CN106947011A - Single-stranded super inner ring fluidized polymer and preparation method thereof - Google Patents
Single-stranded super inner ring fluidized polymer and preparation method thereof Download PDFInfo
- Publication number
- CN106947011A CN106947011A CN201710150145.3A CN201710150145A CN106947011A CN 106947011 A CN106947011 A CN 106947011A CN 201710150145 A CN201710150145 A CN 201710150145A CN 106947011 A CN106947011 A CN 106947011A
- Authority
- CN
- China
- Prior art keywords
- inner ring
- polymer
- stranded
- fluidized polymer
- ring fluidized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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
- C08F122/00—Homopolymers 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 a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
- C08F122/10—Esters
- C08F122/12—Esters of phenols or saturated alcohols
- C08F122/20—Esters containing oxygen in addition to the carboxy oxygen
-
- 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
- A61L24/0031—Hydrogels or hydrocolloids
-
- 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
- A61L24/0042—Materials resorbable by the body
-
- 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
- A61L24/046—Surgical adhesives or cements; Adhesives for colostomy devices containing macromolecular materials obtained otherwise than 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0019—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
-
- 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
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/009—Materials resorbable by the body
-
- 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
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- 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
-
- 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
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- C08J2335/00—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 a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
- C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
Landscapes
- Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Public Health (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Veterinary Medicine (AREA)
- General Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Surgery (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The present invention discloses single-stranded super inner ring fluidized polymer and preparation method thereof, using polyethyleneglycol diacrylate as monomer, monomer polyethyleneglycol diacrylate is carried out homopolymerization by the Controlled Living Radical Polymerization method regulated and controled using zerovalent copper, chain increases and intramolecular cyclization reaction is promoted, intermolecular cross-linking reaction is suppressed, to obtain single-stranded super inner ring fluidized polymer, i.e., in the single-stranded middle formation linear polyethylene glycol diacrylate of polymer and annular polyethyleneglycol diacrylate.Proved by the sign of polymer, mark's Huo Wenke formula constant of single-stranded super inner ring fluidized polymer is less than 0.5, and its structure is similar to spherical.Aqueous solutions of polymers solidification can be prepared by hydrogel material by ultraviolet light cross-linking.
Description
Technical field
The invention belongs to new bio field of medical materials, new single-stranded super inner ring fluidized polymer and its preparation are related generally to
Method.
Background technology
Wound dressing is the major way for treating acute and chronic wound.In recent decades, according to different traumatic events
A variety of special wound dressings have been invented in research.Wherein as one kind in novel wound dressing, hydrogel wound dressing is because of table
Face is smooth, good biocompatibility, with the out-of-flatness surface of a wound be tightly combined, promote epithelial cell growth the advantages of and obtained extensively
Use.But now widely used synthesis aerogel dressing generally existing poor wound tissue's adhesive power, mechanical property and wound
The problems such as mouth tissue is mismatched and bio-toxicity is larger.Research is found, the polymer used of hydrogel is synthesized by control
Composition, structure, the degree of polymerization etc. are achievable to improve the performance of synthesis hydrogel wound dressing.In control polymer architecture and performance side
Face, multi-vinyl monomer is conveniently easy to get and it has multiple reaction site and receives much concern due to it.Particularly many vinyl lists
The polymer of syntaxy has substantial amounts of unreacting ethylene group, can further be modified the default functional group of acquisition, optimization biofacies
Capacitive and bioadhesive etc., possibility is provided for its application in aerogel dressing.
But the polymerization of multi-olefin monomer is always a major challenge that field of polymer technology faces, famous early in before more than 70 years
Theoretical (F-S the is theoretical) predictions of Flory-Stockmayer：The polymerization of multi-vinyl monomer can extremely low monomer conversion (<
10%) gel point formation gel is issued to, and the theory is confirmed by extensive experiment.But it is how anti-due to multi-vinyl monomer
Answer site, control the polymerization process of multi-vinyl monomer not only can delayed gel point, or even can obtain the poly- of novel labyrinth
Compound.Most of polymer prepared currently with multi-vinyl monomer is all used for non-viral gene vector, or synthesis of super branched
Polymer and then the hydrogel material for preparing different structure.The new single-stranded super intramolecular cyclization polymerization synthesized using multi-vinyl monomer
Thing makes it can obtain extensive use after modified because of the vinyl with special cyclized structure and high level.But close at present
The report for preparing hydrogel material in single-stranded super inner ring fluidized polymer is not proposed yet.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide single-stranded super inner ring fluidized polymer and its preparation side
Method, the controllable/active free radical polymerization method (Cu adjusted by zerovalent copper0- mediated CRP) homopolymerization polyethylene glycol dipropyl
Olefin(e) acid ester (PEGDA700) synthesize new single-stranded super inner ring fluidized polymer poly (PEGDA700)SK, and prepared by its aqueous solution
Into hydrogel wound dressing.The novel hydrogels material of preparation have higher storage modulu G', stronger tissue adhension ability,
Relatively low swelling ratio, moderate degradation behavior and good biocompatibility, be expected to be used for as new material wound dressing,
In tissue adhesive and bioengineering.
The technical purpose of the present invention is achieved by following technical proposals：
Single-stranded super inner ring fluidized polymer, using polyethyleneglycol diacrylate as monomer, the controllable work regulated and controled using zerovalent copper
Monomer polyethyleneglycol diacrylate is carried out homopolymerization by free love base polymerization, and chain increases and intramolecular cyclization reaction is promoted
Enter, intermolecular cross-linking reaction is suppressed, to obtain single-stranded super inner ring fluidized polymer, i.e., in the single-stranded middle linear poly- second of formation of polymer
Omega-diol diacrylate and annular polyethyleneglycol diacrylate.
The number-average molecular weight of polyethyleneglycol diacrylate is 700.
The weight average molecular weight of single-stranded super inner ring fluidized polymer is 10KDa -40KDa, and PDI is 1.19-1.48.
The contents of ethylene of single-stranded super inner ring fluidized polymer is 20-50%.
The degree of cyclization of single-stranded super inner ring fluidized polymer is 50-80%.
Mark's-Huo Wenke formula constant of single-stranded super inner ring fluidized polymer is 0.29-0.34.
Single-stranded super intramolecular cyclization polymer architecture is fine and close, appears similar to a diameter of 7.25 ± 1.5nm spherical structure.
