CN108822326B - Zwitterionic copolymer, preparation method and method for constructing coating by utilizing zwitterionic copolymer - Google Patents

Zwitterionic copolymer, preparation method and method for constructing coating by utilizing zwitterionic copolymer Download PDF

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CN108822326B
CN108822326B CN201810588595.5A CN201810588595A CN108822326B CN 108822326 B CN108822326 B CN 108822326B CN 201810588595 A CN201810588595 A CN 201810588595A CN 108822326 B CN108822326 B CN 108822326B
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zwitterionic copolymer
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CN108822326A (en
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张世平
卢倩
李�荣
宫永宽
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Northwestern University
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Abstract

The invention provides a zwitterionic copolymer, which is shown as a formula (I), and is prepared by free radical polymerization; a method of constructing a coating using the zwitterionic copolymer, comprising the steps of: preparing a dopamine hydrochloride solution with the pH value of 6-9; immersing a base material to be modified into the dopamine hydrochloride solution, and constructing a poly-dopamine mediated layer on the surface of the base material; and activating the zwitterionic copolymer to obtain an activated zwitterionic copolymer solution, and spraying or dip-coating the activated copolymer solution on the surface of the base material containing the poly-dopamine mediated layer to construct a zwitterionic copolymer coating. The method for constructing the coating has the advantages of mild conditions, no metal catalyst and the like, and the constructed coating has good stability, strong hydrophilicity and anti-pollution capability, long service life and good biological pollution resistance to biological pollution such as bacteria, protein and the like.

Description

Zwitterionic copolymer, preparation method and method for constructing coating by utilizing zwitterionic copolymer
Technical Field
The invention relates to the technical field of polymer synthesis and substrate surface modification, in particular to a zwitterionic copolymer, a preparation method and a method for constructing a coating by using the zwitterionic copolymer.
Background
In recent years, a series of problems such as inflammation, blood coagulation, infection and the like caused by biological pollution such as protein, cells, bacteria and the like in clinical application of biomedical materials and devices severely limit the clinical application of the materials and the devices. The surface modification of the existing biomedical materials, namely the biological pollution resistance of the materials is realized by controlling the interface, which is a simple and easy method for solving the biological pollution problem of the surfaces of the existing biological materials.
The biocompatibility of the material is improved by constructing a hydrophilic polymer or a hydrophilic group on the surface of the material, improving the hydrophilicity of the surface of the material, forming a hydration layer on the surface of the material and utilizing the repulsive interaction between the hydration layer and in-vivo proteins, cells, bacteria and the like. The most commonly used hydrophilic polymers or groups to improve biocompatibility of materials are polyethylene glycol (PEG), zwitterionic groups, and zwitterionic polymers.
PEG has larger size exclusion effect, good hydrophilicity and flexibility, and can effectively prevent biological pollutants such as protein from contacting the surface of the material by forming super-strong water and a layer, thereby showing excellent nonspecific protein adsorption resistance. The performance of the PEG coating is closely related to the covering density of the PEG coating on the surface of the base material, and the surface of the material modified by the single-chain PEG is difficult to achieve higher surface coverage rate. The branched structure of the multi-arm PEG can realize high surface density, and can effectively improve the anti-biological pollution capability of the coating.
Common zwitterions such as Phosphorylcholine (PC), Carboxybetaine (CB), Sulfobetaine (SB), and the like, exhibit electrical neutrality due to the presence of equal amounts of positive and negative charges. The zwitterion group or the polymer can be combined with a large number of water molecules to form a hydration layer, and the good biocompatibility and the anti-fouling effect are shown. After the surface of the material is subjected to hydrophilic modification by the zwitterion groups or the polymer containing the zwitterion groups, the surface of the material shows excellent biocompatibility. Methods that can be used to build the hydrophilic coating are:
(1) utilizing trimethoxy silicon to react with hydroxyl on the surface of a substrate, directly fixing a copolymer on the surface of the substrate or fixing an initiator on the surface of the substrate, and then constructing a hydrophilic coating by using surface-initiated atom transfer radical polymerization (SI-ATRP);
(2) utilizing the reaction of gold (Au) and sulfydryl or disulfide (-S-S-) bonds, fixing an initiator on the surface of Au, and constructing a hydrophilic coating by using SI-ATRP;
(3) utilizing the universal adhesion function of dopamine, fixing the dopamine on the surface of a base material, and constructing a hydrophilic coating by methods such as codeposition, addition reaction, reaction of amino and active ester and the like;
(4) hydrophilic coatings are built up by photo-polymerization.
