CN107383290B - A kind of polyacrylate grafting modified gelatin-adhesive and preparation method thereof - Google Patents
A kind of polyacrylate grafting modified gelatin-adhesive and preparation method thereof Download PDFInfo
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- CN107383290B CN107383290B CN201710676932.1A CN201710676932A CN107383290B CN 107383290 B CN107383290 B CN 107383290B CN 201710676932 A CN201710676932 A CN 201710676932A CN 107383290 B CN107383290 B CN 107383290B
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- 239000000853 adhesive Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 24
- 108010010803 Gelatin Proteins 0.000 claims abstract description 53
- 229920000159 gelatin Polymers 0.000 claims abstract description 53
- 239000008273 gelatin Substances 0.000 claims abstract description 53
- 235000019322 gelatine Nutrition 0.000 claims abstract description 53
- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 53
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 230000001070 adhesive effect Effects 0.000 claims abstract description 27
- 238000004026 adhesive bonding Methods 0.000 claims abstract description 19
- 238000004090 dissolution Methods 0.000 claims abstract description 15
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920000858 Cyclodextrin Polymers 0.000 claims abstract description 13
- 229930006711 bornane-2,3-dione Natural products 0.000 claims abstract description 13
- 239000001116 FEMA 4028 Substances 0.000 claims abstract description 12
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 claims abstract description 12
- 235000011175 beta-cyclodextrine Nutrition 0.000 claims abstract description 12
- 229960004853 betadex Drugs 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- 238000005286 illumination Methods 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000005138 cryopreservation Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- ARJOQCYCJMAIFR-UHFFFAOYSA-N prop-2-enoyl prop-2-enoate Chemical compound C=CC(=O)OC(=O)C=C ARJOQCYCJMAIFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000008213 purified water Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 6
- 239000000017 hydrogel Substances 0.000 abstract description 5
- 229920003169 water-soluble polymer Polymers 0.000 abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 206010052428 Wound Diseases 0.000 abstract description 3
- 208000002565 Open Fractures Diseases 0.000 abstract description 2
- 230000001154 acute effect Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000023597 hemostasis Effects 0.000 abstract description 2
- 238000007711 solidification Methods 0.000 abstract description 2
- 230000008023 solidification Effects 0.000 abstract description 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- -1 hydroxyl radicals Chemical class 0.000 description 14
- 239000002253 acid Substances 0.000 description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- OZFAFGSSMRRTDW-UHFFFAOYSA-N (2,4-dichlorophenyl) benzenesulfonate Chemical compound ClC1=CC(Cl)=CC=C1OS(=O)(=O)C1=CC=CC=C1 OZFAFGSSMRRTDW-UHFFFAOYSA-N 0.000 description 7
- 239000012591 Dulbecco’s Phosphate Buffered Saline Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000007853 buffer solution Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229940044192 2-hydroxyethyl methacrylate Drugs 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229920002472 Starch Polymers 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- DCUFMVPCXCSVNP-UHFFFAOYSA-N methacrylic anhydride Chemical compound CC(=C)C(=O)OC(=O)C(C)=C DCUFMVPCXCSVNP-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- NHJVRSWLHSJWIN-UHFFFAOYSA-N 2,4,6-trinitrobenzenesulfonic acid Chemical compound OS(=O)(=O)C1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O NHJVRSWLHSJWIN-UHFFFAOYSA-N 0.000 description 1
- GJKGAPPUXSSCFI-UHFFFAOYSA-N 2-Hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone Chemical compound CC(C)(O)C(=O)C1=CC=C(OCCO)C=C1 GJKGAPPUXSSCFI-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 102000009123 Fibrin Human genes 0.000 description 1
- 108010073385 Fibrin Proteins 0.000 description 1
- BWGVNKXGVNDBDI-UHFFFAOYSA-N Fibrin monomer Chemical compound CNC(=O)CNC(=O)CN BWGVNKXGVNDBDI-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000227 bioadhesive Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 210000000845 cartilage Anatomy 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 1
- 229950003499 fibrin Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- VUVZASHBYYMLRC-UHFFFAOYSA-N heptane-2,3-diol Chemical compound CCCCC(O)C(C)O VUVZASHBYYMLRC-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/001—Use of materials characterised by their function or physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/06—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L24/00—Surgical adhesives or cements; Adhesives for colostomy devices
- A61L24/04—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials
- A61L24/10—Polypeptides; Proteins
- A61L24/104—Gelatin
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Materials For Medical Uses (AREA)
- Medicinal Preparation (AREA)
Abstract
The present invention relates to a kind of polyacrylate grafting modified gelatin-adhesives and preparation method thereof, the embedded object of ultrasonic dissolution formation is blended as photoinitiator with camphorquinone using the water soluble polymer for including beta-cyclodextrin, more reactive hydroxyl radicals are provided using glycerol for medium, by acrylic modified grafted gelatin, acrylate monomer and crosslinking agent polyethylene glycol double methyl methacrylate, in 1200~2000mw/cm of wavelength 420~480nm light intensity2Promote gluing to form hydrogel under blue light illumination and coheres effect to reach solidification.Adhesive provided by the invention have photopolymerization it is high-efficient, adhesive property is good, it is nontoxic to the human body the features such as, can be widely used in various acute open wounds closing hemostasis, operative incision or cavity cohere closing, fixation is cohered in the reply of non-open fracture.
