A method for preparing an amino-functionalized polymer

Abstract

This invention discloses a method for preparing an amino-functionalized polymer, belonging to the field of polymer materials technology. The amino-functionalized polymer of this invention contains structural units derived from furfurylamine monomers and structural units derived from electron-withdrawing monomers in its molecular structure. This material is prepared by copolymerizing furfurylamine-derived monomers and electron-withdrawing monomers, followed by hydrolysis. It features a tunable molecular structure, high amino content, and exhibits excellent hydrophilicity and interfacial control capabilities. In terms of preparation method, this invention achieves the controllable synthesis of the polymer through monomer construction, free radical copolymerization, and post-treatment modification steps. The process is simple and easy to scale up industrially. This polymer possesses both excellent oil-water separation and adhesive properties. In the field of oil-water separation, this material can effectively demulsify and achieve efficient separation. When used in the field of wood adhesives, it exhibits good adhesion properties, high internal bond strength, and no formaldehyde release.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a method for preparing an amino-functionalized polymer. Background Technology

[0002] With the continuous advancement of industrialization, the treatment of large quantities of oily wastewater and emulsified oil systems poses a severe challenge to ecological security and water resource utilization efficiency. Especially in industries such as oil extraction, machinery manufacturing, food processing, and textile printing and dyeing, stable oil-water emulsions are widespread, and their separation is far more difficult than traditional oil-water separation systems. Therefore, developing efficient, stable, and environmentally friendly oil-water separation materials has become a current research hotspot.

[0003] Common oil-water separation materials include porous membranes, inorganic particulate materials, and surface-modified fabrics. Among these, polymer-based materials have attracted widespread attention due to their strong structural designability, ease of processing, and relatively low cost. However, traditional polymer materials generally suffer from insufficient hydrophilicity, poor antifouling properties, and poor stability in complex environments (such as high-salt and high-acid / alkaline conditions), which limits their practical applications.

[0004] In recent years, introducing polar groups (such as hydroxyl, carboxyl, and amino groups) into polymers to improve their hydrophilicity and interfacial properties has become an effective strategy. Among them, amino-functionalized polymers, due to their ability to form stable hydration layers and their certain reactivity, have shown excellent performance in oil-water separation and interfacial regulation. However, existing amino-functionalized polymers often suffer from problems such as complex preparation processes, high raw material costs, or poor structural tunability. For example, some studies have used metal-organic framework materials or complex multi-step reactions for functionalization modification, which, while exhibiting outstanding performance, are difficult to scale up for application.

[0005] On the other hand, in the wood industry, traditional adhesives (such as urea-formaldehyde resin and phenolic resin), while possessing good bonding properties, suffer from formaldehyde release, posing potential hazards to human health and the environment. Therefore, developing environmentally friendly adhesives with low or even no formaldehyde release has become an important direction for industry development. Amino-functionalized polymers, due to their presence of active amino groups, can form hydrogen bonds or covalent bonds with hydroxyl groups in wood components, thus offering the potential advantage of low formaldehyde release while improving bonding strength.

[0006] Furfurylamine compounds are derived from biomass resources (such as furfural), possessing both renewability and good reactivity. By reacting furfurylamine with aldehydes or carbonyl compounds to form polymerizable monomers, and then introducing electron-withdrawing monomers through free radical polymerization, structurally tunable functionalized polymer systems can be constructed. However, systematic research on these systems remains relatively scarce, particularly regarding the balance between oil-water separation and adhesive properties.

[0007] Therefore, it is of great significance to develop an amino-functionalized polymer with controllable structure, simple preparation, excellent performance, and both oil-water separation and adhesive properties. Summary of the Invention

[0008] The purpose of this invention is to provide a method for preparing an amino-functionalized polymer to solve the aforementioned problems in the background art. This amino-functionalized polymer is prepared by copolymerizing furfurylamine-derived monomers with electron-withdrawing monomers followed by hydrolysis. It features a tunable molecular structure, high amino content, and exhibits excellent hydrophilicity and interfacial control capabilities. In terms of preparation method, this invention achieves controllable synthesis of the polymer through monomer construction, free radical copolymerization, and post-treatment modification steps. The process is simple and easily scaled up for industrial applications. This polymer possesses both excellent oil-water separation and adhesive properties. In the field of oil-water separation, this material can effectively demulsify and achieve efficient separation. When used in the field of wood adhesives, it exhibits good bonding properties, high internal bond strength, and no formaldehyde release.

