CN110283320A - A kind of synthetic method for the anti-bacterial hydrogel that can be hydrolyzed under alkalescent - Google Patents
A kind of synthetic method for the anti-bacterial hydrogel that can be hydrolyzed under alkalescent Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/392—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing sulfur
Abstract
The invention discloses the synthetic methods for the anti-bacterial hydrogel that one kind can hydrolyze under alkalescent, this method are as follows: sequentially add the tetrahydrofuran of octavinyl-POSS, tertiary amine mercaptan and drying in the reactor, then reactor is wrapped with aluminium foil, is sealed after photoinitiator is added, uses high purity N2Purging mixture removes aluminium foil under the ultraviolet light irradiation of 365nm, 1~12h of reaction is stirred at room temperature to remove oxygen.After reaction, rotary evaporation removes solvent and extra tertiary amine mercaptan, obtains thick liquid.At room temperature after mixing, reaction a period of time is placed in film tool and had both obtained the curing gel, is immersed in ultrapure water and is sufficiently swollen, obtain product the halogenated hydrocarbons ester of the halogenated hydrocarbons ester and single halogen that take above-mentioned product and double halogens.The hydrogel gelation time that the present invention obtains is short, preparation process is simple, can hydrolyze under alkalescent, have excellent antibacterial effect, can apply in fields such as biological dressings.
Description
Technical field
The present invention relates to the synthetic method for the anti-bacterial hydrogel that one kind can hydrolyze under alkalescent, specially one kind contains season
Ammonium salt, chain alkyl antibacterial group, and the gelatin polymer of silicon oxygen silicon key and ester bond that can be hydrolyzed under alkalescent.
Background technique
Anti-bacterial hydrogel is a kind of important anti-biotic material, has weight in medical dressing, medical device coatings, organizational project
The application wanted.Currently, common antibacterial polymer has quaternary ammonium salts polymer, quaternary phosphonium salt quasi polymer, halogen amine polymer, guanidine
Quasi polymer etc..Ideal antibacterial hydrogel material should have efficient antibacterial activity, good biocompatibility, good life
Biodegradable, the preparation method of Simple temperature sum and cheap cost.But it is rarely reported out this various performances at present and takes into account
Hydrogel.Therefore developing the anti-bacterial hydrogel that novel satisfaction requires comprehensively is still a kind of challenge.
The sterilizing mechanisms of general quaternary ammonium salts antibacterial polymer are between cation and microbial cell in quaternary ammonium salt
There is certain interaction.Then it acts on the lipid bilayer structure of microbial cell film, to kill microorganism.Quaternary amine
Introducing generally interacted by tertiary amine and halogenated alkane or the quaternary ammonium reaction of halogen and tertiary amine, tertiary amine and halogen atom,
Ionic structure is formed, but that there are preparation methods is cumbersome for many quaternary ammonium salts anti-bacterial hydrogels at present, biodegradability is poor, makes
With place the deficiencies of a large amount of solvents, the research for going deep into effort is still needed to.
The QAS polymer that the present invention synthesizes has synthesized a kind of antibacterial water-setting containing quaternary ammonium salt and chain alkyl simultaneously
The synergistic effect of glue, chain alkyl and quaternary ammonium salt is so that the hydrogel has better antibacterial effect.The product is eight vinyl
POSS is mercaptan modified at the compound for containing multiple tertiary amine groups by tertiary amine, reuses the halogen containing a halogen or multiple halogens
For hydrocarbon ester, directly mixing is crosslinked, and forms hydrogel.During being crosslinked, it is not suitable for any solvent, it is directly mixed
It closes, and crosslinking rate is very fast.The polymer of invention synthesis contains two kinds of antimicrobial factors of chain alkyl and quaternary ammonium salt, has good
Good antibacterial effect, and gelation time is short, can hydrolyze under alkalescent (usual pH is 8 or so), can apply and apply in biology
The fields such as material.
