A bio-based emulsifier and a method for preparing the same

Abstract

The application discloses a kind of bio-based emulsifier and preparation method thereof, belong to surfactant field.The application uses the root bark acid of biological source and different carbon atom number alcohol as raw material, and ester group structure bio-based alkyl phenol is prepared by simple esterification reaction, and ester group is a functional group that can be chemically hydrolyzed and biodegraded.The application provides that bio-based alkyl phenol formaldehyde resin is obtained by the condensation reaction of the bio-based alkyl phenol with aldehyde, and the synthesis step is simple, and the reaction yield is high.The application also provides that bio-based emulsifier is obtained by the condensation reaction of the bio-based alkyl phenol formaldehyde resin with ethylene oxide, and the bio-based emulsifier is novel in structure, and excellent in emulsifying performance, is a kind of bio-based, green, environmental protection product, has the dual effect of saving petroleum resources and protecting environment.It has important significance to promote the sustainable development of surfactant field.

Description

Technical Field

[0001] This invention belongs to the field of surfactants, and designs a bio-based emulsifier containing a root bark acid structure and its preparation method. Technical Background

[0002] Pesticide emulsifiers, as pesticide synergists, have greatly improved the effectiveness of pesticides, enhanced their biological activity, and reduced dosage, bringing significant benefits to agriculture. It can be said that pesticide emulsifiers play an irreplaceable role in pesticide production and application. my country is a major producer and user of pesticides, with pesticide emulsifiers accounting for approximately 70% of the total pesticide formulation output, making them a crucial component of my country's pesticide industry. Commonly used pesticide emulsifiers are mainly classified into types such as 300#, 500#, 600#, and 700#. Among them, 700#, also known as alkylphenol formaldehyde resin polyoxyethylene ether, is a typical high-molecular-weight pesticide emulsifier with excellent performance. It is suitable as an emulsification performance modifier for organochlorine and organophosphorus pesticides and is a highly effective monomer for herbicide emulsifiers. The synthesis process first involves the polycondensation of alkylphenols, such as nonylphenol (NP) and octylphenol (OP), with aldehydes to generate alkylphenol formaldehyde resin. Then, using KOH as a catalyst, under specific pressure and temperature, it undergoes condensation with ethylene oxide to produce alkylphenol formaldehyde resin polyoxyethylene ether. The preparation route is as follows:

[0003]

[0004] Wherein, R1 is a straight-chain alkyl group with 3-10 carbon atoms, n≥2, m≥10 (n, m are natural numbers).

[0005] Alkylphenols are not easily decomposed in the environment, and because their chemical structure is very similar to that of animal and human estrogen, they can interfere with the normal physiological function of the endocrine system once they enter the human body, thus attracting attention. In particular, after the promulgation of the EU REACH regulation in 2003, alkylphenols such as (NP) and (OP) were listed as restricted substances (J Surfact Deterg. 2024; 27(1): 103-113). With people's increasing attention to the environment and health, green and environmentally friendly surfactants have been valued, and the development of new bio-based surfactants is of great significance. At present, surfactants based on bio-based sources are gradually being developed, such as surfactants based on cashew phenol. Cashew phenol is considered a good alternative to fossil-based alkylphenols (NP and OP) (Materials Science and Engineering 592(2019)012039). However, the side chain of cashew phenol is a mixture of 1-3 unsaturated olefins, which has high activity, is not suitable for storage, and the reaction is difficult to control.

[0006] Phlorenic acid (PA) is a naturally occurring phenolic compound whose synthesis involves enzymatic or chemical treatment of phloretin. A byproduct of apple tree leaves, it has been shown to be a promising bio-based material for preparing advanced polybenzoxazine precursors (Green Chem., 2017, 19, 5065-5073). Research on bio-based surfactants based on the PA structure is largely unreported. PA is a compound containing both carboxyl and phenolic hydroxyl groups, with a propionic acid side chain at the para position suitable for esterification. It can undergo esterification reactions with alcohols of varying carbon numbers to obtain bio-based alkylphenols with ester groups. The ester group is a chemically hydrolyzable and biodegradable functional group, commonly used in a range of biodegradable surfactants (Journal of Colloid and Interface Science 329(2009)153-159). Therefore, this patent aims to construct a novel alkylphenol containing a phlorenic acid structure and, initially, to prepare a bio-based emulsifier containing a phlorenic acid structure using this as a raw material. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a novel class of bio-based alkylphenols, bio-based alkylphenol formaldehyde resins, and bio-emulsifiers containing phloroglucinic acid structures, as well as their preparation methods. The raw materials can be derived from bio-based phloroglucinic acid, and have the advantages of being inexpensive, readily available, having low potential toxicity, and being biodegradable.