[0009] To achieve the above objectives, the present invention provides the following technical solution: One of the technical solutions of the present invention is to provide an amino-functionalized polymer, wherein the molecular structure of the amino-functionalized polymer contains structural units derived from furfurylamine monomers and structural units derived from electron-withdrawing monomers. The structural units derived from furfurylamine monomers include at least one of structural unit I and structural unit II, and the structural units derived from electron-withdrawing monomers include one or more of structural units III-VII: The structural formulas of structural units I-VII are as follows: , , , , , , ; Among them, R1 and R4 are independently selected from oxygen atoms, aliphatic tertiary amine groups with 1-10 carbon atoms, and aromatic tertiary amine groups with 6-10 carbon atoms, respectively. , , and One of them; R2, R3, R5, R6, R9, R 10 R 13 R 14 R 16 Each is independently selected from one of the hydrogen atom and the methyl group; R7, R8, R 11 R 12 R 15Each of the following is independently selected from hydroxyl, amino, aliphatic amines with 1-10 carbon atoms, aromatic amines with 6-10 carbon atoms, aliphatic oxy groups with 1-10 carbon atoms, aromatic oxy groups with 6-10 carbon atoms, hydroxyethoxy, hydroxypropoxy, hydroxybutoxy, and hydroxypentoxy.

[0010] Furthermore, the molar ratio of the structural units derived from furfurylamine monomers to the structural units derived from electron-withdrawing monomers is 1:0.1-50.

[0011] Furthermore, the number-average molecular weight of the amino-functionalized polymer is 500-100000 g / mol.

[0012] Furthermore, the amino content of the amino-functionalized polymer is 0.03-5 mmol / g.

[0013] The second technical solution of the present invention provides a method for preparing the above-mentioned amino-functionalized polymer, comprising the following steps: (1) Furfurylamine and a compound containing polar unsaturated bonds are mixed in a solvent to obtain a mixture, and a condensation reaction is carried out to obtain monomer A; (2) The monomer A, the electron-withdrawing monomer and the initiator are mixed in a solvent to obtain a precursor solution, and a polymerization reaction is carried out to obtain a copolymer; The copolymer was subjected to a hydrolysis reaction to obtain an amino-functionalized polymer; The compound containing a polar unsaturated bond is a compound containing an aldehyde group, a compound containing a carbonyl group, or a compound containing a thionyl group; The aldehyde-containing compound includes one of formaldehyde, acetaldehyde, n-butyraldehyde, isobutyraldehyde, glyoxal, glutaraldehyde, furfural, benzaldehyde, and pyromellitic methylformaldehyde, preferably formaldehyde, acetaldehyde, or glyoxal; The carbonyl-containing compound includes one of acetone, butanone, pentanone, and cyclohexanone, preferably acetone or butanone; The thionyl group-containing compound includes one of dimethyl sulfoxide, diphenyl sulfoxide, and methylphenyl sulfoxide, preferably dimethyl sulfoxide.

[0014] In this invention, the core role of compounds containing polar unsaturated bonds is to undergo a condensation reaction with the amino group of furfurylamine during the monomer construction stage, forming a protecting group on the amino group and preventing unintended side reactions with the electron-withdrawing monomer. The introduced electron-withdrawing monomer provides reaction sites for subsequent modification of the copolymer. After copolymerization, the protecting group on the amino group is removed by hydrolysis, releasing the free amino group and achieving amino functionalization of the polymer. Furthermore, amination reactions can further chemically modify the structural units derived from the electron-withdrawing monomer to endow them with stronger reactivity and hydrophilicity.

[0015] Further, in step (1): the solvent is an alcohol solvent, an ether solvent, a halohydrocarbon solvent or an aromatic hydrocarbon solvent.

[0016] Furthermore, the alcohol solvent includes one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, sec-butanol, ethylene glycol, glycerol, n-pentanol, cyclohexanol, and benzyl alcohol, preferably at least one of methanol and ethanol.

[0017] Further, the ether solvent includes one or more of dimethyl ether, methyl ethyl ether, diethyl ether, ethyl propyl ether, dipropyl ether, dibutyl ether, methyl propyl ether, methyl butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl isopentyl ether, methyl tert-amyl ether, methyl cyclopentyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane, preferably one or more of diethyl ether, tetrahydrofuran, methyl tert-butyl ether, and 1,4-dioxane.

[0018] Furthermore, the halogenated hydrocarbon solvent includes one or more of dichloromethane, chloroform, carbon tetrachloride, and chlorobenzene, preferably at least one of dichloromethane and chloroform.

[0019] Furthermore, the aromatic hydrocarbon solvent includes one of benzene, toluene, ethylbenzene, xylene, and cumene, preferably one or more of benzene and toluene.

[0020] Furthermore, the molar ratio of the amino group in the furfurylamine to the polar unsaturated bond in the compound containing the polar unsaturated bond is 1:0.8-10, preferably 1:0.8-1.5.

[0021] Furthermore, the total mass of the furfurylamine and the compound containing polar unsaturated bonds accounts for 1-50% of the mass of the mixture, preferably 5-20%.

[0022] Furthermore, the condensation reaction is carried out at a temperature of 20-130°C, preferably 30-60°C, for a time of 1-24 h, preferably 2-10 h.

