CN105985523A - Zwitterionic polymer, and synthetic method and application thereof - Google Patents
Zwitterionic polymer, and synthetic method and application thereof Download PDFInfo
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Abstract
The invention provides a zwitterionic polymer. The zwitterionic polymer has a main chain with a polysiloxane structure and a side chain containing zwitterions; and the zwitterionic polymer is stable in structure, and has better durability in environments of wetness, biological degradation and the like compared with common zwitterionic polymers. The zwitterionic polymer provided by the invention can be applied in medical materials and food packaging materials needing resisting adhesion of proteins, and has good use durability. The invention also provides a method for synthesizing the zwitterionic polymer. The method comprises the following steps: subjecting tertiary amino thiol and alkenyl-contained polysiloxane to addition polymerization reaction so as to obtain polysiloxane containing a great amount of tertiary amino groups, and carrying out functionalization reaction so as to obtain the zwitterionic polymer with polysiloxane as the main chain. The method has the advantages of rapidness, high efficiency, simple and convenient process, and high yield.
Description
Technical field
The present invention relates to amphoteric ion polymer technical field, be specifically related to a kind of amphion with polysiloxanes as main chain
Polymer, its synthetic method and application.
Background technology
Amphoteric ion polymer is containing amphion group or the polymer of mixing zwitterion in a base polymer chain, it
Positive and negative charge sum equal, hydration capability is strong and is susceptible to solution ph impact, has that " anti-polyelectrolyte effect is molten
Liquid behavior ", it is widely used for the fields such as bio-medical material, petroleum industry, sewage disposal and fabric printing.
At present, amphoteric ion polymer has had multiple.Wherein, it is most commonly that with zwitterionic (methyl)
Acrylate monomer carries out being polymerized the amphoteric ion polymer obtained.But, owing to ester bond is ined succession electron withdraw group, these are two years old
Property ionomer easily hydrolyze, thus cause during long-time use, amphion functional group constantly comes off.Literary composition
Offering J.Mater.Chem., 2012,22,19418 report Heesoo Kim etc. have synthesized the poly-amphion of polyether backbone,
But this polyether backbone is during long-time use, can suffer oxidation degradation.() is therefore, it is necessary to prepare
The amphoteric ion polymer of preferable durability can be had in the environment of humidity, biodegradation.
Organosilicon polymer is a kind of important medical macromolecular materials and packaging material for food.As medical macromolecular materials,
Organosilicon polymer is widely used on conduit, eyeglass, microfluid instrument.But, organosilicon easily by protein attachment,
Blood coagulation etc. is such as easily caused when clinical practice.To this end, using at organosilyl surface grafting amphoteric ion polymer is to solve
Certainly one of method of this problem.Current report, such as, report Biomacromolecules, 2012,13,1683, generally
The method grafting amphoteric ion polymer of the atom transfer radical polymerization (ATRP) that employing surface is caused, but this side
Method needs to carry out under anaerobic, needs to use and urges with ATRP with zwitterionic (methyl) acrylate monomer
Agent system, condition is harsh.Therefore, seeking a kind of organosilicon polymer containing amphion group, it has preparation
The advantage that method is simple, stability is high, is one of the research topic of this area scientific worker, resists protein at needs
The aspects such as the medical macromolecular materials of attachment and packaging material for food, this polymer has a good application prospect.
Summary of the invention
The invention provides a kind of amphoteric ion polymer, its main chain is polysiloxanes, the group Han amphion in side chain,
Its molecular structural formula is as follows:
Wherein, n is the integer between 5～100, including 5 and 100；R1For-CH3、-CH2CH3, or-C5H6；R2
For-CH2CH2-or-CH2CH2CH2-；R3For-(CH2)n1-, n1It it is the integer between 2～10；R4、R5It is respectively fat
Fat alkyl, includes but not limited to ethyl, propyl group, butyl, amyl group, heptyl, octyl group etc.；R6For-(CH2)n2PO4、
-(CH2)n3SO3 -、-(CH2)n4CO2 -, wherein n2It is 2～10；n3It is 2～6；n4It is 1～10.
