CN110964153B - Method for regulating and controlling highest critical miscible temperature of zwitterionic star polymer by using pH - Google Patents
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Abstract
The invention discloses a method for regulating and controlling the highest critical miscible temperature of a zwitterionic star polymer by using pH. Firstly, polymerizing a zwitterionic monomer 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS) by using a carboxyl-terminated RAFT reagent 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid (ECT) to obtain a zwitterionic homopolymer, and then polymerizing and crosslinking to obtain a star polymer capable of regulating UCST by using pH. The zwitterionic Linear polymer Linear-PDMAPS is crosslinked to obtain a Star polymer which is named as Star-PDMAPS. Z is SCH2CH3And R is COOH. The star polymer has more terminal carboxyl groups, so the maximum critical solution temperature (UCST) of the star polymer can be greatly regulated and controlled by changing the pH, the UCST is obviously improved under the condition of low pH, and the UCST is obviously reduced under the condition of high pH. The problems that the responsiveness of the zwitterionic polymer is single and UCST is difficult to improve are well solved.
Description
Technical Field
The invention relates to a method for regulating the highest critical miscible temperature (UCST) of a zwitterionic Star polymer (Star-PDMAPS) by using pH. More particularly, the present invention relates to a method for polymerizing sulfobetaine type zwitterionic monomer 3- (2-methacryloyloxyethyldimethylamino) propanesulfonate (DMAPS) using carboxyl-terminated RAFT reagent 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid (ECT), introducing the carboxyl-terminated groups onto a Linear polymer (Linear-PDMAPS), and then crosslinking the Linear homopolymer into a Star polymer (Star-PDMAPS) having more carboxyl-terminated groups. The star polymer has more terminal carboxyl groups, so the maximum critical solution temperature (UCST) of the star polymer can be greatly regulated and controlled by changing the pH, the UCST is obviously improved under the condition of low pH, and the UCST is obviously reduced under the condition of high pH. The problems that the responsiveness of the zwitterionic polymer is single and UCST is difficult to improve are well solved.
Background
A zwitterionic polymer is a polymer that is both positively and negatively charged within a polymer segment. Taking sulfobetaine zwitterionic polymer as an example, the polymer chain segment of the sulfobetaine zwitterionic polymer contains positively charged quaternary ammonium groups and negatively charged sulfonic acid groups in the molecule, and strong electrostatic force is generated between the positively charged groups and the negatively charged groups. Therefore, in an aqueous solution, the sulfobetaine zwitterionic polymer shows the property of the highest critical solution temperature (UCST), the mechanism is that at low temperature, polymer chain segments attract and shrink due to strong electrostatic force between molecules in the molecule, the polymer is agglomerated, and the solution is represented as a turbid phase; at high temperature, the acting force between polymer chain segments is reduced, the chain segments relax, the solvation degree is increased, and the solution is clear and transparent. The temperature response characteristic of the zwitterionic polymer becomes a hot spot of research in recent years, and the zwitterionic polymer is designed in the fields of intelligent response materials such as biosensors, controllable drug release, membrane modification and the like. The temperature response property of the zwitterionic polymer has the following defects: 1. UCST is highly dependent on molecular weight and does not exhibit UCST at lower molecular weight. 2. The zwitterionic polymer exhibits only temperature response properties, with a single response. In order to compensate for these defects, the current research direction mainly focuses on designing new zwitterionic monomers or copolymerizing other responsive monomers, and has the problems of high cost, complex operation, time consumption and the like. For sulfobetaine zwitterionic polymers, no simple and effective method has been found to improve UCST and increase responsiveness.