[0023] Furthermore, the electron-withdrawing monomer is maleic anhydride, maleimide, N -Phenyl maleimide, itaconic anhydride, dimethyl maleate, diallyl maleate, acrylic acid, α-methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate or 2-ethylhexyl acrylate, preferably maleic anhydride, maleimide, itaconic anhydride, acrylic acid, hydroxyethyl acrylate or hydroxyethyl methacrylate.

[0024] Furthermore, the initiator is a peroxide initiator or an azo initiator; The peroxide initiator includes one or more of benzoyl peroxide, dicumyl peroxide, cumyl hydroperoxide, ditert-butyl peroxide, dodecyl peroxide, and benzoic acid peroxide, preferably benzoyl peroxide; The azo initiator includes one or more of azobisisobutyronitrile, azobisisovalerate, azobisisoheptanenitrile, azoisobutylcyanoformamide, azobiscyclohexylformitrile, and dimethyl azobisisobutyrate, preferably at least one of azobisisobutyronitrile and azobisisoheptanenitrile.

[0025] Further, in step (2): the solvent is an organic acid alkyl ester solvent, an aromatic solvent, an ether solvent, an alkane solvent, or a ketone solvent.

[0026] Furthermore, the organic acid alkyl ester solvent includes one of ethyl formate, propyl formate, isobutyl formate, amyl formate, ethyl acetate, butyl acetate, isobutyl acetate, amyl acetate, isoamyl acetate, benzyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, butyl butyrate, isobutyl butyrate, isoamyl butyrate, ethyl isobutyrate, ethyl isovalerate, isoamyl isovalerate, methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate, ethyl phenylacetate, propyl phenylacetate, butyl phenylacetate, and isoamyl phenylacetate, preferably one of ethyl acetate, butyl acetate, amyl acetate, and isoamyl acetate; Furthermore, the aromatic solvent includes one of toluene, ethylbenzene, xylene, and cumene, preferably toluene; Furthermore, the ether solvent includes one of dimethyl ether, methyl ethyl ether, ethyl ether, ethyl propyl ether, dipropyl ether, dibutyl ether, methyl propyl ether, methyl butyl ether, methyl isobutyl ether, methyl tert-butyl ether, methyl isopentyl ether, methyl tert-amyl ether, methyl cyclopentyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane, preferably one of ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and tetrahydrofuran; Furthermore, the alkane solvent includes one of n-pentane, isopentane, n-hexane, cyclohexane, isohexane, n-heptane, methylcyclohexane, n-octane, isooctane, n-nonane, and n-decane, preferably one of n-hexane, cyclohexane, and n-heptane.

[0027] Furthermore, the ketone solvent includes one of acetone, butanone, cyclohexanone, methyl isobutyl ketone, and methyl isopropyl ketone, preferably acetone or butanone.

[0028] Furthermore, the molar ratio of monomer A to electron-withdrawing monomer is 0.1-2:1, preferably 0.1-1.5:1.

[0029] Furthermore, the initiator has a mass percentage of 0.00001-1% in the precursor solution, preferably 0.001-1%.

[0030] Furthermore, the total mass of monomer A and electron-withdrawing monomer in the precursor solution accounts for 1-20% of the total mass, preferably 5-20%.

[0031] Furthermore, the polymerization reaction is carried out at a temperature of 40-100°C, preferably 45-80°C, for a time of 1-12 h.

[0032] Furthermore, the hydrolysis reaction is carried out in an acidic solution or in water.

[0033] Furthermore, the acidic solution is an inorganic acid solution, an organic acid solution, or a solid acid catalyst solution; The inorganic acid solution is a hydrochloric acid solution with a concentration of 0.01-12 mol / L, a sulfuric acid solution with a concentration of 0.01-6 mol / L, or a phosphoric acid solution with a concentration of 0.1-1 mol / L, preferably a hydrochloric acid solution with a concentration of 0.1-6 mol / L, and more preferably a hydrochloric acid solution with a concentration of 0.1-1 mol / L. The organic acid solution contains one or more of formic acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, citric acid, and oxalic acid, and the mass fraction of the organic acid in the organic acid solution is 1-10%; preferably, it is an acetic acid solution with a mass fraction of 10%. The solid acid catalyst in the solid acid catalyst solution is at least one of HZSM-5 and Amberlyst-15.

[0034] Furthermore, the concentration of the copolymer in the acidic solution or water is 0.001-0.2 kg / L, preferably 0.01-0.2 kg / L.

[0035] Furthermore, the hydrolysis reaction is carried out at a temperature of 0-50°C, preferably 30-50°C, for a time of 0.1-24 h.

[0036] Furthermore, after the polymerization reaction is completed, the step of amination reaction of the copolymer is included, specifically: mixing the copolymer with an amine compound, performing an amination reaction to obtain an amination copolymer, and then hydrolyzing the amination copolymer to obtain an amino-functionalized polymer.