However, the above-mentioned methods for constructing a coating layer have disadvantages of poor coating stability, difficulty in quantification, complexity in purification steps of the copolymer used, and the like to various degrees.
Disclosure of Invention
The present invention has been made to solve the above-mentioned problems occurring in the prior art, and an object of the present invention is to provide a zwitterionic copolymer and a preparation method thereof;
it is another object of the present invention to provide a method of constructing a coating using the above zwitterionic copolymer.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a zwitterionic copolymer of the formula (I):
Figure BDA0001690056730000021
wherein R is a zwitterionic group and R is1Is H or methyl, said R2Is H or methyl; x is an integer of 1-50; m is an integer of 1-30, n is an integer of 10-50, m: n is 20:1 to 1: 20.
Preferably, the zwitterionic group R is at least one of formula (1) to formula (3):
Figure BDA0001690056730000022
wherein y is an integer of 2 to 4, and z is an integer of 1 to 3.
A method of making the zwitterionic copolymer, comprising:
dissolving a monomer shown in a formula (II) and a monomer shown in a formula (III) in a solvent, carrying out free radical polymerization at 30-80 ℃, and purifying to obtain the zwitterionic copolymer;
Figure BDA0001690056730000031
wherein R is a zwitterionic group and R is1Is H orMethyl, said R2Is H or methyl, and x is an integer of 1-50.
Preferably, the solvent is at least one of water, methanol and ethanol.
A method of constructing a coating using the zwitterionic copolymer, the method comprising the steps of:
(1) construction of a polydopamine-mediated layer: preparing a dopamine hydrochloride solution with the pH value of 6-9; immersing a base material to be modified into the dopamine hydrochloride solution, and constructing a poly-dopamine mediated layer on the surface of the base material;
(2) construction of the zwitterionic copolymer coating: activating a zwitterionic copolymer to obtain an activated zwitterionic copolymer solution, and spraying or dip-coating the activated copolymer solution on the surface of the base material containing the poly-dopamine mediated layer to construct a zwitterionic copolymer coating; the structural formula of the zwitterionic copolymer is as follows:
Figure BDA0001690056730000032
wherein R is a zwitterionic group and R is1Is H or methyl, said R2Is H or methyl; x is an integer of 1-50; m is an integer of 1-30, n is an integer of 10-50, m: n is 20:1 to 1: 20.
Preferably, the concentration of the dopamine hydrochloride solution in the step (1) is 1-5 mg/mL; and immersing the base material into the dopamine hydrochloride solution for 10-60 min.
Preferably, the base material in step (1) is nylon, glass, cellulose resin, polysulfone, polyvinylidene fluoride, polyethersulfone, polyacrylonitrile, polyvinyl chloride or polypropylene sheet base.
Preferably, the zwitterion group R in the step (2) is one or more of phosphorylcholine group, carboxylic acid betaine group or sulfonic acid betaine group.
Preferably, the activating agent used for the activation in step (2) is DCC/NHS, EDC/NHS, DCC/DMAP or EDC/DMAP; the activation temperature is between room temperature and 60 ℃; the activation time is 2-24 h.
Preferably, the spraying method in the step (2) is as follows: the concentration of the zwitterionic copolymer in the solution is 1-10 mg/mL, the pH value of the solution is 6-9, the activated zwitterionic copolymer solution is sprayed on the surface of a base material containing a polydopamine dielectric layer, and DMSO, DMF or H is carried out at the temperature of room temperature to 60 DEG C2Reacting for 1-10 h in an O atmosphere;
the dip coating method in the step (2) comprises the following steps: the concentration of the zwitterionic polymer in the solution is 1-10 mg/mL, the pH value of the solution is 6-9, and a base material containing a polydopamine dielectric layer is immersed into the activated zwitterionic copolymer solution and reacts at room temperature to 60 ℃.
