CN116731239A - pH-temperature dual-response acrylic emulsion and preparation method and application thereof - Google Patents
pH-temperature dual-response acrylic emulsion and preparation method and application thereof Download PDFInfo
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- CN116731239A CN116731239A CN202310736490.0A CN202310736490A CN116731239A CN 116731239 A CN116731239 A CN 116731239A CN 202310736490 A CN202310736490 A CN 202310736490A CN 116731239 A CN116731239 A CN 116731239A
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
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- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
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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
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- A—HUMAN NECESSITIES
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
- A61L2300/406—Antibiotics
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/602—Type of release, e.g. controlled, sustained, slow
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Abstract
The invention discloses a pH-temperature dual-response acrylic emulsion, a preparation method and application thereof, wherein the acrylic emulsion is prepared from the following raw materials in parts by weight: 8-15 parts of acid monomer, preferably 10-13 parts of unsaturated amide, 5-10 parts of unsaturated amide, preferably 6-8 parts of acrylic monomer, 15-30 parts of acrylic monomer, preferably 18-26 parts of emulsifier, 3-7 parts of emulsifier, preferably 5-7 parts of emulsifier, 40-60 parts of water, preferably 45-55 parts of initiator, 1-3 parts of initiator, preferably 1.5-2 parts of initiator; the acrylic monomer is a mixture of unsaturated diacid and unsaturated monoacid in a mass ratio of (2-3): 1. The pH-temperature dual-response release of the medicine can be realized by adding the pH-response monomer and the temperature-response monomer with specific contents into the acrylic emulsion when the medicine is used as a medical dressing, and the medicine is particularly suitable for the application of wound dressing containing antibacterial medicines.
Description
Technical Field
The invention relates to an acrylic emulsion for wound dressing, in particular to a pH-temperature dual-response acrylic emulsion and a preparation method and application thereof.
Background
With advances in medicine and increased understanding of pharmacokinetics, modern drug delivery research is directed to the use of novel materials and manufacturing techniques to prepare powerful drug delivery systems for maximum drug efficacy and minimal side effects. Wherein pH and temperature response are new strategies for achieving intelligent drug delivery. For example, the intact skin is naturally weak acidic, the pH value is between 4 and 6, when the skin is damaged, the acid-base microenvironment is destroyed, the pH value of the wound surface is increased (pH is 7.4 to 8.9), the skin barrier is reduced in the capability of resisting external damage, bacteria can be possibly caused to grow, and at the moment, the antibacterial drug is released to prevent wound infection; meanwhile, the local temperature of the wound is increased after the wound is infected, so that the design of a related temperature-sensitive drug release system is of great significance. The wound dressing with pH-temperature dual response is designed according to the change of the wound microenvironment, and has important significance for realizing accurate drug release and avoiding drug side effects and drug resistance.
Patent CN102807657a reports an amphiphilic block copolymer drug carrier with pH responsiveness and biodegradability. The amphiphilic block copolymer consists of a segment containing carboxyl modified by polyphosphate and polyhydroxyethyl methacrylate, and the release of the medicine is controlled by adjusting the pH value of a medium and reversibly changing a polyanion segment into a hydrophilic segment or a hydrophobic segment. The polymer drug carrier needs to release the drug under the micelle form, namely, the drug can be realized under the condition of water, the application is very limited, and the polymer drug carrier cannot be prepared and applied on a large scale. Patent CN102807657a reports a method for forming drug sustained-release nano-particles by using inverse miniemulsion, the invention uses chitosan as a base material, modified chitosan miniemulsion latex particles are formed in situ by a miniemulsion polymerization method, and water-soluble drugs are loaded to prepare the water-soluble drug sustained-release nano-particles. The nanoparticle has a drug slow release function to delay the drug release time, but cannot sense the external pH change to realize intelligent release, and can cause the occurrence of drug waste and side effects. There is currently no report of acrylic emulsion for use in the field of pH-temperature responsive wound dressings.
