CN109320653B - Anionic polyglycerol hydrogel and preparation method thereof - Google Patents
Anionic polyglycerol hydrogel and preparation method thereof Download PDFInfo
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- CN109320653B CN109320653B CN201811216022.6A CN201811216022A CN109320653B CN 109320653 B CN109320653 B CN 109320653B CN 201811216022 A CN201811216022 A CN 201811216022A CN 109320653 B CN109320653 B CN 109320653B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
- C08F220/287—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polypropylene oxide in the alcohol moiety
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Abstract
The invention relates to an anionic polyglycerol hydrogel and a preparation method thereof, belonging to the field of polymer synthetic chemistry and biomedical materials. The hydrogel is prepared from the following raw materials in parts by mass: 50 parts of oligopolytriol, 1-10 parts of strong inorganic acid and 7-21 parts of acrylic acid, wherein the raw material can also comprise deionized water with the mass part not more than 8 parts. The water-coagulating agent is prepared by mixing 50 parts of oligomeric glycerol and 7-16 parts of acrylic acid, adding 1-10 parts of inorganic strong acid and no more than 8 parts of deionized water, and stirring and reacting at 40-55 ℃ for 1-4 hours; after the reaction is finished, adding no more than 5 parts of acrylic acid into the reaction system, and finally heating to 60-90 ℃ to perform cationic polymerization initiated by strong acid. The method has the advantages of few reaction steps, simple and convenient operation, high controllability, few side reactions, high product purity and the like, and realizes the crosslinking and functionalization of the PG gel.
Description
Technical Field
The invention belongs to the field of polymer synthetic chemistry and biomedical materials, and particularly relates to an anionic polyglycerol hydrogel and a preparation method thereof.
Background
Polyglycerol (PG), also known as Polyglycerol, is a hyperbranched aliphatic polyether compound which has good hydrophilicity, biocompatibility and properties of a large number of functionalizable hydroxyl groups and polyhydroxy structures interacting with biological tissues and is easily subject to photo-oxidative degradation, and its excellent properties have received high attention and favor from the international biomedical materials community (Sisson, a.l.; steinhibber, d.; Rossow, t.; Welker, p.; Licha, k.; hag, r.angew.chem. int. ed.,2009,48:7540-7545.Wilms, d.; stiiriba, s. -e.; Frey, h.Accounts of chemical research,2010,43:129-141. shen., r.a.; Abbina s.; kizzakedak.j. biocrals, 2016, 3683). At present, polyglycerol has been used as a high-loading, multi-binding drug and catalyst scaffold, a multifunctional initiation monomer, a gene transfection vector, a drug sustained release vector and a tissue engineering scaffold material.
The oligopolyglycerol is a short polymer formed by repeatedly linking glycerol monomers with covalent bonds in a small number, and the number of the monomers is generally less than 20, and is usually 2 to 10.
Since PG has excellent properties and contains a large number of hydroxyl groups that can be functionalized, it is very suitable for the preparation of hydrogels with biomedical applications. Hydrogels are the most similar systems in morphology to biological tissue structures among the synthetic polymers discovered to date. It is a three-dimensional network system formed by chemical crosslinking or physical crosslinking of hydrophilic macromolecules, and can absorb a large amount of water and is insoluble in water. The ionic PG hydrogel also has the characteristic of being very sensitive to external environment stimulation such as temperature, pH, ionic strength, light, electric field and the like, the structure, the morphology and the interaction between the ionic PG hydrogel and a load substance can generate corresponding changes, and the ionic PG hydrogel can be used for transportation and release of medicines, release of DNA, trapping and release of enzyme, biosensors, skin cosmetology, tissue engineering bracket materials and the like, so that the PG functional hydrogel has great application value and wide development prospect in high and new technical fields such as biomedicine and the like.
