CN110041199B - Monomer containing o-phthalaldehyde, polymer prepared from monomer, preparation method and application - Google Patents

Monomer containing o-phthalaldehyde, polymer prepared from monomer, preparation method and application Download PDF

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CN110041199B
CN110041199B CN201910064411.XA CN201910064411A CN110041199B CN 110041199 B CN110041199 B CN 110041199B CN 201910064411 A CN201910064411 A CN 201910064411A CN 110041199 B CN110041199 B CN 110041199B
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phthalaldehyde
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卢江
陈旭
朱月泉
黄建兵
梁晖
龚兴宇
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Sun Yat Sen University
Keshun Waterproof Technology Co Ltd
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Keshun Waterproof Technology Co Ltd
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Abstract

The invention discloses a monomer containing o-phthalaldehyde, a polymer prepared from the monomer, a preparation method and application. The structure of the monomer of the o-phthalaldehyde is shown as the formula (I). The monomer structure of the invention contains o-phthalaldehyde, and is suitable for preparing a macromolecular antibacterial agent; the polymer prepared by the method has good antibacterial activity, does not need to be released into the environment in the using process, does not have content reduction,the antibacterial effect is reduced, and the problem of residual toxicity does not exist; meanwhile, the conjugate can be efficiently conjugated, and the immunogenicity of the protein is not influenced; in addition, in the preparation process of the polymer, lipophilic or hydrophilic monomers can be selected for polymerization, so that polymers with different solubilities can be prepared according to requirements, and the polymer is convenient to apply.
Figure 447853DEST_PATH_IMAGE001

Description

Monomer containing o-phthalaldehyde, polymer prepared from monomer, preparation method and application
Technical Field
The invention relates to the field of functional polymers, in particular to a monomer containing o-phthalaldehyde, a polymer prepared from the monomer, a preparation method and application.
Background
O-phthalaldehyde is dialdehyde with two adjacent aromatic aldehyde groups, is a high-efficiency and safe antibacterial agent, has strong killing effect on bacteria, fungi, viruses and even certain parasites, has been developed into a novel high-efficiency antibacterial agent and passes the American FDA certification.
The low molecular organic antibacterial agent belongs to a release type antibacterial agent, and is released into the environment to act on bacteria through being loaded on a proper carrier, so that the antibacterial effect is exerted. The content of the active ingredients is reduced continuously in such a way, and the antibacterial performance is reduced continuously until the antibacterial performance disappears, so that the release rate needs to be controlled strictly, and the effective period needs to be prolonged; at the same time, there is a problem of residual toxicity, which may endanger human health and environmental safety. In contrast, the polymer antibacterial agents have the advantages of stable performance, non-volatility, safety, long-term effect, and the like compared with low-molecular organic antibacterial agents, and thus have become important points of research in the field in recent years.
Therefore, compared with the direct use of the o-phthalaldehyde, the preparation of the o-phthalaldehyde polymer used as a macromolecular antibacterial agent can well avoid the problems. Further, depending on the monomer selected, the water-soluble polymer antibacterial agent can be obtained by polymerizing the monomer with other water-soluble monomers; the antibacterial agent can be polymerized with other oil-soluble monomers to obtain the oil-soluble polymer antibacterial agent, and the application range is wider.
In addition, protein-polymer conjugates combine the biological functions of proteins with the property versatility, ease of handling, of polymers; after conjugation to polymers, many properties of the protein, such as solubility, stability and bioavailability, are improved, but at the same time, the immunogenicity of the protein is greatly reduced. The use of protein-polymer conjugates is greatly facilitated if the immunogenicity of the protein conjugated to the polymer is not reduced.
However, at present, the research and report on the o-phthalaldehyde polymer are few, and the o-phthalaldehyde polymer also has great research, development and application prospects.
Disclosure of Invention
The invention aims to provide a monomer containing o-phthalaldehyde aiming at the defects and shortcomings in the prior art. The monomer structure of the invention contains the o-phthalaldehyde, is suitable for preparing a high molecular antibacterial agent, can select lipophilic or hydrophilic monomers to be polymerized into polymers with different solubilities according to requirements, can overcome the defects of a low molecular antibacterial agent while keeping the original antibacterial effect, can prepare the polymers with different solubilities according to the requirements, and is convenient to apply.
