Fluid-responsive intelligent hydrophobic polymer material and preparation method and use method thereof

Abstract

The present invention provides a fluid-responsive intelligent hydrophobic polymer material and its preparation and use methods. The fluid-responsive intelligent hydrophobic polymer material comprises the following raw materials, measured in parts by weight: a dispersant, 0-2 parts; an emulsifier, 0-2 parts; a structural monomer, 10-20 parts; a cross-linking agent, 0-4 parts; a functional monomer, 0.5-5 parts; an initiator, 0.115-1 parts; deionized water, 0-210 parts; and an organic solvent, 0-100 parts. The material is obtained by solution polymerization, emulsion polymerization, or suspension polymerization. The fluid-responsive intelligent hydrophobic polymer material can be immersed in a treatment solution or sprayed with the treatment solution. The hydrophobic function of the fluid-responsive intelligent hydrophobic polymer material can be released in a controlled manner, and the water contact angle can be adjusted within a range of 50° to 150°. The timing of the onset of the hydrophobic function can be adjusted within a time range of 5 minutes to 5 days.

Description

Technical Field

[0001] The present invention relates to functional polymer materials, and in particular to a fluid-responsive intelligent hydrophobic polymer material and a preparation method and a use method thereof. Background Art

[0002] Due to the characteristics of polymer products such as low density, easy functionalization, strong toughness and easy processing performance, they are widely used in the fields of environment, biotechnology and chemical industry. Especially after the hydrophobic functionalization of polymers, their application areas are further expanded.

[0003] On the one hand, existing hydrophobic surface modification work is mostly carried out around inorganic products such as ceramsite, quartz sand, glass, and concrete. The effect is achieved by high-temperature curing a layer of hydrophobic resin on the surface of the inorganic product. This surface hydrophobic modification method that relies on a high-temperature curing process will cause the polymer to age, melt, or even decompose at high temperatures, and therefore cannot be copied for general polymer surface modification. On the other hand, conventional hydrophobic surface preparation methods, including surfactants, fluorine-containing or non-fluorine-containing silicone material impregnation or spraying, have a weak hydrophobic effect and poor durability.

[0004] Furthermore, certain applications require that the surface wettability of polymer products be adjustable during use, necessitating the development of new intelligent hydrophobic materials and their preparation methods. For example, in oil and gas production, to address the high water content of deep reservoirs and older wells in the later stages of production, the surface of proppant microspheres must be hydrophobic. However, proppants with hydrophobic surfaces tend to aggregate due to hydrophobic interactions during migration with the fracturing fluid, resulting in a reduction in fracture proppant efficiency. This requires that the proppant surface be hydrophilic or neutral during migration, and then become hydrophobic upon entering the fracture. Summary of the Invention

[0005] To address the problems existing in the prior art, the present invention provides a fluid-responsive intelligent hydrophobic polymer material, its preparation method, and its use method. The hydrophobicity of the fluid-responsive intelligent hydrophobic polymer material proposed in the present invention is gradually released from scratch, and the release rate can be controlled by the molecular structure of the structural and functional monomers, the composition characteristics of the treatment solution, and the treatment temperature. The water contact angle can be adjusted within a range of 50° to 150°, and the onset of hydrophobicity can be controlled within a time range of 5 minutes to 5 days.

[0006] The technical solution adopted in the present invention is:

[0007] The fluid-responsive intelligent hydrophobic polymer material comprises the following raw materials, calculated in parts by weight:

[0008] Dispersant, 0-2 parts;

[0009] Emulsifier, 0-2 parts;

[0010] Structural monomer, 10-20 parts;

[0011] Cross-linking agent, 0-4 parts;

[0012] Functional monomer, 0.5~5 parts;

[0013] Initiator, 0.115~1 part;

[0014] Deionized water, 0-210 parts;

[0015] Organic solvent, 0-100 parts;

[0016] Wherein, the structural monomer is one or more of ethyl methacrylate, acrylic acid, acrylonitrile, methyl acrylate, butyl acrylate, methacrylonitrile, and acrylamide;

[0017] The cross-linking agent is one or more of isoprene, butadiene, triethylene glycol divinyl ether, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, and trimethylolpropane triacrylate;

[0018] The functional monomer is one of vinyl triacetoxysilane, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, and dimethyl hexadecylaminoethanol chlorinated methacrylate;

[0019] The hydrophobic function of the fluid-responsive smart hydrophobic polymer material can be released in a controlled manner, the water contact angle can be regulated within the range of 50° to 150°, and the timing of starting to exhibit the hydrophobic function can be regulated within the time range of 5 minutes to 5 days.

