CN105985523B - A kind of amphoteric ion polymer, its synthetic method and application - Google Patents
A kind of amphoteric ion polymer, its synthetic method and application Download PDFInfo
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- CN105985523B CN105985523B CN201510055490.XA CN201510055490A CN105985523B CN 105985523 B CN105985523 B CN 105985523B CN 201510055490 A CN201510055490 A CN 201510055490A CN 105985523 B CN105985523 B CN 105985523B
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Abstract
The present invention provides a kind of amphoteric ion polymer, main chain is polysiloxane structure, and side chain contains amphoteric ion, the amphoteric ion polymer stable structure, has the better durability of more typical amphoteric ion polymer under the environment such as humidity, biodegrade.The amphoteric ion polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and having good is useful life longevity.The present invention also provides a kind of methods for synthesizing the amphoteric ion polymer, the polysiloxanes containing a large amount of tertiary amine groups is obtained using tertiary amine groups mercaptan and the polysiloxanes polyaddition reaction with alkenyl first, then through reaction kinetic obtain polysiloxanes be main chain amphoteric ion polymer, this method rapidly and efficiently, simple process, high income.
Description
Technical field
The present invention relates to amphoteric ion polymer technical fields, and in particular to it is a kind of using polysiloxanes as the both sexes of main chain from
Sub- polymer, its synthetic method and application.
Background technique
Amphoteric ion polymer is the polymer in a kind of polymer chain containing amphoteric ion group or mixing zwitterion,
Its positive and negative charge sum is equal, and hydration capability is strong and does not influence vulnerable to solution ph, has " anti-polyelectrolyte effect solution row
For ", it is widely used for the fields such as bio-medical material, petroleum industry, sewage treatment and fabric printing.
Currently, amphoteric ion polymer there are many.Wherein, most commonly with zwitterionic (methyl)
The amphoteric ion polymer that acrylate monomer is polymerize.But since ester bond is ined succession electron-withdrawing group, the both sexes from
Sub- polymer is easy hydrolysis, to cause in long-time use process, amphoteric ion functional group constantly falls off.Document
J.Mater.Chem., 2012,22,19418 report Heesoo Kim etc. have synthesized the poly- amphoteric ion of polyether backbone, but this
Kind polyether backbone, can be by oxidation degradation in long-time use process.It can be moist, raw therefore, it is necessary to prepare
Amphoteric ion polymer with preferable durability in the environment of object degradation.
Organosilicon polymer is a kind of important medical macromolecular materials and packaging material for food.As medical high polymer material
Material, organosilicon polymer are widely used in conduit, eyeglass, on microfluid instrument.But organosilicon is easy by protein attachment,
Such as blood coagulation is easily caused in clinical application etc..For this purpose, being to solve using in organosilyl surface grafting amphoteric ion polymer
One of method of the problem.Current report, such as report Biomacromolecules, 2012,13,1683, generally use table
The method for the atom transfer radical polymerization (ATRP) that face is caused is grafted amphoteric ion polymer, but this method is needed in anaerobic
Under the conditions of carry out, need using with zwitterionic (methyl) acrylate monomer and ATRP catalyst system, condition is harsh.
Therefore, a kind of organosilicon polymer containing amphoteric ion group is sought, high excellent of, stability simple with preparation method
Point is one of the research topic of this field scientific worker, in the medical macromolecular materials and food for needing to resist protein attachment
Product packaging material etc., the polymer have a good application prospect.
Summary of the invention
The present invention provides a kind of amphoteric ion polymer, main chain is polysiloxanes, group containing amphoteric ion in side chain,
Its molecular structural formula is as follows:
Wherein, n is the integer between 5~100, including 5 and 100；R1For-CH3、-CH2CH3Or-C5H6；R2For-
CH2CH2Or-CH2CH2CH2-；R3For-(CH2)n1, n1For the integer between 2~10；R4、R5Respectively aliphatic group, including but
It is not limited to ethyl, propyl, butyl, amyl, heptyl, octyl 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 be polysiloxane structure, side chain include amphoteric ion, stable structure,
There is the better durability of more typical amphoteric ion polymer under the environment such as wet environment, biodegrade.The zwitterion polymerization
Object can be applied as medical material, packaging material for food that can resist protein attachment etc., and due to its high stable structure,
It can be used for a long time under the environment such as wet environment, biodegrade, there is preferable durability.