Summary of the invention
Synthetic method can be hydrolyzed under alkalescent the object of the present invention is to provide one kind, anti-bacterial hydrogel.
To achieve the above object, the following technical schemes are provided:
A kind of synthetic method for the anti-bacterial hydrogel that can be hydrolyzed under alkalescent the following steps are included:
(1) tetrahydrofuran of octavinyl-POSS, tertiary amine mercaptan and drying, eight second are sequentially added in the reactor
The molar ratio of alkenyl POSS and tertiary amine mercaptan is 1:(8~12)；Then, reactor is wrapped with aluminium foil, photoinitiator is added,
Sealing, uses high purity N2Mixture is in purge to remove oxygen, and then, the ultraviolet light for removing aluminium foil in 365nm irradiates
Under, 1~12h of reaction is stirred at room temperature.After reaction, rotary evaporation removes solvent and extra tertiary amine mercaptan, obtains viscous fluid
Body.
(2) above-mentioned product is uniformly mixed at room temperature with the halogenated hydrocarbons ester of the halogenated hydrocarbons ester of double halogens and single halogen, instead
Ying Hou is placed in film tool and obtains curing gel, is immersed in ultrapure water and is sufficiently swollen, and obtains to hydrolyze under alkalescent anti-
Bacterium hydrogel.
In above-mentioned technical proposal, it is preferred that the tertiary amine mercaptan be selected from dimethylamino ethyl mercaptan, dimethylamino ethyl mercaptan,
Dimethylamino butanethiol, dimethylamino amyl hydrosulfide, diethylamino ethanethiol, diethylamino ethanethiol, lignocaine butanethiol, two
Ethylamino amyl hydrosulfide, diethylamino ethanethiol, diethylamino ethanethiol, lignocaine butanethiol, lignocaine amyl hydrosulfide, but not
It is confined to this.
Preferably, the photoinitiator is selected from benzyl phenyl ketone, styrax diethyl ether, benzoin derivatives, benzil ketals
Derivative, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, esterification oximinoketone compound, aryl peroxy esters chemical combination
Object, Dialkoxy acetophenones, phenylacetyl acetic acid esters, benzyl phenyl ketone, but not limited to this.
Preferably, the halogenated hydrocarbons ester of double halogens is selected from propylene glycol chloracetate, butanediol chloracetate, pentanediol
Chloracetate, hexylene glycol chloracetate, heptandiol chloracetate, ethohexadiol chloracetate, nonanediol chloracetate, certain herbaceous plants with big flowers glycol chlorine
Acetic acid esters, propylene glycol bromacetate, butanediol bromacetate, pentanediol bromacetate, hexylene glycol bromacetate, heptandiol bromine second
Acid esters, ethohexadiol bromacetate, nonanediol bromacetate, certain herbaceous plants with big flowers glycol bromacetate, propylene glycol Alkyl Iodoacetates, butanediol iodoacetic acid
Ester, pentanediol Alkyl Iodoacetates, hexylene glycol Alkyl Iodoacetates, heptandiol Alkyl Iodoacetates, ethohexadiol Alkyl Iodoacetates, nonanediol iodoacetic acid
Ester, certain herbaceous plants with big flowers glycol Alkyl Iodoacetates, but not limited to this.
