Bio-based dispersant and preparation method thereof

Abstract

The invention discloses a bio-based dispersant and a preparation method thereof, and belongs to the field of surfactants. According to the preparation method, phloremic acid from a biological source and alcohols with different carbon atom numbers are adopted as raw materials, phloremic acid ester containing an ester group structure is prepared through a simple esterification reaction, and an ester group is a functional group capable of being chemically hydrolyzed and biodegraded. The invention provides the stilbene-based phlorobark acid ester obtained by reacting the phlorobark acid ester with styrene, the synthesis steps are simple, and the reaction yield is high. The invention also provides a bio-based dispersing agent obtained by condensation reaction of the stilbene radical bark acid ester and ethylene oxide, and the bio-based dispersing agent is novel in structure and excellent in dispersing performance, is a bio-based, green and environment-friendly product, and has dual effects of saving petroleum resources and protecting the environment. And the method has important significance for promoting sustainable development in the field of surfactants.

Description

Technical Field

[0001] The invention belongs to the field of surfactants, and in particular relates to a bio-based dispersant containing a phlorotactic acid structure and a preparation method thereof. Technical Background

[0002] As a pesticide synergist, pesticide emulsifiers are used in the field of pesticides to greatly improve the use effect of pesticides, improve the biological activity of pesticides, reduce the amount of pesticides used, and bring huge benefits to agriculture. It can be said that pesticide emulsifiers play an irreplaceable role in the production and application of pesticides. my country is a major country in the production and use of pesticides. Pesticide emulsifiers account for about 70% of the total output of pesticide preparations and are an important part of my country's pesticide industry. Commonly used pesticide emulsifiers are mainly divided into agricultural emulsion 300#, 500#, 600# and 700#, among which agricultural emulsion 600#, also known as styrene phenol polyoxyethylene ether, is a type of non-ionic surfactant with excellent performance and wide application. It has excellent emulsification, temperature viscosity and bactericidal properties, low volatility and stable performance. It is an important component of pesticides, paint emulsifiers, and cleaning agents. The annual domestic demand is more than 10,000 tons. The synthesis process is to first react phenol and styrene with p-toluenesulfonic acid as a catalyst to generate styrylphenol, and then use KOH as a catalyst to condense with ethylene oxide under certain pressure and temperature to generate styrylphenol polyoxyethylene ether. The specific preparation route is as follows:

[0003]

[0004] Phenol is a toxic substance with strong irritation. It can cause damage to the skin, eyes, respiratory tract, etc. Long-term exposure to phenol may also affect the human immune system and reproductive system. Moreover, phenol affects the survival of aquatic organisms and endangers the survival of microorganisms in the soil. It is difficult to degrade in nature and will cause great harm to the environment. At present, the domestic styrenated phenol production process has problems such as low product yield, low trisubstituted content, high cost, serious equipment corrosion, and environmental pollution. In the document with patent publication number CN103880603A, there are problems such as poor heat resistance of the catalyst and easy deactivation, and poor reactivity selectivity of the polystyrenated phenol product. For example, in the document with patent publication number CN106631704A, although the catalytic reaction process is gentle, the phenol conversion rate decreases, impurities and residues reach about 3%, and the content of distyrenated phenol in the product can only be more than 50%, the selectivity of styrenated phenol is low, and the impurity content in the product is high. With people's concern about the environment and health, green and environmentally friendly surfactants are valued, and the development of new bio-based surfactants is of great significance. At present, bio-based surfactants are gradually being developed, using renewable resources as raw materials to improve the biocompatibility and biodegradability of bio-based surfactants. Currently, bio-based surfactants account for 30% of surfactants, and with the future development trend of surfactants, this proportion will increase.

