CN107189115A - A kind of preparation method of crosslinked poly amylose microballoon - Google Patents
A kind of preparation method of crosslinked poly amylose microballoon Download PDFInfo
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- CN107189115A CN107189115A CN201710538916.6A CN201710538916A CN107189115A CN 107189115 A CN107189115 A CN 107189115A CN 201710538916 A CN201710538916 A CN 201710538916A CN 107189115 A CN107189115 A CN 107189115A
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- microballoon
- starch
- oil phase
- preparation
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- 229920000856 Amylose Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- 229920002472 Starch Polymers 0.000 claims abstract description 45
- 235000019698 starch Nutrition 0.000 claims abstract description 36
- 239000008107 starch Substances 0.000 claims abstract description 36
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 21
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 20
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 20
- 229940068984 polyvinyl alcohol Drugs 0.000 claims abstract description 20
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 20
- 229920000881 Modified starch Polymers 0.000 claims abstract description 18
- 239000004368 Modified starch Substances 0.000 claims abstract description 18
- 235000019426 modified starch Nutrition 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 238000004945 emulsification Methods 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 235000019890 Amylum Nutrition 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 239000003921 oil Substances 0.000 claims description 45
- 239000012071 phase Substances 0.000 claims description 45
- 235000019198 oils Nutrition 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 22
- 239000004005 microsphere Substances 0.000 claims description 22
- 230000002439 hemostatic effect Effects 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 11
- 241000196324 Embryophyta Species 0.000 claims description 10
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 8
- 230000002776 aggregation Effects 0.000 claims description 8
- 238000004220 aggregation Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 230000001804 emulsifying effect Effects 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000013517 stratification Methods 0.000 claims description 8
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 6
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008346 aqueous phase Substances 0.000 claims description 4
- 229920001592 potato starch Polymers 0.000 claims description 4
- 235000013339 cereals Nutrition 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000012875 nonionic emulsifier Substances 0.000 claims description 3
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 claims description 3
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 3
- 239000008158 vegetable oil Substances 0.000 claims description 3
- 244000046052 Phaseolus vulgaris Species 0.000 claims description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 235000012055 fruits and vegetables Nutrition 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 239000013049 sediment Substances 0.000 claims description 2
- -1 sorbitan fatty acid ester Chemical class 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 239000000725 suspension Substances 0.000 abstract description 3
- 238000002715 modification method Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 238000010521 absorption reaction Methods 0.000 description 13
- 230000006872 improvement Effects 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 229920002261 Corn starch Polymers 0.000 description 6
- 239000008120 corn starch Substances 0.000 description 6
- 229940099112 cornstarch Drugs 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 230000008859 change Effects 0.000 description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000023597 hemostasis Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- 210000000481 breast Anatomy 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 230000000025 haemostatic effect Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- ANRCFKDSDRXMCZ-UHFFFAOYSA-N [Cl].C(C1=CC=C(C(=O)N)C=C1)(=O)N Chemical compound [Cl].C(C1=CC=C(C(=O)N)C=C1)(=O)N ANRCFKDSDRXMCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000010108 arterial embolization Effects 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000001772 blood platelet Anatomy 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000005341 metaphosphate group Chemical group 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
- C08L3/02—Starch; Degradation products thereof, e.g. dextrin
-
- 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
- A61L24/08—Polysaccharides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/246—Intercrosslinking of at least two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/02—Homopolymers or copolymers of unsaturated alcohols
- C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/04—Materials for stopping bleeding
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2303/00—Characterised by the use of starch, amylose or amylopectin or of their derivatives or degradation products
- C08J2303/02—Starch; Degradation products thereof, e.g. dextrin
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2429/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2429/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2429/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
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- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Organic Chemistry (AREA)
- Public Health (AREA)
- Surgery (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Medicinal Preparation (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Include following preparation process the invention discloses a kind of preparation method of crosslinked poly amylose microballoon：Using plant amylum as raw material, compound concentration is 5%~30%g/ml starch lye solution, adds a certain amount of poly-vinyl alcohol solution as modifying agent；The modified starch lye solution of preparation is added in the oil phase containing emulsifying agent, clipped machine emulsification etc. at a high speed again, present invention employs unique material modification method, gelatinization process is dissolved in plant amylum to find to add appropriate poly-vinyl alcohol solution, presence and its viscosity due to polyvinyl alcohol itself great amount of hydroxy group, so that in the reversed suspension crosslinking reaction of next step, stable solution particles are more readily formed, it is easier occur more cross-linking reaction simultaneously, the application of this novel material method of modifying is the core and key technology of the present invention.
