CN112538142B - Preparation method and application of thickening polymer - Google Patents
Preparation method and application of thickening polymer Download PDFInfo
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- CN112538142B CN112538142B CN202011332966.7A CN202011332966A CN112538142B CN 112538142 B CN112538142 B CN 112538142B CN 202011332966 A CN202011332966 A CN 202011332966A CN 112538142 B CN112538142 B CN 112538142B
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Abstract
The invention belongs to the field of polymers, and provides a preparation method of a thickening polymer, aiming at solving the problem that the light transmittance of the traditional thickening polymer cannot be improved under the condition of low viscosity, wherein the preparation method comprises the following steps: step 1: placing the solvent in a reaction vessel and heating to reflux temperature; step 2: adding part of monomer, dispersant and first cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature; and step 3: adding the rest monomers, the dispersing agent and the second cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, wherein the reaction time is 0.2-0.8h; and 5: filtering and drying to obtain polymer powder; the 1% hydrogel prepared by this method had a light transmittance of greater than 99% and monomer residue of less than 50ppm. Meanwhile, the scheme also provides the application of the thickening polymer in the eye drop thickening agent.
Description
Technical Field
The invention relates to the field of polymers, in particular to a preparation method and application of a thickening polymer.
Background
Acrylic thickeners are lightly crosslinked acrylic polymers which provide excellent stability and thickening properties to the surfactant system and excellent suspendability even in low viscosity formulations, and insoluble and difficult to stabilize ingredients such as silicones can be co-emulsified and stabilized.
It is widely used in the field of daily chemicals, and is characterized in that:
excellent suspension and thickening performance, and improves the working efficiency of a formulator;
the compatibility is strong, and the product is almost compatible with all nonionic, anionic and amphoteric surfactants and various cationic polymers;
can be used for transparent products, is convenient to use and is an ideal matching of personal cleaning products.
However, the acrylic acid thickeners which are matured to be applied in the field of medicines are not many in the market at present, and no matter the Chinese pharmacopoeia or the actual application requirements, the acrylic acid thickeners have no two non-concerned points, namely light transmittance and monomer residue.
The monomer residue is easier to control now, and can be controlled below 100ppm mostly by adding the initiator at one time in the later period, and can be controlled below 50ppm if the monomer is added in a dropwise manner.
The medical acrylic acid thickening agent hydrogel with low viscosity has the advantage that the light transmittance is difficult to control to be more than 98% under the condition of low residue. In general, light transmittance is most easily controlled at medium viscosity, and is relatively difficult to control at low and high viscosities.
Therefore, the technical problem to be solved by the scheme is as follows: how to control both the light transmittance and the residue of the low viscosity acrylic thickener hydrogel.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for preparing a thickening polymer, by which 1% of hydrogel prepared by the method has a light transmittance of more than 99% and a monomer residue of less than 50ppm. Meanwhile, the scheme also provides the application of the thickening polymer in the eye drop thickening agent.
In order to achieve the purpose, the invention provides the following technical scheme:
a method of preparing a thickening polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel, and heating to reflux temperature;
step 2: adding part of monomer, dispersant and first cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;
and step 3: adding the rest monomers, the dispersing agent and the second cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.2-0.8h;
and 5: filtering and drying to obtain polymer powder;
the first cross-linking agent is a cross-linking agent with three functional groups, and the second cross-linking agent is a cross-linking agent with two functional groups;
the first cross-linking agent is 0.1-0.2% of the weight of the monomer; the second cross-linking agent is 0.2-0.4% of the weight of the monomer;
the weight ratio of the monomers in the step 2 to the monomers in the step 3 is 6-7.
Preferably, the monomers comprise a first monomer, a second monomer and a third monomer, and the ratio of the first monomer, the second monomer and the third monomer is 80-90;
the first monomer is acrylic acid or methacrylic acid;
the second monomer is methyl acrylate, ethyl acrylate or methyl methacrylate or ethyl methacrylate;
the third monomer is long-chain alkyl polyoxyethylene ether acrylate or long-chain alkyl polyoxyethylene ether methacrylate.