Description
Technical field
The invention belongs to medical adhesive preparation technical fields, are related to a kind of polyacrylate grafting modified gelatin-gluing
Agent and preparation method thereof.
Background technique
Gelatin hydrogel is a kind of with good biocompatibility, degradable biological material, has been widely used as such as glue
The medicinal and bio-medical material of softgel shell etc., but its aqueous solution melt temperature is low, it is liquid that 35 DEG C, which just melt, and its state of congealing
The disadvantages of Young's modulus of elasticity is smaller, not shock resistance, poor toughness hinders gelatin in the utilization of field of medical materials.With cyano
This kind of " Instant adhesive " based on propionic ester is although curing time is very short, and brittleness is big, and biological degradability is poor, even
It is possible that influencing the life security of user because of the generation of toxic degradation object.Accordingly, it is considered to adhesive strength, solidfied material suppleness
Etc. factors and to greatest extent reduce toxicity be such adhesive improvement direction.
A kind of novel photo-sensitive hydrogel material-methacrylic acid anhydridization gelatin developed in recent years is above-mentioned because effectively combining
The advantages of two kinds of materials, has obtained very big concern.And in the prior art, to Water-soluble methyls third such as methacrylic acid anhydridization gelatin
The gluing of olefin(e) acid esters monomer polymerize, and mostly uses BASF photoinitiator (Irgacure 2959) as photoinitiator greatly, utilizes
The ultraviolet light of wavelength 365nm.The gluing time of this method is long, aggregate rate is low, and ultraviolet light is larger to human body cell injury, no
Preferably it is used as clinical medical treatment to use.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is: utilize the water soluble polymer and camphorquinone of beta-cyclodextrin
The embedded object of formation provides more reactive hydroxyl radicals as a kind of novel photoinitiator, using glycerol for medium, visible
Acrylate monomer gluing is promoted to polymerize under light irradiation.The adhesive has efficiency of initiation high, and polymerization time is short, and adhesive property is good
Good, the harmless feature of gluing polymerizing condition can operate with the closing hemostasis of various acute open wounds, operative incision or
Closing is cohered in cavity, and fixation is cohered in the reply of non-open fracture.