In order to form the crosslinked structure of the PG hydrogel, a method of introducing a double-bond functional group and then performing photopolymerization is generally adopted, but the introduction of the double-bond functional group is difficult and complicated. The preparation method of introducing double bond functional group using epichlorohydrin as main raw material is reported in the patent "preparation method of polypropylene triol hydrogel" (ZL 201410410848.1) by Yangtze Steel, etc. Under the action of strong base and phase transfer catalyst, epoxy chloropropane reacts with acrylic acid to generate epoxy chloropropane derivative containing acrylic group; then adding water and inorganic strong base, controlling the reactions of hydrolysis, ring opening, elimination and the like, preparing the polyglycerol macromonomer containing acrylic groups, realizing the successful introduction of double bond functional groups, and well solving the problems of uncertain (incapable of crosslinking) and non-uniformity of hydrogel crosslinking. However, the method has the problems of high reaction toxicity and pollution, multiple reaction steps, complex operation, high control difficulty and the like. In particular, the raw material epichlorohydrin has high toxicity, is very unfavorable for the preparation and production of biomedical materials, and has high potential risk. The hydrogel prepared by the method is non-ionic PG hydrogel, namely non-functional PG hydrogel.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an anionic polyglycerol hydrogel and a preparation method thereof. The method realizes the functionalization of the PG hydrogel, solves the technical problems of high toxicity of raw materials, more reaction steps, complex operation, high control difficulty and the like in the prior art for synthesizing the polyglycerol hydrogel, and has the advantages of few reaction steps, simple and convenient operation, high controllability, less side reaction and high product purity.
In order to realize the first purpose of the invention, the invention adopts the following technical scheme:
the anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
50 parts of oligopolytriol
1-10 parts of inorganic strong acid
7-21 parts of acrylic acid.
Further, according to the technical scheme, the raw material also comprises deionized water with the mass part not more than 8 parts.
Further, in the above technical means, the oligoglycerol is preferably polyglycerol-10.
Further, in the above technical scheme, the strong inorganic acid is sulfuric acid or phosphoric acid.
The second objective of the present invention is to provide a preparation method of the above anionic polyglycerol hydrogel, wherein the method uses oligomeric glycerol and acrylic acid as main raw materials, and links a cross-linking group containing a double bond in acrylic acid to oligomeric polyglycerol through esterification reaction under the catalysis of strong inorganic acid to generate an oligomeric glycerol monomer containing an acrylic group double bond; then, acid initiation is adopted to cause cationic polymerization reaction to occur among the double-bond-containing oligomeric monomers and between the oligomeric monomers and acrylic acid, so as to prepare the target product, namely the anionic PG hydrogel, and realize crosslinking and functionalization of gel.
The second objective of the present invention is achieved by the following technical solutions:
a method of making an anionic polyglycerol hydrogel, the method comprising the steps of:
mixing 50 parts of oligomeric glycerol and 7-16 parts of acrylic acid at normal temperature and normal pressure in parts by mass, adding 1-10 parts of inorganic strong acid and no more than 8 parts of deionized water, and stirring and reacting at 40-55 ℃ for 1-4 hours; and after the reaction is finished, adding no more than 5 parts of acrylic acid into the reaction system, and finally heating to 60-90 ℃ to perform cationic polymerization initiated by strong acid to obtain the anionic polyglycerol hydrogel.
Further, according to the technical scheme, the cationic polymerization reaction time is 8-30 min.
Further, in the above technical means, the oligoglycerol is preferably polyglycerol-10.
The invention changes the polymerized monomer, adopts the oligoglycerol as the main raw material, controls the reaction by temperature and time under the action of strong acid, and realizes the functionalization of PG gel by a new route of preparing the anionic polyglycerol hydrogel by esterification reaction and cationic polymerization reaction in a 'one-pot method'. The invention controls the equilibrium swelling ratio and the functionalization degree of the polyglycerol hydrogel by changing the addition of the acrylic acid, simplifies the synthesis operation steps, reduces side reactions, toxicity and pollution, and improves the controllability and the safety of gel products.
Compared with the prior art, the anionic polyglycerol hydrogel and the preparation method thereof have the following beneficial effects:
(1) according to the invention, acrylic acid is linked on the oligomeric polyglycerol to obtain an oligomeric monomer containing double bonds; and then, the problem of PG gel functionalization is solved by adopting cationic polymerization reaction among oligomeric monomers and between the oligomeric monomers and acrylic acid, and the anionic PG hydrogel is synthesized.
