CN113929807B - Olefin acid resin and preparation method thereof - Google Patents
Olefin acid resin and preparation method thereof Download PDFInfo
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- CN113929807B CN113929807B CN202111215492.2A CN202111215492A CN113929807B CN 113929807 B CN113929807 B CN 113929807B CN 202111215492 A CN202111215492 A CN 202111215492A CN 113929807 B CN113929807 B CN 113929807B
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Abstract
The invention belongs to the technical field of polymers, and discloses an olefin acid resin which is prepared from 60-80wt% of olefin acid and olefin acid ester: 20-40wt% of mixed monomer, and carrying out free radical polymerization to obtain the product; wherein the alkene acid consists of the following components: vinyl acetic acid: 15-35 wt%; acrylic acid: 20-35 wt%; butenoic acid: 40-60 wt%; the olefin acid ester consists of the following components: hydroxyethyl methacrylate: 10-15 wt%; 2-hydroxyethyl acrylate: 5-10 wt%; ethyl 2-propylacrylate: 30-35 wt%; ethyl acrylate: 40-45 wt%. The auxiliary material can be quickly swelled/dissolved within the pH range of 5.5-6, and the swelling/dissolving speed is obviously slowed down beyond the pH range.
Description
Technical Field
The invention belongs to the technical field of polymers, and particularly relates to an olefin acid resin and a preparation method thereof.
Background
The olefin acid resin is prepared by copolymerizing olefin acids, olefin acid esters and other olefinic monomers, and can be synthesized into olefin acid resins with different types, different properties and different application occasions by selecting different resin structures, different formulas, different production processes and different solvents. Foreign pharmaceutical excipient enterprises are mainly concentrated in developed pharmaceutical countries such as Europe and America, and typical enterprises include ten world-leading companies such as Germany Rohm company, UK Sheerer company, American Carlekang company, Allerga company and Du-drawn drug company. The companies master the leading-edge product technology of the pharmaceutic adjuvant, and also monopolize most of the world market, so that the economic benefit is remarkable. The pharmaceutical composition continuously researches and develops products of novel pharmaceutical excipients and technical application, especially participates in application and popularization of the pharmaceutical excipients in the pharmaceutical process, organically combines production and research, and mutually promotes and develops. The production enterprises in the developed countries show obvious specialization and scale, and have advantages in the development direction of products.
Through search, the research in the prior art can find that the coating preparation by using acrylic acid and derivatives and esters thereof is the key point of research in this year.
CN03824013.0 discloses a multilayer dosage form comprising: a) a neutral core; b) an inner coating consisting of a methacrylate copolymer; c) an outer coating of a copolymer consisting of 40 to 95% by weight of a free-radically polymerized C1-C4 alkyl ester of acrylic or methacrylic acid and 5 to 60% by weight of a (meth) acrylate monomer having an anionic group in the alkyl group. The invention is characterized in that: the inner coating consists essentially of a methacrylate copolymer which consists of at least 90% by weight of (meth) acrylate monomers containing neutral groups, has a minimum film-forming temperature of not more than 30 ℃ in accordance with DIN53787 and contains the pharmaceutically active substance in bound form.
CN201710942016.8 discloses a modified polyacrylate drug coating material and a preparation method thereof, and concretely relates to ethyl methacrylate, n-butyl acrylate, itaconic acid, trimethylolpropane trimethacrylate, 1, 3-butanediol dimethacrylate and pentaerythritol triacrylate are used as monomers, pre-emulsification is carried out at a certain temperature under the protection of nitrogen to obtain pre-emulsion, and the modified polyacrylate emulsion is synthesized by prepolymerization of seed emulsion under the action of a peroxide initiator. By introducing functional monomers of itaconic acid, trimethylolpropane trimethacrylate, pentaerythritol triacrylate and 1, 3-butanediol dimethacrylate, the emulsion has small particle size, is suitable for coating, and has good stability and molding processability, and meanwhile, the coating material prepared from the emulsion has reduced moisture absorption rate, certain waterproofness, compact coating and excellent comprehensive performance, and can be used as a medicine coating material with good performance.
CN00808605.2 discloses a new sustained release oral formulation of morphine sulfate in particulate form. Each microgranule comprising a neutral carrier particle coated with an active layer and a sustained-release layer, characterized in that the sustained-release layer comprises a copolymer of methacrylic acid and of methyl methacrylate having a relative proportion of free carboxyl groups and ester groups equal to about 0.5, and silica exhibiting hydrophobic properties. The invention also relates to a method for preparing these microparticles, which is carried out entirely in an aqueous medium by coating neutral support particles.
