CN106957397A - Anti- all leak gel rubber materials and preparation method thereof - Google Patents
Anti- all leak gel rubber materials and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 108
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000000499 gel Substances 0.000 claims abstract description 59
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000000017 hydrogel Substances 0.000 claims abstract description 53
- 239000000178 monomer Substances 0.000 claims abstract description 34
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 26
- AUNGANRZJHBGPY-UHFFFAOYSA-N D-Lyxoflavin Natural products OCC(O)C(O)C(O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-UHFFFAOYSA-N 0.000 claims abstract description 24
- AUNGANRZJHBGPY-SCRDCRAPSA-N Riboflavin Chemical compound OC[C@@H](O)[C@@H](O)[C@@H](O)CN1C=2C=C(C)C(C)=CC=2N=C2C1=NC(=O)NC2=O AUNGANRZJHBGPY-SCRDCRAPSA-N 0.000 claims abstract description 24
- 229930003471 Vitamin B2 Natural products 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 229960002477 riboflavin Drugs 0.000 claims abstract description 24
- 239000011716 vitamin B2 Substances 0.000 claims abstract description 24
- 235000019164 vitamin B2 Nutrition 0.000 claims abstract description 24
- 238000004132 cross linking Methods 0.000 claims abstract description 9
- 239000008363 phosphate buffer Substances 0.000 claims abstract description 8
- ODKSFYDXXFIFQN-BYPYZUCNSA-N L-arginine Chemical compound OC(=O)[C@@H](N)CCCN=C(N)N ODKSFYDXXFIFQN-BYPYZUCNSA-N 0.000 claims description 24
- 229930064664 L-arginine Natural products 0.000 claims description 24
- 235000014852 L-arginine Nutrition 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 23
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 17
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 17
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 150000002148 esters Chemical class 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 229920002554 vinyl polymer Polymers 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000004475 Arginine Substances 0.000 abstract description 3
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 abstract description 3
- VAYOSLLFUXYJDT-RDTXWAMCSA-N Lysergic acid diethylamide Chemical compound C1=CC(C=2[C@H](N(C)C[C@@H](C=2)C(=O)N(CC)CC)C2)=C3C2=CNC3=C1 VAYOSLLFUXYJDT-RDTXWAMCSA-N 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 13
- 229940088594 vitamin Drugs 0.000 description 9
- 229930003231 vitamin Natural products 0.000 description 9
- 235000013343 vitamin Nutrition 0.000 description 9
- 239000011782 vitamin Substances 0.000 description 9
- 150000003722 vitamin derivatives Chemical class 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000004971 Cross linker Substances 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 239000010452 phosphate Substances 0.000 description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 5
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010019280 Heart failures Diseases 0.000 description 2
- 210000000709 aorta Anatomy 0.000 description 2
- 206010002906 aortic stenosis Diseases 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 210000004204 blood vessel Anatomy 0.000 description 2
- 230000002308 calcification Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 210000003709 heart valve Anatomy 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000018102 proteins Nutrition 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 241000165940 Houjia Species 0.000 description 1
- 208000003430 Mitral Valve Prolapse Diseases 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 238000012382 advanced drug delivery Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 208000007502 anemia Diseases 0.000 description 1
- 235000009697 arginine Nutrition 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 206010014665 endocarditis Diseases 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 102000005525 fibrillarin Human genes 0.000 description 1
- 108020002231 fibrillarin Proteins 0.000 description 1
- 230000009975 flexible effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 230000001435 haemodynamic effect Effects 0.000 description 1
- 201000001505 hemoglobinuria Diseases 0.000 description 1
- 201000007119 infective endocarditis Diseases 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000005395 methacrylic acid group Chemical class 0.000 description 1
- -1 methacrylic acids Ester Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000036285 pathological change Effects 0.000 description 1
- 231100000915 pathological change Toxicity 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 230000002980 postoperative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a kind of anti-all leak gel rubber materials and preparation method thereof, and the preparation method includes step：The hydrophilic monomer and crosslinking agent that prepare hydrogel material are mixed in proportion and are dissolved in phosphate buffer, then the catalyst being made up of vitamin B2 and L arginine is added, poured into after well mixed in mould, under normal temperature, it is crosslinked under ultraviolet light, obtains hydrogel material product, then ethanol wash is used, unreacted monomer and catalyst are removed, is then dried, anti-all leak gel rubber materials are obtained.Preparation method of the present invention is reacted by using vitamin B2 and L arginine catalyst systems catalytic crosslinking, what is used is the good raw material of biocompatibility, using green syt route, have the advantages that simple to operate, cost is relatively low, universality is wide, controllability is high.Using anti-all leak gel rubber materials made from preparation method of the present invention, thickness is uniform, and pliability is good, and absorption speed is fast, with good anti-week leakage effect.
