Phytic acid-based temperature stimuli-responsive polymer and preparation method thereof
By using raw materials such as the multi -arm function monomer and NIPAM and DAAM, the water bath heating method under nitrogen reaction and nitrogen protection is used to successfully synthesize the temperature -based star -shaped temperature -based temperature stimulating response polymer, which solves the present. In the process of technology synthesis, the problem of using transition metal catalysts has achieved efficient and low -cost production, and has extensive application potential.
Patent Information
- Application Number
- CN202411494084.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-10-24
- Publication Date
- 2025-01-28
AI Technical Summary
The prior art is difficult to efficiently synthesize temperature stimulus-responsive star polymers, and a large number of transition metal catalysts are required during the synthesis process, resulting in high production costs and difficulty in separation.
By using raw-based multi-arm function monomers PA-GMA and N-isopropyyl acrylamide NIPAM and bifonarone acrylamide DAAM and other raw materials, the heating method of water bath under nitrogen reaction and nitrogen protection is used to synthesize temperature sensitivity and A polymer of the star structure.
Achieved efficient synthetic temperature -based star -shaped base temperature stimulating response polymers, avoiding the use of transition metal catalysts, reducing production costs, and having high solubility, low crystalline and easy surface modification. It is suitable for water water Treatment, oil harvest, drug release and other fields.
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Figure CN119371600A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the technical field of high molecular polymers, and in particular relates to a phytic acid-based temperature stimulus responsive polymer and a preparation method thereof. Background Art
[0002] Thermosensitive polymers are polymers that can produce corresponding chemical property changes or physical structure changes according to external temperature changes, thereby causing changes in their own performance. Such polymers usually have a low critical solution temperature (LCST). When the temperature is lower than the LCST, there is a strong hydrogen bond between the polymer side chain and the water molecule, showing hydrophilicity, so the entire graft is a water-soluble polymer; when the temperature is higher than the LCST, the polymer side chain undergoes hydrophobic association, showing hydrophobicity, and the entire graft polymer is amphiphilic. Due to the hydrophobic association between the side chains, a physical cross-linked network structure is formed between the main chains. Thermosensitive polymers have significant fluid dynamic volume changes during the response process, and can be effectively used in water treatment, enhanced oil recovery, controlled drug release, fluid drag reduction, personal care products, etc., and have become one of the important research directions of emerging materials in recent years.
[0003] Star polymers are branched polymers formed by multiple linear branches (at least three) connected to the same central support or core by chemical bonds. They are a type of polymer with a non-linear structure. Star polymers have a relatively symmetrical spherical structure, a smaller spatial arrangement size, and the molecular chains are not easily entangled. The molecular forces are weak, so star polymers have many unique electrical, magnetic, mechanical and chemical properties, and are currently one of the hot topics in the field of polymer science research. Compared with traditional linear polymers, star polymers have the characteristics of high solubility, low crystallinity, small fluid mechanics volume, high-density functional group distribution, and easy surface modification and modification. They have shown advantages and application prospects that surpass linear polymers in the fields of medicine, rubber, petroleum industry, sewage treatment, etc.
[0004] However, star polymers are difficult to prepare through general polymerization methods. They are mainly synthesized through living radical polymerization methods such as living anionic polymerization, atom transfer radical polymerization, stable radical polymerization, and reversible addition-fragmentation chain transfer polymerization. These living radical polymerization methods require the use of a large amount of transition metals as catalysts in the actual production process, which are difficult to effectively separate and remove after the polymerization reaction, which greatly increases the cost of industrial production. Therefore, creating an efficient and simple synthetic route to prepare new temperature stimulus-responsive star polymers will have potential application value in water treatment, enhanced oil recovery, controlled drug release, fluid drag reduction, personal care products, etc. Summary of the invention
[0005] The purpose of this section is to summarize some aspects of embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the specification abstract and the invention title of this application to avoid blurring the purpose of this section, the specification abstract and the invention title, and such simplifications or omissions cannot be used to limit the scope of the present invention.
[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.
[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide a phytic acid-based temperature-stimulation-responsive polymer.