CN200710041457.7 discloses the use of supercritical CO 2 The fluid coating technology is characterized in that methacrylic acid-ethyl acrylate copolymer (Eudragit L100-55) is used as a coating material to coat recombinant nattokinase medicine particles to prepare an oral preparation, and the recombinant nattokinase medicine particles prepared by the invention are regular, smooth in surface, uniform in appearance, free of adhesion, high in drug loading rate and encapsulation efficiency, and have the average particle size of 135 +/-30 mu m. The results of experiments show that the invention realizes the gastric acid resistance and the sustained release function of the recombinant nattokinase oral preparation.
From the above comparison documents, we can find that the carboxylic acid monomers commonly used in the prior art include: acrylic acid, itaconic acid, methacrylic acid, and the like; commonly used carboxylate monomers include, but are not limited to, ethyl methacrylate, n-butyl acrylate, trihydroxypropyl trimethacrylate, methyl methacrylate, ethyl acrylate.
The problems of the scheme are as follows: in the coating technology field, no company develops auxiliary materials aiming at a specific small pH range, and the auxiliary materials capable of swelling/dissolving in the small pH range have positive effects on the aspects of realizing accurate release of effective components of medicines in the medical field, realizing coating and release of the specific effective components in the daily chemical field and the like.
The technical problem that the present scheme will solve is: how to develop an auxiliary material with a swelling/dissolving pH value range of 5.5-6.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention aims to provide an olefin acid resin and a preparation method thereof.
The resin has the advantages that: the resin can be rapidly swelled/dissolved in a pH range of 5.5 to 6, and the swelling/dissolving speed is significantly slowed beyond the pH range.
The purpose of the invention is realized by the following technical scheme:
an olefin acid resin, which is prepared from olefin acid and olefin acid ester according to the weight ratio of 60-80%: 20-40wt% of mixed monomer, and free radical polymerization to obtain the final product; wherein the alkene acid consists of the following components:
vinyl acetic acid: 15-35 wt%;
acrylic acid: 20-35 wt%;
butenoic acid: 40-60 wt%;
the sum of the vinyl acetic acid, the acrylic acid and the butenoic acid is 100 percent;
the alkene acid ester consists of the following components:
hydroxyethyl methacrylate: 10-15 wt%;
2-hydroxyethyl acrylate: 5-10 wt%;
ethyl 2-propylacrylate: 30-35 wt%;
ethyl acrylate: 40-45 wt%;
the sum of the hydroxyethyl methacrylate, the 2-hydroxyethyl acrylate, the 2-ethyl propyl acrylate and the ethyl acrylate is 100 percent.
The following are particularly noted: unless otherwise specified, the crotonic acids in the invention are all 2-butenoic acids.
In the above-mentioned olefin acid resin, the ratio of the olefin acid to the olefin acid ester is 65 to 75% by weight: 25-35 wt%.
In the above-mentioned olefin acid resin, the olefin acid is composed of:
vinyl acetic acid: 25-30 wt%;
acrylic acid: 25-30 wt%;
butenoic acid: 45-50 wt%;
the sum of the vinyl acetic acid, the acrylic acid and the butenoic acid is 100 percent.
In the above-mentioned olefin acid resin, the olefin acid ester is composed of:
hydroxyethyl methacrylate: 13-14 wt%;
2-hydroxyethyl acrylate: 7-8 wt%;
ethyl 2-propylacrylate: 33-34 wt%;
ethyl acrylate: 44-45 wt%;
the sum of the hydroxyethyl methacrylate, the 2-hydroxyethyl acrylate, the 2-propyl ethyl acrylate and the ethyl acrylate is 100 percent.
Meanwhile, the invention also discloses a synthesis method of the olefin acid resin, which is obtained by solution free radical polymerization, and the monomer composition of the olefin acid resin is as in any one of claims 1-3.
In the above method for synthesizing an olefin acid resin, the initiator is one or a combination of two or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide and dicumyl peroxide;
the amount of the initiator is 1-4% of the total amount of the monomers.
In the above method for synthesizing olefin acid resin, the surfactant involved in the synthesis method is one or a combination of two or more of cetyltrimethylammonium chloride, sodium cocoanut alcohol sulfate, sodium lauryl alcohol sulfate, sodium fatty alcohol-polyoxyethylene ether sulfate, sodium dodecyl sulfate and octadecyltrimethylammonium chloride;
the amount of the surfactant is 1-6% of the total amount of the monomers.
