CN109735230A - A kind of amphoteric polymer base marine anti-pollution surface and preparation method thereof - Google Patents
A kind of amphoteric polymer base marine anti-pollution surface and preparation method thereof Download PDFInfo
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- CN109735230A CN109735230A CN201910063421.1A CN201910063421A CN109735230A CN 109735230 A CN109735230 A CN 109735230A CN 201910063421 A CN201910063421 A CN 201910063421A CN 109735230 A CN109735230 A CN 109735230A
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Abstract
The invention belongs to the lossless protection technology fields of marine organisms, more particularly to a kind of amphoteric polymer base marine anti-pollution surface and preparation method thereof, by designing and preparing the zwitterionic monomer containing norbornene structure, then under Grubbs catalyst, caused by the method that ring-opening metathesis polymerization is caused on surface and be grafted amphoteric polymer in modified dimethyl silicone polymer surface, antifouling surface can be obtained.Operation of the present invention is easy, and the polymer grafting density of acquisition is high, has the effect of good marine anti-pollution.
Description
Technical field
The invention belongs to the lossless protection technology fields of marine organisms, and in particular to a kind of amphoteric polymer base marine anti-pollution table
Face and preparation method thereof.
Background technique
Marine fouling organism refer to attachment alow with the animal on oceanographic equipment surface, plant and microorganism general name.With
Continuous utilization of the people for marine resources, economic problems and social concern caused by marine biofouling are also increasingly tight
Weight.Equipment by marine biological polution is numerous, including hull bottom, pipeline, dykes and dams, submarine cable, seabed tunnel, pontoon bridge and net
Tool etc..Coverage caused by it is polluted is also very wide, such as increases the ship resistance of ship and the consumption of fuel；It is clear to increase ship
Manage the number of maintenance；Cause the distorted signals of offshore platform facility；Form the blocking of submarine pipeline；The mesh of device is mended in blocking fishing
Deng.Therefore, being stained for marine organisms is eliminated, there is important strategic importance for the development of China's marine cause.
Currently, preventing the main means of marine biofouling is spraying antifouling coating.However, traditional antifouling paint is due to it
The toxicity and heavy metal ion released causes serious destruction to the marine eco-environment, in the world, is gradually forbidden
It uses.Marine antifouling coating just changes from high pollution type to environmentally friendly direction, wherein polymer brush is because of it in material
The outstanding role of modified aspect and it is of interest by people.Its principle is: by atom transfer radical polymerization (ATRP), open loop is easy
Position polymerize polymerizations such as (ROMP), on the surface of the material grafted polymer brushes, so that adherency, growth and the breeding of biology are influenced,
And the physico-chemical property by regulating and controlling polymer brush and structure grow to control the adherency of biology.Antifouling polymeric reported at present
Main species include: polyethylene glycol and its derivative, amphoteric polymer, pyridine, quaternary ammonium salt etc..Wherein, containing zwitterionic
Polymer extensive concern by researchers by its excellent anti-protein adsorption effect, at present by amphoteric ion polymer
It is had not been reported applied to marine anti-pollution surface.
Summary of the invention
The object of the present invention is to provide amphoteric polymer base marine anti-pollution surfaces and preparation method thereof, to solve above-mentioned background
The problem of proposed in technology.