[0008] In order to solve the above technical problems, the present invention provides the following technical solution:
[0009] a. derived from a repeating unit of a phytic acid multi-arm functional monomer PA-GMA having a structural formula as shown in formula (I);
[0010]
[0011] b. A repeating unit of N-isopropylacrylamide NIPAM and diacetoneacrylamide DAAM connected by a terminal C=C double bond of a phytic acid multi-arm functional monomer PA-GMA having a structural formula as shown in formula (I), wherein m and n represent the number of repeating units, and m and n are non-zero integers;
[0012]
[0013] c. The molar ratio of the phytic acid multi-arm functional monomer PA-GMA in the repeating unit to the N-isopropylacrylamide NIPAM and diacetoneacrylamide DAAM in the repeating unit is 1:10:5-30.
[0014] As a preferred embodiment of the phytic acid-based temperature-responsive polymer of the present invention, the polymer is a star polymer PAGMA-sP (NIPAM-co-DAAM).
[0015] As a preferred embodiment of the phytic acid-based temperature-responsive polymer of the present invention, the polymer is temperature-sensitive, and the higher the content of the repeating unit diacetone acrylamide DAAM is, the higher the lower critical solution temperature of the polymer is.
[0016] Another object of the present invention is to provide a method for preparing a phytic acid-based temperature-stimulus-responsive polymer.
[0017] In order to solve the above technical problems, the present invention provides the following technical solutions: comprising:
[0018] After the phytic acid-based multi-arm functional monomer, N-isopropylacrylamide, diacetoneacrylamide and distilled water are stirred and dissolved, nitrogen is passed through for reaction, an initiator is added, and the reaction is heated in a water bath under nitrogen protection. After the reaction is completed, the reaction solution is dropped into acetone to precipitate a white precipitate. After suction filtration, the filter cake is vacuum dried to obtain a phytic acid-based temperature stimulus responsive polymer.
[0019] As a preferred solution of the method for preparing the phytic acid-based temperature-responsive polymer of the present invention, the reaction time of the nitrogen-passing reaction is 30 to 60 minutes.
[0020] As a preferred solution of the method for preparing the phytic acid-based temperature-responsive polymer of the present invention, the initiator is composed of a water-soluble oxidant and a reducing agent.
[0021] As a preferred embodiment of the method for preparing the phytic acid-based temperature-responsive polymer of the present invention, the oxidant includes one or more of potassium persulfate, ammonium persulfate, hydrogen peroxide, etc.; the reducing agent includes one or more of sulfite, bisulfite, ascorbic acid, and pyrosulfite.
[0022] As a preferred embodiment of the method for preparing the phytic acid-based temperature-responsive polymer of the present invention, the molar ratio of the oxidant to the reductant in the initiator is >1.
[0023] As a preferred solution of the method for preparing the phytic acid-based temperature-responsive polymer of the present invention, the glycidyl methacrylate is added dropwise to the mixed solution I for a time of 30 minutes to 3 hours.
[0024] As a preferred solution of the method for preparing the phytic acid-based temperature-responsive polymer of the present invention, the reaction time of the water bath heating reaction is 6 to 12 hours, and the reaction temperature is 20 to 50°C.
[0025] Beneficial effects of the present invention:
[0026] The present invention successfully synthesizes a thermosensitive star-shaped phytic acid-based temperature stimulus responsive polymer. The selected raw materials are cheap and easily available, the synthesis process is simple, and it is green and environmentally friendly. It avoids the use of a large amount of transition metal catalysts and the difficulty in effective separation and removal after the polymerization reaction, and is easy to produce on an industrial scale.
[0027] In addition, the response temperature of the phytic acid-based temperature stimulus-responsive star polymer can be adjusted according to the actual application field, and it has the characteristics of high solubility, low crystallinity, small fluid mechanics volume, high-density functional group distribution, and easy surface modification and modification. It has potential application value in water treatment, improving oil recovery, controlling drug release, fluid drag reduction, personal care products, etc. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without creative labor. Among them:
[0029] Figure 1 The figure is a schematic diagram of the preparation process of the phytic acid-based temperature-responsive polymer of the present invention.
