Polymer with efficient and long-acting demulsification and coalescence functions for emulsified water as well as preparation method and application of polymer

Abstract

The invention discloses a polymer with efficient and long-acting demulsification and coalescence functions of emulsified water as well as a preparation method and application of the polymer. The polymer is prepared from the following components in parts by mass: 100 parts of a monomer, 1-4 parts of an initiator, 2-6 parts of a surfactant and 300-600 parts of water, the monomer is composed of the following components in parts by mass: 15-30 parts of an acrylate zwitterionic monomer, 3-7 parts of a crosslinking monomer, 10-20 parts of a vinyl polyether monomer and 43-72 parts of other acrylate monomers, and the surfactant is a mixture of a zwitterionic surfactant and polyvinyl alcohol. The polymer provided by the invention can be applied to surface coating modification of various porous filter materials, can enable emulsified water drops to contact and collide with the surface in the process of flowing through the porous filter materials and then instantly generate efficient demulsification coalescence to form large water drops to realize separation, and has a wide application prospect in the field of coalescence separation of emulsified water in fuel oil.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and filter materials, and specifically relates to a polymer with high-efficiency and long-lasting emulsified water demulsification and coalescence functions, and a preparation method and application thereof. Background Art

[0002] Contaminated water in fuels such as diesel or aviation kerosene is an important indicator of oil quality and one of the main causes of engine failure. Contaminated water in fuel can decompose certain additives in the oil to form acid, which can corrode the engine injection system and the engine itself; at the same time, the presence of contaminated water will accelerate the oxidation of the oil and generate viscous sludge, which can easily block microporous parts such as nozzles and filters. In addition, under low temperature conditions, the contaminated water in the fuel will freeze and block the engine oil circuit, affecting the fuel supply; the water in the oil will reduce the combustion value of the oil and lead to an increase in pollutant gas emissions. Therefore, it is particularly necessary to separate water from the oil. However, with the development of ultra-low sulfur fuel and biofuel, in order to ensure that the fuel has sufficient lubricity, the content of surfactants added to the oil continues to increase. The added surfactant will not only adsorb on the oil-water interface, resulting in a decrease in the oil-water interfacial tension (IFT), a decrease in the particle size of water droplets in diesel, and an increase in stability, which will increase the difficulty of oil-water separation. What is more serious is that the surfactant in the oil will be adsorbed on the surface of the filter material, causing the wettability of the filter material to change, thereby affecting the stability of the filter material's oil-water separation efficiency and causing a sharp decline in the material's oil-water separation performance.

[0003] In the early stage of this research team (Chinese patent CN 110330586 B), a polymer with amphiphilic molecular segments on the surface was prepared for the preparation of coalescing materials, which showed good demulsification and coalescence functions for emulsified water in oil containing non-ionic surfactants. However, in fact, there are many types of additives in fuel. In addition to some non-ionic additives, there are also many cationic or anionic additives in the oil system. For additives with different ionic properties, different material surfaces are required to demulsify and coalesce the emulsified water formed by them. Therefore, this also poses a higher challenge to the surface design of oil-water separation materials for fuel. The prior art (Jing Yang et al., Janus membranes with controllable asymmetric configurations for highly efficient separation of oil-in-water emulsions.) reported two positively charged polydopamine / polydiallyldimethylammonium chloride deposited polypropylene microfiltration membranes and negatively charged polydopamine / sodium polystyrene sulfonate deposited polypropylene microfiltration membranes. The two filter membranes can be used to separate emulsions stabilized by anionic and cationic surfactants, respectively. This shows the effectiveness of the method of electrostatic demulsification based on the interaction between different charges. Chinese patent [CN 114225563B] brushes the first viscous solution and the second viscous solution on both sides of the stainless steel mesh soaked in a dopamine solution with a buffer solvent, and obtains a Janus stainless steel mesh with asymmetric charge performance after a series of post-treatments. This Janus stainless steel mesh has one side showing positive charge and the other side showing negative charge, and can simultaneously separate the emulsion stabilized by anionic / cationic surfactants to achieve efficient demulsification. However, the above-reported method requires the preparation of different charge brushing liquid materials, the substrate must also be specially selected and processed, and a relatively complex and sophisticated process is required to achieve the material with asymmetric charge performance characteristics, and the general applicability of the application is poor. Summary of the invention