The object of the present invention is to provide a kind of preparation methods on amphoteric polymer base marine anti-pollution surface, including following step
It is rapid:
S1, the zwitterionic monomer preparation containing norbornene structure:
After esterification is occurred for norbornene acid and hydroxyalkyl imidazoles, then open loop occurs with 1,3-propane sultone and obtains
Zwitterionic monomer, wherein the molar ratio of norbornene acid and hydroxyalkyl imidazoles is 1:1.1~1.2；Norbornene acid and 1,3-
The molar ratio of propane sultone is 1:1~1.2；
The preparation of S2, modified dimethyl polysiloxane:
Norbornene acid butene esters and polydimethylsiloxane prepolymer body are mixed in a certain proportion, after being sufficiently stirred, Gu
Modified dimethyl polysiloxane can be obtained in chemical conversion film, wherein norbornene acid butene esters and polydimethylsiloxane prepolymer body
Mass ratio is 1:20~1:100；
The preparation on the surface of S3, marine anti-pollution:
Under Grubbs catalyst, modified dimethyl polysiloxane is caused to the side of ring-opening metathesis polymerization by surface
Method causes the zwitterionic monomer polymerization of the structure containing norbornene, and amphoteric polymer base marine anti-pollution surface can be obtained.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, in S1, hydroxyalkyl imidazoles is ethoxy
One of imidazoles, hydroxypropyl imidazoles, hydroxyl butyl imidazole, reaction dissolvent are methylene chloride, in chloroform, 1,2- dichloroethanes
It is one or more.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, in S1, norbornene acid and hydroxyalkyl
The temperature of imidazoles esterification is 0~20 DEG C, and the reaction time is 18~36h.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, in S1, norbornene acid and hydroxyalkyl
It after esterification occurs for imidazoles, then be concentration with the solvent of 1,3-propane sultone ring-opening reaction is 0.1g/ml~0.5g/ml
Acetonitrile, reaction temperature are room temperature, and the reaction time is 24~48h.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, in S2, the temperature of film-forming is 60
~100 DEG C, 2~6h of time.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, in S3, Grubbs catalyst is
Grubbs Ru carbene complex.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, in S3, Grubbs catalyst concn is
1~5 mg/ml.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, in S3, Grubbs catalyst and both sexes
The mass ratio of ion monomer is 1:50~1:300.
Preferably, the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface, modified dimethyl polysiloxane pass through
When the method that ring-opening metathesis polymerization is caused on surface causes the zwitterionic monomer polymerization of the structure containing norbornene, solvent for use N,
One of dinethylformamide, n,N-dimethylacetamide, N-Methyl pyrrolidone, methylene chloride are a variety of, and polymerization is anti-
It is 15min~2h between seasonable, reaction temperature is room temperature.
The present invention also protects the both sexes being prepared by the preparation method on above-mentioned amphoteric polymer base marine anti-pollution surface to gather
Close object base marine anti-pollution surface.
Compared with prior art, a kind of amphoteric polymer base marine anti-pollution surface of the present invention and preparation method thereof, have with
It is lower the utility model has the advantages that
Operation of the present invention is easy, at low cost, and modified dimethyl polysiloxane is caused ring-opening metathesis polymerization by surface
Method causes the amphoteric polymer base marine anti-pollution surface that the zwitterionic monomer of the structure containing norbornene polymerize, acquisition
Polymer grafting density is high, has the effect of good marine anti-pollution.
In addition, with background technique mentioned in marine biofouling is prevented by spraying antifouling coating method, due to it
The toxicity and heavy metal ion released, the problem of serious destruction is caused to the marine eco-environment, present invention environmental protection, pollution
It is small.
Detailed description of the invention
Fig. 1 is that the prepared surface PDMS carries out anti-microbial property and algae-resistant adheres to SEM figure,
Wherein 1. Escherichia coli-PDMS, 2. Escherichia coli-PDMS- amphoteric ion, 3. staphylococcus aureus-PDMS, 4.
Staphylococcus aureus-PDMS- amphoteric ion；
Fig. 2 is that the SEM of surface algae adhesion results schemes,
Wherein 1. Du Shi algae-PDMS, 2. Du Shi algae-PDMS- amphoteric ion, 3. purple ball algae-PDMS, 4. purple ball algae-PDMS-
Amphoteric ion；
Fig. 3 is modified molecular structure figure of the present invention；
Fig. 4 is zwitterionic monomer structure chart of the present invention.
Specific embodiment
The present invention is described in detail combined with specific embodiments below, but should not be construed as limitation of the invention.It is following
Test method without specific conditions in embodiment, operates usually according to normal condition, due to not being related to inventive point, thus it is not right
Its step is described in detail.
