The polyurethane elastomer for blood environmental self-repair produced by the production method according to any one of claims 1 to 8, wherein the polyurethane elastomer has a number average molecular weight of 2.5 x 10 4 -9×10 4 The method comprises the steps of carrying out a first treatment on the surface of the The tensile strength is 2.5MPa-4.5MPa; the elastic modulus is 1.6MPa-5.0MPa.
10. Use of the polyurethane elastomer for blood environment self-repair according to claim 9 for preparing artificial blood vessels, heart stents, artificial heart valves.
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