Technical solution of the present invention includes:
A kind of polyacrylate grafting modified gelatin-adhesive, the preparation of adhesive the following steps are included:
(1) preparation of methacrylic acid anhydridization gelatin: gelatin mixes shape according to 1g:10~15ml with the first buffer solution
At the first mixed solution, stirs the first mixed solution to gelatin and be completely dissolved；Take the methyl for being 0.08~0.2 with gelatin molar ratio
Mixed liquor is added in acrylic anhydride, is warming up to 35~50 DEG C, after 2~6h of isothermal reaction, forms the second mixed solution；To the second mixing
The the second buffer solution formation third mixed liquor for being equivalent to 1~4 times of the first buffer solution amount is added in solution；Third is mixed again
Freezen protective obtains methacrylic acid anhydridization gelatin after liquid dialysis, freeze-drying；
(2) polyacrylate grafting modified gelatin-adhesive preparation: by include beta-cyclodextrin water soluble polymer,
Camphorquinone and water ultrasonic dissolution formation embedded object after being mixed according to 2~3g:1~2g:5~10ml；Embedded object is dried under reduced pressure again
After grind, photoinitiator is made；By methacrylic acid anhydridization gelatin, polyethylene glycol methacrylate, acrylate list
Body and water are mixed according to 3~5g:0.5~1g:1~3ml:3~5ml, and constant temperature is prepared under the conditions of 30~50 DEG C and obtains gluing
Agent；It after photoinitiator is mixed with glycerol, then mixes with adhesive, with 1200~2000mw/cm of wavelength 420~480nm light intensity2
Blue light illumination promotes gluing to form hydrogel and coheres effect to reach solidification.
Further, in preferred embodiments of the present invention, (1) first buffer solution of step is PBS solution, DPBS is molten
Liquid or CB solution.
Further, in preferred embodiments of the present invention, (1) second buffer solution of step is PBS solution, DPBS is molten
Liquid or CB solution.
Further, in preferred embodiments of the present invention, the temperature of the freezen protective of third mixed liquor in step (1)
It is -20~-40 DEG C.
Further, in preferred embodiments of the present invention, step (2) water soluble polymer is β-cyclodextrin or β-
What one of cyclodextrin and starch, chitosan, carboxymethyl cellulose, hydroxypropyl cellulose or hydroxypropyl methyl cellulose were formed
Mixture.
Further, in preferred embodiments of the present invention, a kind of polyacrylate grafting modified gelatin-adhesive and
Preparation method, it is characterised in that: the supersonic frequency in step (2) is 40~120kHz.
Further, in preferred embodiments of the present invention, step (2) acrylic ester monomer is acrylic acid, methyl-prop
Olefin(e) acid, hydroxy-ethyl acrylate, hydroxypropyl acrylate, 4- hydroxybutyl acrylate or 2-hydroxyethyl methacry-late.
Further, in preferred embodiments of the present invention, step (2) photoinitiator and glycerol are according to 0.1~0.5g:
10~20ml mixing.
A kind of polyacrylate that the preparation method such as above-mentioned polyacrylate grafting modified gelatin-adhesive is prepared
Graft modification gelatin-adhesive.
The beneficial effects of the present invention are: the beta-cyclodextrin in photoinitiator has the special ring-type of external hydrophilic inner hydrophobic
Structure, making it with camphorquinone, ultrasonic dissolution forms embedded object in aqueous solution, so that it is not soluble in water to compensate for camphorquinone, Bu Neng
The defect of gluing water-soluble acrylic ester class monomer is catalyzed under the conditions of water system.Meanwhile it being dissolved in glycerol using gelatin, and glycerol provides
Great amount of hydroxy group free radical can be improved photopolymerization efficiency, shorten the time that gluing solidifies polyacrylate grafting modified gelatin.This
Inventive method is simple to operation, and at low cost and efficiency of initiation is high, and curing time is short, and keeps gluing polymerizing condition harmless just
In the extensive utilization of medical field.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Embodiment 1
A kind of preparation method of polyacrylate grafting modified gelatin-adhesive, comprising the following steps:
(1) preparation of methacrylic acid anhydridization gelatin: gelatin is mixed to form first according to 1g:10ml with PBS solution and mixes
First mixed solution is stirred dissolution 1h by solution under the conditions of 100r/min；Then taking with gelatin molar ratio is 0.08
Mixed liquor is added in methacrylic anhydride, is warming up to 50 DEG C, forms the second mixed solution after isothermal reaction 3h, molten to the second mixing
It is added in liquid and forms third mixed solution with the DPBS solution of PBS solution equivalent, third mixed solution is transferred to Spectro/
Por molecular porous type tubulose, MWCO12-14000 film strips are dialysed 5 days, after replacing a purified water daily, after freeze-drying ,-
20 DEG C of freezen protectives；
(2) polyacrylate grafting modified gelatin-adhesive preparation: by beta-cyclodextrin, camphorquinone and water according to 2g:
The ratio of 1g:5ml mixes, and forms embedded object in 200r/min stirring, 40kHz ultrasound dissolution；Embedded object is depressurized at 40 DEG C again
Vacuum drying, it is stand-by to grind rear cryo-conservation；Then embedded object and glycerol are mixed to prepare according to 0.5g:10ml light-initiated
Agent；Again by methacrylated gelatin, polyethylene glycol double methyl methacrylate, 2-hydroxyethyl methacry-late and water according to
5g:1g:1ml:5ml mixing, constant temperature stir preparation under the conditions of 40 DEG C and obtain adhesive；Then adhesive and photoinitiator are mixed
After closing uniformly, rubber gun mixing tube is added；The mixture in mixing tube is coated on again and needs to use wavelength on the object being bonded
420nm light intensity 1200mw/cm2Blue light illumination makes the polymerization of its gluing achieve the purpose that bonding.
