CN109761843A - It is a kind of for binding metal material and the bridging molecule of hydrogel and its preparation method and application - Google Patents
It is a kind of for binding metal material and the bridging molecule of hydrogel and its preparation method and application Download PDFInfo
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- CN109761843A CN109761843A CN201910042373.8A CN201910042373A CN109761843A CN 109761843 A CN109761843 A CN 109761843A CN 201910042373 A CN201910042373 A CN 201910042373A CN 109761843 A CN109761843 A CN 109761843A
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Abstract
The invention belongs to organic functional moleculars to synthesize field, disclose a kind of for binding metal material and the bridging molecule of hydrogel and its preparation method and application.The present invention introduces the functional group that can be acted on metal surface and hydrogel in bridging molecule, as " molecular interface tie ", chemical anchor point is accessed in metal surface by surface modification methods such as spraying in situ, dip-coatings, and by home position polymerization reaction two terminal functionalities of bridging molecule are bonded respectively with hydrogel and metal surface, reach high-strength adhesive between the two.When using the bridging molecule containing responsiveness group, bridging molecule can be disconnected by outside stimulus response quickly on the basis of realizing high-strength adhesive, and then achieve the effect that separation should be needed.In the present invention synthesis of bridging molecule it is simple, it is reproducible, can amplify preparation, and whole surface processing and adhesion process are convenient, efficient, are expected to be widely applied to biomedical related fields, clinical value with higher.
Description
Technical field
Synthesize field the invention belongs to organic functional molecular, in particular to it is a kind of for binding metal material and hydrogel
Bridging molecule and its preparation method and application.
Background technique
With the development of modern medicine, artificial implantable medical device is by industry extensive concern and great attention.However,
The height structural complexity of tissue and organ is unable to satisfy single structure and the artificial repair the device of component in clinic
Diversified actual demand.Based on this, in conjunction with flexible hydro-gel material and rigid medical alloy developing material one kind Novel imitation
Raw implantable medical device becomes a kind of feasible new approaches.
Currently, although people technically still can not mimic biology system labyrinth, development have biomimetic features
Still there is important basic research meaning and wide potential applicability in clinical practice with the medical implantable apparatus of a new generation of function.Water-setting
Glue class material refers to a kind of hydrophilic macromolecule with three-dimensional network shape cross-linked structure, because its water content with higher, can
The features such as mechanical performance of adjusting, preferable biocompatibility and degradability, can preferably adapt to the biochemistry of tissue
With mechanical environment；And by chemical modification appropriate, biologically active functional group can be introduced, is realized to various kinds of cell row
For regulation.Therefore, hydrogel material is widely used for substituting and repairing soft histoorgan in human body.On the other hand, it cures
With metal/alloy material, such as titanium alloy and magnesium alloy, because it is with high mechanical strength and fatigue resistance, can be used for supporting,
Protect and the reparation of sclerous tissues is substituted etc..However, how to realize high-strength between hydrogel and rigid medical metal material
Degree bonding, is the difficult point and innovative point of currently associated area research.
In addition, such as: repair tissue and physiological environment complexity need Iterim Change hydrogel medical in practical application
Infection class problem, which occurs, behind position, implantation material on metal to re-replace, and need hydrogel material and medical metal
Material is conveniently separated, and therefore, how to realize the quick separating between hydrogel and rigid medical metal material,
It is the hot spot of currently associated area research.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of for bonding
The bridging molecule of metal material and hydrogel.
Another object of the present invention is to provide the above-mentioned preparation side for binding metal material and the bridging molecule of hydrogel
Method.
Still a further object of the present invention is to provide the above-mentioned bridging molecule for being used for binding metal material and hydrogel in realization water
Application in gel and metal material interface high-strength adhesive especially combines flexible hydro-gel material and rigidity medical in preparation
Application in the bionical implantable medical device of metal material.
The purpose of the present invention is realized by following proposal:
A kind of bridging molecule for binding metal material and hydrogel, general structure are as follows:
Wherein, R1The group containing at least one functional group that can be crosslinked with hydrogel network is indicated, wherein with water-setting
The functional group of glue network cross-linked includes but is not limited to alkenyl, alkynyl, amino, catechol, methacrylate, methacryl
Amine, acrylate, acrylamide, sulfydryl and hydroxyl；R1Preferably methacrylamide group, methacrylate group or
Acrylate group；
R2Indicate the group for containing at least one functional group that can be bonded with metal material, wherein be bonded with metal material
Functional group includes but is not limited to carboxylate, catechol, phosphate, pyridines nitrogen-containing heterocycle and lipoic acid；Preferably carboxylate
Or lipoic acid group；
X1-X2Indicate dynamic chemical key, simple linking group or the connection containing at least one irritation response group
Group, wherein simple linking group includes but is not limited to one of alkyl, alkenyl, ketone group and ether or the above linking group
In at least two combinations；Stimuli responsive group includes but is not limited to pH sensitive group, temperature sensitive group, isotope of redox-sensitive
Group and photoresponse group act on metal when containing irritant response functional group in bridging molecule with such bridging molecule
When the interface of material and hydrogel material, the high-strength adhesive that both can be realized and it should be needed point under extraneous particular stimulation
From.
Preferably, the pH sensitive group includes but is not limited to tertiary amine, secondary amine, sulfonic group；The temperature sensitivity base
Group includes but is not limited to amide groups and ether；The isotope of redox-sensitive group include but is not limited to disulfide group, amino, alkynyl and
Alkenyl；The photoresponse group includes but is not limited to chlorophyllin, aromatic series azido group and nitro alcohol derivative.
Preferably, the structural formula of the bridging molecule is one of following structural formula:
In the structural formula of above-mentioned preferred bridging molecule, the functional group with hydrogel network crosslinking is methacryl amido
Group, methacrylate group or acrylate group；Group with the functional group of metal bonding is respectively carboxylate or sulphur
Sad group, and contain isotope of redox-sensitive group disulfide group in bridging molecule 2.
A kind of above-mentioned preparation method for binding metal material and the bridging molecule of hydrogel, comprising the following steps:
When for bridging molecule 1, preparation method includes the following steps: 12-aminolauric acid and triethylamine, which are dissolved in, to be had
In solvent, methacrylic anhydride is then added and is stirred to react, obtains bridging molecule 1, the following institute of reaction equation after reaction
Show:
In the preparation method of bridging molecule 1:
The amount ratio of the 12-aminolauric acid, methacrylic anhydride and triethylamine is 1~10.0g:1~20mL:1
~50mL；The dosage of the organic solvent meets the organic of 20~300mL of the corresponding addition of 12-aminolauric acid of every 1~10g
Solvent；
The organic solvent is at least one of tetrahydrofuran, methylene chloride, chloroform and acetone；
Described be stirred to react refers to and is stirred to react 4~36h in ice-water bath；After the completion of being stirred to react, further include spend from
The step of sub- water extraction removes impurity.