Star polymers are a class of branched macromolecular polymers formed from multiple linear polymer "arms" chemically linked to the same central "core". The star-shaped polymer can be divided into regular (composed of the same homo-or co-polymer arm) star-shaped polymer and hetero-arm (composed of different homo-or co-polymer arms) star-shaped polymer according to the different polymer arm components. The synthesis methods of star polymers are roughly divided into three categories: a core-first arm-second arm method, an arm-first core-second arm method, and a graft coupling method. The unique topological structure endows the star polymer with excellent physicochemical properties. Compared with a linear polymer, the star polymer has lower solution viscosity due to less entanglement of molecular chains; the three-dimensional spherical structure of the polymer enables the polymer to have unique hydrodynamic volume and carrier encapsulation capacity; and the active groups of the arms and the core of the star polymer endow the star polymer with various functionalities; in addition, the star polymer has high-density functional modification capability, so that the star polymer has excellent stimulus response capability.
Disclosure of Invention
The invention aims to synthesize a zwitterionic Star polymer (Star-PDMAPS) capable of adjusting the highest critical solution temperature (UCST) by using a 'arm first and then nucleus' method. A zwitterionic Linear polymer with terminal carboxyl groups (Linear-PDMAPS) is initially prepared by RAFT polymerization and is crosslinked to form a Star polymer with more terminal carboxyl groups (Star-PDMAPS) by using a crosslinking agent N, N' -Methylenebisacrylamide (MBA). The Star polymer (Star-PDMAPS) has sensitive pH response, and has wider corresponding temperature range, larger increasing or reducing amplitude and stronger controllability compared with a linear homopolymer because of more terminal carboxyl groups. Thereby better solving the problems of low response temperature and single response of the zwitterionic polymer.
Star polymers with more terminal carboxyl groups (Star-PDMAPS) were prepared using the "arm-then-core" method described at the outset. A zwitterionic Linear polymer with terminal carboxyl groups (Linear-PDMAPS) is initially prepared by RAFT polymerization and subsequently crosslinked to a Star polymer (Star-PDMAPS) with the crosslinking agent MBA. The structural formulas are respectively shown as follows:
Linear-PDMAPS, named zwitterionic monomer 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS), and Linear polymer named Linear-PDMAPS, polymerizedThe molar ratio of DMAPS to RAFT agent in the system was n:1 (n: 80). Z is SCH2CH3,R＝COOH
Star-PDMAPS, a zwitterionic Linear polymer, Linear-PDMAPS, is crosslinked to give a Star polymer, designated Star-PDMAPS. Z is SCH2CH3,R＝COOH。
The Star polymer (Star-PDMAPS) was prepared by the "arm-nucleus" method as follows:
1) synthesis of zwitterionic Linear homopolymer (Linear-PDMAPS) by RAFT method
Adding a zwitterionic monomer 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS), a free radical initiator 4,4' -azo (4-cyanovaleric acid) (ACVA) and a carboxyl terminated RAFT reagent 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid (ECT) into a solvent, and stirring and dissolving to obtain a reaction solution; the reaction solution is heated to 70 ℃ under the protection of nitrogen and reacts for 24 hours to obtain the zwitter-ion Linear homopolymer (Linear-PDMAPS). Molar ratio of DMAPS and ECT is n:1 (n-80) and the amount of ECT is 5 times the amount of initiator (ACVA).
In the above preparation method, the solvent is a 0.5M aqueous solution of sodium chloride.
In the preparation method, the solid content of the reaction system (the solid content is the ratio of the sum of the mass of the initiator, the RAFT test and the monomer to the total mass of the system) is 10-30%.
In the above preparation method, the RAFT agent is selected from carboxyl group-containing trithioesters.
In the above preparation method, the initiator is selected from 4,4' -azo (4-cyanovaleric acid) (ACVA).
2) Cross-linker MBA cross-links the linear homopolymer to a Star polymer (Star-PDMAPS)
Adding a zwitterionic monomer 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS), a zwitterionic Linear homopolymer (Linear-PDMAPS), a free radical initiator 4,4 '-azo (4-cyanovaleric acid) (ACVA) and a cross-linking agent N, N' -Methylene Bisacrylamide (MBA) into saline, and stirring and dissolving to obtain a reaction solution; the reaction mixture was heated to 70 ℃ under nitrogen protection and reacted for 24 hours to obtain Star polymer (Star-PDMAPS). The molar ratio of DMAPS and PDMAPS was 6: 1, the amount of the Linear-PDMAPS substance is 5 times that of the initiator (ACVA), and the amount of the Linear-PDMAPS substance is 3-20 times that of the cross-linking agent (MBA).