[0020] Furthermore, the dispersant is one or more of polyacrylic acid, starch, polyvinyl alcohol and graphite.

[0021] Furthermore, the emulsifier is one or more of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and methylcellulose.

[0022] Furthermore, the initiator is one of benzoyl peroxide, azobisisoheptanonitrile, azobisisobutyronitrile, and tert-butylcumene peroxide.

[0023] Furthermore, the solvent is one of chloroform, dichloroethane, toluene, tetrahydrofuran, and acetone.

[0024] Based on the same inventive concept, the present invention also provides a method for preparing the aforementioned fluid-responsive smart hydrophobic polymer material, which is obtained by solution polymerization, emulsion polymerization or suspension polymerization.

[0025] Furthermore, when solution polymerization is adopted, the following steps are included:

[0026] Step S11, dissolving the structural monomer, cross-linking agent, functional monomer and initiator in an organic solvent under mechanical stirring, and stirring thoroughly;

[0027] Step S12, maintaining stirring, setting the system temperature to 60-150° C., heating to 60-150° C. and reacting for 1-12 hours;

[0028] Step S13, ethanol is used to precipitate the polymer, and after multiple centrifugation, washing, dissolution, reprecipitation and washing, drying is performed to obtain a fluid-responsive smart hydrophobic polymer material;

[0029] When using emulsion polymerization, the following steps are included:

[0030] Step S21, dissolving the structural monomer, cross-linking agent, functional monomer, emulsifier and initiator in deionized water under mechanical stirring, and stirring thoroughly;

[0031] Step S22, maintaining stirring, setting the system temperature to 60-150° C., heating to 60-150° C. and reacting for 1-12 hours;

[0032] Step S23, using centrifugal demulsification, washing, dissolving, reprecipitating and washing for multiple times, and then drying to obtain a fluid-responsive smart hydrophobic polymer material;

[0033] When suspension polymerization is used, the following steps are included:

[0034] Step S31, under the action of mechanical stirring, the structural monomer, cross-linking agent, functional monomer, dispersant, initiator and water are mixed and stirred thoroughly;

[0035] Step S32: maintaining stirring, setting the system temperature to 60-150° C., heating to 60-150° C. and reacting for 1-12 hours;

[0036] Step S33: filtration, washing the polymer microspheres on the filter cake with acetone, ethanol, and water in sequence, and drying to obtain a fluid-responsive intelligent hydrophobic polymer material.

[0037] Based on the same inventive concept, the present invention also provides a method for using the aforementioned fluid-responsive smart hydrophobic polymer material, comprising the following steps:

[0038] According to the time required to release the hydrophobic function and the size of the hydrophobic capacity, the treatment liquid is prepared with a treatment agent or clean water is used as the treatment liquid;

[0039] The fluid-responsive smart hydrophobic polymer material is immersed in the treatment liquid or the treatment liquid is sprayed on the surface of the fluid-responsive smart hydrophobic polymer material.

[0040] Furthermore, when the treatment liquid is prepared using the treatment agent, the mass concentration of the treatment liquid is 1-50%;

[0041] And / or, the contact temperature between the fluid-responsive smart hydrophobic polymer material and the treatment liquid is controlled within a range of 25-130°C.

[0042] Furthermore, the treatment agent is one of 1-methyl-3-butylimidazole chloride-aluminum trichloride, alkaline ionic liquid, citric acid, and ascorbic acid.

