CN115417983A

CN115417983A - Cardanol polyether sulfate and preparation method and application thereof

Info

Publication number: CN115417983A
Application number: CN202211077261.4A
Authority: CN
Inventors: 王利民; 龚新奇; 车飞; 巩宇; 罗威; 沈丹艳; 韩建伟
Original assignee: Shanghai Bronkow Chemical Co ltd; East China University of Science and Technology
Current assignee: Shanghai Bronkow Chemical Co ltd; East China University of Science and Technology
Priority date: 2022-09-05
Filing date: 2022-09-05
Publication date: 2022-12-02

Abstract

The invention discloses cardanol polyether sulfate, which has a structural general formula as follows:

a =1 to 15, b =1 to 5. The cardanol polyether sulfate ester salt structure provided by the invention comprises a benzene ring, an unsaturated long alkane chain, a hydrophilic polyoxyethylene chain, a hydrophobic polyoxypropylene chain and a hydrophilic ionic head group. The sulfate anionic surfactant derived from cardanol polyether has good wetting, emulsifying, corrosion inhibiting, dispersing and other performances.

Description

Cardanol polyether sulfate and preparation method and application thereof

Technical Field

The invention belongs to the technical field of surfactants, and particularly relates to cardanol polyether sulfate with good dispersibility as well as a preparation method and application thereof.

Background

The cardanol is prepared by refining natural cashew nut shell oil serving as a raw material through a series of process technologies, the molecular structure of the cardanol contains three functional groups with high chemical activity, namely phenolic hydroxyl, benzene ring and a long carbon chain with unsaturated side chains, and the cardanol becomes an ideal substrate molecule for preparing various functional materials due to the chemical characteristics.

The surfactant synthesized by taking cardanol as a substrate has good biodegradability, is called as a green surfactant or a biomass surfactant, is the best choice for replacing petroleum phenol surfactants, is applied to numerous fields due to the characteristic of amphiphilic structure of cardanol, and can further improve the using effect of the cardanol surfactant through synergistic effect during application.

The organic pigment has low surface polarity and weak hydrophilicity, and is not easy to maintain stable dispersion state in a water-based system. The addition of a dispersant capable of providing effective repulsion to the surface of the ultrafine pigment particles in a dispersion system is a main method for controlling the stable dispersion of the ultrafine organic pigment in an aqueous system. In 1998, diwu et al focused on the relationship between the dispersibility and the shade of a pigment paste and the surface activity of a surfactant, and found that surfactants of different structures have different effects on pigments of different structures ([ J ]. Dye industry, 1998, (2): 33-38.). The group studied the influence of anionic or nonionic surfactants with different structures and the compound thereof on the dispersibility of the pigment, and found that the binary compound enables the particle size of the pigment to be dispersed more finely, and has no obvious influence on the dispersibility of the pigment paste, while the ternary compound system can greatly weaken the dispersibility of the pigment paste. In 2009, hearolonum and the like prepared three anionic ultrafine organic pigment water dispersion systems, discussed the influence of different dispersants on the pigment particle size, viscosity, stability and dyeing property of cotton fabric in the systems, and discussed the action mechanism of anionic surfactants on the pigment dispersion stability (J. Printing and dyeing assistant, 2009,26 (4): 10-13.). In 2014, wang nan et al reviewed the action mechanism and application research progress of surfactants in pigment dispersion, and summarized the double-layer theory and steric hindrance theory for aqueous systems and solvent-based systems (J. Daily chemical industry, 2014,44 (12): 666-670, 675.). In 2017, cao Raichun et al found that the use of a surfactant, especially a hyper-dispersant, can effectively improve the dispersibility of pigments in aqueous inks ([ J ] packaging engineering, 2017,38 (1): 62-66.).

In conclusion, the high molecular surfactant product with cardanol as a substrate is developed, and has great application potential in the field of pigment dispersion.

Disclosure of Invention

The first purpose of the invention is to provide a novel cardanol polyether sulfate with good dispersion effect.

The second purpose of the invention is to provide a preparation method of the cardanol polyether sulfate.

The third purpose of the invention is to provide an application of the cardanol polyether sulfate in preparation of an organic pigment dispersing agent.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

the first purpose of the invention is to provide cardanol polyether sulfate, which has the following structural general formula:

where a and b are the sum of ethylene oxide and propylene oxide, respectively, and the sulfation of the product is determined by two-phase titration.

a＝1～15，b＝1～5。

The sulfation range of the cardanol polyether sulfate is as follows: 89 to 96 percent.

Preferably, the structure of the cardanol polyether sulfate salt is selected from one of the following structures:

wherein, a =13, b =5;

wherein, a =11,b =3;

wherein a =11,b =5.