Another object of the present invention is to provide a method for preparing the phthalaldehyde-containing monomer.
It is still another object of the present invention to provide a polymer prepared from the ortho-phthalaldehyde-containing monomer.
Still another object of the present invention is to provide a method for preparing the phthalaldehyde-containing polymer.
It is still another object of the present invention to provide uses of the phthalaldehyde-containing polymer.
The above object of the present invention is achieved by the following scheme:
an ortho-phthalaldehyde-containing monomer has a structure shown as a formula (I):
Figure BDA0001955209150000021
the monomer containing the o-phthalaldehyde is a methacrylate monomer, and can be copolymerized with a common commercialized acrylate monomer and an acrylamide monomer to prepare a polymer containing a phthalic aldehyde functional group.
The invention also provides a preparation method of the monomer containing the o-phthalaldehyde, which comprises the following preparation processes: hydroxyethyl methylacrylate, dicyclohexylcarbodiimide and dimethylaminopyridine are dissolved in an organic solvent, 4- (3, 4-diformaldehyde) -phenylpropionic acid is added dropwise under the ice bath condition, and the temperature is raised to room temperature for reaction, so that the current product can be obtained.
Preferably, the molar ratio of hydroxyethyl methacrylate, dicyclohexylcarbodiimide, dimethylaminopyridine and 4- (3, 4-dicarboxaldehyde) -phenylpropionic acid is: 0.5-1.5: 0.1-0.3: 0.5-2; the organic solvent is one or more of tetrahydrofuran, 1, 4-dioxane and dimethyl acrylamide; the reaction time is 6-48 h.
Preferably, the molar ratio of hydroxyethyl methacrylate, dicyclohexylcarbodiimide, dimethylaminopyridine and 4- (3, 4-dicarboxaldehyde) -phenylpropionic acid is: 1.2:1.2:0.24: 1; the organic solvent is tetrahydrofuran; the reaction time was 24 h.
The invention also discloses a polymer containing o-phthalaldehyde, which is prepared by the free radical copolymerization of a o-phthalaldehyde-containing monomer shown in the formula (I) and an acrylate monomer or an acrylamide monomer.
Preferably, the acrylic ester monomer is one or more of methyl acrylate, n-butyl acrylate, methyl methacrylate or n-butyl methacrylate; the acrylamide monomer is acrylamide or N, N-dimethyl acrylamide.
More preferably, when the acrylate monomer is butyl acrylate, the structural formula of the obtained polymer is shown as a formula (II),
Figure BDA0001955209150000031
more preferably, when the acrylamide monomer is N, N-dimethylacrylamide, the structural formula of the obtained polymer is shown as a formula (III),
Figure BDA0001955209150000032
the polymer contains the o-phthalaldehyde with an antibacterial active group, so that the polymer has good antibacterial activity, and compared with the o-phthalaldehyde with low molecular weight, the polymer does not need to be released into the environment in the using process while having good antibacterial activity, so that the conditions of content reduction and antibacterial effect reduction are avoided, and the problem of residual toxicity is also avoided. In addition, in the preparation process of the polymer, lipophilic or hydrophilic monomers can be selected for polymerization, so that polymers with different solubilities can be prepared according to requirements, and the preparation method is convenient to apply.
Furthermore, covalent attachment is one of the major methods currently used for the preparation of protein-polymer conjugates, which relies critically on efficient coupling reactions between polymer and protein, with primary amine groups (from the N-terminus or lysine residues) in the protein molecule being the most commonly utilized coupling reaction sites. The reaction between phthalaldehyde and primary amine satisfies ideal conditions for biocompatible chemical transformation, including rapidity, high selectivity, and can be carried out in neutral (or near neutral) aqueous solution at room temperature and low substrate concentration. Therefore, according to actual needs, through copolymerization of the monomer with the phthalaldehyde group and other functional monomers, the polymer with the chemical characteristics and other specific functions of the o-phthalaldehyde can be customized according to biocompatibility, biodegradability and other physical properties such as intelligent responsiveness, and efficient conjugation of the o-phthalaldehyde-containing polymer and protein molecules is realized through the o-phthalaldehyde-primary amine reaction, and meanwhile, the immunogenicity of the protein is not influenced.