[0005] Phloroglucic acid (p-hydroxyphenylpropionic acid) is a naturally occurring phenolic compound, mainly derived from the peel and root peel of fruits such as apples and pears, and is a promising bio-based material for preparing advanced polybenzoxazine precursors (Green Chem., 2017, 19, 5065-5073). Phloroglucic acid is a compound containing both carboxyl and phenolic hydroxyl groups, and has a propionic acid side chain suitable for esterification in its para position, which can be esterified with alcohols of different carbon atoms to obtain esters containing ester groups. The ester group is a functional group that can be chemically hydrolyzed and biodegraded, and is commonly used in a series of biodegradable surfactants (Journal of Colloid and Interface Science 329 (2009) 153-159). Patent Publication No. CN118684873A shows that a bio-based alkylphenol formaldehyde resin polyoxyethylene ether is prepared using phloroglucic acid from biological sources as a raw material, which has the characteristics of excellent emulsification performance and green environmental protection.

[0006] To this end, this patent aims to construct a new type of distyryl phylloxetate containing a phylloxetine structure, and initially use it as a raw material to prepare a bio-based dispersant containing a phylloxetine structure. Summary of the invention

[0007] In view of the shortcomings of the prior art, the present invention aims to provide a new class of phlorothiol esters, distyryl phlorothiol esters and bio-based dispersants containing phlorothiol structure and their preparation methods. The raw materials can be started from phlorothiol of biological origin, which has the advantages of being cheap, easily available, low potential toxicity and biodegradable.

[0008] The present invention provides a type of phlorothiic acid ester containing a phlorothiic acid structure, as shown in formula (I):

[0009]

[0010] Here, R is a linear or branched alkyl group having 4 to 16 carbon atoms.

[0011] The specific preparation method of the phlorothiolane acid ester of formula (I) prepared by the present invention is: esterification reaction of phlorothiolane acid and alcohol occurs under the action of a catalyst, and then the reaction solution is washed three times with a weak alkaline aqueous solution, and dried, filtered and the solvent is removed to finally obtain the product. The reaction equation is as follows:

[0012]

[0013] Here, R is a linear or branched alkyl group having 4 to 16 carbon atoms.

[0014] The alcohol can be any one of n-butanol, n-pentanol, n-hexanol, 2-ethylbutanol, n-heptanol, n-octanol, isooctyl alcohol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, and n-hexadecanol.

[0015] The acid can be phosphoric acid, boric acid, sulfonic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, preferably p-toluenesulfonic acid.

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

[0017] The molar ratio of phloric acid to alcohol is 1.1:1-1.5:1, preferably 1.2:1.

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

[0019] The washing solution is a 7wt% sodium bicarbonate aqueous solution.

[0020] The present invention provides a type of distyryl phlorothiol ester containing a phlorothiol structure, as shown in formula (II):

[0021]

[0022] Here, R is a linear or branched alkyl group having 4 to 16 carbon atoms.

[0023] The specific preparation method of the distyryl phthalate of formula (II) prepared by the present invention is: reacting the phthalate shown in formula (D) with styrene under the action of a catalyst, then adding triethylamine for neutralization, filtering and removing the solvent, and finally obtaining the product.

[0024] The molar ratio of styrene to phenoxy ester is 2:1-2.5:1, preferably 2.1:1.

[0025] The catalyst is an acid, which can be any one of oxalic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid or stannous octoate, preferably p-toluenesulfonic acid.

[0026] The molar ratio of the catalyst to the phylloxetine acid ester is 1:100-1:50.

[0027] The reaction temperature is 85-120°C.

[0028] The present invention provides a type of distyryl phylloxetate polyoxyethylene ether containing phylloxetate structure, i.e., a bio-based dispersant, such as formula (III):

[0029]

[0030] Wherein, n≥10 (n is a natural number), and R is a straight-chain or branched alkyl group having 4 to 16 carbon atoms.

[0031] The invention provides a method for preparing a bio-based dispersant containing a phlorothiol structure, which comprises the steps of: adding distyryl phlorothiol ester shown in formula (ID) and ethylene oxide into a reaction kettle, causing a condensation reaction under certain conditions by the action of a catalyst, and aging the mixture under heat and pressure for a period of time, and finally obtaining the bio-based dispersant.

[0032] The condensation reaction temperature is 50-80°C.

[0033] The condensation reaction is characterized in that the reaction is carried out under certain pressure conditions, and the pressure is 0.2Mpa.