The preparation method of single-stranded super inner ring fluidized polymer, by polyethyleneglycol diacrylate, 2 bromo 2 methyl propionic acid second
Ester, CuBr2And N, N, N ', N ", N "-pentamethyl-diethylenetriamines are according to mol ratio 100：1：(0.4—0.5)：(0.8-1) is put
It is dispersed in dimethyl sulfoxide (DMSO), and the stirrer for winding copper wire is placed in dimethyl sulfoxide (DMSO) reaction system is stirred
Mix, reacted under the conditions of deoxygenation, the Controlled Living Radical Polymerization method regulated and controled using zerovalent copper is by monomer polyethylene glycol
Diacrylate carries out homopolymerization, and chain increases and intramolecular cyclization reaction is promoted, and intermolecular cross-linking reaction is suppressed.
When carrying out the preparation of single-stranded super inner ring fluidized polymer, reaction temperature is 20-25 degrees Celsius, the reaction time is 1-
5 hours.
Based on the hydrogel of single-stranded super inner ring fluidized polymer, the Controlled Living Radical Polymerization side that will be regulated and controled using zerovalent copper
The single-stranded super inner ring fluidized polymer that method obtains the progress homopolymerization of monomer polyethyleneglycol diacrylate is as presoma, with 2,2- bis-
Methoxyl group-phenyl acetophenone is ultraviolet initiator, and water is solvent, triggers carbon-carbon double bond in presoma to enter under ultra violet lamp
Row crosslinking is hydrogel material.
Ultra violet lamp intensity is 0.5-2W/cm2, preferably 0.8-1.5W/cm2.The ultra violet lamp time is 15-20s.
The mass ratio of presoma and light trigger is 100：(1—1.2).
The concentration of presoma is the volume (μ L) of 10-30wt%, i.e. forerunner's weight (mg)/water.
Controllable/active free radical polymerization method (the Cu of new zerovalent copper regulation and control is used in the present invention0-
Mediated CRP), it is adaptable to the controllable polymerization of many vinyl-functionals.Cu0- mediated CRP polymerizations are also referred to as single electron and turned
Active free radical polymerization (SET-LRP) is moved, its course of reaction contains the equilibrium process of dormancy kind and activation kind, as shown in Figure 1.
Activator Cu0Occur redox reaction with halogen-containing initiator, capture halogen element X generations Cu from initiatorIX/L, simultaneously
Produce free radical Pn- X, generated in-situ CuIX rapid Cu for being disproportionated into nascent state in the presence of solvation and part0
With passivator CuIIX2/ L, free radical PnWith passivator Cu while monomer polymerization is triggeredIIX2Redox reaction occurs for/L
Produce CuIX/L and dormancy kind PnX, CuIThe nascent state Cu that X/L disproportionations are produced0Continue the progress of catalytic polymerization again, so that will freely
Base is controlled in relatively low concentration, it is suppressed that the generation of side reaction.
As shown in Figure 2 during SET-LRP catalytic cycle, Cu0With PnIt is instantaneous that X generations redox reaction is obtained
Intermediate [Pn----X]·—Radical anion, rapid heterolytic fission is PnFree radical and X-Anion, X-Anion and Cu+/ L is tied
Conjunction forms CuIX/L, hence into catalytic cycle process.SET-LRP activation process is turned by heterogeneous outer layer single electron
(OSET) realization is moved, and its passivation is by macromolecular radical and CuIIX2/ L homogeneous outer layer single electron transfer control, it is blunt
Excessive Cu needed for changingIIX2/ L is by CuIX/L is disproportionated rapidly in-situ preparation.
Controllable/active free radical polymerization method (the Cu that this patent is regulated and controled by zerovalent copper0- mediated CRP) homopolymerization
PEGDA700Monomer obtains single-stranded super inner ring fluidized polymer poly (PEGDA700)SK.The formation of its single-stranded super interior ring structure is depended on
The polymerisation of dynamics Controlling, its chain increases and intramolecular cyclization reaction is promoted, and intermolecular cross-linking reaction is suppressed.Pass through
The sign of polymer proves that the α of single-stranded super inner ring fluidized polymer is less than 0.5, and its structure is similar to spherical.Pass through ultraviolet light cross-linking
Aqueous solutions of polymers solidification can be prepared hydrogel material.Pass through ultraviolet light-rheology joint test, single-stranded super intramolecular cyclization
Polymer can it is rapid-result soon (<20s) and height cyclized structure and a large amount of vinyl make it have higher storage modulu G'.Pass through
The tissue adhension performance discovery of Lap-shear, Pull-off and Burst test evaluation hydrogel material, single-stranded super intramolecular cyclization water
Gel has higher adhesion strength.In addition, single-stranded super intramolecular cyclization hydrogel has relatively low swelling behavior and slower degraded
Performance.By cytotoxicity test, single-stranded super intramolecular cyclization hydrogel has preferable cell compatibility.That is list of the invention
Application of the hydrogel in as wound dressing or tissue adhesive after the super inner ring fluidized polymer of chain and crosslinking.
Brief description of the drawings
Fig. 1 is single electron transfer active free radical polymerization (SET-LRP) mechanism of polymerization schematic diagram.
Fig. 2 is the catalytic mechanism schematic diagram in single electron transfer active free radical polymerization (SET-LRP).
Fig. 3 is the synthesis schematic diagram of technical solution of the present invention.
Fig. 4 is gel permeation chromatography (GPC) test result schematic diagram, and wherein a changes over time figure for polymer molecular weight,
B is the GPC of the single-stranded super inner ring fluidized polymer of different molecular weight after purification, and the abscissa reaction time is GPC retention time.
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the single-stranded super inner ring fluidized polymer of different molecular weight in the embodiment of the present invention.
Fig. 6 is that mark's-Huo Wenke formula of the single-stranded super inner ring fluidized polymer of different molecular weight in the embodiment of the present invention are normal
Number α schematic diagram.
Fig. 7 is the stereoscan photograph for the single-stranded super inner ring fluidized polymer that embodiment of the present invention middle-molecular-weihydroxyethyl is 20KDa.
Fig. 8 is the grain size distribution for the single-stranded super inner ring fluidized polymer that embodiment of the present invention middle-molecular-weihydroxyethyl is 20KDa.