The invention also provides a preparation method of the polymer containing the o-phthalaldehyde, which comprises the following steps: firstly, dissolving a monomer containing o-phthalaldehyde in an acrylate monomer or an acrylamide monomer to obtain a monomer mixed solution; and then dissolving the monomer mixed solution in an organic solvent, adding an initiator for reaction, and after the reaction is finished, adding n-hexane for precipitation to obtain the polymer containing the o-phthalaldehyde.
Preferably, the molar ratio of the acrylate monomer to the monomer containing the phthaloyl group is 5-20; the molar ratio of the acrylamide monomer to the phthaloyl group-containing monomer is 5-25
Preferably, the initiator is a free radical polymerization initiator; preferably, the initiator is azobisisobutyronitrile or dibenzoyl peroxide; the reaction temperature is 60-80 ℃, and the reaction time is 6-48 h.
More preferably, the reaction temperature is 65 ℃ and the reaction time is 12 h.
The use of the phthalaldehyde-containing polymer as an antimicrobial agent is also within the scope of the present invention.
Preferably, the polymer containing the ortho-phthalaldehyde is applied as an antibacterial agent in the fields of coatings and plastics.
The use of the phthalaldehyde-containing polymer for the preparation of protein-polymer conjugates is also within the scope of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
(1) the monomer structure of the invention contains the o-phthalaldehyde, is suitable for preparing a high molecular antibacterial agent, can select lipophilic or hydrophilic monomers to be polymerized into polymers with different solubilities according to requirements, can overcome the defects of a low molecular antibacterial agent while keeping the original antibacterial effect, can prepare the polymers with different solubilities according to the requirements, and is convenient to apply.
(2) The polymer contains the o-phthalaldehyde with an antibacterial active group, has good antibacterial activity, does not need to be released into the environment in the using process while having good antibacterial activity compared with the o-phthalaldehyde with low molecular weight, does not have the conditions of content reduction and antibacterial action reduction, and does not have the problem of residual toxicity. In addition, in the preparation process of the polymer, lipophilic or hydrophilic monomers can be selected for polymerization, so that polymers with different solubilities can be prepared according to requirements, and the preparation method is convenient to apply.
(3) The reaction between the polymer containing the phthalaldehyde and the primary amine meets the ideal conditions of biocompatibility chemical conversion, comprises rapidness and high selectivity, and can be carried out in a neutral (or nearly neutral) aqueous solution at room temperature and low substrate concentration; meanwhile, the conjugate is efficiently conjugated with the protein, and meanwhile, the immunogenicity of the protein is not influenced.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of a phthaloyl group-containing monomer prepared in example 1.
FIG. 2 is a nuclear magnetic hydrogen spectrum of the phthaloyl group-containing polymer prepared in example 2.
FIG. 3 is a nuclear magnetic hydrogen spectrum of the phthaloyl group-containing polymer prepared in example 3.
FIG. 4 is a gel permeation chromatogram of the polymer, bovine serum albumin and conjugate product prepared in example 3, blue being the conjugate product, red being bovine serum albumin and black being the polymer.
FIG. 5 is a UV absorption spectrum of bovine serum albumin and the product of the polymer-protein conjugate prepared in example 4 catalyzing hydrolysis of 4-nitrophenyl acetate.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
EXAMPLE 1 Synthesis of a phthalic acid group-containing monomer
15.6g (0.12mol) of hydroxyethyl methacrylate, 24.4g (0.12mol) of Dicyclohexylcarbodiimide (DCC) and 2.9g (0.24mol) of Dimethylaminopyridine (DMAP) were dissolved in 100mL of THF, 100mL of a tetrahydrofuran solution containing 20g (0.1mol) of 4- (3, 4-dicarbaldehyde) -benzenepropanoic acid was slowly dropped in an ice bath, and after the dropping, the reaction was carried out at room temperature for 24 hours. After the reaction is finished, removing the precipitate by suction filtration, and spin-drying the solvent; the crude product was separated by column chromatography using ethyl acetate/petroleum ether (3: 2 by volume) mobile phase to give 20g of a pale red liquid product.
The product is subjected to nuclear magnetic hydrogen spectrum characterization, and the spectrogram is shown in figure 1, so that the synthesis of the phthaloyl group-containing monomer can be proved.