Disclosure of Invention
In order to solve the technical problems, the invention provides a pH-temperature dual-response acrylic emulsion and a preparation method and application thereof. The pH-temperature dual-response release of the medicine can be realized by adding the pH-response monomer and the temperature-response monomer with specific contents into the acrylic emulsion when the medicine is used as a medical dressing, and the medicine is particularly suitable for the application of wound dressing containing antibacterial medicines.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the pH-temperature dual-response acrylic emulsion is prepared from the following raw materials in parts by weight:
8 to 15 parts, preferably 10 to 13 parts,
5 to 10 parts, preferably 6 to 8 parts,
15-30 parts, preferably 18-26 parts,
3 to 7 parts, preferably 5 to 7 parts,
40 to 60 parts, preferably 45 to 55 parts,
1-3 parts of initiator, preferably 1.5-2 parts;
the acrylic monomer is a mixture of unsaturated diacid and unsaturated monoacid in a mass ratio of (2-3): 1. The invention uses unsaturated diacid as main acrylic acid component, which can not only participate in the addition polymerization of emulsion, but also have different proton forms under different pH values, and has the characteristic of quick response of pH value under the slightly acidic environment, thus being called as pH response monomer. The inventors have further studied to find that the content of the unsaturated diacid in the emulsion formulation is critical to perform its pH response function, and in particular the ratio of unsaturated diacid to acrylic monomer is critical. When the mass ratio of unsaturated diacid to unsaturated monoacid in the acrylic monomer is below 2:1, the prepared acrylic emulsion cannot effectively play the function of pH response, and when the mass ratio of unsaturated diacid to unsaturated monoacid in the acrylic monomer is above 3:1, the polymer film is hard and brittle, and the processability is not good. Therefore, the present invention has been completed by controlling the mass ratio of unsaturated diacid to unsaturated monoacid in the acrylic monomer within the range of (2-3): 1.
As a preferred embodiment of the present invention, the unsaturated diacid is at least one of maleic acid, fumaric acid, 2-pentenedioic acid, 2-hexenedioic acid, preferably maleic acid and/or 2-pentenedioic acid.
As a preferred embodiment of the present invention, the unsaturated monoacid is one or both of acrylic acid and methacrylic acid.
As a preferred embodiment of the present invention, the unsaturated amide is at least one of 2-acrylamide, N-isopropylacrylamide and N, N-methylenebisacrylamide, preferably 2-acrylamide. The inventor finds that the unsaturated amide of the above type has different swelling properties at different temperatures through a great deal of researches, and the unsaturated amide is selected as a temperature response monomer to participate in the polymerization of the acrylic emulsion, so that quick response can be realized according to temperature change, for example, when the emulsion is applied to the preparation of wound dressing, pH-temperature dual response can be realized through the combined action of the emulsion and the pH response monomer, and the accurate and quick release of the medicine can be realized, thereby solving the problems.
As a preferred embodiment of the present invention, the acrylic monomer is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate and n-butyl methacrylate, preferably n-butyl acrylate and/or n-octyl acrylate.
As a preferred embodiment of the present invention, the emulsifier is at least one of sodium dodecyl sulfate, sodium hexadecyl sulfate and sodium dodecyl benzene sulfonate;
preferably, the initiator is potassium persulfate and/or ammonium persulfate.
A method for preparing a pH-temperature double-responsive acrylic emulsion as described above, comprising the steps of:
1) Mixing an acid monomer, a part of acrylic ester monomer and a part of emulsifier in water to obtain a pre-emulsion A;
2) Mixing unsaturated amide, the balance of acrylic ester monomer, the balance of emulsifier and part of initiator in water to obtain pre-emulsion B;
3) Taking 10-20% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to the polymerization temperature, and adding the rest initiator to start polymerization;
4) Then dripping the pre-emulsion B into a reactor, and continuing the polymerization reaction;
5) Dripping the rest of the pre-emulsion A into a reactor, and continuing the polymerization reaction; after the reaction is finished, preserving heat; and finally, cooling and discharging to obtain the acrylic emulsion.
According to the invention, through continuous research, the pH change is more obvious than the local temperature change when the wound is infected by bacteria, so that in order to ensure the rapid release of the emulsion to the medicine when the emulsion is applied to wound dressing, the invention preferably takes the pre-emulsion A containing the pH response type monomer as a primer, continuously puts the pre-emulsion B containing the temperature response type monomer into polymerization, and finally adds a large amount of pre-emulsion A to form a core-shell-like structure so as to strengthen the rapid pH response.
As a preferred embodiment of the invention, in the steps 1) and 2), the mass ratio of the acrylic monomer is 1 (1.2-1.5);
preferably, in the steps 1) and 2), the mass ratio of the emulsifying agent is 1 (1.3-1.6);
preferably, in the steps 2) and 3), the mass ratio of the initiator is 1 (0.3-0.5).
As a preferred embodiment of the present invention, the polymerization temperature in step 3) is 70 to 90℃and the reaction time is 1 to 2 hours;
preferably, the reaction time in step 4) is 2-4.5h;
preferably, the reaction time in step 5) is 1-2h, and the temperature is kept for 0.5-1h after the reaction is finished.