(2) The oligomeric glycerol, the acrylic acid and other raw materials used in the invention have rich sources and low price, the raw materials have no toxicity, the production is pollution-free, and the invention has very important significance for preparing and using PG functional gel as biomedical materials.
(3) The PG functional hydrogel with different equilibrium swelling ratios and response rates can be obtained by controlling the addition amount and the sequence of the acrylic acid.
(4) The raw materials used in the method are all water-soluble, a phase transfer catalyst is not needed, the prepared polyglycerol hydrogel is better in uniformity, and the product is easier to purify.
(5) Compared with the traditional preparation method, the method has the advantages of few reaction steps, simple and convenient operation, high controllability, few side reactions, high product purity and the like, and realizes the functionalization of PG gel.
Detailed Description
The invention initiates a new route for preparing the anionic polyglycerol hydrogel by using the oligoglycerol as a main raw material and controlling the reaction by temperature and time under the action of strong acid, wherein the new route comprises the following steps: linking acrylic acid on the oligomeric polyglycerol through esterification reaction under the catalysis of strong acid at low temperature (40-55 ℃); and then under the initiation of high temperature (55-90 ℃) and strong acid, carrying out cationic polymerization reaction to complete the crosslinking, functionalization and controllability of the gel. In the new route, the reaction is controlled by the reaction time and temperature, side reactions are hardly generated, the intermediate product is not separated and purified, and the functions and the action configuration of the raw materials are very reasonable. The properties of the acrylic acid are comprehensively utilized and exerted, and the acrylic acid is a raw material for introducing double-bond functional groups in an esterification stage and a raw material for PG hydrogel functional groups in a polymerization reaction stage; meanwhile, strong acid also has two functions: esterification catalyst and cationic initiator. The method has the advantages of mild reaction conditions, simple and convenient operation and control, pure product, easy control of the proportion of acrylic acid to obtain PG functional gel with different swelling ratios and response rates, and better uniformity of the prepared polyglycerol functional hydrogel. Particularly, all the used raw materials are nontoxic or low-toxicity, which has very important significance for the preparation and the use of the polyglycerol functional hydrogel used as the biomedical material.
The embodiment is implemented on the premise of the technical scheme of the invention, and a detailed implementation mode and a specific operation process are given, but the protection scope of the invention is not limited to the following embodiment.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in this specification and attached claims are approximations. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Example 1
The anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
polyglycerol-1050 parts
2 portions of sulfuric acid
10 parts of acrylic acid;
the anionic polyglycerol hydrogel of the embodiment is prepared by the following method, which comprises the following steps:
adding 50 parts of polyglycerol-10 and 2 parts of sulfuric acid into a 150ml beaker, stirring at normal temperature on a magnetic stirrer, adding 10 parts of acrylic acid after uniformly stirring, heating to 50 ℃ after uniformly stirring, and reacting for 2 hours, wherein the system is a transparent uniform solution; stopping stirring, and increasing the reaction temperature to 80 ℃ for reaction for 10min to obtain uniform white hydrogel, wherein the hydrogel is anionic polyglycerol hydrogel.
The hydrogel prepared in the embodiment is placed in a beaker, soaked in deionized water for three days, and the deionized water is replaced twice a day to obtain the polyglycerol functional hydrogel with sufficient swelling. The equilibrium swell ratio was found to be 125 after swelling equilibrium. The hydrogel has remarkable pH and ionic strength sensitivity, the equilibrium swelling ratio is 36 and 98 respectively in a buffer solution with the pH value of 1.5(I ═ 0.04M) and the pH value of 7(I ═ 0.04M), and the shrinkage and swelling equilibrium response time is about 120min and 300min respectively.
Example 2
The anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
the anionic polyglycerol hydrogel of the embodiment is prepared by the following method, which comprises the following steps:
adding 50 parts of polyglycerol-10, 2 parts of deionized water and 7 parts of sulfuric acid into a 150ml beaker, stirring at normal temperature on a magnetic stirrer, adding 10 parts of acrylic acid after uniformly stirring, heating to 50 ℃ after uniformly stirring, and reacting for 3 hours, wherein the system is a transparent uniform solution; stopping stirring, and increasing the reaction temperature to 80 ℃ for reaction for 15min to obtain uniform white hydrogel, wherein the hydrogel is anionic polyglycerol hydrogel.
