CN101787136B - Method for preparing polyurethane function material with surface modified by polyvinyl pyrrolidone - Google Patents
Method for preparing polyurethane function material with surface modified by polyvinyl pyrrolidone Download PDFInfo
- Publication number
- CN101787136B CN101787136B CN2010100181526A CN201010018152A CN101787136B CN 101787136 B CN101787136 B CN 101787136B CN 2010100181526 A CN2010100181526 A CN 2010100181526A CN 201010018152 A CN201010018152 A CN 201010018152A CN 101787136 B CN101787136 B CN 101787136B
- Authority
- CN
- China
- Prior art keywords
- pvp
- ethyl
- methyl
- preparation
- chloride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to a method in which atom transfer radical polymerization (ATRP) and 'click' mistry are comprehensively utilized to improve surface hydrophilism of the polyurethane material, specifically, polyvinyl pyrrolidone is grafted on the surface of the polyurethane material to obtain surface functional polyurethane material. The invention aims to provide a simple and practical method for modifying the polyurethane surface and obtaining required high-degree wettability. The method comprises the following steps: first, vinyl pyrrolidone monomer is polymerized to obtain polyvinyl pyrrolidone (Init-PVP-X, X=CI, Br) with a terminal group thereof being halogen atom through the atom transfer radical polymerization reaction, then sodium azide is employed to convert the terminal group of the polyvinyl pyrrolidone from chlorine or bromine to triazon. with the method of the invention, surface hydrophily of high polymer material polyurethane with excellent mechanical properties can be noticeably improved and the question that the PVP combines with polyurethane is solved, so that a novel polyurethane function material featuring simple technology and economy and practicability is formed.
Description
Technical field
The invention belongs to the field of medical polymer functionalizing material surface, be specifically related to a kind of synthetic preparing methods in medical polyurethane material surface such as high-end medical catheter, seal wire and angiocarpy bracket that prepare with hydrophilic coating of stiff stability.
Background technology
Urethane (polyurethanes; PU) be that the basic raw material addition polymerization obtains mainly through vulcabond and divalent alcohol or polyvalent alcohol; Synthetic first by Bayer company in nineteen forty-seven, up to the present there has been the variety of historical [1] the .PU backbone structure of 60 years of development to determine it to have very abundant and unique physicochemical property, surface-functionalized PU has been widely used as bio-medical material. for example; Get involved the polyurethane medical catheter that clinic uses in the surgical operation at present; Grafting has polyoxyethylene glycol (PEG) or heparin on the surface, plays the wetting ability oilness that strengthens catheter surface, the sedimentary effect of anticoagulation and anti-protein; Can be applied in the patient's blood vessel. one of urethane application prerequisite in can the orthopaedic surgical operations intervention diagnosis and therapy must be to have good biocompatibility; Comprise wetting ability, high surface lubrication property, anticoagulation and functions such as proteinic deposition of prevention or absorption. and wherein the wetting ability of polyurethane surface is one of most important research contents.The damage at interface between organ and the conduit can be reduced in the PU surface that in moist environment, becomes lubricated, reduces the absorption of platelet aggregation and fibrinogen, also can reduce the absorption of bacterium to material surface simultaneously.
The hydrophilic lubrication property that improves polyurethane surface mainly comprises following several method: the hydrogel modification of surfaces, and polyoxyethylene (PEO) is modified, and PVP K120 (PVP) is modified, and graft polymerization is modified or the double-deck silicon conduit etc. of modifying.The PEO modification technique is used widely at present.In the world, the high-end medical PU conduit commercialization that has functions such as the antibiotic antithrombotic of hydrophilic lubrication property.At home, the Chang Jin of University Of Tianjin, the Zhang Xingdong academician of Sichuan University; The clock elecscreen, the Zheng Zhensheng of Zhongshan University, the meter sword of Zhejiang University; Envelope squama elder generation, a lot of study group such as Feng Xinde academician of Shen piebald horse academician of man and Peking University are all carrying out the research of this respect, and have obtained certain progress.But the oilness of PU material surface still can not reach requirement, and thrombocyte or absorption of proteins still exist, and the weather resistance of top coat is also not enough.Because the protection of a large amount of patents and the shortage of gordian technique; China can't produce the high-end polyurethane medical catheter material with excellent hydrophilic lubrication characteristic at present; Overseas Company is monopolizing the production technology of high-end polyurethane catheter, and high-end medical PU conduit costs an arm and a leg on the home market.
This presses for us and develops the product with independent intellectual property right.Calendar year 2001; Sharpless etc. have proposed the notion of " click " chemical technology (" click " or " link " chemical technology). and these " click " react easy handling; The title product productive rate is high; Seldom even do not have by product, under many conditions, go on well (good especially in water usually), and other functional group that can not be connected together influences.Wherein, at azido-(N
3) and ethynyl (C ≡ CH) between Huisgen 1; The 3-Dipolar Cycloaddition is studied the most extensively. and this is because the high efficiency of this addition reaction; Multi-functional and to the inertia of other functional group. under Cu (I) catalysis, the speed of reaction of trinitride-alkynes class can increase about 10
6Doubly, almost optionally generate 1 quantitatively, the substituted 1,2,3-triazoles of 4-, reaction can be carried out in all kinds of SOLVENTS, even in pure water, also can carry out well. at azido-(N
3) and ethynyl (C ≡ CH) between Huisgen 1; The 3-Dipolar Cycloaddition. since Hawker in 2004 and Sharpless etc. have at first reported the application of " click " chemical technology in Polymer Synthesizing; Through " click " technology construct complicated polymkeric substance and accurately the structure of controlling polymers just become a research field .Qin who increases fast and DPrez etc. to report in succession all that recently employing " click " chemical technology constructs the example of the urethane with special construction. present, the research of this respect is also rare.