In the preparation method, the addition amount of water can be arbitrarily adjusted according to the guidance of the known technology or the requirement of the solid content of the product. Preferably, the total amount of water added is such that the emulsion solids content is 45-55%.
Use of a pH-temperature double-responsive acrylic emulsion as described hereinbefore or a pH-temperature double-responsive acrylic emulsion as prepared by a process as described hereinbefore in a medical dressing, in particular in a wound dressing comprising an antibacterial agent. Further, the antibacterial agent in the wound dressing containing the antibacterial agent can be one or more of penicillin, cefixime, cefazolin and cefalexin. The wound dressing can be prepared by mixing antibacterial agent with the acrylic emulsion, drying, and forming film, wherein the addition amount of the antibacterial agent can be 1-5wt% of the acrylic emulsion.
The polymer film formed by drying the acrylic emulsion has good pH responsiveness and temperature responsiveness, can be widely applied to preparing the pH-temperature dual-response wound dressing, and is more suitable for mass production and preparation due to the simple preparation method. The wound dressing can be swelled in a wound infection environment, and can accelerate the release of the antibacterial drugs, but not reduce the release of the drugs in the wound environment, so that the use efficiency of the drugs is improved, and the unnecessary side effects of the drugs and the generation of drug resistance are reduced.
Detailed Description
The invention will now be further illustrated by means of specific examples which are given solely by way of illustration of the invention and do not limit the scope thereof.
The raw materials in the following examples were purchased from commercial sources unless otherwise specified.
Drug release test: and adding antibacterial agent accounting for 1.5wt% of the mass of the acrylic emulsion into the acrylic emulsion, uniformly mixing, coating the mixture on a tetrafluoro plate in a spray coating or roll coating mode, controlling the dry film thickness to be 0.5mm, and drying at 37 ℃ to obtain the polymer film. Cutting to obtain a 2 x 2cm polymer film, placing the polymer film into a 10mL centrifuge tube, adding 8mL of phosphate buffer solution with specific pH, and performing simulated drug release experiments at a test temperature. Taking 1mL of test solution at different times, determining the concentration of the drug in the solution according to a drug standard curve (absorbance-concentration) by an enzyme-labeled instrument, calculating the corresponding drug release amount, and supplementing a phosphate buffer solution in the experimental process to keep the total amount of the solution unchanged.
[ example 1 ]
The following raw materials for preparing the acrylic emulsion are respectively weighed according to parts by weight:
10 parts of acid-type monomer,
8 parts of 2-acrylamide, wherein the components are as follows,
20 parts of n-octyl acrylate,
5 parts of sodium dodecyl sulfate,
54 parts of water, and the water content is equal to or higher than the water content,
3 parts of potassium persulfate, namely, 3 parts of potassium persulfate,
wherein the acid monomer is a mixture of maleic acid and acrylic acid in a mass ratio of 3:1.
The method for preparing the acrylic emulsion by using the raw materials comprises the following steps:
1) 10 parts of acid monomer, 8 parts of n-octyl acrylate and 2 parts of sodium dodecyl sulfate are mixed in 27 parts of water to obtain a pre-emulsion A;
2) 8 parts of 2-acrylamide, 12 parts of n-octyl acrylate, 3 parts of sodium dodecyl sulfate and 2 parts of potassium persulfate are mixed in 27 parts of water to obtain a pre-emulsion B;
3) Taking 10% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to 70 ℃ of polymerization temperature, and adding 1 part of potassium persulfate to start polymerization;
4) Reacting for 1.5h, then dripping the pre-emulsion B into a reactor, and continuing the polymerization for 2.5h;
5) And (3) dropwise adding the rest of the pre-emulsion A into a reactor, continuing the polymerization reaction for 1.5h, preserving the heat for 0.5h after the reaction is finished, and finally cooling to 35 ℃, and discharging to obtain the acrylic emulsion.
[ example 2 ]
The following raw materials for preparing the acrylic emulsion are respectively weighed according to parts by weight:
12 parts of acid monomer and the like,
6 parts of 2-acrylamide, which is prepared from the following components,
23 parts of n-butyl acrylate,
7 parts of sodium dodecyl sulfate,
50 parts of water, and the water content is equal to or higher than the water content,
2 parts of potassium persulfate.
Wherein the acid monomer is a mixture of 2-glutaronic acid and methacrylic acid in a mass ratio of 2:1.