Description
Technical field
It is a kind of preparation side of crosslinked poly amylose microballoon specifically the present invention relates to a kind of chemical preparation process
Method.
Background technology
Spherex is a kind of artificial derivatives of native starch, be starch initiator effect under, on starch hydroxyl with
Crosslinking agent carries out a kind of appropriately crosslinked and obtained microballoon.Spherex has certain particle diameter and size distribution profile, and this is itself and one
As crosslinked starch significant difference.Spherex is because with biocompatibility, biodegradable, nontoxicity, storage stabilization, raw material
Wide material sources, it is cheap the advantages of, as targeting preparation pharmaceutical carrier nasal drug delivery system, arterial embolization technique,
The fields such as radiation treatment, immunoassay are applied；Spherex also acts as adsorbent and embedding medium absorption or embedding is removed
Other materials outside medicine, such as essence, spices and some enzymes, spore；Crosslinked starch microspheres are separated or useless in adsorption of metal ions
The field such as water process application prospect is also very wide.
Surgical hemostasis are one of cores of surgical technic, and good hemostatic technique is the key for ensureing successful surgery.With
Various countries' medical field finds biomaterial excellent in nature, exploitation to hemostatic material validity and the raising of security requirement
Go out haemostatic effect more preferably, have no toxic side effect, hemostatic material nonirritant, easily processed into type, it is imperative.
Absorbable hemostatic microballoon scientific name micropore polysaccharide (MPH).Absorbable hemostatic microballoon is made by plant amylum, its surface
Spread all over crack, considerably increase microsphere surface product.Large area makes it have very strong water absorbing capacity.Absorbable hemostatic microballoon application
In arterial hamorrhage.Bleeding part is sprinkled upon, absorbable hemostatic microballoon can play molecular sieve effect, rapid to absorb in blood
Moisture, condenses blood platelet, red blood cell, so as to reach hemostasis purpose.
Medafor companies of the U.S. earliest utilize absorbable hemostatic microballoon in hemostasis, its safe styptic powder of Ali Si developed
It is first plant source hemostatic material in the world.2000, the safe styptic powder of Ali Si turned into U.S. army's field standard configuration.2010 Ah
Li Sitai styptic powders enter Chinese market.The current country has 200 multiple hospitals to use the safe styptic powder of Ali Si.The country can inhale
Hemostatic microsphere market is received to be monopolized by the safe styptic powder of Ali Si always.In April, 2013, by Hangzhou Singclean Medical Products Co., Ltd.
" glad speed is listened " MPH hemostatic microspheres of research and development have passed through the approval of state food pharmaceuticals administration general bureau.The product turns into the country
The unique one domestic artery Absorbable hemostatic material ratified by CFDA.
The preparation method of spherex mainly has Physical, chemical method and reverse microemulsion process.Physical uses ball milling skill
Art, using ethanol or water as medium, starch granules occurs broken in the presence of mechanical force.Spherex grain prepared by this method
Footpath is larger, uneven, and power consumption is big, and cost is high, the rupture of small part starch granules outer surface, coarse, and hydrolysis, enzymolysis speed are big
Big to accelerate, though individual particles surface does not change, inside has ruptured.Chemical method is generally used to prepare magnetic starch microcapsule,
Typically containing Fe2+And Fe3+Solution mix in the basic conditions generation precipitation, embedded or adsorbed with starch, obtain magnetic
Property spherex.Reverse microemulsion method is the new method for preparing spherex grown up the nearly more than ten years, and it is by solubility shallow lake
Powder is soluble in water, as Aqueous dispersions in the organic solution containing proper amount of surfactant, formed it is uniform, stably, it is transparent
Microemulsion, under quick stirring, adds appropriate crosslinking agent, is cross-linked into the starch molecule in dissolved state tiny
Microballoon is separated out from liquid phase.It is noteworthy characterized by：Drop in system is Water-In-Oil, compared with positive suspension polymerisation, anti-phase outstanding
Floating polymerization is exchanged equivalent to by interior with foreign minister, mainly include in system water-soluble monomer, water, oil-soluble dispersant,
Non-polar organic solvent, initiator etc..Conventional crosslinking agent has epichlorohydrin, epoxychloropropane, bisacrylamide, paraphenylene terephthalamide
Chlorine, metaphosphate etc., its consumption are relevant with the species, molecular weight distribution and meltage of starch.