Description
Technical field
The present invention relates to field of biomedical materials, more particularly to anti-all leak gel rubber materials and preparation method thereof.
Background technology
Aortostenosis (aortic stenosis) refers to that a variety of causes causes plump aorta petal, calcification and/or leaflet, valve
Film is merged, and then causes a kind of disease of Left ventricular outflow tract obstruction.With the intensification of aging population, the hair of aortic stenosis
Sick rate is gradually increasing, and the common valvular disease for being only second to mitral valve prolapse is had become in China.In past 50 years,
Surgical operation implantable prosthetic valve is the successful therapeutic modality of comparison.However, this operation needs out chest to carry out, it is high for some
For age and the weak patient of physical qualification, this modus operandi risk is too high.At present, for such case, through conduit sustainer
Valve implantation (TAVI) is most promising technology.
It is a kind of on the basis of original diseased valve is not cut off through the implantation of conduit aorta petal, is moved by conduit through periphery
Arteries and veins or apex of the heart path feeding biovalve, the operation fixed by the anchoring device of balloon expandable and valve.First by the artificial heart
Dirty valve is compressed in a kind of conveyer, and valve is transported at heart change by conveyer by blood vessel, then discharges the artificial heart
Dirty valve makes it replace the native valve of lesion.Perivalvular leakage (PPL) is the postoperative distinctive severe complication of valve replacement, is common
One of re-treatm ent reason.Its occurrence cause mainly with the pathological change of annulus tissue, artificial valve and annulus size mismatch,
And prosthetic valve endocarditis is relevant.After perivalvular leakage occurs, following harm is often associated with：(1) perivalvular leakage causes serious molten
Blood, anaemia and hemoglobinuria progressive are aggravated；(2) the larger abnormal change for causing haemodynamics of perivalvular leakage leak, makes the heart
Even heart failure occurs for hypofunction, and symptom and sign improve unobvious after internal medicine conservative treatment；(3) though perivalvular leakage leak
It is small, but it is associated with infectious endocarditis；(4) perivalvular leakage merges targeted biology therapy.
The cardiac valves of currently commercially development has balloon to expand valve or self-expansion type valve, and heart valve prosthesis is put
Changing device generally comprises the netted support being made up of memory metal material, and the valve that can unidirectionally open being sewn in the support
Film is constituted, and is tried one's best by expansion strength and the lesion locations of support identical, although can reduce perivalvular leakage in certain limit, but because
The irregular form of blood vessel after autologous calcification, still occurs that different degrees of perivalvular leakage and periphery are backflowed.
So far, various methods are employed to carry out encapsulation process to improve the effect of anti-week leakage.US7780725B2,
US0122587A1 etc. reaches certain anti-week leakage effect using shirt rim is increased in valve end, and US7577477 is fine using injection
Fibrillarin glue is sealed, but both of which is only applicable to the situation of slight week leakage.CN105232187A,
CN103889472B reaches the effect of anti-week leakage, used ammonium persulfate (APS) by using the hydrogel component of sealing
There is the effect of Rapid gelation with tetramethylethylenediamine (TEMED) catalyst system, but responseless peroxide and
TEMED can destroy protein (W.E.Hennink, Advanced Drug Delivery Reviews, the 64th phase, 223-226
Page), while plastic speed is too fast (typically solidifying in 30 seconds), it is unfavorable for shaping.