Fig. 9 is rheometer test schematic diagram in the embodiment of the present invention, wherein a for single-stranded super intramolecular cyclization hydrogel concussion-when
Between photo-crosslinking rheometer test schematic diagram, b be concussion-frequency mode rheometer test schematic diagram.
Figure 10 be in the embodiment of the present invention concentration for 30% (mass percent 30wt%) different molecular weight list
The swelling behavior test result schematic diagram of hydrogel material prepared by the super inner ring fluidized polymer of chain.
Figure 11 be in the embodiment of the present invention concentration for 30% (mass percent 30wt%) different molecular weight list
The degradation property test result schematic diagram of hydrogel material prepared by the super inner ring fluidized polymer of chain.
Embodiment
Technical scheme is further illustrated with reference to specific embodiment, the experimental raw and instrument used is as follows
Shown in the form of two, face：
Experimental raw
Laboratory apparatus
Technical solution of the present invention utilizes the controllable/active free radical polymerization method (Cu that zerovalent copper regulates and controls0-mediated
CRP) homopolymerization polyethyleneglycol diacrylate (PEGDA700) prepare new single-stranded super inner ring fluidized polymer poly (PEGDA700)SK,
And hydrogel material is cured as by photo-crosslinking.In order to which obtained hydrogel material is used for into wound dressing adhesive, lead to
Cross rheology instrument and levied its mechanical property, the means such as Lap-shear, Pull-off and Burst test evaluate its tissue adherence
Can, be swelled, degrade and cytotoxicity experiment further characterization hydrogel material biocompatibility there is provided a kind of new group
Knit adhesive.The method of new single-stranded super inner ring fluidized polymer prepared by the active free radical polymerization method regulated and controled using zerovalent copper
It is as follows：
(1) 5mg/mL copper bromide (CuBr is configured2) solution：Weigh 100mg CuBr2Powder, is put into the disposable of 20mL
In Clear glass bottles and jars, 20mL dimethyl sulfoxide (DMSO) (DMSO) is added.5min in Ultrasound Instrument is placed on, CuBr is treated2It is completely dissolved
After take out standby.
(2) precise polyethyleneglycol diacrylate (PEGDA successively700, 15mmol, 10.5g), DMSO
(137.94mL), CuBr2Solution (0.06mmol, 2.68mL), 2 bromo 2 methyl propionic acid ethyl ester (EBriB, 0.15mmol,
22.25 μ L), N, N, N ', N ", N "-pentamethyl-diethylenetriamine (PMDETA, 0.12mmol, 25.06 μ L) add the two of 250mL
In mouth round-bottomed flask.Wherein PEGDA700:EBriB:CuBr2:PMDETA=100:1:0.4:0.8 (mol ratio).Successively use respectively
Rubber stopper and the sealed membrane sealing cleaned up, leads to argon gas 30min with deoxygenation.At the same time, by a diameter of 1mm, long 5cm copper
Silk, uniform winding is simultaneously fixed on bar-shaped stirrer.First with hydrochloric acid (the hydrogen chloride water of mass percent 32% that concentration is 32%
Solution) immersion 10min, then uses acetone, ultra-pure water and acetone cleaning, and dry successively.
(3) after after deoxygenation 30min, the rapid one of bottleneck for opening round-bottomed flask is simultaneously added clean copper wire is handled
In reaction system, it is again sealed off, continues deoxygenation 2min or so.After deoxygenation terminates, two mouthfuls of round-bottomed flasks are placed in 25 DEG C, 700r/
In min oil bath heater, start reaction and timing.
(4) when being spaced the identical time, first lead to argon gas, then inserted with the 5mL syringes cleaned up below liquid level,
Sample is set to flow in syringe by malleation.When sample size reaches 2mL, syringe is taken out and then stopped logical argon gas.It will obtain
Sample be placed in 20mL disposable vial, and mark.100 μ L samples are therefrom taken with liquid-transfering gun and N is used, N- dimethyl methyls
Acid amides (DMF) is diluted to 1mL, is sufficiently mixed uniform.Small-sized alumina column is selected, and is soaked with DMF, then after filtering dilution
Polymer samples, remove Cu therein.Now it was observed that sample is by light blue bleach.Diameter 0.4mm filter mistake is used afterwards
Sample is filtered, finally sample is positioned in GPC test bottles, and labeled test.
(5) progress of reaction is monitored by GPC, when molecular weight achieves the goal molecular weight, by two mouthfuls of round-bottomed flasks from oil
Bathe in heater and take out, and open the bottleneck of sealing, make it fully and air contact, taken the magneton for being tied with copper wire with bar magnet
Go out.The 5-7 times of ether for reacting stoste volume is added in the 1000mL cleaned up large beaker, setting speed is 600r/
min.Under conditions of high-speed rotation, reaction stoste is added dropwise in ether dropwise by separatory funnel and beaker is sealed with tinfoil
Mouthful.After after completion of dropwise addition, continuing to stir 30min or so, 5-7h is stood at room temperature.Liquid stratification to be mixed and upper liquid is more
When as clear as crystal, supernatant liquor is poured out.Continue the ether of the 3-5 times of subnatant volume of addition in the state of high-speed stirred,
30min is stirred in the state of tinfoil sealing, again stratification.So repeatedly twice after, the polymer viscosity of lower floor gradually increases
Adduction sticks to beaker bottom.
(6) medium-sized alumina column is selected, a small amount of cotton and sand is first sequentially added, paves it.Then add about
The alumina powder of 3/5 alumina column height, prepares alumina filter post.Soaked using preceding with acetone.With a small amount of third
The polymer of beaker bottom is gathered in after ketone dilution precipitation, is fully poured into after dissolving along post jamb in alumina filter post, with weighing
The disposable vial of good quality collects the limpid polymer solution after filtering.
(7) all products being collected into after filtering are all sealed with tinfoil and uniformly pricks upper aperture, be then placed into true
Empty drying box, removes solvent, obtains transparent straight polymer.Then weigh, calculate yield.
Gel permeation chromatography (GPC) test result such as Fig. 4 understands that the reaction of multi-vinyl monomer has obtained good control
Make and delay gel.Progress over time, the polymerization process of single-stranded super inner ring fluidized polymer is mainly shown as two stages.
Reaction starting stage (<3.5h), the molecular weight of polymer linearly increases and is Unimodal Distribution (PDI is 1.19-1.48).