In the above preparation method, the solvent is 0.5 mol per liter of an aqueous solution of sodium chloride.
In the preparation method, the solid content of the reaction system (the solid content is the ratio of the sum of the mass of the initiator, the RAFT reagent, the linear homopolymer and the monomer to the total mass of the system) is 10-30%.
In the above preparation method, the crosslinking agent is selected from N, N' -Methylenebisacrylamide (MBA).
The zwitterionic Star polymer (Star-PDMAPS) capable of adjusting the highest critical solution temperature (UCST) by using the pH is prepared according to the preparation method, and is characterized in that a method of 'arm first and core second' is utilized, a functional RAFT reagent is utilized to start to polymerize the zwitterionic monomer DMAPS, carboxyl end groups are introduced to a Linear homopolymer (Linear-PDMAPS), so that an 'arm' (Linear-PDMAPS) with pH-temperature dual responsiveness is obtained, and on the basis, a cross-linking agent MBA is utilized to cross-link the 'arm' and the core, so that a Star polymer (Star-PDMAPS) with more carboxyl end groups is obtained. Compared with Linear homopolymer (Linear-PDMAPS), UCST of the zwitterionic Star polymer (Star-PDMAPS) is more greatly increased or decreased by changing pH, and is more controllable.
The temperature response performance of the zwitterionic polymer (Star-PDMAPS) is evaluated by measuring the critical phase transition temperature by an ultraviolet spectrophotometry, the temperature rise speed is fixed, and the temperature response is evaluated by measuring the transmittance change of a polymer (Star-PDMAPS) aqueous solution at the fixed temperature.
The pH response performance of the zwitterionic polymer (Star-PDMAPS) is evaluated by measuring the critical transition temperature by an ultraviolet spectrophotometry method, and the pH response effect is evaluated by measuring the critical transition temperature of the polymer (Star-PDMAPS) at different pH values.
The invention aims to obtain Star polymer (Star-PDMAPS) with more terminal carboxyl groups on zwitterionic Linear homopolymer (Linear-PDMAPS) with the highest critical solution temperature (UCST) which can be regulated by pH value by relying on the action of the terminal carboxyl groups. Compared with a zwitterionic Linear polymer (Linear-PDMAPS), the temperature response and pH response of the zwitterionic Linear polymer (Linear-PDMAPS) and the Star polymer (Star-PDMAPS) under the condition of similar polymerization degrees are compared, so that the pH response of the Star polymer (Star-PDMAPS) is more sensitive and better.
The invention has the advantages that the pH value can be used for regulating and controlling the highest critical mutual solution temperature (UCST) zwitterionic Star polymer (Star-PDMAPS) is as follows: (1) the method is simple, Linear homopolymer (Linear-PDMAPS) can be prepared by only using RAFT polymerization method to polymerize in one step, and Star polymer (Star-PDMAPS) with narrow relative molecular weight can be obtained by using a cross-linking agent on the basis; (2) on the basis of a linear polymer, the terminal carboxyl groups are introduced into the Star polymer, and the number of the terminal carboxyl groups is increased, so that the response temperature of the zwitterionic polymer (Star-PDMAPS) can be better adjusted by adjusting the pH, and the adjustment amplitude is larger; (3) the structures of the zwitterionic monomer and the homopolymer are not required to be changed; (4) no copolymerization of the remaining responsive monomers is required. The advantages greatly widen the application prospect of the zwitterionic polymer in the direction of preparing intelligent materials.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of RAFT reagent ECT for carboxyl-terminated Linear zwitterionic homopolymers (Linear-PDMAPS);
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of a zwitterionic Linear polymer (Linear-PDMAPS);
FIG. 3 is a NMR spectrum of zwitterionic Star polymer (Star-PDMAPS);
FIG. 4 is a gel permeation chromatogram of a homopolymer with a zwitterionic Star polymer (Star-PDMAPS);
FIG. 5 shows the transmittance of Star polymer (Star-PDMAPS) with designed linear homopolymer polymerization degree of 80 and grafting degree of 8 as a function of temperature at different pH conditions, measured by UV spectrophotometry.