The main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain comprises amphion, its Stability Analysis of Structures,
There is under the environment such as wet environment, biodegradation the more typically more preferable durability of amphoteric ion polymer.This amphion gathers
Compound can be applied as resisting the medical material of protein attachment, packaging material for food etc., and due to its high stable
Structure, even if also can use for a long time under the environment such as wet environment, biodegradation, has preferable durability.
Present invention also offers the synthetic method of a kind of above-mentioned amphoteric ion polymer, the method is initially with tertiary amine groups mercaptan
The polysiloxanes containing a large amount of tertiary amine groups is obtained, then through reaction kinetic with the polysiloxanes polyaddition reaction with thiazolinyl
Obtaining the amphoteric ion polymer that polysiloxanes is main chain, it is excellent that the method has rapidly and efficiently, simple process, yield are high
Point.
The method specifically includes following steps:
Step 1: be sequentially added into tertiary amine groups mercaptan, the polysiloxanes with thiazolinyl, initiator in the reactor, is causing
Under the effect of source and under inert gas shielding, carry out sulfydryl-alkene polyaddition reaction；
Step 2: be dissolved in solvent by step (1) products therefrom, adds phosphoric acid, carboxylic acid or sulfonic acid, or adds phosphorous
The ester of acid groups, hydroxy-acid group or sulfonic acid group or salt, heating reflux reaction, obtain the solution containing amphoteric ion polymer；
Step 3: by step (2) products therefrom solvent remove, then by precipitation, be dried be purified, obtain
Amphoteric ion polymer.
Described tertiary amine groups thiol molecule structural formula is
Wherein, R3For-(CH2) n1-, n1 is the integer between 2～10；R4、R5For aliphatic group, include but not limited to ethyl,
Propyl group, butyl, amyl group, heptyl, octyl group etc..
The molecular structural formula of the described polysiloxanes with thiazolinyl is
Wherein, R1For-CH3、-CH2CH3, or-C5H6；R7For-CH2=CH or-CH2-CH2=CH.
Described tertiary amine groups mercaptan include but not limited to 3-(dimethylamino)-1-propanethiol, 4-(dimethylamino)-1-butyl mercaptan,
3-(1-methyl isophthalic acid-ethylamino)-1-propanethiol, 3-(lignocaine)-1-propanethiol, 5-(dimethylamino)-1-amyl hydrosulfide, 3-(two
Phenylamino) one or more mixture in-1-propanethiol etc..
Described initiator type is different according to initiating accident sequence difference.Such as, when initiating accident sequence is heat, select temperature-sensitive freely
Base initiator；When initiating accident sequence is for radiation energy, select photosensitive radical initiator.Described temperature-sensitive radical initiator bag
Include but be not limited to azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl,
2,2-azo double (4-methoxy-2,4-methyl pentane nitrile), benzoyl peroxide, potassium peroxydisulfate or Ammonium persulfate. etc..Described
Photosensitive radical initiator is including, but not limited to dimethoxybenzoin, 1-hydroxycyclohexyl phenyl ketone or benzoyl formic acid
Methyl ester etc..
As preferably, in described step 1, with the polysiloxanes of thiazolinyl, tertiary amine groups mercaptan, the mol ratio of initiator
For 1:(0.9～1): (0.01～0.1).
As preferably, in described step 1, polyaddition reaction 0.5-24 hour.
In described step 2, solvent include but not limited to toluene, chloroform, dichloromethane, oxolane, dioxane,
In hexane, ether, ethyl acetate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone
One or several mixture.
As preferably, the addition of the polysiloxanes with thiazolinyl in step 1 is for calculating equivalent, described step 2
The amount of phosphoric acid group, hydroxy-acid group or the sulfonic acid group of middle addition is 0.9～1.3 equivalents.
As preferably, in described step 2, it is heated to solvent boiling reflux.
As preferably, in described step 2, reaction hour is 1～24 hour.
In described step 2, as preferably, especially for having the phosphoric acid group of acyclic portion, hydroxy-acid group
Or the ester of sulfonic acid group, and there is the salt of phosphoric acid group, hydroxy-acid group or the sulfonic acid group of chain structure, work as heating
Add a small amount of water after back flow reaction and continue reaction certain time, be beneficial to obtain the solution containing amphoteric ion polymer.