The second aspect of the invention provides a preparation method of the cardanol polyether sulfate salt, which comprises the following steps:

the first step, etherification: firstly putting a catalyst into a polymerization kettle, adding cardanol to seal the polymerization kettle, replacing air in the kettle with nitrogen for 3 times, raising the temperature in the kettle to 100-110 ℃, vacuumizing and dehydrating, keeping the vacuum degree at-0.09 MPa, dehydrating for 1-60 min, slowly introducing ethylene oxide when the temperature is raised to 130 ℃, controlling the reaction temperature in the kettle to be 140-150 ℃, controlling the pressure in the kettle to be 0.1-0.25 MPa, continuing to react until the pressure in the kettle is basically constant after the ethylene oxide is dripped, curing for 20-120 min under the condition of 120-130 ℃, introducing propylene oxide, still controlling the reaction temperature in the kettle to be 140-150 ℃ after the reaction is started, controlling the pressure in the kettle to be 0.15-0.25 MPa, continuing to react until the pressure in the kettle is constant after the propylene oxide is dripped, curing for 50-70 min under the condition of 120-130 ℃, then reducing the temperature in the kettle to 80-90 ℃, 5-15 min, reducing the temperature in the kettle to 60-70 ℃, adding acetic acid for neutralizing for 1-10 min, vacuum, removing water, and discharging polyether to obtain a degassed product;

or, in the first step, etherification: firstly putting a catalyst into a polymerization kettle, adding cardanol to seal the polymerization kettle, replacing air in the kettle with nitrogen for 3 times, raising the temperature in the kettle to 100-110 ℃, vacuumizing and dehydrating, keeping the vacuum degree at-0.09 MPa, dehydrating for 1-60 min, slowly introducing propylene oxide when the temperature is raised to 130 ℃, controlling the reaction temperature in the kettle to be 140-150 ℃, controlling the pressure in the kettle to be 0.1-0.25 MPa, continuing to react until the pressure in the kettle is basically constant after the propylene oxide is dripped, curing for 20-70 min under the condition of 120-130 ℃, introducing ethylene oxide, still controlling the reaction temperature in the kettle to be 140-150 ℃ after the reaction is started, controlling the pressure in the kettle to be 0.15-0.25 MPa, continuing to react until the pressure in the kettle is constant after the ethylene oxide is dripped, curing for 50-70 min under the condition of 120-130 ℃, then reducing the temperature in the kettle to 80-90 ℃, 5-15 min, reducing the temperature in the kettle to 60-70 ℃, adding acetic acid for neutralizing for 1-10 min, vacuum, removing water, and discharging polyether to obtain a degassed product;

the catalyst in the first step is KOH.

In the first step, the mol ratio of cardanol, ethylene oxide and propylene oxide is 1: (11-150): (1-60).

The dosage of the catalyst in the first step is 1-5 per mill, preferably 2 per mill, 3.2 per mill and 2.85 per mill of the total mass of cardanol, ethylene oxide and propylene oxide.

The dosage of the glacial acetic acid in the first step is 1-5 per mill, preferably 1.72 per mill, 2.7 per mill and 2.4 per mill of the total mass of the cardanol, the ethylene oxide and the propylene oxide.

The hydroxyl value of the cardanol polyether product is 40-80, and the molecular weight is 800-1200.

Second step, sulfation: adding a catalyst into the cardanol polyether product prepared in the first step, heating to 80-100 ℃, performing vacuum dehydration for 20-60 min, heating to 120-130 ℃, adding sulfamic acid in three batches, completing the addition within 20-40 min, stirring for reaction for 1-5 h, finishing the reaction, and cooling to 80-90 ℃ to obtain a primary cardanol polyether ammonium sulfate product.

The catalyst in the second step is urea.

The dosage of the catalyst in the second step is 1.5-1.7% (preferably 1.5%) of the total mass of the materials (the total mass refers to the total mass of the cardanol polyether product and the sulfamic acid required by the materials added for reaction after theoretical calculation).

In the second step, the molar ratio of the cardanol polyether product to the sulfamic acid is 1: 1.5-2 (preferably 1.

Step three, neutralization: and (3) dropwise adding a 30wt% sodium hydroxide aqueous solution into the primary cardanol polyether ammonium sulfate product prepared in the second step, wherein the mass ratio of the primary cardanol polyether ammonium sulfate product prepared in the second step to the 30wt% sodium hydroxide aqueous solution is 5-15: 1, cooling to 50-60 ℃ until no ammonia gas is generated, adding absolute ethyl alcohol (stirring while adding until the system becomes clear from a turbid state, generally adding absolute ethyl alcohol with the mass of 1/3 to 1/2 of that of the obtained product) to dissolve the product, filtering out insoluble substances, heating the filtrate to 60-70 ℃, and distilling under reduced pressure to remove the absolute ethyl alcohol to obtain the cardanol polyether sulfate.