Detailed Description
The technical means and effects of the present invention will be described below by way of specific examples, but the present invention is not limited to the following examples.
Example 1:
taking the design that the polymerization degree of the zwitterionic Linear homopolymer (Linear-PDMAPS) is 80 and the grafting degree of the Star polymer (Star-PDMAPS) is 6 as an example:
1) 8mL of 0.5M sodium chloride solvent, 2.0g of zwitterionic 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS) monomer, and ECT 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid (ECT) (structural formula and NMR) as trithioester RAFT reagent with one carboxyl group were added to a round-bottomed flask1The H NMR spectrum is shown in figure 1)0.024g and initiator 4,4' -azo (4-cyanovaleric acid) (ACVA)0.005g, the reaction is carried out at 70 ℃ for 24H, and the product is dialyzed by a 3000MW molecular weight dialysis bag for 48H to obtain linear zwitterionic polymer (Line-PDMAPS) (structural formula and nuclear magnetic resonance) with terminal carboxyl functional groups1H NMR spectrum is shown in figure 2), and the dialyzed product is dried in a freeze dryer for 72H to constant weight.
2) A round-bottomed flask was charged with 7mL of 0.5M sodium chloride solvent, 1.5g of zwitterionic linear polymer (Line-PDMAPS), 0.109g of zwitterionic monomer- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS), 0.0037g of initiator 4,4 '-azo (4-cyanovaleric acid) (ACVA), and 0.0603g of crosslinking agent MBA N, N' -Methylenebisacrylamide (MBA), reacted at 70 ℃ for 24 hours to obtain a star polymer having a grafting degree of 6, which was dialyzed and then dried in a lyophilizer for 72 hours to constant weight.
3) Compared with linear homopolymer (Line-PDMAPS), the obtained star polymer UCST with the grafting degree of 6 is greatly improved, the pH responsiveness is also greatly improved due to the increase of the number of terminal carboxyl groups, when the pH is 3, the UCST is improved to 30 ℃, when the pH is 10, the UCST is reduced to 10 ℃, and the corresponding interval range of the whole pH reaches 20 ℃. The problem that the dependency of the zwitterionic polymer UCST on the molecular weight is too large is solved skillfully, and the problem of single responsiveness of the zwitterionic polymer is solved on the basis, so that the zwitterionic polymer UCST has multiple responsibilities.
Example 2:
taking the design that the polymerization degree of the zwitterionic Linear homopolymer (Linear-PDMAPS) is 80 and the grafting degree of the Star polymer (Star-PDMAPS) is 8 as an example:
1) 8mL of 0.5M sodium chloride solvent, 2.0g of zwitterionic 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS) monomer, and ECT 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid (ECT) (structural formula and NMR) as trithioester RAFT reagent with one carboxyl group were added to a round-bottomed flask1The H NMR spectrum is shown in figure 1)0.024g and initiator 4,4' -azo (4-cyanovaleric acid) (ACVA)0.005g, the reaction is carried out at 70 ℃ for 24H, and the product is dialyzed by a 3000MW molecular weight dialysis bag for 48H to obtain linear zwitterionic polymer (Line-PDMAPS) (structural formula and nuclear magnetic resonance) with terminal carboxyl functional groups1H NMR spectrum is shown in figure 2), and the dialyzed product is dried in a freeze dryer for 72H to constant weight.