The present invention also provides a kind of synthetic method of above-mentioned amphoteric ion polymer, this method uses tertiary amine groups sulphur first
Alcohol obtains the polysiloxanes containing a large amount of tertiary amine groups with the polysiloxanes polyaddition reaction with alkenyl, then through reaction kinetic
Obtain polysiloxanes be main chain amphoteric ion polymer, this method have the advantages that rapidly and efficiently, simple process, high income.
This method specifically includes the following steps:
Step 1: sequentially adding tertiary amine groups mercaptan, the polysiloxanes with alkenyl, initiator in the reactor, causing source
Under effect and under inert gas shielding, sulfydryl-alkene polyaddition reaction is carried out；
Step 2: step (1) products therefrom being dissolved in solvent, phosphoric acid, carboxylic acid or sulfonic acid is added, or phosphoric acid is added
The ester or salt of group, carboxylic acid group or sulfonic acid group, heating reflux reaction obtain the solution containing amphoteric ion polymer；
Step 3: the solvent in step (2) products therefrom being removed, is then purified by precipitating, drying, obtains two
Property ionomer.
The tertiary amine groups thiol molecule structural formula is
Wherein, R3For-(CH2) n1, n1 is the integer between 2~10；R4、R5For aliphatic group, including but not limited to second
Base, propyl, butyl, amyl, heptyl, octyl etc..
The molecular structural formula of the polysiloxanes with alkenyl is
Wherein, R1For-CH3、-CH2CH3Or-C5H6；R7For-CH=CH2 Or-CH2- CH=CH2 。
The tertiary amine groups mercaptan includes but is not limited to 3- (dimethylamino) -1- propanethiol, 4- (dimethylamino) -1- fourth sulphur
Alcohol, 3- (1- methyl-1-ethylamino)-1- propanethiol, 3- (lignocaine)-1- propanethiol, penta sulphur of 5- (dimethylamino)-1-
The mixture of one or more of alcohol, 3- (diphenylamino) -1- propanethiol etc..
The initiator type is different according to source difference is caused.For example, selecting temperature-sensitive free when causing source is heat
Base initiator；When causing source is radiation energy, photosensitive free radical initiator is selected.The temperature-sensitive radical initiator include but
It is not limited to azodiisobutyronitrile, azobisisoheptonitrile, azo dicyano valeric acid, azo-bis-iso-dimethyl, 2,2- azo
Bis- (4- methoxy -2,4- methyl pentane nitriles), benzoyl peroxide, potassium peroxydisulfate or ammonium persulfate etc..The photosensitive free radical
Initiator includes but is not limited to dimethoxybenzoin, 1- hydroxycyclohexyl phenyl ketone or methyl benzoylformate etc..
Preferably, in the step 1, the molar ratio of polysiloxanes, tertiary amine groups mercaptan, initiator with alkenyl is
1:(0.9~1): (0.01~0.1).
Preferably, in the step 1, polyaddition reaction 0.5-24 hours.
In the step 2, solvent include but is not limited to toluene, chloroform, methylene chloride, tetrahydrofuran, dioxanes, oneself
One of alkane, ether, ethyl acetate, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or N-Methyl pyrrolidone or
Several mixture of person.
Preferably, being to calculate equivalent, the step 2 with the additional amount of the polysiloxanes with alkenyl in step 1
The amount of the phosphoric acid group of middle addition, carboxylic acid group or sulfonic acid group is 0.9~1.3 equivalent.
Preferably, being heated to solvent boiling reflux in the step 2.
Preferably, reaction hour is 1~24 hour in the step 2.