The stage mainly happens is that the chain of polymer increases and intramolecular cyclization reaction.With reaction progress (>3.5h), polymer
Multi-modal is gradually rendered as, intermolecular reaction is now happens is that.This is due in the controllable/active free of dynamics Controlling
In base polymerization, the growth border (depending on kinetic chain length) of polymer is smaller, and which has limited only close on activated centre on a small quantity
Vinyl may participate in reaction.And due to increasing most of vinyl in border from monomer and with spike in same primary
The vinyl of suspension on chain, therefore it is greatly promoted the probability of intramolecular cyclization reaction.Although intermolecular cross-linking reaction meeting
Increase with the growth of polymer chain, but because chain concentration is relatively low, thus the rate of chain growth of polymerization is more than intramolecular cyclization
Reaction rate is more than intermolecular reaction speed.The stage has primarily formed the monochain polymer containing a large amount of intramolecular cyclizations, i.e.,
Single-stranded super inner ring fluidized polymer.It is about respectively 10KDa by (number is equal) molecular weight, 20KDa, 40KDa's is single-stranded super interior in the present invention
Cyclopolymer is referred to as K1, K2, k3.
Fig. 5 is the proton nmr spectra test of the single-stranded super inner ring fluidized polymer of different molecular weight, it is known that contained in polymer
Substantial amounts of vinyl-functional, calculates its contents of ethylene and degree of cyclization.The content and degree of cyclization of polymer medium vinyl can
To calculate (Zhao T, Zhang H, Zhou D, et al.Water soluble by formula (1) and (2)
hyperbranched polymers from controlled radical homopolymerization of PEG
diacrylate[J].RSC Advances.2015,5(43):33823-33830.)。
A, d and d ' peak value size (peak area) in proton nmr spectra is represented respectively.The result of table 1 shows with polymer
The growth of molecular weight, contents of ethylene gradually reduces (K1:50.31%, K2:41.36%, K3:21.93%), degree of cyclization is gradually
Increase (K1:49.68%, K2:58.64%, K3:78.07%).This is due to the progress with reaction, and system interpolymer is dense
Degree and linear polymer chain increase, and the probability of polymer progress intramolecular cyclization is more than the second on linear increase, polymer chain
Intramolecular cyclization occurs for alkenyl, has consumed vinyl group of the polymer with.
The reaction result of the single-stranded super inner ring fluidized polymer of the different molecular weight of table 1
The conformation of polymer in a solvent is relevant with its mark's-Huo Wenke formula constant α.As α≤0.5, polymer is in
Existing comparatively dense structure.As 0.5≤α≤0.8, random coil conformation is presented in polymer；And polymer coil more stretches,
α is closer to 0.8；When polymer is in rigid Coiling-type, 1≤α.The α values of polymer can (poor refractive power be examined by tri- kinds of detectors of GPC
Survey RI, viscosity detector VS and Laser Light Scattering detector LS) combination measure.As a result test result as shown in fig. 6, show list
Mark-Huo Wener constant αs of the super inner ring fluidized polymer of chain are 0.29-0.34, and this shows that the structure for the polymer to be formed more is caused
It is close.
Polymer retouch Electronic Speculum as shown in fig. 7, as a result show single-stranded super inner ring fluidized polymer it is spherical in shape in aqueous and
It is uniformly distributed.Fig. 8 laser particle distribution tests (LPSD) result shows that the particle diameter of single-stranded super inner ring fluidized polymer is about 7.25
±1.5nm.The Controlled Living Radical Polymerization method polymerization polyethyleneglycol diacrylate adjusted using zerovalent copper can be synthesized newly
The single-stranded super inner ring fluidized polymer of type, and the polymer architecture is fine and close, appears similar to the spherical of a diameter of 7.25 ± 1.5nm
Structure.
By1H-NMR test results understand, the content of single-stranded super inner ring fluidized polymer medium vinyl functional group it is more and
PEGDA700Water miscible, thus after being mixed with light trigger under ultra violet lamp can Quick cross-linking be hydrogel material simultaneously
It is expected to be used as bioadhesive.Can by the test of rheological property, adhesion property, swelling behavior, degradation property and biocompatibility
Specifically characterize the physical property and biological property of the hydrogel material.
Respectively using the different single-stranded super inner ring fluidized polymer of molecular weight as presoma, 2,2- dimethoxy-phenylf acetophenones
(Irgacure 2959) be ultraviolet initiator, water is solvent, using Light lnduced Free Radicals polymerisation be prepared for it is a series of not
With the hydrogel material of concentration.Specific preparation method is as follows：As shown in table 2, the single-stranded super intramolecular cyclization of different molecular weight is polymerize
Thing is configured to the aqueous solutions of polymers of various concentrations, is placed in disposable vial and fully dissolves.Due to Irgacure 2959
Dissolubility in pure water is very poor, therefore is dissolved in acetone, and with being Irgacure that mass percent is 5%
2959/ acetone soln, takes the solution of respective volume to be added in aqueous solutions of polymers, whirlpool is used rapidly before photo-crosslinking with liquid-transfering gun
Instrument concussion is revolved to mix.Take the colourless transparent solution of appropriate volume to be placed in corresponding container, be put under UV lamp, in certain illumination bar
Hydrogel is solidified under part.
Table 2 prepares the rate of charge of hydrogel material
The research of the rheological property of polymer and ultraviolet initiation solidification plastic can pass through the plate (d=by Stress control
8mm) AR2000 rheometers are realized.In the research of photo-crosslinking rheological property, wavelength is used for 320-390nm, light intensity
Spend for 100mW/cm2The type uviol lamps of Omnicure 1000.In test process, ultraviolet light may pass through PMMA chassis, so poly-
Compound can be by ultraviolet lighting until plastic.This test is at room temperature 5Hz in frequency after photo-crosslinking 20s, is strained as 5%,
Tested under the concussion-temporal mode for being highly 0.8mm.The mixed with polymers solution configured is placed on testboard, entered
Row 1min steady testing, then carries out ultraviolet light cross-linking 20s., can be in the shake that frequency is 0.1 to 100Hz after the completion of to be tested
Swing-frequency mode under further test hydrogel material storage modulu G' and loss modulus G ".Earthquake-time test pattern
Under, the storage modulu G' and loss modulus G " of aqueous solutions of polymers are in preceding 1min without significant change.After ultraviolet lighting, polymer
G' start to sharply increase and be far longer than G' and G " in G ", and 10 seconds and occur in that intersection point, indicate the formation of hydrogel material.