[0008] This invention provides a class of bio-based alkylphenols containing a phloroglucinic acid structure, as shown in formula (I):

[0009]

[0010] R2 is a straight-chain or branched alkyl group with 4-16 carbon atoms.

[0011] The specific preparation method of the bio-based alkylphenol of formula (I) prepared in this invention is as follows: phloem acid and alcohol undergo esterification under the action of a catalyst; the reaction solution is then washed three times with a weak alkaline aqueous solution, dried, filtered, and the solvent removed to finally obtain the product. The reaction equation is as follows:

[0012]

[0013] R2 is a straight-chain or branched alkyl group with 4-16 carbon atoms.

[0014] The alcohol is any one of n-butanol, n-pentanol, n-hexanol, 2-ethylbutanol, n-heptanol, n-octanol, isooctanol, n-nonanol, n-decanol, n-undecanol, n-dodecylol, n-tridecylol, n-tetradecylol, n-pentadecanol, and n-hexadecylol.

[0015] The acid may be phosphoric acid, boric acid, sulfonic acid, p-toluenesulfonic acid, hydrochloric acid, or sulfuric acid, with p-toluenesulfonic acid being preferred.

[0016] Preferably, the esterification reaction is carried out under solvent conditions, wherein the organic solvent includes, but is not limited to, any one of toluene, benzene, and cyclohexane.

[0017] The molar ratio of the root bark acid to the alcohol is 1.1:1 to 1.5:1, preferably 1.1:1.

[0018] The catalyst is in a molar ratio of 1:100 to 1:20 with the alcohol, preferably 1:50.

[0019] The washing solution is a 5 wt% sodium bicarbonate aqueous solution.

[0020] This invention provides a class of bio-based alkylphenol formaldehyde resins containing a root bark acid structure, as shown in formula (II):

[0021]

[0022] Where n≥2 (n is a natural number), and R2 is a straight-chain or branched alkyl group with 4 to 16 carbon atoms.

[0023] The specific preparation method of the bio-based alkylphenol formaldehyde resin of formula (II) prepared by the present invention is as follows: the bio-based alkylphenol shown in formula (I) is subjected to a polycondensation reaction with an aldehyde under the action of a catalyst, an organic solvent is added for azeotropic dehydration, the solvent is filtered and removed, and finally the product is obtained.

[0024] The aldehyde can be paraformaldehyde, formaldehyde, acetaldehyde, propionaldehyde, or butyraldehyde, preferably paraformaldehyde.

[0025] The molar ratio of the aldehyde to the bio-based alkylphenol is 1.2:1 to 2:1, preferably 1.5:1.

[0026] The catalyst can be an acid or a base, wherein the acid can be any one of oxalic acid, zinc acetate, hydrochloric acid, sulfuric acid, or stannous octoate, preferably oxalic acid; and the base can be any one of sodium hydroxide, potassium hydroxide, or sodium carbonate, preferably sodium hydroxide.

[0027] The molar ratio of the catalyst to the bio-based alkylphenol is 1:50 to 1:20.

[0028] The polycondensation reaction temperature is 90-110℃.

[0029] The organic solvents include, but are not limited to, any one of toluene, xylene, benzene, n-heptane, and cyclohexane.

[0030] This invention provides a class of bio-based alkylphenol formaldehyde resin polyoxyethylene ethers containing a phloroglucinic acid structure, i.e., bio-based emulsifiers, as shown in formula (III):

[0031]

[0032] Where n≥2, m≥10 (n, m are natural numbers), and R is a straight-chain or branched alkyl group with 4 to 16 carbon atoms.

[0033] The present invention provides a method for preparing a bio-based emulsifier containing a root bark acid structure: by adding the bio-based alkylphenol formaldehyde resin shown in formula (II) and ethylene oxide into a reaction vessel, and under certain conditions, a condensation reaction occurs through the action of a catalyst, and the mixture is kept at a constant temperature and pressure for a period of time to finally obtain the bio-based emulsifier.

[0034] The condensation reaction temperature is 50-80℃.

[0035] The condensation reaction is characterized in that the reaction is carried out under a certain pressure condition, namely 0.2 MPa.

[0036] The catalyst is boron trifluoride ethyl ether, and the molar ratio of bio-based alkylphenol formaldehyde resin to catalyst is 50:1-10:1, preferably 20:1.

[0037] The heat preservation and pressure holding time is 1 hour.

[0038] The molar ratio of the bio-based alkylphenol formaldehyde resin to ethylene oxide is 1:10-1:15, preferably 1:12.