In hydrophilic monomer; The structure of N-vinyl pyrrolidone (NVP) is given it and polymkeric substance special nature thereof: it is easy to polymerization; And its polymer poly vinyl pyrrolidone (PVP) has good wetting ability, complex ability and physiological compatibility low toxicity; Chemicalstability all has no stimulation to skin and eyes.Have very strong solublization, can increase that some is water insoluble basically and the water-soluble of pharmacological active substance arranged.
The polymkeric substance that is used for improving PU material surface oilness at present mainly contains T 46155, Vinylpyrrolidone polymer, SEPIGEL 305 based polyalcohol and SEPIGEL 305 etc.The lubricating coating on commodity PU both domestic and external surface, promptly the main raw material of hydrogel coating is disclosed, its key of problem is how to improve the efficient of grafting and the stability of hydrogel coating.For example patent US5290585A1 and US5179174A1 adopt the ultraviolet grafting to prepare Vinylpyrrolidone polymer; Polyoxyethylene is a kind of flexible, the lubricated organic coating of hydrophilic polymer, and is main through adding isocyanate, polyol raising grafting rate and stability.At home, the sample with lubricating coating of part Study, the main problem that exists is that coating comes off easily, can't use widely and promote.Therefore, domestic high-end medical catheter and dependent merchandise thereof with high lubricity relies on import basically.
In the medical catheter of clinical use, polyurethane material has high added value, and for example the conduit consumptive material of percutaneous transluminal coronary angioplasty (PTCA) is more than 10,000 yuan.In China, the market sales revenue relevant with interventional medical device and material was about 5,000,000,000 in 2005, and in 2015, market demand was expected to reach 300～40,000,000,000 yuan.
We combine atom transferred free radical reaction and " click " chemical technology with the surface of polymer P VP grafting to urethane for the first time, promptly control the physicochemical property of polyurethane surface through the structure of adjustment PVP.These new trials are expected to break the monopolization of Overseas Company to high-end medical catheter production technology, for the development of the high-end medical catheter of China provides theory and experiment basis, thereby have huge potential economic worth.
Shortcomings such as the lubricity that the present invention has the existence of polyurethane surface lubricating coating is low, and is firm inadequately through improving technology and prescription, obtain high lubricity and high persistent lubricating coating at polyurethane surface.
Summary of the invention
The present invention relates to a kind of comprehensive utilization ATRP and " click " chemofacies bonded method and improve the surface hydrophilicity of polyurethane material; Be exactly surface graft PVP K120 specifically, obtain surface-functionalized polyurethane material at polyurethane material.The present invention includes following steps:
Step 1: at first urethane raw is processed 1%～40% solution with the THF dissolving;
Step 2: the tetrahydrofuran solution that sodium hydride is joined above-mentioned urethane handles and obtains to have-activating surface (PU-N-) of N-negative ion structure;
Step 3: join in the solution with excessive 3-propargyl bromide again the surface have-THF of the urethane of N-negative ion structure dissolves the reaction certain hour, obtains the urethane (PU-≡) that the surface has the alkynyl structure; Thereby perhaps through vulcabond with contain polyaddition reaction between the polyvalent alcohol of alkynyl architecture and directly alkynyl is incorporated on the main chain of urethane and obtains (PU-≡);
Step 4: obtaining end group through atom transition free radical polymerization reaction is the Vinylpyrrolidone polymer (Init-PVP-Br (Cl)) of the different molecular weight of chlorine (or bromine);
Step 5: is that the PVP K120 of chlorine or bromine is converted into the PVP K120 (Init-PVP-N that end group is an azido-through using sodiumazide with end group
3);
Step 6: through click chemistry (" click " chemistry) be the PVP K120 (Init-PVP-N of azido-with end group
3) be grafted on the urethane (PU-≡) that the surface has the alkynyl structure, thereby obtain the surface with PVP K120 grafted function urethane (PU-g-PVP) material.
Said urethane raw comprises polyether(poly)urethane, PAUR, and the segmented copolymer of urethane and other polymkeric substance.
Operative temperature scope in the said step 2 is from 25 ℃ to 60 ℃.
Solvent in the said step 2 is ether, sherwood oil, THF, normal hexane and THF.
Be from 10 minutes to 24 hours the action time in the said step 2.
Temperature of reaction in the said step 3 is between 25 ℃ to 100 ℃.
Solvent in the said step 3 is an ether, sherwood oil, normal hexane.
The catalyzer of the polymerization method atom transition free radical polymerization reaction in the said step 4 is: triphenylphosphine ruthenous chloride (RuCl
2(PPh
3)
2), triphenylphosphine iodate rhenium dioxide (ReO
2I (PPh
3)
2), triphenylphosphine chlorination lawrencium (RhCl (PPh
3)
3), triphenylphosphine nickelous bromide (NiBr
2(PPh
3)
2), tri-n-butyl phosphine nickelous bromide NiBr
2(PnBu
3)
2, ferrous bromide (FeBr
2), iron protochloride (FeCl
2), the ferrous (FeCl of chlorination two (triphenylphosphine)
2(PPh
3)
2), cuprous bromide (CuBr), cuprous chloride (CuCl), bromination three (triphenylphosphine) copper (Cu (I) Br (PPh
3)
2), N, N, N ', N ", N " five methyl diethylentriamine (PMDETA), L-SODIUM ASCORBATE (Na
Asc), α，α′-Lian Biding (bipy), γ, γ '-dipyridyl (bipy), N, N-diisopropylethylamine, the inferior n-propyl of N--2-pyridyl methylamine (NPPMI), the inferior n-octyl of N--2-pyridyl methylamine (NOPMI), N; N, N ", N " and tetramethylethylened (TMEDA), 4,4 '-two (9-heptadecyls)-2,2 '-dipyridyl (dHDbpy), 4,4 '-two (5-nonyls)-2,2 '-dipyridyl (dNbpy); N-(2-dimethylaminoethyl)-N, N ', N '-trimethylammonium-1,3-tn (N [2,3]), N, N-two (2-pyridylmethyl) stearylamine (BPMODA) 4,4 ', 4 " and three (5-nonyls)-2; 2 ', 6 ', 2 " terpyridyl (tNtpy), 2,5,9,12-tetramethyl--2,5,9; 12-four azepine tridecanes (N [2,3,2]), 2,6,9,13-tetramethyl--2,6,9; The 13-four azepine tetradecanes (N [3,2,3]), 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA; N [2,2,2]), 2,5,8,12-tetramethyl-1-2,5,8; 12-four azepine tridecanes (N [2,2,3]), N ', N " dimethyl--N ', N " two-((2-pyridyl) methyl) ethane-1,2-diamines (BPED), three (2-(two (2-cyanoethyl)-amino) ethyl) amine (AN6TREN), three (2-(diethylamino) ethyl) amine (Et
5TREN), three (2-(two (2-methoxycarbonyl amino-ethyl) amino) ethyl) amine (MA
6TREN), three (2-(two (2-(n-butoxy carbonyl) ethyl) amino) ethyl) amine (BA
6TREN), three-[(2-pyridyl) methyl] amine (TPMA), three (2-(methyl amido) ethyl) amine (Me
6TREN) N, N, N ', N '-four-[(the 2-picolyl] ethylene diamine (TPEDA), 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TAN), 1,4,8,11-tetramethyl--1,4,8,11-tetraazacyclododecane tetradecane (Me
4Cyclam), 4,11-dimethyl--1,4,8,11-4-azabicyclo [6.6.2] n-Hexadecane (Cyclam-B); Cupric sulfate pentahydrate (CuSO
45H
2O), L-SODIUM ASCORBATE (Na
Asc).