Example 2 Synthesis and application of oil-soluble phthalate-containing aldehyde group-containing Polymer
(1) Synthesis of polymers
The monomer prepared in the embodiment 1 is used as a raw material and is prepared together with a n-butyl methacrylate monomer, azodiisobutyronitrile is used as an initiator, a phthaloyl group-containing monomer and the n-butyl methacrylate are firstly mixed and dissolved in a dioxane or tetrahydrofuran solvent according to the proportion in the table 1, and every 1g of the monomer is dissolved in 1mL of the solvent; then adding an initiator azobisisobutyronitrile, mixing, reacting for 12h at 65 ℃, and precipitating a polymer product by using normal hexane after the reaction is finished to obtain the oil-soluble phthalic aldehyde group-containing polymer.
TABLE 1 raw material proportion
Figure BDA0001955209150000051
Figure BDA0001955209150000061
According to the mixture ratio in the table 1, polymer 1 and polymer 2, 2 polymers were prepared for nuclear magnetic hydrogen spectrum characterization, and the spectra are shown in fig. 2, which shows that the target polymer is synthesized.
The molecular weight distributions of the 2 polymers are shown in Table 2.
TABLE 22 molecular weights and molecular weight distributions of the polymers
Number average molecular weight Weight average molecular weight Molecular weight distribution
Polymer 1 18300 23900 1.31
Polymer 2 16500 22300 1.35
(2)2 polymers for testing antibacterial Properties
The obtained polymer was made into a film by a coating method, and then an antibacterial property test was performed according to the method described in GB/T21866-2008, and the test results are shown in Table 3.
Antibacterial property test results of 32 polymers in Table
Figure BDA0001955209150000062
Wherein the negative control sample A is a blank of 50X50mm area size in a 90mm diameter sterilized petri dish without any test plate; blank panel B is a paint panel without an antimicrobial polymer film added. As can be seen from Table 3, the polymer in the group 2 prepared in this example has a good antibacterial effect on Escherichia coli and Staphylococcus aureus, the antibacterial rate is as high as 99%, and the polymer obtained on the surface has a good antibacterial effect.
Example 3 Synthesis and application of Water-soluble phthalic aldehyde group-containing Polymer
(1) Synthesis of polymers
Referring to the method of example 2, a water-soluble phthalic-aldehyde group-containing polymer was prepared according to the formulation table in table 4 by replacing N-butyl methacrylate monomer with N, N-dimethylacrylamide monomer.
TABLE 4 raw material proportion
Monomers containing phthaloyl groups N, N-dimethylacrylamide Azobisisobutyronitrile
Copolymer 3 3.0g(0.011mol) 27g(0.272mol) 0.465g(0.00283mol)
Copolymer 4 6.0g(0.022mol) 24g(0.242mol) 0.434g(0.00264mol)
According to the proportion in Table 4, polymer 3 and polymer 4, 2 polymers were prepared for nuclear magnetic hydrogen spectrum characterization, and the spectra are shown in FIG. 3, which can prove that the target polymer has been synthesized.
The molecular weight distributions of the 2 polymers are shown in Table 5.
Molecular weight and molecular weight distribution of the 52 polymers in Table 52
Number average molecular weight Weight average molecular weight Molecular weight distribution
Copolymer 3 15800 21500 1.36
Copolymer 4 14900 19800 1.33
(2)2 polymers for testing antibacterial Properties
The antibacterial property test was carried out by referring to the method in example 2, and the test results are shown in table 6.
Results of antibacterial property test of polymers in Table 62
Figure BDA0001955209150000071
As can be seen from Table 6, the polymer in 2 prepared in the embodiment has a good antibacterial effect on Escherichia coli and Staphylococcus aureus, the antibacterial rate is as high as 99%, and the polymer obtained on the surface has a good antibacterial effect.
Example 4 conjugates of phthalidyl-containing polymers and proteins
12mg of bovine serum albumin was dissolved in 2mL of Phosphate Buffered Saline (PBS), and 12mg of copolymer 3 was added thereto, and the conjugation reaction was stirred at room temperature for 40 minutes. The reaction solution was subjected to gel permeation chromatography and copolymer 3, bovine serum albumin, was used as a reference. As shown in fig. 4, the molecular weight of the conjugate product was increased compared to both the polymer and bovine serum albumin, demonstrating successful conjugation of bovine serum albumin to the polymer.