The third aspect of the invention provides an application of the cardanol polyether sulfate in preparation of an organic pigment dispersing agent.

The organic pigment dispersant is a DPP red pigment dispersant.

Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:

the cardanol is a biomass resource, has the advantages of being renewable, free of pollution and the like, has an unsaturated side carbon chain and a phenolic hydroxyl group in the structure, and compared with other petroleum phenol products, the prepared surfactant has the advantages of being high in surface activity (shown in the attached drawing 3) and good in biodegradability.

The cardanol polyether sulfate provided by the invention has a good dispersing effect, and shows application potential in the field of organic pigment dispersion.

The cardanol polyether sulfate ester salt structure provided by the invention comprises a benzene ring, an unsaturated long alkane chain, a hydrophilic polyoxyethylene chain, a hydrophobic polyoxypropylene chain and a hydrophilic ionic head group. The sulfate anionic surfactant derived from cardanol polyether has good wetting (shown in figure 4), emulsifying (shown in figure 5), dispersing (shown in figures 1 and 2) and other performances.

The synthesis process of the cardanol polyether sulfate provided by the invention is simple and convenient, has no harmful side products, and shows good application potential in the aspect of organic pigment dispersion.

Drawings

Fig. 1 is a graph showing the results of testing the dispersing performance of cardanol polyether sulfate salts prepared in examples 1 to 3 on DPP red pigment with reference to a commercially available pigment dispersant 4290.

FIG. 2 is a bar graph showing the results of the storage stability tests of the pigments of test examples 1 to 3.

FIG. 3 is a graph showing the surface tension curves of cardanol polyether sulfate salt prepared in examples 1 to 3 and comparative example 2.

FIG. 4 is a schematic diagram of a wettability test of cardanol polyether sulfate salt prepared in examples 1 to 3 and comparative example 2.

FIG. 5 is a schematic diagram showing emulsification properties of cardanol polyether sulfate salt prepared in examples 1 to 3 and comparative example 2.

FIG. 6 is a schematic infrared spectrum of cardanol polyether and cardanol polyether sulfate salt prepared in examples 1 to 3.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.

The parameter information of the cardanol raw material adopted by the invention is shown in table 1:

TABLE 1

Basic parameters	Numerical values or explanations
		Color intensity	1～5
Density (20 ℃ C.)/(g/cm) ³ )	0.93
		Viscosity (30 ℃ C.)/mPa. Multidot.s	30
Water content/%)	≦0.5
		Ash content%	≦0.5
Iodine value/(gI) ₂ /100g)	240
		Average relative molecular mass	302
Manufacturer(s) of	Cigarette Tai Invitrogen biological Co Ltd

Example 1

The preparation method of the cardanol polyether sulfate BEPS-135 comprises the following steps:

step one, etherification: adding KOH (0.021mol, 1.16g) into a polymerization kettle, adding cardanol (0.5mol, 150.68g) into the polymerization kettle, sealing the polymerization kettle, replacing air in the kettle with nitrogen for 3 times, raising the temperature in the kettle to 100-110 ℃, vacuumizing and dehydrating by using a vacuum pump, keeping the vacuum degree at-0.09 MPa for dehydration for 30min, slowly introducing ethylene oxide when the temperature in the kettle is raised to 130 ℃, controlling the reaction temperature in the kettle to be 140-150 ℃, controlling the pressure in the kettle to be 0.1-0.25 MPa, continuing to react until the pressure in the kettle is basically constant after the ethylene oxide (6.500mol, 286 g) is completely dripped, curing for half an hour under the temperature of 120-130 ℃, introducing propylene oxide, controlling the reaction temperature in the kettle to be 140-150 ℃ after the reaction is started, controlling the pressure in the kettle to be 0.15-0.25 MPa, dropping the pressure in the propylene oxide (2.500mol, 145g) after the reaction is completed, continuing to react until the pressure in the kettle is constant, controlling the temperature of 120-130 ℃, controlling the pressure in the kettle to be 0.15-0.25 MPa, reducing the pressure in the kettle to 80 min, degassing to obtain a product, adding cardanol, removing moisture in the cardanol (BEP) after the product is obtained, and removing the product at 1-70 ℃, and removing the product under the temperature of the polyether (1-60, and the product obtained after the product obtained by vacuum, and removing the product obtained by vacuum.