[0043] The beneficial effects of the present invention are:

[0044] 1. The present invention provides a fluid-responsive intelligent hydrophobic polymer material, the components of which include structural monomers, crosslinking agents, and functional monomers. The structural monomers are one or more of ethyl methacrylate, acrylic acid, acrylonitrile, methyl acrylate, butyl acrylate, methacrylonitrile, and acrylamide; the crosslinking agent is one or more of isoprene, butadiene, triethylene glycol divinyl ether, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, and trimethylolpropane triacrylate; and the functional monomer is one of vinyltriacetoxysilane, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, and dimethylhexadecylaminoethanol chloromethacrylate. The hydrophobicity of this fluid-responsive intelligent hydrophobic polymer material stems from the chemically bonded micro-nano rough structures firmly grown on its surface, rather than a simple physical coating resin layer or impregnated surfactant / organic silicone layer. Therefore, it is less susceptible to erosion and corrosion from the working fluid. At the same time, the hydrophobic function of the fluid-responsive smart hydrophobic polymer material can be released in a controlled manner, the water phase contact angle can be adjusted in the range of 50°~150°, and the timing of the onset of the hydrophobic function can be adjusted in the time range of 5 minutes to 5 days.

[0045] 2. The preparation method of the fluid-responsive smart hydrophobic polymer material of the present invention is simple and can be obtained by solution polymerization, emulsion polymerization or suspension polymerization, and can be made into smart hydrophobic polymer products in the shape of nanopowders, spheres, blocks, films, sheets, etc.

[0046] 3. The present invention also provides a method for using a fluid-responsive smart hydrophobic polymer material. First, a treatment solution is prepared using a treatment agent or water, depending on the required time for releasing the hydrophobic function and the required hydrophobic capacity. The fluid-responsive smart hydrophobic polymer material is then immersed in the treatment solution or sprayed with the treatment solution on its surface. Unlike traditional hydrophobic products, the hydrophobicity of the fluid-responsive smart hydrophobic polymer material proposed in the present invention is gradually released from scratch, and the release rate can be controlled by the molecular structure of the structural and functional monomers, the composition of the treatment solution, and the treatment temperature. DETAILED DESCRIPTION

[0047] The following describes it in detail with reference to the embodiments.

[0048] A fluid-responsive smart hydrophobic polymer material comprises the following raw materials, measured in parts by weight:

[0049] Dispersant, 0-2 parts; emulsifier, 0-2 parts; structural monomer, 10-20 parts; cross-linking agent, 0-4 parts; functional monomer, 0.5-5 parts; initiator, 0.115-1 parts; deionized water, 0-210 parts; organic solvent, 0-100 parts.

[0050] The structural monomer is one or more of ethyl methacrylate, acrylic acid, acrylonitrile, methyl acrylate, butyl acrylate, methacrylonitrile, and acrylamide; the cross-linking agent is one or more of isoprene, butadiene, triethylene glycol divinyl ether, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, and trimethylolpropane triacrylate; the functional monomer is one of vinyl triacetoxysilane, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, and dimethylhexadecylaminoethanol chloromethacrylate; the dispersant is one or more of polyacrylic acid, starch, polyvinyl alcohol, and graphite; the emulsifier is one or more of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and methylcellulose; the initiator is one of benzoyl peroxide, azobisisoheptonitrile, azobisisobutyronitrile, and tert-butyl peroxide isopropylbenzene; and the solvent is one of chloroform, ethylene dichloride, toluene, tetrahydrofuran, and acetone.

[0051] The method for using the aforementioned fluid-responsive smart hydrophobic polymer material includes the following steps: using a treatment agent to prepare a treatment liquid or using clean water (such as tap water) as the treatment liquid based on the time required to release the hydrophobic function and the size of the hydrophobic capacity; immersing the fluid-responsive smart hydrophobic polymer material in the treatment liquid or spraying the treatment liquid on the surface of the fluid-responsive smart hydrophobic polymer material.