Embodiment 1
The present embodiment provides a kind of preparation methods on amphoteric polymer base marine anti-pollution surface, comprising the following steps:
S1, zwitterionic monomer preparation:
It takes 1.38g norbornene acid and 1.34g hydroxyethyl imidazole to be added in 100ml round-bottomed flask, 50ml dichloromethane is added
Then the N of 1.86g, the 4-dimethylaminopyridine of N- dicyclohexylcarbodiimide and 0.06g is added in alkane stirring and dissolving.Reaction
Temperature control react and terminates after 0 DEG C, 24 hours, sediment is filtered to remove, acquired solution successively uses water, sodium bicarbonate with
The saturated solution of sodium chloride washs, and is evaporated under reduced pressure after dry and removes solvent.Then the 1,3- of 1.46g is added into first step product
Propane sultone and 4ml acetonitrile after reacting 48 hours at room temperature, are added ether and white solid are precipitated, drying at room temperature obtains both sexes
Ion monomer.
The preparation of S2, modified dimethyl polysiloxane (PDMS):
PDMS performed polymer 10g is taken, norbornene acid butene esters 0.5g is added, curing agent 1g strong stirring 15 minutes, is allowed to
It is sufficiently mixed, vacuumizes and eliminate PDMS air entrapment, pour into mold, solidify 3 hours at 80 DEG C to get norbornene acid butylene
Ester modified PDMS film.
The preparation on the surface of S3, marine anti-pollution:
Under argon atmosphere, in 10ml n,N-Dimethylformamide solution, Grubbs catalyst 10mg, stirring and dissolving is added
Obtain catalyst solution.Modified PDMS is put into catalyst solution, 15 minutes is stood, is quickly rushed after taking-up with methylene chloride
Wash surface twice.PDMS film is then first put into zwitterionic monomer solution to (zwitterionic monomer 500mg is dissolved in 10ml
N,N-Dimethylformamide), stand reaction 2 hours, after taking-up, get surface express developed with methylene chloride to remove the list of absorption
Body dries the rear antifouling surface up to amphoteric polymer grafting.
Embodiment 2
S1, zwitterionic monomer preparation:
It takes 1.38g norbornene acid and 1.23g hydroxyethyl imidazole to be added in 100ml round-bottomed flask, 50ml dichloromethane is added
Then the N of 1.86g, the 4-dimethylaminopyridine of N- dicyclohexylcarbodiimide and 0.06g is added in alkane stirring and dissolving.Reaction
Temperature control terminate to react after 20 DEG C, 18 hours, sediment is filtered to remove, acquired solution successively uses water, sodium bicarbonate
It is washed with the saturated solution of sodium chloride, is evaporated under reduced pressure after dry and removes solvent.Then the 1 of 1.22g is added into first step product,
3- propane sultone and 3ml acetonitrile after reacting 24 hours at room temperature, are added ether and white solid are precipitated, drying at room temperature obtains two
Property ion monomer.
The preparation of S2, modified dimethyl polysiloxane (PDMS):
PDMS performed polymer 10g is taken, norbornene acid butene esters 0.2g is added, curing agent 1g strong stirring 15 minutes, is allowed to
It is sufficiently mixed, vacuumizes and eliminate PDMS air entrapment, pour into mold, solidify 2 hours at 90 DEG C to get norbornene acid butylene
Ester modified PDMS film.
The preparation on the surface of S3, marine anti-pollution:
Under argon atmosphere, in 5ml n,N-Dimethylformamide solution, Grubbs catalyst 10mg is added, stirring and dissolving obtains
To catalyst solution.Modified PDMS is put into catalyst solution, 10 minutes is stood, is got express developed after taking-up with methylene chloride
Surface is twice.First then PDMS film is put into zwitterionic monomer solution (zwitterionic monomer 1g is dissolved in the N of 10ml,
Dinethylformamide), reaction 30 minutes are stood, after taking-up, get surface express developed with methylene chloride to remove the monomer of absorption,
Dry the rear antifouling surface up to amphoteric polymer grafting.
