Hydrolysis-resistant polymer as well as preparation method and application thereof

Abstract

The invention relates to a hydrolysis-resistant polymer as well as a preparation method and application thereof. The hydrolysis-resistant polymer is prepared from the following raw materials: a polymeric monomer, an initiator, a pH regulator and a chain transfer agent, the polymeric monomer comprises an acrylate compound, an alkene compound containing an oxazolinyl group and conjugated diene; based on the total mass of the polymeric monomer as 100%, the mass percentage of the acrylate compound in the polymeric monomer is 10%-30%, and the mass percentage of the alkene compound containing oxazolinyl and the conjugated diene in the polymeric monomer is 70%-90%; the mass ratio of the alkene compound containing oxazolinyl to the conjugated diene is (0.4-2.5): 1, and the hydrolysis-resistant polymer can improve the hydrolysis resistance and toughness of carboxyl-containing resin.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and in particular to a hydrolysis-resistant polymer and a preparation method and application thereof. Background Art

[0002] Carboxyl resins are widely used in coatings, adhesives, plastics, and other fields. However, these materials often suffer from poor resistance to hydrolysis, water absorption, or other toxicity during use, making them susceptible to erosion and degradation by water molecules, thus affecting their service life and performance. Furthermore, carboxyl resins, due to their polar carboxyl structure, exhibit excellent adhesion, compatibility, and reactivity. However, their rigid structure often results in poor toughness, brittle cracking, and insufficient elasticity. Therefore, in practical applications, they require toughness enhancement or elasticity modification.

[0003] To improve the hydrolysis resistance, water absorption resistance, or durability of carboxyl-containing resins, existing technologies typically use crosslinking agents. However, traditional crosslinking agents, such as epoxy resins and isocyanates, have certain drawbacks, such as low crosslinking efficiency and the generation of harmful substances during the crosslinking process, making them difficult to meet the long-term use requirements of the materials.

[0004] CN111635466A discloses a terminal oxazoline-based polybutadiene compound and a preparation method thereof, wherein the terminal oxazoline-based polybutadiene compound adopts carboxyl-terminated polybutadiene, thionyl chloride, and ethanolamine to react in an organic solvent under certain conditions to prepare the terminal oxazoline-based polybutadiene compound. The carboxyl-terminated polybutadiene itself is an elastomer, has a toughening effect, and has good compatibility with high-impact polystyrene, acrylonitrile-butadiene-styrene copolymer, and polypropylene, and the carboxyl group generated by aging can react to achieve molecular chain repair and reaction expansion. However, the technical solution still has the low carboxyl content reaction degree of oxazoline-based groups, which is not enough, and the hydrolysis resistance of carboxyl-containing resins is improved to insufficient conditions, and the use of organic solvents is not environmentally friendly.

[0005] Therefore, it is necessary to develop an anti-hydrolysis polymer that can effectively improve the hydrolysis resistance and toughness of carboxyl-containing resins, extend the service life of the material, avoid the production of harmful by-products, and meet environmental protection requirements. Summary of the Invention

[0006] To solve the above technical problems, the present invention provides a hydrolysis-resistant polymer and its preparation method and application. The hydrolysis-resistant polymer has the effect of improving the hydrolysis resistance and toughness of carboxyl-containing resins and extending their service life. The preparation process does not require organic solvents and is safe and environmentally friendly.

[0007] To achieve this object, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a hydrolysis-resistant polymer, wherein raw materials for preparing the hydrolysis-resistant polymer include a polymerizable monomer, an initiator, a pH regulator, and a chain transfer agent; the polymerizable monomer includes an acrylate compound, an oxazoline-containing olefin compound, and a conjugated diene; and based on the total mass of the polymerizable monomer as 100%, the mass percentage of the acrylate compound in the polymerizable monomer is 10% to 30% (e.g., 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, or 28%, etc.); The mass percentage of the oxazoline-containing olefin compound and the conjugated diene in the polymerized monomer is 70% to 90% (for example, 72%, 74%, 76%, 78%, 80%, 82%, 84%, 86% or 88%, etc.); the mass ratio of the oxazoline-containing olefin compound to the conjugated diene is (0.4 to 2.5):1, for example, 0.5:1, 0.7:1, 0.9:1, 1.1:1, 1.3:1, 1.5:1, 1.7:1, 1.9:1, 2.1:1 or 2.3:1, etc.