When for bridging molecule 2, preparation method includes the following steps: by sub- dimercapto diethyl acid be dissolved in acetic anhydride into
Row reaction obtains annular two sulfuric anhydrides, is then dissolved in obtained two sulfuric anhydride of annular with hydroxyethyl methacrylate organic molten
Agent is stirred to react to get to bridging molecule 2, and reaction equation is as follows:
In the preparation method of bridging molecule 2:
The mass volume ratio of the sub- dimercapto diethyl acid and acetic anhydride is 0.1~2.0g:1.0~20mL；Described
The dosage of organic solvent meets the corresponding organic solvent that 10~30mL is added of hydroxyethyl methacrylate of every 0.2~2.0g；Institute
The temperature that state be dissolved in sub- dimercapto diethyl acid is reacted in acetic anhydride is 0~40 DEG C, the reaction time is 4~for 24 hours；
The organic solvent is chloroform, N,N-dimethylformamide, acetone, tetrahydrofuran, isopropanol, N, N- dimethyl
At least one of acetamide and methylene chloride, preferably methylene chloride or tetrahydrofuran；
The dosage of two sulfuric anhydride of annular and hydroxyethyl methacrylate meets the raw material Asia two of annular two sulfuric anhydrides
The mass ratio of sulfydryl oxalic acid and hydroxyethyl methacrylate is 0.1~2.0:0.2~2.0；The dosage of the organic solvent
Meet the corresponding organic solvent that 10~30mL is added of hydroxyethyl methacrylate of every 0.2~2.0g；
Described being stirred to react refers to that in ice water bath environment, revolving speed is to be stirred to react 12~72h under 100~1000rpm,
After reaction further including one uses gel chromatographic columns in petroleum ether and ethyl acetate volume ratio (0.5~4): 1 mixed solvent
The step of being purified under effect.
When for bridging molecule 3, preparation method includes the following steps: by lipoic acid, 4-dimethylaminopyridine, two hexamethylenes
Base carbodiimide and hydroxy-ethyl acrylate are added in the organic solvent under ice bath, are stirred to react, and obtain bridge after reaction
Even molecule 3, reaction equation is as follows:
In the preparation method of bridging molecule 3:
The amount ratio of the lipoic acid, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and hydroxy-ethyl acrylate is
(0.5~20g): (0.05~2g): (1.5~60g): (0.3~12mL)；The dosage of the organic solvent meets every 0.5~
The corresponding organic solvent that 10~300mL is added of the lipoic acid of 20g；
The organic solvent is at least one of tetrahydrofuran, methylene chloride, chloroform and acetone；
Described be stirred to react refer to and be stirred to react 4~36h under ice bath, further include after reaction one by go from
The step of sub- water washing purifies.
Stirring described in preparation method of the invention is for making adequately contacting between raw material, accelerates reaction speed
Degree, the mixing speed of this field routine can be achieved, therefore not need restriction mixing speed, and mixing speed is preferably 100~
1000rpm。
Above-mentioned is realizing that hydrogel and metal material interface are high for the bridging molecule of binding metal material and hydrogel
Application in intensity bonding especially combines the bionical implantable of flexible hydro-gel material and rigid medical metal material in preparation
Application in medical instrument.
The hydrogel includes various energy based on in-situ polymerization mechanism of crosslinking and R1The hydrogel that group is crosslinked；Institute
The metal material stated includes the various metal and its alloy for being usually used in medical equipment.
Described is realizing that hydrogel and metal material interface are high for the bridging molecule of binding metal material and hydrogel
Application in intensity bonding, specifically includes the following steps:
(1) bridging molecule is dissolved in solvent and is configured to bridging molecule solution, the surface for then acting on metal material obtains
The metal material surface modified to bridging molecule；
(2) hydrogel precursor is coated on to the metal material surface of the modification of bridging molecule obtained by step (1), passes through certain item
Reaction under part can be completed at the same time the solidification of hydrogel and hydrogel passes through the high-strength of bridging molecule and metal material interface
Degree bonding.
Step (1) solvent be acetone, ethyl alcohol, tetrahydrofuran, methylene chloride, chloroform and isopropanol at least
It is a kind of.
Step (1) metal material be one of metals such as nickel, magnesium, titanium, chromium, aluminium, cobalt, gold, silver, platinum or with
At least two alloys or stainless steel formed in upper metal.
The mass fraction of bridging molecule is 0.1~10wt% in step (1) the bridging molecule solution；
The dosage of step (1) the bridging molecule solution meets: every 1cm2Metal material surface it is corresponding using 0.001~
The bridging molecule solution of 10mL, preferably every 1cm2The corresponding bridging molecule for using 0.001~0.01mL of metal material surface
Solution.
Step (1) surface for acting on metal material refers to by spraying, adhering to immediately, in dip-coating and immersion extremely
It is few it is a kind of by solution effects in the surface of metal material, action time is 0.01~for 24 hours；
Step (2) hydrogel precursor is selected from one of the component A and B of following mass fraction:
Component A:1.5~3.5 part polyethyleneglycol diacrylate (PEGDA), 0.1~0.5 part of sodium alginate, 0.001~
0.5 part contains Ca2+Compound, 0.027~0.063 part of photoinitiator and 5~15 parts of water；
Component B:1~4 part acrylamide (AAm), 0.1~0.5 part of sodium alginate, 0.001~0.5 part contain Ca2+Compound,
0.02~0.04 part of N, N '-bismethacrylamide (crosslinking agent), 0.025~0.095 part of ammonium persulfate (initiator), 5~
15 parts of water and 0.0025~0.01 part of tetramethylethylenediamine.
Contain Ca described in component A and component B2+Compound be calcium sulfate, calcium carbonate, calcium oxalate, in calcium chloride at least
It is a kind of.
Reaction described in step (2) includes the cross-linking and curing reaction of hydrogel precursor and the original of hydrogel and bridging molecule
Position polymerization reaction, two kinds are reacted while being carried out.The cross-linking and curing reaction refer to 200~400nm ultraviolet light or 400~
Under 900nm visible light irradiation 0.01~for 24 hours；The home position polymerization reaction refer at room temperature reaction 0.01~for 24 hours；
When containing irritant response group in bridging molecule, hydrogel and metal material interface can be carried out when needed
It stress separate, the following example of specific implementation method.
As X in bridging molecules1-X2When containing pH sensitive group, the method that stress be separated is in hydrogel and metal material
Expect interface coated acid, base reagent, change environment pH value, selected pH sensitive group can dissociate；As X in bridging molecules1-
X2When containing temperature sensitive group, the method that stress be separated is to change temperature between 0~100 DEG C, and then destroy molecule knot
Structure；As X in bridging molecules1-X2When containing isotope of redox-sensitive group, the method that stress be separated is coating oxidized form paddy Guang
At least one of sweet peptide, reductive glutathione and dithiothreitol (DTT) or other reagents with similar reduction effect；It is preferred that
Glutathione or the dosage of dithiothreitol (DTT) meet 1cm2Adhesive interface use 0.005~5g.