Embodiment 3
S1, zwitterionic monomer preparation:
It takes 1.38g norbornene acid and 1.34g hydroxyethyl imidazole to be added in 100ml round-bottomed flask, 50ml dichloromethane is added
Then the N of 1.86g, the 4-dimethylaminopyridine of N- dicyclohexylcarbodiimide and 0.06g is added in alkane stirring and dissolving.Reaction
Temperature control react and terminate after 10 DEG C, 36 hours, sediment is filtered to remove, acquired solution successively uses water, sodium bicarbonate
It is washed with the saturated solution of sodium chloride, is evaporated under reduced pressure after dry and removes solvent.Then the 1 of 1.34g is added into first step product,
3- propane sultone and 6ml acetonitrile after reacting 48 hours at room temperature, are added ether and white solid are precipitated, drying at room temperature obtains two
Property ion monomer.
The preparation of S2, modified dimethyl polysiloxane (PDMS):
PDMS performed polymer 10g is taken, norbornene acid butene esters 0.1g is added, curing agent 1g strong stirring 15 minutes, is allowed to
It is sufficiently mixed, vacuumizes and eliminate PDMS air entrapment, pour into mold, solidify 6 hours at 60 DEG C to get norbornene acid butylene
Ester modified PDMS film.
The preparation on the surface of S3, marine anti-pollution:
Under argon atmosphere, in 5ml n,N-Dimethylformamide solution, Grubbs catalyst 15mg is added, stirring and dissolving obtains
To catalyst solution.Modified PDMS is put into catalyst solution, 5 minutes is stood, is got express developed after taking-up with methylene chloride
Surface is twice.PDMS film is then first put into zwitterionic monomer solution to (zwitterionic monomer 1.5g is dissolved in 10ml's
N,N-Dimethylformamide), reaction 20 minutes are stood, after taking-up, get surface express developed with methylene chloride to remove the list of absorption
Body dries the rear antifouling surface up to amphoteric polymer grafting.
Below by taking the amphoteric polymer base marine anti-pollution surface that embodiment 1 is prepared as an example, illustrate effect of the invention.
Anti-pollution characterization:
Anti-microbial property and algae-resistant adhesion property characterization are carried out by the surface PDMS prepared by embodiment 1, wherein Fig. 1 is
It whether is grafted the obtained surface of zwitterionic monomer on the surface of the material to the antibacterial knot of Escherichia coli and staphylococcus aureus
Fruit, Fig. 2 are whether to be grafted the obtained surface of zwitterionic monomer on the surface of the material to Du Shi algae and purple two kinds of ball algae typical algaes
The adhesion results of class；The anti-bacterial result to Escherichia coli and staphylococcus aureus is as shown in Figure 1, Fig. 1 is from 30 random views
The average result selected in figure.1. and 3. there are a large amount of bacteriums and its bacterium colony attachment in the surface of figure in Fig. 1, shows unmodified
The surface PDMS does not have resilience to bacterium.2. and 4. the surface of figure is smooth uniform in Fig. 1, and only a small amount of bacterium is attached on surface
, it was demonstrated that the surface PDMS for being grafted zwitterionic monomer has excellent anti-microbial property.To Du Shi algae and purple ball two kinds of typical cases of algae
The adhesion results of algae are as shown in Fig. 2, Fig. 2 is equally the average result selected from 30 random views.With in Fig. 2 1. and 3.
It compares, 2. and 4. any surface finish of figure, algae adherency are few, it was demonstrated that the surface algae-resistant adhesion property after modification is excellent.To sum up, originally
The surface of the prepared amphoteric polymer base of invention has good antibacterial and algae-resistant adhesion property.