Preferably, the halogenated hydrocarbons ester of single halogen, propyl alcohol chloracetate, amylalcohol chloracetate, hexanol chloracetate,
Enanthol chloracetate, octanol chloracetate, nonyl alcohol chloracetate, certain herbaceous plants with big flowers alcohol chloracetate, undecyl alcohol chloracetate, lauryl alcohol chloroethene
Acid esters, tridecanol chloracetate, tetradecyl alchohol chloracetate, pentadecanol chloracetate, hexadecanol chloracetate, propyl alcohol bromoacetic acid
Ester, amylalcohol bromacetate, hexanol bromacetate, enanthol bromacetate, octanol bromacetate, nonyl alcohol bromacetate, certain herbaceous plants with big flowers alcohol bromine second
Acid esters, undecyl alcohol bromacetate, lauryl alcohol bromacetate, tridecanol bromacetate, tetradecyl alchohol bromacetate, pentadecanol bromoacetic acid
Ester, hexadecanol bromacetate, propyl alcohol Alkyl Iodoacetates, amylalcohol Alkyl Iodoacetates, hexanol Alkyl Iodoacetates, enanthol Alkyl Iodoacetates, octanol iodine
Acetic acid esters, nonyl alcohol Alkyl Iodoacetates, certain herbaceous plants with big flowers alcohol Alkyl Iodoacetates, undecyl alcohol Alkyl Iodoacetates, lauryl alcohol Alkyl Iodoacetates, tridecanol iodoacetic acid
Ester, tetradecyl alchohol Alkyl Iodoacetates, pentadecanol Alkyl Iodoacetates, hexadecanol Alkyl Iodoacetates, but not limited to this.
The invention has the advantages that the synthesis of the antibacterial gel, have rapidly and efficiently, the spies such as simple process, yield height
Point.And the hydrogel has good bactericidal effect, can hydrolyze under weak basic condition, is that a kind of good Degradable environment protection is poly-
Object is closed, resulting polymer has application prospect in fields such as bio-medical dressing.
Detailed description of the invention
Fig. 1 is the compound of the eight tertiary amino POSS synthesized with octavinyl-POSS with dimethylamino ethyl mercaptan in the present invention
Nucleus magnetic hydrogen spectrum；
Fig. 2 is the shows fluorescent microscopy images of anti-bacterial hydrogel in the present invention: (1) a, b, c, d respectively correspond different single halogens
Halogenated hydrocarbons ester is formed by the antibacterial shows fluorescent microscopy images of gel；(2) A, B, C, D are the dead bacterium numbers of corresponding work；
Fig. 3 is the hydrolysis of the hydrogel of different hexylene glycol chloracetates (HCA) and hexadecanol chloracetate (CCA) molar ratio
Weightless map；Four curves are successively that the ratio of HCA and CCA is 4:0,3:2,2:4,1:6 from top to bottom；
Fig. 4 is reacted with the mercaptan modified octavinyl-POSS of tertiary amine is modified with halogen-containing halogenated hydrocarbons ester in the present invention
Product picture.
Specific embodiment
The principle of the present invention is that " alkene-click " thiol reaction occurs using the monomer of tertiary amine mercaptan and more vinyl, is generated
Compound containing more tertiary amines.The compound of more tertiary amines and halogenated hydrocarbons ester containing one or more halogens are mixed again,
Quaternization reaction occurs, generates the gel containing quaternary ammonium salt and chain alkyl.Quaternary ammonium salt has good under the action of chain alkyl
Good antibacterial effect, and under weak basic condition, which is easy to hydrolyze, because the carbon atom of this season ammonium root is in α-carbon
When on atom, strong inhale can electrically make ester bond be easier to hydrolyze than common ester bond.
Further illustrate that the present invention, the objects and effects of the present invention will become brighter below according to drawings and examples
It is aobvious.
Embodiment 1:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol chloracetate of 1mmol, the hexadecanol chlorine of 6mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Following formula expression can be used in entire reaction process:
Embodiment 2:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol chloracetate of 1mmol, the tetradecyl alchohol chlorine of 6mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 3:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol chloracetate of 1mmol, the lauryl alcohol chlorine of 6mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 4:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol chloracetate of 1mmol, the ten alcohol chloroethenes of 6mmol
Acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 5:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol chloracetate of 2mmol, the hexadecanol chlorine of 4mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 6:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol chloracetate of 3mmol, the hexadecanol chlorine of 2mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 7:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol chloracetate of 4mmol directly mixes, reaction one
Section the time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 8:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent DMPA (41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed,
And at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in
In solution.After 1 hour, ultraviolet light is closed.Excessive 3- (dimethylamino) -1- rosickyite is removed by being evaporated in vacuo at 30 DEG C
Alcohol.Obtained thick liquid, yield 87.45%.