The hydrogel prepared in the embodiment is placed in a beaker, soaked in deionized water for three days, and the deionized water is replaced twice a day to obtain saturated swelling polyglycerol functional hydrogel, so that the polyglycerol functional hydrogel can be fully swelled, and the volume change is obvious. The equilibrium swell ratio was 204 as measured after swelling equilibrium. The hydrogel has remarkable pH and ionic strength sensitivity, and the equilibrium swelling ratio in a buffer solution with the pH value of 1.5(I ═ 0.15M) and the pH value of 7(I ═ 0.15M) is 68 and 122 respectively.
Example 3
The anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
polyglycerol-1050 parts
2 portions of sulfuric acid
12 parts of acrylic acid;
the anionic polyglycerol hydrogel of the embodiment is prepared by the following method, which comprises the following steps:
adding 50 parts of polyglycerol-10 and 2 parts of sulfuric acid into a 150ml beaker, stirring at normal temperature on a magnetic stirrer, adding 10 parts of acrylic acid after uniformly stirring, heating to 50 ℃ after uniformly stirring, and reacting for 3 hours, wherein the system is a transparent uniform solution; adding 2 parts of acrylic acid, fully stirring, raising the reaction temperature to 80 ℃, and reacting for 15min to obtain uniform white hydrogel, wherein the hydrogel is anionic polyglycerol hydrogel.
The hydrogel prepared in the embodiment is placed in a beaker, soaked in deionized water for three days, and the deionized water is replaced twice a day to obtain saturated swelling polyglycerol functional hydrogel, so that the polyglycerol functional hydrogel can be fully swelled, and the volume change is obvious. The equilibrium swell ratio after swelling equilibrium was found to be 151. The gel had equilibrium swelling ratios of 67 and 92 in buffer solutions of pH 1.5(I ═ 0.04M) and pH 7(I ═ 0.04M), respectively. The shrinkage and swelling equilibrium response times were about 90min and 240min, respectively.
Example 4
The anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
polyglycerol-1050 parts
6 portions of sulfuric acid
12 parts of acrylic acid;
the anionic polyglycerol hydrogel of the embodiment is prepared by the following method, which comprises the following steps:
adding 50 parts of polyglycerol-10 and 6 parts of sulfuric acid into a 150ml beaker, stirring at normal temperature on a magnetic stirrer, adding 12 parts of acrylic acid after uniformly stirring, heating to 55 ℃ after uniformly stirring, and reacting for 2 hours, wherein the system is a transparent uniform solution; stopping stirring, and increasing the reaction temperature to 80 ℃ for reacting for 18min to obtain uniform white hydrogel, wherein the hydrogel is anionic polyglycerol hydrogel.
The hydrogel prepared in the embodiment is placed in a beaker, soaked in deionized water for three days, and the deionized water is replaced twice a day to obtain saturated swelling polyglycerol functional hydrogel, so that the polyglycerol functional hydrogel can be fully swelled, and the volume change is not obvious. The equilibrium swelling ratio was 69 as measured after the swelling equilibrium.
Example 5
The anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
polyglycerol-1050 parts
Sulfuric acid 4 parts
14 parts of acrylic acid;
the anionic polyglycerol hydrogel is prepared by the following method, and the method comprises the following steps:
adding 50 parts of polyglycerol-10 and 4 parts of sulfuric acid into a 150ml beaker, stirring at normal temperature on a magnetic stirrer, adding 14 parts of acrylic acid after uniformly stirring, heating to 55 ℃ after uniformly stirring, and reacting for 2 hours, wherein the system is a transparent uniform solution; stopping stirring, and increasing the reaction temperature to 70 ℃ for reaction for 25min to obtain uniform white hydrogel, wherein the hydrogel is anionic polyglycerol hydrogel.