The invention has the beneficial effects that: the zwitterionic copolymer provided by the invention contains carboxyl, the preparation method is carried out by free radical polymerization, and the zwitterionic copolymer has the advantages of simplicity, easiness, clear structure and adjustable composition proportion; the construction method of the zwitterionic copolymer coating utilizes the universal adhesion effect of the dopamine coating and the amidation reaction of the carboxyl-containing zwitterionic copolymer and amino to bond and fix the zwitterionic copolymer on the surface of the substrate to construct the zwitterionic copolymer coating, establishes a universal technical method for firstly coating a polydopamine dielectric layer on the surface of the substrate and then constructing the zwitterionic copolymer coating, has the advantages of mild conditions, no metal catalyst and the like, and the constructed coating has good stability, strong hydrophilicity and pollution resistance, long service life and good biological pollution resistance to bacteria, proteins and the like.
Drawings
FIG. 1 is a NMR spectrum of Carboxyl-HEMA described in example 1;
FIG. 2 shows the NMR spectrum of the zwitterionic copolymer PCPC described in example 1;
FIG. 3 shows the NMR spectrum of the zwitterionic copolymer PCPC described in example 2;
FIG. 4 shows the NMR spectrum of the zwitterionic copolymer PCSB described in example 3;
FIG. 5 nuclear magnetic resonance hydrogen spectrum of the zwitterionic copolymer PCSB described in example 4;
FIG. 6 static contact angle test results for zwitterionic copolymer coatings.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention are described below clearly and completely, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The synthetic route of the zwitterionic copolymer is as follows:
Figure BDA0001690056730000051
wherein R is a zwitterionic group and R is1Is H or methyl, said R2Is H or methyl; x is an integer of 1-50; m is an integer of 1-30, n is an integer of 10-50, m: n is 20:1 to 1:20, and R is at least one of formula (1) to formula (3):
Figure BDA0001690056730000052
y is an integer of 2 to 4, and z is an integer of 1 to 3.
To further illustrate the present invention, a zwitterionic copolymer, a method of making the same, and a method of forming a coating using the same are described in detail in the following examples, wherein DCC is N, N-dicyclohexylcarbodiimide, EDC is 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide, NHS is N-hydroxysuccinimide, DMAP is 4-dimethylaminopyridine, and MPC has the formula
Figure BDA0001690056730000053
MSB has the structural formula
Figure BDA0001690056730000054
Example 1
Preparation of zwitterionic copolymer:
(1) adding 11.22g succinic anhydride into a 250mL round bottom flask containing 120mL dioxane, after fully dissolving, sequentially adding 12mL pyridine, 11.99g hydroxyethyl methacrylate and 1.08g 2-dimethylaminopyridine, reacting for 24h in an oil bath at 40 ℃, taking out a reaction bottle, spin-drying the reaction liquid by using a rotary evaporator, adding 40mL dichloromethane, washing the solution by using 1M glacial hydrochloric acid and distilled water until the solution is neutral, drying the organic phase obtained by liquid separation overnight by using anhydrous sodium sulfate, filtering, and pumping out the solvent by using the rotary evaporator and an oil pump to obtain 17.15g light yellow viscous liquid carboxylated alkenyl monomer Carboxyl-HEMA. FIG. 1 is a drawing thereof1H NMR spectrum, wherein the attribution of each characteristic peak in the spectrum is as follows: 6.14 (-CH)2＝C(CH3)-)；5.61(-CH2＝C(CH3)-)；4.37(-OOC(CH2)2OCO-)；2.69(HOOC(CH2)2COO-)；1.95(H3CC(COO-)CH2)。
(2) In N2Under protection, 5mL of anhydrous ethanol and 5mL of tetrahydrofuran were added to a 250mL of water-and oxygen-removing three-necked flask, 65.2mg of AIBN was weighed and dissolved in 4mL of tetrahydrofuran, and after complete dissolution, 1/4 volumes of the solution were transferred to the three-necked flask, the reaction temperature was adjusted to 75 ℃, and the mixture was magnetically stirred and kept in this state for 30 min. The constant pressure dropping funnel is filled with a mixed solution of 0.26g Carboxyl-HEMA in 10mL tetrahydrofuran, 3.0g MPC in 30mL absolute ethanol and the rest AIBN in tetrahydrofuran, the mixed solution is slowly dropped (3 s/drop) into a three-neck flask, and after the dropping is finished, the sealing reaction is continued for 24h to obtain a colorless transparent solution. Putting the solution into a dialysis bag with the molecular weight cutoff of 3500Da for dialysis for 3 days (the dialysis external solution is distilled water; the dialysis external solution is replaced every 3-5 h), and freeze-drying to obtain 1.96g of the zwitterionic polymer PCPC. FIG. 2 is a drawing thereof1H NMR spectrum from peak c [ - (CH) in the figure2)2COOH，4mH]And d peak [ -N [ ]+(CH3)3，9nH]Integrated area ofThe molar ratio of the copolymerized units of Carboxyl-HEMA and MPC in the zwitterionic polymer PCPC was calculated to be 1: 9.