In the step 2, preferably, especially for phosphorous acid groups, carboxylic acid group with acyclic portion
Or the ester of sulfonic acid group, and the salt of the phosphorous acid groups with chain structure, carboxylic acid group or sulfonic acid group, when being heated to reflux
A small amount of water is added after reaction the reaction was continued certain time, in favor of obtaining the solution containing amphoteric ion polymer.
Detailed description of the invention
It is anti-using dimethylamino propanethiol and polyvinyl methylsiloxane in the step of Fig. 1 is the embodiment of the present invention 1 (1)
The product that should be obtained1H nmr spectrum；
It is reacted with dimethylamino propanethiol with polyvinyl methylsiloxane in the step of Fig. 2 is the embodiment of the present invention 1 (1)
Obtained product13C nmr spectrum；
It is reacted with dimethylamino propanethiol with polyvinyl methylsiloxane in the step of Fig. 3 is the embodiment of the present invention 1 (3)
The amphoteric ion polymer that obtained product is reacted with propane sultone1H nmr spectrum.
Specific embodiment
Present invention is further described in detail for embodiment with reference to the accompanying drawing, it should be pointed out that implementation as described below
Example is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (dimethylamino) -1- propanethiol containing 1 molar part, 0.9 molar part methyl second are sequentially added in the reactor
It is poly- to carry out sulfydryl-alkene addition at 80 DEG C of temperature and nitrogen protection for alkenyl polysiloxanes, 0.01 molar part azodiisobutyronitrile
Close reaction 24 hours；
(2) step (1) products therefrom is dissolved in 1 molar part methylene chloride, the propane sultone of 1.1 molar parts is added,
Heating is condensed back 10 hours, obtains the solution containing amphoteric ion polymer；(3) evaporation of step (2) products therefrom is removed two
Then chloromethanes is purified by precipitating, drying, obtains amphoteric ion polymer.
Fig. 1 is that product is made in above-mentioned steps (1)1H nmr spectrum.
Fig. 2 is that product is made in above-mentioned steps (1)13C nmr spectrum.
Fig. 3 is that step (3) react obtained amphoteric ion polymer1H nmr spectrum.
Its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion, stable structure, in tide
There is the better durability of more typical amphoteric ion polymer under the environment such as wet, biodegradable.The amphoteric ion polymer can answer
With in the medical material for needing to resist protein attachment, in packaging material for food, and due to its stable structure, have good
Durability.
Embodiment 2:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (dimethylamino) -1- propanethiol, 1 molar part ethylene methacrylic containing 1 molar part are sequentially added in the reactor
It is anti-to carry out sulfydryl-alkene addition polymerization at 80 DEG C of temperature and nitrogen protection for based polysiloxane, 0.1 molar part azodiisobutyronitrile
It answers 24 hours；
(2) step (1) products therefrom is dissolved in 10 molar part methylene chloride, the bromoacetic acid 11 of 1.1 molar parts is added
Enol ester, heating are condensed back 1 hour, and a small amount of water is then added, and are further continued for reaction 2 hours, are obtained containing zwitterion polymerization
The solution of object；
(3) step (2) products therefrom is evaporated and removes methylene chloride, then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 3:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (dimethylamino) -1- propanethiol, 1 molar part ethylene methacrylic containing 1 molar part are sequentially added in the reactor
It is anti-to carry out sulfydryl-alkene addition polymerization at 80 DEG C of temperature and nitrogen protection for based polysiloxane, 0.1 molar part azodiisobutyronitrile
It answers 24 hours；
(2) step (1) products therefrom is dissolved in 10 molar part methylene chloride, the 4- bromo-butyric acid of 1.1 molar parts is added, adds
Heat is condensed back 1 hour, obtains the solution containing amphoteric ion polymer；
(3) step (2) products therefrom is evaporated and removes methylene chloride, then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 4:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (diphenylamino) -1- propanethiol, 0.95 molar part methyl containing 1 molar part are sequentially added in the reactor
Propylene based polysiloxane, 0.04 molar part dimethoxybenzoin under nitrogen protection, carry out sulfydryl-alkene under ultraviolet light irradiation
Polyaddition reaction 24 hours；
(2) step (1) products therefrom is dissolved in 3 molar part solvents, the acrylic acid of 0.9 molar part is added, in 50-120
It is reacted 3 hours at DEG C, obtains the solution containing amphoteric ion polymer；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 5:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (dimethylamino) -1- propanethiol, 0.95 molar part ethyl containing 1 molar part are sequentially added in the reactor
Vinyl polysiloxane, 0.02 molar part azobisisoheptonitrile carry out sulfydryl-alkene addition under temperature 70 C and nitrogen protection
Polymerization reaction 0.5-24 hours；
(2) step (1) products therefrom is dissolved in 2 molar part tetrahydrofurans, 1.1 molar part 2- bromoethyl sulfonic acid is added
Sodium, heating reflux reaction 8 hours, a small amount of water is then added, and the reaction was continued 2 hours, obtains containing the molten of amphoteric ion polymer
Liquid；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion, stable structure, in tide
There is the better durability of more typical amphoteric ion polymer under wet, biodegradable environment.The amphoteric ion polymer can be applied
In the medical material for needing to resist protein attachment, in packaging material for food, and due to its stable structure, have good resistance to
Long property.