The hydrogel prepared in the embodiment is placed in a beaker, soaked in deionized water for three days, and the deionized water is replaced twice a day to obtain saturated swelling polyglycerol functional hydrogel, so that the polyglycerol functional hydrogel can be fully swelled, and the volume change is not obvious. The equilibrium swell ratio after swelling equilibrium was found to be 27.
Example 6
The anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
polyglycerol-1050 parts
1 part of phosphoric acid
7 parts of acrylic acid;
the anionic polyglycerol hydrogel of the embodiment is prepared by the following method, which comprises the following steps:
adding 50 parts of polyglycerol-10 and 1 part of phosphoric acid into a 150ml beaker, stirring at normal temperature on a magnetic stirrer, adding 7 parts of acrylic acid after uniformly stirring, heating to 40 ℃ after uniformly stirring, and reacting for 4 hours, wherein the system is a transparent uniform solution; stopping stirring, and increasing the reaction temperature to 60 ℃ for reaction for 30min to obtain uniform white hydrogel, wherein the hydrogel is anionic polyglycerol hydrogel.
Example 7
The anionic polyglycerol hydrogel is prepared from the following raw materials in parts by mass:
the anionic polyglycerol hydrogel of the embodiment is prepared by the following method, which comprises the following steps:
adding 50 parts of polyglycerol-10, 8 parts of deionized water and 10 parts of phosphoric acid into a 150ml beaker, stirring at normal temperature on a magnetic stirrer, adding 16 parts of acrylic acid after uniformly stirring, heating to 55 ℃ after uniformly stirring, and reacting for 1h, wherein the system is a transparent uniform solution; adding 5 parts of acrylic acid, fully stirring, raising the reaction temperature to 90 ℃, and reacting for 8min to obtain uniform white hydrogel, wherein the hydrogel is anionic polyglycerol hydrogel.
From the above examples, it can be seen that the equilibrium swelling ratio of the prepared polyglycerol functional hydrogel becomes smaller and smaller with the increase of the input amount of acrylic acid in the esterification reaction stage; in the polymerization reaction stage, along with the increase of the input amount of acrylic acid, the carboxyl amount of the prepared polyglycerol functional hydrogel is more, the functionalization degree is higher, and the response rate of the hydrogel to the environment is improved. The invention can prepare the polyglycerol functional hydrogel with different equilibrium swelling ratios and response rates by controlling the input amount of acrylic acid in different reaction stages, and has mild reaction conditions and simple and convenient operation.
Claims (5)
1. An anionic polyglycerol hydrogel characterized by: the hydrogel is prepared from the following raw materials in parts by mass:
2. the anionic polyglycerol hydrogel of claim 1, wherein: the oligomeric glycerol is polyglycerol-10.
3. The anionic polyglycerol hydrogel of claim 1, wherein: the inorganic strong acid is sulfuric acid or phosphoric acid.
4. The method for producing an anionic polyglycerol hydrogel according to claim 1, wherein: the method comprises the following steps:
mixing 50 parts of oligomeric glycerol and 7-16 parts of acrylic acid at normal temperature and normal pressure in parts by mass, adding 1-10 parts of inorganic strong acid and 0-8 parts of deionized water, and stirring and reacting at 40-55 ℃ for 1-4 hours; and after the reaction is finished, adding 0-5 parts of acrylic acid into the reaction system, and finally heating to 60-90 ℃ to perform strong acid initiated cationic polymerization reaction to obtain the anionic polyglycerol hydrogel.
5. The method for producing an anionic polyglycerol hydrogel according to claim 4, wherein: the cationic polymerization reaction time is 8-30 min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104151464A (en) * | 2014-08-20 | 2014-11-19 | 武汉大学 | Preparation method of polyglycerol hydrogel |
| CN107849363A (en) * | 2015-09-25 | 2018-03-27 | 积水化成品工业株式会社 | Hydrogel and its manufacture method |
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| CN104151464A (en) * | 2014-08-20 | 2014-11-19 | 武汉大学 | Preparation method of polyglycerol hydrogel |
| CN107849363A (en) * | 2015-09-25 | 2018-03-27 | 积水化成品工业株式会社 | Hydrogel and its manufacture method |
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