Therefore, prior art has yet to be improved and developed.
The content of the invention
In view of above-mentioned the deficiencies in the prior art, it is an object of the invention to provide the anti-all leak gel rubber materials of one kind and its system
Preparation Method, it is intended to when solving to prepare anti-all leak gel rubber materials using existing method, unreacted peroxide and catalyst
Protein can be destroyed, while plastic excessive velocities, the problem of being unfavorable for shaping.
Realize that technical scheme is as follows：
A kind of preparation method of anti-all leak gel rubber materials, including step are provided：
The hydrophilic monomer and crosslinking agent that prepare hydrogel material are mixed in proportion and are dissolved in phosphate buffer, Ran Houjia
Enter the catalyst being made up of vitamin B2 and L-arginine, poured into after being well mixed in mould, under normal temperature, in 300~400nm ripples
It is crosslinked under long ultraviolet light, obtains hydrogel material product；
The hydrogel material product is washed with detergent, unreacted monomer and catalyst is removed, then dries
It is dry, obtain anti-all leak gel rubber materials.
The preparation method of described anti-all leak gel rubber materials, wherein, the hydrophilic monomer for preparing hydrogel material
Including one kind in acrylic acid, acrylate, methacrylic acid, methacrylate, acrylamide, NVP
Or the combination of two kinds and the above.
The preparation method of described anti-all leak gel rubber materials, wherein, the crosslinking agent includes polyethylene glycol dimethyl propylene
In olefin(e) acid ester, polyvinyl alcohol graft copolymerized methacrylate, polyacrylic acid grafted methacrylate one or two and more than
Combination.
The preparation method of described anti-all leak gel rubber materials, wherein, by mass, the parent for being easy to light initiation polymerization
Aqueous monomers and the adding proportion of crosslinking agent are (3~6)：(0.1~0.56).
The preparation method of described anti-all leak gel rubber materials, wherein, it is by mass, described by vitamin B2 and the smart ammonia of L-
In the catalyst of acid composition, vitamin B2：L-arginine=2~16：1.
The preparation method of described anti-all leak gel rubber materials, wherein, it is by mass, described by vitamin B2 and the smart ammonia of L-
In the catalyst of acid composition, vitamin B2：L-arginine=4~8：1.
The preparation method of described anti-all leak gel rubber materials, wherein, under normal temperature, enter under the ultraviolet light of 365nm wavelength
Row 1~3h of crosslinking, obtains hydrogel material product.
The preparation method of described anti-all leak gel rubber materials, wherein, by the hydrogel material product ethanol wash
The step of specifically include：Priority washs 20 every time with 50% alcohol, 75% alcohol and absolute alcohol respectively washing at least 1 time
~40min.
The preparation method of described anti-all leak gel rubber materials, wherein, the drying temperature is 30~50 DEG C.
The present invention, which also provides a kind of anti-all leak gel rubber materials, to be included being calculated as in mass ratio (3~6)：(0.1~0.56)
Hydrophilic monomer and crosslinking agent；Wherein, described hydrophilic monomer includes acrylic acid, acrylate, methacrylic acid, methyl-prop
One or more kinds of combinations in olefin(e) acid ester, acrylamide, NVP；The crosslinking agent includes poly- second two
Alcohol dimethylacrylate, polyvinyl alcohol graft copolymerized methacrylate, one kind in polyacrylic acid grafted methacrylate or
Two or more combinations.
The invention provides another anti-all leak gel rubber materials, it uses the preparation method system described in any of the above
Into.
Beneficial effect：Preparation method of the present invention is anti-by using vitamin B2 and L-arginine catalyst system catalytic crosslinking
Should, what is used is the good raw material of biocompatibility, relatively low, general with simple to operate, cost using green syt route
The advantage that adaptive is wide, controllability is high.Using anti-all leak gel rubber materials made from preparation method of the present invention, thickness is uniform,
Pliability is good, and absorption speed has good anti-week leakage effect soon.