Figure BDA0001690056730000061
In the above formula, m and n are the number of repeating units of the copolymer units of Carboxyl-HEMA and MPC in the zwitterionic polymer PCPC, respectively; i iscAnd IdThe integrated areas of the c and d peaks in fig. 2, respectively.
Example 2
Preparation of zwitterionic copolymer:
Carboxyl-HEMA was prepared in the same manner as in step (1) of example 1; a zwitterionic polymer, PCPC, was prepared in the same manner as in step (2) in example 1, except that the amount of Carboxyl-HEMA added was 0.59g, to give PCPC1The H NMR spectrum is shown in FIG. 3, which shows that the molar ratio of the copolymerized units of Carboxyl-HEMA and MPC in the zwitterionic polymer PCPC is 2: 8.
Example 3
Preparation of zwitterionic copolymer:
Carboxyl-HEMA was prepared in the same manner as in step (1) of example 1; preparation of zwitterionic Polymer Using the same procedure as in step (2) of example 1, except that 3.0g of MPC was replaced with 2.85g of MSB, the zwitterionic Polymer PCSB obtained was1The H NMR spectrum is shown in FIG. 4, and it can be seen that the molar ratio of the copolymerized units of Carboxyl-HEMA and MSB in the zwitterionic polymer PCSB is 1: 9.
Figure BDA0001690056730000071
In the formula, m and n are the number of the repeating units of the Carboxyl-HEMA and MSB copolymerized units in the zwitterionic polymer PCSB respectively; i iscAnd IeThe integrated areas of the c and e peaks in fig. 4, respectively.
Example 4
Preparation of zwitterionic copolymer:
Carboxyl-HEMA was prepared in the same manner as in step (1) of example 1; a zwitterionic Polymer was prepared in the same manner as in step (2) in example 1, except that 2.85g of MSB was used in place of 3.0g of MPC and that Carboxyl-HEMA was added in an amount of 0.59g, to give a zwitterionic Polymer PCSB1The H NMR spectrum is shown in FIG. 5, and it can be seen that the molar ratio of the copolymerized units of Carboxyl-HEMA and MSB in the zwitterionic polymer PCSB is 2: 8.
Example 5
Construction of zwitterionic copolymer coatings
(1) Cleaning a glass substrate (BG) to be modified (1cm multiplied by 1cm), immersing the cleaned glass substrate into a Tris-HCl solution with the concentration of 2.0mg/mL dopamine at 25 ℃, pouring reaction liquid after 1h, washing and soaking the glass substrate with distilled water for 20min, and drying the glass substrate with cold air to obtain the BG/PDA containing the dopamine dielectric layer;
(2) 6.08mg of EDC, 3.68mg of NHS and 150mg of the zwitterionic copolymer PCPC prepared in example 1 are dissolved in 30mL of PBS with the pH value of 5.0, the mixture is activated for 20min at 50 ℃, 20mL of PBS with the pH value of 8.5 is supplemented in the activated copolymer solution, a glass substrate containing a dopamine dielectric layer is immersed in the solution, the system is sealed and modified at 60 ℃ for 10h, the glass substrate is taken out and naturally cooled to the room temperature, then the glass substrate is repeatedly washed by distilled water and immersed for 20min, and the glass substrate BG/PDA/PCPC containing the zwitterionic copolymer coating is obtained by cold air blow drying.
Example 6
Construction of zwitterionic copolymer coatings
The same procedure as in example 5 was followed, except that 150mg of the zwitterionic copolymer PCPC prepared in example 1 was replaced with 150mg of the zwitterionic polymer PCSB prepared in example 3 in step (2), to give a glass substrate BG/PDA/PCSB containing a zwitterionic copolymer coating.