The method for preparing the acrylic emulsion by using the raw materials comprises the following steps:
1) Mixing 12 parts of acid monomer, 10 parts of n-butyl acrylate and 3 parts of sodium dodecyl sulfate in 25 parts of water to obtain a pre-emulsion A;
2) 6 parts of 2-acrylamide, 13 parts of n-butyl acrylate, 4 parts of sodium dodecyl sulfate and 1.5 parts of potassium persulfate are mixed in 25 parts of water to obtain a pre-emulsion B;
3) Taking 15% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to the polymerization temperature of 80 ℃, and adding 0.5 part of potassium persulfate to start polymerization;
4) Reacting for 2h, dripping the pre-emulsion B into a reactor, and continuing the polymerization reaction for 3h;
5) And (3) dropwise adding the rest of the pre-emulsion A into a reactor, continuing the polymerization reaction for 2 hours, preserving heat for 1 hour after the reaction is finished, and finally cooling to 45 ℃, and discharging to obtain the acrylic emulsion.
[ example 3 ]
The following raw materials for preparing the acrylic emulsion are respectively weighed according to parts by weight:
13 parts of acid monomer and the like,
10 parts of 2-acrylamide, which is prepared from the following components,
29 parts of n-octyl acrylate,
6.5 parts of sodium dodecyl sulfate,
40 parts of water, and the water is mixed with the water,
1.5 parts of ammonium persulfate.
Wherein the acid monomer is a mixture of maleic acid and methacrylic acid in a mass ratio of 2.5:1.
The method for preparing the acrylic emulsion by using the raw materials comprises the following steps:
1) 13 parts of acid monomer, 13 parts of n-octyl acrylate and 2.5 parts of sodium dodecyl sulfate are mixed in 20 parts of water to obtain a pre-emulsion A;
2) 10 parts of 2-acrylamide, 16 parts of n-octyl acrylate, 4 parts of sodium dodecyl sulfate and 1 part of ammonium persulfate are mixed in 20 parts of water to obtain a pre-emulsion B;
3) Taking 20% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to a polymerization temperature of 85 ℃, and adding 0.5 part of ammonium persulfate to start polymerization;
4) Reacting for 1h, dripping the pre-emulsion B into a reactor, and continuing the polymerization for 4.5h;
5) And (3) dropwise adding the rest of the pre-emulsion A into a reactor, continuing the polymerization reaction for 1h, preserving the heat for 0.8h after the reaction is finished, and finally cooling to 30 ℃, and discharging to obtain the acrylic emulsion.
[ example 4 ]
The following raw materials for preparing the acrylic emulsion are respectively weighed according to parts by weight:
9 parts of acid-type monomer,
9 parts of 2-acrylamide, which is prepared from the following components,
17.5 parts of n-butyl acrylate,
3.5 parts of sodium dodecyl sulfate,
60 parts of water, and the water is mixed with the water,
1 part of potassium persulfate.
Wherein the acid monomer is a mixture of 2-glutaronic acid and acrylic acid in a mass ratio of 2.9:1.
The method for preparing the acrylic emulsion by using the raw materials comprises the following steps:
1) 9 parts of acid monomer, 7 parts of n-butyl acrylate and 1.5 parts of sodium dodecyl sulfate are mixed in 25 parts of water to obtain a pre-emulsion A;
2) 9 parts of 2-acrylamide, 10.5 parts of n-butyl acrylate, 2 parts of sodium dodecyl sulfate and 0.8 part of ammonium persulfate are mixed in 30 parts of water to obtain a pre-emulsion B;
3) Taking 17% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to the polymerization temperature of 90 ℃, and adding 0.2 part of potassium persulfate to start polymerization;
4) Reacting for 1.8h, then dripping the pre-emulsion B into a reactor, and continuing the polymerization reaction for 1h;
5) And (3) dropwise adding the rest of the pre-emulsion A into a reactor, continuing the polymerization reaction for 1.8 hours, preserving the heat for 0.7 hour after the reaction is finished, and finally cooling to 50 ℃, and discharging to obtain the acrylic emulsion.
[ example 5 ]
The following raw materials for preparing the acrylic emulsion are respectively weighed according to parts by weight:
8 parts of acid monomer, namely, a mixture of two or more of the following components,
10 parts of N-isopropyl acrylamide,
28 parts of isobutyl acrylate, which is used for preparing the emulsion,
3.2 parts of sodium cetyl sulfate,
48 parts of water, and the water is mixed with the water,
2.8 parts of ammonium persulfate.
