CN113185830A - Polyurethane nano-particle with polycaprolactone and brominated copolymer thereof as soft segment and preparation method thereof - Google Patents
Polyurethane nano-particle with polycaprolactone and brominated copolymer thereof as soft segment and preparation method thereof Download PDFInfo
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- CN113185830A CN113185830A CN202110479062.5A CN202110479062A CN113185830A CN 113185830 A CN113185830 A CN 113185830A CN 202110479062 A CN202110479062 A CN 202110479062A CN 113185830 A CN113185830 A CN 113185830A
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- polyurethane
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 72
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 72
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 55
- 229920001577 copolymer Polymers 0.000 title claims abstract description 34
- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 29
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 8
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- OMQFCTMVUFQKDS-UHFFFAOYSA-N 3-bromooxepan-2-one Chemical compound BrC1CCCCOC1=O OMQFCTMVUFQKDS-UHFFFAOYSA-N 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 11
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 11
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- -1 small molecule diol Chemical class 0.000 claims description 4
- 229940008841 1,6-hexamethylene diisocyanate Drugs 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 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
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012071 phase Substances 0.000 claims description 2
- 238000009826 distribution Methods 0.000 abstract description 7
- 125000001246 bromo group Chemical group Br* 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000725 suspension Substances 0.000 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 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000005711 Benzoic acid Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 235000010233 benzoic acid Nutrition 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000007306 functionalization reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000012703 microemulsion polymerization Methods 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- FBMQNRKSAWNXBT-UHFFFAOYSA-N 1,4-diaminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C(N)=CC=C2N FBMQNRKSAWNXBT-UHFFFAOYSA-N 0.000 description 1
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000002260 anti-inflammatory agent Substances 0.000 description 1
- 229940124599 anti-inflammatory drug Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UREBDLICKHMUKA-CXSFZGCWSA-N dexamethasone Chemical compound C1CC2=CC(=O)C=C[C@]2(C)[C@]2(F)[C@@H]1[C@@H]1C[C@@H](C)[C@@](C(=O)CO)(O)[C@@]1(C)C[C@@H]2O UREBDLICKHMUKA-CXSFZGCWSA-N 0.000 description 1
- 229960003957 dexamethasone Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007764 o/w emulsion Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- 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
- C08G18/65—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
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
-
- 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)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane nano-particle taking polycaprolactone and a brominated copolymer thereof as soft segments and a preparation method thereof. The polyurethane nano-particles are prepared by quickly mixing an organic solution containing polyurethane, an aqueous solution containing a surfactant and deionized water through a four-channel vortex mixer of FNC at a certain flow rate by a quick nano-precipitation technology to prepare the polyurethane nano-particles with the particle size of 50-300 nm. The polyurethane nano-particles prepared by the preparation method have uniform size distribution and high batch repeatability, and the obtained polyurethane nano-particles contain bromine groups, can be used for subsequent functional research and have a wide application prospect.
Description
Technical Field
The invention relates to the technical field of polymer nano materials, in particular to polyurethane nano particles taking polycaprolactone and brominated copolymer thereof as soft segments and a preparation method thereof.
Background
Because the polyurethane material has the advantages of good biocompatibility and biodegradability, good mechanical property and the like, the polyurethane nanoparticles show bright application prospects in the biomedical field including drug delivery, biological imaging, antibiosis and antiphlogosis and the like for nearly ten years. Currently, polyurethane nanoparticles are generally obtained by microemulsion polymerization, self-assembly, emulsification and the like. For example, in 2001, university of south Jiangjiang C.Wang et al reported the synthesis of polyurethane nanoparticles containing 1, 4-diaminoanthraquinone with a size of 500nm by a one-step microemulsion process (Polymer Chemistry 39(14), 2520). In 2020, polyurethane containing disulfide bond is synthesized by the project group of Y.hong at the university of Texas in USA, and then polyurethane nanoparticles (J Control Release 2020,321,363) with size of 250nm are obtained by ultrasonic method with polyvinyl alcohol as surfactant. The polythioketal-containing polyurethane material was synthesized by Cao group at Zhejiang university, 2021, and then the anti-inflammatory drug dexamethasone-loaded polyurethane nanoparticles were prepared by oil-in-water emulsion (Chemical Engineering Journal 2021,409).