Embodiment 2
A kind of preparation method of polyacrylate grafting modified gelatin-adhesive, comprising the following steps:
(1) preparation of methacrylic acid anhydridization gelatin: gelatin is mixed to form first according to 1g:13ml with PBS solution and mixes
First mixed solution is stirred dissolution 2h by solution under the conditions of 150r/min；Then the first for being 0.1 with gelatin molar ratio is taken
Mixed liquor is added in base acrylic anhydride, is warming up to 50 DEG C, forms the second mixed solution after isothermal reaction 3h, into the second mixed solution
It is added and forms third mixed solution with the PBS solution of 4 times of PBS solution amounts, third mixed solution is transferred to Spectro/Por points
Sub- porous type tubulose, MWCO12-14000 film strips are dialysed 5 days, and after replacing a purified water daily, after freeze-drying, -20 DEG C cold
Freeze and saves；
(2) polyacrylate grafting modified gelatin-adhesive preparation: by starch, beta-cyclodextrin, camphorquinone and water according to
The ratio of 1g:1g:1g:5ml mixes, and forms embedded object in 250r/min stirring, 60kHz ultrasound dissolution；Again by embedded object 40
DEG C reduced vacuum is dry, and it is stand-by to grind rear cryo-conservation；Then embedded object and glycerol are mixed to prepare according to 0.5g:12ml
Photoinitiator；Again by methacrylated gelatin, polyethylene glycol double methyl methacrylate, methacrylic acid and water according to 3g:
1g:1ml:4ml mixing, constant temperature stir preparation under the conditions of 40 DEG C and obtain adhesive；Then adhesive is mixed with photoinitiator
After uniformly, rubber gun mixing tube is added；The mixture in mixing tube is coated on again on the object for needing to be bonded with wavelength 420nm
Light intensity 1200mw/cm2Blue light illumination makes the polymerization of its gluing achieve the purpose that bonding.
Embodiment 3
A kind of preparation method of polyacrylate grafting modified gelatin-adhesive, comprising the following steps:
(1) preparation of methacrylic acid anhydridization gelatin: gelatin and CB solution according to 1g:10ml be mixed to form first mix it is molten
First mixed solution is stirred dissolution 4h by liquid under the conditions of 150r/min；Then the first for being 0.12 with gelatin molar ratio is taken
Mixed liquor is added in base acrylic anhydride, is warming up to 50 DEG C, forms the second mixed solution after isothermal reaction 3h, into the second mixed solution
The PBS solution that 4 times of CB solution amounts are added forms third mixed solution, and third mixed solution is transferred to Spectro/Por molecule
Porous type tubulose, MWCO12-14000 film strips are dialysed 6 days, and after replacing a purified water daily, after freeze-drying, -20 DEG C cold
Freeze and saves；
(2) polyacrylate grafting modified gelatin-adhesive preparation: chitosan, beta-cyclodextrin, camphorquinone and water are pressed
According to the ratio mixing of 0.5g:1g:1.5g:5ml, embedded object is formed in 200r/min stirring, 80kHz ultrasound dissolution；It again will embedding
Object is dry in 30 DEG C of reduced vacuums, and it is stand-by to grind rear cryo-conservation；Then embedded object and glycerol are mixed according to 0.5g:10ml
It closes and photoinitiator is made；Again by methacrylated gelatin, polyethylene glycol double methyl methacrylate, acrylic acid and water according to
4g:0.8g:1.5ml:5ml mixing, constant temperature stir preparation under the conditions of 40 DEG C and obtain adhesive；Then by adhesive with it is light-initiated
After mixing, rubber gun mixing tube is added in agent；The mixture in mixing tube is coated on again and needs to use wave on the object being bonded
Long 420nm light intensity 1200mw/cm2Blue light illumination makes the polymerization of its gluing achieve the purpose that bonding.