[0039] Beneficial effects:

[0040] (1) The raw material used in this invention is biogenic phloem acid, which has the advantages of being cheap, readily available, green and non-toxic. Bio-based alkylphenols with the structure of formula (I) can be obtained through a simple esterification reaction and can be produced on a large scale using existing chemical equipment.

[0041] (2) The prepared bio-based alkylphenol of formula (I) contains an ester group structure. The ester group is a functional group that can be chemically hydrolyzed and biodegraded, thereby reducing harm to the environment and human body.

[0042] (3) Bio-based alkylphenol-formaldehyde resin with structure (II) can be prepared by reacting bio-based alkylphenols with structure (I) with paraformaldehyde. The synthesis steps of this resin are simple and the reaction yield is high. In addition, the prepared bio-based emulsifier with structure (III) has a novel structure that has not been reported before. It is a bio-based, green, and environmentally friendly product with the dual benefits of saving petroleum resources and protecting the environment. It is of great significance to promoting the sustainable development of the surfactant field. Attached Figure Description

[0043] The embodiments of the present invention will be described in detail with reference to the accompanying drawings, wherein...

[0044] Figure 1 Example 1: Bio-based alkylphenol (PABA) 1 H NMR image

[0045] Figure 2 Example 3: Bio-based alkylphenol (PAHA) 1 H NMR image

[0046] Figure 3 Example 6: Bio-based alkylphenol (PAOA) 1 H NMR image

[0047] Figure 4 Example 7: Bio-based alkylphenol (PAIOA) 1 H NMR image

[0048] Figure 5 Example 8: Bio-based alkylphenol (PANA) 1 H NMR image

[0049] Figure 6 Example 14: Bio-based alkylphenol formaldehyde resin (PAOA-POM) 1 H NMR image

[0050] Figure 7 Example 15: Bio-based alkylphenol formaldehyde resin (PAIOA-POM) 1 H NMR image

[0051] Figure 8 Example 21: Bio-based emulsifier (PAOA-POM-EO) 1 H NMR image

[0052] Figure 9 Example 22: Bio-based emulsifier (PAIOA-POM-EO) 1 H NMR image Detailed Implementation

[0053] Unless otherwise specified, the experimental methods described in the following examples are conventional methods; unless otherwise specified, the reagents and materials are commercially available.

[0054] The 1H NMR spectra involved in the examples were measured using a Bruker Ascend™-400 1H NMR spectrometer, and the deuterated reagent used was deuterated dimethyl sulfoxide (DMSO-d6).

[0055] Example 1

[0056] Preparation of bio-based alkylphenol (PABA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), n-butanol (25.94 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PABA) was obtained in 94% yield. 1 H NMR (500MHz, DMSO-d6) δ7.03 (s, J=7.3, 1.1Hz, 1H), 6.59-6.53 (m, 1H), 4.12 (t, J=4.6Hz, 1H), 2.91 (d, J=8.7 , 7.4Hz, 1H), 2.56 (t, J=8.2Hz, 1H), 1.54 (m, J=7.9, 4.6Hz, 1H), 1.33 (m, J=7.8Hz, 1H), 0.91 (t, J=8.0Hz, 2H).

[0057] Example 2

[0058] Preparation of bio-based alkylphenol PAAA: Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), n-pentanol (30.85 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol PAAA was obtained in 93% yield. 1 H NMR (500MHz, DMSO-d6) δ9.18 (s, 1H), 7.04-6.98 (m, 2H), 6.56 (d, J=7.6Hz, 2H), 4.12 (t, J=7.5Hz, 2H), 2.94-2.8 8 (m, 2H), 2.56 (t, J=5.5Hz, 2H), 1.59 (m, J=7.6Hz, 2H), 1.39 (m, J=8.0, 5.7, 3.6, 2.2Hz, 4H), 0.95-0.85 (m, 3H).

[0059] Example 3

[0060] Preparation of bio-based alkylphenol (PAHA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), n-hexanol (35.76 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed. The reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature. The reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PAHA) was obtained in 93% yield. 1 H NMR (400MHz, DMSO-d6) δ9.16 (s, 1H), 6.99 (d, J = 8.5Hz, 2H), 6.65 (d, J = 8.5Hz, 2H), 3.97 (t, J = 6.6H z, 2H), 3.35 (s, 2H), 2.72 (t, J=7.5Hz, 2H), 1.56-1.46 (m, 2H), 1.25 (d, J=9.9Hz, 6H), 0.84 (s, 3H).