Embodiment 6:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned poly- amphoteric ion polymer includes the following steps:
(1) 4- (dimethylamino) -1- butanethiol, 0.98 molar part methyl containing 1 molar part are sequentially added in the reactor
Propylene based polysiloxane, 0.05 molar part benzoyl peroxide carry out sulfydryl-alkene addition in temperature 70 C and lower nitrogen protection
Polymerization reaction 24 hours；
(2) step (1) products therefrom is dissolved in 5 molar part methylene chloride, the propane sultone of 1.2 molar parts is added,
It is carried out ring-opening reaction 18 hours in being heated to reflux, obtains the solution containing amphoteric ion polymer；(3) by step (2) products therefrom
Then evaporation of solvent is purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 7:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (dimethylamino) -1- propanethiol, 0.98 molar part phenyl containing 1 molar part are sequentially added in the reactor
Vinyl polysiloxane, 0.03 molar part azo-bis-iso-dimethyl carry out sulfydryl-under temperature 70 C and nitrogen protection
Alkene polyaddition reaction 10 hours；
(2) step (1) products therefrom is dissolved in 3 molar part tetrahydrofurans, the 2- bromoethyl sulfonic acid of 1.3 molar parts is added
Heating reflux reaction 10 hours, a small amount of water was then added in sodium, and the reaction was continued 2 hours, obtained containing the molten of amphoteric ion polymer
Liquid；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 8:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (1- methyl-1-ethyl) amino-1- propanethiol, 1 mole containing 1 molar part is sequentially added in the reactor
Part phenylethylene based polysiloxane, 0.04 molar part azodiisobutyronitrile carry out sulfydryl-under temperature 70 C and nitrogen protection
Alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 5 molar part tetrahydrofurans, the butyl sultone of 1.1 molar parts is added,
It is heated to reflux progress ring-opening reaction 10 hours, obtains the solution containing amphoteric ion polymer；(3) step (2) products therefrom is steamed
Hair removes solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 9:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (lignocaine) -1- propanethiol containing 1 molar part, 0.9 molar part phenyl second are sequentially added in the reactor
Alkenyl polysiloxanes, 0.1 molar part azodiisobutyronitrile carry out sulfydryl-alkene addition polymerization under temperature 70 C and nitrogen protection
Reaction 12 hours；
(2) step (1) products therefrom is dissolved in 2 molar part methylene chloride, the propiolactone of 1.2 molar parts, heating is added
Reflux carries out ring-opening reaction 24 hours, obtains the solution containing amphoteric ion polymer；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 10:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (lignocaine) -1- propanethiol, 0.95 molar part methyl containing 1 molar part are sequentially added in the reactor
Propylene based polysiloxane, 0.03 molar part dimethoxybenzoin under nitrogen protection, carry out sulfydryl-alkene under ultraviolet light irradiation
Polyaddition reaction 24 hours；
(2) step (1) products therefrom is dissolved in 5 molar part tetrahydrofurans, the vinvlsulfonamido of 0.1 molar part is added
Chlorine, is heated to reflux condensing reflux 5 hours, obtains the solution containing amphoteric ion polymer；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 11:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (dimethylamino) -1- propanethiol, 0.9-1 molar part methyl containing 1 molar part are sequentially added in the reactor
Propylene based polysiloxane, 0.02 molar part, 2,2 '-azo are bis- (4- methoxy -2,4- methyl pentane nitrile), at 60 DEG C, nitrogen protection