Embodiment 4
A kind of preparation method of polyacrylate grafting modified gelatin-adhesive, comprising the following steps:
(1) preparation of methacrylic acid anhydridization gelatin: gelatin and CB solution according to 1g:10ml be mixed to form first mix it is molten
First mixed solution is stirred dissolution 1h by liquid under the conditions of 100r/min；Then the first for being 0.16 with gelatin molar ratio is taken
Mixed liquor is added in base acrylic anhydride, is warming up to 50 DEG C, forms the second mixed solution after isothermal reaction 3h, into the second mixed solution
The DPBS solution that 4 times of CB solution amounts are added forms third mixed solution, and third mixed solution is transferred to Spectro/Por molecule
Porous type tubulose, MWCO12-14000 film strips are dialysed 5 days, and after replacing a purified water daily, after freeze-drying, -20 DEG C cold
Freeze and saves；
(2) polyacrylate grafting modified gelatin-adhesive preparation: by carboxymethyl cellulose, beta-cyclodextrin, camphorquinone
It is mixed with water according to the ratio of 1g:2g:1g:5ml, forms embedded object in 200r/min stirring, 40kHz ultrasound dissolution；It again will packet
It is dry in 40 DEG C of reduced vacuums to bury object, it is stand-by to grind rear cryo-conservation；Then by embedded object and glycerol according to 0.3g:10ml
It is mixed to prepare photoinitiator；Again by methacrylated gelatin, polyethylene glycol double methyl methacrylate, hydroxypropyl acrylate and
Water is mixed according to 5g:1g:3ml:5ml, and constant temperature stirs preparation under the conditions of 40 DEG C and obtains adhesive；Then adhesive and light are drawn
It sends out agent after mixing, rubber gun mixing tube is added；The mixture in mixing tube is coated on again and needs to use on the object being bonded
Wavelength 480nm light intensity 1800mw/cm2Blue light illumination makes the polymerization of its gluing achieve the purpose that bonding.
Embodiment 5
A kind of preparation method of polyacrylate grafting modified gelatin-adhesive, comprising the following steps:
(1) preparation of methacrylic acid anhydridization gelatin: gelatin is mixed to form first according to 1g:15ml with DPBS solution and mixes
First mixed solution is stirred dissolution 5h by solution under the conditions of 100r/min；Then the first for being 0.2 with gelatin molar ratio is taken
Mixed liquor is added in base acrylic anhydride, is warming up to 35 DEG C, forms the second mixed solution after isothermal reaction 6h, to the second mixed solution
The middle DPBS solution that 4 times of DPBS solution amounts are added forms third mixed solution, and third mixed solution is transferred to Spectro/Por
Molecular porous type tubulose, MWCO12-14000 film strips are dialysed 5 days, after replacing a purified water daily, after freeze-drying, and -20
DEG C freezen protective；
(2) polyacrylate grafting modified gelatin-adhesive preparation: by hydroxypropyl methyl cellulose, β-cyclodextrin,
Camphorquinone and water are mixed according to the ratio of 1g:1g:2g:10ml, form embedding in 200r/min stirring, 120kHz ultrasound dissolution
Object；It is again that embedded object is dry in 50 DEG C of reduced vacuums, it is stand-by to grind rear cryo-conservation；Then by embedded object and glycerol according to
0.1g:10ml is mixed to prepare photoinitiator；Again by methacrylated gelatin, polyethylene glycol double methyl methacrylate, 4- hydroxyl
Base butyl propyleneglycol acid esters and water are mixed according to 3g:0.5g:1ml:3ml, and constant temperature stirs preparation under the conditions of 40 DEG C and obtains gluing
Agent；Then after mixing by adhesive and photoinitiator, rubber gun mixing tube is added；The mixture in mixing tube is coated with again
With wavelength 420nm light intensity 1600mw/cm on the object for needing to be bonded2Blue light illumination makes its gluing polymerize the mesh for reaching bonding
's.