Second step, sulfation: putting the cardanol polyether product BEP-135 (0.043 mol, 50.38g) prepared in the first step into a three-neck flask, adding urea (0.014mol, 0.86g), heating the oil bath to 90 ℃, dehydrating in vacuum for half an hour, heating the temperature to 125 ℃, putting sulfamic acid (0.074 mol, 7.14g) into the three-neck flask in three batches, completing the putting within 30min, stirring for reaction for 3h, completing the reaction, cooling to 80-90 ℃, and obtaining 54.57g of a primary cardanol polyether ammonium sulfate product.

The urea consumption is 1.5% of the total mass of the fed materials (the total mass is the total mass of the cardanol polyether product and the sulfamic acid required by the fed reaction after theoretical calculation), and the molar ratio of the cardanol polyether product to the sulfamic acid in the second step is 1:1.7.

step three, neutralization: 4.1-4.6 mL of 30wt% sodium hydroxide aqueous solution (density is 1.33 g/mL) is added into 54.57g of cardanol polyether ammonium sulfate primary product prepared in the second step dropwise until no ammonia is generated, the temperature is reduced to 60 ℃, 25mL of absolute ethyl alcohol is added while stirring until the system is clear from a turbid state, generally 1/3 to 1/2 of the mass of the obtained product is added to dissolve the product, insoluble substances such as impurity salt are filtered out, the filtrate is transferred into a distillation flask, the temperature is raised to 65 ℃, and absolute ethyl alcohol is removed by reduced pressure distillation to obtain 54.61g of cardanol polyether sulfate BEPS-135.

The infrared spectrum of the product is shown in fig. 6, and fig. 6 is a schematic infrared spectrum of cardanol polyether and cardanol polyether sulfate prepared in examples 1 to 3. Can be found at 1100cm ^-1 The strong absorption peaks appearing at the left and right are stretching vibration peaks of ether bond C-O-C, which indicates the successful progress of the alkoxylation process. At 1254cm ^-1 Is an absorption peak of C-O-S and is at 778cm in the fingerprint region ^-1 The absorption peak appeared here is a characteristic absorption peak of S = O bond, and therefore it can be judged that the sulfate salt type surfactant was successfully synthesized.

The structural formula of cardanol polyether sulfate BEPS-135 prepared in this example is as follows:

wherein a =13,b =5.n is 0, 1, 2, 3.

The functionality of the cardanol polyether is 1.2, the measured hydroxyl value of the cardanol polyether product BEP-135 is 57.86, the molecular weight of the cardanol polyether product BEP-135 is 1163.50 according to the hydroxyl value, and the calculation formula is as follows:

theoretical hydroxyl number = (56100 × polyether product functionality)/molecular weight

The sulfation ratio of cardanol polyether sulfate BEPS-135 measured by a two-phase titration method according to surfactant anionic active determination method GBT5173-1995 was 89.15%.

Example 2

The preparation method of the cardanol polyether sulfate BPES-311 comprises the following steps:

the first step, etherification: adding KOH (0.027mol, 1.50g) into a polymerization kettle, adding cardanol (0.495mol, 149.60g) into the polymerization kettle, sealing the polymerization kettle, replacing air in the kettle with nitrogen for 3 times, raising the temperature in the kettle to 100-110 ℃, performing vacuum pumping dehydration by using a vacuum pump, keeping the vacuum degree at-0.09 MPa, performing dehydration for 30min, slowly introducing epoxypropane when the temperature in the kettle is raised to 130 ℃, controlling the reaction temperature in the kettle to be 140-150 ℃, controlling the pressure in the kettle to be 0.1-0.25 MPa, continuing to react until the pressure in the kettle is basically constant after the epoxypropane (1.483mol, curing for 1h under the condition of 120-130 ℃, introducing ethylene oxide, controlling the reaction temperature in the kettle to be 140-150 ℃ after the reaction is started, controlling the pressure in the kettle to be 0.15-0.25 MPa, dropping the pressure in the ethylene oxide (5.455mol, 240g) after the temperature is constant, continuing to react until the pressure in the kettle is 140-150 ℃, controlling the pressure in the kettle to be 0.15-0.25 MPa, decreasing the temperature in the kettle to 60-60 min, degassing temperature after the temperature is constant, adding the temperature of the kettle is 60-60.461 ℃, and discharging the product to obtain a product, and then, removing moisture in the product after the product is obtained, removing the product, wherein the product obtained by adding acetone (0.022311 g, and the product after the product is obtained, and the product obtained by vacuum pump is removed under the temperature is 60-60,461 ℃, the temperature is constant.