Preferably, the third monomer is eicosyl polyoxyethylene ether acrylate, docosyl polyoxyethylene ether acrylate, hexadecyl polyoxyethylene ether acrylate, eicosyl polyoxyethylene ether methacrylate, docosyl polyoxyethylene ether methacrylate, and hexadecyl polyoxyethylene ether methacrylate.
Preferably, the dispersant is sodium dodecyl benzene sulfonate or polyoxyethylene fatty acid ester with HLB value of 9-10; the amount of the dispersant used in step 2 and step 3 is 0.5 to 1% by weight based on the weight of the monomer, respectively.
Preferably, the solvent is a mixture of cyclohexane and ethyl acetate; the weight ratio of the cyclohexane to the ethyl acetate is 2.5-3. The dosage of the solvent is 3-4 times of the weight of the monomer;
preferably, the polymer powder is dispersed in a water body, the hydrogel viscosity under the condition of 1% concentration is 4000-11000mpa.s, and the light transmittance of the hydrogel is not lower than 99%.
Preferably, the reflux temperature is 75 ± 5 ℃.
Preferably, the initiator is azobisisobutyronitrile or azobisisoheptonitrile, and in step 3, the amount of the initiator is 1.0-1.5 of the weight of the monomer; the amount of initiator used in step 4 is 0.2 to 0.4% by weight based on the weight of the monomers.
Preferably, the first crosslinking agent is pentaerythritol triallyl ether and the second crosslinking agent is pentaerythritol diallyl ether or diallyl phthalate.
Finally, the present invention also provides the use of a thickening polymer prepared as described above as a thickening additive for ophthalmic hydrogels.
The invention has the beneficial effects that:
according to the preparation method of the thickening polymer, the dosage of the first cross-linking agent and the dosage of the second cross-linking agent are controlled to be less so as to achieve the purpose of reducing viscosity, meanwhile, most of monomers are added into a reactor, then the rest is synchronously dripped and synchronously initiated to react for production, the phenomenon that the reaction is performed too fast is avoided, the reaction speed is controlled, the viscosity is improved under the condition of delaying the reaction speed, in general, the proper viscosity is achieved through the least cross-linking agent, and the light transmittance can be improved by reducing the addition of the cross-linking agent. Meanwhile, the product obtained by the method is subjected to suction filtration at normal pressure and is dried for 12 hours, and then a finished product can be obtained.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following embodiments, but the present invention is not limited thereto.
Example 1
A method of preparing a thickening polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel and heating to reflux temperature;
the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.7 to 1, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300g;
step 2: adding part of monomer, dispersant and first cross-linking agent (pentaerythritol triallyl ether, 0.2 g) into a reaction vessel at one time, and keeping the temperature at the reflux temperature;
and step 3: adding the rest monomer, the dispersing agent and the second cross-linking agent (pentaerythritol diallyl ether, 0.3 g) into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2h, and the temperature is kept for 2h;
the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, and eicosyl polyoxyethylene ether acrylate; the weight ratio is 90: 5; 70g of monomers in the step 2 and 30g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.2g of initiator is used in the step 3;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5h; 20g of solvent is used for the initiator solution, and 0.4g of initiator is used in the step 4; the initiators in steps 3 and 4 are all azobisisobutyronitrile.
And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;
the proportion of the dispersing agent in the step 2 and the step 3 is 7, the total amount of the dispersing agent is 0.8g, and the dispersing agent consists of 1.
Example 2
A method of preparing a thickening polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel and heating to reflux temperature;
the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.9, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300g;
step 2: adding part of monomer, dispersant and first cross-linking agent (pentaerythritol triallyl ether, 0.15 g) into a reaction vessel at one time, and keeping the temperature at the reflux temperature;
and step 3: adding the rest monomer, the dispersing agent and the second cross-linking agent (pentaerythritol diallyl ether, 0.4 g) into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 3 hours, and the temperature is kept for 2 hours;
the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, and eicosyl polyoxyethylene ether acrylate; the weight ratio is 85: 5; 60g of monomers in the step 2 and 40g of monomers in the step 3; 30g of solvent is used for the initiator solution, and the amount of the initiator in the step 3 is 1.0g;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.3g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.