Embodiment
The present invention provides a kind of anti-all leak gel rubber materials and preparation method thereof, to make the purpose of the present invention, technical scheme
And effect is clearer, clear and definite, the present invention is described in more detail below.It should be appreciated that specific implementation described herein
Example is not intended to limit the present invention only to explain the present invention.
There is the caltalyst of bio-toxicity with existing use ammonium persulfate (APS) and tetramethylethylenediamine (TEMED)
System compares, and the vitamin B2 and L-arginine catalyst system using green of the invention carry out ultraviolet polymerization, preparation
Anti- all leak gel sealing materials of rapid expanding in situ are obtained, with good anti-week leakage effect, blood backflow are prevented from,
Further improve surgical effect, success rate of operation is improved, so as to reduce heart failure and the mortality risk of patient.
The preparation method of the anti-all leak gel rubber materials of the present invention, including step：
S100, the hydrophilic monomer and crosslinking agent that prepare hydrogel material mixed in proportion are dissolved in phosphate buffer,
Then add the catalyst being made up of vitamin B2 and L-arginine, it is well mixed after pour into mould, under normal temperature, 300~
It is crosslinked under the ultraviolet light of 400nm wavelength, obtains hydrogel material product；The preferred 365nm of wavelength of ultraviolet light or
300nm、320nm、350nm、400nm。
S200, the hydrogel material product washed with detergent, remove unreacted monomer and catalyst, so
After dry, obtain anti-all leak gel rubber materials.Described detergent preferably ethanol or deionized water or other can be to water
Gel rubber material product is washed and removed the material of unreacted monomer and catalyst.
Preparation method of the present invention is reacted by using vitamin B2 and L-arginine catalyst system catalytic crosslinking, is used
Be the good raw material of biocompatibility, using green syt route, with simple to operate, cost is relatively low, universality is wide, can
The high advantage of control property.
Further, the hydrophilic monomer for preparing hydrogel material includes but is not limited to acrylic acid, acrylate, first
The group of one or two and the above in base acrylic acid, methacrylate, acrylamide, NVP (NVP)
Close.The above hydrophilic monomer is the hydrophilic monomer for being easy to light initiation polymerization.
Further, crosslinking agent of the present invention be many methacrylates (>2), it includes but is not limited to polyethylene glycol
Dimethylacrylate (molecular weight 500D), polyvinyl alcohol graft copolymerized methacrylate (PVA-GMA), polyacrylic acid (molecular weight 6
Ten thousand) combination of the one or two and the above in grafted methacrylic acid ester (PAA-g-GMA).
The water absorption rate of the hydrogel of the hydrophily of monomer and the type of crosslinking agent on obtaining has vital influence.Such as
Shown in table 1, table 1 is influence of the different many methacrylate cross-linkers to hydrogel performance.As it can be seen from table 1 embodiment 1
~3 use acrylic acid be monomer, polyethylene glycol dimethacrylate as crosslinking agent, than using polyvinyl alcohol graft copolymerized methyl-prop
Olefin(e) acid ester and polyacrylic acid grafted methacrylate are as crosslinking agent, and obtained hydrogel material water absorption rate is high.The He of embodiment 4
5 are handed over using hydroxyethyl methacrylate (HEMA) and NVP monomer with polyvinyl alcohol graft copolymerized methacrylate
The water absorption rate for the hydrogel material that connection agent copolymerization is obtained is less than embodiment 2, and this is mainly due to hydroxyethyl methacrylate and N-
The hydrophily of vinyl pyrrolidone is weaker than polyacrylic acid.