Second step, sulfation: putting the cardanol polyether product BPE-311 (0.039mol, 37.40g) prepared in the first step into a three-neck flask, adding urea (0.011mol, 0.66g), heating the oil bath to 90 ℃, dehydrating in vacuum for half an hour, heating the temperature to 125 ℃, putting sulfamic acid (0.066mol, 6.42g) into the three-neck flask in three batches, completing the putting within 30min, stirring for reaction for 3h, finishing the reaction, cooling to 80-90 ℃, and obtaining 41.18g of a cardanol polyether ammonium sulfate primary product.

The urea consumption is 1.5% of the total mass of the fed materials (the total mass refers to the total mass of the cardanol polyether product and the sulfamic acid required by the fed reaction after theoretical calculation), and the molar ratio of the cardanol polyether product to the sulfamic acid in the second step is 1:1.7.

step three, neutralization: and (3) dropwise adding 3-4 mL of 30wt% sodium hydroxide aqueous solution into 41.18g of cardanol polyether ammonium sulfate primary product prepared in the second step until no ammonia gas is generated, cooling to 60 ℃, adding 25mL of absolute ethyl alcohol to dissolve the product, filtering insoluble substances such as impurity salt and the like, transferring filtrate into a distillation flask, heating to 65 ℃, and removing the absolute ethyl alcohol by reduced pressure distillation to obtain 41.26g of cardanol polyether sulfate BPES-311.

The structural formula of cardanol polyether sulfate BPES-311 prepared in this example is as follows:

wherein a =11,b =3.n is 0, 1, 2, 3.

The cardanol polyether functionality was 1.2, the measured hydroxyl value of cardanol polyether product BPE-311 was 70.26, and the molecular weight of cardanol polyether product BPE-311, calculated from the hydroxyl value, was 958.16.

The sulfation rate of cardanol polyether sulfate BEPS-311 measured by a two-phase titration method was 95.12%.

Example 3

The preparation method of the cardanol polyether sulfate BPES-511 comprises the following steps:

step one, etherification: adding KOH (0.021mol, 1.20g) into a polymerization kettle, adding cardanol (0.391mol, 118.00g) into the polymerization kettle, sealing the polymerization kettle, replacing air in the kettle with nitrogen for 3 times, raising the temperature in the kettle to 100-110 ℃, vacuumizing and dehydrating by using a vacuum pump, keeping the vacuum degree at-0.09 MPa, dehydrating for 30min, slowly introducing epoxypropane when the temperature in the kettle is raised to 130 ℃, controlling the reaction temperature in the kettle to be 140-150 ℃, controlling the pressure in the kettle to be 0.1-0.25 MPa, after the epoxypropane (1.966 mol, 114g) is dropwise added, continuing to react until the pressure in the kettle is basically constant, curing for 1h under the condition of 120-130 ℃, introducing ethylene oxide, controlling the reaction temperature in the kettle to be 140-150 ℃ after the reaction is started, controlling the pressure in the kettle to be 0.15-0.25 MPa, after the epoxyethane (4.29mol, 189g) is finished, continuing to react until the pressure in the kettle is constant, controlling the reaction temperature in the kettle to be 120-150 ℃, reducing the pressure in the kettle to 0.511-0.511, discharging moisture in the kettle, reducing the product obtained by adding acetone (0080) and discharging, after the temperature is reduced, and the product obtained after the temperature is reduced, and the temperature is reduced to 60.8-60.511, and the temperature is reduced.

Second step, sulfation: putting the cardanol polyether product BPE-511 (0.038mol, 40.44g) prepared in the first step into a three-neck flask, adding urea (0.012mol, 0.70g), heating the oil bath to 90 ℃, performing vacuum dehydration for half an hour, heating the temperature to 125 ℃, putting sulfamic acid (0.064mol, 6.20g) into the three-neck flask in three batches, completing the putting within 30min, stirring for reaction for 3h, finishing the reaction, cooling to 80-90 ℃, and obtaining 44.08g of a cardanol polyether ammonium sulfate primary product.

step three, neutralization: and (3) dropwise adding 3-4 mL of 30wt% sodium hydroxide aqueous solution into 44.08g of the primary cardanol polyether ammonium sulfate prepared in the second step until no ammonia gas is generated, cooling to 60 ℃, adding 25mL of absolute ethanol to dissolve a product, filtering out insoluble substances such as impurity salt and the like, transferring the filtrate into a distillation flask, heating to 65 ℃, and removing the absolute ethanol by reduced pressure distillation to obtain 44.15g of cardanol polyether sulfate BPES-511.