Accompanying drawing explanation
Fig. 1 is step (1) middle employing dimethylamino propanethiol and the polyvinyl methylsiloxane of the embodiment of the present invention 1
The product that reaction obtains1H nmr spectrum；
Fig. 2 is that the middle dimethylamino propanethiol of step (1) of the embodiment of the present invention 1 is anti-with polyvinyl methylsiloxane
The product that should obtain13C nmr spectrum；
Fig. 3 is that the middle dimethylamino propanethiol of step (3) of the embodiment of the present invention 1 is anti-with polyvinyl methylsiloxane
The product that should obtain and propane sultone react the amphoteric ion polymer that obtains1H nmr spectrum.
Detailed description of the invention
The present invention is described in further detail by embodiment below in conjunction with the accompanying drawings, it should be pointed out that embodiment described below
It is intended to be easy to the understanding of the present invention, and it is not played any restriction effect.
Embodiment 1:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the dimethylamino)-1-propanethiol containing 1 molar part, 0.9 molar part methyl second it are sequentially added in the reactor
Thiazolinyl polysiloxanes, 0.01 molar part azodiisobutyronitrile, under temperature 80 DEG C and nitrogen are protected, carry out sulfydryl-alkene and add
Become polyreaction 24 hours；
(2) step (1) products therefrom is dissolved in 1 molar part dichloromethane, adds in the propane sulfonic acid of 1.1 molar part
Ester, heating condensing reflux 10 hours, obtain the solution containing amphoteric ion polymer；(3) by step (2) products therefrom
Evaporation remove dichloromethane, then by precipitation, be dried be purified, obtain amphoteric ion polymer.
Fig. 1 is to prepare product in above-mentioned steps (1)1H nmr spectrum.
Fig. 2 is to prepare product in above-mentioned steps (1)13C nmr spectrum.
Fig. 3 is that step (3) reacts the amphoteric ion polymer obtained1H nmr spectrum.
Its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion, and its Stability Analysis of Structures, at tide
Under the environment such as wet, biodegradation, there is the more preferable durability of more typically amphoteric ion polymer.This amphoteric ion polymer energy
Apply and needing in the opposing medical material of protein attachment, packaging material for food, and due to its Stability Analysis of Structures, have
Good durability.
Embodiment 2:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the dimethylamino)-1-propanethiol containing 1 molar part, 1 molar part ethylene methacrylic it are sequentially added in the reactor
Based polysiloxane, 0.1 molar part azodiisobutyronitrile, under temperature 80 DEG C and nitrogen are protected, carry out sulfydryl-alkene addition and gather
Close reaction 24 hours；
(2) step (1) products therefrom is dissolved in 10 molar part dichloromethane, adds the bromoacetic acid ten of 1.1 molar part
One enol ester, heating condensing reflux 1 hour, it is subsequently adding a small amount of water, is further continued for reacting 2 hours, obtains containing both sexes
The solution of ionomer；
(3) by step (2) products therefrom evaporation remove dichloromethane, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 3:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the dimethylamino)-1-propanethiol containing 1 molar part, 1 molar part ethylene methacrylic it are sequentially added in the reactor
Based polysiloxane, 0.1 molar part azodiisobutyronitrile, under temperature 80 DEG C and nitrogen are protected, carry out sulfydryl-alkene addition and gather
Close reaction 24 hours；
(2) step (1) products therefrom is dissolved in 10 molar part dichloromethane, adds the 4-bromine fourth of 1.1 molar part
Acid, heating condensing reflux 1 hour, obtain the solution containing amphoteric ion polymer；
(3) by step (2) products therefrom evaporation remove dichloromethane, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability..