[0061] Example 4

[0062] Preparation of bio-based alkylphenol (PAIHA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), isohexanol (35.76 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PAIHA) was obtained in 88% yield. 1 H NMR (500MHz, DMSO-d6) δ9.18 (s, 1H), 7.05-6.99 (m, 2H), 6.56 (d, J = 7.6Hz, 2H), 3.88 (d, J = 6.9Hz, 2H), 2.94-2.88 (m, 2H), 2.56 (t , J=5.5Hz, 2H), 1.56 (m, J=16.1, 7.6, 3.8Hz, 2H), 1.42 (mJ=19.7, 9.8, 6.9, 3.4Hz, 1H), 1.10-0.97 (m, 2H), 0.95 (t, J=7.7Hz, 6H).

[0063] Example 5

[0064] Preparation of bio-based alkylphenol (PATA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), n-heptanol (40.67 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PATA) was obtained in 87% yield. 1 H NMR (500MHz, DMSO-d6) δ7.03 (dt, J=7.7, 1.2Hz, 1H), 6.59-6.53 (m, 1H), 4.12 (t, J=7.5Hz, 1H), 2.94-2.88 (m, 1H), 2 .56 (t, J=5.5Hz, 1H), 1.60 (p, J=7.7Hz, 1H), 1.47-1.37 (m, 1H), 1.30-1.22 (m, 1H), 1.26 (s, 2H), 0.91-0.83 (m, 1H).

[0065] Example 6

[0066] Preparation of bio-based alkylphenol (PAOA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), n-octanol (45.58 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PAOA) was obtained in 92% yield. 1H NMR (400MHz, DMSO-d6) δ9.10 (s, 1H), 6.91 (d, J = 8.5Hz, 2H), 6.63-6.53 (m, 2H), 3.90 (t, J = 6.6Hz, 2H), 2 .66 (t, J=7.5Hz, 2H), 2.47 (d, J=7.5Hz, 2H), 1.44 (t, J=6.8Hz, 2H), 1.17 (s, 11H), 0.79 (t, J=6.7Hz, 3H).

[0067] Example 7

[0068] Preparation of bio-based alkylphenol (PAIOA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), isooctanol (45.58 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PAIOA) was obtained in 90% yield. 1 H NMR (400MHz, DMSO-d6) δ9.17 (s, 1H), 6.99 (d, J = 8.5Hz, 2H), 6.65 (d, J = 8.5Hz, 2H), 3.90 (d, J = 6 .8Hz, 2H), 3.35 (s, 7H), 2.73 (t, J=7.4Hz, 2H), 1.24 (m, J=14.3, 7.6Hz, 8H), 0.90-0.77 (m, 6H).

[0069] Example 8

[0070] Preparation of bio-based alkylphenol (PANA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), n-nonanol (50.49 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PANA) was obtained in 89% yield. 1H NMR (400MHz, DMSO-d6) δ9.10 (s, 1H), 6.91 (d, J = 8.5Hz, 2H), 6.63-6.53 (m, 2H), 3.90 (t, J = 6.6Hz, 2H), 2 .66 (t, J=7.5Hz, 2H), 2.47 (d, J=7.5Hz, 2H), 1.44 (t, J=6.8Hz, 2H), 1.17 (s, 13H), 0.79 (t, J=6.7Hz, 3H).

[0071] Example 9

[0072] Preparation of bio-based alkylphenol (PADA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), n-decanol (55.39 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PADA) was obtained as a pale yellow transparent liquid with a yield of 86%. 1 H NMR (500MHz, DMSO-d6) δ9.18 (s, 1H), 7.05-6.99 (d, 2H), 6.59-6.53 (d, 2H), 4.12 (t, J=7.5Hz, 2H), 2.91 (d, J=8.6, 7.5Hz, 2H), 2.56 (t, J=8.2Hz, 2H), 1.60 (p, J=7.7Hz, 2H), 1.47-1.37 (m, 2H), 1.35-1.20 (m, 2H), 1.26 (m, 12H), 0.91-0.83 (m, 3H).

[0073] Example 10

[0074] Preparation of bio-based alkylphenol (PADOA): Phloroglucinic acid (63.98 g, 0.385 mol, 1.1 eq.), dodecanol (65.216 g, 0.35 mol, 1 eq.), p-toluenesulfonic acid (1.33 g, 0.0077 mol, 0.02 eq.), and 200 mL of cyclohexane were added to a 500 mL two-necked flask. Water generated during the reaction was collected using a water separator. The mixture was heated in an oil bath at 105 °C until cyclohexane refluxed, and the reaction progress was monitored using thin-layer chromatography. After the reaction was complete, the mixture was cooled to room temperature, and the reaction solution was washed three times with 300 mL of 5 wt% NaHCO3 aqueous solution to remove residual phloroglucinic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Bio-based alkylphenol (PADOA) was obtained as a pale yellow transparent liquid with a yield of 81%.