Initiator in the said step 4 is: 2-isobutyl ethyl bromide, 2-methyl chloropropionate, methyl chloroacetate, α-toluene bromide, 1,2; The 4-trichlorobenzene, 2 bromopropionic acid-2-hydroxy methacrylate, 2 bromopropionic acid-2,3-epoxidation-1-propyl ester, 2 bromopropionic acid-3-propylene ester, 2 bromopropionic acid-tert-butyl ester; α-bromo-butyrolactone, 2 bromopropionic acid-2-(4-carboxyl phenoxy) ethyl ester, 2-vinyl chloroacetate, methylsulfonyl chloride (MSC), trichlorine methylsulfonyl chloride (TCMSC), Tosyl chloride (HBSC); To the anisole SULPHURYL CHLORIDE, to the fluorobenzene SULPHURYL CHLORIDE, benzene sulfonyl chloride, to the carboxyl benzene sulfonyl chloride, 4-(N, N-dimethylamino) nitrogen benzide 4 '-SULPHURYL CHLORIDE; 2,5-two chloro phenylsulfonyl chloride, 2,5-dimethoxy benzene sulfonyl chloride, 3,5-two chloro-2-hydroxybenzene SULPHURYL CHLORIDEs; The 1-naphthalic sulfonic chloride, 2-naphthalic sulfonic chloride, 5-(N, N-dimethylamino)-1-naphthalic sulfonic chloride, 2-chlor(o)acetamide; Bromination 4-methyl benzyl, cyanobenzyl bromine, bromination-4-bromobenzyl, 2-bromopropionitrile, bromoacetonitrile or allyl bromide 98.
Polymerization single polymerization monomer in the said step 4 is the 2-vinyl pyrrolidone.
Carry out in the atom transition free radical polymerization reaction body in the said step 4 or medium does, water, methyl alcohol, ethanol, propyl alcohol, Virahol; Acetonitrile, ETHYLE ACETATE, ethylene carbonate, ether, methyl-phenoxide; Phenyl ether, acetone, toluene, N, dinethylformamide (DMF) and methyl-sulphoxide (DMSO) etc.
The used solvent of PVP K120 end group conversion reaction in the said step 5 is N, dinethylformamide (DMF) and methyl-sulphoxide (DMSO) etc.
The used temperature of PVP K120 end group conversion reaction in the said step 5 is 25 ℃ to 100 ℃.
Huisgen 1 in the said step 6, catalyzer used in the 3-Dipolar Cycloaddition is: triphenylphosphine ruthenous chloride (RuCl
2(PPh
3)
2), triphenylphosphine iodate rhenium dioxide (ReO
2I (PPh
3)
2), triphenylphosphine chlorination lawrencium (RhCl (PPh
3)
3), triphenylphosphine nickelous bromide (NiBr
2(PPh
3)
2), tri-n-butyl phosphine nickelous bromide NiBr
2(PnBu
3)
2, ferrous bromide (FeBr
2), iron protochloride (FeCl
2), the ferrous (FeCl of chlorination two (triphenylphosphine)
2(PPh
3)
2), cuprous bromide (CuBr), cuprous chloride (CuCl), bromination three (triphenylphosphine) copper (Cu (I) Br (PPh
3)
2), N, N, N ', N ", N " five methyl diethylentriamine (PMDETA), α，α′-Lian Biding (bipy), γ; γ '-dipyridyl (bipy), N, N-diisopropylethylamine, the inferior n-propyl of N--2-pyridyl methylamine (NPPMI), the inferior n-octyl of N--2-pyridyl methylamine (NOPMI), N, N, N ", N " tetramethylethylened (TMEDA); 4,4 '-two (9-heptadecyls)-2,2 '-dipyridyl (dHDbpy), 4,4 '-two (5-nonyls)-2,2 '-dipyridyl (dNbpy), N-(2-dimethylaminoethyl)-N, N ', N '-trimethylammonium-1; 3-tn (N [2,3]), N, N-two (2-pyridylmethyl) stearylamine (BPMODA), 4,4 ', 4 " three (5-nonyls)-2,2 ', 6 '; 2 "-terpyridyl (tNtpy), 2,5,9,12-tetramethyl--2,5,9, (N [2,3 for 12-four azepine tridecanes; 2]), 2,6,9,13-tetramethyl--2,6,9, (N [3,2 for the 13-four azepine tetradecanes; 3]), 1,1,4,7,10,10-hexamethyl Triethylenetetramine (TETA) (HMTETA, N [2; 2,2]), 2,5,8,12-tetramethyl-1-2,5,8; 12-four azepine tridecanes (N [2,2,3]), N ', N " dimethyl--N ', N " two-((2-pyridyl) methyl) ethane-1,2-diamines (BPED), three (2-(two (2-cyanoethyl)-amino) ethyl) amine (AN
6TREN), three (2-(diethylamino) ethyl) amine (Et
5TREN), three (2-(two (2-methoxycarbonyl amino-ethyl) amino) ethyl) amine (MA
6TREN), three (2-(two (2-(n-butoxy carbonyl) ethyl) amino) ethyl) amine (BA
6TREN), three-[(2-pyridyl) methyl] amine (TPMA), three (2-(methyl amido) ethyl) amine (Me
6TREN) N, N, N ', N '-four-[(the 2-picolyl] ethylene diamine (TPEDA), 1,4,7-trimethylammonium-1,4,7-7-triazacyclononane (Me
3TAN), 1,4,8,11-tetramethyl--1,4,8,11-tetraazacyclododecane tetradecane (Me
4Cyclam), 4,11-dimethyl--1,4,8,11-4-azabicyclo [6.6.2] n-Hexadecane (Cyclam-B); Cupric sulfate pentahydrate (CuSO
45H
2O), L-SODIUM ASCORBATE (Na
Asc).