Existing various methods also have that prepared spherex size controlling is not good, and energy consumption is higher, properties of product compared with
The shortcoming of difference.
The content of the invention
There is provided a kind of crosslinked poly amylose is micro- exactly for various weak points present in prior art by the present invention
The preparation method of ball.
The present invention is realized to reach above-mentioned purpose by such technical scheme：
The invention discloses a kind of preparation method of crosslinked poly amylose microballoon, including following preparation process：
1), using plant amylum as raw material, compound concentration is 5%~30%g/ml starch lye solution, is added certain
The poly-vinyl alcohol solution of amount is used as modifying agent；
2), by step 1) prepare modified starch lye solution be added in the oil phase containing emulsifying agent, then clipped machine at a high speed
Emulsification, emulsifying rate is 500rpm~2000rpm, and the time is 10~20 minutes；
3), treat step 2) emulsification after the completion of add a certain amount of crosslinking agent, wherein crosslinking agent mass percent in oil phase
For 0.2~2%, 1~5h is stirred at room temperature and carries out cross-linking reaction, after the completion of stratification；
4) oil phase layer, is removed, using organic solvent washing to remove the oil phase of microsphere surface residual, then is washed with ethanol,
After separation, a kind of crosslinked poly amylose microballoon can be obtained through drying.
As a further improvement, step 1 of the present invention) in plant amylum be native starch, including bean starch,
One or more in potato starch, fruits and vegetables class and cereal starch, its molecule aggregation degree DP is 500-5000, polyvinyl alcohol and starch
Weight ratio be 1:20-100.
As a further improvement, the preparation method of crosslinked poly amylose microballoon of the present invention, it is characterised in that
Described plant amylum is preferably potato starch.
As a further improvement, step 2 of the present invention) in oil phase emulsifying agent mass percent be 0.5~
10%, the weight ratio of modified starch lye solution and oil phase is 1:1~1:20, oil phase be atoleine, vegetable oil, n-hexane,
One or more kinds of in hexamethylene, toluene, emulsifying agent is nonionic emulsifier.
As a further improvement, nonionic emulsifier of the present invention be sorbitan fatty acid ester Span,
The one or several kinds of tween, OP emulsifying agents or emulsifying agent peregal.
As a further improvement, emulsifying agent mass percent is 1-5%, described modification in oil phase of the present invention
The weight ratio of starch lye solution and oil phase is 1:1-1:10.
As a further improvement, step 3 of the present invention) in crosslinking agent be Isosorbide-5-Nitrae-butanediol diglycidyl ether
BDDE or sodium tetraborate decahydrate.
As a further improvement, step 4 of the present invention) in obtained crosslinked poly amylose microballoon pass through control
Starch concentration, aqueous phase/oil phase weight ratio, emulsifying rate and dosage of crosslinking agent prepares different-grain diameter and different performance in aqueous phase processed
Microsphere particle, the particle size range of microsphere particle is between 80~2000 μm.
As a further improvement, the crosslinked poly amylose microballoon obtained by the present invention is sterilized rear for medical hemostatic
Material.