Knowable to Fig. 9 (a), high 4 orders of magnitude of the modulus of the modular ratio no cross-linked polymer of the hydrogel material after crosslinking, and reach
Steady state value and do not change over time.This further demonstrated that single-stranded super inner ring fluidized polymer can in 20s rapid polymerization and completely
Form hydrogel material.In addition, the G' of single-stranded super inner ring fluidized polymer reduces (K1 with the increase of molecular weight:0.29MPa,
K2:0.23MPa,K3:0.08MPa), this is due to the progress with reaction, and polymer chain rate of rise is reduced, and molecule inner ring
The part vinyl changed in reaction probabilities increase, polymer chain itself is consumed, and shows as increasing of the contents of ethylene with molecular weight
Plus and reduce so that crosslink density reduction cause G' decline.
Single-stranded super inner ring fluidized polymer because with fine and close structure and higher contents of ethylene, therefore its crosslink density it is high and
Show that there is higher G'.Under earthquake-frequency test pattern, the stability to hydrogel material is further characterized.Such as Fig. 9
(b) shown in, under the conditions of 0.01Hz to 256Hz test frequency, the G' of single-stranded super inner ring fluidized polymer is in the frequency range
(0.01Hz-256Hz) is always maintained at stabilization.Further demonstrate that the structure of single-stranded super inner ring fluidized polymer is relatively stablized, this is poly-
Compound structure and the coefficient result of crosslink density.
, can be by Lap-shear in order to characterize the adhesion property of hydrogel material, Pull-off, Burst tests respectively from
Laterally adhesion, longitudinal direction adhesion and impact resistance degree carry out the sign of mechanics adhesion property.
Understand that the intensity of ultraviolet light cross-linking and time can influence the adhesion strength of hydrogel by experiment, therefore handed over changing light
The intensity of connection and under conditions of the time by Lap-shear test can obtain hydrogel adhesion strength up to maximum when crosslinking bar
Part.It is 10kDa, 20kDa, 40kDa that molecular weight is used in Optimal Experimental, and mass percent is 30% single-stranded super intramolecular cyclization
The aqueous solution of polymer.Photo-crosslinking intensity is 0.8W/cm2、1.2W/cm2、1.7W/cm2, the photo-crosslinking time is 10s, 15s, 20s.
From test result table 3, under the conditions of identical crosslinking time, the adhesion strength of hydrogel is with the increase of photo-crosslinking intensity
Increase.Similar, under the conditions of identical cross-link intensity, the adhesion strength of hydrogel increases with the increase of photo-crosslinking time.
Thus, it can be known that single-stranded super inner ring fluidized polymer is 1.7W/cm in cross-link intensity2, crosslinking time cross-linkable solidifying and reaches when being 20s
To maximum adhesion intensity (16kPa).Therefore, the optimal photo-crosslinking condition is used in the test of hydrogel adhesion property.
As shown in table 4, (the 1.7W/cm under the conditions of photo-crosslinking is optimized2, 20s), it is single-stranded super interior with identical molecular weight
The adhesion strength of cyclisation hydrogel increases with the increase of polymer concentration (10%, 20%, 30%).Such as molecular weight is K1
When, concentration for 10%, 20%, 30% single-stranded super intramolecular cyclization hydrogel Lap-shear adhesion strengths be respectively 3.43kPa,
7.86kPa, 15.67kPa, Pull-off adhesion strengths are respectively 1.83kPa, 3.68kPa, 5.39kPa.Molecular weight is K2, K3
When, show identical variation tendency.This is due to that polymer solution concentration is higher, and contents of ethylene is higher, its crosslink density
Also it is higher.
Lap-shear test of the single-stranded super intramolecular cyclization hydrogel of the different molecular weight of table 3 under the conditions of different photo-crosslinkings
The adhesion property test of single-stranded super intramolecular cyclization hydrogel material under the optimal cross linking conditions of table 4
When polymer concentration is identical, the adhesion strength of single-stranded super intramolecular cyclization hydrogel is with the increase of polymer molecular weight
When reduction, such as polymer concentration are 30%, molecular weight glues for the Lap-shear of K1, K2, K3 single-stranded super intramolecular cyclization hydrogel
Attached intensity is respectively 15.67kPa, 12.84kPa, 8.11kPa, Pull-off adhesion strengths be respectively 5.39kPa, 3.89kPa,
2.97kPa, Burst adhesion strength are respectively 0.367MPa, 0.309MPa, 0.236MPa.This is attributed to part vinyl group and existed
It is consumed in intramolecular cyclization reaction, causes crosslink density to reduce, the conclusion is identical with the result of hydrogel rheology testing.
In summary, the Lap-shear adhesion strengths of single-stranded super intramolecular cyclization hydrogel are up to 15.67kPa, and Pull-off adhesion strengths reach
5.39kPa, Burst adhesion strength are up to 0.367MPa.It follows that the hydrogel has stronger adhesion property, it is expected to use
Make wound dressing.
Polyalcohol hydrogel is made up of water and polymer network structure, and it can absorb a certain amount of moisture and be swelled
For swollen hydrogel.The swelling ratio of poised state can be considered a direct parameter for characterizing crosslinked polymer degree, therefore can pass through
Equilibrium swelling experiments characterize the architectural feature of polymer.Swelling ratio can change with the difference of the degree of cross linking.
In order to evaluate the swelling behavior of hydrogel in physiological conditions, the hydrogel prepared is immersed in PBS during test
In 24 orifice plates of buffer solution, in the shaking table for being placed in 37 DEG C.Swelling ratio can be by the change of hydrogel material weight in certain time
Change to calculate.It is swelled test result as shown in Figure 10, the stage is swelled comparatively fast and at 15 days single-stranded super intramolecular cyclization hydrogel in the early stage
Poised state is reached when left and right, volume now is original 1.29-1.38 times.When polymer molecular weight be respectively 10kDa,
When 20kDa, 40kDa, swelling ratio during single-stranded super intramolecular cyclization hydrogel balance is respectively 15.61%, 20.86%, 29.72%.
This is due to that single-stranded super intramolecular cyclization hydrogel medium vinyl content is reduced with the increase of molecular weight, therefore under its crosslink density
Drop.Solvent molecule is more easy to enter in polymer network so that strand is expanded, and then causes the increase of polymer volume.