[0075] Example 11

[0076] Preparation of bio-based alkylphenol formaldehyde resin (PABA-POM): Bio-based alkylphenol (PABA) (44.4 g, 0.2 mol, 1 eq), paraformaldehyde (9 g, 0.3 mol, 1.5 eq), and sodium hydroxide (0.4 g, 0.01 mol, 0.05 eq) were added to a 250 mL two-necked flask. The mixture was heated to 85 °C to allow the paraformaldehyde to gradually dissolve, and the reaction was allowed to proceed for 4 h. The temperature was then raised to 110 °C, and 80 mL of cyclohexane was added and refluxed for 8 h to remove water generated during the reaction. After the reaction was complete, the mixture was cooled to room temperature, the residue was filtered, and the organic phase was collected to remove the solvent. Bio-based alkylphenol formaldehyde resin (PABA-POM) was obtained in 85% yield. The molecular weight was determined to be 1500 by GPC. 1 H NMR (500MHz, DMSO-d6) δ9.68 (s, 1H), 8.09 (s, 5H), 7.26 (s, 1H), 7.02 (t, J=5.0Hz, 1H), 6.9 5(m, J=15.0, 1.9, 1.0Hz, 3H), 6.86 (d, J=1.3Hz, 11H), 6.61 (d, J=7.5Hz, 1H), 4.46 (m, J=4.9 , 0.9Hz, 2H), 4.12 (t, J=7.1Hz, 14H), 3.96 (d, J=1.2Hz, 12H), 2.96-2.88 (m, 14H), 2.56 (t, J =7.1Hz, 14H), 1.54 (m, J = 7.1Hz, 14H), 1.33 (m, J = 7.7, 7.3Hz, 14H), 0.91 (t, J = 8.0Hz, 21H).

[0077] Example 12

[0078] Preparation of bio-based alkylphenol formaldehyde resin (PAHA-POM): Bio-based alkylphenol (PAHA) (50.03 g, 0.2 mol, 1 eq), paraformaldehyde (9 g, 0.3 mol, 1.5 eq), and sodium hydroxide (0.4 g, 0.01 mol, 0.05 eq) were added to a 250 mL two-necked flask. The mixture was heated to 85 °C to allow the paraformaldehyde to gradually dissolve, and the reaction was allowed to proceed for 4 h. The temperature was then raised to 110 °C, and 80 mL of cyclohexane was added and refluxed for 8 h to remove water generated during the reaction. After the reaction was complete, the mixture was cooled to room temperature, the residue was filtered, and the organic phase was collected to remove the solvent. Bio-based alkylphenol formaldehyde resin (PAHA-POM) was obtained, with a yield of 81%.

[0079] Example 13

[0080] Preparation of bio-based alkylphenol formaldehyde resin (PAIHA-POM): Bio-based alkylphenol (PAIHA) (50.03 g, 0.2 mol, 1 eq), paraformaldehyde (9 g, 0.3 mol, 1.5 eq), and sodium hydroxide (0.4 g, 0.01 mol, 0.05 eq) were added to a 250 mL two-necked flask. The mixture was heated to 85 °C to allow the paraformaldehyde to gradually dissolve, and the reaction was allowed to proceed for 4 h. The temperature was then raised to 110 °C, and 80 mL of cyclohexane was added and refluxed for 8 h to remove water generated during the reaction. After the reaction was complete, the mixture was cooled to room temperature, the residue was filtered, and the organic phase was collected to remove the solvent. Bio-based alkylphenol formaldehyde resin (PAIHA-POM) was obtained, with a yield of 79%.

[0081] Example 14

[0082] Preparation of bio-based alkylphenol formaldehyde resin (PAOA-POM): Bio-based alkylphenol (PAOA) (55.68 g, 0.2 mol, 1 eq), paraformaldehyde (9 g, 0.3 mol, 1.5 eq), and sodium hydroxide (0.4 g, 0.01 mol, 0.05 eq) were added to a 250 mL two-necked flask. The mixture was heated to 85 °C to allow the paraformaldehyde to gradually dissolve, and the reaction was allowed to proceed for 4 h. The temperature was then raised to 110 °C, and 80 mL of cyclohexane was added and refluxed for 8 h to remove water generated during the reaction. After the reaction was complete, the mixture was cooled to room temperature, the residue was filtered, and the organic phase was collected to remove the solvent. Bio-based alkylphenol formaldehyde resin (PAOA-POM) was obtained, which was a yellow, transparent, viscous liquid with a yield of 82%. The molecular weight was determined to be 2200 by GPC. 1H NMR (400MHz, DMSO-d6) 69.16 (s, 1H), 7.05 (d, J = 45.6Hz, 2H), 6.65 (d, J = 8.4Hz, 1H), 4.48 (d, J = 30.7Hz, 2H), 3.9 6 (d, J=6.5Hz, 2H), 2.71 (d, J=7.6Hz, 2H), 2.55 (s, 2H), 1.59-1.42 (m, 2H), 1.24 (s, 10H), 0.85 (d, J=7.0Hz, 3H).