Embodiment 4:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the diphenylamino)-1-propanethiol containing 1 molar part, 0.95 molar part methyl it are sequentially added in the reactor
Acrylic polysiloxanes, 0.04 molar part dimethoxybenzoin, under ultraviolet light irradiation, under nitrogen protection, carry out sulfydryl
-alkene polyaddition reaction 24 hours；
(2) step (1) products therefrom is dissolved in 3 molar part solvents, adds the acrylic acid of 0.9 molar part, in 50-120 DEG C
Lower reaction 3 hours, obtains the solution containing amphoteric ion polymer；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 5:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the dimethylamino)-1-propanethiol containing 1 molar part, 0.95 molar part ethyl it are sequentially added in the reactor
Vinyl polysiloxane, 0.02 molar part 2,2'-Azobis(2,4-dimethylvaleronitrile), under temperature 70 C and nitrogen are protected, carry out sulfydryl-alkene
Polyaddition reaction 0.5-24 hour；
(2) step (1) products therefrom is dissolved in 2 molar part oxolanes, adds 1.1 molar part 2-bromoethyl sulphurs
Acid sodium, heating reflux reaction 8 hours, it is subsequently adding a small amount of water and continues reaction 2 hours, obtain containing zwitterion polymerization
The solution of thing；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion, and its Stability Analysis of Structures, at tide
Under wet, biodegradation environment, there is the more preferable durability of more typically amphoteric ion polymer.This amphoteric ion polymer can be answered
It is used in and needs to resist in the medical material of protein attachment, packaging material for food, and due to its Stability Analysis of Structures, have good
Good durability.
Embodiment 6:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned poly-amphoteric ion polymer comprises the steps:
(1) 4-(the dimethylamino)-1-butyl mercaptan containing 1 molar part, 0.98 molar part methyl it are sequentially added in the reactor
Acrylic polysiloxanes, 0.05 molar part benzoyl peroxide, protect at temperature 70 C and lower nitrogen, carry out sulfydryl-alkene
Polyaddition reaction 24 hours；
(2) step (1) products therefrom is dissolved in 5 molar part dichloromethane, adds in the propane sulfonic acid of 1.2 molar part
Ester, carries out ring-opening reaction 18 hours in being heated to reflux, obtains the solution containing amphoteric ion polymer；(3) by step (2)
Products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 7:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the dimethylamino)-1-propanethiol containing 1 molar part, 0.98 molar part phenyl it are sequentially added in the reactor
Vinyl polysiloxane, 0.03 molar part azo-bis-iso-dimethyl, under temperature 70 C and nitrogen are protected, carry out mercapto
Base-alkene polyaddition reaction 10 hours；
(2) step (1) products therefrom is dissolved in 3 molar part oxolanes, adds the 2-bromoethyl of 1.3 molar part
Sodium sulfonate, heating reflux reaction 10 hours, be subsequently adding a small amount of water, continue reaction 2 hours, obtain containing both sexes from
The solution of sub-polymer；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 8:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(1-methyl isophthalic acid-ethyl) amino-1-propanethiol containing 1 molar part, 1 molar part it are sequentially added in the reactor
Phenylethylene based polysiloxane, 0.04 molar part azodiisobutyronitrile, under temperature 70 C and nitrogen are protected, carry out sulfydryl
-alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 5 molar part oxolanes, adds in the fourth sulfonic acid of 1.1 molar part
Ester, is heated to reflux carrying out ring-opening reaction 10 hours, obtains the solution containing amphoteric ion polymer；(3) by step (2)
Products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 9:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the lignocaine)-1-propanethiol containing 1 molar part, 0.9 molar part phenyl second it are sequentially added in the reactor
Thiazolinyl polysiloxanes, 0.1 molar part azodiisobutyronitrile, under temperature 70 C and nitrogen are protected, carry out sulfydryl-alkene addition
Polyreaction 12 hours；
(2) step (1) products therefrom is dissolved in 2 molar part dichloromethane, adds the propiolactone of 1.2 molar part,
It is heated to reflux carrying out ring-opening reaction 24 hours, obtains the solution containing amphoteric ion polymer；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 10:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the lignocaine)-1-propanethiol containing 1 molar part, 0.95 molar part methyl it are sequentially added in the reactor
Acrylic polysiloxanes, 0.03 molar part dimethoxybenzoin, under ultraviolet light irradiation, under nitrogen protection, carry out sulfydryl