And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;
the proportion of the dispersing agent in the step 2 and the step 3 is 6, the total amount of the dispersing agent is 1g, and the dispersing agent consists of 1.
Example 3
A method of preparing a thickening polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel and heating to reflux temperature;
the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.6; the total weight of the solvent is 300g;
step 2: adding part of monomer, dispersant and first cross-linking agent (pentaerythritol triallyl ether, 0.1 g) into a reaction vessel at one time, and keeping the temperature at the reflux temperature;
and step 3: adding the rest monomer, the dispersing agent and the second cross-linking agent (pentaerythritol diallyl ether, 0.2 g) into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 3 hours, and the constant temperature is kept for 3 hours;
the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, and eicosyl polyoxyethylene ether acrylate; the weight ratio is 85: 10; 65g of monomers in the step 2 and 35g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.0g of initiator is used in the step 3;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.4g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.
And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;
the proportion of the dispersing agent in the step 2 and the step 3 is 6.5, the total amount of the dispersing agent is 0.5g, and the dispersing agent is polyoxyethylene fatty acid ester with HLB value of 9-10.
Example 4
A method of preparing a thickening polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel and heating to reflux temperature;
the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.7, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300g;
step 2: adding part of monomers, a dispersing agent and a first cross-linking agent (pentaerythritol triallyl ether, 0.2 g) into a reaction vessel at one time, and keeping the temperature at the reflux temperature;
and step 3: adding the rest monomer, the dispersing agent and the second cross-linking agent (pentaerythritol diallyl ether, 0.4 g) into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours;
the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, ethyl acrylate, and hexadecyl polyoxyethylene ether acrylate; the weight ratio is 85:5:10; 65g of monomers in the step 2 and 35g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.0g of initiator is used in the step 3;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.2g; the initiators in steps 3 and 4 are all azobisisoheptonitrile.
And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;
the proportion of the dispersing agent in the step 2 and the step 3 is 6.5, the total amount of the dispersing agent is 1g, and the dispersing agent is polyoxyethylene fatty acid ester with HLB value of 9-10.
Example 5
A method of preparing a thickening polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel and heating to reflux temperature;
the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.7, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300g;
step 2: adding part of monomer, dispersant and first cross-linking agent (pentaerythritol triallyl ether, 0.1 g) into a reaction vessel at one time, and keeping the temperature at the reflux temperature;
and step 3: adding the rest monomer, the dispersing agent and the second cross-linking agent (pentaerythritol diallyl ether, 0.2 g) into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container; the dripping time is controlled to be 2 hours, and the temperature is kept for 2 hours;
the monomer compositions in the step 2 and the step 3 are the same and are both: acrylic acid, methyl acrylate, ethyl acrylate and behenyl polyoxyethylene ether methacrylate; the weight ratio is 85:5:10; 70g of monomers in the step 2 and 30g of monomers in the step 3; 30g of solvent is used for the initiator solution, and 1.0g of initiator is used in the step 3;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5h; 20g of solvent is used for the initiator solution, and 0.2g of initiator is used in the step 4; the initiators in steps 3 and 4 are all azobisisoheptonitrile.
And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;
the proportion of the dispersing agent in the step 2 and the step 3 is 7, the total amount of the dispersing agent is 1g, and the dispersing agent is polyoxyethylene fatty acid ester with HLB value of 9-10.
Comparative example 1
Analogously to example 1, the points of distinction are: the first crosslinking agent and the second crosslinking agent are both pentaerythritol diallyl ether.
Comparative example 2
Analogously to example 1, the points of distinction are: the monomers were chosen as acrylic acid and methyl acrylate in a weight ratio of 9.