Wherein the acid monomer is a mixture of 2-hexenedioic acid and acrylic acid in a mass ratio of 2.5:1.
The method for preparing the acrylic emulsion by using the raw materials comprises the following steps:
1) Mixing 8 parts of acid monomer, 11 parts of isobutyl acrylate and 1.3 parts of sodium hexadecyl sulfate in 24 parts of water to obtain a pre-emulsion A;
2) 10 parts of N-isopropyl acrylamide, 17 parts of isobutyl acrylate, 1.9 parts of sodium dodecyl sulfate and 2 parts of ammonium persulfate are mixed in 24 parts of water to obtain a pre-emulsion B;
3) Taking 12% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to a polymerization temperature of 75 ℃, and adding 0.8 part of ammonium persulfate to start polymerization;
4) Reacting for 1.2h, then dripping the pre-emulsion B into a reactor, and continuing the polymerization for 3.5h;
5) And (3) dropwise adding the rest of the pre-emulsion A into a reactor, continuing the polymerization reaction for 1.7h, preserving the heat for 0.9h after the reaction is finished, and finally cooling to 40 ℃, and discharging to obtain the acrylic emulsion.
[ example 6 ]
The following raw materials for preparing the acrylic emulsion are respectively weighed according to parts by weight:
15 parts of acid monomer and the like,
7 parts of N, N-methylene bisacrylamide,
15 parts of n-octyl acrylate,
5 parts of sodium dodecyl sulfate,
55 parts of water, and the water is mixed with the water,
3 parts of potassium persulfate.
Wherein the acid monomer is a mixture of fumaric acid and acrylic acid in a mass ratio of 2.9:1.
The method for preparing the acrylic emulsion by using the raw materials comprises the following steps:
1) Mixing 15 parts of acid monomer, 6 parts of n-octyl acrylate, 2 parts of sodium dodecyl sulfate and 27.5 parts of water to obtain a pre-emulsion A;
2) 10 parts of N-isopropyl acrylamide, 17 parts of isobutyl acrylate, 1.9 parts of sodium dodecyl sulfate and 2 parts of potassium persulfate are mixed in 27.5 parts of water to obtain a pre-emulsion B;
3) Taking 18% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to the polymerization temperature of 80 ℃, and adding 1 part of potassium persulfate to start polymerization;
4) Reacting for 1.6h, then dripping the pre-emulsion B into a reactor, and continuing the polymerization reaction for 3h;
5) And (3) dropwise adding the rest of the pre-emulsion A into a reactor, continuing the polymerization reaction for 2 hours, preserving the heat for 0.6 hour after the reaction is finished, and finally cooling to 35 ℃, and discharging to obtain the acrylic emulsion.
Comparative example 1
An acrylic emulsion was prepared in substantially the same raw material ratio and method as in example 1, except that the acid-based monomer was replaced with acrylic acid of the same quality.
Comparative example 2
An acrylic emulsion was prepared in substantially the same raw material ratio and method as in example 1, except that 2-acrylamide was not added.
[ comparative example 3 ]
An acrylic emulsion was prepared in substantially the same raw material ratio and method as in example 1, except that the acid-based monomer was replaced with acrylic acid of the same quality, while 2-acrylamide was not added.
[ comparative example 4 ]
An acrylic emulsion was prepared in substantially the same raw material ratio and method as in example 1, except that the acid-based monomer was replaced with a mixture of maleic acid and acrylic acid in a mass ratio of 1:1.
Comparative example 5
An acrylic emulsion was prepared in substantially the same raw material proportions and methods as in example 1, except that the whole of the pre-emulsion A was added in step 3).
[ application example ]
The acrylic emulsions prepared in examples 1 to 6 and comparative examples 1 to 6 were mixed with an antibacterial agent (penicillin) to prepare wound dressings, respectively, and drug release tests at different temperatures and pH were performed, respectively. The test results are shown in tables 1 and 2.
Table 1, results of the percent (%) drug release test for examples 1-6
Table 2, comparative examples 1-6 results of the percent (%) drug release test
Wherein, the drug release percentage refers to the percentage of the accumulated drug release mass to the total mass of the drug loaded on the sample.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and additions may be made to those skilled in the art without departing from the method of the present invention, which modifications and additions are also to be considered as within the scope of the present invention.