Experimental example 1
Experimental subjects: (Xu Jielong changes the methyl olefin(e) acid anhydridization gelatin and existing literature for taking equivalent embodiment 1-5 to provide
Property gelatin/polyacrylamide composite hydrogel and its for cartilage defect repair research [D] China: Southwest Jiaotong University,
2016.) the methyl olefin(e) acid anhydridization gelatin being prepared in, is set as experimental group 1-6；
Experimental procedure: the test method of the degree of substitution of the sample of experimental group 1-6 is as follows；
The sample of experimental group 1-6 is separately added into 0.1M sodium bicarbonate buffer liquid (pH=8.5) and forms the molten of 1.6mg/ml
Liquid；The 0.01%2,4,6- trinitrobenzene sulfonic acid solution of 6 groups of 0.5ml is taken to be added in the above-mentioned 6 groups of solution of 0.5ml respectively；Mixing
After uniformly, the container for containing solution is wrapped up with masking foil, influence of the illumination to reaction is avoided, reacts 2h at 37 DEG C；Xiang Shi
Testing in group 1-6 and the mass concentration of 0.5ml is added is the 1mol/L hydrochloric acid of 10% lauryl sodium sulfate and 0.25ml, and it is anti-to terminate it
It answers, then measures its absorbance in 340nm；According to the linear relationship that the glycine standard liquid prepared in advance obtains, experimental group is measured
The degree of substitution of 1-6 is shown in Table 1:
The degree of substitution for the methyl olefin(e) acid anhydridization gelatin that 1 experimental group 1-6 of table is provided
| Experimental group | 1 | 2 | 3 | 4 | 5 | 6 |
| Degree of substitution (%) | 76 | 78 | 90 | 88 | 75 | 62 |
It is by 1 test result of table it is found that obvious by the degree of substitution of 1-5 of the embodiment of the present invention methyl olefin(e) acid anhydridization gelatin provided
Higher than the prior art provide methyl olefin(e) acid anhydridization gelatin degree of substitution, should the result shows that, use is provided in an embodiment of the present invention
Method prepares methyl olefin(e) acid anhydridization gelatin, can significantly improve the degree of substitution of methyl olefin(e) acid anhydridization gelatin；The methyl alkene of experimental group 3
The degree of substitution of acid anhydrides gelatin is optimal, illustrates each test parameters range (gelatin and especially obtained in inventor's creativeness
One buffer solution ratio is classified as 1g:10~15ml；The molar ratio of methacrylic anhydride and gelatin is 0.08~0.2:1；Second buffering
The volume ratio of liquid and the first buffer is the experiment carried out in 1~4:1), and the degree of substitution presentation of methyl olefin(e) acid anhydridization gelatin is most
Excellent state.