[0037] Furthermore, the amine compound is ammonia or monomethylamine.

[0038] Furthermore, the molar ratio of the amino group in the amine compound to the structural unit of the derived electron-withdrawing monomer in the copolymer is 1-1.5:1.

[0039] Furthermore, the amination reaction is carried out at a temperature of 20-180°C for a time of 0.1-10 h.

[0040] The third technical solution of the present invention provides an application of the above-mentioned amino-functionalized polymer in the field of oil-water separation.

[0041] The fourth technical solution of the present invention provides an application of the above-mentioned amino-functionalized polymer in the field of adhesives.

[0042] Furthermore, the adhesive is a wood adhesive.

[0043] The beneficial technical effects of the present invention are as follows: This invention provides an amino-functionalized polymer, which is prepared by copolymerizing furfurylamine-derived monomers with electron-withdrawing monomers followed by hydrolysis. This polymer features a tunable molecular structure and high amino content, exhibiting excellent hydrophilicity and interfacial control capabilities.

[0044] In terms of preparation method, the present invention achieves the controllable synthesis of the polymer through monomer construction, free radical copolymerization and post-treatment modification, which is simple and easy to scale up industrially.

[0045] In terms of applications, this polymer combines excellent oil-water separation performance with adhesive properties. In the field of oil-water separation, this material can effectively demulsify and achieve highly efficient separation, with a separation efficiency of over 95% and a water flux of up to 500 L·m³. -2 ·h -1 The above properties indicate that when used in the field of wood adhesives, it exhibits excellent bonding performance, with an internal bond strength exceeding 1 MPa, and it releases no formaldehyde, making it suitable as an environmentally friendly wood adhesive.

[0046] Compared with existing technologies, this invention has the advantages of wide availability of raw materials, some of which are derived from biomass resources, being green and environmentally friendly, having a simple preparation process, controllable structure, and a wide range of applications. Attached Figure Description

[0047] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0048] Figure 1 The image shows the 1H NMR spectrum of monomer A from Example 1.

[0049] Figure 2 The image shows the carbon NMR spectrum of monomer A from Example 1.

[0050] Figure 3 The image shows the infrared spectrum of the copolymer in Example 2.

[0051] Figure 4 The image shows the infrared spectrum of the amino-functionalized polymer in Example 3.

[0052] Figure 5 The image shows the 1H NMR spectrum of the amino-functionalized polymer in Example 5.

[0053] Figure 6 The infrared spectrum of the amino-functionalized polymer in Example 6 is shown. Detailed Implementation

[0054] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0055] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, are also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0056] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. It should be noted that any aspects of this invention not described in detail are conventional practices in the art and are not the focus of this invention.

[0057] The terms “comprising,” “including,” “having,” “containing,” etc., used in this invention are all open-ended terms, meaning that they include but are not limited to.

[0058] Unless otherwise specified, all percentages in this invention are expressed as mass percentages.

[0059] The PET nonwoven fabric used in this invention was purchased from Jialianda Nonwoven Fabric Enterprise Store on Taobao. Product name: Nonwoven PET high temperature resistant 250 degrees Celsius black and white fabric, heat transfer printing, custom-made, wear-resistant, breathable, waterproof, thickened; Model: PET white 120g, thickness 0.25±0.02 mm, areal density 80±5 g / m². 2 The average pore size is approximately 25 μm.

[0060] All raw materials used in the following embodiments and comparative examples of the present invention are commercially available products.

[0061] The technical solution of the present invention will be further illustrated by the following embodiments.

[0062] Example 1 A method for preparing an amino-functionalized polymer, comprising the following steps: 10 g of furfurylamine (0.14 mol) and 5 g of formaldehyde solution (37% aqueous solution) were dissolved in 50 mL of ethanol. The mixture was then subjected to a condensation reaction at 40 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 95%. Figure 1 , Figure 2 The images show the hydrogen NMR spectrum and carbon NMR spectrum of monomer A in Example 1, respectively.

[0063] 1.09 g of monomer A, 0.98 g of maleic anhydride, and 0.01 g of azobisisobutyronitrile were dissolved in 25 mL of isoamyl acetate. After three freeze-drain cycles, polymerization was carried out at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 1800 g / mol, n1+n3=n2=9, and the yield is 83%.

[0064] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (Amino content is 5 mmol / g).

[0065] Example 2 10 g of furfurylamine (0.14 mol) and 5 g of glyoxal were dissolved in 50 mL of ethanol. The mixture was then subjected to a condensation reaction at 40 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 95%.

[0066] 1.09 g of monomer A, 0.98 g of maleic anhydride, and 0.01 g of azobisisobutyronitrile were dissolved in 25 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The yield was 95%. Figure 3 The image shows the infrared spectrum of the copolymer in Example 2.

[0067] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). The number-average molecular weight is approximately 3600 g / mol, n=18, and the amino content is 5 mmol / g.