Gained 1mmol is contained to the compound of eight tertiary amines, the butanediol chloracetate of 2mmol, the lauryl alcohol chlorine of 4mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 9:
By octavinyl-POSS (0.63g, 1mmol) and 2- (dimethylamino) -1- ethyl mercaptan (1.05g, 10mmol), do
Dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, photoinitiator DMPA is then added thereto
(41mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed, and in room
The lower triggering reaction of ultraviolet light irradiation under temperature in 365nm.With the progress of reaction, octavinyl-POSS is gradually dissolved in solution
In.After 1 hour, ultraviolet light is closed.Excessive 2- (dimethylamino) -1- ethyl mercaptan is removed by being evaporated in vacuo at 30 DEG C.
Obtained thick liquid, yield 91.09%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol bromacetate of 1mmol, the hexadecanol bromine of 6mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 10:
By octavinyl-POSS (0.63g, 1mmol) and 3- (dimethylamino) -1- propanethiol (DPT) (1.19g,
10mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, ultraviolet light is then added thereto
Initiator Dialkoxy acetophenones (34mg, 0.16mmol).After sealing, with the N of high-purity2Mixture is purged to remove oxygen.
Then, aluminium foil is removed, and at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With the progress of reaction, eight vinyl
POSS is gradually dissolved in solution.After 2 hours, ultraviolet light is closed.Excessive 3- (diformazan is removed by being evaporated in vacuo at 30 DEG C
Base amino) -1- propanethiol, obtained thick liquid, yield 81.23%.
Gained 1mmol is contained to the compound of eight tertiary amines, the hexylene glycol bromacetate of 2mmol, the hexadecanol bromine of 4mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 11:
By octavinyl-POSS (0.63g, 1mmol) and 4- (dimethylamino) -1- butanethiol (DPT) (1.43g,
12mmol), dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, is then added thereto light-initiated
Agent 1173 (2- hydroxy-2-methyl -1- phenyl -1- acetone 26.3mg, 0.16mmol).After sealing, with the N of high-purity2Purging is mixed
Object is closed to remove oxygen.Then, aluminium foil is removed, and at room temperature in the lower triggering reaction of the ultraviolet light irradiation of 365nm.With reaction
Progress, octavinyl-POSS is gradually dissolved in solution.After 4 hours, ultraviolet light is closed.It is removed by being evaporated in vacuo at 30 DEG C
Remove excessive 3- (dimethylamino) -1- propanethiol.Obtained thick liquid, yield 85.15%.
Gained 1mmol is contained to the compound of eight tertiary amines, the butanediol bromacetate of 1mmol, the tetradecyl alchohol bromine of 6mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Embodiment 12:
By octavinyl-POSS (0.63g, 1mmol) and 2- (dimethylamino) -1- ethyl mercaptan (1.05g, 10mmol), do
Dry THF (5mL) sequentially adds in 25mL flask.Flask is wrapped up with aluminium foil, photoinitiator 1173 is then added thereto.Sealing
Afterwards, with the N of high-purity2Mixture is purged to remove oxygen.Then, aluminium foil is removed, and is shone at room temperature in the ultraviolet light of 365nm
Penetrate lower triggering reaction.With the progress of reaction, octavinyl-POSS is gradually dissolved in solution.After 1 hour, ultraviolet light is closed.
Excessive 2- (dimethylamino) -1- ethyl mercaptan is removed by being evaporated in vacuo at 30 DEG C.Obtained thick liquid, yield are
91.09%.
Gained 1mmol is contained to the compound of eight tertiary amines, the propylene glycol chloracetate of 3mmol, the hexadecanol chlorine of 2mmol
Acetic acid esters directly mixes, react a period of time after injection film tool, arrive the gel containing quaternary ammonium salt and chain alkyl.