Do not indicate temperature in the present invention is all to operate at room temperature, and the room temperature is 5~35 DEG C.
Mechanism of the invention are as follows:
The present invention from formed hydrogel polymer network chemical functional groups structure and metal material self attributes,
The functional group that can be acted on respectively with metal surface and hydrogel is introduced in bridging molecule, designs the chemical crosslinking of its exposed terminated groups
Site (such as bridging molecule end group double bond and hydrogel crosslinking copolymerization, end group carboxyl and metal coordination).Further, at it
Intramolecule introduces responsiveness group, can realize that bridging molecule should need to crack under outer signals appropriate stimulation.With this
Class bridging molecule is " molecular interface tie ", can be by the instant efficient surface modification method such as spraying in situ, dip-coating a variety of
Chemical anchor point is accessed in metal surface, and by home position polymerization reaction so that two terminal functionalities of bridging molecule can respectively with
Hydrogel and metal surface are bonded, and high-strength adhesive effect between the two is reached.Contain responsiveness group when using
When bridging molecule, then it can further be responded by outside stimulus on the basis for realizing high-strength adhesive, quickly disconnect bridge
Even molecule, and then hydrogel is made to achieve the effect that need to separate with metal.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
In the present invention synthesis of bridging molecule it is simple, it is reproducible, can amplify preparation, and whole surface processing and bonding
Process is convenient, efficient, mild, has preferable biological safety, is expected to be widely applied to biomedical related fields, has
Higher clinical value.
Detailed description of the invention
Fig. 1 is bridging molecule 1 prepared by embodiment 11H NMR spectra.
Fig. 2 is bridging molecule 2 prepared by embodiment 31H NMR spectra.
Fig. 3 is bridging molecule 3 prepared by embodiment 71H NMR spectra.
Fig. 4 is that the bridging molecule 1 of adhesive interface (a) and embodiment 9 preparation of blank aluminium surface and hydrogel modifies aluminium table
The macrograph of the adhesive interface (b) of face and hydrogel.
Fig. 5 is that bridging molecule bond to metal material substrate and hydrogel and be separated using glutathione in the present invention
The process schematic at interface.
Fig. 6 is that the bridging molecule 2 of adhesive interface (a) and embodiment 12 preparation of blank aluminium surface and hydrogel modifies aluminium table
Adhesive interface (b) macrograph in face and hydrogel.
Fig. 7 is that hydrogel with metal separates figure after acting on glutathione at interfacial adhesion in embodiment 12.
The adhesive interface and blank of the modification stainless steel surface of bridging molecule 2 and hydrogel that Fig. 8 is prepared for embodiment 13 are not
The adhesive interface of steel surface of becoming rusty and hydrogel removes curve graph.
Fig. 9 is (a) (b) hydrogel and substrate surface separation process figure afterwards before the processing of 13 GSH-PX activity of embodiment.
Figure 10 is the interface peel intensity before and after acting on glutathione at interfacial adhesion in embodiment 14.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited
In this.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.The equal of temperature is not specified in embodiment
Finger carries out at room temperature.
Embodiment 1
1g 12-aminolauric acid and 1mL triethylamine are dissolved in 20mL tetrahydrofuran, 1mL methacrylic acid is then added
Acid anhydride, mechanical stirring (revolving speed 1000rpm) 4h in ice-water bath.Impurity is then removed using the extraction of 1L deionized water, obtains bridging
Molecule 1.
Bridging molecule prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) as shown in Figure 1, can from Fig. 1
The present invention successfully synthesizes bridging molecule 1 out.
Embodiment 2
10g 12-aminolauric acid and 50mL triethylamine are dissolved in 300mL tetrahydrofuran, 20mL methyl-prop is then added
Olefin(e) acid acid anhydride, mechanical stirring (revolving speed 300rpm) 36h in ice-water bath.Impurity is then removed using the extraction of 10L deionized water, is obtained
Bridging molecule 1.
Bridging molecule prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) it is consistent with Fig. 1, illustrate the present invention
Successfully synthesize bridging molecule 1.
Embodiment 3
The Asia 0.1g dimercapto diethyl acid is dissolved in the acetic anhydride of 1.0mL, is reacted under the conditions of 0 DEG C and obtains within 24 hours annular two
The hydroxyethyl methacrylate and 10mL methylene chloride of 0.2g, under ice water bath environment, mechanical stirring is then added in sulfuric anhydride
(revolving speed 100rpm) 72h, finally using gel chromatographic columns under petroleum ether and the effect of ethyl acetate volume ratio 4:1 mixed solvent
Purifying obtains bridging molecule 2.
Bridging molecule 2 prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) as shown in Fig. 2, can be with from Fig. 2
Find out that the present invention successfully synthesizes bridging molecule 2.
Embodiment 4
The Asia 2.0g dimercapto diethyl acid is dissolved in the acetic anhydride of 20mL, is reacted under the conditions of 40 DEG C and obtains within 4 hours annular two
The hydroxyethyl methacrylate and 30mL methylene chloride of 2.0g, under ice water bath environment, mechanical stirring is then added in sulfuric anhydride
(revolving speed 1000rpm) 12h is finally made using gel chromatographic columns in petroleum ether and ethyl acetate volume ratio 0.5:1 mixed solvent
Bridging molecule 2 is obtained with lower purifying.
Bridging molecule 2 prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) it is consistent with Fig. 2, illustrate the present invention
Successfully synthesize bridging molecule 2.
Embodiment 5
The Asia 1.82g dimercapto diethyl acid is dissolved in the acetic anhydride of 15mL, is reacted 18 hours under the conditions of 25 DEG C and obtains annular
The hydroxyethyl methacrylate and 25mL methylene chloride of 1.6g, under ice water bath environment, mechanical stirring is then added in two sulfuric anhydrides
(revolving speed 600rpm) 18h, finally using gel chromatographic columns under petroleum ether and the effect of ethyl acetate volume ratio 3:1 mixed solvent
Purifying obtains bridging molecule 2.
Bridging molecule 2 prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) it is consistent with Fig. 2, illustrate the present invention
Successfully synthesize bridging molecule 2.
Embodiment 6
The Asia 1.5g dimercapto diethyl acid is dissolved in the acetic anhydride of 12mL, is reacted under the conditions of 30 DEG C and obtains within 12 hours annular two
The hydroxyethyl methacrylate and 20mL methylene chloride of 1.3g, under ice water bath environment, mechanical stirring is then added in sulfuric anhydride
(revolving speed 300rpm) 20h is finally acted on using gel chromatographic columns in petroleum ether and ethyl acetate volume ratio 1.5:1 mixed solvent
Lower purifying obtains bridging molecule 2.