[0004] In order to solve the shortcomings and deficiencies of the prior art, the main purpose of the present invention is to provide a polymer with efficient and long-lasting emulsified water demulsification and coalescence function and its preparation method and application. The polymer surface can not only produce efficient and long-lasting demulsification and coalescence effect on emulsified water in the presence of surfactants with different ionic properties, but also can achieve efficient and long-lasting oil-water separation performance for emulsified water with different surface charge properties in the oil after the polymer emulsion is dried by a simple surface treatment agent on the porous coalescence substrate.

[0005] The purpose of the present invention is achieved through the following technical solutions:

[0006] A polymer with high efficiency and long-lasting emulsification water demulsification and coalescence function is prepared from the following components by weight: 100 parts of monomer, 1-4 parts of initiator, 2-6 parts of surfactant and 300-600 parts of water;

[0007] The monomers are composed of the following components by weight: 15-30 parts of acrylate zwitterionic monomers, 3-7 parts of crosslinking monomers, 10-20 parts of vinyl polyether monomers, and 43-72 parts of other acrylate monomers;

[0008] The structure of the acrylate zwitterionic monomer is as follows:

[0009]

[0010] Where a = 2-4, b = 2-6, X = COO - or SO3 - ;

[0011] The structure of the vinyl polyether monomer is as follows:

[0012]

[0013] Where n = 2-4, m = 3-8;

[0014] The surfactant is a mixture of a zwitterionic surfactant and polyvinyl alcohol.

[0015] Preferably, the polymer having high efficiency and long-lasting emulsified water demulsification and coalescence function is prepared from the following components by weight: 100 parts of monomer, 2-3 parts of initiator, 2-4 parts of surfactant and 400-500 parts of solvent;

[0016] Preferably, the monomers are composed of the following components by mass: 15-25 parts of acrylate zwitterionic monomers, 3-5 parts of crosslinking monomers, 15-20 parts of vinyl polyether monomers, and 50-70 parts of other common acrylate monomers;

[0017] Preferably, in the acrylate zwitterionic monomer, b is 4 to 6;

[0018] Preferably, in the vinyl polyether monomer, m is 4 to 6;

[0019] Preferably, the cross-linking monomer is a mixture of a polyvinyl cross-linking monomer and a self-cross-linking monomer, and the mass ratio of the two is 1:1-1:4.

[0020] Further preferably, the polyvinyl crosslinking monomer is selected from at least one of divinylbenzene and ethylene glycol dimethacrylate;

[0021] More preferably, the self-crosslinking monomer is selected from at least one of vinyltrimethoxysilane and N-hydroxyethyl acrylamide.

[0022] Preferably, the other acrylate monomer is selected from at least one of butyl acrylate, isooctyl acrylate, ethyl acrylate, n-octyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, and tert-butyl methacrylate;

[0023] Further preferably, the other acrylate monomers are selected from at least one of butyl acrylate, isooctyl acrylate, ethyl acrylate, n-octyl acrylate, dodecyl acrylate and at least one of methyl methacrylate, ethyl methacrylate, tert-butyl methacrylate.

[0024] Preferably, the degree of polymerization of the polyvinyl alcohol is 1500-1900, and the degree of alcoholysis is ≥80%;

[0025] Preferably, the mass ratio of the zwitterionic surfactant to polyvinyl alcohol is 2:1-4:1;

[0026] Further preferably, the mass ratio of the zwitterionic surfactant to polyvinyl alcohol is 2:1-3:1.

[0027] Preferably, the zwitterionic surfactant is selected from at least one of dodecyl dimethyl betaine, sodium dodecyl aspartate and dodecyl hydroxyethyl imidazoline;

[0028] Preferably, the initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile and azoisobutylcyanamide.

[0029] The method for preparing the polymer having the functions of efficient and long-lasting emulsified water demulsification and coalescence comprises the following steps:

[0030] The monomer, initiator, surfactant and water are mixed and reacted at 70-80°C for 2-8 hours to obtain a polymer with high efficiency and long-lasting emulsification, water demulsification and coalescence functions.