Influence of the different many methacrylate cross-linkers of table 1. to hydrogel performance
Further, polyvinyl alcohol graft copolymerized many methacrylates of the present invention are prepared by following methods：By the poly- second of 2g
Enol (molecular weight 80,000, all-hydrolytic) is dissolved in 150mL pure water, is added NaOH regulation pH=10.5, is then added 1mL first
Base glycidyl fat, reacts 24h at 50 DEG C, then with acetone precipitation, after vacuum drying, obtains polyvinyl alcohol graft copolymerized
Many methacrylates.The preparation method of polyacrylic acid grafted many methacrylates and polyvinyl alcohol graft copolymerized many methacrylic acids
Ester is essentially identical, the difference is that its reaction is carried out under conditions of pH=3.5.
It is preferred that, by mass, the adding proportion of the hydrophilic monomer for being easy to light initiation polymerization and crosslinking agent is (3
~6)：(0.1~0.56).For example, can be 3：0.1、4：0.3、6：0.56.
Dosage of crosslinking agent is also to influence the important factor of water absorption rate, as shown in table 2, and table 2 is difference under the conditions of embodiment 1
Dosage of crosslinking agent to hydrogel water absorption rate influence (wherein water absorption rate be 30min after measure).From Table 2, it can be seen that with
The increase of dosage of crosslinking agent, water absorption rate is gradually reduced.To obtain aquagel with high water absorbing capacity, the dosage of crosslinking agent that uses of the present invention for
0.1~0.56g.
Influence of the different dosage of crosslinking agent to hydrogel water absorption rate under the conditions of the embodiment 1 of table 2.
It is preferred that, in the step S100, the hydrophilic monomer and crosslinking agent that prepare hydrogel material are mixed in proportion
After being dissolved in phosphate buffer, first add NaOH solution and adjust pH value to neutrality, then add by vitamin B2 and L-arginine
The catalyst of composition.The efficiency of cross-linking reaction can be improved by adding NaOH solution regulation pH value to neutrality, help to obtain flexible
Property, the more preferable anti-all leak gel rubber materials of the performance parameter such as water absorption rate.
It is preferred that, by mass, in the catalyst being made up of vitamin B2 and L-arginine, vitamin B2：L- essences
Propylhomoserin=2~16：1.For example, can be 2：1、10：1、16：1.
It is furthermore preferred that by mass, in the catalyst being made up of vitamin B2 and L-arginine, vitamin B2：L-
Arginine=4~8：1.For example, can be 4：1、6：1、8：1.
Vitamin B2 and L-arginine joint group share to generate initiation spike, therefore both ratios are for efficiency of initiation
There is very big influence, work as L-arginine：Vitamin B2 is 2 in ratio:1~16:When 1, monomer conversion is higher than 80%.
Further, in the step S100, the phosphate buffer (phosphate buffer, PBS) is pH7.4 phosphoric acid
Salt buffer solution.
Further, in the step S100, under normal temperature, 1~3h of crosslinking is carried out under the ultraviolet light of 365nm wavelength, is obtained
To hydrogel material product.
In the present invention, still there is unreacted monomer in the hydrogel of UV-crosslinked preparation, because the monomers such as acrylic acid are molten
In water and ethanol, so being washed using ethanol solution, unreacted monomer is removed.
Further, specifically included in the step S200, the step of by the hydrogel material product with ethanol wash：
Priority washs 20~40min every time with 50% alcohol, 75% alcohol and absolute alcohol respectively washing at least 1 time.For example, with
50% alcohol, 75% alcohol and absolute alcohol are washed 1 time respectively, and 30min is washed every time.
Further, in the step S200, the drying temperature is 30~50 DEG C.For example, can for 30 DEG C, 40 DEG C,
50℃。
Based on made as described above method, the present invention also provides a kind of anti-all leak gel rubber materials, and it uses the above
Preparation method be made.Using anti-all leak gel rubber materials made from preparation method of the present invention, thickness is uniform, and pliability is good
Good, absorption speed is fast, or even can reach Quick Extended in situ to original 40 times of volume, with good anti-week leakage effect.
Species and consumption of the invention by adjusting catalyst system ratio and crosslinking agent, obtains different crosslinkings and water suction
The hydrogel of rate.