[0068] Example 3 10 g of furfurylamine (0.14 mol) and 13.5 g of furfural were dissolved in 50 mL of methanol. The mixture was then subjected to a condensation reaction at 40 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 91%.

[0069] 1.75 g of monomer A, 0.98 g of maleic anhydride, and 0.01 g of azobisisobutyronitrile were dissolved in 25 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The yield was 77%.

[0070] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). The number-average molecular weight is approximately 3600 g / mol, n=18, and the amino content is 5 mmol / g. Figure 4 The image shows the infrared spectrum of the amino-functionalized polymer in Example 3.

[0071] Example 4 10 g of furfurylamine (0.14 mol) and 15 g of benzaldehyde were dissolved in 50 mL of methanol. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 98%.

[0072] 1.85 g of monomer A, 0.98 g of maleic anhydride, and 0.01 g of azobisisobutyronitrile were dissolved in 25 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The yield was 83%.

[0073] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). The number-average molecular weight is approximately 3600 g / mol, n=18, and the amino content is 5 mmol / g.

[0074] Example 5 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0075] 1.23 g of monomer A, 0.72 g of acrylic acid, and 0.01 g of azobisisobutyronitrile were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 82,000 g / mol, n1+n3=5, n2=1200, and the yield is 92%.

[0076] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (Amino content is 0.06 mmol / g). Figure 5 The image shows the 1H NMR spectrum of the amino-functionalized polymer in Example 5.

[0077] Example 6 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0078] 1.23 g of monomer A, 0.97 g of maleimide, and 0.01 g of azobisisobutyronitrile were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 4000 g / mol, and the yield is 84%.

[0079] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (n1=10, n2=30, amino content is 2.5 mmol / g). Figure 6 The infrared spectrum of the amino-functionalized polymer in Example 6 is shown.

[0080] Example 7 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0081] 1.23 g of monomer A, 1.94 g of maleimide, and 0.03 g of azobisisobutyronitrile were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 3000 g / mol, and the yield is 71%.

[0082] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (n1=5, n2=25, amino content is 1.67 mmol / g).

[0083] Example 8 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0084] 1.23 g of monomer A, 0.49 g of maleimide, and 0.03 g of azobisisobutyronitrile were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 800 g / mol, and the yield is 76%.

[0085] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (n1=1, n2=7, amino content is 1.25 mmol / g).

[0086] Example 9 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0087] 1.23 g of monomer A, 0.49 g of maleimide, and 0.03 g of benzoyl peroxide were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 85 °C for 6 h. After the reaction was complete, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 1800 g / mol, and the yield is 83%.

[0088] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (n1=1, n2=17, amino content is 0.56 mmol / g).

[0089] Example 10 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0090] 1.23 g of monomer A, 0.49 g of maleimide, and 0.03 g of benzoyl peroxide were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 60 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 600 g / mol, and the yield is 67%.

[0091] 0.5 g of the obtained copolymer was hydrolyzed in 25 mL of 0.5 mol / L hydrochloric acid at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (n1=3, n2=3, amino content is 5mmol / g).

[0092] Example 11 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0093] 1.23 g of monomer A, 0.49 g of maleimide, and 0.03 g of benzoyl peroxide were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 60 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 600 g / mol, and the yield is 67%.

[0094] 0.5 g of the obtained copolymer was hydrolyzed in 50 mL of 5% acetic acid solution at 40 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (n1=3, n2=3, amino content is 5mmol / g).

[0095] Example 12 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0096] 1.23 g of monomer A, 0.49 g of maleimide, and 0.03 g of benzoyl peroxide were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 60 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 600 g / mol, and the yield is 67%.

[0097] 0.5 g of the obtained copolymer was hydrolyzed in 50 mL of 5% acetic acid solution at 30 °C for 4 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer (…). (n1=3, n2=3, amino content is 5mmol / g).

[0098] Example 13 10 g of furfurylamine (0.14 mol) and 7 g of acetaldehyde were dissolved in 50 mL of dichloromethane. The mixture was then subjected to a condensation reaction at 30 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 88%.

[0099] 1.23 g of monomer A, 0.49 g of maleimide, and 0.03 g of benzoyl peroxide were dissolved in 30 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 60 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 600 g / mol, and the yield is 67%.

[0100] 0.5 g of the obtained copolymer and 0.1 g of Amberlyst-15 were hydrolyzed in 20 mL of deionized water at 30 °C for 8 h. After the reaction was completed, the copolymer was separated, washed, and dried to obtain the amino-functionalized polymer. (n1=3, n2=3, amino content is 5 mmol / g).

[0101] Example 14 10 g of furfurylamine (0.14 mol) and 5 g of formaldehyde solution (37% aqueous solution) were dissolved in 50 mL of ethanol. The mixture was then subjected to a condensation reaction at 40 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 95%.