[0030] Figure 2 This is the infrared spectrum of the phytic acid-based temperature-responsive polymer.
[0031] Figure 3 The light transmittance of aqueous solutions of phytic acid-based temperature-responsive polymers (samples in Example 4) with different concentrations varies with temperature.
[0032] Figure 4 The light transmittance of a 20% phytic acid-based temperature-responsive polymer (products of Examples 1 to 4) in aqueous solution changes with temperature. DETAILED DESCRIPTION
[0033] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.
[0034] In the following description, many specific details are set forth to facilitate a full understanding of the present invention, but the present invention may also be implemented in other ways different from those described herein, and those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.
[0035] Secondly, the term "one embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The term "in one embodiment" that appears in different places in this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive with other embodiments.
[0036] Unless otherwise specified, the raw materials used in the present invention are all commercially available in the art.
[0037] The preparation method of the phytic acid functional monomer (PA-GMA) of the present invention is as follows:
[0038] In a 500mL four-necked round-bottom flask equipped with a thermometer, an electric stirrer, a constant pressure dropping funnel, and a nitrogen conduit, 0.15mol of a phytic acid solution of 70% phytic acid, 1% of urea, and 0.1% of p-hydroxyanisole were added and stirred to dissolve, and then heated to 30°C in a water bath. Under nitrogen protection, 0.9mol of glycidyl methacrylate was added to the constant pressure dropping funnel. Under stirring, glycidyl methacrylate was added dropwise within 2h, and the dropping speed was strictly controlled to ensure that the temperature did not exceed 40°C during the dropping process. After all the additions were completed, the reaction was carried out at a constant temperature of 45°C for 5h, the reaction solution became homogeneous, and the reaction was stopped to obtain PA-GMA with a structural formula as shown in formula (I).
[0039] The temperature-sensitive performance test method of the present invention is as follows: the solution transmittance is measured by a UV-visible spectrophotometer, a sample solution of a certain concentration is subjected to spectral scanning within a wavelength range of 380 to 800 nm, and the optimal wavelength for measurement is determined to be 560 nm. The temperature change rate is 1.0°C / min, and the curve of the change of the transmittance of the sample solution with temperature is measured at the optimal wavelength to determine the high and low critical solution temperature responsiveness.
[0040] Example 1
[0041] Reference Figure 1 This embodiment provides a method for preparing a phytic acid-based temperature-responsive polymer, specifically:
[0042] 2) Preparation of phytic acid-based temperature-responsive polymers:
[0043] In a 500mL three-necked round-bottom flask equipped with a thermometer, an electric stirrer, and a nitrogen conduit, 15.12g PA-GMA, 11.3g N-isopropylacrylamide (NIPAM), 8.45g diacetoneacrylamide (DAAM) and 52.31g distilled water (wherein the molar ratio of PA-GMA, NIPAM and DAAM is 1:10:5) were added, and after stirring and dissolving, nitrogen was passed through for 30min, and then 0.35g sodium bisulfite and 0.35g ammonium persulfate were added in sequence, and the mixture was heated to 30°C in a water bath, and reacted for 6h under nitrogen protection. After the reaction was completed, the reaction solution was dropped into acetone to precipitate a white precipitate, and the filter cake was vacuum dried after suction filtration to obtain the phytic acid-based temperature stimulus responsive polymer of this embodiment.
[0044] Figure 2 The infrared spectrum of the phytic acid-based temperature-responsive polymer prepared in this example shows that 1640 cm -1 The carbonyl stretching vibration absorption peak appears at 1460cm -1 The bending vibration absorption peak of -NH is 1250cm -1 The CN stretching vibration absorption peak is at 1353 cm -1The absorption peak at 1250cm is formed by the coupling splitting of the symmetric stretching vibration of the dimethyl group on CH(CH3)2. -1 The peak of P=O stretching vibration is 3440cm -1 The -OH stretching vibration peak is at 1093 cm －1 The peak at is the typical stretching vibration absorption peak of phytic acid POC. The infrared spectrum analysis shows that the three functional monomers have undergone polymerization and the functional group absorption peak unique to the target product has appeared.