Using hydrogel made from the method for the present invention, the killing effect to staphylococcus aureus is as shown in Fig. 2, wherein
A, b, c, d respectively correspond embodiment 4, embodiment 3, embodiment 2, embodiment 1, it can be seen that with the halogenated hydrocarbons ester of single halogen
It is to be continuously improved that the length of carbochain, which increases antibacterial ability, when wherein carbon chain lengths are more than or equal to 12, has all been shown good
Antibacterial effect；Hydrolysis situation of the hydrogel in the PBS buffer solution of pH=8 as shown in figure 3, wherein four curves from top to bottom according to
Secondary is hexylene glycol chloracetate (HCA) and hexadecanol chloracetate (CCA) molar ratio is 4:0,3:2,2:4,1:6, is respectively corresponded
Embodiment 7, embodiment 6, embodiment 5, embodiment 1.As can be seen that the reduction of the content with the halogenated hydrocarbons ester of double halogens, water
The weightless ratio of gel is bigger, that is to say, that the halogenated hydrocarbons ester content of double halogens is fewer, the easier hydrolysis of hydrogel.
Claims (6)
1. the synthetic method for the anti-bacterial hydrogel that one kind can hydrolyze under alkalescent, which comprises the steps of:
(1) tetrahydrofuran of octavinyl-POSS, tertiary amine mercaptan and drying, eight vinyl are sequentially added in the reactor
The molar ratio of POSS and tertiary amine mercaptan is 1:(8~12)；Then reactor is wrapped with aluminium foil, photoinitiator is added, sealed,
Use high purity N2Mixture to be in purge to remove oxygen, removes after aluminium foil under the ultraviolet light irradiation lower than 365nm, room
Temperature is stirred to react 1~12h, and after reaction, rotary evaporation removes solvent and extra tertiary amine mercaptan, obtains thick liquid；
(2) above-mentioned thick liquid and the halogenated hydrocarbons ester of the halogenated hydrocarbons ester of double halogens and single halogen is taken to be uniformly mixed at room temperature, instead
Ying Hou is placed in film tool and obtains curing gel, is immersed in ultrapure water and is sufficiently swollen, and obtains to hydrolyze under alkalescent anti-
Bacterium hydrogel.
2. the preparation method of the anti-bacterial hydrogel according to claim 1 that can be hydrolyzed under alkalescent, which is characterized in that institute
The tertiary amine mercaptan stated be selected from dimethylamino ethyl mercaptan, dimethylamino propanethiol, dimethylamino butanethiol, dimethylamino amyl hydrosulfide,
Diethylamino ethanethiol, lignocaine propanethiol, lignocaine butanethiol, lignocaine amyl hydrosulfide, dipropyl amino propyl mercaptan, two
Third amino propyl mercaptan, dipropyl amino butanethiol, dipropyl amino amyl hydrosulfide.
3. the synthetic method of the anti-bacterial hydrogel according to claim 1 that can be hydrolyzed under alkalescent, which is characterized in that institute
It is derivative that the photoinitiator stated is selected from two propiophenones, 2- hydroxy-2-methyl -1- phenyl -1- acetone, styrax dipropyl ether, benzoin
Object, benzil ketals derivative, alpha-hydroxyalkyl benzophenone, α-amine alkyl phenones, acylphosphine oxide, esterification oximinoketone compound, virtue
Base peroxide ester compounds, dialkoxy propiophenone, phenylpropyl alcohol acyl propionic ester.
4. the synthetic method of the anti-bacterial hydrogel according to claim 1 that can be hydrolyzed under alkalescent, which is characterized in that institute
The halogenated hydrocarbons ester for the double halogens stated is selected from propylene glycol chloracetate, butanediol chloracetate, pentanediol chloracetate, hexylene glycol chlorine
Acetic acid esters, heptandiol chloracetate, ethohexadiol chloracetate, nonanediol chloracetate, certain herbaceous plants with big flowers glycol chloracetate, propylene glycol bromine second
Acid esters, butanediol bromacetate, pentanediol bromacetate, hexylene glycol bromacetate, heptandiol bromacetate, ethohexadiol bromoacetic acid
Ester, nonanediol bromacetate, certain herbaceous plants with big flowers glycol bromacetate, propylene glycol Alkyl Iodoacetates, butanediol Alkyl Iodoacetates, pentanediol iodoacetic acid
Ester, hexylene glycol Alkyl Iodoacetates, heptandiol Alkyl Iodoacetates, ethohexadiol Alkyl Iodoacetates, nonanediol Alkyl Iodoacetates, certain herbaceous plants with big flowers glycol iodoacetic acid
Ester.