Test example
The zwitterionic copolymer coatings constructed in examples 5 and 6 were characterized for hydrophilicity and hydrophobicity by static contact angle (WCA). The static water contact angles of the various modified glass substrate surfaces were measured using a DSA 25 standard contact angle measuring instrument (KR US, Germany). And (3) selecting a Sessile drop method, dripping 2 mu L of ultrapure water to the surface of the glass sheet to be measured each time, and fitting and measuring the static Water Contact Angle (WCA) by using an Ellipse method. Each set of samples was tested in duplicate 6 times, and the average was the WCA of the substrate surface, with the results shown in figure 6. As can be seen, the substrates constructed from the copolymers PCSB (12.7. + -. 1.3 ℃ C.) and PCPC (14.5. + -. 1.0 ℃ C.) all had good hydrophilicity.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. A zwitterionic copolymer, wherein the copolymer is of formula (i):
Figure FDA0002882481030000011
wherein R is a zwitterionic group and R is1Is H or methyl, said R2Is H or methyl; x is an integer of 1-50; m is an integer of 1-30, n is an integer of 10-50, m: n is 20:1 to 1:20, and the zwitterionic group R is at least one of the following formulas (1) to (3):
Figure FDA0002882481030000012
wherein y is an integer of 2 to 4, and z is an integer of 1 to 3.
2. A method of preparing the zwitterionic copolymer of claim 1, comprising:
dissolving a monomer shown in a formula (II) and a monomer shown in a formula (III) in a solvent, carrying out free radical polymerization at 30-80 ℃, and purifying to obtain the zwitterionic copolymer;
Figure FDA0002882481030000013
wherein R is a zwitterionic group and R is1Is H or methyl, said R2Is H or methyl, and x is an integer of 1-50.
3. The method of claim 2, wherein the solvent is at least one of water, methanol, and ethanol.
4. A method of constructing a coating using the zwitterionic copolymer described in claim 1 or the zwitterionic copolymer prepared according to any one of claims 2 to 3, the method comprising the steps of:
(1) construction of a polydopamine-mediated layer: preparing a dopamine hydrochloride solution with the pH value of 6-9; immersing a base material to be modified into the dopamine hydrochloride solution, and constructing a poly-dopamine mediated layer on the surface of the base material;
(2) construction of the zwitterionic copolymer coating: activating a zwitterionic copolymer to obtain an activated zwitterionic copolymer solution, and spraying or dip-coating the activated copolymer solution on the surface of a base material containing a poly-dopamine mediated layer to construct a zwitterionic copolymer coating; the structural formula of the zwitterionic copolymer is as follows:
Figure FDA0002882481030000021
wherein R is a zwitterionic group and R is1Is H or methyl, said R2Is H or methyl; x is an integer of 1-50; m is an integer of 1-30, n is an integer of 10-50, m: n is 20:1 to 1: 20.
5. The method for forming a coating using the zwitterionic copolymer of claim 4, wherein the concentration of the dopamine hydrochloride solution in step (1) is 1-5 mg/mL; and immersing the base material into the dopamine hydrochloride solution for 10-60 min.
6. The method for constructing a coating by using the zwitterionic copolymer as described in claim 4, wherein the matrix material in the step (1) is nylon, glass, cellulose resin, polysulfone, polyvinylidene fluoride, polyethersulfone, polyacrylonitrile, polyvinyl chloride or polypropylene sheet base.
7. The method for forming a coating layer by using the zwitterionic copolymer as recited in claim 4, wherein the zwitterionic group R in the step (2) is one or more of phosphorylcholine group, carboxylic acid betaine group or sulfonic acid betaine group.
8. The method of claim 4, wherein the activating agent used in the step (2) is DCC/NHS, EDC/NHS, DCC/DMAP or EDC/DMAP; the activation temperature is between room temperature and 60 ℃; the activation time is 2-24 h.
9. The method of claim 4, wherein the spraying method in step (2) is: the concentration of the zwitterionic copolymer in the solution is 1-10 mg/mL, the pH value of the solution is 6-9, the activated zwitterionic copolymer solution is sprayed on the surface of a base material containing a polydopamine dielectric layer, and DMSO, DMF or H is carried out at the temperature of room temperature to 60 DEG C2Reacting for 1-10 h in an O atmosphere;
the dip coating method in the step (2) comprises the following steps: the concentration of the zwitterionic polymer in the solution is 1-10 mg/mL, the pH value of the solution is 6-9, and a base material containing a polydopamine dielectric layer is immersed into the activated zwitterionic copolymer solution and reacts at room temperature to 60 ℃.
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