[0045] Example 2
[0046] The difference between this embodiment and embodiment 1 is that step 2) is adjusted, specifically:
[0047] In a 500 mL three-necked round-bottom flask equipped with a thermometer, an electric stirrer, and a nitrogen inlet, 15.12 g PA-GMA, 11.3 g N-isopropylacrylamide (NIPAM), 16.9 g diacetoneacrylamide (DAAM), and 64.98 g distilled water (wherein the molar ratio of PA-GMA, NIPAM, and DAAM is 1:10:10) were added. ， After stirring and dissolving, nitrogen was passed for 30 minutes, and then 0.43 g of sodium bisulfite and 0.43 g of ammonium persulfate were added in sequence, heated to 30°C in a water bath, and reacted for 6 hours under nitrogen protection. After the reaction was completed, the reaction solution was dropped into acetone to precipitate a white precipitate. After filtration, the filter cake was vacuum dried to obtain the phytic acid-based temperature stimulus responsive polymer of this embodiment.
[0048] Example 3
[0049] The difference between this embodiment and embodiment 1 is that the preparation process of step 2) the phytic acid-based temperature-stimulation-responsive polymer is adjusted, specifically:
[0050] In a 500mL three-necked round-bottom flask equipped with a thermometer, an electric stirrer, and a nitrogen conduit, 15.12g PA-GMA, 11.3g N-isopropylacrylamide (NIPAM), 33.8g diacetoneacrylamide (DAAM) and 90.33g distilled water (wherein the molar ratio of PA-GMA, NIPAM and DAAM is 1:10:20) were added, and after stirring and dissolving, nitrogen was passed through for 30min, and then 0.60g sodium bisulfite and 0.60g ammonium persulfate were added in sequence, and the mixture was heated to 30°C in a water bath, and reacted for 6h under nitrogen protection. After the reaction was completed, the reaction solution was dropped into acetone to precipitate a white precipitate, and the filter cake was vacuum dried after suction filtration to obtain the phytic acid-based temperature stimulus responsive polymer of this embodiment.
[0051] Example 4
[0052] The difference between this embodiment and embodiment 1 is that the preparation process of step 2) the phytic acid-based temperature-stimulation-responsive polymer is adjusted, specifically:
[0053] In a 500mL three-necked round-bottom flask equipped with a thermometer, an electric stirrer, and a nitrogen conduit, 15.12g PA-GMA, 11.3g N-isopropylacrylamide (NIPAM), 50.7g diacetoneacrylamide (DAAM) and 115.68g distilled water (wherein the molar ratio of PA-GMA, NIPAM and DAAM is 1:10:30) were added, and after stirring and dissolving, nitrogen was passed through for 30min, and then 0.77g sodium bisulfite and 0.77g ammonium persulfate were added in sequence, and the mixture was heated to 30°C in a water bath, and reacted for 6h under nitrogen protection. After the reaction was completed, the reaction solution was dropped into acetone to precipitate a white precipitate. After suction filtration, the filter cake was vacuum dried to obtain the phytic acid-based temperature stimulus responsive polymer of this embodiment.
[0054] Figure 3 The transmittance of aqueous solutions of phytic acid-based temperature-responsive polymers (samples in Example 4) with different concentrations varies with temperature. It can be seen that the transmittance of aqueous solutions of phytic acid-based temperature-responsive polymers has a significant dependence on concentration. As the concentration increases, the curve moves toward the low temperature direction, the transmittance curve becomes steeper, and the temperature sensitivity increases.
[0055] Figure 4 The light transmittance of a phytic acid-based temperature-responsive polymer (products of Examples 1 to 4) aqueous solution with a concentration of 20% changes with temperature. It can be seen that with the increase in DAAM content, the light transmittance curve of a phytic acid-based temperature-responsive polymer aqueous solution with a concentration of 20% changes with temperature moves toward the high temperature direction. This is because the higher the content of DAAM monomer units in the polymer, the higher the hydrophilic force of the phytic acid-based temperature-responsive polymer. As the force between the phytic acid-based temperature-responsive polymer and water in the aqueous solution increases, greater resistance must be overcome to produce phase separation through hydrophobic association, which means that the temperature must be increased to achieve this, i.e., the lower critical solution temperature (LCST) increases; at the same time, the number of hydrogen bonds formed between the phytic acid-based temperature-responsive polymer molecular chain and the water molecules increases, and the interaction between the hydrophobic groups within and between the polymer molecules weakens, and the LCST becomes higher.