In the above method for synthesizing an olefin acid resin, the solvent used in the method is deionized water, and the amount of the deionized water is 1 to 3 times of the total weight of the monomers.
In the above method for synthesizing an olefin acid resin, the method comprises the following steps:
step 1: preparing a monomer emulsion from the mixed monomer, water and an emulsifier;
step 2: putting the monomer emulsion not less than 70% in a reaction container, heating to the initiation temperature, and dropwise adding an initiator solution and the residual monomer emulsion;
and step 3: and (5) preserving the heat for a period of time and then discharging.
In the above method for synthesizing the olefin acid resin, the initiation temperature is 50-65 ℃; the dripping time of the step 2 is 1-2h, the heat preservation temperature is 50-65 ℃, and the heat preservation time is 2-4h
Compared with the prior art, the invention has the beneficial effects that:
the olefin acid resin can be quickly swelled under the release environment with the pH value of 5.5-6, so that the release of the active ingredients of cosmetics and medicines is realized, and the release of the active ingredients becomes very slow under the environment with the pH value lower than 5.5 or higher than 6, which is particularly beneficial to the slow release and release under the environment with the specific pH value, such as the application scene of a specific human body environment or a daily chemical product with the specific pH value.
Drawings
FIGS. 1 and 2 are graphs of the swelling effect of the membrane sheet of example 1;
FIGS. 3 and 4 are graphs showing the swelling effect of the membrane sheet of comparative example 1;
fig. 5 and 6 are graphs showing swelling effects of the membrane sheet of comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
A method for synthesizing olefin acid resin comprises the following steps:
step 1: preparing a monomer emulsion from the mixed monomer, water and an emulsifier;
the mixed monomer is 100g, wherein, the olefin acid is 70g, and the olefin acid ester is 30 g;
the olefin acid consists of the following components:
vinyl acetic acid: 30 wt%;
acrylic acid: 25 wt%;
butenoic acid: 45 wt%;
the olefin acid ester consists of the following components:
hydroxyethyl methacrylate: 13 wt%;
2-hydroxyethyl acrylate: 8 wt%;
ethyl 2-propylacrylate: 32 wt%;
ethyl acrylate: 42 wt%;
the emulsifier is hexadecyl trimethyl ammonium chloride, and the dosage is 4 g;
300g of water;
step 2: placing 80% of monomer emulsion in a reaction container, heating to the initiation temperature of 50-65 ℃, and dropwise adding an initiator solution and the rest monomer emulsion for 1 h;
the initiator is benzoyl peroxide, and the initiator is 2 g;
and step 3: keeping the temperature at 50-65 ℃, keeping the temperature for 2h, and discharging.
Example 2
A method for synthesizing olefin acid resin comprises the following steps:
step 1: preparing a monomer emulsion from the mixed monomer, water and an emulsifier;
the mixed monomer is 100g, wherein, the olefin acid is 80g, and the olefin acid ester is 20 g;
the olefin acid consists of the following components:
vinyl acetic acid: 35 wt%;
acrylic acid: 20 wt%;
butenoic acid: 45 wt%;
the olefin acid ester consists of the following components:
hydroxyethyl methacrylate: 15 wt%;
2-hydroxyethyl acrylate: 5 wt%;
ethyl 2-propylacrylate: 35 wt%;
ethyl acrylate: 45 wt%;
the emulsifier is hexadecyl trimethyl ammonium chloride, and the dosage is 2 g;
300g of water;
step 2: placing 80% of monomer emulsion in a reaction container, heating to the initiation temperature of 50-65 ℃, and dropwise adding an initiator solution and the rest monomer emulsion for 1 h;
the initiator is benzoyl peroxide, and the initiator is 1 g;
and step 3: keeping the temperature at 50-65 ℃, keeping the temperature for 2h, and discharging.