[0102] 1.09 g of monomer A, 0.98 g of maleic anhydride, and 0.01 g of azobisisobutyronitrile were dissolved in 25 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 1800 g / mol, n1+n3=n2=9, and the yield is 90%.

[0103] In a closed environment, 0.044 mL of methylamine was introduced into 0.5 g of the copolymer, and the reaction was carried out at 180 °C for 10 h to obtain the amination copolymer ( , n1+n3=9, n2=5, n4=4).

[0104] 0.5 g of the obtained amination copolymer and 0.1 g of Amberlyst-15 were hydrolyzed in 20 mL of deionized water at 30 °C for 8 h. After the reaction was completed, the mixture was separated, washed, and dried to obtain the amino-functionalized polymer (…). (Amino content is 5 mmol / g).

[0105] Example 15 10 g of furfurylamine (0.14 mol) and 5 g of formaldehyde solution (37% aqueous solution) were dissolved in 50 mL of ethanol. The mixture was then subjected to a condensation reaction at 40 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 95%.

[0106] 1.09 g of monomer A, 0.98 g of maleic anhydride, and 0.01 g of azobisisobutyronitrile were dissolved in 25 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 1800 g / mol, n1+n3=n2=9, and the yield is 90%.

[0107] In a closed environment, 0.060 mL of ammonia gas was introduced into 0.5 g of the copolymer, and the reaction was carried out at 60 °C for 2 h to obtain the amination copolymer ( ).

[0108] 0.5 g of the obtained amination copolymer and 0.1 g of Amberlyst-15 were hydrolyzed in 20 mL of deionized water at 30 °C for 8 h. After the reaction was completed, the mixture was separated, washed, and dried to obtain the amino-functionalized polymer (…). (Amino content is 5 mmol / g).

[0109] Example 16 10 g of furfurylamine (0.14 mol) and 5 g of formaldehyde solution (37% aqueous solution) were dissolved in 50 mL of ethanol. The mixture was then subjected to a condensation reaction at 40 °C for 6 h. After the reaction was complete, monomer A was obtained by separation, washing, and drying, with a yield of 95%.

[0110] 1.09 g of monomer A, 0.98 g of maleic anhydride, and 0.01 g of azobisisobutyronitrile were dissolved in 25 mL of isoamyl acetate. After three freeze-drain cycles, the mixture was reacted at 70 °C for 6 h. After the reaction was completed, the copolymer was obtained by separation, washing, and drying. The number-average molecular weight is approximately 1800 g / mol, n1+n3=n2=9, and the yield is 90%.

[0111] In a closed environment, 0.060 mL of ammonia gas was introduced into 0.5 g of the copolymer, and the reaction was carried out at 120 °C for 6 h to obtain the amination copolymer ( ).

[0112] 0.5 g of the obtained amination copolymer and 0.1 g of Amberlyst-15 were hydrolyzed in 20 mL of deionized water at 30 °C for 8 h. After the reaction was completed, the mixture was separated, washed, and dried to obtain the amino-functionalized polymer (…). (Amino content is 5 mmol / g).

[0113] The reason for the corresponding changes in the structural formula of the amination copolymers in Examples 14-16 after the amination reaction is that the maleic anhydride structural unit in the copolymer has strong electrophilicity and undergoes a nucleophilic ring-opening reaction under the action of amine compounds (methylamine, ammonia) to generate an amide-carboxylic acid structure. Subsequently, the amide-carboxylic acid structure dehydrates at high temperature to form an imide structure.

[0114] Example 17 1 g of the amino-functionalized polymer prepared in Example 1 was dissolved in 1 L of deionized water. Then, PET nonwoven fabric was immersed in the solution for 10 min. Afterward, it was removed and placed in an oven at 80°C for 8 h to obtain hydrophilic modified PET, denoted as PET-1.

[0115] Under gravity, xylene / water emulsion (prepared by adding 1% sodium dodecyl sulfonate by volume of xylene and water at a ratio of 1:100, and emulsifying at 10,000 rpm for 30 min) was performed using a PET-1. Five experiments were conducted, with a separation volume of 40 mL each. The separation efficiency and water flux were averaged across the five experiments.

[0116] Example 18 1 g of the amino-functionalized polymer prepared in Example 3 was dissolved in 1 L of deionized water. Then, PET nonwoven fabric was immersed in the solution for 10 min. Afterward, it was removed and placed in an oven at 80°C for 8 h to obtain hydrophilic modified PET, denoted as PET-3.

[0117] Under gravity, a mixed emulsion of n-octane and 3wt% NaCl aqueous solution (volume ratio of n-octane to 3wt% NaCl aqueous solution was 5:95) was separated using PET-3. Five experiments were conducted, and the separation efficiency and water flux were averaged across the five experiments.

[0118] Example 19 1 g of the amino-functionalized polymer prepared in Example 5 was dissolved in 1 L of deionized water. Then, PET nonwoven fabric was immersed in the solution for 10 min. Afterward, it was removed and placed in an oven at 80°C for 8 h to obtain hydrophilic modified PET, denoted as PET-5.