[0052] When the treatment liquid is prepared using the treatment agent, the mass concentration of the treatment liquid is 1~50%; the contact temperature between the fluid-responsive intelligent hydrophobic polymer material and the treatment liquid is controlled at 25~130°C; and the treatment agent is one of chloro-1-methyl-3-butylimidazole-aluminum trichloride, alkaline ionic liquid, citric acid, and ascorbic acid.

[0053] The following is a more specific example. Examples 1 to 4 are solution polymerizations, Examples 5 to 8 are emulsion polymerizations, and Examples 9 to 12 are suspension polymerizations. The raw material compositions in each example are shown in Tables 1 to 3.

[0054] Table 1 Fluid-responsive smart hydrophobic polymer materials (solution polymerization)

[0055]

[0056] Table 2 Fluid-responsive smart hydrophobic polymer materials (emulsion polymerization)

[0057]

[0058] Table 3 Fluid-responsive smart hydrophobic polymer materials (suspension polymerization)

[0059]

[0060] The fluid-responsive smart hydrophobic polymer materials of Examples 1-12 were immersed in water, a 1% solids 1-methyl-3-butylimidazole chloride-aluminum trichloride aqueous solution, a 1% solids alkaline ionic liquid aqueous solution, a 1% solids citric acid aqueous solution, and a 1% solids ascorbic acid aqueous solution, respectively, at a temperature of 28°C. The water contact angles of the fluid-responsive smart hydrophobic polymer materials were measured before and after immersion and at different immersion times. The water contact angle test results for Examples 1-12 are shown in Table 4.

[0061]

[0062]

[0063]

[0064]

[0065]

[0066] From the data in Table 4, it can be seen that, on the one hand, by designing the raw material composition and process method of the fluid-responsive smart hydrophobic polymer material, the fluid-responsive smart hydrophobic polymer material can be made to have or not have a hydrophobic function in the initial state.

[0067] On the other hand, the fluid-responsive smart hydrophobic polymer material in this embodiment, after being immersed in 100% clean water, a 1% solid content 1-methyl-3-butylimidazole-aluminum trichloride aqueous solution, a 1% solid content alkaline ionic liquid aqueous solution, a 1% solid content citric acid aqueous solution, and a 1% solid content water-soluble ascorbic acid aqueous solution, all showed a gradual release of hydrophobic function from zero to one (generally speaking, a water contact angle greater than 60° is considered to have hydrophobic function), or a further improvement of the hydrophobic function.

[0068] On the one hand, by selecting different treatment agents, the fluid-responsive smart hydrophobic polymer material can be controlled to rapidly release the strongest hydrophobic function at a specific time point (i.e., reach near the maximum value of the water contact angle). For example, the time for the fluid-responsive smart hydrophobic polymer material to rapidly release the strongest hydrophobic function in 100% clean water is 3 days; the time for the fluid-responsive smart hydrophobic polymer material to rapidly release the strongest hydrophobic function in a 1% solid content 1-methyl-3-butylimidazole-aluminum chloride aqueous solution and a 1% solid content alkaline ionic liquid aqueous solution is 5 minutes; the time for the fluid-responsive smart hydrophobic polymer material to rapidly release the strongest hydrophobic function in a 1% solid content citric acid aqueous solution is 12 hours; and the time for the fluid-responsive smart hydrophobic polymer material to rapidly release the strongest hydrophobic function in a 1% solid content water-soluble ascorbic acid aqueous solution is 24 hours. This also shows that the hydrophobic function of the fluid-responsive smart hydrophobic polymer material in this embodiment can be controlled to release, the water contact angle can be adjusted within the range of 50° to 150°, and the time when the hydrophobic function begins to be displayed can be adjusted within the time range of 5 minutes to 5 days.

[0069] The fluid-responsive smart hydrophobic polymer materials of Examples 1 to 12 were immersed in a citric acid aqueous solution with a solid content of 5%, a citric acid aqueous solution with a solid content of 10%, a citric acid aqueous solution with a solid content of 30%, and a citric acid aqueous solution with a solid content of 50%, respectively. The temperature of the treatment liquid was maintained at 28°C. The water contact angles of the fluid-responsive smart hydrophobic polymer materials were measured before and after immersion and at different immersion times. The test results of the water contact angles are shown in Table 5.