The structural formula of cardanol polyether sulfate BPES-511 prepared in this example is as follows:

wherein a =11,b =5.n is 0, 1, 2, 3.

The functionality of the cardanol polyether was 1.2, the hydroxyl value of cardanol polyether product BPE-511 was measured to be 62.64, and the molecular weight of cardanol polyether product BPE-511 was calculated as 1074.71 based on the hydroxyl value.

The sulfation rate of cardanol polyether sulfate BPES-511 measured by a two-phase titration method was 94.68%.

DPP red pigment dispersibility test:

the following table shows the composition parameters of the materials used in the pigment dispersion application experiment:

TABLE 2

TABLE 3

TABLE 4

Name of the product	JONCRYL 8330
		Purchasing manufacturer	BASF
Function(s)	Acrylic acid film-forming resin
		Appearance of the product	Translucent emulsion
Solid content	38％
		pH value	8.1
Viscosity (25 ℃ C.)	50mPa.s
		Specific gravity at 25 ℃	1.04
Film formation temperature	33℃
		Freeze-thaw resistance	Anti-freezing device

TABLE 5

Name of the product	Rheovis PU 1191
		Purchasing manufacturer	BASF
Function(s)	Thickening agent
		Appearance of the product	Opaque white liquid
Solid content	～30％
		Density of	～1.03g/cm ³
Brookfield viscosity (73 ℃ F.)	～2.700mPa.s

Taking 40g of DPP red pigment powder, adding 12g of dispersing agent (shown in Table 2, the dispersing agent used in the comparative example is shown in the table and is compared with the cardanol polyether sulfate prepared by the self-made products of examples 1-3) and 5g of water-based resin (shown in Table 3), diluting the mixture to 100g with deionized water, adding 120g of glass beads with the diameter of 2mm, placing the mixture in a high-speed shaking machine, grinding the mixture until the fineness is less than 5 microns, and taking out the mixture for later use. 3.0g of the mixed color paste (the color paste is a mixture prepared in the previous step and is not a purchased color paste) is taken and added into 9.45g of white ink, 71g of film-forming resin (shown in a table 4) and 0.3g of thickening agent (shown in a table 5) are additionally added, the mixture is placed into a high-speed mixer for mixing, a wet film preparation device is used for blade-coating a film with a fixed film thickness on black-white cardboard, finger-grinding experiments are carried out to judge whether the color is floating, if the color is floating, floating color control is carried out (the floating color problem can be basically solved by adding an organic silicon surfactant capable of strongly reducing the surface tension) until the color is not floating, the mixture is flashed for flash drying for 10 minutes and is placed into a 70-degree oven for baking for 30 minutes, an Alice SP65 color tester is used for testing the color data and calculating the tinting strength, and the color data and the tinting strength are measured again after the diluted white ink is stored for 10 days.

Results as shown in fig. 1 and 2, the dispersion performance of cardanol polyether sulfate salt prepared in examples 1 to 3 on DPP red pigment is schematically shown in fig. 1 and 2, with a commercially available pigment dispersant 4290 as a comparative example, and with a commercially available pigment dispersant 4290 as a reference in fig. 1. As can be seen from FIG. 1, when the cardanol polyether sulfate prepared in examples 1-3 is used as a dispersing agent, the relative tinting strength of the pigment paste is higher than that of the comparative example, which shows that the cardanol polyether sulfate prepared in examples 1-3 has better dispersibility on DPP red organic pigment.

Compared with the comparative example 1, the relative tinting strength of the pigment is improved by 0.12 times in the example 1 of the invention, the relative tinting strength of the pigment is improved by 0.06 times in the example 2 of the invention, and the relative tinting strength of the pigment is improved by 0.14 times in the example 3 of the invention, compared with the comparative example 1, the particle size of the pigment molecules has larger influence on the tinting strength of the pigment, and the pigment has smaller particle size and higher tinting strength when the distribution is uniform. The property of the dispersant determines whether the particle size distribution of the pigment is uniform, so that the self-prepared cardanol polyether sulfate can more efficiently disperse the pigment compared with the dispersant used in a comparative example as seen from the improvement of relative tinting strength.

FIG. 2 is a bar graph showing the results of the storage stability tests of the pigments of test examples 1 to 3. As can be seen from the data in fig. 2, the tinting strength was greatly improved after 10 days of storage compared to that before storage, which indicates that the cardanol polyether sulfate salt prepared in test examples 1 to 3 has good dispersion stability for DPP red organic pigment.