Under, carry out sulfydryl-alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 3 molar part tetrahydrofurans, the butyl sultone of 1.3 molar parts is added,
It is carried out ring-opening reaction 12 hours at 80 DEG C, obtains the solution containing amphoteric ion polymer；(3) step (2) products therefrom is steamed
Hair removes solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 12:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (lignocaine) -1- propanethiol, 0.95 molar part methyl containing 1 molar part are sequentially added in the reactor
Propylene based polysiloxane, 0.02 molar part 1- hydroxycyclohexyl phenyl ketone under nitrogen protection, carry out under ultraviolet light irradiation
Sulfydryl-alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 5 molar part tetrahydrofurans, 1.2 molar part Bromopropyl etherophosphoric acids,
Heating reflux reaction 12 hours, a small amount of water is then added, the reaction was continued 2 hours, obtains the solution containing amphoteric ion polymer；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 13:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 3- (dimethylamino) -1- propanethiol, 0.95 molar part methyl containing 1 molar part are sequentially added in the reactor
Propylene based polysiloxane, 0.05 molar part azodiisobutyronitrile carry out sulfydryl-alkene addition at 80 DEG C of temperature and nitrogen protection
Polymerization reaction 12 hours；
(2) step (1) products therefrom is dissolved in 1 molar part tetrahydrofuran, the 4- chloro-butyric acid first of 0.9 molar part is added
Heating reflux reaction 12 hours, a small amount of water was then added in ester, and the reaction was continued 2 hours, obtained containing the molten of amphoteric ion polymer
Liquid；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Embodiment 14:
In the present embodiment, the structural formula of amphoteric ion polymer are as follows:
The preparation method of above-mentioned amphoteric ion polymer includes the following steps:
(1) 5- (dimethylamino) -1- amyl hydrosulfide, 0.95 molar part ethyl containing 1 molar part are sequentially added in the reactor
Vinyl polysiloxane, 0.02 molar part 1- hydroxycyclohexyl phenyl ketone under nitrogen protection, carry out under ultraviolet light irradiation
Sulfydryl-alkene polyaddition reaction 20 hours；
(2) step (1) products therefrom is dissolved in 5 molar part tetrahydrofurans, 1.1 molar part bromoethyl sulfonic acid second rouge,
It is reacted 12 hours at 70 DEG C, a small amount of water is then added, the reaction was continued 2 hours, obtains the solution containing amphoteric ion polymer；
(3) it by step (2) products therefrom evaporation of solvent, is then purified by precipitating, drying.
It is same as Example 1, product is made in above-mentioned steps (1)1H nmr spectrum,13C nmr spectrum, with
And product is made in step (3)1H nmr spectrum show by above-mentioned reaction obtain having the both sexes of structure above from
Sub- polymer.
Same as Example 1, its main chain of above-mentioned amphoteric ion polymer is polysiloxane structure, and side chain is amphoteric ion,
Its stable structure has the better durability of more typical amphoteric ion polymer under moist, biodegradable environment.The both sexes from
Sub- polymer can be applied in the medical material for needing to resist protein attachment, in packaging material for food, and since its structure is steady
It is fixed, there is good durability.
Above-described embodiment is used to illustrate the present invention, rather than limits the invention, in spirit of the invention and
In scope of protection of the claims, to any modifications and changes that the present invention makes, protection scope of the present invention is both fallen within.