[0034] The catalyst is boron trifluoride ethyl ether, and the molar ratio of distyryl root pyrophosphate to the catalyst is 50:1-10:1, preferably 20:1.

[0035] The heat preservation and pressure holding time is 1 hour.

[0036] The molar ratio of the distyryl root pyrophosphate to ethylene oxide is 1:10-1:15, preferably 1:12.

[0037] Beneficial effects:

[0038] (1) The raw material used in the present invention is phloric acid of biological origin, which has the advantages of being cheap, readily available, green and non-toxic. The phloric acid ester having the structure of formula (I) can be obtained through a simple esterification reaction, and can be mass-produced using existing chemical equipment.

[0039] (2) The prepared phylloxetine ester of formula (I) contains an ester structure, which is a functional group that can be chemically hydrolyzed and biodegraded, thereby reducing the harm to the environment and human body.

[0040] (3) By reacting the phylloxetate with the structure of formula (I) with styrene, a distyryl phylloxetate with the structure of formula (II) can be prepared, and the synthesis steps are simple and the reaction yield is high. In addition, the prepared bio-based dispersant with the structure of formula (III) has a novel structure, which has not been reported before. It is a bio-based, green, and environmentally friendly product with the dual effects of saving petroleum resources and protecting the environment. It is of great significance to promote the sustainable development of the field of surfactants. BRIEF DESCRIPTION OF THE DRAWINGS

[0041] The embodiments of the present invention are described in detail with reference to the accompanying drawings, wherein

[0042] Figure 1 Example 6: PAOA 1 H NMR spectra;

[0043] Figure 2 Example 7 PAEH 1 H NMR spectra;

[0044] Figure 3 Example 14: Distyryl Root Peel Acid (PAOA-SM) 1 H NMR spectra;

[0045] Figure 4 Example 15: Distyryl Root Peel Acid Ester (PAEH-SM) 1 H NMR spectra;

[0046] Figure 5 Example 21 Distyryl Root Peel Acid Polyoxyethylene Ether (PAOA-SM-EO) 1 H NMR spectra;

[0047] Figure 6 : Fourier transform infrared spectrum of Example 21 distyryl root styrene ester polyoxyethylene ether (PAOA-SM-EO);

[0048] Figure 7 Example 22 Distyryl Root Peel Acid Polyoxyethylene Ether (PAEH-SM-EO) 1 H NMR spectra;

[0049] Figure 8 : Fourier infrared spectrum of Example 22 distyryl root phthalate polyoxyethylene ether (PAEH-SM-EO). DETAILED DESCRIPTION

[0050] The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are commercially available unless otherwise specified.

[0051] The H NMR spectra involved in the examples were measured using a Bruker Ascend TM-400 H NMR spectrometer from Bruker, and the deuterated reagent used was deuterated dimethyl sulfoxide (DMSO-d6); the infrared spectra of the bio-based surfactants were recorded on a Nicolet 5700 Fourier transform infrared spectrometer (Thermo Fisher Scientific Inc., Waltham, MA, USA), and the samples were coated on a 20 mm KBr disk and scanned 32 times (from 4000 to 500 cm -1 ) were analyzed for each sample.

[0052] Example 1

[0053] Preparation of phylloxetine (PABA): 500mL two-necked flask was added with phylloxetine (69.80g, 0-42mol, 1.2eq), n-butanol (25.94g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), and 200mL of cyclohexane. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phylloxetine. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. PABA was obtained with a yield of 91%.

[0054] Example 2

[0055] Preparation of phylloxetate (PAAA): 500mL two-necked flask was added with phylloxetate (69.80g, 0.42mol, 1.2eq), n-pentanol (30.85g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), 200mL of cyclohexane. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phylloxetate. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. PAAA was obtained with a yield of 90%.

[0056] Example 3

[0057] Preparation of phlorothiolane acid ester (PAHA): phlorothiolane acid (69.80g, 0.42mol, 1.2eq), n-hexanol (35.76g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), 200mL of cyclohexane were added to a 500mL two-necked flask. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phlorothiolane acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. phlorothiolane acid ester (PAHA) was obtained with a yield of 89%.

[0058] Example 4

[0059] Preparation of phlorothiolane acid ester (PAIHA): phlorothiolane acid (69.80g, 0.42mol, 1.2eq), isohexanol (35.76g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), 200mL of cyclohexane were added to a 500mL two-necked flask. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phlorothiolane acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. PHlorothiolane acid ester (PAIHA) was obtained with a yield of 88%.

[0060] Example 5

[0061] Preparation of chlorophyll acid ester (PATA): chlorophyll acid (69.80g, 0.42mol, 1.2eq), n-heptanol (40.67g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), 200mL of cyclohexane were added to a 500mL two-necked flask. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual chlorophyll acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. chlorophyll acid ester (PATA) was obtained with a yield of 86%.

[0062] Example 6

[0063] Preparation of phylloxetate (PAOA): 500mL two-necked flask was added with phylloxetate (69.80g, 0.42mol, 1.2eq), n-octanol (45.58g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), 200ml of cyclohexane. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phylloxetate. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. phylloxetate (PAOA) was obtained with a yield of 92%. 1 H NMR (400MHz, DMSO-d6) 69.10 (s, 1H), 6.91 (d, J = 8.5Hz, 2H), 6.59 (d, J = 8.5Hz, 2H), 3.90 (t, J = 6.6Hz, 2H ), 2.66 (t, J=7.5Hz, 2H), 2.47 (d, J=7.6Hz, 2H), 1.51-1.37 (m, 2H), 1.17 (s, 11H), 0.79 (t, J=6.8Hz, 3H).

[0064] Example 7

[0065] Preparation of phylloxetate (PAEH): 500mL two-necked flask was added with phylloxetate (69.80g, 0.42mol, 1.2eq), isooctyl alcohol (45.58g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), 200mL of cyclohexane. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phylloxetate. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. PAEH was obtained with a yield of 90%. 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 (dd, J=14.3, 7.6Hz, 8H), 0.90-0.77 (m, 6H).

[0066] Example 8

[0067] Preparation of phylloxetate (PANA): 500mL two-necked flask was added with phylloxetate (69.80g, 0.42mol, 1.2eq), n-nonanol (50.49g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), 200mL of cyclohexane. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phylloxetate. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. PANA was obtained with a yield of 89%.

[0068] Example 9

[0069] Preparation of phylloxetate (PADA): 500mL two-necked flask was added with phylloxetate (69.80g, 0.42mol, 1.2eq), n-decanol (55.39g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), and 200mL of cyclohexane. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phylloxetate. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. PADA was obtained as a light yellow transparent liquid with a yield of 86%.

[0070] Example 10

[0071] Preparation of phylloxetate (PADOA): 500mL two-necked flask was added with phylloxetate (69.80g, 0.42mol, 1.2eq), dodecanol (65.216g, 0.35mol, 1eq), p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq), cyclohexane 200mL. A water separator was installed to collect the water generated during the reaction, and an oil bath was heated to 105°C to reflux the cyclohexane, and the reaction process was monitored by thin layer chromatography. After the reaction was completed, it was cooled to room temperature, and the reaction solution was washed 3 times with 300mL 7wt% NaHCO3 aqueous solution to remove residual phylloxetate. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Padoxetate (PADOA) was obtained as a light yellow transparent liquid with a yield of 81%.

[0072] Embodiment 11

[0073] Preparation of distyryl benzoate (PABA-SM): Add benzoate (PABA) (22.2g, 0.1mol, 1eq) and p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq) to a 100mL three-necked flask, heat under a nitrogen atmosphere to melt benzoate phenol, and when the temperature reaches 85°C, begin to drop styrene (21.87g, 0.21mol, 2.1eq), maintain the temperature at 85-95°C, and heat to 120°C for 2h after the dropwise addition. After the insulation is complete, add 1.2g of triethylamine to neutralize, stir thoroughly and filter. Start the vacuum pump, adjust the vacuum degree to 0.095Mpa, and the kettle temperature does not exceed 140°C until no liquid evaporates. Cool down to below 80°C to discharge, and finally obtain the product with a yield of 97.3%.

[0074] Example 12

[0075] Preparation of distyryl phthalate (PAHA-SM): phthalate (PAHA) (25.01 g, 0.1 mol, 1 eq) and p-toluenesulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added to a 100 mL three-necked flask, and heated under a nitrogen atmosphere to melt the phthalate. When the temperature reached 85°C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise, and the temperature was maintained at 85-95°C. After the addition was completed, the temperature was raised to 120°C and kept warm for 2 h. After the insulation was completed, 1.2 g of triethylamine was added to neutralize, and the mixture was filtered after sufficient stirring. The vacuum pump was started, and the vacuum degree was adjusted to 0.095 MPa. The kettle temperature did not exceed 140°C until no liquid was evaporated. The material was discharged after cooling to below 80°C, and the product was finally obtained with a yield of 95%.

[0076] Embodiment 13

[0077] Preparation of distyryl phthalate (PAIHA-SM): phthalate (PAIHA) (25.01 g, 0.1 mol, 1 eq) and p-toluenesulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added to a 100 mL three-necked flask, and heated under a nitrogen atmosphere to melt the phthalate. When the temperature reached 85°C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise, and the temperature was maintained at 85-95°C. After the addition was completed, the temperature was raised to 120°C and kept warm for 2 h. After the insulation was completed, 1.2 g of triethylamine was added to neutralize, and the mixture was filtered after sufficient stirring. The vacuum pump was started, and the vacuum degree was adjusted to 0.095 MPa. The kettle temperature did not exceed 140°C until no liquid was evaporated. The temperature was lowered to below 80°C and the product was finally obtained with a yield of 92%.

[0078] Embodiment 14

[0079] Preparation of distyryl oxystyrene ester (PAOA-SM): oxystyrene ester (PAOA) (27.84 g, 0.1 mol, 1 eq) and p-toluenesulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added to a 100 mL three-necked flask, and heated under a nitrogen atmosphere to melt the oxystyrene ester. When the temperature reached 85 ° C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise, and the temperature was maintained at 85-95 ° C. After the addition was completed, the temperature was raised to 120 ° C and kept warm for 2 h. After the insulation was completed, 1.2 g of triethylamine was added to neutralize, and the mixture was filtered after sufficient stirring. The vacuum pump was started, and the vacuum degree was adjusted to 0.095 MPa, and the kettle temperature did not exceed 140 ° C until no liquid was evaporated. The material was discharged below 80 ° C, and the product was finally obtained with a yield of 90%. 1H NMR (400MHz, DMSO-d6) δ8.15 (d, J=17.7Hz, 1H), 7.21 (s, 9H), 7.12 (s, 2H), 6.87 (s, 1H), 6.77 (s, 1H), 4.52 (s, 2H) ), 3.92 (s, 2H), 2.70 (d, J=23.4Hz, 2H), 2.54-2.51 (m, 1H), 2.47 (s, 1H), 1.46 (s, 8H), 1.23 (s, 11H), 0.85 (s, 3H).

[0080] Embodiment 15

[0081] Preparation of distyryl phthalate (PAEH-SM): phthalate (PAEH) (27.84 g, 0.1 mol, 1 eq) and p-toluenesulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added to a 100 mL three-necked flask, and heated under a nitrogen atmosphere to melt the phthalate. When the temperature reached 85 ° C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise, and the temperature was maintained at 85-95 ° C. After the addition was completed, the temperature was raised to 120 ° C and kept warm for 2 h. After the insulation was completed, 1.2 g of triethylamine was added to neutralize, and the mixture was filtered after sufficient stirring. The vacuum pump was started, and the vacuum degree was adjusted to 0.095 MPa. The kettle temperature did not exceed 140 ° C until no liquid was evaporated. The temperature was lowered to below 80 ° C and the material was discharged. Finally, the product was obtained with a yield of 89%. 1 H NMR (400MHz, DMSO-d6) δ8.11 (s, 1H), 7.21 (s, 8H), 7.12 (tt, J=6.7, 1.9Hz, 2H), 6.87 (s, 1H), 6.77 (s, 1H), 4.55 (s, 2H), 3.86 (s , 2H), 2.73 (s, 2H), 2.53 (dd, J=9.3, 6.4Hz, 1H), 2.47 (d, J=7.4Hz, 1H), 1.46 (dd, J=9.7, 7.2Hz, 7H), 1-21 (s, 9H), 0.79 (s, 6H).

[0082] Example 16

[0083] Preparation of distyryl benzoate (PANA-SM): Add benzoate (PANA) (29.22g, 0.1mol, 1eq) and p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq) to a 100mL three-necked flask, heat to melt the benzoate under a nitrogen atmosphere, and when the temperature reaches 85°C, begin to drop styrene (21.87g, 0.21mol, 2.1eq), maintain the temperature at 85-95°C, and heat to 120°C for 2h after the addition is complete. After the insulation is complete, add 1.2g of triethylamine to neutralize, stir well and filter. Start the vacuum pump, adjust the vacuum degree to 0.095Mpa, and the kettle temperature does not exceed 140°C until no liquid evaporates. Cool down to below 80°C to discharge, and finally obtain the product with a yield of 85.5%.

[0084] Embodiment 17

[0085] Preparation of distyryl root styrene ester (PADOA-SM): Add root styrene ester (PADOA) (33.43g, 0.1mol, 1eq) and p-toluenesulfonic acid (0.345g, 0.002mol, 0.02eq) to a 100mL three-necked flask, heat under a nitrogen atmosphere to melt the root styrene ester, and when the temperature reaches 85°C, start to drop styrene (21.87g, 0.21mol, 2.1eq), and maintain the temperature at 85-95°C. After the dropwise addition is completed, the temperature is raised to 120°C and kept warm for 2h. After the insulation is completed, 1.2g of triethylamine is added to neutralize, and the mixture is filtered after sufficient stirring. Start the vacuum pump, adjust the vacuum degree to 0.095Mpa, and the kettle temperature does not exceed 140°C until no liquid evaporates. Cool down to below 80°C to discharge, and finally obtain the product with a yield of 80%.

[0086] Embodiment 18

[0087] Preparation of bio-based dispersant (PABA-SM-EO): Add distyryl root phthalate (PABA-SM) (21g) and catalyst boron trifluoride etherate (0.106g) into the reactor at room temperature, first replace with nitrogen three times, then evacuate to -0.1Mpa, turn off the vacuum, heat to 50°C and slowly add ethylene oxide (7.92g), the reaction temperature is 50-70°C, the pressure does not exceed 0.2Mpa, after adding ethylene oxide, the temperature is maintained at 70-80°C for aging until the pressure does not change for 1h, and finally cool and discharge to obtain the finished product.

[0088] Embodiment 19

[0089] Preparation of bio-based dispersant (PAHA-SM-EO): Add distyryl benzoate (PABA-SM) (23.5 g) and catalyst boron trifluoride etherate (0.106 g) into a reactor at room temperature, first replace with nitrogen three times, then evacuate to -0.1 MPa, turn off the vacuum, raise the temperature to 50°C and slowly add ethylene oxide (7.92 g), the reaction temperature is 50-70°C, the pressure does not exceed 0.2 MPa, after adding ethylene oxide, the temperature is maintained at 70-80°C for aging until the pressure does not change for 1 hour, and finally cool and discharge to obtain the finished product.

[0090] Embodiment 20

[0091] Preparation of bio-based dispersant (PAIHA-SM-EO): Add distyryl root phthalate (PAIHA-SM) (23.5g) and catalyst boron trifluoride etherate (0.106g) into the reactor at room temperature, first replace with nitrogen three times, then evacuate to -0.1Mpa, turn off the vacuum, heat to 50°C and slowly add ethylene oxide (7.92g), the reaction temperature is 50-70°C, the pressure does not exceed 0.2Mpa, after adding ethylene oxide, the temperature is maintained at 70-80°C for aging until the pressure does not change for 1h, and finally cool and discharge to obtain the finished product.

[0092] Embodiment 21

[0093] Preparation of bio-based dispersant (PAOA-SM-EO): Add distyryl root ester (PAOA-SM) (34 g) and catalyst boron trifluoride etherate (0.106 g) into the reactor at room temperature, first replace with nitrogen three times, then evacuate to -0.1 MPa, turn off the vacuum, heat to 50°C and slowly add ethylene oxide (7.92 g), the reaction temperature is 50-70°C, the pressure does not exceed 0.2 MPa, after adding ethylene oxide, the temperature is maintained at 70-80°C for aging until the pressure does not change for 1 hour, and finally cool and discharge to obtain the finished product. 1 H NMR (400MHz, DMSO-d6) δ7.25 (d, J=13.0Hz, 7H), 7.08 (d, J=31.8Hz, 3H), 6.97 (s, 1H), 6.83 (d, J=8.7Hz, 1H), 4.08 (s, 2 H), 3.71 (s, 3H), 3.51 (s, 33H), 2.76 (s, 2H), 2.57 (s, 2H), 1.49 (s, 5H), 1.22 (d, J = 11.7Hz, 9H), 0.84 (d, J = 7.3Hz, 6H).

[0094] The Fourier infrared spectrum of PAOA-SM-EO is shown in Figure 6 As shown in the figure, the characteristic peak of ether bond is 1130cm -1The result showed that the epoxy groups had been successfully introduced into PAOA-SM, indicating that the bio-based dispersant (PAOA-SM-EO) was successfully prepared.

[0095] Embodiment 22

[0096] Preparation of bio-based dispersant (PAEH-SM-EO): Add distyryl root ester (PAEH-SM) (34g) and catalyst boron trifluoride etherate (0.106g) into the reactor at room temperature, first replace with nitrogen three times, then evacuate to -0.1Mpa, turn off the vacuum, heat to 50°C and slowly add ethylene oxide (7.92g), the reaction temperature is 50-70°C, the pressure does not exceed 0.2Mpa, after adding ethylene oxide, the temperature is maintained at 70-80°C for aging until the pressure does not change for 1h, and finally cool and discharge to obtain the finished product. 1 H NMR (400MHz, DMSO-d6) δ7.40-6.76(m, 3H), 4.62-4.41(m, 1H), 4.12-3.63(m, 2H), 3.42-3.21(m, 2H), 2.77( tt, J=8.0, 4.3Hz, 1H), 2.57 (tq, J=8.3, 3.9Hz, 1H), 1.60-1.09 (m, 4H), 0.83 (ddq, J=13.7, 9.8, 6.6Hz, 1H).

[0097] The Fourier infrared spectrum of PAEH-SM-EO is shown in Figure 8 As shown in the figure, the characteristic peak of ether bond is 1130cm -1 It showed that the epoxy groups had been successfully introduced into PAEH-SM, indicating that the bio-based dispersant (PAEH-SM-EO) was successfully prepared.

[0098] Embodiment 23

[0099] Preparation of bio-based dispersant (PANA-SM-EO): Add distyryl root ester (PANA-SM) (65g) and catalyst boron trifluoride etherate (0.106g) into the reactor at room temperature, first replace with nitrogen three times, then evacuate to -0.1Mpa, turn off the vacuum, raise the temperature to 50°C and start to slowly add ethylene oxide (7.92g), the reaction temperature is 50-70°C, and the pressure does not exceed 0.2Mpa. After adding ethylene oxide, the temperature is maintained at 70-80°C for aging until the pressure does not change for 1 hour, and finally cool and discharge to obtain the finished product.

[0100] Embodiment 24

[0101] Preparation of bio-based dispersant (PADOA-SM-EO): Add distyryl root phthalate (PADOA-SM) (92g) and catalyst boron trifluoride etherate (0.106g) into the reactor at room temperature, first replace with nitrogen three times, then evacuate to -0.1Mpa, turn off the vacuum, raise the temperature to 50°C and start to slowly add ethylene oxide (7.92g), the reaction temperature is 50-70°C, the pressure does not exceed 0.2Mpa, after adding ethylene oxide, the temperature is maintained at 70-80°C for aging until the pressure does not change for 1h, and finally cool and discharge to obtain the finished product.

[0102] Performance Testing

[0103] First, a water emulsion of prochloraz containing a bio-based dispersant was prepared according to: 45 g of prochloraz, 22 g of xylene, 4 g of a bio-based dispersant, 0.04 g of xanthan gum, 0.2 g of an organosilicon defoamer, 8 g of propylene glycol, and 20.76 g of deionized water, and a total of 100 g of the water emulsion was obtained by stirring and shearing.

[0104] The dispersibility test of bio-based pesticide dispersants is carried out according to "GB / T 32775-2016 Pesticide Dispersibility Test Method", and the dispersibility test of 45% prochloraz water emulsion is carried out: take water emulsion samples, dilute 20, 100, 200, 1000 times with 30±2℃ standard hard water (according to the standard hard water configuration described in GB / T1603-2001 Pesticide Emulsion Stability Test Method) in a stoppered measuring cylinder, and place it at a constant temperature of 25℃~30℃ for 24h. Use a syringe to slowly drop 1mL of water emulsion into a beaker filled with hard water at a height of 2cm, and observe the natural dispersion and emulsification state of the water emulsion in water to determine the co-emulsification performance index.

[0105] Table 1. Emulsification performance index of water emulsion

[0106] Dispersants Example Dispersed state Emulsified state Rating PABA-SM-EO 18 White particles sink After stirring, it becomes a white transparent emulsion Level 4 PAHA-SM-EO 19 Automatically disperse evenly A little stirring will turn it into a blue translucent emulsion Level 2 PAIHA-SM-EO 20 Dispersed in white cloud or filaments After stirring, it becomes a blue translucent emulsion Level 3 PAOA-SM-EO 21 Automatically disperse evenly A little stirring will turn it into a blue translucent emulsion Level 2 PAEH-SM-EO 22 Automatically disperse evenly at a constant speed Stir slightly to form an egg white emulsion Level 1 PANA-SM-EO 23 Dispersed in white cloud or filaments After stirring, it becomes a blue translucent emulsion Level 3 PADOA-SM-EO 24 White particles sink After stirring, it becomes a white transparent emulsion Level 4

[0107] As shown in Table 1, Examples 19 (PAHA-SM-EO), 21 (PAOA-SM-EO) and 22 (PAIOA-SM-EO) can be automatically and evenly dispersed and stirred to form emulsions, and have good dispersion and emulsification states, and the emulsion dispersion performance is good. The results show that the emulsion dispersibility is qualified. This shows that the bio-based pesticide dispersant containing phlorothiolane structure is expected to become a good substitute for Nongru 600# through structural design.

Claims

1. A bio-based dispersant, characterized in that It has the following structure: Wherein, n≥10 (n is a natural number), and R is a straight-chain or branched alkyl group having 4 to 16 carbon atoms.

2. The bio-based emulsifier of formula (III) as claimed in claim 1 is prepared by reacting distyryl phthalate with ethylene oxide in the presence of a catalyst.

3. The molar ratio of the distyryl phthalate to ethylene oxide as claimed in claim 2 is 1:10-1:15, preferably 1:

12.

4. The catalyst as claimed in claim 2 is boron trifluoride etherate.

5. The molar ratio of the catalyst as claimed in claim 4 to distyryl phthalate is 1:50-1:10, preferably 1:

20.

6. The distyryl phthalate according to claim 2, characterized in that Has the following structure: Here, R is a linear or branched alkyl group having 4 to 16 carbon atoms.

7. The preparation method of the distyryl phthalate as described in claim 6 (ID) is: esterifying phthalic acid with alcohol to obtain phthalate containing ester group, and then reacting it with styrene under the action of catalyst, certain temperature and time to finally obtain distyryl phthalate.

8. The alcohol as claimed in claim 7 can be any one of n-butanol, n-pentanol, n-hexanol, 2-ethylbutanol, n-heptanol, n-octanol, isooctyl alcohol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol and n-hexadecanol.

9. The molar ratio of styrene to phylloxetine as claimed in claim 7 is 2:1-2.5:1, preferably 2.1:

1.

10. The catalyst as claimed in claim 7 is p-toluenesulfonic acid, the reaction temperature is 85-120°C, and the reaction time is 7 hours.

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