Example 3
A method for synthesizing olefin acid resin comprises the following steps:
step 1: preparing a monomer emulsion from the mixed monomer, water and an emulsifier;
the mixed monomer is 100g, wherein, the olefin acid is 60g, and the olefin acid ester is 40 g;
the olefin acid consists of the following components:
vinyl acetic acid: 15 wt%;
acrylic acid: 35 wt%;
butenoic acid: 50 wt%;
the olefin acid ester consists of the following components:
hydroxyethyl methacrylate: 10 wt%;
2-hydroxyethyl acrylate: 10 wt%;
ethyl 2-propylacrylate: 35 wt%;
ethyl acrylate: 45 wt%;
the emulsifier is hexadecyl trimethyl ammonium chloride, and the dosage is 2 g;
300g of water;
step 2: putting 90% of monomer emulsion into a reaction container, heating to the initiation temperature of 50-65 ℃, and dropwise adding an initiator solution and the rest monomer emulsion for 2 hours;
the initiator is benzoyl peroxide, and the initiator is 3 g;
and step 3: keeping the temperature at 50-65 ℃, keeping the temperature for 2h, and discharging.
Example 4
A method for synthesizing olefin acid resin comprises the following steps:
step 1: preparing a monomer emulsion from the mixed monomer, water and an emulsifier;
the mixed monomer is 100g, wherein, the olefin acid is 60g, and the olefin acid ester is 40 g;
the olefin acid consists of the following components:
vinyl acetic acid: 30 wt%;
acrylic acid: 30 wt%;
butenoic acid: 40 wt%;
the olefin acid ester consists of the following components:
hydroxyethyl methacrylate: 14 wt%;
2-hydroxyethyl acrylate: 7 wt%;
ethyl 2-propylacrylate: 34 wt%;
ethyl acrylate: 45 wt%;
the emulsifier is sodium lauryl sulfate, and the dosage is 4 g;
200g of water;
step 2: placing the monomer emulsion in a reaction container, heating to the initiation temperature of 50-65 ℃, and dropwise adding an initiator solution for 1 h;
the initiator is benzoyl peroxide, and the initiator is 2 g;
and 3, step 3: keeping the temperature at 50-65 ℃, keeping the temperature for 1h, and discharging.
Example 5
A method for synthesizing olefin acid resin comprises the following steps:
step 1: preparing a monomer emulsion from the mixed monomer, water and an emulsifier;
the mixed monomer is 100g, wherein, the olefin acid is 60g, and the olefin acid ester is 40 g;
the olefin acid consists of the following components:
vinyl acetic acid: 28 wt%;
acrylic acid: 27 wt%;
butenoic acid: 45 wt%;
the olefin acid ester consists of the following components:
hydroxyethyl methacrylate: 14 wt%;
2-hydroxyethyl acrylate: 8 wt%;
ethyl 2-propylacrylate: 34 wt%;
ethyl acrylate: 44 wt%;
the emulsifier is sodium dodecyl sulfate, and the dosage is 4 g;
100g of water;
step 2: placing the monomer emulsion in a reaction container, heating to the initiation temperature of 50-65 ℃, and dropwise adding an initiator solution for 1 h;
the initiator is benzoyl peroxide, and the initiator is 4 g;
and 3, step 3: keeping the temperature at 50-65 ℃, keeping the temperature for 1h, and discharging.
Comparative example 1
Generally as in example 1, except that the olefinic acid consists of:
vinyl acetic acid: 40 wt%;
acrylic acid: 40 wt%;
butenoic acid: 20 wt%.
Comparative example 2
Generally as in example 1, except that the olefin acid ester consists of:
ethyl 2-propylacrylate: 45 wt%;
ethyl acrylate: 55 wt%.
Performance testing
Preparing a membrane: preparing resin powder into 10% solid content solution with 95V% alcohol and water soluble dye (2-3 drops, green), pouring the solution into a mold with a depth of 3mm and a diameter of 15mm, and drying to obtain colored film.
Putting the membrane into a plurality of beakers with different pH values of aqueous solutions with the pH value of 4.5-6.5, soaking for 6h, and observing the result.
FIGS. 1 and 2 are the effect diagrams of the top view and the front view of example 1, and FIG. 1 shows that the film sheet swells in the solution of pH5, pH5.5 and pH6, the water-soluble pigment in the film sheet dissolves out, and the film sheet turns white; the film pieces in the solution with pH4.5 and pH6.0 are basically not swelled, the water-soluble pigment in the film pieces is not dissolved out, and the film pieces are still green. It can be seen that the solution of the invention ensures swelling in the smaller range of pH5-6, with swelling being particularly preferred at pH5 and 5.5.
Examples 2-5 of the present invention are all swellable states in the range of pH5-6, with the difference that there is a slight difference in swelling rate between the cells.