However, the microemulsion polymerization method is difficult to adjust the size of the polymer nanoparticles, the size distribution of the nanoparticles prepared by the self-assembly method is uniform, but the batch repeatability is poor, the dispersibility of the nanoparticles prepared by the emulsion method is poor, the batch repeatability is poor and other general problems exist, and the existing polyurethane nanoparticles are difficult to perform subsequent functionalization, so that the application of the polyurethane nanoparticles is limited. Therefore, it is necessary to develop a method for preparing polyurethane nanoparticles, which is easy for subsequent functionalization, has high controllability of particle size, uniform size distribution and high repeatability, and can be produced in a large scale.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide polyurethane nanoparticles with polycaprolactone and brominated copolymer thereof as soft segments.
The first purpose of the invention is to provide a preparation method of the polyurethane nano-particles taking polycaprolactone and brominated copolymer thereof as soft segments.
The above object of the present invention is achieved by the following technical solutions:
a polyurethane nanoparticle with polycaprolactone and brominated copolymer thereof as soft segment, wherein the structural formula of the polycaprolactone and the brominated copolymer thereof is shown as a formula (I); the particle size of the polyurethane nanoparticles is 50-300 nm;
the molecular weight of the polycaprolactone and the brominated copolymer thereof is 2000-10000; wherein n is 0-1, and m is 15-60.
The polyurethane nano-particles contain bromine groups, can be used for subsequent functional research, and are potential functional polymer nano-particles.
Preferably, the molecular weight of the polycaprolactone and the brominated copolymer thereof is 3000-7000; wherein n is 15-30 and m is 1.
Preferably, the dispersion degree of the particle size of the polyurethane nano particles is 0.05-0.3.
The invention also provides a preparation method of any polyurethane nanoparticle taking polycaprolactone and brominated copolymer thereof as soft segments, which comprises the following steps:
s1, adding caprolactone or caprolactone and bromo-caprolactone into an organic solvent, uniformly mixing, adding micromolecule dihydric alcohol and an organic catalyst into a mixed solution, and reacting for 9-15 hours at 20-50 ℃ to obtain polycaprolactone or a caprolactone-bromo-caprolactone copolymer;
s2, adding diisocyanate, micromolecular diol and a catalyst into a solution of polycaprolactone or a caprolactone-brominated caprolactone copolymer, and reacting for 3-48 hours at 50-120 ℃ to obtain polyurethane taking polycaprolactone and the polycaprolactone copolymer as soft segments;
s3, dissolving the polyurethane which is synthesized in the step S2 and takes polycaprolactone and copolymer thereof as a soft segment in an organic solvent at a concentration of 2-30 mg/mL to serve as an organic phase, dissolving a surfactant at a concentration of 1-60 mg/mL in deionized water to serve as a water phase, filling the organic phase solution into a channel 1 of FNC, filling the surfactant solution into a channel 2 of FNC, and filling deionized water into the rest channels 3 and 4 of FNC; controlling the flow rate of four channels of the FNC to be 20-40 mL/min, and preparing the polyurethane nano-particles through the FNC.
Preferably, the molar ratio of the caprolactone to the brominated caprolactone in the step S1 is 15-60: 0-1.
Further preferably, the molar ratio of the caprolactone to the brominated caprolactone in the step S1 is 15-30: 1.
Preferably, the organic solvent in step S1 is toluene.
Preferably, the small molecule diol in step S1 is 1, 2-ethanediol or 1, 4-butanediol.
Preferably, the organic catalyst of step S1 is diphenyl phosphate, 1,5, 7-triazabicyclo (4.4.0) sunflower-5-ene or 1, 8-diazabicycloundec-7-ene; caprolactone and
preferably, the diisocyanate in step S2 is 1, 6-hexamethylene diisocyanate or 4, 4-diphenylmethane diisocyanate.
Preferably, the small molecule diol of step S2 is 1, 2-ethanediol, 1, 4-butanediol, or 1, 6-hexanediol.
Preferably, the concentration of the polyurethane solution in the step S3 is 5-15 mg/mL; the concentration of the surfactant is 2-30 mg/mL.
Preferably, the organic solvent in step S3 is N, N-Dimethylformamide (DMF) or tetrahydrofuran.