Comparative example 3
Analogously to example 1, the points of distinction are: the monomers are selected from acrylic acid and methyl acrylate in a weight ratio of 9; the first crosslinking agent and the second crosslinking agent are both pentaerythritol diallyl ether.
Comparative example 4
A method of preparing a thickening polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel and heating to reflux temperature;
the solvent is a mixture of cyclohexane and ethyl acetate with the weight ratio of 2.7, and the reflux temperature is 70-75 ℃; the total weight of the solvent is 300g;
step 2: adding part of monomer, dispersant and first cross-linking agent (pentaerythritol triallyl ether, 0.2 g) into a reaction vessel at one time, and keeping the temperature at the reflux temperature; 0.8g of initiator was added dropwise to the reaction vessel over 2h
And step 3: adding the rest of monomer, dispersant and second cross-linking agent (pentaerythritol diallyl ether, 0.3 g) into a reaction container in a dropwise manner, and synchronously dropwise adding 0.4g of initiator into the reaction container; the dropping time of the monomer, the dispersant, the second cross-linking agent and the initiator in the step is controlled to be 1h; then keeping the temperature for 1h;
the monomer compositions in the step 2 and the step 3 are the same and are as follows: acrylic acid, methyl acrylate, and eicosyl polyoxyethylene ether acrylate; the weight ratio is 90: 5; 70g of monomers in the step 2 and 30g of monomers in the step 3; 30g of solvent was used for the initiator solution;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, and reacting for 0.5h; 20g of solvent is used for the initiator solution, and the amount of the initiator in the step 4 is 0.4g; the initiators in steps 3 and 4 are all azobisisobutyronitrile.
And 5: carrying out suction filtration at normal pressure and drying in a vacuum drying oven for half a day to obtain polymer powder;
the proportion of the dispersing agent in the step 2 and the step 3 is 7.
Test items
The test items are that under the condition that the hydrogel is 1% of the addition amount of the polymer thickener powder, the viscosity, the monomer residue and the light transmittance are tested, and the monomer residue meets the standard requirement that the residue is less than 50ppm.
The viscosity was measured as follows: viscosity measured at 20 revolutions per minute with a Brookfield DV-II viscometer;
the light transmittance test instrument is as follows: (model 725 ultraviolet-visible spectrophotometer, shanghai prism technology Co., ltd.).
TABLE 1 test results of examples and comparative examples
| Serial number | Viscosity of the oil | Light transmittance | Whether the residue reaches the standard |
| Example 1 | 8300 | 99.70％ | Is that |
| Example 2 | 7800 | 99.40％ | Is that |
| Example 3 | 5300 | 99.20％ | Is that |
| Example 4 | 10500 | 99.80％ | Is that |
| Example 5 | 4700 | 99.40％ | Is that |
| Comparative example 1 | 4100 | 96.60％ | Is that |
| Comparative example 2 | 9200 | 92.60％ | Is that |
| Comparative example 3 | 6600 | 94.30％ | Is that |
| Comparative example 4 | 11000 | 91.5％ | Is that |
Through the test and analysis of the above cases, it can be known that:
the cross-linking agent should adopt the cross-linking agent of two functional groups and cross-linking agent of three functional groups to cooperate and use as far as possible, it is low to use the cross-linking agent of two functional groups alone, the light transmittance is not high; the viscosity of the cross-linking agent with three functional groups is too high, and the light transmittance is not high;
after the monomer is added at one time, the initiator is added dropwise to react for a period of time, and then the rest monomer and the initiator are added dropwise, so that the viscosity is increased, and the gel light transmittance is reduced;
the more the initiator is used, the smaller the viscosity is; the more the amount of the cross-linking agent, the smaller the viscosity; the light transmittance of the composition needs to be improved without using a hydrophobic monomer.
In view of the above, in order to prepare a suitable low viscosity hydrogel thickener, it is necessary to control the monomer dropping manner and the use of a crosslinking agent.