It should be noted that the chemical reagent in the present invention is unless specified or limited otherwise analyzes pure.
The present invention determines reaction conversion ratio using infrared spectrum, and suitable hydrogel membrane material is screened by water absorption rate measure
Material.
The dried thickness of hydrogel material prepared by the present invention is less than 300 μm (micron), and resulting materials are more uniform, soft
Toughness is good, and absorption speed is fast.The present invention is green syt route, and what is used is the good raw material of biocompatibility, tool
There is simple to operate, cost relatively low, universality is wide, the high advantage of controllability.
The present invention uses gravimetric detemination hydrogel water absorption rate, weighs the hydrogel (W after dryingdry), then material is put
In culture dish, deionized water is added, after 10min and 30min is swelled, takes out and weighs hydrogel weight (Wwet), computing formula
It is as follows：
Water absorption rate (100%)=(Wwet-Wdry)/Wdry。
The present invention is elaborated with specific embodiment below：
Embodiment 1
(1) 3.5g acrylic acid and 0.14g polyethylene glycol dimethacrylates, are dissolved in 20mL phosphate buffer solutions
(pH7.4) in, add NaOH solution and adjust pH value to neutrality, add 50mg vitamin B2s and 400mg L-arginine, mixing is equal
Poured into after even in mould, react 3h in the UV-crosslinked instrument of 365nm wavelength, obtain hydrogel material product；
(2), the hydrogel material product for obtaining step (1) washs 3 respectively with 50%, 75% and absolute alcohol respectively
Secondary, each 30min removes unreacted monomer, and then 40 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 10~15 times, and 30min is
40~60 times, and thickness is uniform, pliability is good.
Embodiment 2
(1) the polyvinyl alcohol graft copolymerized many methacrylate cross-linkers of 3.2g acrylic acid and 0.2g, are added into 20mL phosphate
(pH7.4) in, add NaOH solution and adjust pH value to neutrality, add 50mg vitamin B2s and 400mg L-arginine, mixing is equal
Poured into after even in mould, react 2h in the UV-crosslinked instrument of 365nm wavelength, obtain hydrogel material product；
(2), the hydrogel material product for obtaining step (1) washs 3 times with 50%, 75% and absolute alcohol respectively, often
Secondary 30min, removes unreacted monomer, and then 40 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 10~15 times, and 30min is
30~40 times, and thickness is uniform, pliability is good.
Embodiment 3
(1) the polyacrylic acid grafted many methacrylate cross-linkers of 3g acrylic acid and 0.2g, are added into 20mL phosphate
(pH7.4) in, add NaOH solution and adjust pH value to neutrality, add 50mg vitamin B2s and 400mg L-arginine, mixing is equal
Poured into after even in mould, react 2h in the UV-crosslinked instrument of 365nm wavelength, obtain hydrogel material product；
(2), the hydrogel material product for obtaining step (1) washs 1 respectively with 50%, 75% and absolute alcohol respectively
It is secondary, each 40min, then 40 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 10~15 times, and 30min is
30~40 times, and thickness is uniform, pliability is good.
Embodiment 4
(1), the polyvinyl alcohol graft copolymerized many methacrylate cross-linkers of 5.8g hydroxyethyl methacrylates and 0.25g are added
In 20mL phosphate (pH7.4), add NaOH solution and adjust pH value to neutrality, add 50mg vitamin B2s and 400mg L- essences
Propylhomoserin, pours into mould after being well mixed, reacts 2h in the UV-crosslinked instrument of 365nm wavelength, obtain hydrogel material product；
(2), the hydrogel material product for obtaining step (1) washs 1 respectively with 50%, 75% and absolute alcohol respectively
Secondary, then 40 DEG C of drying, obtain hydrogel material product.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 10~15 times, and 30min is
20~30 times, and thickness is uniform, pliability is good.