Bridging molecule 2 prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) it is consistent with Fig. 2, illustrate the present invention
Successfully synthesize bridging molecule 2.
Embodiment 7
By the lipoic acid of 0.5g, the 4-dimethylaminopyridine of 0.05g, 1.5g dicyclohexylcarbodiimide and 0.3mL propylene
Sour hydroxyl ethyl ester is added in the tetrahydrofuran in ice bath environment (10mL), and mechanical stirring (revolving speed 700rpm) 4h completes reaction.
Then cleaned using 1L ionized water to get bridging molecule 3.
Bridging molecule 3 prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) as shown in figure 3, can be with from Fig. 3
Find out that the present invention successfully synthesizes bridging molecule 3.
Embodiment 8
By the lipoic acid of 20g, the 4-dimethylaminopyridine of 2g, 60g dicyclohexylcarbodiimide and 12mL acrylic acid hydroxyl second
Ester is added in the methylene chloride in ice bath environment (300mL), and mechanical stirring (revolving speed 100rpm) 36h completes reaction.Then
It is cleaned using 10L ionized water to get bridging molecule 3.
Bridging molecule 3 prepared by the present embodiment hydrogen nuclear magnetic resonance spectrogram (1H NMR) it is consistent with Fig. 3, illustrate the present invention
Successfully synthesize bridging molecule 3.
Embodiment 9
(1) bridging molecule 1 that embodiment 1 is prepared is dissolved in dehydrated alcohol, is configured to the bridging point that concentration is 1wt%
Sub- solution is sprayed at the surface (10mL/cm of metallic aluminium2), reaction 1h obtains the aluminium surface of the modification of bridging molecule 1；
(2) 1.5g PEGDA (Mn=20000), 0.10g natural polymer sodium alginate and 27mg photoinitiator are taken
Irgacure 2959 is dissolved in the deionized water of 5mL, and 68mg calcium sulfate is then added and is uniformly mixed obtained hydrogel precursor；
(3) using the aluminium surface that bridging molecule 1 obtained in step (1) is modified as substrate, by hydrogel obtained by step (2)
Precursor is coated in the aluminium surface that bridging molecule 1 is modified, and reaction 4h completes hydrogel-aluminium interfacial adhesion, wherein in 200nm purple
Outer photo-crosslinking solidifies the preparation that 1h completes hydrogel, while completing hydrogel-aluminium interfacial adhesion by home position polymerization reaction 4h.
As control, the crosslinking curing of hydrogel is carried out using step (3) identical method in blank aluminium surface, is completed
Hydrogel-aluminium interfacial adhesion.
Fig. 4 is that the bridging molecule 1 of adhesive interface (a) and embodiment 9 preparation of blank aluminium surface and hydrogel modifies aluminium table
The macrograph of the adhesive interface (b) of face and hydrogel.Figure 4, it is seen that due to the presence of bridging molecule 1, hydrogel with
Superpower adhesive effect has occurred in metal interface, when being stripped it can be seen that typically tearing phenomenon.
Embodiment 10
(1) bridging molecule 1 that embodiment 2 is prepared is dissolved in ethyl alcohol, it is molten is configured to the bridging molecule that concentration is 1wt%
Liquid, dip-coating is in the surface (1mL/cm of metallic nickel2), 0.5h is reacted, the nickel surface of the modification of bridging molecule 1 is obtained；
(2) N of 4.0g AAm monomer, 0.50g natural polymer sodium alginate, 10mg calcium sulfate, 40mg, N '-diformazan are taken
Base bisacrylamide (crosslinking agent), 95mg ammonium persulfate (initiator), 15mL deionized water (solvent) and 10mg tetramethyl second two
Amine is uniformly mixed and obtains hydrogel precursor；
(3) nickel surface modified using the bridging molecule 1 of step (1) preparation is substrate, by hydrogel precursor obtained by step (2)
Coated in the nickel surface that bridging molecule 1 is modified, reaction 18h completes hydrogel-nickel interfacial adhesion, wherein 400nm visible light is handed over
Connection solidification 15h completes hydrogel preparation, while completing hydrogel-nickel interfacial adhesion by home position polymerization reaction 18h.
Embodiment 11
(1) bridging molecule 2 that embodiment 3 is prepared is dissolved in dehydrated alcohol, is configured to the bridging that concentration is 0.1wt%
Molecular solution is sprayed at the surface (10mL/cm of Titanium2), reaction 0.01h obtains the titanium surface of the modification of bridging molecule 2；
(2) 1.5g PEGDA (Mn=20000), 0.10g natural polymer sodium alginate and 27mg photoinitiator are taken
Irgacure 2959 is dissolved in the deionized water of 5mL, and 68mg calcium sulfate is then added and is uniformly mixed obtained hydrogel precursor；
(3) using the titanium surface that bridging molecule 2 obtained in step (1) is modified as substrate, by hydrogel obtained by step (2)
Precursor is coated in the titanium surface of bridging molecule modification, and reaction 4h completes hydrogel-titanium interfacial adhesion, wherein ultraviolet in 200nm
Photo-crosslinking solidifies the preparation that 0.5h completes hydrogel, while completing hydrogel-titanium interfacial adhesion by home position polymerization reaction 4h.
Glutathione is acted at interfacial adhesion, dosage 0.005g/cm2, detection hydrogel and bridging molecule are modified
Titanium surface separation process, bridging molecule carries out metal substrate and hydrogel to bond and utilize glutathione point in the present invention
It is as shown in Figure 5 from the process schematic at interface.
Embodiment 12
(1) bridging molecule 2 that embodiment 4 is prepared is dissolved in tetrahydrofuran, is configured to the bridge that concentration is 10wt%
Even molecular solution, is sprayed at the surface (0.001mL/cm of metallic aluminium2), reaction obtains the aluminium surface of the modification of bridging molecule 2 for 24 hours；
(2) 3.5g PEGDA (Mn=20000), 0.10g natural polymer sodium alginate and 63mg photoinitiator are taken
Irgacure 2959 is dissolved in the deionized water of 15mL, and 340mg calcium sulfate is then added and is uniformly mixed obtained hydrogel precursor；
(3) using the aluminium surface of the modification of bridging molecule 2 obtained in step (1) as substrate, before hydrogel obtained by step (2)
Body is coated in the aluminium surface of bridging molecule modification, and hydrogel-aluminium interfacial adhesion is completed in reaction for 24 hours, wherein ultraviolet in 400nm
Photo-crosslinking solidifies the preparation for completing hydrogel for 24 hours, while completing hydrogel-aluminium interfacial adhesion for 24 hours by home position polymerization reaction.