Furthermore, the kinds and proportions of the monomers, the amount of the initiator and the amount of the crosslinking agent are controlled as much as possible.
Examples of specific applications
A topical ophthalmic formulation comprising the following table:
| composition (A) | Dosage of |
| Levofloxacin hydrochloride | 3.3g |
| Sample of this patent | 1.0g |
| Sodium chloride | 9.0g |
| Benzalkonium bromide | 1.0g |
| EDTA | Proper amount of |
| Water for injection | Adding to 1000ml |
Claims (8)
1. A method of making a thickened polymer, the method comprising the steps of:
step 1: placing the solvent in a reaction vessel, and heating to reflux temperature;
step 2: adding part of monomer, dispersant and first cross-linking agent into a reaction vessel at one time, and keeping the temperature at the reflux temperature;
and step 3: adding the rest monomers, the dispersing agent and the second cross-linking agent into a reaction container in a dropwise manner, and synchronously dropwise adding the initiator into the reaction container;
and 4, step 4: adding an initiator solution for eliminating residual monomers in the solution at one time, wherein the reaction time is 0.2-0.8h;
and 5: filtering and drying to obtain polymer powder;
the first cross-linking agent is a cross-linking agent with three functional groups, and the second cross-linking agent is a cross-linking agent with two functional groups;
the first cross-linking agent is 0.1-0.2% of the weight of the monomer; the second cross-linking agent is 0.2-0.4% of the weight of the monomer;
the weight ratio of the monomers in the step 2 to the monomers in the step 3 is 6-7;
the monomers comprise a first monomer, a second monomer and a third monomer, and the proportion of the first monomer, the second monomer and the third monomer is 80-90;
the first monomer is acrylic acid or methacrylic acid;
the second monomer is methyl acrylate, ethyl acrylate or methyl methacrylate or ethyl methacrylate;
the third monomer is eicosyl polyoxyethylene ether acrylate, docosyl polyoxyethylene ether acrylate, hexadecyl polyoxyethylene ether acrylate, eicosyl polyoxyethylene ether methacrylate, docosyl polyoxyethylene ether methacrylate or hexadecyl polyoxyethylene ether methacrylate.
2. The method of claim 1, wherein: the dispersant is sodium dodecyl benzene sulfonate or polyoxyethylene fatty acid ester with HLB value of 9-10; the amount of the dispersant used in step 2 and step 3 is 0.5 to 1% by weight based on the weight of the monomer, respectively.
3. The method of claim 1, wherein: the solvent is a mixture of cyclohexane and ethyl acetate; the weight ratio of the cyclohexane to the ethyl acetate is 2.5-3.
4. The method for producing a thickening polymer according to claim 1, wherein: the polymer powder is dispersed in a water body, the hydrogel viscosity under the condition of 1% concentration is 4000-11000mpa.s, and the light transmittance of the hydrogel is not lower than 99%.
5. The production method according to claim 3, characterized in that: the reflux temperature was 75 ± 5 ℃.
6. The production method according to claim 3, characterized in that: the initiator is azobisisobutyronitrile or azobisisoheptonitrile, and in step 3, the amount of the initiator is 1.0-1.5% of the weight of the monomer; the amount of initiator used in step 4 is 0.2 to 0.4% by weight based on the weight of the monomers.
7. The production method according to any one of claims 1 to 6, characterized in that: the first cross-linking agent is pentaerythritol triallyl ether, and the second cross-linking agent is pentaerythritol diallyl ether or diallyl phthalate.
8. Use of a thickening polymer prepared by the process according to any one of claims 1 to 7 as a thickening additive for ophthalmic hydrogels.
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Denomination of invention: Preparation method and application of a thickened polymer Effective date of registration: 20230810 Granted publication date: 20230324 Pledgee: Bank of Guiyang Limited by Share Ltd. Danzhai branch Pledgor: GUIZHOU XINZIHONG PHARMACEUTIC ADJUVANT Co.,Ltd. Registration number: Y2023980051498 |