2) A round-bottomed flask was charged with 7mL of 0.5M sodium chloride solvent, 1.5g of zwitterionic linear polymer (Line-PDMAPS), 0.109g of zwitterionic monomer- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS), 0.0037g of initiator 4,4 '-azo (4-cyanovaleric acid) (ACVA), and 0.0804g of crosslinking agent MBA N, N' -Methylenebisacrylamide (MBA), reacted at 70 ℃ for 24 hours to obtain a star polymer having a grafting degree of 8, and the star polymer was dialyzed and dried in a lyophilizer for 72 hours to constant weight.
3) Compared with linear homopolymer (Line-PDMAPS), the obtained star polymer UCST with the grafting degree of 6 is greatly improved, the pH responsiveness is also greatly improved due to the increase of the number of terminal carboxyl groups, when the pH is 3, the UCST is improved to 37 ℃, when the pH is 10, the UCST is reduced to 9 ℃, and the corresponding interval range of the whole pH reaches 28 ℃. The problem that the dependency of the zwitterionic polymer UCST on the molecular weight is too large is solved skillfully, and the problem of single responsiveness of the zwitterionic polymer is solved on the basis, so that the zwitterionic polymer UCST has multiple responsibilities.
Example 3:
taking the polymerization degree of a designed zwitterionic Linear homopolymer (Linear-PDMAPS) as 80 and the grafting degree of a Star polymer (Star-PDMAPS) as 10 as an example:
1) in a circle8mL of 0.5M sodium chloride solvent, 2.0g of zwitterion 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate (DMAPS) monomer and trithioester RAFT reagent ECT 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid (ECT) (structural formula and nuclear magnetic resonance) are added into a bottom flask1The H NMR spectrum is shown in figure 1)0.024g and initiator 4,4' -azo (4-cyanovaleric acid) (ACVA)0.005g, the reaction is carried out at 70 ℃ for 24H, and the product is dialyzed by a 3000MW molecular weight dialysis bag for 48H to obtain linear zwitterionic polymer (Line-PDMAPS) (structural formula and nuclear magnetic resonance) with terminal carboxyl functional groups1H NMR spectrum is shown in figure 2), and the dialyzed product is dried in a freeze dryer for 72H to constant weight.
2) A round-bottomed flask was charged with 7mL of 0.5M sodium chloride solvent, 1.5g of zwitterionic linear polymer (Line-PDMAPS), 0.109g of zwitterionic monomer- (2-methacryloyloxyethyldimethylamino) propanesulfonate (DMAPS), 0.0037g of initiator 4,4 '-azo (4-cyanovaleric acid) (ACVA), and crosslinking agent MBA N, N' -Methylenebisacrylamide (MBA)
0.1005g, reacting at 70 ℃ for 24h to obtain a star polymer with the grafting degree of 10, dialyzing, and drying in a freeze dryer for 72h to constant weight.
3) Compared with linear homopolymer (Line-PDMAPS), the obtained star polymer UCST with the grafting degree of 6 is greatly improved, the pH responsiveness is also greatly improved due to the increase of the number of terminal carboxyl groups, when the pH is 3, the UCST is improved to 43 ℃, when the pH is 10, the UCST is reduced to 6 ℃, and the corresponding interval range of the whole pH reaches 37 ℃. The problem that the dependency of the zwitterionic polymer UCST on the molecular weight is too large is solved skillfully, and the problem of single responsiveness of the zwitterionic polymer is solved on the basis, so that the zwitterionic polymer UCST has multiple responsibilities.
