Polyterpene itaconic acid polyethylene glycol ester polymer as well as preparation method and application thereof
By synthesizing a polyterpene itaconic acid polyethylene glycol ester polymeric emulsifier using industrial dipentene and bio-based itaconic acid, the ecological and economic problems of petroleum-based emulsifiers are solved, achieving high surface activity and good emulsifying performance, making it suitable for the daily chemical and pesticide fields.
Patent Information
- Application Number
- CN202510610737.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-13
- Publication Date
- 2025-08-19
AI Technical Summary
Most existing emulsifiers rely on petroleum-based raw materials, leading to ecological and economic problems. Furthermore, traditional emulsifiers have poor biodegradability, making it difficult to meet the sustainability requirements of green chemistry.
A polyterpene itaconic acid polyethylene glycol emulsifier was synthesized using industrial dipentene and bio-based itaconic acid as raw materials under solvent-free and catalyst-free conditions. It was prepared through DA reaction and esterification reaction, achieving high surface activity and good emulsifying performance.
The prepared emulsifier has excellent emulsifying properties, good biocompatibility, and high biodegradability, making it suitable for the daily chemical and pesticide fields and meeting the sustainability requirements of green chemistry.
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Figure CN120504827A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to a polyterpene itaconate polyethylene glycol polymer, a preparation method and application thereof, and belongs to the technical field of green emulsifiers. Background Art
[0002] In the surfactant sector, global dependence on petrochemical raw materials has led to serious ecological and economic challenges. According to statistics, approximately 75% of commercial emulsifiers are still made from petroleum-based raw materials, whose non-renewable nature makes them incompatible with the current "dual carbon" strategy. Against this backdrop, the development of new emulsifiers that are both environmentally friendly and economically viable has become a key area of breakthrough for the industry.
[0003] This invention uses industrial dipentene as its core raw material. This byproduct of turpentine distillation is chemically modified to form the main structure of a polymer emulsifier, achieving value-added utilization of waste resources. It also innovatively incorporates bio-based itaconic acid as a functional monomer. This substance can be extracted through fermentation of agricultural waste, such as corncobs. Derived from renewable plant resources, it meets the green chemistry requirement for sustainable raw materials.
[0004] The raw materials for the polyterpene itaconate polyethylene glycol ester polymer emulsifier of the present invention are all derived from natural products, which are inexpensive, readily available, and economically profitable. Because the emulsifier uses natural product raw materials, it has good biocompatibility, meeting the green chemistry demand for sustainable raw materials. Its biodegradability is far higher than that of traditional petroleum-based products, demonstrating significant competitive advantages in high-end fields such as pesticide sustained-release and cosmetics. This innovative strategy of integrating by-product resource utilization, bio-based raw material functionalization, and performance optimization provides a new path for the green transformation of the surfactant industry. Summary of the Invention
[0005] The present invention aims to provide a polyterpene itaconate polyethylene glycol ester polymer, a preparation method, and uses thereof. The present invention uses dipentene, an industrial byproduct, and bio-based itaconic acid as raw materials. The dipentene and itaconic acid react in the absence of solvents or catalysts to produce a terpene adduct, which is then reacted with polyethylene glycol to produce a polyterpene itaconate polyethylene glycol ester polymer emulsifier. This emulsifier exhibits high surface activity and excellent emulsifying properties, is readily available from inexpensive raw materials, and is environmentally friendly.
[0006] In order to solve the above technical problems, the technical solutions adopted by the present invention are as follows:
[0007] A polyterpene itaconate polyethylene glycol polymer, the structural formula of which is:
[0008] Where n is 8 to 14.
[0009] The above-mentioned polyterpene itaconate polyethylene glycol ester polymer is made from low-cost, renewable industrial dipentene and itaconic acid, and has excellent emulsification properties, realizing the high added value transformation of green and low-cost raw materials.
[0010] The molecular weight of the polyterpene itaconate polyethylene glycol ester polymer is in the range of 2329-6797, the surface tension is ≤34.1 mN / m, and the critical micelle concentration is ≤2.5 mg / L.
[0011] The above-mentioned polyterpene itaconic acid polyethylene glycol ester polymer uses raw materials including industrial dipentene, itaconic acid and polyethylene glycol. During preparation, no solvent and catalyst are required, and the preparation is simple and environmentally friendly.