[0070]

[0071]

[0072]

[0073]

[0074] The data in Table 5 show that varying the solid content of the citric acid solution (that is, the mass concentration of the treatment fluid) can shorten the time it takes for the fluid to rapidly release its strongest hydrophobic properties in response to the smart hydrophobic polymer material. For example, increasing the solid content of the citric acid solution from 1% to 50% shortens the time it takes for the strongest hydrophobic properties to be released from 12 hours to 30 minutes. In other words, varying the mass concentration of the treatment fluid can control the time it takes for the fluid to rapidly release its strongest hydrophobic properties in response to the smart hydrophobic polymer material.

[0075] A citric acid aqueous solution with a solid content of 1% was used as the treatment liquid. Equal amounts of the treatment liquid were heated to 50°C, 80°C, and 100°C, respectively. The fluid-responsive smart hydrophobic polymer materials of Examples 1 to 12 were immersed in the aforementioned treatment liquids. The water contact angles of the fluid-responsive smart hydrophobic polymer materials were measured before and after immersion and at different immersion times. The test results of the water contact angles are shown in Table 6.

[0076]

[0077]

[0078]

[0079] The data in Table 6 show that changing the temperature of the citric acid solution (that is, the contact temperature between the treatment solution and the fluid-responsive smart hydrophobic polymer material) can shorten the time it takes for the fluid-responsive smart hydrophobic polymer material to rapidly release its strongest hydrophobic function. For example, increasing the temperature of the citric acid solution from 28°C to 100°C shortens the time it takes for the fluid-responsive smart hydrophobic polymer material to release its strongest hydrophobic function from 12 hours to 15 minutes. This means that changing the temperature of the treatment solution can also control the time it takes for the fluid-responsive smart hydrophobic polymer material to rapidly release its strongest hydrophobic function.

[0080] In summary, unlike the performance of traditional hydrophobic products, the hydrophobicity of the fluid-responsive smart hydrophobic polymer material proposed in the embodiments of the present invention is gradually released from scratch, and the release rate can be controlled by the molecular structure of the structural monomers and functional monomers, the composition characteristics of the treatment liquid, and the treatment temperature.

[0081] The fluid-responsive smart hydrophobic polymer material prepared in the embodiments of the present invention is in the form of nanopowder, sphere or block. Similarly, the fluid-responsive smart hydrophobic polymer material can also be processed into films or sheets, regardless of the polymerization method and molding process.

[0082] The fluid-responsive smart hydrophobic polymer materials prepared in the examples of the present invention were tested for water contact using an immersion method, but could also be sprayed on the surface, regardless of the contact method. Because the hydrophobic function of the fluid-responsive smart hydrophobic polymer materials can be controlled to release, the water contact angle can be adjusted within a range of 50° to 150°, and the onset of hydrophobicity can be controlled within a timeframe of 5 minutes to 5 days, embracing a wide range of applications.

Claims

1. Fluid-responsive smart hydrophobic polymer material, characterized in that: In parts by weight, it includes the following raw materials: Dispersant, 0-2 parts; Emulsifier, 0-2 parts; Structural monomer, 10-20 parts; Cross-linking agent, 0-4 parts; Functional monomer, 0.5~5 parts; Initiator, 0.115~1 part; Deionized water, 0-210 parts; Organic solvent, 0-100 parts; Wherein, the structural monomer is one or two of ethyl methacrylate, acrylic acid, acrylonitrile, methyl acrylate, butyl acrylate, methacrylonitrile, and acrylamide; The cross-linking agent is one of isoprene, butadiene, triethylene glycol divinyl ether, 3,9-divinyl-2,4,8,10-tetraoxaspiro[5.5]undecane, and trimethylolpropane triacrylate; The functional monomer is one of vinyl triacetoxysilane, hexafluorobutyl acrylate, dodecafluoroheptyl methacrylate, and dimethyl hexadecylaminoethanol chlorinated methacrylate; The hydrophobic function of the fluid-responsive smart hydrophobic polymer material can be released in a controlled manner, the water contact angle can be regulated within the range of 50° to 150°, and the timing of starting to exhibit the hydrophobic function can be regulated within the time range of 5 minutes to 5 days.