Example 4:
Star-PDMAPS synthesized in example 1, A series of Star polymer solutions of varying pH were prepared at a solution concentration of 10mg mL-1The transmittance at different temperatures is measured by an ultraviolet spectrophotometer, the temperature rise speed is fixed to be 1 ℃ per minute, and the temperature with the maximum transmittance change is taken as the phase change temperature. See fig. 5. As can be seen from the figure, the StarPDMAPS solution with the polymerization degree of 80 and the designed grafting degree of 8The phase transition temperature of the solution under the condition of pH 7 is about 28 ℃; the phase transition temperature under the condition of pH 3 is about 36.5 ℃; the phase transition temperature at pH 10 was around 9 ℃, demonstrating that carboxyl-terminated star polymers can dramatically increase or decrease the maximum critical solution temperature (UCST) on a linear polymer basis by changing the solution pH (as shown in fig. 5). Provides a simple and effective solution for solving a plurality of problems of single responsiveness, large molecular weight dependence and the like of the zwitterionic polymer.
Claims (7)
1. A method for regulating and controlling the maximum critical miscible temperature of a zwitterionic star polymer by using pH is characterized by comprising the following steps:
1) adding a zwitterionic monomer 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate, a free radical initiator 4,4' -azo (4-cyanovaleric acid) and a carboxyl-terminated RAFT reagent 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid into a solvent, and stirring and dissolving to obtain a reaction solution; heating the reaction solution to 70 ℃ under the protection of nitrogen to react for 24 hours to obtain a zwitter-ion linear homopolymer; the molar ratio of the zwitterionic monomer 3- (2-methacryloyloxyethyldimethylamino) propanesulfonate to 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid is n:1, wherein n is 80; the amount of the substance of 4-cyano-4- (((ethylthio) thiocarbonyl) thio) pentanoic acid is 5 times that of the initiator 4,4' -azo (4-cyanopentanoic acid);
2) adding 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate, the zwitter-ion linear homopolymer obtained in the step (1), 4 '-azo (4-cyanovaleric acid) and N, N' -methylene bisacrylamide into saline, and stirring to dissolve to obtain a reaction solution; heating the reaction solution to 70 ℃ under the protection of nitrogen, and reacting for 24 hours to obtain the zwitterion star polymer; the amount of the substance of the 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonic acid salt is 6 times that of the zwitterionic linear homopolymer, and the amount of the substance of the zwitterionic linear homopolymer is 5 times that of 4,4 '-azo (4-cyanovaleric acid) and is 3-20 times that of N, N' -methylene bisacrylamide;
the specific structural formulas of the zwitterionic linear homopolymer and the zwitterionic star polymer are respectively as follows:
a zwitterionic linear homopolymer, wherein the zwitterionic monomer is 3- (2-methacryloyloxyethyl dimethylamino) propane sulfonate;
Z＝SCH2CH3,R＝COOH
a zwitterionic star polymer, which is obtained by crosslinking a zwitterionic linear polymer; z is SCH2CH3,R＝COOH。
2. The process of claim 1, wherein the solvent is 0.5 moles per liter of aqueous sodium chloride solution.
3. The method of claim 1, wherein in step 1) the zwitterionic monomer 3- (2-methacryloyloxyethyldimethylamino) propanesulfonate, the free radical initiator 4,4' -azo (4-cyanovaleric acid) and the carboxyl terminated RAFT agent 4-cyano-4- (((ethylthio) thiocarbonyl)
The sulfur radical) valeric acid accounts for 10-30 wt% of the reaction liquid.
4. The method of claim 1, wherein in step 2) the zwitterionic monomer 3- (2-methacryloyloxyethyl dimethylamino) propanesulfonate, the zwitterionic linear homopolymer, the free radical initiator 4,4 '-azo (4-cyanovaleric acid), and the crosslinker N, N' -methylenebisacrylamide comprise 10% to 30% by weight of the reaction solution.
5. The method of claim 1, wherein the product is obtained and dialyzed against deionized water using a dialysis bag having a molecular weight of 3000.
6. The method of claim 1, wherein the product obtained by dialysis is lyophilized in a lyophilizer for 72 hours to constant weight.
7. The method of claim 1, wherein: the star polymer changes the highest critical miscible temperature (UCST) of the polymer by changing pH on the basis of retaining the sensitive response of the linear homopolymer.
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