Beneficial effects of the present invention are as follows：
1st, present invention employs unique material modification method.Common plant starch molecule amount is high, and gelatinization dissolving is difficult, knot
Crystalline region is not susceptible to reaction.We dissolve gelatinization process in plant amylum and find to add appropriate poly-vinyl alcohol solution, due to poly-
The presence of vinyl alcohol itself great amount of hydroxy group and its viscosity so that in the reversed suspension crosslinking reaction of next step, it is easier to form steady
Fixed solution particles, while it is easier occur more cross-linking reaction, and the crosslinked poly amylose finally prepared is micro-
More preferably, water absorbing properties are higher, and haemostatic effect is excellent for ball mechanical strength.The application of this novel material method of modifying is of the invention
Core and key technology.
2nd, present invention employs cutter high speed emulsification method.Because starch solution viscosity is high, it is difficult to disperse, has a strong impact on
The speed and uniformity of cross-linking reaction, and then have impact on the application performance of product.Cutter breast at a high speed is employed in the present invention
Change method, coordinates suitable emulsifying agent, and the Quick uniform for realizing starch solution disperses, and is conducive to shortening cross-linking reaction time,
Improve final products performance.
3rd, present invention employs unique crosslinking agent, crosslinking agent is Isosorbide-5-Nitrae-butanediol diglycidyl ether BDDE or ten
Water sodium tetraborate.The conventional crosslinking agent of conventional method has epichlorohydrin, epoxychloropropane, bisacrylamide, paraphthaloyl chloride, partially
Phosphate etc., it is slow all to there is reaction rate in these crosslinking agents, the problem of cross-linking efficiency is low, this patent use crosslinking agent for Isosorbide-5-Nitrae-
Butanediol diglycidyl ether BDDE or sodium tetraborate decahydrate, substantially improve above-mentioned crosslinking problem, so as to obtain faster
Cross-linking reaction speed and properties of product.
Embodiment
The invention discloses a kind of preparation method of crosslinked poly amylose microballoon, the present invention is with reference to specific embodiment
Make detailed description further to technical scheme, but the scope of the present invention is not limited to embodiment.
Embodiment 1
(1) 20g is weighed for raw material using cornstarch (molecule aggregation degree DP is 500), with 1% NaOH solution, prepared dense
Spend the starch lye solution for 30%g/ml, and add poly-vinyl alcohol solution as modifying agent, polyvinyl alcohol and cornstarch
Weight ratio is 1:20；
(2) in atoleine add 0.5% span80 emulsifying agents, by step (1) prepare modified starch lye solution
It is added in atoleine, the weight ratio of modified starch lye solution and oil phase is 1:20, then the emulsification at a high speed of clipped machine, emulsification speed
Spend for 500rpm, the time is 20 minutes；
(3) treat after the completion of step (2) emulsification, add crosslinking agent Isosorbide-5-Nitrae-butanediol that mass percent in oil phase is 0.2%
Diglycidyl ether BDDE, at room temperature stir 5h carry out cross-linking reaction, after the completion of stratification；
(4) oil phase layer is removed, microballoon is repeatedly washed using ethyl acetate, to remove the oil phase of microsphere surface residual, then is used
Industrial alcohol is repeatedly washed, and is finally repeatedly washed with ethanol, after separation, and it is micro- to obtain a kind of crosslinked poly amylose through drying
Ball；
(5) gained crosslinked poly amylose microballoon, by detection, the particle size range of microsphere particle between 80~500 μm,
Microballoon water absorption and swelling rate is 450% in 5min, and water absorption rate is 16 times.