It should be noted that when the present invention provides numberical range, it should be appreciated that except non-present invention is otherwise noted, every number
Being worth any one numerical value between two endpoints and two endpoints of range can be selected.Unless otherwise defined, make in the present invention
All technical and scientific terms are identical as the normally understood meaning of those skilled in the art of the present technique.Although this hair has been described
Bright preferred embodiment, once a person skilled in the art knows basic creative concepts, then can be to these embodiments
Make other change and modification.So the following claims are intended to be interpreted as including preferred embodiment and falls into the present invention
All change and modification of range.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (10)
1. a kind of preparation method on amphoteric polymer base marine anti-pollution surface, which comprises the following steps:
S1, the zwitterionic monomer preparation containing norbornene structure:
After esterification is occurred for norbornene acid and hydroxyalkyl imidazoles, then open loop occurs with 1,3-propane sultone and obtains both sexes
Ion monomer, wherein the molar ratio of norbornene acid and hydroxyalkyl imidazoles is 1:1.1~1.2；Norbornene acid and 1,3- propane
The molar ratio of sultone is 1:1~1.2；
The preparation of S2, modified dimethyl polysiloxane:
Norbornene acid butene esters and polydimethylsiloxane prepolymer body are mixed in a certain proportion, after being sufficiently stirred, are solidified into
Modified dimethyl polysiloxane can be obtained in film, wherein the quality of norbornene acid butene esters and polydimethylsiloxane prepolymer body
Than for 1:10~20；
The preparation on the surface of S3, marine anti-pollution:
Under Grubbs catalyst, modified dimethyl polysiloxane is drawn by the method that ring-opening metathesis polymerization is caused on surface
The zwitterionic monomer polymerization for sending out the structure containing norbornene, can be obtained amphoteric polymer base marine anti-pollution surface.
2. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as described in claim 1, which is characterized in that S1
In, hydroxyalkyl imidazoles is one of hydroxyethyl imidazole, hydroxypropyl imidazoles, hydroxyl butyl imidazole；Reaction dissolvent is methylene chloride, three
One of chloromethanes, 1,2- dichloroethanes are a variety of.
3. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as claimed in claim 2, which is characterized in that S1
In, the temperature of norbornene acid and hydroxyalkyl imidazoles esterification is 0~20 DEG C, and the reaction time is 18~36h.
4. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as described in claim 1, which is characterized in that S1
In, it after esterification occurs for norbornene acid and hydroxyalkyl imidazoles, then with the solvent of 1,3-propane sultone ring-opening reaction is dense
Degree is the acetonitrile of 0.1g/ml~0.5g/ml, and reaction temperature is room temperature, and the reaction time is 24~48h.
5. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as described in claim 1, which is characterized in that S2
In, the temperature of film-forming is 60~100 DEG C, 2~6h of time.
6. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as described in claim 1, which is characterized in that S3
In, Grubbs catalyst is Grubbs Ru carbene complex.
7. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as claimed in claim 6, which is characterized in that
Grubbs catalyst concn is 1~5 mg/ml.
8. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as claimed in claim 7, which is characterized in that
The mass ratio of Grubbs catalyst and zwitterionic monomer is 1:50~1:300.
9. a kind of preparation method on amphoteric polymer base marine anti-pollution surface as claimed in claim 8, which is characterized in that modified
Dimethyl silicone polymer causes the zwitterionic monomer of the structure containing norbornene by the method that ring-opening metathesis polymerization is caused on surface
When polymerization, solvent for use is n,N-Dimethylformamide, in n,N-dimethylacetamide, N-Methyl pyrrolidone, methylene chloride
It is one or more, polymerization reaction time be 15min~2h, reaction temperature is room temperature.
10. such as the preparation-obtained amphoteric polymer base marine anti-pollution surface of claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808291A (en) * | 2020-06-24 | 2020-10-23 | 苏州天澜生物材料科技有限公司 | Amphiphilic silicon-based functional polymer and preparation method and application thereof |
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| CN104072795A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院兰州化学物理研究所 | Method for preparing polyimide film with low surface energy |
| CN107602867A (en) * | 2017-09-06 | 2018-01-19 | 济南大学 | A kind of fluorine-containing and/or silicon polyolefin polyarylate copolymer and preparation method and application |
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2019
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Patent Citations (5)
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| WO2009029979A1 (en) * | 2007-09-03 | 2009-03-12 | Deakin University | Coating composition and process for the preparation thereof |
| CN103288712A (en) * | 2012-03-02 | 2013-09-11 | 华东师范大学 | Norbornene monomer, as well as polymer and preparation method thereof |
| CN104072795A (en) * | 2013-03-29 | 2014-10-01 | 中国科学院兰州化学物理研究所 | Method for preparing polyimide film with low surface energy |
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