The increase in the relative tinting strength compared to the level before storage may be due to a higher pigment content during storage due to solvent evaporation, and a decrease in tinting strength compared to the level before storage due to flocculation of the pigment during storage is indicative of inadequate stability, and a decrease in tinting strength after storage is not observed in the pigment systems used in examples 1-3, and is indicative of better storage stability of the pigment.

Comparative example 1

Commercially available pigment dispersant 4290.

Comparative example 2

BES-10, cardanol polyoxyethylene ether sulfate.

And (3) testing the surface tension: preparing 0.01mol/L aqueous solution of a sample to be tested, opening a surface tension meter to connect with a test program, and preheating the system for 30min until the temperature displayed by the instrument reaches 25 ℃. Immersing the platinum sheet in ethanol, burning the platinum sheet to red by using an alcohol lamp after soaking (the platinum sheet is placed vertically as much as possible when burning is noticed, and the platinum sheet is prevented from being deformed due to uneven heating), and cooling the platinum sheet to room temperature before the test is started. And (3) cleaning a glass dish used for testing, measuring the surface tension of 20mL of deionized water, recording the surface tension and the temperature at the moment, and representing that the surface dish meets the testing requirement cleanliness only by the deionized water surface tension of 71 mN/m-73 mN/m. The platinum plate was removed and re-fired and cooled as described above. The alkynol polyether solution was added in increments to a petri dish washed and containing 20mL of deionized water according to the set concentration gradient, and the test was started after mixing well. Surface tension and temperature were recorded faithfully. FIG. 3 is a graph showing the surface tension curves of the cardanol polyether sulfate salts prepared in examples 1 to 3 and comparative example 2. As can be seen from fig. 3, the cardanol polyether sulfate prepared in examples 1 to 3 has a higher surface activity because it can lower the surface tension of water to a lower value than the cardanol polyoxyethylene ether sulfate of the comparative example.

And (3) wettability testing: preparing a 1g/L sample solution, controlling the room temperature to be 25 ℃, transferring the prepared solution into a 1000mL beaker, standing until the surface layer of the liquid surface is free of foam, taking out a cotton canvas sheet special for testing (wearing nitrile gloves during experimental operation to prevent grease on hands from polluting the surface of the cotton canvas sheet), starting timing from the contact of the lower end of the cotton canvas sheet with the liquid surface until the cotton canvas sheet automatically sinks to the bottom of the beaker, and stopping timing, and recording the time difference. The above operation was repeated three times and the time difference was recorded as an average value. FIG. 4 is a schematic diagram of a wettability test of cardanol polyether sulfate salt prepared in examples 1 to 3 and comparative example 2. As can be seen from fig. 4, the cardanol polyether sulfate prepared in examples 1 to 3 has a shorter wetting time than that of the cardanol polyoxyethylene ether sulfate in the comparative example, indicating that the cardanol polyether sulfate has better wetting performance than that of the comparative example.

And (3) testing emulsibility: the experimental steps for measuring the emulsifying property by the water-splitting method are as follows: the prepared 1g/L sample aqueous solution was transferred to a 100mL volumetric flask and left for use. To the stoppered cylinder were added 20mL of the aqueous alkynol polyether solution and 20mL of liquid paraffin, and 20mL of the liquid paraffin was removed. The bottle stopper is covered, the thumb tightly buckles the bottle stopper, the neck of the measuring cylinder with the stopper is tightly held in the palm, the bottle is placed on a horizontal table after oscillating up and down for 30 times, the stopwatch is pinched off to start timing, and the measuring cylinder stops timing when 10mL of water is separated from bottom to top. Each sample was run in triplicate and the time to emulsify and demulsify was recorded as an average. FIG. 5 is a schematic diagram showing emulsification properties of cardanol polyether sulfate salt prepared in examples 1 to 3 and comparative example 2. The data in fig. 5 show that the emulsification time of the cardanol polyether sulfate prepared in examples 1-3 is longer than that of the cardanol polyoxyethylene ether sulfate prepared in the comparative example, which indicates that the cardanol polyether sulfate has better emulsification performance.

Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims

1. The cardanol polyether sulfate is characterized by having the following structural general formula:

a＝1～15，b＝1～5。

2. the cardanol polyether sulfate according to claim 1, wherein the sulfation ratio of cardanol polyether sulfate is in the range of: 89 to 96 percent.

3. The cardanol polyether sulfate according to claim 1, characterized in that the structure of the cardanol polyether sulfate is selected from one of the following structures:

wherein, a =13, b =5;

wherein, a =11,b =3;

where a =11,b =5.