Preferably, the surfactant in step S3 is sodium lauryl sulfate.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides polyurethane nanoparticles with polycaprolactone and brominated copolymer thereof as soft segments, wherein the particle size of the polyurethane nanoparticles is 50-300 nm, and the polyurethane nanoparticles contain bromine groups, so that subsequent functionalization is easy, such as substitution reaction of sodium azide or quantitative reaction with sulfydryl micromolecules; the polyurethane nano-particles are prepared by quickly mixing an organic solution containing polyurethane, an aqueous solution containing a surfactant and deionized water at a certain flow rate through a four-channel vortex mixer of FNC (FNC) by a quick nano-precipitation technology.
Drawings
FIG. 1 is a schematic diagram of the rapid nano-precipitation (FNC) process for preparing polyurethane nanoparticles according to the present invention.
FIG. 2 is a TEM image of a polyurethane nanoparticle prepared by using SDS as a surfactant and using a caprolactone-bromocaprolactone copolymer containing 10 mol% of bromocaprolactone as a soft segment in example 2.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1 preparation of polyurethane nanoparticles with polycaprolactone as soft segment
The method comprises the following steps: in a glove box in a nitrogen environment, weighing 10.0g of caprolactone and 57mg of diphenyl phosphate, adding 80mL of toluene, uniformly mixing the solutions, adding 16mg of 1, 2-glycol into the mixed solution, reacting at room temperature for 16h, adding 25mg of benzoic acid to stop the reaction, precipitating the mixed solution in frozen methanol to purify the product, obtaining a white precipitate, and drying in a vacuum drying box to obtain the white powdery polycaprolactone copolymer.
Step two: in a glove box in a nitrogen environment, 6.0g of polycaprolactone, 10mg of diisobutyronitrile and 201.2mg of 4, 4-diphenylmethane diisocyanate are weighed into 30mL of N, N-dimethylformamide, the solutions are uniformly mixed, 920.1mg of 4, 4-diphenylmethane diisocyanate and 315.2mg of ethylene glycol are added into the mixed solution, and the mixed solution reacts at 70 ℃ for 60min, and then the reaction is stopped by cooling.
Step three: preparing a 10mg/mL polyurethane solution and a 10mg/mL sodium dodecyl sulfate solution, respectively taking a pipe of polyurethane solution, a pipe of sodium dodecyl sulfate solution and two pipes of deionized water by using a 20mL threaded injector, installing the injectors of the polyurethane solution and the sodium dodecyl sulfate solution on a No. 1 high-pressure pump, installing the injectors of the two pipes of deionized water on a No. 2 high-pressure pump, and setting the extrusion flow rate of the No. 1 high-pressure pump to be 10mL/min and the extrusion flow rate of the No. 2 high-pressure pump to be 15 mL/min. Four syringes were then connected to the vortex mixer. And after the high-pressure pump starts to work, the suspension flowing out of the mixer is the polyurethane nano particle suspension. Finally, the organic solution was removed by dialysis in deionized water to obtain polyurethane nanoparticles dispersed in water.
Example 2 preparation of polyurethane nanoparticles having a Soft segment of a copolymer of caprolactone and bromocaprolactone with a Bromocaprolactone content of 10 mol%
The method comprises the following steps: weighing 10g of caprolactone, 1.6107g of bromocaprolactone and 57mg of diphenyl phosphate in a glove box in a nitrogen environment, adding 80mL of toluene, uniformly mixing the solutions, adding 16mg of EG into the mixed solution, reacting at room temperature for 16h, adding 25mg of benzoic acid to stop the reaction, precipitating the mixed solution in frozen methanol to purify the product, obtaining a white precipitate, and drying the white precipitate in a vacuum drying box to obtain a caprolactone-bromocaprolactone copolymer with the white powdery bromocaprolactone content of 10 mol%.
Step two: in a glove box in a nitrogen environment, weighing 4g of the polycaprolactone-bromocaprolactone copolymer, 7mg of diisobutyronitrile and 168.2mg of diphenylmethane diisocyanate into 18mL of N, N-dimethylformamide, uniformly mixing the solution, adding 887.9mg of diphenylmethane diisocyanate and 227.2mg of ethylene glycol into the mixed solution, reacting the mixed solution at 70 ℃ for 60min, and cooling to stop the reaction.