[0119] Under gravity, a PET-5 was used to separate a mixed solution of n-heptane and 3wt% NaCl aqueous solution (volume ratio of n-heptane to 3wt% NaCl aqueous solution was 1:1). The experiment was repeated five times, and the separation efficiency and water flux were averaged across the five trials.

[0120] Example 20 1 g of the un-amino-functionalized copolymer prepared in Example 6 was dissolved in 1 L of deionized water. Then, PET nonwoven fabric was immersed in the solution for 10 min. Afterward, it was removed and placed in an oven at 80°C for 8 h to obtain hydrophilic modified PET, denoted as PET-6.

[0121] Under gravity, a petroleum ether / water emulsion (prepared by adding 1% sodium dodecyl sulfonate by volume of petroleum ether and water, and emulsifying at 10,000 rpm for 30 min) was separated using PET-6. Five experiments were conducted, and the separation efficiency and water flux were averaged across the five experiments.

[0122] Comparative Example 1 Immerse PET nonwoven fabric in 1 L of deionized water for 10 min. Then, remove it and place it in an oven at 80℃ for 8 h to obtain hydrophilic modified PET, denoted as PET.

[0123] Under gravity, xylene / water emulsion (prepared by adding 1% sodium dodecyl sulfonate by volume of xylene and water at a ratio of 1:100, and emulsifying at 10,000 rpm for 30 min) was separated using PET. Five experiments were conducted, and the separation efficiency and water flux were averaged across the five experiments.

[0124] The formula for calculating the separation efficiency of this invention is as follows: in, J It is water flux; η It is the separation efficiency; m 0 and m The masses of the oil phase before and after separation are respectively; A It is the effective separation area of ​​the nonwoven fabric; t It is the separation time.

[0125] Table 1. Oil-water separation efficiency and water flux of Examples 17-19 and Comparative Example 1 In Table 1, xylene / water emulsions failed to pass through unhydrophilic PET under gravity. Petroleum ether / water emulsions also failed to pass through PET-6 under gravity, primarily because the copolymers used in these emulsions were not amino-functionalized, resulting in insufficient surface hydrophilicity and demulsification ability.

[0126] Example 20 20 g of the amino-functionalized polymer prepared in Example 6 was dissolved in 100 g of deionized water. Subsequently, the solution was coated between 14 cm × 14 cm × 2 mm linden wood strips and hot-pressed at 0.1 MPa and 140 °C for 5 min.

[0127] The sample was adjusted and its internal bond strength was tested according to the test requirements of GB / T 11718-2009, and the result was 0.9 MPa.

[0128] Example 21 20 g of the amino-functionalized polymer prepared in Example 9 was dissolved in 100 g of deionized water. Subsequently, the solution was coated between 14 cm × 14 cm × 2 mm linden wood strips and hot-pressed at 0.1 MPa and 140 °C for 5 min.

[0129] The sample was adjusted and its internal bond strength was tested according to the test requirements of GB / T 11718-2009, and the measured value was 1.1 MPa.

[0130] Example 22 20 g of the amino-functionalized polymer prepared in Example 12 was dissolved in 100 g of deionized water. Subsequently, the solution was coated between 14 cm × 14 cm × 2 mm linden wood strips and hot-pressed at 0.1 MPa and 140 °C for 5 min.

[0131] The sample was adjusted and its internal bond strength was tested according to the test requirements of GB / T 11718-2009, and the measured value was 1.1 MPa.

[0132] Example 23 20 g of the amino-functionalized polymer prepared in Example 14 was dissolved in 100 g of deionized water. Subsequently, the solution was coated between 14 cm × 14 cm × 2 mm linden wood strips and hot-pressed at 0.1 MPa and 140 °C for 5 min.

[0133] The sample was adjusted and its internal bond strength was tested according to the test requirements of GB / T 11718-2009, and the measured value was 1.3 MPa.

[0134] Example 24 20 g of the amino-functionalized polymer prepared in Example 15 was dissolved in 100 g of deionized water. Subsequently, the solution was coated between 14 cm × 14 cm × 2 mm linden wood strips and hot-pressed at 0.1 MPa and 140 °C for 5 min.

[0135] The sample was adjusted and its internal bond strength was tested according to the test requirements of GB / T 11718-2009, and the measured value was 1.5 MPa.

[0136] Comparative Example 2 20 g of the un-amino-functionalized amination copolymer prepared in Example 15 was dissolved in 100 g of deionized water. Subsequently, the solution was coated between 14 cm × 14 cm × 2 mm linden wood strips and hot-pressed at 0.1 MPa and 140 °C for 5 min.

[0137] The sample was adjusted and its internal bond strength was tested according to the test requirements of GB / T 11718-2009, and the measured value was 0.7 MPa.