As control, the crosslinking curing of hydrogel is carried out using step (3) identical method in blank aluminium surface, is completed
Hydrogel-aluminium interfacial adhesion.
The bonding situation at substrate interface both before and after the modification of bridging molecule 2 is detected, Fig. 6 is blank aluminium surface and hydrogel
Adhesive interface (a) and embodiment 12 prepare bridging molecule 2 modify aluminium surface and hydrogel adhesive interface (b) macrograph.
It will be appreciated from fig. 6 that superpower adhesive effect has occurred in hydrogel and metal interface, when being stripped due to the presence of bridging molecule 2
It can be seen that typical tearing phenomenon.
Glutathione is acted at interfacial adhesion, dosage 5g/cm2, Fig. 7 is to act on glutathione in embodiment 12
Hydrogel separates figure with metal after at the interfacial adhesion.As can be seen from the figure hydrogel is separated with metal, glutathione
The cystine linkage in bridging molecule 2 is destroyed, and then disconnects bridging molecule 2.
Embodiment 13
(1) bridging molecule 2 that embodiment 5 is prepared is dissolved in dehydrated alcohol, is configured to the bridging point of concentration 1wt%
Sub 2 solution, are infiltrated on the surface (0.01mL/cm of stainless steel metal2), reaction 0.1h obtains the stainless steel of the modification of bridging molecule 2
Surface；
(2) by the AAm monomer of 1.0g, 0.15g natural polymer sodium alginate, 5mg calcium sulfate, 20mg N, N '-diformazan
Base bisacrylamide (crosslinking agent), 25mg ammonium persulfate (initiator), 5mL deionized water (solvent) and 2.5mg tetramethyl second two
Amine is mixed to prepare hydrogel precursor；
(3) stainless steel surface modified using the bridging molecule 2 of step (1) preparation is substrate, by hydrogel obtained by step (2)
Precursor is coated in the stainless steel surface that bridging molecule 2 is modified, and reaction 18h completes hydrogel-stainless steel interfacial adhesion, wherein
Hydrogel preparation is completed in the visual light cross-linked solidification 1h of 900nm, while stainless by home position polymerization reaction 18h completion hydrogel-
The interfacial adhesion of steel.
As control, the crosslinking curing of hydrogel is carried out using step (3) identical method on blank stainless steel surface,
Complete hydrogel-stainless steel interfacial adhesion.
Pass through interfacial adhesion of the peeling strength test machine quantitative test hydrogel-stainless steel before and after the modification of bridging molecule 2
Intensity.Fig. 8 is the adhesive interface and blank stainless steel that bridging molecule 2 prepared by embodiment 13 modifies stainless steel surface and hydrogel
The adhesive interface of surface and hydrogel removes curve graph.The results show that the stainless steel modified through bridging molecule 2-hydrogel interface
Bond strength is much higher than blank stainless steel-hydrogel, illustrates that hydrogel and rigidity may be implemented in bridging molecule 2 prepared by the present invention
High-strength adhesive between medical metal material.
Glutathione can be acted at the interfacial adhesion of stainless steel surface and hydrogel that bridging molecule 2 is modified, dosage
For 0.5g/cm2, investigate the separation process for the stainless steel surface that hydrogel and bridging molecule 2 are modified.Before glutathione processing (a)
(b) hydrogel and substrate surface separation process figure are as shown in Figure 9 afterwards.
Embodiment 14
(1) bridging molecule 2 that embodiment 6 is prepared is dissolved in methylene chloride, is configured to the bridging point that concentration is 1wt%
Sub 2 solution, dip-coating is in the surface (0.01mL/cm of metallic nickel2), 0.5h is reacted, the nickel surface of the modification of bridging molecule 2 is obtained；
(2) N of 4.0g AAm monomer, 0.50g natural polymer sodium alginate, 10mg calcium sulfate, 40mg, N '-diformazan are taken
Base bisacrylamide (crosslinking agent), 95mg ammonium persulfate (initiator), 15mL deionized water (solvent) and 10mg tetramethyl second two
Amine is uniformly mixed and obtains hydrogel precursor；
(3) nickel surface modified using the bridging molecule 2 of step (1) preparation is substrate, by hydrogel precursor obtained by step (2)
Nickel surface coated in bridging molecule modification, reaction 18h complete hydrogel-nickel interfacial adhesion, wherein 400nm visible light is handed over
Connection solidification 15h completes hydrogel preparation, while completing hydrogel-nickel interfacial adhesion by home position polymerization reaction 18h.
Glutathione is acted at interfacial adhesion, dosage 0.25g/cm2, quantitatively surveyed using peeling strength test machine
The variation of peel strength before and after glutathione is added in examination.Figure 10 is to act on glutathione at interfacial adhesion in embodiment 14
The interface peel intensity of front and back.Adhesive effect is set to disappear it can be seen that glutathione destroys 2 structure of bridging molecule
It loses, adhesive strength significantly reduces.
Embodiment 15
(1) bridging molecule 2 that embodiment 5 is prepared is dissolved in isopropanol, is configured to the bridging molecule that concentration is 1wt%
Metallic cobalt is immersed (0.01mL/cm in solution by 2 solution2) reaction 0.1h, obtain the cobalt surface of the modification of bridging molecule 2；
(2) 2.5g PEGDA (Mn=20000), 0.15g natural polymer sodium alginate and 30mg photoinitiator are taken
Irgacure 2959 is dissolved in the deionized water of 10mL, and 80mg calcium sulfate is then added and is uniformly mixed obtained hydrogel precursor；
(3) substrate is in the cobalt surface modified using the bridging molecule 2 of step (1) preparation, by hydrogel precursor obtained by step (2)
Coated in the cobalt surface that bridging molecule 2 is modified, hydrogel-cobalt interfacial adhesion is completed in reaction for 24 hours, wherein in 200nm ultraviolet light
Crosslinking curing 4h completes the preparation of hydrogel, while completing hydrogel-cobalt interfacial adhesion for 24 hours by home position polymerization reaction.
Dithiothreitol (DTT) is acted at interfacial adhesion, dosage 0.1g/cm2, it has also been observed that hydrogel and gold
Belong to the separation of material substrate.
Embodiment 16
(1) bridging molecule 2 that embodiment 4 is prepared is dissolved in acetone, is configured to the bridging molecule that concentration is 0.5wt%
2 solution are sprayed at the surface (0.01mL/cm of crome metal2) reaction 0.1h, obtain the chromium surface of the modification of bridging molecule 2；
(2) N of 2.5g AAm monomer, 0.20g natural polymer sodium alginate, 6mg calcium sulfate, 25mg, N '-dimethyl are taken
Bisacrylamide (crosslinking agent), 80mg ammonium persulfate (initiator), 12.5mL deionized water (solvent) and 7.5mg tetramethyl second two
Amine is uniformly mixed and obtains hydrogel precursor；
(3) chromium surface modified using the bridging molecule 2 of step (1) preparation is substrate, by hydrogel precursor obtained by step (2)
Coated in the chromium surface that bridging molecule 2 is modified, reaction 18h completes hydrogel-chromium interfacial adhesion, wherein in 450nm visible light
Crosslinking curing completes the preparation of hydrogel for 24 hours, while completing hydrogel-chromium interfacial adhesion for 24 hours by home position polymerization reaction.