Embodiment 5
(1), 5g NVPs and the polyvinyl alcohol graft copolymerized many methacrylate cross-linkers of 0.25g are added
In 20mLPBS (pH7.4), add NaOH solution and adjust pH value to neutrality, add the smart ammonia of the L- of 50mg vitamin B2s and 400mg
Acid, pours into mould after being well mixed, reacts 3h in the UV-crosslinked instrument of 320nm wavelength, obtain hydrogel material product；
(2), the hydrogel material product for obtaining step (1) washs 1 respectively with 50%, 75% and absolute alcohol respectively
Secondary, then 30 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 10~15 times, and 30min is
20~30 times, and thickness is uniform, pliability is good.
Embodiment 6
(1), 6g NVPs and the polyvinyl alcohol graft copolymerized many methacrylate cross-linkers of 0.56g are added
In 20mLPBS (pH7.4), add NaOH solution and adjust pH value to neutrality, add the smart ammonia of the L- of 50mg vitamin B2s and 100mg
Acid, pours into mould after being well mixed, reacts 1h in the UV-crosslinked instrument of 365nm wavelength, obtain hydrogel material product；
(2), the hydrogel material product for obtaining step (1) washs 1 respectively with 50%, 75% and absolute alcohol respectively
It is secondary, each 20min, then 50 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 5~10 times, and 30min is 10
~20 times, and thickness is uniform, pliability is good.
Embodiment 7
(1), by 3.2g acrylic acid and the polyvinyl alcohol graft copolymerized many methacrylic acids of 2.6g hydroxyethyl methacrylates and 0.2g
Ester crosslinking agent is added in 20mL phosphate (pH7.4), is added NaOH solution and is adjusted pH value to neutrality, add 50mg vitamin B2s and
400mg L-arginine, pours into mould after being well mixed, reacts 2h in the UV-crosslinked instrument of 400nm wavelength, obtain water-setting
Glue material product；
(2), the hydrogel material product for obtaining step (1) is respectively with 75% ethanol wash 3 times, and each 30min is removed
Unreacted monomer, then 40 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 10~15 times, and 30min is
30~40 times, and thickness is uniform, pliability is good.
Embodiment 8
(1), by the polyvinyl alcohol graft copolymerized many poly- second of methacrylate and 0.1g of 5.8g NVPs and 0.1g
Diol dimethacrylate crosslinking agent is added in 20mL phosphate (pH7.4), is added NaOH solution and is adjusted pH value to neutrality, plus
Enter 50mg vitamin B2s and 400mg L-arginine, poured into after being well mixed in mould, in the UV-crosslinked instrument of 400nm wavelength
Middle reaction 2h, obtains hydrogel material product；
(2), the hydrogel material product for obtaining step (1) is washed with deionized 5 times, each 30min, removes not anti-
Monomer is answered, then 40 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 10~15 times, and 30min is
30~40 times, and thickness is uniform, pliability is good.
Embodiment 9
(1), by 3g acrylic acid, 2g NVPs and 1g acrylamides and 0.1g polyethylene glycol dimethyl propylenes
The polyvinyl alcohol graft copolymerized methacrylate cross-linker of olefin(e) acid ester, 0.1g is added in 20mL phosphate (pH7.4), adds NaOH solution
PH value is adjusted to neutrality, 50mg vitamin B2s and 400mg L-arginine is added, is poured into after being well mixed in mould, in 350nm
2h is reacted in the UV-crosslinked instrument of wavelength, hydrogel material product is obtained；
(2), the hydrogel material product for obtaining step (1) is respectively with 75% ethanol wash 3 times, and each 30min is removed
Unreacted monomer, then 40 DEG C of drying, obtain anti-all leak gel rubber materials.
Anti- all leak gel rubber materials manufactured in the present embodiment are translucent, and 10min water absorption rates are 5~10 times, and 30min is 10
~20 times, and thickness is uniform, pliability is good.