2. The fluid-responsive smart hydrophobic polymer material according to claim 1, characterized in that: The dispersant is one or more of polyacrylic acid, starch, polyvinyl alcohol and graphite.

3. The fluid-responsive smart hydrophobic polymer material according to claim 1, wherein: The emulsifier is one or more of sodium dodecylbenzenesulfonate, sodium lauryl sulfate, and methylcellulose.

4. The fluid-responsive smart hydrophobic polymer material according to claim 1, wherein: The initiator is one of benzoyl peroxide, azobisisoheptanenitrile, azobisisobutyronitrile and tert-butylcumene peroxide.

5. The fluid-responsive smart hydrophobic polymer material according to claim 1, wherein: The solvent is one of chloroform, dichloroethane, toluene, tetrahydrofuran and acetone.

6. The method for preparing a fluid-responsive smart hydrophobic polymer material according to any one of claims 1 to 5, wherein: It is obtained by solution polymerization, emulsion polymerization or suspension polymerization.

7. The method for preparing a fluid-responsive smart hydrophobic polymer material according to claim 6, wherein: When solution polymerization is used, the following steps are included: Step S11, dissolving the structural monomer, cross-linking agent, functional monomer and initiator in an organic solvent under mechanical stirring, and stirring thoroughly; Step S12, maintaining stirring, setting the system temperature to 60-150° C., heating to 60-150° C. and reacting for 1-12 hours; Step S13, ethanol is used to precipitate the polymer, and after multiple centrifugation, washing, dissolution, reprecipitation and washing, drying is performed to obtain a fluid-responsive smart hydrophobic polymer material; When using emulsion polymerization, the following steps are included: Step S21, dissolving the structural monomer, cross-linking agent, functional monomer, emulsifier and initiator in deionized water under mechanical stirring, and stirring thoroughly; Step S22, maintaining stirring, setting the system temperature to 60-150° C., heating to 60-150° C. and reacting for 1-12 hours; Step S23, using centrifugal demulsification, washing, dissolving, reprecipitating and washing for multiple times, and then drying to obtain a fluid-responsive smart hydrophobic polymer material; When suspension polymerization is used, the following steps are included: Step S31, under the action of mechanical stirring, the structural monomer, cross-linking agent, functional monomer, dispersant, initiator and water are mixed and stirred thoroughly; Step S32: maintaining stirring, setting the system temperature to 60-150° C., heating to 60-150° C. and reacting for 1-12 hours; Step S33: filtration, washing the polymer microspheres on the filter cake with acetone, ethanol, and water in sequence, and drying to obtain a fluid-responsive intelligent hydrophobic polymer material.

8. The method for using the fluid-responsive smart hydrophobic polymer material according to any one of claims 1 to 5, wherein: The following steps are involved: According to the time required to release the hydrophobic function and the size of the hydrophobic capacity, the treatment liquid is prepared with a treatment agent or clean water is used as the treatment liquid; The fluid-responsive smart hydrophobic polymer material is immersed in the treatment liquid or the treatment liquid is sprayed on the surface of the fluid-responsive smart hydrophobic polymer material.

9. The method for using the fluid-responsive smart hydrophobic polymer material according to claim 8, wherein: When the treatment liquid is prepared using the treatment agent, the mass concentration of the treatment liquid is 1-50%; And / or, the contact temperature between the fluid-responsive smart hydrophobic polymer material and the treatment liquid is controlled within a range of 25-130°C.

10. The method for using the fluid-responsive smart hydrophobic polymer material according to claim 8, wherein: The treatment agent is one of chloro-1-methyl-3-butylimidazole-aluminum trichloride, alkaline ionic liquid, citric acid and ascorbic acid.

Images