The used solvent of " click " chemical reaction in the said step 6 is a water, methyl-sulphoxide (DMSO), N, dinethylformamide (DMF), toluene, acetonitrile.
The present invention can significantly improve the problem that combines of surface hydrophilic performance and PVP with the urethane of the polymer material polyurethane with excellent mechanical property, thereby obtains simple, the economical and practical new polyurethane functional materials of production technique.
Embodiment
Embodiment 1
1) the preparation end group is the PVP K120 (Init-PVP-N of azido-
3): remove stopper through the vacuum distilling purification of N-vinylpyrrolidone earlier.Under nitrogen protection, with 0.135g (0.94mmol) cuprous bromide (CuBr) 0.39mL (1.88mmol) N, N; N ', N ", N " '-five methyl diethylentriamine (PMDETA) and 10mL (0.094mol) N-V-Pyrol RC are added in the 50mL three neck round-bottomed flasks that reflux condensing tube is housed; And stir with magnetic stirring apparatus continuously; And then (1.57g 0.0094mol), was heated to 90 ℃ and back flow reaction 72 hours to add initiator 2-isobutyl bromide.After reaction finished, cool to room temperature was poured into the flask reaction mixture in the acetic acid soln of a 100mL, filter, and successively with excessive deionized water rinsing, it was the PVP K120 (Init-PVP-Br) of bromine that vacuum-drying obtains end group.(～the end group that obtains above 0.04mmol) is the PVP K120 (Init-PVP-Br) and 0.163g (2.50mmol) sodiumazide (NaN of bromine to get 0.130g
3) be dissolved in the N of the deoxidation of 20mL; Among the N '-N (DMF); Be heated to 50 ℃ and stirred 8 hours, then with the mixture rotary evaporation of reaction to doing, be dispersed in the chloroform and concentrate; Add methanol extraction, it is the PVP K120 (Init-PVP-N of azido-that filtration drying obtains end group
3).
2) the surperficial polyurethane film (PU-≡) of preparation: the film that earlier urethane is dissolved in exsiccant THF (THF) and curtain coating Cheng Houyue 0.2mm with alkynyl structure; Be cut into the film of about 1cm * 1cm size; Place the exsiccant ether to add the sodium hydride (NaH) of about 0.6g this PU film under the nitrogen protection then, the 3-propargyl bromide that adds 0.5mL after 2 hours again continues reaction 2 hours.The PU film is taken out and washes with ether earlier and use a large amount of deionized water rinsings again, and the dry PU film (PU-≡) that obtains surperficial alkynyl functionalization is treated next step use in the vacuum drying oven.
3) the PU film (PU-≡) of surperficial alkynyl functionalization is placed in the round-bottomed flask of a 50mL who has been added with deionized water, adding end group again is the PVP K120 (Init-PVP-N of azido-
3) and copper catalyst (CuBr/PMDETA), under 50 ℃ temperature, react and spend the night, at last the PU film is taken out and just obtained the urethane (PU-g-PVP) that surface graft has PVP K120 with drying in a large amount of deionized water rinsings and the vacuum drying oven.
Embodiment 2
1) the preparation end group is the PVP K120 (Init-PVP-N of azido-
3): remove stopper through the vacuum distilling purification of N-vinylpyrrolidone earlier.Under nitrogen protection, with 0.135g (0.94mmol) cuprous bromide (CuBr) 0.39mL (1.88mmol) N, N; N ', N ", N ' " five methyl diethylentriamine (PMDETA) and 10mL (0.094mol) N-V-Pyrol RC are added in the 50mL three neck round-bottomed flasks that reflux condensing tube is housed; And stir with magnetic stirring apparatus continuously; And then (1.57g 0.0094mol), was heated to 90 ℃ and back flow reaction 72 hours to add initiator 2-isobutyl bromide.After reaction finished, cool to room temperature was poured into the flask reaction mixture in the acetic acid soln of a 100mL, filter, and successively with excessive deionized water rinsing, it was the PVP K120 (Init-PVP-Br) of bromine that vacuum-drying obtains end group.(～the end group that obtains above 0.04mmol) is the PVP K120 (Init-PVP-Br) and 0.163g (2.50mmol) sodiumazide (NaN of bromine to get 0.130g
3) be dissolved in the N of the deoxidation of 20mL; Among the N '-N (DMF); Be heated to 50 ℃ and stirred 8 hours, then with the mixture rotary evaporation of reaction to doing, be dispersed in the chloroform and concentrate; Add methanol extraction, it is the PVP K120 (Init-PVP-N of azido-that filtration drying obtains end group
3).