Claims (10)
1. The pH-temperature dual-response acrylic emulsion is characterized by being prepared from the following raw materials in parts by weight:
8 to 15 parts, preferably 10 to 13 parts,
5 to 10 parts, preferably 6 to 8 parts,
15-30 parts, preferably 18-26 parts,
3 to 7 parts, preferably 5 to 7 parts,
40 to 60 parts, preferably 45 to 55 parts,
1-3 parts of initiator, preferably 1.5-2 parts;
the acrylic monomer is a mixture of unsaturated diacid and unsaturated monoacid in a mass ratio of (2-3): 1.
2. The pH-temperature double-responsive acrylic emulsion according to claim 1, characterized in that the unsaturated diacid is at least one of maleic acid, fumaric acid, 2-pentenedioic acid, 2-hexenedioic acid, preferably maleic acid and/or 2-pentenedioic acid.
3. The pH-temperature double-responsive acrylic emulsion according to claim 2, wherein the unsaturated mono-acid is one or both of acrylic acid and methacrylic acid.
4. A pH-temperature double-responsive acrylic emulsion according to claim 3, characterized in that the unsaturated amide is at least one of 2-acrylamide, N-isopropylacrylamide and N, N-methylenebisacrylamide, preferably 2-acrylamide.
5. The pH-temperature double-responsive acrylic emulsion according to any one of claims 1 to 4, wherein the acrylic monomer is at least one of methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate and n-butyl methacrylate, preferably n-butyl acrylate and/or n-octyl acrylate.
6. The pH-temperature double-responsive acrylic emulsion according to any one of claims 1 to 4, wherein the emulsifier is at least one of sodium dodecyl sulfate, sodium hexadecyl sulfate and sodium dodecyl benzene sulfonate;
preferably, the initiator is potassium persulfate and/or ammonium persulfate.
7. A method for preparing the pH-temperature double-responsive acrylic emulsion according to any one of claims 1 to 6, comprising the steps of:
1) Mixing an acid monomer, a part of acrylic ester monomer and a part of emulsifier in water to obtain a pre-emulsion A;
2) Mixing unsaturated amide, the balance of acrylic ester monomer, the balance of emulsifier and part of initiator in water to obtain pre-emulsion B;
3) Taking 10-20% of the total mass of the pre-emulsion A as kettle bottom liquid of a reactor, heating to the polymerization temperature, and adding the rest initiator to start polymerization;
4) Then dripping the pre-emulsion B into a reactor, and continuing the polymerization reaction;
5) Dripping the rest of the pre-emulsion A into a reactor, and continuing the polymerization reaction; after the reaction is finished, preserving heat; and finally, cooling and discharging to obtain the acrylic emulsion.
8. The method for preparing a pH-temperature dual-response type acrylic emulsion according to claim 7, wherein in the steps 1) and 2), the mass ratio of the acrylic ester monomer is 1 (1.2-1.5);
preferably, in the steps 1) and 2), the mass ratio of the emulsifying agent is 1 (1.3-1.6);
preferably, in the steps 2) and 3), the mass ratio of the initiator is 1 (0.3-0.5).
9. The method for preparing a pH-temperature double-responsive acrylic emulsion according to claim 7 or 8, wherein the polymerization temperature in step 3) is 70 to 90 ℃ and the reaction time is 1 to 2 hours;
preferably, the reaction time in step 4) is 2-4.5h;
preferably, the reaction time in step 5) is 1-2h, and the temperature is kept for 0.5-1h after the reaction is finished.
10. Use of a pH-temperature double-responsive acrylic emulsion as defined in any one of claims 1 to 6 or a pH-temperature double-responsive acrylic emulsion as defined in any one of claims 7 to 9 in a medical dressing, in particular in a wound dressing comprising an antibacterial agent.
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| US4248685A (en) * | 1972-07-10 | 1981-02-03 | Johnson & Johnson | Method for making hydrophilic random interpolymer compositions |
| US4574130A (en) * | 1982-07-03 | 1986-03-04 | Smith & Nephew Associated Companies P.L.C. | Polymerizable compounds |
| US20060204555A1 (en) * | 2003-07-18 | 2006-09-14 | Yang Yi Y | Thermosensitive polymers for therapeutic use and methods of preparation |
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| US4248685A (en) * | 1972-07-10 | 1981-02-03 | Johnson & Johnson | Method for making hydrophilic random interpolymer compositions |
| US4574130A (en) * | 1982-07-03 | 1986-03-04 | Smith & Nephew Associated Companies P.L.C. | Polymerizable compounds |
| US20060204555A1 (en) * | 2003-07-18 | 2006-09-14 | Yang Yi Y | Thermosensitive polymers for therapeutic use and methods of preparation |
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