Dithiothreitol (DTT) is acted at interfacial adhesion, dosage 2g/cm2, it has also been observed that hydrogel and metal
The separation of baseplate material.
Embodiment 17
(1) bridging molecule 3 that embodiment 7 is prepared is dissolved in tetrahydrofuran, is configured to the bridging that concentration is 0.1wt%
Molecular solution, dip-coating is in the surface (1mL/cm of metallic copper2), 0.8h is reacted, the copper surface of the modification of bridging molecule 3 is obtained；
(2) N of 4.0g AAm monomer, 0.50g natural polymer sodium alginate, 10mg calcium sulfate, 40mg, N '-diformazan are taken
Base bisacrylamide (crosslinking agent), 95mg ammonium persulfate (initiator), 15mL deionized water (solvent) and 10mg tetramethyl second two
Amine is uniformly mixed and obtains hydrogel precursor；
(3) substrate is in the copper surface modified using the bridging molecule 3 of step (1) preparation, by hydrogel precursor obtained by step (2)
Coated in the copper surface that bridging molecule 3 is modified, reaction 20h completes hydrogel-copper interfacial adhesion, wherein 400nm visible light is handed over
Connection solidification 15h completes hydrogel preparation, while completing hydrogel-copper interfacial adhesion by home position polymerization reaction 20h.Work as progress
When removing, it can be seen that typically tear phenomenon.
Embodiment 18
(1) bridging molecule 3 that embodiment 8 is prepared is dissolved in ethyl alcohol, it is molten is configured to the bridging molecule that concentration is 1wt%
Liquid, dip-coating is in the surface (5mL/cm of metallic gold2), 1h is reacted, the gold surface of the modification of bridging molecule 3 is obtained；
(2) N of 4.0g AAm monomer, 0.50g natural polymer sodium alginate, 10mg calcium sulfate, 40mg, N '-diformazan are taken
Base bisacrylamide (crosslinking agent), 95mg ammonium persulfate (initiator), 15mL deionized water (solvent) and 10mg tetramethyl second two
Amine is uniformly mixed and obtains hydrogel precursor；
(3) gold surface modified using the bridging molecule 3 of step (1) preparation is substrate, by hydrogel precursor obtained by step (2)
Coated in the gold surface that bridging molecule 3 is modified, reaction 18h completes hydrogel-gold interfacial adhesion, and wherein 200nm ultraviolet light is handed over
Connection solidification 18h completes hydrogel preparation, while completing hydrogel-nickel interfacial adhesion for 24 hours by home position polymerization reaction.Work as progress
When removing, it can be seen that typically tear phenomenon.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of bridging molecule for binding metal material and hydrogel, it is characterised in that general structure is as follows:
Wherein, R1The group containing at least one functional group that can be crosslinked with hydrogel network is indicated, wherein with hydrogel network
The functional group of crosslinking includes but is not limited to alkenyl, alkynyl, amino, catechol, methacrylate, Methacrylamide, third
Olefin(e) acid ester, acrylamide, sulfydryl and hydroxyl；
R2The group for containing at least one functional group that can be bonded with metal material is indicated, wherein the function being bonded with metal material
Group includes but is not limited to carboxylate, catechol, phosphate, pyridines nitrogen-containing heterocycle and lipoic acid；
X1-X2Indicate dynamic chemical key, simple linking group or the linker containing at least one irritation response group
Group, wherein simple linking group includes but is not limited in one of alkyl, alkenyl, ketone group and ether or the above linking group
At least two combinations；Stimuli responsive group includes but is not limited to pH sensitive group, temperature sensitive group, isotope of redox-sensitive base
Group and photoresponse group.
2. the bridging molecule according to claim 1 for binding metal material and hydrogel, it is characterised in that:
The pH sensitive group includes but is not limited to tertiary amine, secondary amine, sulfonic group；The temperature sensitive group includes but unlimited
In amide groups and ether；The isotope of redox-sensitive group includes but is not limited to disulfide group, amino, alkynyl and alkenyl；Described
Photoresponse group includes but is not limited to chlorophyllin, aromatic series azido group and nitro alcohol derivative.
3. the bridging molecule according to claim 1 for binding metal material and hydrogel, it is characterised in that bridging point
The structural formula of son is one of following structural formula:
4. a kind of systems for binding metal material and the bridging molecule of hydrogel described in any item according to claim 1~3
Preparation Method, it is characterised in that:
When the bridging molecule is bridging molecule 1, preparation method includes the following steps: by 12-aminolauric acid and three second
Amine is dissolved in organic solvent, and methacrylic anhydride is then added and is stirred to react, obtains bridging molecule 1 after reaction；
When the bridging molecule is bridging molecule 2, preparation method includes the following steps: sub- dimercapto diethyl acid is dissolved in second
It is reacted in acid anhydrides, obtains annular two sulfuric anhydrides, it is then that obtained two sulfuric anhydride of annular and hydroxyethyl methacrylate is molten
In organic solvent, it is stirred to react to get bridging molecule 2 is arrived；
When the bridging molecule is bridging molecule 3, preparation method includes the following steps: by lipoic acid, 4- dimethylamino pyrrole
Pyridine, dicyclohexylcarbodiimide and hydroxy-ethyl acrylate are added in the organic solvent under ice bath, are stirred to react, after reaction
Obtain bridging molecule 3.