[0012] To ensure emulsification performance, the molecular weight of the polyethylene glycol is any one of 200, 400, 600, 800, and 1000. Polyethylene glycol 400 is more preferred. The inventors discovered during research and development experiments that when the molecular weight of polyethylene glycol is too low, the surface activity decreases. However, in this application, the molecular weight of polyethylene glycol is not necessarily better. When the molecular weight of polyethylene glycol exceeds 600, the surface activity tends to decrease. When the molecular weight exceeds 1000, the polyethylene glycol becomes gel-like, further reducing the surface activity.
[0013] The molecular weights not specifically stated in this application are all number average molecular weights.
[0014] The preparation method of the polyterpene itaconate polyethylene glycol ester polymer is to react industrial dipentene with itaconic acid to produce DA, and then react with polyethylene glycol to produce the product; the reaction process is solvent-free and catalyst-free.
[0015] In order to ensure the product yield and performance, as one of the preferred embodiments, the preparation of polyterpene itaconate polyethylene glycol ester polymer is prepared by a one-pot method, without adding solvent or catalyst during the reaction process, including the following steps:
[0016] S1, itaconic acid and industrial dipentene, react at a temperature of 150-190°C for 2-4 hours, until the acid value reaches about 400 mgKOH / g, to obtain terpene itaconic acid adduct (DI);
[0017] S2, the terpene itaconic acid adduct and polyethylene glycol are reacted at a temperature of 230-270° C. for 6-9 hours, and the acid value is lower than 20 mgKOH / g to obtain a polyterpene itaconic acid polyethylene glycol ester polymer emulsifier (DIP).
[0018] In the above steps S1 and S2, no solvent or catalyst needs to be added.
[0019] In step S1, the reaction temperature is selected from, for example, 150°C, 160°C, 170°C, 180°C, etc., and the reaction time is selected from, for example, 2h, 3h, 4h, etc.; in step S2, the reaction temperature is selected from, for example, 240°C, 250°C, 260°C, 270°C, etc., and the reaction time is selected from, for example, 6h, 7h, 8h, 9h, etc.
[0020] In the above step S1, the molar ratio of itaconic acid to industrial dipentene is (0.5-2):1, for example, the ratio is 0.5:1, 1:1, 2:1, etc.
[0021] In the above step S2, the molar ratio of the hydroxyl group in the polyethylene glycol to the carboxyl group in the terpene itaconic acid adduct is (1-3):1, for example, 1:1, 2:1, 3:1, etc.
[0022] The polyterpene itaconate polyethylene glycol ester polymer has beneficial emulsifying properties and can be used as an emulsifier, having a good emulsifying effect on emulsifying toluene, xylene, mixed terpinene or tea tree essential oil.
[0023] Tea tree oil is a pure, natural plant essential oil extracted from Melaleuca alternifolia by steam distillation. It is a colorless to pale yellow liquid with a distinctive aroma, and its main component is 4-terpineol.
[0024] The overall molecule of the above-mentioned polyterpene itaconate polyethylene glycol ester polymer emulsifier has both the pH universality of a non-ionic surfactant and the shear stability of a high molecular polymer, and can maintain stable emulsification properties in multiple environments.
[0025] % in this application are all mass percentages unless otherwise specified.
[0026] The technologies not mentioned in this invention are all referred to the prior art.
[0027] The present invention has the following beneficial effects:
[0028] 1. The polyterpene itaconate polyethylene glycol ester polymer of the present invention can be used as an emulsifier and has good surface activity, with a critical micelle concentration of ≤2.5 mg / L and a surface tension of ≤34.1 mN / m.
[0029] 2. The polyterpene itaconate polyethylene glycol ester polymer of the present invention is prepared by a one-pot method, which is synthesized through DA addition and esterification reaction. The preparation process is simple and solvent-free and catalyst-free.
[0030] 3. The present invention uses industrial by-product dipentene and bio-based itaconic acid as raw materials, combining resource recycling and renewable characteristics. Itaconic acid is introduced into the emulsifier. The emulsifier has good biocompatibility, excellent emulsification performance, and the raw materials are cheap and easily available. It is suitable for the fields of daily chemicals, pesticides and industrial emulsification. BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Figure 1 This is the infrared spectrum of the polyterpene itaconate polyethylene glycol ester polymer emulsifier product (DIP) obtained in Example 1;
[0032] Figure 2 This is a surface tension curve of the polyterpene itaconate polyethylene glycol ester polymer emulsifier product (DIP) obtained in Example 1;
[0033] Figure 3 This is a surface tension curve of the polyterpene itaconate polyethylene glycol ester polymer emulsifier product (DIP) obtained in Example 2;
[0034] Figure 4 This is the gel permeation chromatogram of the polyterpene itaconate polyethylene glycol ester polymer emulsifier product (DIP) obtained in Example 1;
[0035] Figure 5 This is the gel permeation chromatogram of the polyterpene itaconate polyethylene glycol ester polymer emulsifier product (DIP) obtained in Example 2; DETAILED DESCRIPTION
[0036] To better understand the present invention, the following examples further illustrate the present invention, but the present invention is not limited to the following examples. Unless otherwise specified, the raw materials and reagents used in the examples are commercially available. Experimental methods without specific conditions in the examples are generally performed according to conventional conditions in the art or according to the conditions recommended by the manufacturer.