2) the surperficial polyurethane film (PU-≡) of preparation: the film that earlier urethane is dissolved in exsiccant THF (THF) and curtain coating Cheng Houyue 0.2mm with alkynyl structure; Be cut into the film of about 1cm * 1cm size; Place the exsiccant ether to add the sodium hydride (NaH) of about 0.6g this PU film under the nitrogen protection then, the 3-propargyl bromide that adds 0.5mL after 2 hours again continues reaction 2 hours.The PU film is taken out and washes with ether earlier and use a large amount of deionized water rinsings again, and the dry PU film (PU-≡) that obtains surperficial alkynyl functionalization is treated next step use in the vacuum drying oven.
3) the PU film (PU-≡) of surperficial alkynyl functionalization is placed in the round-bottomed flask of a 50mL who has been added with deionized water, adding end group again is the PVP K120 (Init-PVP-N of azido-
3) and copper catalyst (CuSO
45H
2O/Na
Asc), under 50 ℃ temperature, react and spend the night, at last the PU film is taken out and just obtained the urethane (PU-g-PVP) that surface graft has PVP K120 with drying in a large amount of deionized water rinsings and the vacuum drying oven.
Embodiment 3
1) the preparation end group is the PVP K120 (Init-PVP-N of azido-
3): remove stopper through the vacuum distilling purification of N-vinylpyrrolidone earlier.Under nitrogen protection, with 0.135g (0.94mmol) cuprous bromide (CuBr) 0.39mL (1.88mmol) N, N; N ', N ", N " '-five methyl diethylentriamine (PMDETA) and 10mL (0.094mol) N-V-Pyrol RC are added in the 50mL three neck round-bottomed flasks that reflux condensing tube is housed; And stir with magnetic stirring apparatus continuously; And then (1.57g 0.0094mol), was heated to 90 ℃ and back flow reaction 72 hours to add initiator 2-isobutyl bromide.After reaction finished, cool to room temperature was poured into the flask reaction mixture in the acetic acid soln of a 100mL, filter, and successively with excessive deionized water rinsing, it was the PVP K120 (Init-PVP-Br) of bromine that vacuum-drying obtains end group.(～the end group that obtains above 0.04mmol) is the PVP K120 (Init-PVP-Br) and 0.163g (2.50mmol) sodiumazide (NaN of bromine to get 0.130g
3) be dissolved in the N of the deoxidation of 20mL; Among the N '-N (DMF); Be heated to 50 ℃ and stirred 8 hours, then with the mixture rotary evaporation of reaction to doing, be dispersed in the chloroform and concentrate; Add methanol extraction, it is the PVP K120 (Init-PVP-N of azido-that filtration drying obtains end group
3).
2) the surperficial polyurethane film (PU-≡) of preparation: the film that earlier urethane is dissolved in exsiccant THF (THF) and curtain coating Cheng Houyue 0.2mm with alkynyl structure; Be cut into the film of about 1cm * 1cm size; Place the exsiccant ether to add the sodium hydride (NaH) of about 0.6g this PU film under the nitrogen protection then, the 3-propargyl bromide that adds 0.5mL after 2 hours again continues reaction 2 hours.The PU film is taken out and washes with ether earlier and use a large amount of deionized water rinsings again, and the dry PU film (PU-≡) that obtains surperficial alkynyl functionalization is treated next step use in the vacuum drying oven.
3) the PU film (PU-≡) of surperficial alkynyl functionalization is placed in the round-bottomed flask of a 50mL who has been added with deionized water, adding end group again is the PVP K120 (Init-PVP-N of azido-
3) and copper catalyst (CuBr/ α; α '-bipy); Under 50 ℃ temperature, react and spend the night, at last the PU film is taken out and just obtained the urethane (PU-g-PVP) that surface graft has PVP K120 with drying in a large amount of deionized water rinsings and the vacuum drying oven.
Embodiment 4
1) the preparation end group is the PVP K120 (Init-PVP-N of azido-
3): remove stopper through the vacuum distilling purification of N-vinylpyrrolidone earlier.Under nitrogen protection, with 0.135g (0.94mmol) cuprous bromide (CuBr) 0.39mL (1.88mmol) N, N; N ', N ", N " '-five methyl diethylentriamine (PMDETA) and 10mL (0.094mol) N-V-Pyrol RC are added in the 50mL three neck round-bottomed flasks that reflux condensing tube is housed; And stir with magnetic stirring apparatus continuously; And then (1.57g 0.0094mol), was heated to 90 ℃ and back flow reaction 72 hours to add initiator 2-isobutyl bromide.After reaction finished, cool to room temperature was poured into the flask reaction mixture in the acetic acid soln of a 100mL, filter, and successively with excessive deionized water rinsing, it was the PVP K120 (Init-PVP-Br) of bromine that vacuum-drying obtains end group.(～the end group that obtains above 0.04mmol) is the PVP K120 (Init-PVP-Br) and 0.163g (2.50mmol) sodiumazide (NaN of bromine to get 0.130g
3) be dissolved in the N of the deoxidation of 20mL; Among the N '-N (DMF); Be heated to 50 ℃ and stirred 8 hours, then with the mixture rotary evaporation of reaction to doing, be dispersed in the chloroform and concentrate; Add methanol extraction, it is the PVP K120 (Init-PVP-N of azido-that filtration drying obtains end group
3).
2) the surperficial polyurethane film (PU-≡) of preparation: earlier urethane is dissolved in exsiccant THF (THF) with alkynyl structure; Place the exsiccant ether to add the sodium hydride (NaH) of about 0.6g this PU film under the nitrogen protection then, the 3-propargyl bromide that adds 0.5mL after 2 hours again continues reaction 2 hours.Question response end back adding ether is precipitated out PU and uses a large amount of deionized water rinsings again with the ether flushing, and the PU of the surperficial alkynyl functionalization of dry acquisition treats next step use in the vacuum drying oven.