To detect the activity of the protein after conjugation, characterization was carried out using methods described in the literature (Journal of Materials Chemistry,2011,21, 10390-10398). By analyzing ultraviolet absorption spectra (figure 5) of products obtained by catalyzing hydrolysis of 4-nitrophenyl acetate before and after conjugation of bovine serum albumin and the copolymer 3, the activity of the bovine serum albumin after conjugation is only reduced by 5% compared with that before conjugation, which proves that conjugation has no influence on the activity of the protein.
It should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and it is obvious to those skilled in the art that other variations or modifications can be made on the basis of the above description and ideas, and all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (13)

1. An o-phthalaldehyde-containing monomer is characterized by having a structure shown as a formula (I):
Figure FDA0003058266840000011
2. a method for preparing a phthalaldehyde-containing monomer as set forth in claim 1, which is prepared by the following steps: hydroxyethyl methacrylate, dicyclohexylcarbodiimide and dimethylaminopyridine are mixed and dissolved in an organic solvent, then 4- (3, 4-diformaldehyde) -phenylpropionic acid is dripped under the ice bath condition, and the temperature is raised to room temperature for reaction to obtain the target product.
3. A method of preparing an o-phthalaldehyde-containing monomer according to claim 2, wherein the molar ratio of hydroxyethyl methacrylate, dicyclohexylcarbodiimide, dimethylaminopyridine and 4- (3, 4-dicarboxaldehyde) -phenylpropionic acid is: 0.5-1.5: 0.1-0.3: 0.5-2; the organic solvent is one or more of tetrahydrofuran, 1, 4-dioxane and dimethylacrylamide; the reaction time is 6-48 h.
4. A method of preparing an o-phthalaldehyde-containing monomer according to claim 3, wherein the molar ratio of hydroxyethyl methacrylate, dicyclohexylcarbodiimide, dimethylaminopyridine and 4- (3, 4-dicarboxaldehyde) -phenylpropionic acid is: 1.2:1.2:0.24: 1; the organic solvent is tetrahydrofuran; the reaction time was 24 h.
5. An o-phthalaldehyde-containing polymer, wherein the polymer is prepared by radical copolymerization of the o-phthalaldehyde-containing monomer according to claim 1 with an acrylate monomer or an acrylamide monomer; the acrylic ester monomer is one or more of methyl acrylate, n-butyl acrylate, methyl methacrylate or n-butyl methacrylate; the acrylamide monomer is acrylamide or N, N-dimethylacrylamide.
6. A phthalaldehyde-containing polymer as claimed in claim 5, wherein when the acrylate monomer is butyl acrylate, the resulting polymer has a structural formula shown in formula (II),
Figure FDA0003058266840000021
when the acrylamide monomer is N, N-dimethylacrylamide, the structural formula of the obtained polymer is shown as a formula (III),
Figure FDA0003058266840000022
7. a method for preparing a phthalaldehyde-containing polymer as set forth in claim 5, comprising the steps of: firstly, dissolving a monomer containing phthaloyl in an acrylate monomer or an acrylamide monomer to obtain a monomer mixed solution; and then dissolving the monomer mixed solution in an organic solvent, adding an initiator for reaction, and after the reaction is finished, adding n-hexane for precipitation to obtain the polymer containing the o-phthalaldehyde.
8. A method of preparing a phthalaldehyde-containing polymer according to claim 7, wherein the initiator is a free radical polymerization initiator.
9. A method for preparing a phthalaldehyde-containing polymer according to claim 8, wherein the initiator is azobisisobutyronitrile or dibenzoyl peroxide; the organic solvent is dioxane or tetrahydrofuran; the reaction temperature is 60-80 ℃, and the reaction time is 6-48 h.
10. A method for preparing a phthalaldehyde-containing polymer as claimed in claim 9, wherein the reaction temperature is 65 ℃ and the reaction time is 12 hours.
11. Use of a phthalaldehyde-containing polymer according to claim 5 or 6 as an antimicrobial agent.
12. Use according to claim 11, wherein the polymer containing phthalaldehyde is used as an antimicrobial agent in the fields of coatings and plastics.
13. Use of a phthalaldehyde-containing polymer of claim 5 or 6 to prepare a protein-polymer conjugate.
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