FIGS. 3 and 4 are effect diagrams of the top view and the front view of comparative example 1, and it can be seen that the swelling properties are all improved with a significantly reduced amount of crotonic acid, swelling is achieved in the range of pH4.5 to 6.5, and unlike FIGS. 1 and 2, the tablets used in FIGS. 3 and 4 have less dye, so that no color is seen by water, whether swelling is observed primarily to show discoloration of the tablets, and it can be seen that the tablets of FIGS. 3 and 4 are both discolored, indicating good swelling.
Fig. 5 and 6 are effect diagrams of a top view and a front view of comparative example 2, and it can be seen that the swelling property was remarkably deteriorated and the tablet color was hardly changed in the absence of the hydroxyl group-containing monomer.
The invention has the significance that the sustained release tablet can swell in a specific narrow pH range and does not swell in other ranges, and can be used for specific medicinal application and daily chemical application to realize the release of medicaments in a specific pH range.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. An olefin acid resin characterized in that: from 60 to 80% by weight of the olefinic acid and the olefinic acid ester: 20-40wt% of mixed monomer, and free radical polymerization to obtain the final product; wherein the alkene acid consists of the following components:
vinyl acetic acid: 15-35 wt%;
acrylic acid: 20-35 wt%;
butenoic acid: 40-60 wt%;
the sum of the vinyl acetic acid, the acrylic acid and the butenoic acid is 100 percent;
the alkene acid ester consists of the following components:
hydroxyethyl methacrylate: 10-15 wt%;
2-hydroxyethyl acrylate: 5-10 wt%;
ethyl 2-propylacrylate: 30-35 wt%;
ethyl acrylate: 40-45 wt%;
the sum of the hydroxyethyl methacrylate, the 2-hydroxyethyl acrylate, the 2-ethyl propyl acrylate and the ethyl acrylate is 100 percent.
2. The olefin acid resin according to claim 1, characterized in that: the ratio of the olefin acid to the olefin acid ester is 65 to 75 wt%: 25-35 wt%.
3. The olefin acid resin according to claim 1, characterized in that: the alkene acid consists of the following components:
vinyl acetic acid: 25-30 wt%;
acrylic acid: 25-30 wt%;
butenoic acid: 45-50 wt%;
the sum of the vinyl acetic acid, the acrylic acid and the butenoic acid is 100 percent.
4. The olefin acid resin according to claim 1, characterized in that: the alkene acid ester consists of the following components:
hydroxyethyl methacrylate: 13-14 wt%;
2-hydroxyethyl acrylate: 7-8 wt%;
ethyl 2-propylacrylate: 33-34 wt%;
ethyl acrylate: 44-45 wt%;
the sum of the hydroxyethyl methacrylate, the 2-hydroxyethyl acrylate, the 2-ethyl propyl acrylate and the ethyl acrylate is 100 percent.
5. A method for synthesizing olefin acid resin is characterized in that: obtained by solution radical polymerization, the monomer composition of which is as described in any one of claims 1 to 3.
6. The method for synthesizing an olefin acid resin according to claim 5, wherein: the method specifically comprises the following steps:
step 1: preparing monomer emulsion from monomers, water and an emulsifier;
step 2: putting the monomer emulsion not less than 70% in a reaction container, heating to the initiation temperature, and dropwise adding an initiator solution and the residual monomer emulsion;
and step 3: and (5) preserving the heat for a period of time and then discharging.
7. The method for synthesizing an olefin acid resin according to claim 6, wherein: the initiator is one or the combination of two or more of benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide and dicumyl peroxide;
the amount of the initiator is 1-4% of the total amount of the monomers.
8. The method for synthesizing an olefin acid resin according to claim 6, wherein: the emulsifier is one or a combination of two or more of hexadecyl trimethyl ammonium chloride, coconut oil alcohol sodium sulfate, lauryl alcohol sodium sulfate, fatty alcohol polyoxyethylene ether sodium sulfate, dodecyl sodium sulfate and octadecyl trimethyl ammonium chloride;
the amount of emulsifier is 1-6% of the total amount of monomers.
9. The method for synthesizing an olefin acid resin according to claim 6, wherein: the water is deionized water, and the amount of the deionized water is 1-3 times of the total weight of the monomers.
10. The method for synthesizing an olefin acid resin according to claim 9, characterized in that: the initiation temperature is 50-65 ℃; the dripping time of the step 2 is 1-2 h; the heat preservation temperature of the step 3 is 50-65 ℃, and the heat preservation time is 2-4 h.
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