3) PU (PU-≡) of surperficial alkynyl functionalization is placed in the round-bottomed flask of a 50mL who has been added with DMF, adding end group again is the PVP K120 (Init-PVP-N of azido-
3) and copper catalyst (CuBr/PMDETA), under 50 ℃ temperature, react and spend the night, add at last that ether is precipitated out PU and vacuum drying oven in dryly just obtained the urethane (PU-g-PVP) that surface graft has PVP K120.
Embodiment 5
1) the preparation end group is the PVP K120 (Init-PVP-N of azido-
3): remove stopper through the vacuum distilling purification of N-vinylpyrrolidone earlier.Under nitrogen protection, with 0.135g (0.94mmol) cuprous bromide (CuBr) 0.39mL (1.88mmol) N, N; N ', N ", N ' " five methyl diethylentriamine (PMDETA) and 10mL (0.094mol) N-V-Pyrol RC are added in the 50mL three neck round-bottomed flasks that reflux condensing tube is housed; And stir with magnetic stirring apparatus continuously; And then (1.57g 0.0094mol), was heated to 90 ℃ and back flow reaction 72 hours to add initiator 2-isobutyl bromide.After reaction finished, cool to room temperature was poured into the flask reaction mixture in the acetic acid soln of a 100mL, filter, and successively with excessive deionized water rinsing, it was the PVP K120 (Init-PVP-Br) of bromine that vacuum-drying obtains end group.(～the end group that obtains above 0.04mmol) is the PVP K120 (Init-PVP-Br) and 0.163g (2.50mmol) sodiumazide (NaN of bromine to get 0.130g
3) be dissolved in the N of the deoxidation of 20mL; Among the N '-N (DMF); Be heated to 50 ℃ and stirred 8 hours, then with the mixture rotary evaporation of reaction to doing, be dispersed in the chloroform and concentrate; Add methanol extraction, it is the PVP K120 (Init-PVP-N of azido-that filtration drying obtains end group
3).
2) the surperficial polyurethane film (PU-≡) of preparation: in the round-bottomed flask of a 100mL with alkynyl structure; Add the normal HDI of 0.1mmol earlier; 0.1mmol the glycol mixture of different glycol (or in two); 0.1mmol DPPD and fresh distillatory ETHYLE ACETATE (EtOAc); Mixture in the above-mentioned flask was heated to 50 ℃ with oil bath in 15 minutes with nitrogen bubble in advance again, then dibutylin dilaureate (about 20-30 μ L). and reaction mixture reacted 2 hours under nitrogen protection, during reaction all had urethane to be precipitated out.After reaction is accomplished, filter and successively with a large amount of ETHYLE ACETATE (EtOAc) and acetone rinsing removing unreacted monomer, dried overnight in the vacuum drying oven obtains the PU film (PU-≡) of surperficial alkynyl functionalization at last, treats next step use.
3) the PU film (PU-≡) of surperficial alkynyl functionalization is placed in the round-bottomed flask of a 50mL who has been added with deionized water, adding end group again is the PVP K120 (Init-PVP-N of azido-
3) and copper catalyst (CuBr/PMDETA), under 50 ℃ temperature, react and spend the night, at last the PU film is taken out and just obtained the urethane (PU-g-PVP) that surface graft has PVP K120 with drying in a large amount of deionized water rinsings and the vacuum drying oven.
Claims (15)
1. the preparation method of the polyurethane material of a surface by utilizing PVP K120 modification is characterized in that, comprises following preparation process:
Step 1: at first urethane raw is processed 1%～40% solution with the THF dissolving;
Step 2: the tetrahydrofuran solution that sodium hydride is joined said urethane handles and obtains to have-activating surface of N-negative ion structure;
Step 3: again the solution of excessive 3-propargyl bromide is joined the surface and have-the tetrahydrofuran solution reaction of the urethane of N-negative ion structure or directly alkynyl is incorporated on the main chain of urethane to obtain the urethane that the surface has the alkynyl structure through vulcabond and the polyaddition reaction that contains between the polyvalent alcohol of alkynyl structure;
Step 4: obtaining end group through atom transition free radical polymerization reaction is the Vinylpyrrolidone polymer of the different molecular weight of chlorine or bromine;
Step 5: is that the PVP K120 of chlorine or bromine is converted into the PVP K120 that end group is an azido-through using sodiumazide with end group;
Step 6: is that the PVP K120 of azido-is grafted on the urethane that the surface has the alkynyl structure through click chemistry with end group, thereby obtains the surface with PVP K120 grafted urethane.
2. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified; It is characterized in that; Said urethane raw comprises polyether(poly)urethane, PAUR, and the segmented copolymer of urethane and other polymkeric substance.
3. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the operative temperature scope in the said step 2 is from 25 ℃ to 60 ℃.
4. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the solvent in the said step 2 is ether, sherwood oil, THF, normal hexane and THF.
5. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that be from 10 minutes to 24 hours the action time in the said step 2.
6. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the temperature of reaction in the said step 3 is between 25 ℃ to 100 ℃.
7. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the solvent in the said step 3 is an ether, sherwood oil, normal hexane.
8. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the catalyzer of the polymerization method atom transition free radical polymerization reaction in the said step 4 is: triphenylphosphine ruthenous chloride, triphenylphosphine iodate rhenium dioxide, triphenylphosphine chlorination lawrencium, triphenylphosphine nickelous bromide, tri-n-butyl phosphine nickelous bromide, ferrous bromide, iron protochloride; Chlorination two (triphenylphosphine) is ferrous, cuprous bromide, cuprous chloride, bromination three (triphenylphosphine) copper, N, N, N ', N ", N " five methyl diethylentriamine; The L-SODIUM ASCORBATE, α，α′-Lian Biding, γ, γ '-dipyridyl, N, N-diisopropylethylamine, the inferior n-propyl of N--2-pyridyl methylamine; The inferior n-octyl of N--2-pyridyl methylamine, N, N, N ", N " and tetramethylethylened, 4,4 '-two (9-heptadecyls)-2,2 '-dipyridyl; 4,4 '-two (5-nonyls)-2,2 '-dipyridyl, N-(2-dimethylaminoethyl)-N, N ', N '-trimethylammonium-1,3-tn (N [2,3]); N, N-two (2-pyridylmethyl) stearylamine, 4,4 ', 4 " three (5-nonyls)-2,2 ', 6 ', 2 " terpyridyls; 2,5,9,12-tetramethyl--2,5,9, (N [2,3 for 12-four azepine tridecanes; 2]), 2,6,9,13-tetramethyl--2,6,9, (N [3 for the 13-four azepine tetradecanes; 2,3]), 1,1,4,7,10, (N [2 for 10-hexamethyl Triethylenetetramine (TETA); 2,2]), N ', N " dimethyl--N ', N " two-((2-pyridyl) methyl) ethane-1,2-diamines, three (2-(two (2-cyanoethyl)-amino) ethyl) amine, three (2-(diethylamino) ethyl) amine; Three (2-(two (2-methoxycarbonyl amino-ethyl) amino) ethyl) amine, three (2-(two (2-(n-butoxy carbonyl) ethyl) amino) ethyl) amine, three-[(2-pyridyl) methyl] amine, three (2-(methyl amido) ethyl) amine N, N, N ', N '-four-[(the 2-picolyl] ethylene diamine, 1; 4,7-trimethylammonium-1,4,7-7-triazacyclononane, 1,4,8,11-tetramethyl--1; 4,8,11-tetraazacyclododecane tetradecane, 4,11-dimethyl--1,4,8,11-4-azabicyclo [6.6.2] n-Hexadecane; Cupric sulfate pentahydrate, the L-SODIUM ASCORBATE.
9. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the initiator in the said step 4 is: 2-isobutyl ethyl bromide, 2-methyl chloropropionate, methyl chloroacetate, α-toluene bromide; 1,2,4-trichlorobenzene, 2 bromopropionic acid-2-hydroxy methacrylate, 2 bromopropionic acid-2,3-epoxidation-1-propyl ester; 2 bromopropionic acid-3-propylene ester, 2 bromopropionic acid-tert-butyl ester, α-bromo-butyrolactone, 2 bromopropionic acid-2-(4-carboxyl phenoxy) ethyl ester, 2-vinyl chloroacetate; Methylsulfonyl chloride, the trichlorine methylsulfonyl chloride, Tosyl chloride is to the anisole SULPHURYL CHLORIDE, to the fluorobenzene SULPHURYL CHLORIDE; Benzene sulfonyl chloride, to the carboxyl benzene sulfonyl chloride, 4-(N, N-dimethylamino) nitrogen benzide 4 '-SULPHURYL CHLORIDE, 2; The 5-two chloro phenylsulfonyl chloride, 2,5-dimethoxy benzene sulfonyl chloride, 3,5-two chloro-2-hydroxybenzene SULPHURYL CHLORIDEs; The 1-naphthalic sulfonic chloride, 2-naphthalic sulfonic chloride, 5-(N, N-dimethylamino)-1-naphthalic sulfonic chloride, 2-chlor(o)acetamide; Bromination 4-methyl benzyl, cyanobenzyl bromine, bromination-4-bromobenzyl, 2-bromopropionitrile, bromoacetonitrile or allyl bromide 98.
10. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the polymerization single polymerization monomer in the said step 4 is the 2-vinyl pyrrolidone.
11. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that, carries out in the atom transition free radical polymerization reaction body in the said step 4 or medium does, water, methyl alcohol; Ethanol, propyl alcohol, Virahol, acetonitrile, ETHYLE ACETATE; Ethylene carbonate, ether, methyl-phenoxide, phenyl ether; Acetone, toluene, N, dinethylformamide and methyl-sulphoxide.
12. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified; It is characterized in that; The used solvent of PVP K120 end group conversion reaction in the said step 5 is N, dinethylformamide and methyl-sulphoxide.
13. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the used temperature of PVP K120 end group conversion reaction in the said step 5 is 25 ℃ to 100 ℃.
14. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that, the Huisgen 1 in the said step 6, and catalyzer used in the 3-Dipolar Cycloaddition is: triphenylphosphine ruthenous chloride, triphenylphosphine iodate rhenium dioxide, triphenylphosphine chlorination lawrencium, triphenylphosphine nickelous bromide, tri-n-butyl phosphine nickelous bromide, ferrous bromide; Iron protochloride, chlorination two (triphenylphosphine) is ferrous, cuprous bromide, cuprous chloride, bromination three (triphenylphosphine) copper, N, N, N ', N "; N "-five methyl diethylentriamine, α，α′-Lian Biding, γ, γ '-dipyridyl, N, N-diisopropylethylamine, the inferior n-propyl of N--2-pyridyl methylamine, the inferior n-octyl of N--2-pyridyl methylamine; N, N, N ", N " and tetramethylethylened, 4,4 '-two (9-heptadecyls)-2,2 '-dipyridyl, 4; 4 '-two (5-nonyls)-2,2 '-dipyridyl, N-(2-dimethylaminoethyl)-N, N ', N '-trimethylammonium-1,3-tn (N [2,3]), N; N-two (2-pyridylmethyl) stearylamine, 4,4 ', 4 " three (5-nonyls)-2,2 ', 6 ', 2 " terpyridyl, 2; 5,9,12-tetramethyl--2,5,9,12-four azepine tridecanes (N [2,3,2]); 2,6,9,13-tetramethyl--2,6,9, (N [3,2 for the 13-four azepine tetradecanes; 3]), 1,1,4,7,10, (N [2,2 for 10-hexamethyl Triethylenetetramine (TETA); 2]), N ', N " dimethyl--N ', N " two-((2-pyridyl) methyl) ethane-1,2-diamines, three (2-(two (2-cyanoethyl)-amino) ethyl) amine, three (2-(diethylamino) ethyl) amine, three (2-(two (2-methoxycarbonyl amino-ethyl) amino) ethyl) amine; Three (2-(two (2-(n-butoxy carbonyl) ethyl) amino) ethyl) amine, three-[(2-pyridyl) methyl] amine, three (2-(methyl amido) ethyl) amine, N, N, N ', N '-four-[(the 2-picolyl] ethylene diamine, 1; 4,7-trimethylammonium-1,4,7-7-triazacyclononane, 1,4,8,11-tetramethyl--1; 4,8,11-tetraazacyclododecane tetradecane, 4,11-dimethyl--1,4,8,11-4-azabicyclo [6.6.2] n-Hexadecane; Cupric sulfate pentahydrate, the L-SODIUM ASCORBATE.