[0009] In the present invention, the anti-hydrolysis polymer has the effect of improving the hydrolysis resistance and toughness of the carboxyl resin and extending the service life. If the content of the acrylic acid ester compound is too low, the water resistance will be reduced. If the content of the acrylic acid ester compound is too high, the proportion of the oxazoline-containing olefin compound and the conjugated diene will be low, which will reduce its crosslinking or toughness. If the conjugated diene content is too low, the toughness cannot be guaranteed to be improved; if it is too high, the content of the other monomers will be reduced, resulting in insufficient improvement in crosslinking performance, poor hydrolysis resistance, etc. If the content of the oxazoline-containing olefin compound is too low, the crosslinking with the carboxyl resin cannot be guaranteed, and sufficient crosslinking cannot be carried out, thereby affecting the hydrolysis resistance; if it is too high, the content of the other monomers will be reduced, resulting in insufficient improvement in toughness or poor hydrolysis resistance. The oxazoline-containing olefin compound and the conjugated diene can effectively improve the role of the anti-hydrolysis polymer in improving the hydrolysis resistance and toughness of the carboxyl resin at a specific content ratio. In the hydrolysis-resistant polymer, the structural units formed by the acrylic acid ester compound, the oxazoline-containing olefin compound and the conjugated diene may be randomly distributed.

[0010] Preferably, the mass ratio of the oxazoline-containing olefin compound to the conjugated diene is (0.7-1.3):1, for example, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.05:1, 1.1:1, 1.:15:1, 1.2:1 or 1.25:1, etc.

[0011] Preferably, the acrylate compound has a structure as shown in Formula I.

[0012]

[0013] In Formula I, R1, R2, R3 are each independently any one of hydrogen, methyl, or ethyl; and R4 is each independently a C1-C30 (e.g., C4, C7, C10, C13, C16, C19, C22, C25, or C28, etc.) hydrocarbyl group.

[0014] Illustratively, in Formula I, R4 is a C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) alkyl group or a C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9, etc.) cycloalkyl group.

[0015] Illustratively, in Formula I, R1, R2 are hydrogen; and R3, R4 are methyl.

[0016] Illustratively, in Formula I, R1, R2 are hydrogen; R3 is methyl; and R4 is 1,7,7- trimethylbicyclo[2.2.1]heptan-2-yl.

[0017] Preferably, the acrylate compound includes any one of or a combination of at least two of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, tridecyl acrylate, tridecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, t-butylcyclohexyl acrylate, t-butylcyclohexyl methacrylate, cyclododecyl acrylate, or cyclododecyl methacrylate.

[0018] Preferably, the oxazoline group-containing olefin compound has a structure as shown in Formula II.

[0019]

[0020] In Formula II, R5is hydrogen or methyl; R6, R7, R8, R9are each independently hydrogen, halogen, C1-C20 (e.g., C3, C5, C7, C9, C11, C13, C15, C17, or C19, etc.) alkyl, C2-C20 (e.g., C3, C5, C7, C9, C11, C13, C15, C17, or C19, etc.) alkenyl, C6-C20 (e.g., C7, C9, C11, C13, C15, C17, or C19, etc.) aryl, C7-C32 (e.g., C10, C13, C16, C19, C22, C25, C28, or C31, etc.) arylalkyl, C1-C20 hydroxyalkyl, C1-C20 (e.g., C3, C5, C7, C9, C11, C13, C15, C17, or C19, etc.) aminoalkyl, or C1-C20 (e.g., C3, C5, C7, C9, C11, C13, C15, C17, or C19, etc.) haloalkyl.

[0021] For example, R6, R7, R8, R9may each independently be any of hydrogen, methyl, or ethyl.

[0022] For example, in Formula II, R5is methyl; R6, R7, R8, and R9are hydrogen.