The ideal biomaterial applied generally, for most of organizational projects should have adjustable, relatively stable
Degradation property.Polymer is under oxidation reaction, radiation, thermal decomposition or hydrolysis, and its main chain or side chain occur fracture and caused
The degraded of polymer.Wherein, the degraded that polymer occurs by hydrolysis is regarded as the main chain in polymer, oligomer or
The fracture of chemical bond is there occurs between monomer under hydrolysis.Because there are ester functional groups in polymer, buffered when being immersed in PBS
It can be degraded after in liquid because of hydrolysis, experimental result is as shown in figure 11.Single-stranded super intramolecular cyclization hydrogel is not shown
Larger degradation behavior, this is due to that it possesses longer carbon backbone chain similar to nondegradation PEG-hydrogel material, only side
The ester group of chain is degraded under hydrolysis, and final depolymerization is longer carbochain polymer and shorter PEG chains
Unit.When polymer molecular weight is different, its degradation behavior is also varied from.When polymer molecular weight is respectively K1, K2, K3
When, residual polymer mass fraction is 79.65%, 85.72%, 89.37% after depolymerization.This variation tendency it is main
Reason is the increase with polymer molecular weight, the structure of polymer formation for the less polymer of molecular weight more
Densification, hydrolysis is relative to be weakened, degradation capability reduction, the mass fraction relative increase of residual polymer.In summary, have
The single-stranded super inner ring fluidized polymer of slower degradation behavior is suitable for wound dressing or the tissue adhesive that need to be healed for a long time.
In order to characterize the biocompatibility of hydrogel material, it can be existed by fibroblast (Fibroblast) metabolic activity
StandardUnder the conditions of test.Cultivated under standard cell culture conditions after mouse 3T3 fibroblasts 24h,
It is put into the hydrogel material of photo-crosslinking preparation.Continue after cultivating 24 hours, take out hydrogel material and be used in combinationMethod
To test its cytotoxicity.As shown in table 5, the cytotoxicity of hydrogel material is with the increase of polymer molecular weight for test result
Reduction.Cell survival rate such as the single-stranded super intramolecular cyclization hydrogel that molecular weight is K1, K2, K3 is respectively 87.9%, 89.4%,
92.1%.Although single-stranded super inner ring fluidized polymer medium vinyl content is higher, due to the presence of cyclized structure, part vinyl
Group is embedded in the structure, and comparatively the vinyl exposed to top layer is reduced, therefore single-stranded super intramolecular cyclization structure hydrogel
With relatively low cytotoxicity.
The concentration of table 5 is the cytotoxicity test of the single-stranded super intramolecular cyclization hydrogel material of 30% different molecular weight
Above-mentioned property method of testing is substantially as follows, for reference：
Lap-shear is tested
Setup test sample is needed before carrying out Lap-shear tests.Specific preparation process is as follows：
1) mixed with polymers solution is configured：The straight polymer of different structure, different molecular weight is respectively configured as different dense
Spend the aqueous solutions of polymers of (10%, 20%, 30%, 50%w/v)；Then ultraviolet initiator Irgacure 2959 is configured
Into the acetone soln that concentration is 5%.Mass ratio according to polymer and light trigger is 100:1 ratio is well mixed.
2) preparation of adhered test sample：Pretreated pigskin is cut to long 40mm, wide 25mm, thick 1mm shape is used
Its fatty side is bonded on long 75mm, wide 25mm, thick 1mm sheet glass by Superglue.Then gathering for 200 μ L is taken with liquid-transfering gun
Compound mixed solution makes it uniformly be laid on pigskin epidermis.Taking an equal amount of sheet glass again makes it gently be covered in polymerization
On thing mixed solution.(the intensity under default light intensity and time conditions：0.8,1.2,1.7W/cm2；Time：10s, 15s, 20s),
And uviol lamp is away from progress photo-crosslinking solidification at the sheet glass 1cm of upper strata.After photo-crosslinking terminates, sample places 2- at ambient temperature
Lap-shear tests are carried out after 3min again.
3) Lap-shear is tested：It is parallel in vertical direction to be placed on test machine by the test sample prepared.
Stretched under 2mm/min constant speed, until fracture.Adhesion strength is the maximum before fracture, and every group of test repeats 3
It is secondary.
Pull-off is tested
Setup test sample is needed before carrying out Pull-off tests.Specific preparation process is as follows：
1) mixed with polymers solution is configured：The straight polymer of different structure, different molecular weight is respectively configured as different dense
Spend the aqueous solutions of polymers of (10%, 20%, 30%, 50%w/v)；Then ultraviolet initiator Irgacure 2959 is configured
Into the acetone soln that concentration is 5%.Mass ratio according to polymer and light trigger is 100:1 ratio is well mixed.
2) preparation of adhered test sample：Pretreated pigskin is cut to diameter 25mm, thick 1mm disc is used
Its fatty side is bonded on a diameter of 25mm aluminium flake by Superglue.Then 100 μ L mixed with polymers solution is taken with liquid-transfering gun
It is set uniformly to be laid on pigskin epidermis.Long 75mm is used again, and wide 25mm, thick 1mm sheet glass is gently covered in polymer and mixed
Close on solution.(the intensity under default light intensity and time conditions：1.7W/cm2；Time：20s), and uviol lamp is away from upper strata sheet glass
Photo-crosslinking solidification is carried out at 1cm.After photo-crosslinking terminates, with Superglue by the aluminium flake station of formed objects on the glass sheet.Sample
Product are placed at ambient temperature carries out Pull-off tests again after 2-3min.
3) Pull-off is tested：It is parallel in horizontal direction to be placed on test machine by the test sample prepared.In 2mm/
Stretched under min constant speed, until fracture.Adhesion strength is the maximum before fracture, and every group of test is repeated 3 times.
Burst is tested
Setup test sample is needed before carrying out Burst tests.Specific preparation process is as follows：
1) mixed with polymers solution is configured：The straight polymer of different structure, different molecular weight is respectively configured as different dense
Spend the aqueous solutions of polymers of (10%, 20%, 30%, 50%w/v)；Then ultraviolet initiator Irgacure 2959 is configured
Into the acetone soln that concentration is 5%.Mass ratio according to polymer and light trigger is 100:1 ratio is well mixed.