4. A method for producing a cardanol polyether sulfate according to any one of claims 1 to 3, characterized by comprising the steps of:

step one, etherification: firstly putting a catalyst into a polymerization kettle, adding cardanol into the polymerization kettle, sealing the polymerization kettle, replacing air in the kettle with nitrogen for 3 times, raising the temperature in the kettle to 100-110 ℃, vacuumizing and dehydrating, keeping the vacuum degree at-0.09 MPa, dehydrating for 1-60 min, slowly introducing ethylene oxide when the temperature is raised to 130 ℃, controlling the reaction temperature in the kettle to 140-150 ℃, controlling the pressure in the kettle to 0.1-0.25 MPa, continuing to react until the pressure in the kettle is basically constant after the ethylene oxide is dripped, curing for 20-120 min at the temperature of 120-130 ℃, introducing propylene oxide, controlling the reaction temperature in the kettle to 140-150 ℃ after the reaction is started, controlling the pressure in the kettle to 0.15-0.25 MPa, continuing to react until the pressure in the kettle is constant after the propylene oxide is dripped, curing for 50-70 min at the temperature of 120-130 ℃, then reducing the temperature in the kettle to 80-90 ℃, 5-15 min, reducing the temperature in the kettle to 60-70 ℃, adding glacial acetic acid and removing water in vacuum for 1-10 min, and degassing to obtain a cardanol product;

or, in the first step, etherification: firstly putting a catalyst into a polymerization kettle, adding cardanol into the polymerization kettle, sealing the polymerization kettle, replacing air in the kettle with nitrogen for 3 times, raising the temperature in the kettle to 100-110 ℃, vacuumizing and dehydrating, keeping the vacuum degree at-0.09 MPa, dehydrating for 1-60 min, slowly introducing propylene oxide when the temperature is raised to 130 ℃, controlling the reaction temperature in the kettle to 140-150 ℃, controlling the pressure in the kettle to 0.1-0.25 MPa, continuing to react until the pressure in the kettle is basically constant after the propylene oxide is dripped, curing for 20-70 min under the condition of 120-130 ℃, introducing ethylene oxide, still controlling the reaction temperature in the kettle to 140-150 ℃ after the reaction is started, controlling the pressure in the kettle to 0.15-0.25 MPa, continuing to react until the pressure in the kettle is constant after the ethylene oxide is dripped, curing for 50-70 min under the condition of 120-130 ℃, then reducing the temperature in the kettle to 80-90 ℃, 5-15 min, reducing the temperature in the kettle to 60-70 ℃, adding glacial acetic acid and removing water in vacuum for 1-10 min, and degassing to obtain a cardanol product;

second step, sulfation: adding a catalyst into the cardanol polyether product prepared in the first step, heating to 80-100 ℃, performing vacuum dehydration for 20-60 min, heating to 120-130 ℃, adding sulfamic acid in three batches, completing the addition within 20-40 min, stirring for reaction for 1-5 h, and cooling to 80-90 ℃ after the reaction is finished to obtain a primary cardanol polyether ammonium sulfate product;

step three, neutralization: and (3) dropwise adding a 30wt% sodium hydroxide aqueous solution into the primary cardanol polyether ammonium sulfate product prepared in the second step, wherein the mass ratio of the primary cardanol polyether ammonium sulfate product prepared in the second step to the 30wt% sodium hydroxide aqueous solution is (5-15): 1, cooling to 50-60 ℃ until no ammonia gas is generated, adding absolute ethyl alcohol to dissolve a product, filtering out insoluble substances, heating the filtrate to 60-70 ℃, and distilling under reduced pressure to remove the absolute ethyl alcohol to obtain the cardanol polyether sulfate.

5. The method for preparing cardanol polyether sulfate according to claim 4, characterized in that the catalyst in the first step is KOH;

in the first step, the mol ratio of cardanol, ethylene oxide and propylene oxide is 1: (11-150): (1-60);

the dosage of the catalyst in the first step is 1-5 per mill of the total mass of cardanol, ethylene oxide and propylene oxide.

6. The preparation method of cardanol polyether sulfate according to claim 4, characterized in that the amount of glacial acetic acid in the first step is 1-5% o of the total mass of cardanol, ethylene oxide and propylene oxide;

the hydroxyl value of the cardanol polyether product is 40-80, and the molecular weight is 800-1200;

the catalyst in the second step is urea.

7. The preparation method of cardanol polyether sulfate according to claim 4, characterized in that the amount of catalyst in the second step is 1.5% -1.7% of the total mass of charge.

8. The method for preparing cardanol polyether sulfate according to claim 4, wherein the molar ratio of cardanol polyether product to sulfamic acid in the second step is 1:1.5 to 2.

9. Use of the cardanol polyether sulfate salt according to any one of claims 1 to 3 in the preparation of an organic pigment dispersant.