[0023] Preferably, the oxazoline group-containing olefin compound includes any of 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline, 2-vinyl-5,5-dimethyl-2-oxazoline, 2-vinyl-4,4,5,5-tetramethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline, 2-isopropenyl-5,5-dimethyl-2-oxazoline, or 2-isopropenyl-4,4,5,5-tetramethyl-2-oxazoline.

[0024] Preferably, the conjugated diene includes a cyclic conjugated diene and / or an acyclic conjugated diene.

[0025] Preferably, the acyclic conjugated diene has a structure as shown in Formula III.

[0026]

[0027] In Formula III, R 10 , R 11 , R 12 , and R 13Each is independently hydrogen or a C1-C4 alkyl group.

[0028] Preferably, the acyclic conjugated diene comprises butadiene and / or isoprene.

[0029] Preferably, the cyclic conjugated diene comprises cyclohexadiene and / or cyclooctadiene.

[0030] In the present invention, "...are each independently..." means that in the raw materials for preparing the hydrolysis-resistant polymer, different raw materials represented by the same general formula may have the same or different groups represented by the same symbol, or, in the same raw material represented by the same general formula, groups represented by different symbols may be the same or different.

[0031] Preferably, the initiator includes a water-soluble polymerization initiator and / or an oil-soluble polymerization initiator.

[0032] Preferably, the water-soluble polymerization initiator comprises a persulfate.

[0033] Preferably, the persulfate includes any one of lithium persulfate, potassium persulfate, sodium persulfate or ammonium persulfate, or a combination of at least two thereof.

[0034] Preferably, the oil-soluble polymerization initiator comprises an organic peroxide.

[0035] Preferably, the organic peroxide includes any one of cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide, acetyl peroxide or diisopropylbenzene hydroperoxide, or a combination of at least two thereof.

[0036] Preferably, the chain transfer agent includes any one or a combination of at least two of alkyl mercaptan, xanthate compounds, phenolic compounds, allyl compounds, halogenated hydrocarbon compounds, vinyl ether, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, mercaptosuccinic acid, terpinolene or α-methylstyrene dimer.

[0037] Preferably, the alkyl mercaptan includes any one of n-hexyl mercaptan, n-octyl mercaptan, tert-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan or n-octadecyl mercaptan, or a combination of at least two thereof.

[0038] Preferably, the xanthate compound includes dimethyl xanthate disulfide and / or diisopropyl xanthate disulfide.

[0039] Preferably, the phenolic compound includes 2,6-di-tert-butyl-4-methylphenol and / or styrenated phenol.

[0040] Preferably, the allyl compound comprises allyl alcohol.

[0041] Preferably, the halogenated hydrocarbon compound includes any one of dichloromethane, dibromomethane or tetrabromomethane, or a combination of at least two thereof.

[0042] Preferably, the vinyl ether includes any one of α-benzyloxystyrene, α-benzyloxyacrylonitrile or α-benzyloxyacrylamide, or a combination of at least two thereof.

[0043] Preferably, the pH adjuster comprises aqueous ammonia.

[0044] Preferably, based on 100% of the total mass of the polymerized monomers, the mass of the initiator is 0.05% to 5%, for example, 0.1%, 0.5%, 1%, 2%, 3%, 4% or 5%.

[0045] Preferably, based on the total mass of the polymerized monomers as 100%, the mass of the chain transfer agent is 0.05% to 5% (eg, 0.1%, 0.5%, 1%, 2%, 3%, 4% or 5%), more preferably 0.5% to 0.8%.

[0046] Preferably, the raw materials for preparing the hydrolysis-resistant polymer further include a reducing agent and / or an emulsifier.

[0047] Preferably, the reducing agent comprises any one or a combination of at least two of reducing inorganic acid salts, reducing carboxylic acids, reducing carboxylates, reducing sugar compounds or amine compounds.

[0048] Preferably, the reducing inorganic acid salt includes any one or a combination of at least two of sulfite, bisulfite, pyrosulfite, dithionite, dithionate, thiosulfate, formaldehyde sulfonate or benzaldehyde sulfonate.