2) preparation of adhered test sample：Pretreated pigskin is cut to diameter 30mm, thick 1mm disc is used
Its greasy is fixed on the surface that Burst tests pump by Superglue, and pricks small on an aperture, with pump on the surface of pigskin
Hole site is parallel, in the same size.Open tap, regulation flow velocity allow the water in the form of water column spray and record now just
Beginning pressure P0.Close tap and remove the water of pig skin surfaces.Then 200 μ L mixed with polymers solution is taken with liquid-transfering gun makes it
Uniformly it is laid on pigskin epidermis.(the intensity under default light intensity and time conditions：1.7W/cm2；Time：20s), it is and ultraviolet
Lamp is away from progress photo-crosslinking solidification at the sheet glass 1cm of upper strata so that water-setting is adhesive on pigskin.After photo-crosslinking terminates, in room temperature
Under the conditions of place 2-3min after carry out Burst tests again.
3) Burst is tested：Tap is opened, is tested under the conditions of preset flow rate, until aquagel breaks, water column spray
Go out, record maximum pressure value Pt.Then maximum adhesion intensity is P=Pt-P0, every group of test be repeated 3 times.
Swelling behavior is characterized
The test of swelling behavior performance can be measured with weight method.Detailed process is as follows：
1) preparation of hydrogel：The polymer of different structure, different molecular weight is configured to the polymer that concentration is 30%
Solution, then adds the solution of light trigger Irgacure 2959 that concentration is 5%, mass ratio is 100:1.Take 50 μ L mixing
Thing solution is placed on the sheet glass weighed, and is 1.7W/cm in intensity2, the time is 20s, highly to carry out light under conditions of 1cm
Crosslinking curing.After photo-crosslinking terminates, hydrogel of weighing at once, and it is designated as initial weight W0, then it is placed on 2mL PBS
In buffer solution, it is placed in 37 DEG C of shaking table and is rocked with slow speed.
2) weigh：The hydrogel being swelled regularly is taken out from PBS, excess surface moisture is gently wiped and claims
Weight, is designated as Wt.Then hydrogel is placed back in PBS.The swelling ratio (SR) of hydrogel can be counted by formula (3-1)
Calculate：
SR=(Wt-W0)/W0× 100% (formula 3-1)
Every kind of hydrogel takes four samples to be tested, and averages, and is designated as final swelling ratio SR.
Degradation property is characterized
The test of hydrogel degradation property can be measured with weight method.Detailed process is as follows：
1) preparation of hydrogel：The polymer of different structure, different molecular weight is configured to the polymer that concentration is 30%
Solution, then adds the solution of light trigger Irgacure 2959 that concentration is 5%, mass ratio is 100:1.Take 50 μ L mixing
Thing solution is placed on the sheet glass weighed, and is 1.7W/cm in intensity2, the time is 20s, highly to carry out light under conditions of 1cm
Crosslinking curing.After photo-crosslinking terminates, it is placed in 2mL PBS, is placed in 37 DEG C of shaking table with slow speed
Rock.One group therein (4) hydrogel is taken, is freeze-dried, is weighed when reaching constant weight, be designated as initial weight W0。
2) weigh：Hydrogel is regularly taken out from PBS, when freeze-dried processing reaches constant weight, weight is recorded
Wt.Residual qualities percentage digit rate can be calculated by formula (3-2) after hydrogel degraded：
Massloss=(W0-Wt)/Wt× 100% (formula 3-2)
Every kind of hydrogel takes four samples to be tested, and averages, and is designated as final residual qualities percentage.
Controllable/active free radical polymerization method (the Cu that this patent is regulated and controled by zerovalent copper0- mediated CRP) homopolymerization
PEGDA700Monomer obtains single-stranded super inner ring fluidized polymer poly (PEGDA700)SK.The formation of its single-stranded super interior ring structure is depended on
The polymerisation of dynamics Controlling, its chain increases and intramolecular cyclization reaction is promoted, and intermolecular cross-linking reaction is suppressed.Pass through
The sign of polymer proves that the α of single-stranded super inner ring fluidized polymer is less than 0.5, and its structure is similar to spherical.Pass through ultraviolet light cross-linking
Aqueous solutions of polymers solidification can be prepared hydrogel material.Pass through ultraviolet light-rheology joint test, single-stranded super intramolecular cyclization
Polymer can it is rapid-result soon (<20s) and height cyclized structure and a large amount of vinyl make it have higher storage modulu G'.Pass through
The tissue adhension performance discovery of Lap-shear, Pull-off and Burst test evaluation hydrogel material, single-stranded super intramolecular cyclization water
Gel has higher adhesion strength.In addition, single-stranded super intramolecular cyclization hydrogel has relatively low swelling behavior and slower degraded
Performance.By cytotoxicity test, single-stranded super intramolecular cyclization hydrogel has preferable cell compatibility.That is list of the invention
Application of the hydrogel in as wound dressing or tissue adhesive after the super inner ring fluidized polymer of chain and crosslinking.
Exemplary description is done to the present invention above, it should explanation, in the situation for the core for not departing from the present invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. single-stranded super inner ring fluidized polymer, it is characterised in that using polyethyleneglycol diacrylate as monomer, regulated and controled using zerovalent copper
Controlled Living Radical Polymerization method by monomer polyethyleneglycol diacrylate carry out homopolymerization, chain increase and intramolecular cyclization it is anti-
It should be promoted, intermolecular cross-linking reaction is suppressed, to obtain single-stranded super inner ring fluidized polymer, i.e., in the single-stranded middle formation line of polymer
Property polyethyleneglycol diacrylate and annular polyethyleneglycol diacrylate.
2. single-stranded super inner ring fluidized polymer according to claim 1, it is characterised in that the number of polyethyleneglycol diacrylate
Average molecular weight is 700.
3. single-stranded super inner ring fluidized polymer according to claim 1, it is characterised in that the weight of single-stranded super inner ring fluidized polymer
Average molecular weight is 10KDa -40KDa, and PDI is 1.19-1.48.
4. single-stranded super inner ring fluidized polymer according to claim 1, it is characterised in that the second of single-stranded super inner ring fluidized polymer
Amount vinyl content is 20-50%.
5. single-stranded super inner ring fluidized polymer according to claim 1, it is characterised in that the ring of single-stranded super inner ring fluidized polymer
Change degree is 50-80%.
6. single-stranded super inner ring fluidized polymer according to claim 1, it is characterised in that the horse of single-stranded super inner ring fluidized polymer
Ke-Huo Wenke formula constant is 0.29-0.34.