Embodiment 2
(1) 20g is weighed, with 1% NaOH solution, is matched somebody with somebody for raw material using farina (molecule aggregation degree DP is 1100)
Concentration processed is 5%g/ml starch lye solution, and adds poly-vinyl alcohol solution as modifying agent, polyvinyl alcohol and cornstarch
Weight ratio be 1:100；
(2) in vegetable oil soybean oil add 10% emulsifying agent paregal O 25, by step (1) prepare modified starch alkali
Liquor is added in soybean oil, and the weight ratio of modified starch lye solution and oil phase is 1:1, then the emulsification at a high speed of clipped machine, breast
Change speed is 2000rpm, and the time is 10 minutes；
(3) treat after the completion of step (2) emulsification, add the crosslinking agent sodium tetraborate decahydrate that mass percent in oil phase is 2%
Solution, at room temperature stir 1h carry out cross-linking reaction, after the completion of stratification；
(4) oil phase layer is removed, microballoon is repeatedly washed using ethyl acetate, to remove the oil phase of microsphere surface residual, then is used
Industrial alcohol is repeatedly washed, and is finally repeatedly washed with ethanol, after separation, and it is micro- to obtain a kind of crosslinked poly amylose through drying
Ball；
(5) gained crosslinked poly amylose microballoon, by detection, the particle size range of microsphere particle 200~2000 μm it
Between, microballoon water absorption and swelling rate is 550% in 5min, and water absorption rate is 19 times.
Embodiment 3
(1) 20g is weighed for raw material using green starch (molecule aggregation degree DP is 1500), with 1% NaOH solution, prepared
Concentration is 10%g/ml starch lye solution, and adds poly-vinyl alcohol solution as modifying agent, polyvinyl alcohol and cornstarch
Weight ratio be 1:50；
(2) in n-hexane add 1% Tween 80 emulsifying agent, by step (1) prepare modified starch lye solution be added to
In n-hexane, the weight ratio of modified starch lye solution and oil phase is 1:2, then clipped machine emulsifies at a high speed, emulsifying rate is
1000rpm, the time is 15 minutes；
(3) treat after the completion of step (2) emulsification, add crosslinking agent Isosorbide-5-Nitrae-butanediol two that mass percent in oil phase is 1%
Glycidol ether BDDE, at room temperature stir 2h carry out cross-linking reaction, after the completion of stratification；
(4) oil phase layer is removed, microballoon is repeatedly washed using ethyl acetate, to remove the oil phase of microsphere surface residual, then is used
Industrial alcohol is repeatedly washed, and is finally repeatedly washed with ethanol, after separation, and it is micro- to obtain a kind of crosslinked poly amylose through drying
Ball；
(5) gained crosslinked poly amylose microballoon, by detection, the particle size range of microsphere particle 100~800 μm it
Between, microballoon water absorption and swelling rate is 610% in 5min, and water absorption rate is 21 times.
Embodiment 4
(1) 20g is weighed for raw material using Rhizoma Nelumbinis starch (molecule aggregation degree DP is 1900), with 1% NaOH solution, prepared dense
Spend the starch lye solution for 15%g/ml, and add poly-vinyl alcohol solution as modifying agent, polyvinyl alcohol and cornstarch
Weight ratio is 1:50；
(2) in hexamethylene add 5% emulsifier op-10, by step (1) prepare modified starch lye solution be added to ring
In hexane, the weight ratio of modified starch lye solution and oil phase is 1:10, then clipped machine emulsifies at a high speed, emulsifying rate is
1000rpm, the time is 10 minutes；
(3) treat after the completion of step (2) emulsification, add crosslinking agent Isosorbide-5-Nitrae-butanediol that mass percent in oil phase is 0.5%
Diglycidyl ether BDDE, at room temperature stir 2h carry out cross-linking reaction, after the completion of stratification；
(4) oil phase layer is removed, microballoon is repeatedly washed using ethyl acetate, to remove the oil phase of microsphere surface residual, then is used
Industrial alcohol is repeatedly washed, and is finally repeatedly washed with ethanol, after separation, and it is micro- to obtain a kind of crosslinked poly amylose through drying
Ball；
(5) gained crosslinked poly amylose microballoon, by detection, the particle size range of microsphere particle between 80~500 μm,
Microballoon water absorption and swelling rate is 720% in 5min, and water absorption rate is 22 times.