[0056] In summary, the present invention designs and synthesizes a thermosensitive polymer with a novel structure. The raw materials used are cheap and readily available, the synthesis process is simple, and it is green and environmentally friendly. It avoids the use of a large amount of transition metal catalysts and the inadequacy of effective separation and removal after the polymerization reaction, and is easy to produce on an industrial scale. In addition, the response temperature of the phytic acid-based temperature stimulus-responsive star polymer can be adjusted according to the actual application field, and it has the characteristics of high solubility, low crystallinity, small fluid mechanics volume, high-density functional group distribution, and easy surface modification and modification. It has potential application value in water treatment, improving oil recovery, controlling drug release, fluid drag reduction, personal care products, etc.
[0057] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.
Claims
1. A phytic acid-based temperature-stimulation-responsive polymer, characterized in that: It is composed of: a. derived from a repeating unit of a phytic acid multi-arm functional monomer PA-GMA having a structural formula as shown in formula (I); b. a repeating unit of N-isopropylacrylamide NIPAM and diacetoneacrylamide DAAM connected to the terminal C=C double bond of the phytic acid multi-arm functional monomer PA-GMA as shown in formula (I), wherein m and n represent the number of repeating units, and m and n are non-zero integers; c. The molar ratio of the phytic acid multi-arm functional monomer PA-GMA in the repeating unit to the N-isopropylacrylamide NIPAM and diacetoneacrylamide DAAM in the repeating unit is 1:10:5-30.
2. The phytic acid-based temperature-responsive polymer according to claim 1, characterized in that: The polymer is a star polymer PAGMA-sP (NIPAM-co-DAAM).
3. The phytic acid-based temperature-responsive polymer according to claim 1, characterized in that: The polymer is temperature sensitive, and the higher the content of the repeating unit diacetone acrylamide DAAM is, the higher the lower critical solution temperature of the polymer is.
4. A method for preparing a phytic acid-based temperature-responsive polymer as claimed in claim 1, characterized in that: include, After the phytic acid-based multi-arm functional monomer, N-isopropylacrylamide, diacetoneacrylamide and distilled water are stirred and dissolved, nitrogen is passed through for reaction, an initiator is added, and the reaction is heated in a water bath under nitrogen protection. After the reaction is completed, the reaction solution is dropped into acetone to precipitate a white precipitate. After suction filtration, the filter cake is vacuum dried to obtain a phytic acid-based temperature stimulus responsive polymer.
5. The method for preparing a phytic acid-based temperature-responsive polymer according to claim 4, wherein: The reaction time of the nitrogen-passing reaction is 30 to 60 minutes.
6. The method for preparing a phytic acid-based temperature-responsive polymer according to claim 4, wherein: The initiator consists of a water-soluble oxidizing agent and a reducing agent.
7. The method for preparing a phytic acid-based temperature-responsive polymer according to claim 6, wherein: The oxidant includes one or more of potassium persulfate, ammonium persulfate, hydrogen peroxide, etc.; the reducing agent includes one or more of sulfite, bisulfite, ascorbic acid, and pyrosulfite.
8. The method for preparing a phytic acid-based temperature-responsive polymer according to claim 6, wherein: The molar ratio of the oxidant to the reductant in the initiator is >1.
9. The method for preparing a phytic acid-based temperature-responsive polymer according to claim 4, wherein: The glycidyl methacrylate is added dropwise to the mixed solution I for a time of 30 minutes to 3 hours.
10. The method for preparing the phytic acid-based temperature-responsive polymer according to claim 4, characterized in that: The reaction time of the water bath heating reaction is 6 to 12 hours, and the reaction temperature is 20 to 50°C.