15. the preparation method of the polyurethane material that surface by utilizing PVP K120 as claimed in claim 1 is modified is characterized in that the used solvent of " click " chemical reaction in the said step 6 is a water; Methyl-sulphoxide, N, dinethylformamide; Toluene, acetonitrile.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100181526A CN101787136B (en) | 2010-01-19 | 2010-01-19 | Method for preparing polyurethane function material with surface modified by polyvinyl pyrrolidone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100181526A CN101787136B (en) | 2010-01-19 | 2010-01-19 | Method for preparing polyurethane function material with surface modified by polyvinyl pyrrolidone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101787136A CN101787136A (en) | 2010-07-28 |
| CN101787136B true CN101787136B (en) | 2012-01-25 |
Family
ID=42530522
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010100181526A Expired - Fee Related CN101787136B (en) | 2010-01-19 | 2010-01-19 | Method for preparing polyurethane function material with surface modified by polyvinyl pyrrolidone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101787136B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181050B (en) * | 2011-03-16 | 2013-09-18 | 营口天元化工研究所股份有限公司 | Azido polyether polyol and synthesis method thereof |
| CN102199234B (en) * | 2011-04-02 | 2012-12-26 | 西南科技大学 | Polyvinyl azidoacetate, preparation method, and application thereof |
| CN102863575B (en) * | 2012-10-24 | 2014-04-16 | 四川化工控股（集团）有限责任公司 | Preparation method of polyvinylpyrrolidone |
| CN103897200B (en) * | 2014-03-31 | 2016-05-11 | 东南大学 | A kind of method of preparing polyether polyols with reduced unsaturation network |
| CN104262668B (en) * | 2014-04-28 | 2017-05-17 | 华东理工大学 | Polyurethane material with protein adsorption resistance and cell adhesion resistance and preparing method thereof |
| EP3286247A4 (en) | 2015-04-24 | 2018-12-26 | The Penn State Research Foundation | Clickable waterborne polymers and click-crosslinked waterborne polymers |
| CN106902396B (en) | 2017-01-05 | 2021-01-19 | 华南理工大学 | Method for preparing antibacterial surface on surface of medical material |
| CN107540805A (en) * | 2017-09-06 | 2018-01-05 | 烟台蓝海博隆超纤新材料有限公司 | A kind of process solvent and its application |
| CN108722413B (en) * | 2018-05-15 | 2020-10-30 | 江苏理工学院 | Preparation method and application of yolk-eggshell structure graphitized carbon-coated transition metal material |
-
2010
- 2010-01-19 CN CN2010100181526A patent/CN101787136B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101787136A (en) | 2010-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101787136B (en) | Method for preparing polyurethane function material with surface modified by polyvinyl pyrrolidone | |
| JP6709780B2 (en) | Functional zwitterionic and mixed charge polymers, related hydrogels and methods of use thereof | |
| TWI313689B (en) | Manufacture method of living radical polymers and the polymers | |
| JP6868395B2 (en) | Multigraft copolymer superelastomer by emulsion polymerization | |
| TW200808842A (en) | Amphiphilic block copolymers | |
| Jing et al. | One-pot synthesis of PS-b-PEO-b-P t BA triblock copolymers via combination of SET-LRP and “click” chemistry using copper (0)/PMDETA as catalyst system | |
| CN102174163A (en) | Side chain functionalized amphiphilic polyurethane and preparation method and application thereof | |
| Yamasaki et al. | Surface mobility of polymers having phosphorylcholine groups connected with various bridging units and their protein adsorption-resistance properties | |
| CN101768278A (en) | Method for preparing functional polyurethane material with surface modified by poly(vinyl methyl ether) | |
| CN102731792B (en) | Preparation method of chitosan grafted polymer with thermosensitivity | |
| CN106750478A (en) | A kind of preparation method of high intensity dual network antibacterial biological hydrogel | |
| CN110760024B (en) | Near-infrared two-region fluorescence imaging polymer and preparation method and application thereof | |
| Jang et al. | Synthesis and properties of rotaxane-cross-linked polymers using a double-stranded γ-CD-based inclusion complex as a supramolecular cross-linker | |
| JP4992708B2 (en) | Graft copolymer and method for producing the same | |
| CN101665576A (en) | Microgel based on cyclodextrins and preparation method thereof | |
| CN102311526A (en) | Composite high-density long-tail-chain-containing bottle brush type polymer chain modified material and preparation method thereof | |
| JP7103912B2 (en) | Proton conductive membrane and fuel cell with bridging structure | |
| CN101787047B (en) | Fluorocarbon chain or/and hydrocarbon chain containing phosphatidylcholine blocking agent with hydroxyl or amino at tail end and polyurethane material for blocking same | |
| JP5656241B2 (en) | Method for modifying surface biocompatibility | |
| JP2001220415A5 (en) | ||
| ES2910984T3 (en) | New polyacrylate-polysilane block copolymers | |
| JP2013515844A5 (en) | ||
| WO2016013370A1 (en) | Antibacterial agent, sterilizing agent, antibacterial material, sterilizing material, antibacterial method, and sterilization method | |
| US6455645B1 (en) | Process for the production of telechelic polymers, telechelic polymers produced in this manner and use thereof | |
| CN108610462A (en) | Star-like amphipathic nature polyalcohol of a kind of pH responses and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120125 Termination date: 20130119 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |