A bio-based dispersant and a method of making the same

Abstract

The application discloses a kind of bio-based dispersant 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 is prepared by simple esterification reaction and obtained from root bark acid ester, and ester group is a functional group that can be chemically hydrolyzed and biodegraded.The application provides that by the reaction of the root bark acid ester with styrene, the stilbene group root bark acid ester is obtained, the synthesis step is simple, and the reaction yield is high.The application also provides that by the condensation reaction of the stilbene group root bark acid ester with ethylene oxide, the bio-based dispersant is obtained, the bio-based dispersant is novel in structure, and excellent in dispersing 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 in the field of surfactant.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of surfactants, and particularly relates to a bio-based dispersant containing phloretic acid structure and a preparation method thereof. BACKGROUND

[0002] Pesticide emulsifiers, as a kind of pesticide synergist, are applied in the field of pesticides to greatly improve the use effect of pesticides, improve the biological activity of pesticides, reduce the amount of pesticides, and bring great benefits to agriculture. It can be said that the pesticide emulsifier plays an irreplaceable role in the production and application of pesticides. China is a big country in pesticide production and use, and the pesticide emulsifier accounts for about 70% of the total pesticide preparation output, which is an important part of China's pesticide industry. The commonly used pesticide emulsifiers are mainly divided into pesticide emulsifier 300#, 500#, 600# and 700# etc., among which the pesticide emulsifier 600# is also called styryl phenol polyoxyethylene ether, which is a kind of non-ionic surfactant with excellent performance and wide application. It has excellent emulsifying property, warm viscosity and bactericidal property, and low volatility, stable performance, and is an important component of pesticide, coating emulsifier and cleaning agent products, and the annual demand in China is more than ten thousand tons. The synthesis process is to first react phenol and styrene with p-toluenesulfonic acid as catalyst to generate styryl phenol, and then to generate styryl phenol polyoxyethylene ether by condensation with ethylene oxide under certain pressure and temperature with KOH as catalyst. The specific preparation route is as follows:

[0003]

[0004] Phenol is a toxic substance with strong irritant. It can cause damage to the skin, eyes, respiratory tract, etc. Long-term exposure to phenol can also affect the human immune system and reproductive system. Moreover, phenol can affect the survival of aquatic organisms and endanger the survival of soil microorganisms, and is difficult to degrade in nature, causing great harm to the environment. The current domestic styrene phenol production process has problems such as low product yield, low content of tri-substituted product, high cost, serious equipment corrosion, and environmental pollution. The document with patent publication number CN103880603A has problems such as poor heat resistance of the catalyst, easy deactivation, and poor reactivity selectivity of the multi-styrene phenol product. For example, the document with patent publication number CN106631704A has a smooth catalytic reaction process, but the phenol conversion rate decreases, the impurities and residues reach about 3%, and the content of diphenyl styrene phenol in the product is only more than 50%, the selectivity of styrene phenol is low, and the impurity content in the product is high. With people's attention to 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 developing, and by using renewable resources as raw materials, the biocompatibility and biodegradability of bio-based surfactants are improved. At present, bio-based surfactants have accounted for 30% of surfactants, and with the future development trend of surfactants, this proportion will continue to increase.

[0005] Phloretic acid (p-hydroxyphenylpropionic acid) is a naturally occurring phenolic compound, mainly derived from the peels of fruits such as apples and pears, and is a promising bio-based material for the preparation of advanced polybenzoxazine precursors (Green Chem., 2017, 19, 5065-5073). Phloretic acid is a compound containing both carboxyl and phenolic hydroxyl groups, with a suitable propionic acid side chain at the para position for esterification, which can undergo esterification with alcohols of different carbon atom numbers to obtain phloretic acid esters containing ester groups. Ester groups are a functional group that can be chemically hydrolyzed and biodegraded, commonly used in a series of biodegradable surfactants (Journal of Colloid and Interface Science 329 (2009) 153-159). The patent publication number CN118684873A discloses a bio-based alkyl phenol formaldehyde resin polyoxyethylene ether prepared from bio-based phloretic acid as raw material, which has excellent emulsifying performance and is green and environmentally friendly.

[0006] Therefore, the present patent aims to construct a novel diphenyl styrene phloretic acid ester containing phloretic acid structure, and preliminarily prepare a bio-based dispersant containing phloretic acid structure using the same as raw material. SUMMARY

[0007] In view of the deficiencies of the prior art, the present application aims to provide a new class of phloroglucinol esters, stilbene phloroglucinol esters and bio-based dispersants containing phloroglucinol structure and a preparation method thereof, which can be prepared from bio-based phloroglucinol, and have the advantages of low cost, low potential toxicity and biodegradability.

[0008] The present application provides a class of phloroglucinol esters containing phloroglucinol structure, as shown in formula (I):

[0009]

[0010] In the formula, R is a linear or branched alkyl group with a carbon number of 4-16.

[0011] The specific preparation method of the phloroglucinol ester of formula (I) prepared by the present application is: phloroglucinol and alcohol are subjected to esterification reaction under the action of a catalyst, then the reaction liquid is washed with a weak alkali aqueous solution for three times, and then dried, filtered and solvent-removed to obtain the product.

[0012]

[0013] In the formula, R is a linear or branched alkyl group with a carbon number of 4-16.

[0014] The alcohol can be 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 and n-hexadecanol.

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

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

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

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

[0020] The present application provides a class of stilbene phloroglucinol esters containing phloroglucinol structure, as shown in formula (II):

[0021]

[0022] In the formula, R is a linear or branched alkyl group with a carbon number of 4-16.

[0023] The specific preparation method of the stilbene phloretate prepared in the present application is as follows: reacting the phloretate 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 the styrene and the phloretate 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, and is preferably p-toluenesulfonic acid.

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

[0027] The reaction temperature is 85-120℃.

[0028] The present application provides a kind of stilbene phloretate polyoxyethylene ether containing phloretate structure, i.e. bio-based dispersant, as shown in formula (III):

[0029]

[0030] Wherein, n≥10 (n is a natural number), R is linear or branched alkyl with carbon number 4 to 16.

[0031] The present application provides a preparation method of bio-based dispersant containing phloretate structure: by adding stilbene phloretate shown in formula (ID) and ethylene oxide into a reaction kettle, condensation reaction occurs under the action of a catalyst under certain conditions, and aging for a period of time, finally obtaining bio-based dispersant.

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

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

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

[0035] The holding time is 1h.

[0036] The molar ratio of stilbene phloretate to ethylene oxide is 1:10-1:15, preferably 1:12.

[0037] Beneficial effects:

[0038] (1) The raw material used in the present application is a biologically derived phloretic acid, which has the advantages of being cheap, easy to obtain, green and non-toxic. The phloretic acid ester with the structure of formula (I) is obtained through a simple esterification reaction, and can be produced on a large scale using existing chemical equipment.

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

[0040] (3) The phloretic acid ester with the structure of formula (I) can be reacted with styrene to prepare the distyryl phloretic acid ester with the structure of formula (II), which has a simple synthesis step and a high reaction yield. In addition, the prepared bio-based dispersant with the structure of formula (III) is novel, and this structure has not been reported before. It is a bio-based, green and environmentally friendly product, which has the dual effects of saving petroleum resources and protecting the environment. It has important significance for promoting the sustainable development of the surfactant field. BRIEF DESCRIPTION OF DRAWINGS

[0041] The embodiments of the present application will be described in detail with reference to the accompanying drawings, in which

[0042] Figure 1 : H NMR chart of phloretic acid ester (PAOA) of Example 6 1

[0043] Figure 2 : H NMR chart of phloretic acid ester (PAEH) of Example 7 1

[0044] Figure 3 : H NMR chart of distyryl phloretic acid ester (PAOA-SM) of Example 14 1

[0045] Figure 4 : H NMR chart of distyryl phloretic acid ester (PAEH-SM) of Example 15 1

[0046] Figure 5 : H NMR chart of distyryl phloretic acid ester polyoxyethylene ether (PAOA-SM-EO) of Example 21 1

[0047] Figure 6 : Fourier infrared spectrum of distyryl phloretic acid ester polyoxyethylene ether (PAOA-SM-EO) of Example 21

[0048] Figure 7 : H NMR chart of distyryl phloretic acid ester polyoxyethylene ether (PAEH-SM-EO) of Example 22 1 H NMR chart of distyryl phloretic acid ester polyoxyethylene ether (PAEH-SM-EO) of Example 22​​​​​

[0049] Figure 8 Figure 22 Fourier transform infrared spectrum of diphenylstyrene phloretate 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 nuclear magnetic resonance hydrogen spectrum involved in the examples was determined by using a Bruker Ascend™-400 nuclear magnetic resonance hydrogen spectrometer of Bruker Company (Bruker). The deuterated reagent used was deuterated dimethyl sulfoxide (DMSO-d6). The infrared spectrum of the biosurfactant was recorded on a Nicolet 5700 Fourier infrared spectrometer (Thermo Fisher Scientific Inc., Waltham, MA, USA), the sample was coated on a 20 mm KBr disc, and 32 scans (from 4000 to 500 cm -1 ) were used to analyze each sample.

[0052] Example 1

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

[0054] Example 2

[0055] Preparation of phloretic acid ester (PAAA): A 500 mL two-necked flask was charged with phloretic acid (69.80 g, 0.42 mol, 1.2 eq), n-pentanol (30.85 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL of cyclohexane. A water trap was attached to collect the water generated during the reaction. The reaction was heated to reflux by an oil bath at 105 °C. The progress of the reaction was monitored by thin layer chromatography. After the reaction was completed, the reaction mixture was cooled to room temperature and washed with 300 mL of 7 wt% aqueous NaHC03solution three times to remove the residual phloretic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Phloretic acid ester (PAAA) was obtained in 90% yield.

[0056] Example 3

[0057] Preparation of phloretic acid ester (PAHA): A 500 mL two-necked flask was charged with phloretic acid (69.80 g, 0.42 mol, 1.2 eq), n-hexanol (35.76 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL of cyclohexane. A water trap was attached to collect the water generated during the reaction. The reaction was heated to reflux by an oil bath at 105 °C. The progress of the reaction was monitored by thin layer chromatography. After the reaction was completed, the reaction mixture was cooled to room temperature and washed with 300 mL of 7 wt% aqueous NaHC03solution three times to remove the residual phloretic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Phloretic acid ester (PAHA) was obtained in 89% yield.

[0058] Example 4

[0059] Preparation of phloretic acid ester (PAIHA): A 500 mL two-necked flask was charged with phloretic acid (69.80 g, 0.42 mol, 1.2 eq), iso-hexanol (35.76 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL of cyclohexane. A water trap was attached to collect the water generated during the reaction. The reaction was heated to reflux by an oil bath at 105 °C. The progress of the reaction was monitored by thin layer chromatography. After the reaction was completed, the reaction mixture was cooled to room temperature and washed with 300 mL of 7 wt% aqueous NaHC03solution three times to remove the residual phloretic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Phloretic acid ester (PAIHA) was obtained in 88% yield.

[0060] Example 5

[0061] Preparation of phthalic acid ester (PATA): A 500 mL two-necked flask was charged with phthalic acid (69.80 g, 0.42 mol, 1.2 eq), n-heptanol (40.67 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL of cyclohexane. A water trap was attached to collect the water generated during the reaction. The reaction was heated to reflux by an oil bath at 105 °C. The progress of the reaction was monitored by thin layer chromatography. After the reaction was completed, the reaction was cooled to room temperature. The reaction was washed with 300 mL of 7 wt% aqueous NaHC03solution three times to remove the residual phthalic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Phthalic acid ester (PATA) was obtained in 86% yield.

[0062] Example 6

[0063] Preparation of phthalic acid ester (PATA): A 500 mL two-necked flask was charged with phthalic acid (69.80 g, 0.42 mol, 1.2 eq), n-heptanol (40.67 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL of cyclohexane. A water trap was attached to collect the water generated during the reaction. The reaction was heated to reflux by an oil bath at 105 °C. The progress of the reaction was monitored by thin layer chromatography. After the reaction was completed, the reaction was cooled to room temperature. The reaction was washed with 300 mL of 7 wt% aqueous NaHC03solution three times to remove the residual phthalic acid. The organic phase was collected, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. Phthalic acid ester (PATA) was obtained in 86% yield. 1 H NMR (400 MHz, DMSO-d6) δ 9.10 (s, 1H), 6.91 (d, J = 8.5 Hz, 2H), 6.59 (d, J = 8.5 Hz, 2H), 3.90 (t, J = 6.6 Hz, 2H), 2.66 (t, J = 7.5 Hz, 2H), 2.47 (d, J = 7.6 Hz, 2H), 1.51 - 1.37 (m, 2H), 1.17 (s, 11H), 0.79 (t, J = 6.8 Hz, 3H).

[0064] Example 7

[0065] Preparation of PAEH: In a 500 mL two-necked flask, add phloretic acid (69.80 g, 0.42 mol, 1.2 eq), iso-octanol (45.58 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL cyclohexane. Equip with a water trap to collect the water generated during the reaction. Heat the oil bath to 105 °C until the cyclohexane refluxes. Monitor the reaction progress by thin layer chromatography. After the reaction is complete, cool to room temperature. Wash the reaction mixture with 300 mL 7 wt% NaHC03 aqueous solution for 3 times to remove the residual phloretic acid. Collect the organic phase, dry over anhydrous magnesium sulfate, filter, and remove the solvent. PAEH is obtained in 90% yield. 1 H NMR (400 MHz, DMSO-d6) δ 9.17 (s, 1H), 6.99 (d, J = 8.5 Hz, 2H), 6.65 (d, J = 8.5 Hz, 2H), 3.90 (d, J = 6.8 Hz, 2H), 3.35 (s, 7H), 2.73 (t, J = 7.4 Hz, 2H), 1.24 (dd, J = 14.3, 7.6 Hz, 8H), 0.90 - 0.77 (m, 6H).

[0066] Example 8

[0067] Preparation of PANA: In a 500 mL two-necked flask, add phloretic acid (69.80 g, 0.42 mol, 1.2 eq), n-nonyl alcohol (50.49 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL cyclohexane. Equip with a water trap to collect the water generated during the reaction. Heat the oil bath to 105 °C until the cyclohexane refluxes. Monitor the reaction progress by thin layer chromatography. After the reaction is complete, cool to room temperature. Wash the reaction mixture with 300 mL 7 wt% NaHC03 aqueous solution for 3 times to remove the residual phloretic acid. Collect the organic phase, dry over anhydrous magnesium sulfate, filter, and remove the solvent. PANA is obtained in 89% yield.

[0068] Example 9

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

[0070] Example 10

[0071] Preparation of phthalic acid ester (PADA): A 500 mL two-necked flask was charged with phthalic acid (69.80 g, 0.42 mol, 1.2 eq), n-decanol (55.39 g, 0.35 mol, 1 eq), p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq), and 200 mL of cyclohexane. A water trap was attached to collect the water generated during the reaction. The oil bath was heated to 105 °C to reflux the cyclohexane. The reaction progress was monitored by thin layer chromatography. After the reaction was completed, the reaction mixture was cooled to room temperature and washed with 300 mL of 7 wt% NaHCO3 aqueous solution three times to remove the residual phthalic acid. The organic phase was collected and dried over anhydrous magnesium sulfate, filtered, and the solvent was removed. The phthalic acid ester (PADA) was obtained as a light yellow transparent liquid with a yield of 86%.

[0072] Example 11

[0073] Preparation of phthalic acid ester (PABA-SM): A 100 mL three-necked flask was charged with phthalic acid ester (PABA) (22.2 g, 0.1 mol, 1 eq) and p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq). The phthalic acid ester phenol was melted by heating under nitrogen atmosphere. When the temperature reached 85 °C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise. The temperature was maintained at 85-95 °C. After the addition was completed, the temperature was increased to 120 °C and maintained for 2 h. After the reaction was completed, 1.2 g of triethylamine was added for neutralization. After the mixture was stirred thoroughly, it was filtered. A vacuum pump was started and the vacuum was adjusted to 0.095 MPa. The temperature of the kettle was not allowed to exceed 140 °C until no liquid was distilled out. The temperature was decreased to below 80 °C and the product was discharged. The yield of the product was 97.3%.

[0074] Example 12

[0075] Preparation of Stilbene-based Phthalic Acid Ester (PAHA-SM): In a 100 mL three-necked flask, phthalic acid ester (PAHA) (25.01 g, 0.1 mol, 1 eq) and p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added, and the phthalic acid ester was melted under nitrogen atmosphere. 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 increased to 120 °C and maintained for 2 h. After the maintenance was completed, 1.2 g of triethylamine was added for neutralization, and the mixture was stirred thoroughly and filtered. A vacuum pump was started, and the vacuum degree was adjusted to 0.095 MPa. The kettle temperature was not allowed to exceed 140 °C until no liquid was evaporated. The temperature was decreased to below 80 °C, and the product was discharged. The yield of the product was 95%.

[0076] Example 13

[0077] Preparation of Stilbene-based Phthalic Acid Ester (PAIHA-SM): In a 100 mL three-necked flask, phthalic acid ester (PAIHA) (25.01 g, 0.1 mol, 1 eq) and p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added, and the phthalic acid ester was melted under nitrogen atmosphere. 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 increased to 120 °C and maintained for 2 h. After the maintenance was completed, 1.2 g of triethylamine was added for neutralization, and the mixture was stirred thoroughly and filtered. A vacuum pump was started, and the vacuum degree was adjusted to 0.095 MPa. The kettle temperature was not allowed to exceed 140 °C until no liquid was evaporated. The temperature was decreased to below 80 °C, and the product was discharged. The yield of the product was 92%.

[0078] Example 14

[0079] Preparation of Stilbene-based Phthalic Acid Ester (PAO A-SM): In a 100 mL three-necked flask, phthalic acid ester (PAO A) (27.84 g, 0.1 mol, 1 eq) and p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added, and the phthalic acid ester was melted under nitrogen atmosphere. 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 increased to 120 °C and maintained for 2 h. After the maintenance was completed, 1.2 g of triethylamine was added for neutralization, and the mixture was stirred thoroughly and filtered. A vacuum pump was started, and the vacuum degree was adjusted to 0.095 MPa. The kettle temperature was not allowed to exceed 140 °C until no liquid was evaporated. The temperature was decreased to below 80 °C, and the product was discharged. The yield of the product was 90%. 1H NMR (400 MHz, DMSO-d6) δ 8.15 (d, J = 17.7 Hz, 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 = 23.4 Hz, 2H), 2.54-2.51 (m, 1H), 2.47 (s, 1H), 1.46 (s, 8H), 1.23 (s, 11H), 0.85 (s, 3H).

[0080] Example 15

[0081] Preparation of Stilbene Phloretate (PAEH-SM): In a 100 mL three-necked flask, phloretate (PAEH) (27.84 g, 0.1 mol, 1 eq) and p-toluenesulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added and heated to melt under nitrogen atmosphere. When the temperature reached 85 °C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise. The temperature was maintained at 85-95 °C. After the addition was completed, the temperature was raised to 120 °C and maintained for 2 h. After the maintenance was completed, 1.2 g of triethylamine was added for neutralization. After sufficient stirring, the mixture was filtered. The vacuum pump was started and the vacuum was adjusted to 0.095 MPa. The kettle temperature was not allowed to exceed 140 °C until no liquid was distilled out. The temperature was lowered to below 80 °C to discharge the product. The yield was 89%. 1 H NMR (400 MHz, DMSO-d6) δ 8.15 (d, J = 17.7 Hz, 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 = 23.4 Hz, 2H), 2.54-2.51 (m, 1H), 2.47 (s, 1H), 1.46 (s, 8H), 1.23 (s, 11H), 0.85 (s, 3H).

[0082] Example 16

[0083] Preparation of Stilbene-based Phthalate (PANA-SM): In a 100 mL three-necked flask, phthalate (PANA) (29.22 g, 0.1 mol, 1 eq) and p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added and heated to melt the phthalate under nitrogen atmosphere. When the temperature reached 85 °C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise. The temperature was maintained at 85-95 °C. After the addition was completed, the temperature was increased to 120 °C and maintained for 2 h. After the incubation, 1.2 g of triethylamine was added for neutralization. After sufficient stirring, the mixture was filtered. The vacuum pump was started and the vacuum was adjusted to 0.095 MPa. The temperature of the kettle was not allowed to exceed 140 °C until no liquid was evaporated. The temperature was decreased to below 80 °C for discharge. The final product was obtained with a yield of 85.5%.

[0084] Example 17

[0085] Preparation of Stilbene-based Phthalate (PADOA-SM): In a 100 mL three-necked flask, phthalate (PADOA) (33.43 g, 0.1 mol, 1 eq) and p-toluene sulfonic acid (0.345 g, 0.002 mol, 0.02 eq) were added and heated to melt the phthalate under nitrogen atmosphere. When the temperature reached 85 °C, styrene (21.87 g, 0.21 mol, 2.1 eq) was added dropwise. The temperature was maintained at 85-95 °C. After the addition was completed, the temperature was increased to 120 °C and maintained for 2 h. After the incubation, 1.2 g of triethylamine was added for neutralization. After sufficient stirring, the mixture was filtered. The vacuum pump was started and the vacuum was adjusted to 0.095 MPa. The temperature of the kettle was not allowed to exceed 140 °C until no liquid was evaporated. The temperature was decreased to below 80 °C for discharge. The final product was obtained with a yield of 80%.

[0086] Example 18

[0087] Preparation of Bio-based Dispersant (PABA-SM-EO): At room temperature, stilbene-based phthalate (PABA-SM) (21 g) and catalyst boron trifluoride etherate (0.106 g) were added to a reaction kettle. Nitrogen was replaced for 3 times and then vacuumed to -0.1 MPa. The vacuum was closed and the temperature was increased to 50 °C. Ethylene oxide (7.92 g) was slowly added. The reaction temperature was 50-70 °C and the pressure was not allowed to exceed 0.2 MPa. After the addition of ethylene oxide was completed, the temperature was maintained at 70-80 °C for aging until the pressure did not change for 1 h. The final product was obtained after the temperature was decreased for discharge.

[0088] Example 19

[0089] Preparation of bio-based dispersant (PAHA-SM-EO): diphenyl styryl phthalate (PABA-SM) (23.5 g) and catalyst boron trifluoride etherate (0.106 g) were added into the reaction kettle at room temperature, replaced with nitrogen for 3 times, then vacuumed to -0.1 Mpa, closed the vacuum, heated to 50°C, then slowly added ethylene oxide (7.92 g), the reaction temperature was 50-70°C, the pressure was not more than 0.2 Mpa, after the addition of ethylene oxide, the temperature was kept at 70-80°C, aged until the pressure did not change for 1 h, finally cooled to discharge the finished product.

[0090] Example 20

[0091] Preparation of bio-based dispersant (PAIHA-SM-EO): diphenyl styryl phthalate (PAIHA-SM) (23.5 g) and catalyst boron trifluoride etherate (0.106 g) were added into the reaction kettle at room temperature, replaced with nitrogen for 3 times, then vacuumed to -0.1 Mpa, closed the vacuum, heated to 50°C, then slowly added ethylene oxide (7.92 g), the reaction temperature was 50-70°C, the pressure was not more than 0.2 Mpa, after the addition of ethylene oxide, the temperature was kept at 70-80°C, aged until the pressure did not change for 1 h, finally cooled to discharge the finished product.

[0092] Example 21

[0093] Preparation of bio-based dispersant (PAOA-SM-EO): diphenyl styryl phthalate (PAOA-SM) (34 g) and catalyst boron trifluoride etherate (0.106 g) were added into the reaction kettle at room temperature, replaced with nitrogen for 3 times, then vacuumed to -0.1 Mpa, closed the vacuum, heated to 50°C, then slowly added ethylene oxide (7.92 g), the reaction temperature was 50-70°C, the pressure was not more than 0.2 Mpa, after the addition of ethylene oxide, the temperature was kept at 70-80°C, aged until the pressure did not change for 1 h, finally cooled to discharge the finished product. 1 H NMR (400 MHz, DMSO-d6) δ 7.25 (d, J = 13.0 Hz, 7H), 7.08 (d, J = 31.8 Hz, 3H), 6.97 (s, 1H), 6.83 (d, J = 8.7 Hz, 1H), 4.08 (s, 2H), 3.71 (s, 3H), 3.51 (s, 33H), 2.76 (s, 2H), 2.57 (s, 2H), 1.49 (s, 5H), 1.22 (d, J = 11.7 Hz, 9H), 0.84 (d, J = 7.3 Hz, 6H).

[0094] The Fourier infrared spectrum of PAOA-SM-EO is shown in Figure 6 The figure shows that the characteristic peak of ether bond is 1130 cm -1The generation indicates that the epoxy group has been successfully introduced into PAOA-SM, indicating that the bio-based dispersant (PAOA-SM-EO) is successfully prepared.

[0095] Example 22

[0096] Preparation of bio-based dispersant (PAEH-SM-EO): Diphenylstyryl phthalate (PAEH-SM) (34 g) and catalyst boron trifluoride ether (0.106 g) were added to a reaction kettle at room temperature, replaced with nitrogen for 3 times, then vacuumized to -0.1 Mpa, closed the vacuum, heated to 50°C, and then slowly added ethylene oxide (7.92 g). The reaction temperature was 50-70°C, and the pressure did not exceed 0.2 Mpa. After the addition of ethylene oxide was completed, the temperature was maintained at 70-80°C, and the pressure was continuously unchanged for 1 h. Finally, the temperature was lowered to discharge the finished product. 1 H NMR (400 MHz, DMSO-d6) δ 7.40-6.76 (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, 4.3 Hz, 1H), 2.57 (tq, J = 8.3, 3.9 Hz, 1H), 1.60-1.09 (m, 4H), 0.83 (ddq, J = 13.7, 9.8, 6.6 Hz, 1H).

[0097] The Fourier infrared spectrum of PAEH-SM-EO is shown in Figure 8 The figure shows that the ether bond characteristic peak 1130 cm -1 The generation indicates that the epoxy group has been successfully introduced into PAEH-SM, indicating that the bio-based dispersant (PAEH-SM-EO) is successfully prepared.

[0098] Example 23

[0099] Preparation of bio-based dispersant (PANA-SM-EO): Diphenylstyryl phthalate (PANA-SM) (65 g) and catalyst boron trifluoride ether (0.106 g) were added to a reaction kettle at room temperature, replaced with nitrogen for 3 times, then vacuumized to -0.1 Mpa, closed the vacuum, heated to 50°C, and then slowly added ethylene oxide (7.92 g). The reaction temperature was 50-70°C, and the pressure did not exceed 0.2 Mpa. After the addition of ethylene oxide was completed, the temperature was maintained at 70-80°C, and the pressure was continuously unchanged for 1 h. Finally, the temperature was lowered to discharge the finished product.

[0100] Example 24

[0101] Preparation of bio-based dispersant (PADOA-SM-EO): Diphenyl styryl phloretate (PADOA-SM) (92 g) and catalyst boron trifluoride ether (0.106 g) were added into a reaction kettle at room temperature, replaced with nitrogen for 3 times, then vacuumized to -0.1 Mpa, closed the vacuum, heated to 50°C, then slowly added ethylene oxide (7.92 g), the reaction temperature was 50-70°C, the pressure was not more than 0.2 Mpa, after the addition of ethylene oxide, the temperature was kept at 70-80°C, and aged until the pressure did not change for 1 h, finally cooled to discharge the finished product.

[0102] Performance test

[0103] First, configure the propanil water emulsion containing bio-based dispersant. According to: propanil 45 g, xylene 22 g, bio-based dispersant 4 g, yellow glue 0.04 g, silicone defoaming agent 0.2 g, propylene glycol 8 g, deionized water 20.76 g, total 100 g of water emulsion was obtained by stirring and shearing.

[0104] The detection of the dispersion performance of the bio-based pesticide dispersant was carried out according to "GB / T 32775-2016 Pesticide Dispersion Test Method", and the dispersion performance of 45% propanil water emulsion was detected: the water emulsion sample was diluted 20, 100, 200, 1000 times in a standard hard water (according to the standard hard water described in GB / T1603-2001 Pesticide Emulsion Stability Test Method) in a graduated cylinder, and placed in a constant temperature of 25-30°C for 24 h. 1 mL of water emulsion was slowly added to a beaker containing hard water at a distance of 2 cm high, and the natural dispersion and emulsion state of the water emulsion in water was observed to determine the co-emulsification performance index.

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

[0106] dispersant Example dispersion state emulsion state evaluation grade PABA-SM-EO 18 white particles sink white transparent emulsion after stirring fourth PAHA-SM-EO 19 uniformly disperse automatically slightly stirred blue translucent emulsion second PAIHA-SM-EO 20 white cloud or silk dispersion slightly stirred blue translucent emulsion third PAOA-SM-EO 21 uniformly disperse automatically slightly stirred blue translucent emulsion second PAEH-SM-EO 22 uniformly disperse automatically slightly stirred white emulsion first PANA-SM-EO 23 white cloud or silk dispersion slightly stirred blue translucent emulsion third PADOA-SM-EO 24 white particles sink white transparent emulsion after stirring fourth

[0107] As shown in Table 1, examples 19 (PAHA-SM-EO), 21 (PAOA-SM-EO) and 22 (PAIOA-SM-EO) can automatically and uniformly disperse, and show emulsion under stirring, with good dispersion and emulsion state, good emulsion dispersion performance, and the results show that the emulsion dispersion is qualified. It is shown that the bio-based pesticide dispersant containing phloretic acid structure is expected to become a good substitute for agricultural emulsion 600# by designing the structure.

Claims

1. A bio-based dispersant characterized in that Has the following structure: Wherein, n >= 10, and n is a natural number, R is linear or branched alkyl of carbon number 4 to 16.

2. The bio-based dispersant of claim 1, wherein, Prepared by the following preparation method: diphenyl styrene phloretate is reacted with ethylene oxide under the action of catalyst.

3. The bio-based dispersant of claim 2, wherein, The molar ratio of the diphenyl styrene phloretate to ethylene oxide is 1:10 to 1:

15.

4. The bio-based dispersant of claim 2, wherein, The catalyst is boron trifluoride etherate.

5. The bio-based dispersant of claim 2, wherein, The molar ratio of the catalyst to diphenyl styrene phloretate is 1:50 to 1:

10.

6. The bio-based dispersant of claim 2, wherein, The diphenyl styrene phloretate has the following structure: Wherein, R is linear or branched alkyl of carbon number 4 to 16.

7. The bio-based dispersant of claim 6, wherein, The preparation method of the diphenyl styrene phloretate comprises the following steps: phloretic acid is esterified with alcohol to obtain phloretic acid ester containing ester group, and then the phloretic acid ester is reacted with styrene in the presence of catalyst at a certain temperature for a period of time to obtain the diphenyl styrene phloretate.

8. The bio-based dispersant of claim 7, wherein, The alcohol is selected from one of n-butanol, n-pentanol, n-hexanol, 2-ethyl butanol, n-heptanol, n-octanol, iso-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol.

9. The bio-based dispersant of claim 7, wherein, The molar ratio of the styrene to phloretic acid ester is 2:1 to 2.5:

1.

10. The bio-based dispersant of claim 7, wherein, The catalyst is p-toluenesulfonic acid, the reaction temperature is 85 to 120 DEG C, and the reaction time is 7h.

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