Claims (8)
1. a kind of synthetic method of amphoteric ion polymer, it is characterised in that: the main chain of the amphoteric ion polymer is poly- silicon
Oxygen alkane, group containing amphoteric ion in side chain, molecular structural formula are as follows:
Wherein, n is the integer between 5~100, including 5 and 100；R1For-CH3、-CH2CH3Or-C5H6；R2For-CH2CH2Or-
CH2CH2CH2-；R3For-(CH2)n1, n1For the integer between 2~10；R4、R5Respectively aliphatic group；R6For-(CH2)
n2PO4 -、-(CH2)n3SO3 -、-(CH2)n4CO2 -, wherein n2It is 2~10；n3It is 1~6；n4It is 1~10；
The synthetic method of amphoteric ion polymer the following steps are included:
(1) tertiary amine groups mercaptan, the polysiloxanes with alkenyl, initiator are sequentially added in the reactor, in the case where causing source effect
Under inert gas shielding, sulfydryl-alkene polyaddition reaction is carried out；
The molecular structural formula of the tertiary amine groups mercaptan are as follows:
The molecular structural formula of the polysiloxanes with alkenyl is
Wherein, R7For-CH=CH2Or-CH2- CH=CH2；
(2) step (1) products therefrom is dissolved in solvent, phosphoric acid, carboxylic acid or sulfonic acid is added, or phosphorous acid groups, carboxylic are added
The ester or salt of acid groups or sulfonic acid group, heating reflux reaction obtain the solution containing amphoteric ion polymer；
(3) solvent in step (2) products therefrom is removed, then precipitates, is dry, obtains containing amphoteric ion polymer.
2. the synthetic method of amphoteric ion polymer as described in claim 1, it is characterised in that: the R4、R5Respectively second
One of base, propyl, butyl, amyl, heptyl, octyl.
3. the synthetic method of amphoteric ion polymer according to claim 1, which is characterized in that the tertiary amine groups mercaptan
Be 3- (dimethylamino)-1- propanethiol, 4- (dimethylamino)-1- butanethiol, 3- (1- methyl-1-ethylamino)-1- propanethiol,
One of 3- (lignocaine) -1- propanethiol, 5- (dimethylamino) -1- amyl hydrosulfide, 3- (diphenylamino) -1- propanethiol or two
Kind or more mixture.
4. the synthetic method of amphoteric ion polymer according to claim 1, which is characterized in that in the step (2),
It is to calculate equivalent, phosphate group, carboxylic acid group or the sulphur of addition with the additional amount of the polysiloxanes with alkenyl in step (1)
Acid groups are 0.9~1.3 equivalent.
5. the synthetic method of amphoteric ion polymer according to claim 1, which is characterized in that in the step (1),
The molar ratio of polysiloxanes, tertiary amine groups mercaptan, initiator with alkenyl is 1:(0.9~1): (0.01~0.1).
6. the synthetic method of amphoteric ion polymer according to claim 1, which is characterized in that in the step (1),
Initiator is temperature-sensitive radical initiator or photosensitive free radical initiator.
7. the synthetic method of amphoteric ion polymer according to claim 6, which is characterized in that the temperature-sensitive free radical
Initiator is azodiisobutyronitrile, azobisisoheptonitrile, azo dicyano valeric acid, azo-bis-iso-dimethyl, 2,2- azo
Bis- (4- methoxy -2,4- methyl pentane nitriles), benzoyl peroxide or potassium peroxydisulfate or ammonium persulfate；The photosensitive free radical draws
Hair agent is dimethoxybenzoin, 1- hydroxycyclohexyl phenyl ketone or methyl benzoylformate.
8. the synthetic method of amphoteric ion polymer according to claim 1, which is characterized in that in the step (2)
Solvent is tetrahydrofuran or methylene chloride.
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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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| "Development and evaluation of new imidazolium-based zwitterionic stationary phases for hydrophilic interaction chromatography";Lizhen Qiao, et al.;《Journal of Chromatography A》;20130228;第1286卷;第137-145页 * |
| "Electrospun Zwitterionic Poly(Sulfobetaine Methacrylate) for Nonadherent, Superabsorbent, and Antimicrobial Wound Dressing Applications";Reza Lalani, et al.;《Biomacromolecules》;20120430;第13卷;第1853-1863页 * |
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