Step three: preparing 20mg/mL polyurethane solution and 20mg/mL lauryl sodium sulfate solution, respectively taking one pipe of polyurethane solution, one pipe of lauryl sodium sulfate solution and two pipes of deionized water by using a 20mL threaded injector, installing the injectors of the polyurethane solution and the lauryl sodium sulfate solution on a No. 1 high-pressure pump, installing the two pipes of deionized water injectors on a No. 2 high-pressure pump, and setting the extrusion flow rate of the No. 1 high-pressure pump to be 10mL/min and the extrusion flow rate of the No. 2 high-pressure pump to be 20 mL/min. Four syringes were then connected to the vortex mixer. And after the high-pressure pump starts to work, the suspension flowing out of the mixer is the polyurethane nano particle suspension. Finally, the organic solution was removed by dialysis in deionized water to obtain polyurethane nanoparticles dispersed in water.
Fig. 1 is a TEM image of a polyurethane nanoparticle prepared by using SDS as a surfactant and using a caprolactone bromide-caprolactone bromide copolymer containing 10 mol% of caprolactone bromide as a soft segment, and it can be seen that the obtained polyurethane nanoparticle has a uniform particle size of about 100 nm. Table 1 shows the size and size distribution of polyurethane nanoparticles having a soft segment of caprolactone-bromocaprolactone copolymer with 10 mol% of bromocaprolactone content when the surfactant is replaced with PF-127 under different FNP process conditions, and it can be seen that the method can adjust the dispersibility and particle size of the polyurethane nanoparticles by adjusting and controlling the concentrations of polyurethane and surfactant, the ratio of organic phase and aqueous phase, and the flow rate.
TABLE 1 size and size distribution of polyurethane nanoparticles having caprolactone bromide content of 10 mol% and soft segment of caprolactone bromide-caprolactone copolymer under different FNP process conditions
a CpRepresents the concentration of the polymer in N, N-dimethylformamide, CsRepresents the concentration of the surfactant PF-127 in deionized water (unit: mg/mL);
b F1flow rates, F, representing the flow rates of the line 1 containing the polymer solution and the line 2 containing the aqueous surfactant solution2Representing the flow rates (in mL/min) of lines 3 and 4 of deionized water only;
crepresenting the ratio of organic phase to aqueous phase, usually to the flow rate F1:F2(ii) related;
d Number Meanthe values are determined by dynamic light scattering (unit: nm).
Example 3 preparation of polyurethane nanoparticles having a Soft segment of a copolymer of caprolactone and bromocaprolactone with a Bromocaprolactone content of 20 mol%
The method comprises the following steps: weighing 10.0g of caprolactone, 3.2214g of bromocaprolactone and 57mg of diphenyl phosphate in a glove box in a nitrogen environment, adding 80mL of toluene, uniformly mixing the solutions, adding 16mg of EG into the mixed solution, reacting at room temperature for 16h, adding 25mg of benzoic acid to stop the reaction, precipitating the mixed solution in frozen methanol to purify the product, obtaining a white precipitate, and drying in a vacuum drying box to obtain a white powdery polycaprolactone-bromocaprolactone copolymer.
Step two: in a glove box in a nitrogen environment, 5g of caprolactone-bromocaprolactone copolymer, 7mg of diisobutyronitrile and 140.2mg of diphenylmethane diisocyanate are weighed into 18mLN, N-dimethylformamide, the solution is uniformly mixed, 756.1mg of diphenylmethane diisocyanate and 156.0mg of ethylene glycol are added into the mixed solution, and the mixed solution reacts at 70 ℃ for 60min, and then the temperature is reduced to stop the reaction.
Step three: preparing a 10mg/mL polyurethane solution and a 10mg/mL sodium dodecyl sulfate solution, respectively taking a pipe of polyurethane solution, a pipe of sodium dodecyl sulfate solution and two pipes of deionized water by using a 20mL threaded injector, installing the injectors of the polyurethane solution and the sodium dodecyl sulfate solution on a No. 1 high-pressure pump, installing the injectors of the two pipes of deionized water on a No. 2 high-pressure pump, and setting the extrusion flow rate of the No. 1 high-pressure pump to be 30mL/min and the extrusion flow rate of the No. 2 high-pressure pump to be 30 mL/min. Four syringes were then connected to the vortex mixer. And after the high-pressure pump starts to work, the suspension flowing out of the mixer is the polyurethane nano particle suspension. Finally, the organic solution was removed by dialysis in deionized water to obtain polyurethane nanoparticles dispersed in water
Table 2 shows that under the same FNP process condition, the size and size distribution of the polyurethane nanoparticles taking the caprolactone with 20 mol% of bromocaprolactone and the bromocaprolactone copolymer as the soft segment are prepared in different batches, so that the method has high batch repeatability, can be used for large-scale production, and has a wide application prospect.