Embodiment 5
(1) 20g is weighed for raw material using tapioca (molecule aggregation degree DP is 5000), with 1% NaOH solution, prepared
Concentration is 12%g/ml starch lye solution, and adds poly-vinyl alcohol solution as modifying agent, polyvinyl alcohol and cornstarch
Weight ratio be 1:75；
(2) in toluene add 4% emulsifying agent peregal O-25, by step (1) prepare modified starch lye solution add
Into toluene, the weight ratio of modified starch lye solution and oil phase is 1:5, then clipped machine emulsifies at a high speed, emulsifying rate is
1000rpm, the time is 10 minutes；
(3) treat after the completion of step (2) emulsification, add crosslinking agent Isosorbide-5-Nitrae-butanediol that mass percent in oil phase is 0.5%
Diglycidyl ether BDDE, at room temperature stir 2h carry out cross-linking reaction, after the completion of stratification；
(4) oil phase layer is removed, microballoon is repeatedly washed using ethyl acetate, to remove the oil phase of microsphere surface residual, then is used
Industrial alcohol is repeatedly washed, and is finally repeatedly washed with ethanol, after separation, and it is micro- to obtain a kind of crosslinked poly amylose through drying
Ball；
(5) gained crosslinked poly amylose microballoon, by detection, the particle size range of microsphere particle between 80~300 μm,
Microballoon water absorption and swelling rate is 700% in 5min, and water absorption rate is 25 times.
Embodiment 6
(1) 20g is weighed, with 1% NaOH solution, is matched somebody with somebody for raw material using farina (molecule aggregation degree DP is 1100)
Concentration processed is 15%g/ml starch lye solution, and adds poly-vinyl alcohol solution as modifying agent, and polyvinyl alcohol forms sediment with corn
The weight ratio of powder is 1:75；
(2) in atoleine add 5% emulsifying agent span80, by step (1) prepare modified starch lye solution add
Into atoleine, the weight ratio of modified starch lye solution and oil phase is 1:5, then the emulsification, emulsifying rate at a high speed of clipped machine
For 1000rpm, the time is 10 minutes；
(3) treat after the completion of step (2) emulsification, add the crosslinking agent sodium tetraborate decahydrate that mass percent in oil phase is 1%
Solution, at room temperature stir 2h carry out cross-linking reaction, after the completion of stratification；
(4) oil phase layer is removed, microballoon is repeatedly washed using ethyl acetate, to remove the oil phase of microsphere surface residual, then is used
Industrial alcohol is repeatedly washed, and is finally repeatedly washed with ethanol, after separation, and it is micro- to obtain a kind of crosslinked poly amylose through drying
Ball；
(5) gained crosslinked poly amylose microballoon, by detection, the particle size range of microsphere particle 80~1000 μm it
Between, microballoon water absorption and swelling rate is 630% in 5min, and water absorption rate is 23 times.
Finally, in addition it is also necessary to it is noted that listed above is only specific embodiment of the invention.Obviously, the present invention is not limited
In above example, there can also be many deformations.One of ordinary skill in the art can directly lead from present disclosure
All deformations for going out or associating, are considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of crosslinked poly amylose microballoon, it is characterised in that it includes following preparation process：
1), using plant amylum as raw material, compound concentration is 5%~30%g/ml starch lye solution, is added a certain amount of
Poly-vinyl alcohol solution is used as modifying agent；
2), by step 1) prepare modified starch lye solution be added in the oil phase containing emulsifying agent, then clipped machine at a high speed emulsify,
Emulsifying rate is 500rpm~2000rpm, and the time is 10~20 minutes；
3) step 2, is treated) a certain amount of crosslinking agent is added after the completion of emulsification, wherein crosslinking agent mass percent in oil phase is 0.2
~2%, at room temperature stir 1~5h carry out cross-linking reaction, after the completion of stratification；
4) oil phase layer, is removed, using organic solvent washing to remove the oil phase of microsphere surface residual, then is washed with ethanol, separated
Afterwards, a kind of crosslinked poly amylose microballoon can be obtained through drying.
2. the preparation method of crosslinked poly amylose microballoon according to claim 1, it is characterised in that
Described step 1) in plant amylum be native starch, including bean starch, potato starch, fruits and vegetables class and cereal starch in
One or more, its molecule aggregation degree DP is 500-5000, and the weight ratio of polyvinyl alcohol and starch is 1:20-100.