-alkene polyaddition reaction 24 hours；
(2) step (1) products therefrom is dissolved in 5 molar part oxolanes, adds the vinyl sulphur of 0.1 molar part
Acyl chlorides, is heated to reflux condensing reflux 5 hours, obtains the solution containing amphoteric ion polymer；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 11:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the dimethylamino)-1-propanethiol containing 1 molar part, 0.9-1 molar part methyl it are sequentially added in the reactor
Acrylic polysiloxanes, 0.02 molar part 2,2 '-azo is double (4-methoxy-2,4-methyl pentane nitrile), at 60 DEG C, nitrogen
Under gas shielded, carry out sulfydryl-alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 3 molar part oxolanes, adds in the fourth sulfonic acid of 1.3 molar part
Ester, carries out ring-opening reaction at 80 DEG C 12 hours, obtains the solution containing amphoteric ion polymer；(3) by step (2)
Products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 12:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the lignocaine)-1-propanethiol containing 1 molar part, 0.95 molar part methyl it are sequentially added in the reactor
Acrylic polysiloxanes, 0.02 molar part 1-hydroxycyclohexyl phenyl ketone, under ultraviolet light irradiation, under nitrogen protection,
Carry out sulfydryl-alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 5 molar part oxolanes, 1.2 molar part Bromopropyl phosphoric acid second
Ester, heating reflux reaction 12 hours, it is subsequently adding a small amount of water, continues reaction 2 hours, obtain containing zwitterion polymerization
The solution of thing；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 13:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 3-(the dimethylamino)-1-propanethiol containing 1 molar part, 0.95 molar part methyl it are sequentially added in the reactor
Acrylic polysiloxanes, 0.05 molar part azodiisobutyronitrile, under temperature 80 DEG C and nitrogen are protected, carry out sulfydryl-alkene
Polyaddition reaction 12 hours；
(2) step (1) products therefrom is dissolved in 1 molar part oxolane, adds the 4-chloro-butyric acid of 0.9 molar part
Methyl ester, heating reflux reaction 12 hours, it is subsequently adding a small amount of water, continues reaction 2 hours, obtain gathering containing amphion
The solution of compound；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Embodiment 14:
In the present embodiment, the structural formula of amphoteric ion polymer is:
The preparation method of above-mentioned amphoteric ion polymer comprises the steps:
(1) 5-(the dimethylamino)-1-amyl hydrosulfide containing 1 molar part, 0.95 molar part ethyl it are sequentially added in the reactor
Vinyl polysiloxane, 0.02 molar part 1-hydroxycyclohexyl phenyl ketone, under ultraviolet light irradiation, under nitrogen protection,
Carry out sulfydryl-alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 5 molar part oxolanes, 1.1 molar part bromoethyl sulfonic acid second
Fat, reacts 12 hours at 70 DEG C, is subsequently adding a small amount of water, continues reaction 2 hours, obtains containing zwitterion polymerization
The solution of thing；
(3) by step (2) products therefrom evaporation of solvent, then by precipitation, be dried be purified.
Same as in Example 1, above-mentioned steps (1) prepares product1H nmr spectrum,13C nuclear magnetic resoance spectrum
Figure, and step (3) prepares product1H nmr spectrum shows and obtains having above-mentioned knot by above-mentioned reaction
The amphoteric ion polymer of structure formula.
Same as in Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphion,
Its Stability Analysis of Structures, has the more preferable durability of more typically amphoteric ion polymer under humidity, biodegradation environment.These are two years old
Property ionomer can apply and resist in the medical material of protein attachment, packaging material for food needing, and due to it
Stability Analysis of Structures, has good durability.
Above-described embodiment is used for illustrating the present invention rather than limiting the invention, in spirit and the power of the present invention
In the protection domain that profit requires, any modifications and changes that the present invention is made, both fall within protection scope of the present invention.
Claims (10)
1. an amphoteric ion polymer, it is characterised in that: main chain is polysiloxanes, the group Han amphion in side chain,
Its molecular structural formula is as follows:
Wherein, n is the integer between 5～100, including 5 and 100；R1For-CH3、-CH2CH3, or-C5H6；R2
For-CH2CH2-or-CH2CH2CH2-；R3For-(CH2)n1-, n1It it is the integer between 2～10；R4、R5It is respectively fat
Fat alkyl；R6For-(CH2)n2PO4 -、-(CH2)n3SO3 -、-(CH2)n4CO2 -, wherein n2It is 2～10；n3It is 1～6；
n4It is 1～10.