[0083] Example 15

[0084] Preparation of bio-based alkylphenol formaldehyde resin (PAIOA-POM): Bio-based alkylphenol (PAIOA) (55.68 g, 0.2 mol, 1 eq), paraformaldehyde (9 g, 0.3 mol, 1.5 eq), and sodium hydroxide (0.4 g, 0.01 mol, 0.05 eq) were added to a 250 mL two-necked flask. The mixture was heated to 85 °C to allow the paraformaldehyde to gradually dissolve, and the reaction was allowed to proceed for 4 h. The temperature was then raised to 110 °C, and 80 mL of cyclohexane was added and refluxed for 8 h to remove water generated during the reaction. After the reaction was complete, the mixture was cooled to room temperature, the residue was filtered, the organic phase was collected, and the solvent was removed. Bio-based alkylphenol formaldehyde resin (PAIOA-POM) was obtained, which was a yellow, transparent, viscous liquid with a yield of 80%. The molecular weight was determined to be 1600 by GPC. 1 H NMR (400MHz, DMSO-d6) δ9.14 (s, 1H), 6.97 (s, 2H), 6.65 (s, 1H), 4.52 (s, 3H), 3. 89(s, 4H), 2.75(s, 3H), 2.56(s, 3H), 1.49(s, 2H), 1.19(s, 10H), 0.79(s, 11H).

[0085] Example 16

[0086] Preparation of bio-based alkylphenol formaldehyde resin (PANA-POM): Bio-based alkylphenol (PANA) (58.44 g, 0.2 mol, 1 eq), paraformaldehyde (9 g, 0.3 mol, 1.5 eq), and sodium hydroxide (0.4 g, 0.01 mol, 0.05 eq) were added to a 250 mL two-necked flask. The mixture was heated to 85 °C to allow the paraformaldehyde to gradually dissolve, and the reaction was allowed to proceed for 4 h. The temperature was then raised to 110 °C, and 80 mL of cyclohexane was added and refluxed for 8 h to remove water generated during the reaction. After the reaction was complete, the mixture was cooled to room temperature, the residue was filtered, the organic phase was collected, and the solvent was removed. Bio-based alkylphenol formaldehyde resin (PANA-POM) was obtained, with a yield of 77%.

[0087] Example 17

[0088] Preparation of bio-based alkylphenol formaldehyde resin (PADOA-POM): Bio-based alkylphenol (PADOA) (66.85 g, 0.2 mol, 1 eq), paraformaldehyde (9 g, 0.3 mol, 1.5 eq), and sodium hydroxide (0.4 g, 0.01 mol, 0.05 eq) were added to a 250 mL two-necked flask. The mixture was heated to 85 °C to allow the paraformaldehyde to gradually dissolve, and the reaction was allowed to proceed for 4 h. The temperature was then raised to 110 °C, and 80 mL of cyclohexane was added and refluxed for 8 h to remove water generated during the reaction. After the reaction was complete, the mixture was cooled to room temperature, the residue was filtered, the organic phase was collected, and the solvent was removed. Bio-based alkylphenol formaldehyde resin (PADOA-POM) was obtained with a yield of 76%.

[0089] Example 18

[0090] Preparation of bio-based emulsifier (PABA-POM-EO): At room temperature, bio-based alkylphenol formaldehyde resin (PABA-POM) (21g) and boron trifluoride diethyl ether catalyst (0.106g) were added to a reactor. The reactor was first purged with nitrogen three times, then evacuated to -0.1 MPa. The vacuum was then closed, and the temperature was raised to 50°C. Ethylene oxide (7.92g) was slowly added. The reaction temperature was 50-70°C, and the pressure did not exceed 0.2 MPa. After the ethylene oxide was added, the temperature was maintained at 70-80°C for aging until the pressure remained constant for 1 hour. Finally, the product was cooled and discharged to obtain the final product.