[0031] Preferably, the method for preparing the polymer having efficient and long-lasting emulsified water demulsification and coalescence functions specifically comprises the following steps:

[0032] (1) adding 1 / 3 to 1 / 2 of a surfactant (1 / 3 to 1 / 2 of a zwitterionic surfactant and 1 / 3 to 1 / 2 of polyvinyl alcohol) to 100 to 150 parts of water, heating and stirring until completely dissolved, then cooling to room temperature, adding an acrylate zwitterionic monomer to form a pre-emulsion; then mixing a crosslinking monomer, a vinyl polyether monomer, other acrylate monomers and an initiator to form a monomer mixture, adding the monomer mixture to the pre-emulsion while stirring at 800 to 1000 rpm, and then continuing emulsification at 5000 to 8000 rpm for 0.5 to 1.0 h to form a monomer emulsion;

[0033] (2) adding the remaining surfactant and the remaining water into the reaction kettle, and then adding 1 / 4 to 1 / 3 of the monomer emulsion in step (1), heating to 70 to 80° C., and keeping the temperature to react for 1.0 to 2 hours;

[0034] (3) Continue to dropwise add the remaining monomer emulsion of step (1) into the reaction kettle within 2 to 3 hours, and then continue to keep the temperature to react for 2 to 3 hours;

[0035] (4) Cooling to 40-50° C., discharging the material, and obtaining a polymer emulsion having high-efficiency and long-lasting emulsified water demulsification and coalescence functions.

[0036] A coalescing filter material with efficient and long-lasting emulsified water demulsification and coalescing functions comprises the above-mentioned polymer with efficient and long-lasting emulsified water demulsification and coalescing functions and a porous substrate, wherein the polymer with efficient and long-lasting emulsified water demulsification and coalescing functions is attached to the porous substrate.

[0037] The preparation method of the above-mentioned coalescing filter material with high efficiency and long-term emulsified water demulsification and coalescence function comprises the following steps:

[0038] The porous substrate is immersed in a polymer emulsion with high-efficiency and long-term emulsified water demulsification and coalescence function, and then taken out for drying and solidification to obtain a coalescence filter material with high-efficiency and long-term emulsified water demulsification and coalescence function.

[0039] Preferably, the concentration of the polymer emulsion having high efficiency and long-lasting emulsification water demulsification and coalescence function is 1 to 3 wt%.

[0040] Application of the above-mentioned polymer with high-efficiency and long-term emulsified water demulsification and coalescence function or the above-mentioned coalescence filter material with high-efficiency and long-term emulsified water demulsification and coalescence function in oil-water separation.

[0041] Preferably, the oil-water contains at least one of a nonionic surfactant, an anionic surfactant and a cationic surfactant.

[0042] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0043] The polymer with efficient and long-lasting emulsified water demulsification and coalescence function of the present invention is introduced by acrylic acid zwitterionic monomers and vinyl polyether monomers, so that the polymer side chain contains anionic and cationic terminal groups and polyether groups at the same time, so it has efficient demulsification and coalescence effect for emulsified water in oil liquids with anionic surfactants, cationic surfactants or non-ionic surfactants; in addition, due to the solvation and hydrogen bonding of the charged terminal functional groups of the zwitterionic groups, a hydration layer can be formed on the surface of the zwitterionic polymer. This hydration layer surface formed based on electrostatic action is also very helpful in preventing the adsorption of oil molecules on the material surface and causing the attenuation of the interaction performance between the material surface and the emulsified water droplets, and has long-lasting water separation performance. In addition, the polymer with efficient and long-lasting emulsified water demulsification and coalescence function of the present invention has a wide range of applications, can be applied to various porous coalescence substrates through simple processes such as dipping or coating, and can have excellent oil-water separation performance for fuels containing surfactants of different charge properties.