TABLE 2 dimension and size distribution of polyurethane nanoparticles prepared in different batches and having caprolactone bromide content of 20 mol% and caprolactone bromide copolymer as soft segment under the same FNP process condition
a CpRepresents the concentration of the polymer in N, N-dimethylformamide, CsRepresents the concentration of surfactant SDS in deionized water (unit: mg/mL);
b F1flow rates, F, representing the flow rates of the line 1 containing the polymer solution and the line 2 containing the aqueous surfactant solution2Representing the flow rates (in mL/min) of lines 3 and 4 of deionized water only;
crepresenting the ratio of organic phase to aqueous phase, usually to the flow rate F1:F2(ii) related;
dthe Number Mean value is determined by dynamic light scattering (unit: nm).
Claims (10)
1. A polyurethane nanoparticle taking polycaprolactone and brominated copolymer thereof as soft segments is characterized in that the structural formula of the polycaprolactone and the brominated copolymer thereof is shown as a formula (I); the particle size of the polyurethane nanoparticles is 50-300 nm;
the molecular weight of the polycaprolactone and the brominated copolymer thereof is 2000-10000; wherein n is 0-1, and m is 15-60.
2. The polyurethane nanoparticle of claim 1, wherein the molecular weight of the polycaprolactone and brominated copolymer thereof is 3000-7000; wherein n is 15-30 and m is 1.
3. A method for preparing polyurethane nanoparticles as claimed in claim 1 or 2, characterized in that it comprises the following steps:
s1, adding caprolactone or caprolactone and bromo-caprolactone into an organic solvent, uniformly mixing, adding micromolecule dihydric alcohol and an organic catalyst into a mixed solution, and reacting for 9-15 hours at 20-50 ℃ to obtain polycaprolactone or a caprolactone-bromo-caprolactone copolymer;
s2, adding diisocyanate, micromolecular diol and a catalyst into a solution of polycaprolactone or a caprolactone-brominated caprolactone copolymer, and reacting for 3-48 hours at 50-120 ℃ to obtain polyurethane taking polycaprolactone and the polycaprolactone copolymer as soft segments;
s3, dissolving the polyurethane which is synthesized in the step S2 and takes polycaprolactone and copolymer thereof as a soft segment in an organic solvent at a concentration of 2-30 mg/mL to serve as an organic phase, dissolving a surfactant at a concentration of 1-60 mg/mL in deionized water to serve as a water phase, filling the organic phase solution into a channel 1 of FNC, filling the surfactant solution into a channel 2 of FNC, and filling deionized water into the rest channels 3 and 4 of FNC; controlling the flow rate of four channels of the FNC to be 20-40 mL/min, and quickly mixing through the FNC to prepare the polyurethane nano-particles.
4. The method according to claim 3, wherein the molar ratio of caprolactone to brominated caprolactone in step S1 is 15-60: 0-1.
5. The method according to claim 3, wherein the small molecule diol of step S1 is 1, 2-ethanediol or 1, 4-butanediol.
6. The method of claim 3, wherein the organic catalyst of step S1 is diphenyl phosphate, 1,5, 7-triazabicyclo (4.4.0) sunflower-5-ene, or 1, 8-diazabicycloundecen-7-ene.
7. The method according to claim 3, wherein the diisocyanate in step S2 is 1, 6-hexamethylene diisocyanate or 4, 4-diphenylmethane diisocyanate.
8. The method according to claim 3, wherein the small molecule diol of step S2 is 1, 2-ethanediol, 1, 4-butanediol, or 1, 6-hexanediol.
9. The preparation method according to claim 3, wherein the concentration of the polyurethane solution in the step S3 is 5-15 mg/mL; the concentration of the surfactant is 2-30 mg/mL.
10. The method according to claim 3 or 9, wherein the surfactant of step S3 is sodium lauryl sulfate.
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