[0037] In each case, the temperature was not specifically stated, and the reaction was carried out at room temperature (15-25° C.). In each case, the stirring speed was 200 r / min, and the stirring speed was 200 r / min.
[0038] Example 1
[0039] Preparation of polyterpene itaconate polyethylene glycol polymer emulsifier:
[0040] 142.8 g of industrial dipentene (from Fujian Senmeida Biotechnology Co., Ltd., containing 90% dipentene and 9.72% p-cymene, with the remainder being impurities such as carene and camphene, the rest being the same) and 273 g of itaconic acid were respectively weighed and poured into a 1000 mL four-necked flask. The mixture was heated to 170° C. and stirred to fully react for 2 h, until the acid value reached 400 mg KOH / g, thereby obtaining a terpene itaconic acid adduct (DI). 440 g of polyethylene glycol 400 was then added, the temperature was raised to 250° C., and the reaction was continued for 8 h until the acid value was less than 20 mg KOH / g. The mixture was then cooled to room temperature to obtain a polyterpene itaconic acid polyethylene glycol ester polymer emulsifier product (DIP-400).
[0041] Example 2
[0042] 142.8g of industrial dipentene (Fujian Senmeida Biotechnology Co., Ltd.) and 273g of itaconic acid were weighed separately and poured into a 1000mL four-necked flask. The mixture was heated to 170°C and stirred to fully react for 2 hours until the acid value reached 400mgKOH / g, yielding terpene itaconic acid adduct (DI). 660g of polyethylene glycol 600 was then added, heated to 250°C, and reacted for 8 hours until the acid value dropped below 20mgKOH / g. The mixture was then cooled to room temperature to yield the polyterpene itaconic acid polyethylene glycol ester polymer emulsifier product (DIP-600).
[0043] Example 3
[0044] IR spectrum identification of product DIP-400 (such as Figure 1 ): 3476cm -1 The characteristic peak of the stretching vibration of the binary ring =CH, 2868cm -1 The absorption peak of methylene -CH2- is 1732 cm -1 Characteristic absorption peak of ester group, 1110 cm -1 The absorption peak is the alcohol-ether bond -COC-. The carboxyl peak disappears in the infrared spectrum, while the ester peak appears. DIP-600 was identified using the same method, and the results were consistent with those for DIP-400, so this will not be repeated here. Further structural characterization by NMR confirmed that the product was a polyterpene itaconate polyethylene glycol ester polymer emulsifier with the correct structure.
[0045] Example 4
[0046] Emulsification performance test: Prepare a DIP-400 aqueous solution with a mass fraction of 0.1%, and take three 40 mL portions and place them in 100 mL stoppered measuring cylinders, then add 40 mL of toluene respectively, shake it up and down vigorously 50 times, let it stand, and record the time required for each stoppered measuring cylinder to separate 10 mL of aqueous phase. This process was repeated 3 times, and the average value was 60 seconds. Under the same operation, toluene was replaced with p-xylene, and it took 75 seconds for the stoppered measuring cylinder to separate 10 ml of water. Toluene was replaced with refined tea tree oil (Fujian Senmeida Biotechnology Co., Ltd., 4-terpineol in tea tree oil ≥40%, the same as in other cases), and it took 2.5 hours to separate 10 ml of aqueous phase, indicating that the emulsifier has good emulsification performance.
[0047] The same method was used to test the emulsification performance of DIP-600. The time to separate 10 mL of aqueous phase from toluene was 35 seconds, the time to separate 10 mL of aqueous phase from xylene was 50 seconds, and the time to separate 10 mL of aqueous phase from refined tea tree oil was 1.5 hours.
[0048] Example 5
[0049] The surface tension was measured using the platinum plate method. A 10% DIP aqueous solution was prepared and 20 ml of the sample was taken for surface tension testing at room temperature. The sample was then gradually diluted and tested until the surface tension reached 70 mN / m. The results showed that the critical micelle concentration of DIP-400 was 2.5 ± 0.3 mg / L; the surface tension was 34.1 ± 0.5 mN / m (e.g. Figure 2 ), indicating that the emulsifier has good surface activity. Under the same conditions, DIP-600 did not find the critical micelle concentration (such as Figure 3 ), indicating that the surface activity of DIP-600 is worse than that of DIP-400.