[0044] Although the vinyl polyether used in the present invention has only slight differences in structure from the amphiphilic monomer structure used in the previously applied patent [CN110330586B], in fact, the vinyl polyether monomer used by the inventor in the present invention can undergo a good free radical copolymerization reaction with the other monomer components of the present invention. The conversion rate of the polymer obtained by copolymerization using the vinyl polyether monomer of the present invention is higher than 95%, while the conversion rate of the monomer using the structure of the patent CN110330586B is lower than 85%. The conversion rate of the prepared product is also the reason why the present invention particularly emphasizes the use of the vinyl polyether of this specific structure. In addition, many studies have reported that the use of zwitterionic polymers to prepare underwater super-hydrophilic and oleophobic materials for the separation of oil pollution in water. The present invention controls the structure of the zwitterionic monomer and its proportion in the polymer, and combines the effect of the hydrophilic polyether monomer to maintain the excellent hydrophilic and oleophilic amphiphilic properties of the material surface and apply it to the water aggregation separation in the fuel, which is also a unique feature of the present invention using zwitterionic polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0045] Figure 1 It is a schematic diagram of the test method for the coalescence and separation of emulsified water in oil.

[0046] Figure 2 This is a SEM image of the glass fiber aggregate substrate used in the present invention.

[0047] Figure 3 This is the SEM image of the glass fiber aggregate substrate treated with the polymer prepared in Example 1 (Example 4).

[0048] Figure 4This is the SEM image of the glass fiber aggregate substrate treated with the polymer prepared in Example 2 (Example 5). DETAILED DESCRIPTION

[0049] The present invention is further described in detail below in conjunction with examples and drawings, but the embodiments of the present invention are not limited thereto.

[0050] The experimental methods described in the examples of the present invention are conventional methods unless otherwise specified; the raw materials and reagents used in the examples are commercially available unless otherwise specified.

[0051] The structural formula of the acrylate zwitterionic monomer used in the embodiment is as follows:

[0052]

[0053] Where a = 2-4, b = 2-6, X = COO - or SO3 - ;

[0054] The structural formula of vinyl polyether monomer is as follows:

[0055]

[0056] Among them, n=2-4, m=3-8.

[0057] Example 1

[0058] The polymer with high efficiency and long-lasting emulsification water demulsification and coalescence function is prepared according to the following formula and the following steps:

[0059] (1) 1.5 g of dodecyl dimethyl betaine and 0.6 g of polyvinyl alcohol (with a degree of polymerization of 1700 and a degree of alcoholysis of 88%) were added to 100 g of water, heated and stirred to completely dissolve, and then cooled to room temperature. Then, an acrylate zwitterionic monomer (where a=2, b=6, X=COO - ) 18.0g to form a pre-emulsion, and then add a monomer mixture under high-speed stirring (800rpm), the monomer mixture specifically comprising a vinyl polyether monomer (n=2, b=4) 20.0g, a cross-linking monomer divinylbenzene 1.0g, N-hydroxyethyl acrylamide 3.0g, methyl methacrylate 30.0g, butyl acrylate 28.0g and azobisisobutyronitrile 1.5g, and then continue high-speed emulsification (5000rpm) for 0.5h to form a stable monomer emulsion;

[0060] (2) The remaining 1.5 g of dodecyl dimethyl betaine, 0.6 g of polyvinyl alcohol and 400 g of water were added to the reactor and mixed evenly, and then 1 / 3 of the monomer emulsion in step (1) was added, heated to 75° C., and kept warm for about 1 hour.

[0061] (3) Continue to dropwise add the remaining monomer emulsion of step (1) into the reaction kettle within 2 hours, and continue to keep the temperature for 3 hours;

[0062] (4) Cooling to 40-50° C., discharging the material, and obtaining a polymer emulsion having high efficiency and long-lasting emulsification water demulsification and coalescence functions. The product is white, has no obvious monomer smell, has a monomer conversion rate of 97.42 wt%, and has a gel fraction of only 1.17 wt%, and is stable after being placed for three months.