[0091] Example 19

[0092] Preparation of bio-based emulsifier (PAHA-POM-EO): At room temperature, bio-based alkylphenol formaldehyde resin (PAHA-POM) (22.5g) and boron trifluoride diethyl ether catalyst (0.106g) were added to a reactor. The reactor was first purged with nitrogen three times, then evacuated to -0.1 MPa. The vacuum was then closed, and the temperature was raised to 50°C. Ethylene oxide (7.92g) was slowly added. The reaction temperature was 50-70°C, and the pressure did not exceed 0.2 MPa. After the ethylene oxide was added, the temperature was maintained at 70-80°C for aging until the pressure remained constant for 1 hour. Finally, the product was cooled and discharged to obtain the final product.

[0093] Example 20

[0094] Preparation of bio-based emulsifier (PAIHA-POM-EO): At room temperature, bio-based alkylphenol formaldehyde resin (PAIHA-POM) (22.5g) and boron trifluoride ethyl ether catalyst (0.106g) were added to a reactor. The reactor was first purged with nitrogen three times, then evacuated to -0.1 MPa. The vacuum was then closed, and the temperature was raised to 50°C. Ethylene oxide (7.92g) was slowly added. The reaction temperature was 50-70°C, and the pressure did not exceed 0.2 MPa. After the ethylene oxide was added, the temperature was maintained at 70-80°C for aging until the pressure remained constant for 1 hour. Finally, the product was cooled and discharged to obtain the final product.

[0095] Example 21

[0096] Preparation of bio-based emulsifier (PAOA-POM-EO): At room temperature, add bio-based alkylphenol formaldehyde resin (PAOA-POM) (33g) and boron trifluoride diethyl ether catalyst (0.106g) to a reactor. First, purge with nitrogen three times, then evacuate to -0.1 MPa, close the vacuum, raise the temperature to 50℃ and slowly add ethylene oxide (7.92g). The reaction temperature is 50-70℃ and the pressure does not exceed 0.2 MPa. After adding ethylene oxide, maintain the temperature at 70-80℃ and age until the pressure remains unchanged for 1 hour. Finally, cool down and discharge to obtain the finished product. 1 H NMR (400MHz, DMSO-d6) δ9.15 (s, 1H), 6.98 (s, 1H), 6.66 (s, 1H), 3.98 (t, J=6.6Hz, 2H), 3.57 (s.12H) , 3.52 (s, 28H), 2.73 (s, 2H), 2.56 (dd, J=12.7, 7.5Hz, 2H), 1.52 (s, 2H), 1.25 (s, 10H), 0.86 (s, 3H).

[0097] Example 22

[0098] Preparation of bio-based emulsifier (PAIOA-POM-EO): At room temperature, bio-based alkylphenol formaldehyde resin (PAIOA-POM) (33g) and boron trifluoride diethyl ether catalyst (0.106g) were added to a reactor. The reactor was first purged with nitrogen three times, then evacuated to -0.1 MPa. The vacuum was then closed, and the temperature was raised to 50°C. Ethylene oxide (7.92g) was slowly added. The reaction temperature was 50-70°C, and the pressure did not exceed 0.2 MPa. After the ethylene oxide was added, the temperature was maintained at 70-80°C for aging until the pressure remained constant for 1 hour. Finally, the product was cooled and discharged to obtain the final product. 11H NMR (400 MHz, DMSO-d6) δ 9.14 (s, 1H), 6.99 (s, 2H), 6.65 (s, 2H), 3.89 (s, 3H), 3.51 (s, 30H), 2.73 (s, 3H), 2.55 (q, J = 7.5, 6.5 Hz, 3H), 1.21 (s, 9H), 0.81 (s, 5H).

[0099] Example 23

[0100] Preparation of bio-based emulsifier (PANA-POM-EO): At room temperature, add bio-based alkylphenol formaldehyde resin (PANA-POM) (63 g) and catalyst boron trifluoride etherate (0.21 g) into the reaction kettle. First, displace with nitrogen 3 times, then evacuate to -0.1 Mpa, close the vacuum, heat up to 50 °C and start to slowly add ethylene oxide (15.8 g). The reaction temperature is 50 - 70 °C, and the pressure does not exceed 0.2 Mpa. After adding ethylene oxide, keep the temperature at 70 - 80 °C for aging until the pressure remains unchanged for 1 h. Finally, cool down and discharge to obtain the finished product.

[0101] Example 24

[0102] Preparation of bio-based emulsifier (PADOA-POM-EO): At room temperature, add bio-based alkylphenol formaldehyde resin (PADOA-POM) (84 g) and catalyst boron trifluoride etherate (0.22 g) into the reaction kettle. First, displace with nitrogen 3 times, then evacuate to -0.1 Mpa, close the vacuum, heat up to 50 °C and start to slowly add ethylene oxide (16.2 g). The reaction temperature is 50 - 70 °C, and the pressure does not exceed 0.2 Mpa. After adding ethylene oxide, keep the temperature at 70 - 80 °C for aging until the pressure remains unchanged for 1 h. Finally, cool down and discharge to obtain the finished product.