5. the synthetic method of the anti-bacterial hydrogel according to claim 1 that can be hydrolyzed under alkalescent, which is characterized in that institute
The halogenated hydrocarbons ester for the single halogen stated be selected from propyl alcohol chloracetate, amylalcohol chloracetate, hexanol chloracetate, enanthol chloracetate,
Octanol chloracetate, nonyl alcohol chloracetate, certain herbaceous plants with big flowers alcohol chloracetate, undecyl alcohol chloracetate, lauryl alcohol chloracetate, tridecanol chlorine
Acetic acid esters, tetradecyl alchohol chloracetate, pentadecanol chloracetate, hexadecanol chloracetate, propyl alcohol bromacetate, amylalcohol bromoacetic acid
Ester, hexanol bromacetate, enanthol bromacetate, octanol bromacetate, nonyl alcohol bromacetate, certain herbaceous plants with big flowers alcohol bromacetate, undecyl alcohol bromine
Acetic acid esters, lauryl alcohol bromacetate, tridecanol bromacetate, tetradecyl alchohol bromacetate, pentadecanol bromacetate, hexadecanol bromine second
Acid esters, propyl alcohol Alkyl Iodoacetates, amylalcohol Alkyl Iodoacetates, hexanol Alkyl Iodoacetates, enanthol Alkyl Iodoacetates, octanol Alkyl Iodoacetates, nonyl alcohol iodine
Acetic acid esters, certain herbaceous plants with big flowers alcohol Alkyl Iodoacetates, undecyl alcohol Alkyl Iodoacetates, lauryl alcohol Alkyl Iodoacetates, tridecanol Alkyl Iodoacetates, tetradecyl alchohol iodoacetic acid
Ester, pentadecanol Alkyl Iodoacetates, hexadecanol Alkyl Iodoacetates.
6. the anti-bacterial hydrogel that one kind can hydrolyze under alkalescent, which is characterized in that using as described in claim any one of 1-5
Method be made.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110951081A (en) * | 2019-11-08 | 2020-04-03 | 东华大学 | Non-volatile multifunctional POSS-based tertiary amine catalyst and preparation and application thereof |
| CN114395078A (en) * | 2021-12-27 | 2022-04-26 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
| CN114716754A (en) * | 2022-05-13 | 2022-07-08 | 安徽康采恩包装材料有限公司 | Antibacterial packaging material and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1870078A2 (en) * | 2006-06-19 | 2007-12-26 | Beiersdorf AG | Combi set for decorative skin treatment |
| US20090252868A1 (en) * | 2004-04-21 | 2009-10-08 | John Christopher Phelan | Curable colored inks for making colored silicone hydrogel lenses |
| CN101595419A (en) * | 2006-11-29 | 2009-12-02 | 普罗康涅控股公司 | The hydrogel contact lens that comprises the polymkeric substance that contains carboxy betaine ester monomer |
| EP2207852B1 (en) * | 2007-10-23 | 2011-12-21 | Bausch & Lomb Incorporated | Silicone hydrogels with amino surface groups |
| CN102603786A (en) * | 2012-01-17 | 2012-07-25 | 浙江大学 | Water-soluble multifunctional group oligomeric silsesquioxane and synthetic method of water-soluble multifunctional group oligomeric silsesquioxane |
| CN102633953A (en) * | 2012-04-18 | 2012-08-15 | 同济大学 | Method for preparing temperature/pH double responsive star hybrid material with POSS (polyhedral oligomeric silsesquioxane) as core |
| CN102781977A (en) * | 2010-02-18 | 2012-11-14 | 道康宁公司 | Siloxane surface-modified hydrogel and hydrogel microparticle compositions |