[0063] Example 2

[0064] The polymer with high efficiency and long-lasting emulsification water demulsification and coalescence function is prepared according to the following formula and the following steps:

[0065] (1) 1.8 g sodium dodecyl aspartate and 0.8 g polyvinyl alcohol (with a polymerization degree of 1700 and a degree of alcoholysis of 99%) were added to 120 g water, heated and stirred to dissolve completely, and then cooled to room temperature. Then, an acrylate zwitterionic monomer (where a=2, b=4, X=SO3) was added. - ) 20.0g to form a pre-emulsion, and then add a monomer mixture under high-speed stirring (1000rpm), the monomer mixture specifically comprising 15.0g of vinyl polyether monomer (n=2, m=6), 1.5g of divinylbenzene, 3.5g of N-hydroxyethyl acrylamide, 30.0g of methyl acrylate, 30.0g of butyl methacrylate and 2.0g of initiator azobisisoheptylnitrile, and then continue high-speed emulsification (5000rpm) for 0.5h to form a stable monomer emulsion;

[0066] (2) The remaining 1.8 g of sodium dodecyl aspartate and 0.8 g of polyvinyl alcohol were added to a reaction kettle and mixed evenly. Then, 1 / 3 of the monomer emulsion in step (1) was added, and the mixture was heated to 75° C. and kept warm for about 1 hour.

[0067] (3) Continue to dropwise add the remaining monomer emulsion of step (1) into the reaction kettle within 2 hours, and continue to keep the temperature for 3 hours;

[0068] (4) Cooling to 45° C., discharging the material, and obtaining a polymer emulsion having high efficiency and long-lasting emulsification water demulsification and coalescence functions. The product is white, has no obvious monomer smell, has a monomer conversion rate of 97.11 wt %, and has a gel fraction of only 1.21 wt %, and is stable after being placed for three months.

[0069] Example 3

[0070] The polymer with high efficiency and long-lasting emulsification water demulsification and coalescence function is prepared according to the following formula and the following steps:

[0071] (1) Add 2.0 g of emulsifier dodecyl hydroxyethyl imidazoline and 0.8 g of polyvinyl alcohol (with a polymerization degree of 1800 and a degree of alcoholysis of 88%) to 100 g of water, heat and stir to dissolve completely, then cool to room temperature, and add acrylate zwitterionic monomer (a=4, m=4, X=SO3 - ) 25.0g to form a pre-emulsion, and then add the remaining monomer mixture under high-speed stirring (800rpm), the monomer mixture specifically comprising vinyl polyether monomer (n=2, m=4) 10.0g, divinylbenzene 2.0g and N-hydroxyethyl acrylamide 2.0g, ethyl acrylate 20.0g, butyl acrylate 41.0g and initiator azobisisoheptylnitrile 2.8g, and then continue high-speed emulsification (8000rpm) for 0.5h to form a stable monomer emulsion;

[0072] (2) The remaining 2.0 g of dodecyl hydroxyethyl imidazoline, 0.80 g of polyvinyl alcohol and 400 g of water were added to the reaction kettle and mixed evenly. Then 1 / 3 of the monomer emulsion in step (1) was added, and the mixture was heated to 75° C. and kept warm for about 1 hour.

[0073] (3) Continue to dropwise add the remaining monomer emulsion of step (1) into the reaction kettle within 2 hours, and continue to keep the temperature for 3 hours;

[0074] (4) Cooling to 40°C, discharging the material, and obtaining a polymer emulsion with high efficiency and long-lasting emulsification water demulsification and coalescence function. The product is white, has no obvious monomer smell, has a gel fraction of only 1.33wt%, a monomer conversion rate of 96.94wt%, and is stable after being placed for three months.

[0075] Comparative Example 1

[0076] The process formula of comparative example 1 is basically the same as that of example 1, except that the acrylate zwitterionic monomer is not added to the system. The final product is a white emulsion with no obvious monomer smell, a gel fraction of only 1.23wt%, a monomer conversion rate of 97.5wt%, and is stable after three months of storage.

[0077] Comparative Example 2

[0078] The process formula of comparative example 2 is basically the same as that of example 1, except that the vinyl polyether monomer is not included in the monomer composition of the mixture. The final product is a white emulsion with no obvious monomer smell, a monomer conversion rate of 96.78wt%, a gel fraction of only 2.17wt%, and is stable after being placed for three months.

[0079] Comparative Example 3

[0080] The process formula of Comparative Example 3 is basically the same as that of Example 1, but the polymer system does not contain acrylate zwitterionic monomers or vinyl polyether monomers, but is an ordinary acrylic emulsion. The final product is a white emulsion with no obvious monomer smell, a monomer conversion rate of 97.25wt%, and a gel fraction of only 1.25wt%, which is stable after being placed for three months.