2. amphoteric ion polymer as claimed in claim 1, it is characterised in that: described R4、R5Be respectively ethyl,
One in propyl group, butyl, amyl group, heptyl, octyl group.
The synthetic method of amphoteric ion polymer the most according to claim 1 and 2, comprises the following steps:
(1) tertiary amine groups mercaptan, the polysiloxanes with thiazolinyl, initiator it are sequentially added in the reactor, at initiating accident sequence
Under effect and under inert gas shielding, carry out sulfydryl-alkene polyaddition reaction；
The molecular structural formula of described tertiary amine groups mercaptan is:
The molecular structural formula of the described polysiloxanes with thiazolinyl is
Wherein, R7For-CH2=CH or-CH2-CH2=CH；
(2) step (1) products therefrom is dissolved in solvent, adds phosphoric acid, carboxylic acid or sulfonic acid, or add phosphoric acid
The ester of group, hydroxy-acid group or sulfonic acid group or salt, heating reflux reaction, obtain the solution containing amphoteric ion polymer；
(3) solvent in step (2) products therefrom is removed, then precipitate, be dried, obtain containing zwitterion polymerization
Thing.
The synthetic method of amphoteric ion polymer the most according to claim 3, it is characterised in that described tertiary amine
Base mercaptan is 3-(dimethylamino)-1-propanethiol, 4-(dimethylamino)-1-butyl mercaptan, 3-(1-methyl isophthalic acid-ethylamino)-1-rosickyite
One in alcohol, 3-(lignocaine)-1-propanethiol, 5-(dimethylamino)-1-amyl hydrosulfide, 3-(diphenylamino)-1-propanethiol or
Two or more mixture.
The synthetic method of amphoteric ion polymer the most according to claim 3, it is characterised in that described step
(2) in, with the addition of the polysiloxanes with thiazolinyl in step (1) for calculating equivalent, the phosphate group of addition,
Hydroxy-acid group or sulfonic acid group are 0.9～1.3 equivalents.
The synthetic method of amphoteric ion polymer the most according to claim 3, it is characterised in that described step
(1), in, it is 1:(0.9～1 with the polysiloxanes of thiazolinyl, tertiary amine groups mercaptan, the mol ratio of initiator): (0.01～0.1).
The synthetic method of amphoteric ion polymer the most according to claim 3, it is characterised in that described step
(1), in, initiator is temperature-sensitive radical initiator or photosensitive radical initiator.
The synthetic method of amphoteric ion polymer the most according to claim 3, it is characterised in that described temperature-sensitive
Radical initiator be azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile), azo dicyano valeric acid, azo-bis-iso-dimethyl,
2,2-azo double (4-methoxy-2,4-methyl pentane nitrile), benzoyl peroxide or potassium peroxydisulfate or Ammonium persulfate.；Described light
Quick radical initiator is dimethoxybenzoin, 1-hydroxycyclohexyl phenyl ketone or methyl benzoylformate.
The synthetic method of amphoteric ion polymer the most according to claim 3, it is characterised in that described step (2)
In solvent be oxolane or dichloromethane.
10. the amphoteric ion polymer described in claim 1 or 2 is as the opposing medical material of protein attachment, food
The application of packaging material.
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| CN102614847A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院大连化学物理研究所 | Amphoteric ion hydrophilic chromatographic stationary phase and preparation method thereof |
| US20140296425A1 (en) * | 2013-02-26 | 2014-10-02 | University Of Massachusetts | Telechelic based networks from novel macromonomers, compositions, preparation and uses thereof |
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| CN102614847A (en) * | 2011-01-28 | 2012-08-01 | 中国科学院大连化学物理研究所 | Amphoteric ion hydrophilic chromatographic stationary phase and preparation method thereof |
| US20140296425A1 (en) * | 2013-02-26 | 2014-10-02 | University Of Massachusetts | Telechelic based networks from novel macromonomers, compositions, preparation and uses thereof |
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| LIZHEN QIAO, ET AL.: ""Development and evaluation of new imidazolium-based zwitterionic stationary phases for hydrophilic interaction chromatography"", 《JOURNAL OF CHROMATOGRAPHY A》 * |
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