7. single-stranded super inner ring fluidized polymer according to claim 1, it is characterised in that single-stranded super intramolecular cyclization polymer architecture
Densification, appears similar to a diameter of 7.25 ± 1.5nm spherical structure.
8. the preparation method of single-stranded super inner ring fluidized polymer, it is characterised in that by polyethyleneglycol diacrylate, the bromo- 2- first of 2-
Base ethyl propionate, CuBr2And N, N, N ', N ", N "-pentamethyl-diethylenetriamines are according to mol ratio 100：1：(0.4—0.5)：
(0.8-1) be placed in it is dispersed in dimethyl sulfoxide (DMSO), and by wind copper wire stirrer be placed in dimethyl sulfoxide (DMSO) to reaction system
System is stirred, and is reacted under the conditions of deoxygenation, and the Controlled Living Radical Polymerization method regulated and controled using zerovalent copper is by monomer
Polyethyleneglycol diacrylate carries out homopolymerization, and chain increases and intramolecular cyclization reaction is promoted, and intermolecular cross-linking reaction is suppressed.
9. the preparation method of single-stranded super inner ring fluidized polymer according to claim 8, it is characterised in that reaction temperature is
20-25 degrees Celsius, the reaction time is 1-5 hours.
10. the single-stranded super inner ring fluidized polymer as described in one of claim 1-7 is in wound dressing or tissue adhesive is prepared
Application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710150145.3A CN106947011A (en) | 2017-03-14 | 2017-03-14 | Single-stranded super inner ring fluidized polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710150145.3A CN106947011A (en) | 2017-03-14 | 2017-03-14 | Single-stranded super inner ring fluidized polymer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106947011A true CN106947011A (en) | 2017-07-14 |
Family
ID=59466952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710150145.3A Pending CN106947011A (en) | 2017-03-14 | 2017-03-14 | Single-stranded super inner ring fluidized polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106947011A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395060A (en) * | 2021-11-30 | 2022-04-26 | 西安交通大学 | Preparation method of cyclic polymer and application of structured gel electrolyte based on polymer in solid-state sodium battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451668A (en) * | 2003-05-07 | 2003-10-29 | 苏州大学 | Controllable/active free radical polymerization method, polymer, controlling agent and preparing process thereof |
| CN107915815A (en) * | 2016-10-08 | 2018-04-17 | 天津大学 | Hyperbranched poly ethylene glycol crosslinking agent and its RAFT active free radical polymerization methods |
-
2017
- 2017-03-14 CN CN201710150145.3A patent/CN106947011A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451668A (en) * | 2003-05-07 | 2003-10-29 | 苏州大学 | Controllable/active free radical polymerization method, polymer, controlling agent and preparing process thereof |
| CN107915815A (en) * | 2016-10-08 | 2018-04-17 | 天津大学 | Hyperbranched poly ethylene glycol crosslinking agent and its RAFT active free radical polymerization methods |
Non-Patent Citations (2)
| Title |
|---|
| 李思蓉 等: "单链超内环化聚合物与线性高分子共混物的粘弹性研究", 《高分子学报》 * |
| 郭琳茹 等: "可控活性聚合多烯基单体制备新型单链超内环化聚合物的研究历史及进展", 《中国科学：化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114395060A (en) * | 2021-11-30 | 2022-04-26 | 西安交通大学 | Preparation method of cyclic polymer and application of structured gel electrolyte based on polymer in solid-state sodium battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108929412B (en) | Preparation method of temperature-responsive adhesive injectable hydrogel | |
| Hu et al. | Electrospinning of poly (glycerol sebacate)-based nanofibers for nerve tissue engineering | |
| Zhou et al. | Photopolymerized maleilated chitosan/thiol-terminated poly (vinyl alcohol) hydrogels as potential tissue engineering scaffolds | |
| Wei et al. | Thermosensitive hydrogels synthesized by fast Diels–Alder reaction in water | |
| CN102481542B (en) | Polymerization reactor for producing a super absorbent polymer and method for producing a super absorbent polymer using the polymerization reactor | |
| JP6085887B2 (en) | Gels and hydrogels | |
| CN101824123B (en) | High-strength temperature-sensitive hydrogel as well as preparation method and application thereof | |
| Wei et al. | Characterisation of N-vinyl-2-pyrrolidone-based hydrogels prepared by a Diels–Alder click reaction in water | |
| CN102325814A (en) | Be used for the preparation of the biodegradable hydrogel of biomedical applications | |
| CN107915815B (en) | Hyperbranched polyethylene glycol cross-linking agent and RAFT (reversible addition-fragmentation chain transfer) active free radical polymerization method thereof | |
| Kemal et al. | Phosphate based 2-hydroxyethyl methacrylate hydrogels for biomedical applications | |
| CN102504229A (en) | Synthesis method of in-situ-enhanced thermosensitive polymer and degradable in-situ-enhanced injectable thermosensitive hydrogel | |
| KR20180062244A (en) | Method for producing photo-crosslinked silk fibroin, and photo-crosslinked silk fibroin produced by the same | |
| CN106893018A (en) | Hydrogel and its application based on single-stranded super inner ring fluidized polymer | |
| JP3913867B2 (en) | Water absorbing agent and method for producing the same | |
| EP2346914B1 (en) | Polymer particles prepared from polymerisable alkylene glycol (meth) acrylate monomers | |
| Zhang et al. | A nucleobase-inspired super adhesive hydrogel with desirable mechanical, tough and fatigue resistant properties based on cytosine and ε-caprolactone | |
| CN106947011A (en) | Single-stranded super inner ring fluidized polymer and preparation method thereof | |
| CN105906766A (en) | Preparation method of light/biological dual-degradation high-water-absorption resin based on natural polymer | |
| CN112442193B (en) | Preparation method of self-repairing bionic hydrogel with toughness and adhesion | |
| CN108623763A (en) | Hydrogel based on linear copolymer and its application | |
| CN108586682A (en) | Dissaving polymer and preparation method thereof | |
| CN108623729A (en) | Hydrogel based on dissaving polymer and its application | |
| CN111138607B (en) | Temperature-sensitive coacervate type hyperbranched polyethylene glycol and preparation method and application thereof | |
| CN108623764A (en) | Linear copolymer and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170714 |
|
| RJ01 | Rejection of invention patent application after publication |