[0081] Comparative Example 4

[0082] The process formula of Comparative Example 4 is basically the same as that of Example 3, except that the amount of the acrylate zwitterionic monomer in the monomer composition of the mixture is increased from 25.0 g to 38.0 g, and the amount of other acrylate monomers is reduced accordingly (specific amounts are: vinyl polyether monomer (n=2, m=4) 10.0 g, divinylbenzene 2.0 g and N-hydroxyethyl acrylamide 2.0 g, ethyl acrylate 15.0 g, butyl acrylate 33.0 g). The final product is a white viscous emulsion with no obvious monomer smell, a monomer conversion rate of 95.84 wt%, and a gel after being left for 2 days, which cannot be used.

[0083] Comparative Example 5

[0084] The process formula of comparative example 5 is basically the same as that of example 1, except that the emulsifier used does not contain polyvinyl alcohol. The emulsion is separated during the polymerization process, and the gel fraction of the obtained product is as high as 10.33wt% and the monomer taste is obvious. The monomer conversion rate is 79.4wt%. After being left for 3 days, obvious precipitation can be observed, and the product cannot be used.

[0085] Comparative Example 6

[0086] The process formula of Comparative Example 6 is basically the same as that of Example 1, except that the vinyl polyether monomer used in the system is the polyether monomer (methacrylate polyethylene glycol (400) monoester) described in patent CN 114225563B. The final product is a white emulsion with a distinct monomer smell. The total monomer conversion rate is only 81.20wt%. After being placed for one week, the product has stratification and cannot be used.

[0087] Examples 4-6 and Comparative Examples 7-9

[0088] Making of glass fiber base paper: Mix 475-79 glass wool and chopped glass fiber in a mass ratio of 7:3, and use a deflaking machine to deflake at 10,000 revolutions, control pH = 2.5-3.5, and set the basis weight at 48 ± 1 g / m 2 After being evenly dispersed, the slurry is poured into a former, and after dehydration and forming, it is dried on a flat plate to obtain a glass fiber substrate.

[0089] After diluting the emulsions prepared in Examples 1-3 and the polymer emulsions prepared in Comparative Examples 1-3 to a suitable concentration (1.5 wt%), the glass fiber substrate is immersed in the diluted polymer glue solution, taken out and dried and solidified, and the polymer glue amount is controlled within the range of 5.0±0.5% to obtain the agglomerated filter materials of Examples 4-6 and Comparative Examples 7-9.

[0090] The water separation performance of Examples 4-6 and Comparative Examples 7-9 was tested by the water separation test method described below.

[0091] Water separation test method: Use the oil-water separation test bench shown in the figure (such as Figure 1 The water separation performance of the treated glass fiber filter material was tested as shown. First, different types of surfactants were dissolved in a measured oil-water mixture (the oil-water mass ratio was 90:10, and the oil was diesel). The nonionic surfactant used in this experiment was SPAN-80, the anionic surfactant was sodium dodecyl sulfate (SDS), and the cationic surfactant was dodecyl trimethyl ammonium chloride (CTAC). The amount of surfactant added was 0.3wt% of the oil-water mixture (if two, the total amount was 0.3wt%). The oil-water mixture was emulsified at 5000rpm using a high-speed disperser to prepare an oil-water emulsion. After the filter material sample was placed in the fixture, the emulsion was pumped into the filter material sample at a set flow rate. The samples taken from the upstream and downstream liquid intake ports were tested for water content using a Karl Fischer titrator (C20 model, METTLER TOLEDO, Switzerland). The samples were sampled and measured every 15 minutes. When the experimental time reached 1 hour, the test was terminated. The average value of several sampling tests was the total water content of the upstream and downstream. According to the calculation formula: emulsified water separation efficiency (%) = upstream water content - downstream water content) / upstream water content * 100%, the calculation result is the water separation efficiency. The water separation test results are shown in Table 1 below:

[0092] Table 1 Performance test results of each embodiment and comparative example

[0093]

[0094]

[0095] From the water separation test data in Table 1, it can be seen that the polymers with efficient and long-lasting emulsified water demulsification and coalescence functions prepared by Examples 1-3 of the present invention are applied to glass fiber coalescence substrates (Examples 4-6). The modified glass fiber coalescence materials can effectively demulsify and coalesce emulsified water droplets in the oil-water mixture after being emulsified by different ion emulsifier systems, thereby achieving efficient water separation effects. Figures 2 to 4From the microscopic morphology of the glass fiber substrate and the modified glass fiber agglomerated filter material, it can be seen that after polymer impregnation modification, the glass fiber substrate has no obvious pore blocking phenomenon and still maintains a good porous structure of the filter material.