3. the preparation method of crosslinked poly amylose microballoon according to claim 2, it is characterised in that described plant is formed sediment
Powder is preferably potato starch.
4. the preparation method of crosslinked poly amylose microballoon according to claim 1, it is characterised in that described step 2)
Emulsifying agent mass percent is 0.5~10% in middle oil phase, and the weight ratio of modified starch lye solution and oil phase is 1:1~1:
20, described oil phase is one or more in atoleine, vegetable oil, n-hexane, hexamethylene, toluene, described emulsifying agent
For nonionic emulsifier.
5. the preparation method of crosslinked poly amylose microballoon according to claim 4, its characteristic is, described non-ionic
Emulsifying agent is the one or several kinds of sorbitan fatty acid ester Span, tween, OP emulsifying agents or emulsifying agent peregal.
6. the preparation method of crosslinked poly amylose microballoon according to claim 4, it is characterised in that in described oil phase
Emulsifying agent mass percent is 1-5%；Described modified starch lye solution and the weight ratio of oil phase are 1:1-1:10.
7. the preparation method of the crosslinked poly amylose microballoon according to claim 1 or 2 or 3 or 4 or 5 or 6, its feature exists
In described step 3) in crosslinking agent be Isosorbide-5-Nitrae-butanediol diglycidyl ether BDDE or sodium tetraborate decahydrate.
8. the preparation method of crosslinked poly amylose microballoon according to claim 7, it is characterised in that described step 4)
In obtained crosslinked poly amylose microballoon by control starch concentration in aqueous phase, aqueous phase/oil phase weight ratio, emulsifying rate and
Dosage of crosslinking agent prepares the microsphere particle of different-grain diameter and different performance, the particle size range of microsphere particle 80~2000 μm it
Between.
9. the preparation method of the crosslinked poly amylose microballoon according to claim 1 or 2 or 3 or 4 or 5 or 6 or 8, it is special
Property be, obtained crosslinked poly amylose microballoon it is sterilized after be used for hemostatic material in medical use.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108620004A (en) * | 2018-05-14 | 2018-10-09 | 河南工业大学 | A kind of starch/PVA complex microspheres and preparation method thereof |
| CN110115776A (en) * | 2018-02-07 | 2019-08-13 | 沈阳药科大学 | A kind of absorbable spherex styptic powder and its application with antibacterial activity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333351A (en) * | 2013-05-02 | 2013-10-02 | 杭州协合医疗用品有限公司 | Process for preparing cross-linked sodium hyaluronate microspheres capable of being adopted as emboliaztion agent by adopting sodium hyaluronate as raw material |
| CN105148327A (en) * | 2015-07-29 | 2015-12-16 | 陕西博与再生医学有限公司 | Preparation method of polysaccharide-polyvinyl alcohol embolism microsphere |
-
2017
- 2017-07-04 CN CN201710538916.6A patent/CN107189115A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333351A (en) * | 2013-05-02 | 2013-10-02 | 杭州协合医疗用品有限公司 | Process for preparing cross-linked sodium hyaluronate microspheres capable of being adopted as emboliaztion agent by adopting sodium hyaluronate as raw material |
| CN105148327A (en) * | 2015-07-29 | 2015-12-16 | 陕西博与再生医学有限公司 | Preparation method of polysaccharide-polyvinyl alcohol embolism microsphere |
Non-Patent Citations (2)
| Title |
|---|
| 叶青萱等: "《胶黏剂（第1版）》", 31 October 1999, 中国物资出版社 * |
| 段久芳: "《天然高分子材料（第1版）》", 30 September 2016, 华中科技大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110115776A (en) * | 2018-02-07 | 2019-08-13 | 沈阳药科大学 | A kind of absorbable spherex styptic powder and its application with antibacterial activity |
| CN108620004A (en) * | 2018-05-14 | 2018-10-09 | 河南工业大学 | A kind of starch/PVA complex microspheres and preparation method thereof |
| CN108620004B (en) * | 2018-05-14 | 2021-10-15 | 河南工业大学 | starch/PVA composite microsphere and preparation method thereof |
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