Experimental example 2
Experimental subjects: the polyacrylate grafting modified gelatin-adhesive and existing for taking equivalent embodiment 1-5 to provide
Document (MR Mehdizadeh, H Weng, D Gyawali, L Tang, J Yang.Injectable citrate-based
mussel-inspired tissue bioadhesives with high wet strength for sutureless
Wound closure [J] .Biomaterials, 2012,33 (32): 7972-83.) in provide fibrin gluing agent, if
It is set to experimental group 1-6；
Experimental procedure: the test method of the shear strength of the sample of experimental group 1-6 is as follows；
Using long 40mm, width 4mm sample faying surface as the test template of experimental group 1-6, sheared using universal material
Power tensile testing machine tests the shear strength of the adhesive in experimental group 1-6, test condition are as follows: and 25 DEG C, rate travel
For 1.3mm/min, the shear strength for obtaining the sample of experimental group 1-6 offer is shown in Table 2:
The shear strength of the adhesive for the polyacrylate grafting modified gelatin that 2 experimental group 1-6 of table is provided
| Experimental group | 1 | 2 | 3 | 4 | 5 | 6 |
| Shear strength (kPa) | 55 | 61 | 90 | 86 | 50 | 15 |
By 2 test result of table it is found that the shearing based on methacrylic acid anhydridization gelatin provided by 1-5 of the embodiment of the present invention
Intensity be apparently higher than the prior art offer adhesive shear strength, should the result shows that, use is provided in an embodiment of the present invention
The adhesive that method is prepared is a kind of good elastomer, and according to acquired results in experimental example 1, with the increasing of degree of substitution
Add shear strength better；The shear strength of the adhesive of experimental group 3 is optimal, illustrates especially to obtain in inventor's creativeness each
(water soluble polymer, camphorquinone and water are according to 2~3g:1~2g:5~10ml for test parameters range；Methacrylic acid anhydridization is bright
Glue, polyethylene glycol double methyl methacrylate, acrylate monomer and water are according to 3~5g:0.5~1g:1~3ml:3~5ml) with
And using beta-cyclodextrin to the embedded object of camphorquinone, it is dissolved in glycerol using gelatin, and glycerol offer great amount of hydroxy group free radical can
It improves photopolymerization efficiency, shorten the test that the principle of photopolymerization time carries out, can be prepared with excellent resilience performance
Adhesive.
Embodiments described above is a part of the embodiment of the present invention, instead of all the embodiments.Reality of the invention
The detailed description for applying example is not intended to limit the range of claimed invention, but is merely representative of selected implementation of the invention
Example.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.
Claims (1)
1. a kind of preparation method of polyacrylate grafting modified gelatin-adhesive, comprising the following steps:
(1) preparation of methacrylic acid anhydridization gelatin: by gelatin and CB solution according to 1g:10ml be mixed to form first mix it is molten
First mixed solution is stirred dissolution 4h by liquid under the conditions of 150r/min；Then the first for being 0.12 with gelatin molar ratio is taken
The first mixed solution is added in base acrylic anhydride, is warming up to 50 DEG C, forms the second mixed solution after isothermal reaction 3h；To the second mixing
The PBS solution that 4 times of CB solution amounts are added in solution forms third mixed solution；Third mixed solution is transferred to Spectro/
Por molecular porous type tubulose, MWCO12-14000 film strips are dialysed 6 days, and after replacing a purified water daily, freeze-drying is obtained
Methacrylated gelatin, -20 DEG C of freezen protectives；
(2) polyacrylate grafting modified gelatin-adhesive preparation: by chitosan, beta-cyclodextrin, camphorquinone and water according to
The ratio of 0.5g:1g:1.5g:5ml mixes, and promotes dissolution to form embedded object in 200r/min stirring, 80kHz ultrasound；It again will packet
Object reduced vacuum drying at 30 DEG C is buried, after grinding, cryo-conservation is stand-by；Then, by embedded object and glycerol according to 0.5g:
10ml is mixed to prepare photoinitiator；Again by methacrylated gelatin, polyethylene glycol double methyl methacrylate, acrylic acid and water
It is mixed according to 4g:0.8g:1.5ml:5ml, constant temperature stirs under the conditions of 40 DEG C, and preparation obtains adhesive；Then, by adhesive with
After mixing, rubber gun mixing tube is added in photoinitiator；Mixture in mixing tube is coated on to the object for needing to be bonded again
On, with wavelength be 420nm and light intensity is 1200mW/cm2Blue light illumination, make its gluing polymerization achieve the purpose that bonding.
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| CN108395859A (en) * | 2018-03-27 | 2018-08-14 | 陕西科技大学 | Modified gelatin based Wood Adhesives and preparation method thereof |
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| CN109453420B (en) * | 2018-11-29 | 2021-01-08 | 成都美益达医疗科技有限公司 | Hemostatic composition, preparation method and application thereof |
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| CN112675357A (en) * | 2020-12-31 | 2021-04-20 | 广东省第二中医院（广东省中医药工程技术研究院） | Skin hydrogel dressing |
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| CN114425097B (en) * | 2022-04-07 | 2022-06-14 | 天新福（北京）医疗器材股份有限公司 | Absorbable tissue occlusion gel and preparation method thereof |
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