5. the preparation method according to claim 4 for binding metal material and the bridging molecule of hydrogel, feature
It is:
When the bridging molecule is bridging molecule 1:
The amount ratio of the 12-aminolauric acid, methacrylic anhydride and triethylamine be 1~10.0g:1~20mL:1~
50mL；The dosage of the organic solvent meets the organic molten of 20~300mL of the corresponding addition of 12-aminolauric acid of every 1~10g
Agent；
The organic solvent is at least one of tetrahydrofuran, methylene chloride, chloroform and acetone；
Described be stirred to react refers to and is stirred to react 4~36h in ice-water bath；It further include using deionized water after the completion of being stirred to react
Extraction removes the step of impurity；
When the bridging molecule is bridging molecule 2:
The amount ratio of the sub- dimercapto diethyl acid and acetic anhydride is 0.1~2.0g:1.0~20mL；The organic solvent
Dosage meet the corresponding organic solvent that 10~30mL is added of hydroxyethyl methacrylate of every 0.2~2.0g；Described will be sub-
It is 0~40 DEG C that dimercapto diethyl acid, which is dissolved in the temperature reacted in acetic anhydride, the reaction time is 4~for 24 hours；
The organic solvent is chloroform, N,N-dimethylformamide, acetone, tetrahydrofuran, isopropanol, N, N- dimethylacetamide
At least one of amine and methylene chloride；
The dosage of two sulfuric anhydride of annular and hydroxyethyl methacrylate meets the raw material Asia dimercapto of annular two sulfuric anhydrides
The mass ratio of oxalic acid and hydroxyethyl methacrylate is 0.1~2.0:0.2~2.0；The dosage of the organic solvent meets
The corresponding organic solvent that 10~30mL is added of the hydroxyethyl methacrylate of every 0.2~2.0g；
Described being stirred to react refers to that in ice water bath environment, revolving speed is to be stirred to react 12~72h under 100~1000rpm, reacts
After further include one using gel chromatographic columns in petroleum ether and ethyl acetate volume ratio (0.5~4): 1 mixed solvent effect
Under the step of being purified；
When the bridging molecule is bridging molecule 3:
The amount ratio of the lipoic acid, 4-dimethylaminopyridine, dicyclohexylcarbodiimide and hydroxy-ethyl acrylate is (0.5
~20g): (0.05~2g): (1.5~60g): (0.3~12mL)；The dosage of the organic solvent meets every 0.5~20g's
The corresponding organic solvent that 10~300mL is added of lipoic acid；
The organic solvent is at least one of tetrahydrofuran, methylene chloride, chloroform and acetone；
Described be stirred to react refers to and is stirred to react 4~36h under ice bath, after reaction further includes one and passes through deionized water
The step of washing purifying.
6. described in any item bridging molecules for being used for binding metal material and hydrogel are in hydrogel according to claim 1~3
With the application in metal material interfacial adhesion, it is characterised in that:
The hydrogel includes various energy based on in-situ polymerization mechanism of crosslinking and R1The hydrogel that group is crosslinked；Described
Metal material includes various metal and its alloy for medical equipment.
7. the bridging molecule according to claim 6 for being used for binding metal material and hydrogel is in hydrogel and metal material
Application in interfacial adhesion, it is characterised in that specifically includes the following steps:
(1) bridging molecule is dissolved in solvent and is configured to bridging molecule solution, the surface for then acting on metal material obtains bridge
The even metal material surface of molecular modification；
(2) hydrogel precursor is coated on to the metal material surface of the modification of bridging molecule obtained by step (1), by under certain condition
Reaction be completed at the same time the solidification of hydrogel and hydrogel passes through the bonding of bridging molecule and metal material interface.
8. the bridging molecule according to claim 7 for being used for binding metal material and hydrogel is in hydrogel and metal material
Application in interfacial adhesion, it is characterised in that:
Step (1) solvent is at least one in acetone, ethyl alcohol, tetrahydrofuran, methylene chloride, chloroform and isopropanol
Kind；
Step (1) metal material be in one of nickel, magnesium, titanium, aluminium, cobalt, gold, silver, platinum or the above metal extremely
The alloy or stainless steel of few two kinds of formation；
The mass fraction of bridging molecule is 0.1~10wt% in step (1) the bridging molecule solution；
The dosage of step (1) the bridging molecule solution meets: every 1cm2Metal material surface corresponding use 0.001~10mL
Bridging molecule solution；
Step (1) surface for acting on metal material refers to by spraying, adhering to immediately, at least one in dip-coating and immersion
Kind by solution effects in the surface of metal material, action time is 0.01~for 24 hours.
9. the bridging molecule according to claim 7 for being used for binding metal material and hydrogel is in hydrogel and metal material
Application in interfacial adhesion, it is characterised in that:
Step (2) hydrogel precursor is selected from one of the component A and B of following mass fraction:
Component A:1.5~3.5 part polyethyleneglycol diacrylate, 0.1~0.5 part of sodium alginate, 0.001~0.5 part contain Ca2+Change
Close object, 0.027~0.063 part of photoinitiator and 5~15 parts of water；
Component B:1~4 part acrylamide, 0.1~0.5 part of sodium alginate, 0.001~0.5 part contain Ca2+Compound, 0.02~
0.04 part of N, N '-bismethacrylamide, 0.025~0.095 part of ammonium persulfate, 5~15 parts of water and 0.0025~0.01 part
Tetramethylethylenediamine；
Contain Ca described in component A and component B2+Compound is at least one of calcium sulfate, calcium carbonate, calcium oxalate, calcium chloride；
The original position of cross-linking and curing reaction and hydrogel and bridging molecule of the reaction described in step (2) including hydrogel precursor is poly-
Reaction is closed, two kinds are reacted while being carried out；The cross-linking and curing reaction refers in 200~400nm ultraviolet light or 400~900nm
Under visible light irradiation 0.01~for 24 hours；The home position polymerization reaction refer at room temperature reaction 0.01~for 24 hours.
10. the bridging molecule according to claim 7 for being used for binding metal material and hydrogel is in hydrogel and metal material
Expect the application in interfacial adhesion, it is characterised in that:
As X in bridging molecules1-X2When containing pH sensitive group, the method that stress be separated is carried out to hydrogel and metal material interface
For in hydrogel and metal material interface coated acid or base reagent；As X in bridging molecules1-X2When containing temperature sensitive group,
Carrying out the method that stress be separated to hydrogel and metal material interface is to change temperature between 0~100 DEG C；When in bridging molecules
X1-X2When containing isotope of redox-sensitive group, the method that stress be separated is carried out for coating oxidation to hydrogel and metal material interface
At least one of type glutathione, reductive glutathione and dithiothreitol (DTT).