| CN106810650A (en) * | 2017-01-20 | 2017-06-09 | 北京中纺化工股份有限公司 | It is a kind of with three-dimensional silane structure without fluoro water proofing agent and preparation method thereof |
| CN109467513A (en) * | 2018-10-22 | 2019-03-15 | 大连百傲化学股份有限公司 | A kind of end group type macromolecular quaternary ammonium salt and preparation method thereof |
-
2019
- 2019-05-13 CN CN201910393657.1A patent/CN110283320B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090252868A1 (en) * | 2004-04-21 | 2009-10-08 | John Christopher Phelan | Curable colored inks for making colored silicone hydrogel lenses |
| US20140039086A1 (en) * | 2004-04-21 | 2014-02-06 | Novartis Ag | Curable colored inks for making colored silicone |
| EP1870078A2 (en) * | 2006-06-19 | 2007-12-26 | Beiersdorf AG | Combi set for decorative skin treatment |
| CN101595419A (en) * | 2006-11-29 | 2009-12-02 | 普罗康涅控股公司 | The hydrogel contact lens that comprises the polymkeric substance that contains carboxy betaine ester monomer |
| EP2207852B1 (en) * | 2007-10-23 | 2011-12-21 | Bausch & Lomb Incorporated | Silicone hydrogels with amino surface groups |
| CN102781977A (en) * | 2010-02-18 | 2012-11-14 | 道康宁公司 | Siloxane surface-modified hydrogel and hydrogel microparticle compositions |
| CN102603786A (en) * | 2012-01-17 | 2012-07-25 | 浙江大学 | Water-soluble multifunctional group oligomeric silsesquioxane and synthetic method of water-soluble multifunctional group oligomeric silsesquioxane |
| CN102633953A (en) * | 2012-04-18 | 2012-08-15 | 同济大学 | Method for preparing temperature/pH double responsive star hybrid material with POSS (polyhedral oligomeric silsesquioxane) as core |
| CN106810650A (en) * | 2017-01-20 | 2017-06-09 | 北京中纺化工股份有限公司 | It is a kind of with three-dimensional silane structure without fluoro water proofing agent and preparation method thereof |
| CN109467513A (en) * | 2018-10-22 | 2019-03-15 | 大连百傲化学股份有限公司 | A kind of end group type macromolecular quaternary ammonium salt and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| OMALI, NEGAR BABAEI等: "Quantification of individual proteins in silicone hydrogel contact lens deposits", 《MOLECULAR VISION》 * |
| ZHOU, CHAO等: "Antibacterial poly(ethylene glycol) hydrogels from combined epoxy-amine and thiol-ene click reaction", 《JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY》 * |
| 康少冉: "聚有机季铵盐的合成与应用性能研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 张晓静等: "八乙烯基多面体低聚倍半硅氧烷-N-异丙基丙烯酰胺共聚物有机-无机杂化水凝胶的合成与表征", 《高分子学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110951081A (en) * | 2019-11-08 | 2020-04-03 | 东华大学 | Non-volatile multifunctional POSS-based tertiary amine catalyst and preparation and application thereof |
| CN114395078A (en) * | 2021-12-27 | 2022-04-26 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
| CN114395078B (en) * | 2021-12-27 | 2024-01-23 | 宁波捷傲创益新材料有限公司 | Humidity control material and preparation method thereof |
| CN114716754A (en) * | 2022-05-13 | 2022-07-08 | 安徽康采恩包装材料有限公司 | Antibacterial packaging material and preparation method thereof |
| CN114716754B (en) * | 2022-05-13 | 2023-07-21 | 安徽康采恩包装材料有限公司 | Antibacterial packaging material and preparation method thereof |
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