[0103] Performance detection

[0104] Detection of the performance of bio-based pesticide emulsifiers. According to the "Determination method of pesticide emulsion stability - GB / T 1603-2001", in a 250 mL beaker, add 100 mL of standard hard water at 30 ± 2 °C (prepared according to Method 1 of National Standard 2.2). Use a pipette to absorb an appropriate amount of the emulsion sample and slowly add it to the hard water while stirring continuously to make 100 mL of emulsion. After adding the emulsion, continue to stir at a speed of 2 - 3 r / min for 30 s. Immediately transfer the emulsion to a clean and dry 100 ml graduated cylinder, and place the graduated cylinder in a constant temperature water bath. Let it stand for 1 h within the range of 30 °C ± 2 °C. Take it out and observe the separation of the emulsion. If there is no floating oil (paste), sediment oil and precipitation in the graduated cylinder, it is determined that the emulsion stability is qualified. The test results are as follows:

[0105] Table 1. Separation of the emulsion after standing for 1 h

[0106]

[0107]

[0108] As shown in Table 1, Examples 19 (PAHA-POM-EO), 21 (PAOA-POM-EO), 22 (PAIOA-POM-EO), and 23 (PANA-POM-EO) exhibited good emulsion stability after standing for 1 hour, with no floating oil, settling oil, or precipitation. The results indicate that the emulsion stability is satisfactory. This suggests that bio-based pesticide emulsifiers containing phloroglucinol structures, through structural design, hold promise as a good alternative to pesticide emulsion 700#.

Claims

1. A bio-based emulsifier, characterized in that has a structure as shown in formula (III): wherein n≥2, m≥10, n and m are natural numbers, and R2 is a linear or branched alkyl group with a carbon number of 4-16.

2. A process for the preparation of a bio-based emulsifier as claimed in claim 1, characterized in that, The bio-based alkyl phenol formaldehyde resin is reacted with ethylene oxide under the action of a catalyst to obtain the bio-based emulsifier.

3. The method of producing a bio-based emulsifier according to claim 2, wherein, The molar ratio of the alkyl phenol formaldehyde resin to ethylene oxide is 1:10-1:

15.

4. The method of producing a bio-based emulsifier according to claim 2, wherein, The catalyst is boron trifluoride etherate.

5. The method of producing a bio-based emulsifier according to claim 2, wherein, The molar ratio of the catalyst to the bio-based alkyl phenol formaldehyde resin is 1:50-1:

10.

6. A bio-based alkyl phenol formaldehyde resin, characterized in that, has a structure as shown in formula (II): wherein n≥2, n is a natural number, and R2 is a linear or branched alkyl group with a carbon number of 4-16.

7. A process for the preparation of a bio-based alkyl phenol formaldehyde resin according to claim 6, characterized in that, The bio-based alkyl phenol formaldehyde resin is obtained by esterification of phloretic acid with a fatty alcohol, followed by condensation polymerization of the bio-based alkyl phenol with an aldehyde under the action of a catalyst.

8. The method of producing a bio-based alkylphenol-formaldehyde resin according to claim 7, characterized in that, The fatty alcohol used in the reaction is any one of n-butanol, n-pentanol, n-hexanol, 2-ethylbutanol, n-heptanol, n-octanol, iso-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, or n-hexadecanol.

9. The method of producing a bio-based alkyl phenol formaldehyde resin according to claim 7, wherein The molar ratio of the fatty alcohol to phloretic acid is 1:1.1-1:1.

5.

10. The method of producing a bio-based alkyl phenol formaldehyde resin according to claim 7, wherein The aldehyde used is any one of paraformaldehyde, formaldehyde, acetaldehyde, propyl aldehyde, or butyl aldehyde.

11. The method of producing a bio-based alkyl phenol formaldehyde resin according to claim 7, wherein The molar ratio of the aldehyde to the bio-based alkyl phenol is 1.2:1-2:

1.

12. The method of producing a bio-based alkyl phenol formaldehyde resin according to claim 7, wherein The catalyst used in the reaction is an acid or a base, wherein the acid is any one of oxalic acid, zinc acetate, hydrochloric acid, sulfuric acid, or stannous octoate; and the base is any one of sodium hydroxide, potassium hydroxide, or sodium carbonate.

13. The method of producing a bio-based alkyl phenol formaldehyde resin according to claim 7, wherein The molar ratio of the catalyst to the bio-based alkyl phenol is 1:50-1:20.

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