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819183A (en) * | 2019-12-02 | 2020-02-21 | 苏州凝智新材料发展有限公司 | Hydrophilic lubricating coating for medical equipment and preparation method thereof |
| CN111423603A (en) * | 2020-04-10 | 2020-07-17 | 苏州凝智新材料发展有限公司 | Method for bonding hydrogel and elastomer, product and application thereof |
| CN112552725A (en) * | 2020-12-11 | 2021-03-26 | 中国科学院海洋研究所 | Underwater self-repairing organic silicon antifouling coating and preparation method thereof |
| CN114209891A (en) * | 2021-12-17 | 2022-03-22 | 福州大学 | Wet-state-adhered super-lubricating hydrogel coating and preparation method thereof |
| CN115779159A (en) * | 2022-12-01 | 2023-03-14 | 中山大学 | High-strength-toughness wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4499251A (en) * | 1983-01-21 | 1985-02-12 | Kuraray Co., Ltd. | Adhesive compositions |
| US5670657A (en) * | 1994-02-04 | 1997-09-23 | Kabushiki Kaisha Shofu | (Meth) arcylic ester derivatives |
| JP2007146108A (en) * | 2005-10-24 | 2007-06-14 | Kazuyuki Tsubone | Anionic surfactant containing 2 polymerizable chains and 2 hydrophilic groups and method for producing the same |
| JP2007230966A (en) * | 2006-03-03 | 2007-09-13 | Kohjin Co Ltd | Method for producing (meth)acrylamide alkyl carboxylic acid |
| JP2007277167A (en) * | 2006-04-07 | 2007-10-25 | Shiseido Co Ltd | Surface-treated powder and cosmetic containing the same |
| JP2008290958A (en) * | 2007-05-23 | 2008-12-04 | Shiseido Co Ltd | Method for synthesizing unsaturated organic compound by using microreactor |
| CN101547930A (en) * | 2006-09-29 | 2009-09-30 | 日本可乐丽医疗器材株式会社 | Novel compound, composition comprising the same, and process for production of polymerizable amide |
| CN104327018A (en) * | 2013-12-01 | 2015-02-04 | 复旦大学 | Disulfide bond-containing polymerizable taxol monomer and synthetic method thereof |
| CN106008995A (en) * | 2016-07-25 | 2016-10-12 | 桂林理工大学 | Preparation method of lipoic acid based hyperbranched polythioether |
| CN107098994A (en) * | 2016-02-10 | 2017-08-29 | 株式会社理光 | Three-dimensional contouring material, three-dimensional contouring combination of materials, the manufacture method and its manufacture device of three-dimensional contouring thing |
| KR101885086B1 (en) * | 2017-03-22 | 2018-08-07 | 주식회사 메가코스 | Hydrogel mask pack and manufacturing thereof |
| WO2018181058A1 (en) * | 2017-03-31 | 2018-10-04 | 富士フイルム株式会社 | Aqueous ink composition, ink set, image forming method, and resin fine particles for inks |
| WO2018213433A1 (en) * | 2017-05-16 | 2018-11-22 | Biocure, Inc. | Hydrogel medical adhesives |
| EP3533844A1 (en) * | 2018-03-02 | 2019-09-04 | Agfa-Gevaert | Inkjet inks for manufacturing printed circuit boards |
-
2019
- 2019-01-17 CN CN201910042373.8A patent/CN109761843B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4499251A (en) * | 1983-01-21 | 1985-02-12 | Kuraray Co., Ltd. | Adhesive compositions |
| US5670657A (en) * | 1994-02-04 | 1997-09-23 | Kabushiki Kaisha Shofu | (Meth) arcylic ester derivatives |
| JP2007146108A (en) * | 2005-10-24 | 2007-06-14 | Kazuyuki Tsubone | Anionic surfactant containing 2 polymerizable chains and 2 hydrophilic groups and method for producing the same |
| JP2007230966A (en) * | 2006-03-03 | 2007-09-13 | Kohjin Co Ltd | Method for producing (meth)acrylamide alkyl carboxylic acid |
| JP2007277167A (en) * | 2006-04-07 | 2007-10-25 | Shiseido Co Ltd | Surface-treated powder and cosmetic containing the same |
| CN101547930A (en) * | 2006-09-29 | 2009-09-30 | 日本可乐丽医疗器材株式会社 | Novel compound, composition comprising the same, and process for production of polymerizable amide |
| JP2008290958A (en) * | 2007-05-23 | 2008-12-04 | Shiseido Co Ltd | Method for synthesizing unsaturated organic compound by using microreactor |
| CN104327018A (en) * | 2013-12-01 | 2015-02-04 | 复旦大学 | Disulfide bond-containing polymerizable taxol monomer and synthetic method thereof |
| CN107098994A (en) * | 2016-02-10 | 2017-08-29 | 株式会社理光 | Three-dimensional contouring material, three-dimensional contouring combination of materials, the manufacture method and its manufacture device of three-dimensional contouring thing |
| CN106008995A (en) * | 2016-07-25 | 2016-10-12 | 桂林理工大学 | Preparation method of lipoic acid based hyperbranched polythioether |
| KR101885086B1 (en) * | 2017-03-22 | 2018-08-07 | 주식회사 메가코스 | Hydrogel mask pack and manufacturing thereof |
| WO2018181058A1 (en) * | 2017-03-31 | 2018-10-04 | 富士フイルム株式会社 | Aqueous ink composition, ink set, image forming method, and resin fine particles for inks |
| WO2018213433A1 (en) * | 2017-05-16 | 2018-11-22 | Biocure, Inc. | Hydrogel medical adhesives |
| EP3533844A1 (en) * | 2018-03-02 | 2019-09-04 | Agfa-Gevaert | Inkjet inks for manufacturing printed circuit boards |
Non-Patent Citations (4)
| Title |
|---|
| BEINN V. O. MUIR ETAL: "Grafting of Cross-Linked Hydrogel Networks to Titanium Surfaces", 《ACS APPL. MATER. INTERFACES》 * |
| KUNIO IKEMURA ETAL: "Synthesis of novel acryloyloxyalkyl and methacryloyloxyalkyl 6,8-dithiooctanoates and evaluation of their bonding performances to precious metals and alloys", 《DENTAL MATERIALS JOURNAL 2011》 * |
| REG: "数据库", 《STN》 * |
| 顾其胜: "《海藻酸盐基生物医用材料与临床医学》", 31 December 2015 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110819183A (en) * | 2019-12-02 | 2020-02-21 | 苏州凝智新材料发展有限公司 | Hydrophilic lubricating coating for medical equipment and preparation method thereof |
| CN111423603A (en) * | 2020-04-10 | 2020-07-17 | 苏州凝智新材料发展有限公司 | Method for bonding hydrogel and elastomer, product and application thereof |
| CN111423603B (en) * | 2020-04-10 | 2022-10-18 | 苏州凝智新材料发展有限公司 | Method for bonding hydrogel and elastomer, product and application thereof |
| CN112552725A (en) * | 2020-12-11 | 2021-03-26 | 中国科学院海洋研究所 | Underwater self-repairing organic silicon antifouling coating and preparation method thereof |
| CN114209891A (en) * | 2021-12-17 | 2022-03-22 | 福州大学 | Wet-state-adhered super-lubricating hydrogel coating and preparation method thereof |
| CN114209891B (en) * | 2021-12-17 | 2023-02-28 | 福州大学 | Wet-state-adhered super-lubricating hydrogel coating and preparation method thereof |
| CN115779159A (en) * | 2022-12-01 | 2023-03-14 | 中山大学 | High-strength-toughness wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof |
| CN115779159B (en) * | 2022-12-01 | 2024-01-16 | 中山大学 | High-strength and high-toughness wear-resistant hydrophilic lubricating coating grafted on surface of medical instrument and preparation method thereof |
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