[0050] Example 6
[0051] Molecular weight distribution test: The molecular weight of DIP can be obtained by gel permeation chromatography analysis. The weight average molecular weight of DIP-400 is 3446 g / mol (such as Figure 4 ), DIP-600 has a weight average molecular weight of 4563 g / mol (such as Figure 5 ).
[0052] Example 7
[0053] Polyterpene itaconic acid polyethylene glycol emulsifier is a terpene emulsifier. Dipentene reacts with itaconic acid through a DA reaction to form an itaconic acid adduct. This adduct has a rigid cyclic structure. Further reaction with polyethylene glycol preserves this rigid cyclic structure, resulting in a rigid, hydrophobic cyclic structure. Compared to other linear emulsifiers, this polyterpene itaconic acid polyethylene glycol emulsifier exhibits superior emulsification for essential oil preparations with similar cyclic structures. This is particularly effective for specific pesticides and essential oils with rigid cyclic structures.
[0054] Comparative Example 1
[0055] Pour 273 g of itaconic acid into a 1000 mL four-necked flask, add 440 g of polyethylene glycol 400, heat to 250°C, react for 8 h, and cool to room temperature until the acid value is less than 20 mgKOH / g to obtain polyterpene itaconic acid polyethylene glycol ester. Emulsification properties were tested using the method of Example 4. The time required to separate 10 ml of aqueous phase from the refined tea tree oil was 30 min.
[0056] Comparative Example 2
[0057] Pour 273 g of itaconic acid into a 1000 mL four-necked flask, add 660 g of polyethylene glycol 600, heat to 250°C, react for 8 h, and cool to room temperature until the acid value is less than 20 mgKOH / g to obtain polyterpene itaconic acid polyethylene glycol ester. Emulsification properties were tested using the method of Example 4. The time required to separate 10 ml of aqueous phase from the refined tea tree oil was 20 min.
[0058] Comparative Example 3
[0059] Weigh 142.8g of industrial dipentene and 273g of itaconic acid into a 1000mL four-necked flask. Heat to 170°C and stir to allow for a complete reaction. Allow to react for 2 hours until the acid value reaches 400mgKOH / g, yielding terpene itaconic acid adduct (DI). This product has no surface activity and cannot be used as an emulsifier.
Claims
1. A polyterpene itaconate polyethylene glycol polymer, characterized in that: Its structural formula is: Where n is 8 to 14.
2. The polyterpene itaconate polyethylene glycol polymer according to claim 1, characterized in that: Its molecular weight range is 2329-6797 g / mol, surface tension ≤34.1 mN / m, and critical micelle concentration ≤2.5 mg / L.
3. The polyterpene itaconate polyethylene glycol polymer according to claim 1 or 2, characterized in that: The raw materials used include industrial dipentene, itaconic acid and polyethylene glycol, and no solvent or catalyst is required.
4. The polyterpene itaconate polyethylene glycol polymer according to claim 3, characterized in that: The molecular weight of polyethylene glycol is any one of 200, 400, 600, 800, and 1000.
5. A method for preparing the polyterpene itaconate polyethylene glycol polymer according to any one of claims 1 to 4, characterized in that: It is produced by the DA reaction of industrial dipentene and itaconic acid, followed by esterification with polyethylene glycol; the reaction process is solvent-free and catalyst-free.
6. The preparation method according to claim 5, characterized in that The one-pot method is used for preparation, and no solvent or catalyst is required during the reaction process, which includes the following steps: S1, itaconic acid and industrial dipentene, react at a temperature of 150-190°C for 2-4 hours to obtain a terpene itaconic acid adduct; S2, reacting the terpene itaconic acid adduct with polyethylene glycol at a temperature of 230-270° C. for 6-9 hours to obtain a polyterpene itaconic acid polyethylene glycol ester polymer emulsifier.
7. The preparation method according to claim 6, characterized in that In step S1, the molar ratio of itaconic acid to industrial dipentene is (0.5-2):
1.
8. The preparation method according to claim 6 or 7, characterized in that In step S2, the molar ratio of the hydroxyl group in the polyethylene glycol to the carboxyl group in the terpene itaconic acid adduct is (1-3):
1.
9. Use of the polyterpene itaconate polyethylene glycol polymer according to any one of claims 1 to 4, characterized in that: Used as an emulsifier.
10. The use according to claim 9, characterized in that Used to emulsify toluene, xylene, mixed terpinene or tea tree oil.