In summary, anti-all leak gel rubber materials provided in an embodiment of the present invention and preparation method thereof, the preparation method
Reacted by using vitamin B2 and L-arginine catalyst system catalytic crosslinking, used to be biocompatibility good
Raw material, relatively low with simple to operate, cost using green syt route, universality is wide, the high advantage of controllability.Using this hair
Anti- all leak gel rubber materials made from the bright preparation method, thickness is uniform, and pliability is good, and absorption speed is fast, with good
It is anti-week leakage effect.
It should be appreciated that the application of the present invention is not limited to above-mentioned citing, for those of ordinary skills, can
To be improved or converted according to the above description, all these modifications and variations should all belong to the guarantor of appended claims of the present invention
Protect scope.
Claims (11)
1. a kind of preparation method of anti-all leak gel rubber materials, it is characterised in that including step：
The hydrophilic monomer and crosslinking agent that prepare hydrogel material are mixed in proportion and are dissolved in phosphate buffer, then add by
The catalyst of vitamin B2 and L-arginine composition, is poured into mould after being well mixed, under normal temperature, in 300~400nm wavelength
It is crosslinked under ultraviolet light, obtains hydrogel material product；
The hydrogel material product is washed with detergent, unreacted monomer and catalyst is removed, then dries, obtain
To anti-all leak gel rubber materials.
2. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that described to prepare hydrogel
The hydrophilic monomer of material includes acrylic acid, acrylate, methacrylic acid, methacrylate, acrylamide, N- vinyl
The combination of one or two and the above in pyrrolidones.
3. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that the crosslinking agent includes
In polyethylene glycol dimethacrylate, polyvinyl alcohol graft copolymerized methacrylate, polyacrylic acid grafted methacrylate
The combination of the one or two kinds of and above.
4. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that by mass, described
The adding proportion of the hydrophilic monomer and crosslinking agent that are easy to light initiation polymerization is (3~6)：(0.1~0.56).
5. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that by mass, described
In the catalyst be made up of vitamin B2 and L-arginine, vitamin B2：L-arginine=2~16：1.
6. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that by mass, described
In the catalyst be made up of vitamin B2 and L-arginine, vitamin B2：L-arginine=4~8：1.
7. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that under normal temperature, in 365nm
1~3h of crosslinking is carried out under the ultraviolet light of wavelength, hydrogel material product is obtained.
8. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that by the water-setting glue material
Expect that the step of product is with ethanol wash is specifically included：Successively use 50% alcohol, 75% alcohol and absolute alcohol are respectively washed extremely
It is few 1 time, 20~40min is washed every time.
9. the preparation method of anti-all leak gel rubber materials according to claim 1, it is characterised in that the drying temperature is
30~50 DEG C.
10. a kind of anti-all leak gel rubber materials, it is characterised in that including being calculated as in mass ratio (3~6)：The parent of (0.1~0.56)
Aqueous monomers and crosslinking agent；Wherein, described hydrophilic monomer includes acrylic acid, acrylate, methacrylic acid, metering system
The combination of one or two and the above in acid esters, acrylamide, NVP；The crosslinking agent includes poly- second two
Alcohol dimethylacrylate, polyvinyl alcohol graft copolymerized methacrylate, one kind in polyacrylic acid grafted methacrylate or
Two kinds and the combination of the above.
11. a kind of anti-all leak gel rubber materials, it is characterised in that using the preparation method as described in any one of claim 1~9
It is made.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111157603A (en) * | 2019-12-23 | 2020-05-15 | 杭州师范大学 | Quick-setting leakage-proof method for small amount of separation gel in plate making by polyacrylamide gel |
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| CN102325814A (en) * | 2009-01-14 | 2012-01-18 | 康奈尔大学 | Be used for the preparation of the biodegradable hydrogel of biomedical applications |
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| WO2006062573A1 (en) * | 2004-12-03 | 2006-06-15 | 3M Innovative Properties Company | Process for making pressure sensitive adhesive hydrogels |
| CN102325814A (en) * | 2009-01-14 | 2012-01-18 | 康奈尔大学 | Be used for the preparation of the biodegradable hydrogel of biomedical applications |
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