[0096] The polymer prepared in Comparative Example 3 contains neither acrylate zwitterionic monomers nor polyether monomers, and its emulsified water separation performance after emulsification with emulsifiers of different properties is very poor (Comparative Example 9). The polymer prepared in Comparative Example 1 contains vinyl polyether monomers but does not contain acrylate zwitterionic monomers. Therefore, after the polymer prepared is applied to glass fiber coalescing filter material (Comparative Example 7), its oil-water separation performance of emulsified water after emulsification with emulsifiers of different systems is relatively poor, especially the system containing ionic surfactants. The polymer prepared in Comparative Example 2 contains acrylate zwitterionic monomers but does not contain vinyl polyether monomers. Therefore, after the polymer prepared is applied to glass fiber coalescing filter material (Comparative Example 8), its oil-water separation performance of emulsified water after emulsification with emulsifiers of different systems is relatively poor, especially the system containing non-ionic emulsifiers. Comparing the above test results, it is shown that the polymer system contains acrylate zwitterionic monomers and vinyl polyether monomers, which play a crucial role in the efficient separation of emulsified water in the oil-water mixture. After the acrylate zwitterionic monomers are introduced into the present invention, not only the demulsification effect of the system containing ionic surfactants can be improved, but also the demulsification effect of the nonionic emulsifier system can be improved. After the vinyl polyether monomers are introduced, not only the demulsification effect of the nonionic emulsifier system can be improved, but also the demulsification effect of the system containing ionic surfactants can be improved, indicating that the acrylate zwitterionic monomers and vinyl polyether monomers have a synergistic effect on the demulsification effect in the polymer system of the present invention. In addition, Comparative Example 6 uses polyether monomers of other structures. The results show that the compatibility of the monomers of this structure with other monomers of the polymer system is poor, resulting in a conversion rate of the polymer monomer of only 81.2%, a large amount of residual monomers, a strong taste, and an unstable product that cannot meet practical applications.

[0097] After the water separation test was performed on the agglomerated materials of Examples 4-6, they were placed in the test system and immersed in the oil-water mixture for 3 days and then tested again for water separation performance using the same method. The test results are shown in Table 2:

[0098] Table 2 Changes in water separation performance after immersion treatment in each embodiment

[0099]

[0100] It can be seen from the water separation test data in Table 2 that the polymer with high-efficiency and long-lasting emulsified water demulsification and coalescence function prepared by Examples 1-3 of the present invention is applied to a glass fiber coalescence substrate (Examples 4-6). After the modified glass fiber coalescence material is immersed in an oil-water mixture for a long time, the glass fiber coalescence filter material can still maintain a high water separation efficiency, indicating that the water separation material prepared by the present invention is not only highly efficient, but also has excellent long-term effectiveness.

Claims

1. A polymer with high efficiency and long-lasting emulsification water demulsification and coalescence function, characterized in that: The composition is prepared from the following components by weight: 100 parts of monomer, 1-4 parts of initiator, 2-6 parts of surfactant and 300-600 parts of water; The monomers are composed of the following components by weight: 15-30 parts of acrylate zwitterionic monomers, 3-7 parts of crosslinking monomers, 10-20 parts of vinyl polyether monomers, and 43-72 parts of other acrylate monomers; The structure of the acrylate zwitterionic monomer is as follows: Where a = 2-4, b = 2-6, X = COO - or SO3 - ; The structure of the vinyl polyether monomer is as follows: Where n = 2-4, m = 3-8; The surfactant is a mixture of a zwitterionic surfactant and polyvinyl alcohol.