[0138] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. An amino-functionalized polymer, characterized in that, The molecular structure of the amino-functionalized polymer contains structural units derived from furfurylamine monomers and structural units derived from electron-withdrawing monomers. The structural units derived from furfurylamine monomers include at least one of structural unit I and structural unit II, and the structural units derived from electron-withdrawing monomers include one or more of structural units III-VII: The structural formulas of structural units I-VII are as follows: 、 、 、 、 、 、 ； Among them, R1 and R4 are independently selected from oxygen atoms, aliphatic tertiary amine groups with 1-10 carbon atoms, and aromatic tertiary amine groups with 6-10 carbon atoms, respectively. , , and One of them; R2, R3, R5, R6, R9, R 10 R 13 R 14 R 16 Each is independently selected from one of the hydrogen atom and the methyl group; R7, R8, R 11 R 12 R 15 Each of the following is independently selected from hydroxyl, amino, aliphatic amines with 1-10 carbon atoms, aromatic amines with 6-10 carbon atoms, aliphatic oxy groups with 1-10 carbon atoms, aromatic oxy groups with 6-10 carbon atoms, hydroxyethoxy, hydroxypropoxy, hydroxybutoxy, and hydroxypentoxy.

2. The amino-functionalized polymer according to claim 1, characterized in that, The molar ratio of the structural units derived from furfurylamine monomers to the structural units derived from electron-withdrawing monomers is 1:0.1-50; The amino-functionalized polymer has a number-average molecular weight of 500-100,000 g / mol and an amino content of 0.03-5 mmol / g.

3. A method for preparing the amino-functionalized polymer according to any one of claims 1-2, characterized in that, Includes the following steps: (1) Furfurylamine and a compound containing polar unsaturated bonds are mixed in a solvent to obtain a mixture, and a condensation reaction is carried out to obtain monomer A; (2) The monomer A, the electron-withdrawing monomer and the initiator are mixed in a solvent to obtain a precursor solution, and a polymerization reaction is carried out to obtain a copolymer; the copolymer is subjected to a hydrolysis reaction to obtain an amino-functionalized polymer; The compound containing a polar unsaturated bond is a compound containing an aldehyde group, a compound containing a carbonyl group, or a compound containing a thionyl group.

4. The preparation method according to claim 3, characterized in that, The aldehyde-containing compounds include one of formaldehyde, acetaldehyde, n-butyraldehyde, isobutyraldehyde, glyoxal, glutaraldehyde, furfural, benzaldehyde, and pyromellitic methylformaldehyde; The carbonyl-containing compound includes one of acetone, butanone, pentanone, and cyclohexanone; The thionyl group-containing compound includes one of dimethyl sulfoxide, diphenyl sulfoxide, and methylphenyl sulfoxide; The molar ratio of the amino group in the furfurylamine to the polar unsaturated bond in the compound containing the polar unsaturated bond is 1:0.8-10; The total mass of furfurylamine and the compound containing polar unsaturated bonds accounts for 1-50% of the mass of the mixture.

5. The preparation method according to claim 3, characterized in that, The condensation reaction is carried out at a temperature of 20-130℃ for 1-24 hours.

6. The preparation method according to claim 3, characterized in that, The electron-withdrawing monomers are maleic anhydride and maleimide. N -Phenyl maleimide, itaconic anhydride, dimethyl maleate, diallyl maleate, acrylic acid, α-methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, n-butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, or 2-ethylhexyl acrylate. The initiator is a peroxide initiator or an azo initiator; The initiator has a mass percentage of 0.00001-1% in the precursor solution; The molar ratio of monomer A to electron-withdrawing monomer is 0.1-2:1; The combined mass of monomer A and electron-withdrawing monomers accounts for 1-20% of the mass of the precursor solution.

7. The preparation method according to claim 3, characterized in that, The polymerization reaction is carried out at a temperature of 40-100℃ for a time of 1-12 h. The hydrolysis reaction is carried out in an acidic solution or in water; The hydrolysis reaction is carried out at a temperature of 0-50℃ for a time of 0.1-24 h.

8. The preparation method according to claim 3, characterized in that, After the polymerization reaction is completed, the copolymer is further subjected to an amination reaction, specifically: the copolymer is mixed with an amine compound and subjected to an amination reaction to obtain an amination copolymer, and then the amination copolymer is subjected to a hydrolysis reaction to obtain an amino-functionalized polymer. The amine compound is ammonia or monomethylamine; The molar ratio of the amino group in the amine compound to the structural unit of the derived electron-withdrawing monomer in the copolymer is 1-1.5:1; The amination reaction is carried out at a temperature of 20-180℃ for a time of 0.1-10 h.

9. The application of the amino-functionalized polymer according to any one of claims 1-2 in the field of oil-water separation.

10. The use of an amino-functionalized polymer according to any one of claims 1-2 in the field of adhesives.

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