2. The polymer with high efficiency and long-lasting emulsified water demulsification and coalescence function according to claim 1, characterized in that: The cross-linking monomer is a mixture of a polyvinyl cross-linking monomer and a self-cross-linking monomer, and the mass ratio of the two is 1:1-1:

4.

3. The polymer with high efficiency and long-lasting emulsified water demulsification and coalescence function according to claim 2, characterized in that: The polyvinyl cross-linking monomer is selected from at least one of divinylbenzene and ethylene glycol dimethacrylate; The self-crosslinking monomer is selected from at least one of vinyltrimethoxysilane and N-hydroxyethyl acrylamide.

4. The polymer with high efficiency and long-lasting emulsified water demulsification and coalescence function according to claim 1, characterized in that: The other acrylate monomer is selected from at least one of butyl acrylate, isooctyl acrylate, ethyl acrylate, n-octyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, and tert-butyl methacrylate; The degree of polymerization of the polyvinyl alcohol is 1500-1900, and the degree of alcoholysis is ≥80%; The mass ratio of the zwitterionic surfactant to polyvinyl alcohol is 2:1-4:1; The zwitterionic surfactant is selected from at least one of dodecyl dimethyl betaine, sodium dodecyl aspartate and dodecyl hydroxyethyl imidazoline; The initiator is selected from at least one of azobisisobutyronitrile, azobisisoheptanenitrile and azoisobutylcyanoformamide.

5. The method for preparing a polymer having high-efficiency and long-lasting emulsified water demulsification and coalescence functions according to any one of claims 1 to 4, characterized in that: The following steps are involved: The monomer, initiator, surfactant and water are mixed and reacted at 70-80°C for 2-8 hours to obtain a polymer with high efficiency and long-lasting emulsification, water demulsification and coalescence functions.

6. The preparation method according to claim 5, characterized in that: The preparation method of the polymer having high efficiency and long-lasting emulsified water demulsification and coalescence function specifically comprises the following steps: (1) adding 1 / 3 to 1 / 2 of a surfactant to 100 to 150 parts of water, heating and stirring until completely dissolved, then cooling to room temperature, adding an acrylate zwitterionic monomer to form a pre-emulsion; then mixing a crosslinking monomer, a vinyl polyether monomer, other acrylate monomers and an initiator to form a monomer mixture, adding the monomer mixture to the pre-emulsion while stirring at 800 to 1000 rpm, and then continuing emulsification at 5000 to 8000 rpm for 0.5 to 1.0 h to form a monomer emulsion; (2) adding the remaining surfactant and the remaining water into the reaction kettle, and then adding 1 / 4 to 1 / 3 of the monomer emulsion in step (1), heating to 70 to 80° C., and keeping the temperature to react for 1.0 to 2 hours; (3) Continue to dropwise add the remaining monomer emulsion of step (1) into the reaction kettle within 2 to 3 hours, and then continue to keep the temperature to react for 2 to 3 hours; (4) Cooling to 40-50° C., discharging the material, and obtaining a polymer emulsion having high-efficiency and long-lasting emulsified water demulsification and coalescence functions.

7. A coalescing filter material with high efficiency and long-lasting emulsified water demulsification and coalescence function, characterized in that: The invention comprises a polymer with high-efficiency and long-lasting emulsified water demulsification and coalescence function as described in any one of claims 1 to 4 and a porous substrate, wherein the polymer with high-efficiency and long-lasting emulsified water demulsification and coalescence function is attached to the porous substrate.

8. The method for preparing the coalescing filter material with high-efficiency and long-lasting emulsified water demulsification and coalescence function as claimed in claim 7, characterized in that: The following steps are involved: The porous substrate is immersed in a polymer emulsion with high-efficiency and long-term emulsified water demulsification and coalescence function, and then taken out for drying and solidification to obtain a coalescence filter material with high-efficiency and long-term emulsified water demulsification and coalescence function.

9. Use of the polymer with high-efficiency and long-term emulsified water demulsification and coalescence function as described in any one of claims 1 to 4 or the coalescence filter material with high-efficiency and long-term emulsified water demulsification and coalescence function as described in claim 7 in oil-water separation.

10. The use according to claim 9, characterized in that The oil-water contains at least one of a nonionic surfactant, an anionic surfactant and a cationic surfactant.

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