[0049] Preferably, the reducing carboxylic acid includes any one of L-ascorbic acid, isoascorbic acid, tartaric acid or citric acid, or a combination of at least two thereof.

[0050] Preferably, the reducing sugar compound includes dextrose and / or sucrose.

[0051] Preferably, the amine compound includes dimethylaniline and / or triethanolamine.

[0052] Preferably, the emulsifier comprises a surfactant.

[0053] Preferably, the surfactant comprises an anionic surfactant and / or a nonionic surfactant.

[0054] Preferably, the nonionic surfactant includes any one of polyethylene glycol alkyl ester, polyethylene glycol alkylphenyl ether or polyethylene glycol alkyl ether, or a combination of at least two thereof.

[0055] Preferably, the anionic surfactant includes any one or a combination of at least two of higher alcohol sulfate esters, aliphatic sulfates, alkylbenzene sulfonates, alkyldiphenyl oxide disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietate or formalin condensates of naphthalenesulfonic acid.

[0056] Illustratively, the sulfate ester salt of the higher alcohol includes sodium lauryl sulfate and / or fatty alcohol polyoxyethylene ether ammonium sulfate.

[0057] Illustratively, the fatty sulfate includes sodium lauryl sulfate.

[0058] Preferably, the molar ratio of the reducing agent to the initiator is (0.1-1):1, for example, 0.2:1, 0.3:1, 0.4:1, 0.5:1, 0.6:1, 0.7:1, 0.8:1 or 0.9:1, etc.

[0059] Preferably, based on 100% of the total mass of the polymerized monomers, the mass of the emulsifier is 0.05% to 5% (eg, 0.1%, 0.5%, 1%, 2%, 3%, 4% or 5%).

[0060] In the present invention, the hydrolysis-resistant polymer, as those skilled in the art will know, inevitably includes some residual impurities in the preparation process, such as emulsifiers, initiators, chain transfer agents or pH regulators, due to some auxiliary materials used in the preparation process.

[0061] In a second aspect, the present invention provides a hydrolysis-resistant polymer solution, comprising the hydrolysis-resistant polymer as described in the first aspect.

[0062] Preferably, the solid content of the hydrolysis-resistant polymer solution is 40% to 55%, for example, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53% or 54%, etc.

[0063] Preferably, the pH of the hydrolysis-resistant polymer solution is 7 to 9, such as 7.2, 7.4, 7.6, 7.8, 8.0, 8.2, 8.4, 8.6 or 8.8.

[0064] In a third aspect, the present invention provides a method for preparing the anti-hydrolysis polymer solution as described in the second aspect, the preparation method comprising the following steps: mixing a polymerization monomer, an initiator, a pH regulator, a chain transfer agent, an optional reducing agent, an optional emulsifier and water, and reacting to obtain the anti-hydrolysis polymer solution.

[0065] In the present invention, the reaction is a free radical polymerization reaction and can be carried out according to conventional procedures and conditions for such reactions in the art. The method for adding the raw materials in the preparation method is not particularly limited and can be any one of, or a combination of, aggregate addition, batch addition, continuous addition, or power feed addition.

[0066] In the present invention, the initiator can be added in the form of an initiator solution, and the adding method can be any one of dropwise addition, all-at-once addition, or batch addition, or a combination of at least two of them.

[0067] Preferably, the reaction is carried out under a protective atmosphere.

[0068] In the present invention, the protective atmosphere refers to an atmosphere that does not react with the reactants, such as an inert gas or nitrogen.

[0069] Preferably, the reaction temperature is 20-90°C, such as 30°C, 40°C, 50°C, 60°C, 70°C or 80°C.

[0070] Preferably, the reaction time is 8 to 12 h, for example, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h or 11.5 h.

[0071] In a fourth aspect, the present invention provides a method for preparing a hydrolysis-resistant polymer, comprising the steps of drying the hydrolysis-resistant polymer solution as described in the second aspect or the hydrolysis-resistant polymer solution obtained by the preparation method as described in the third aspect to obtain the hydrolysis-resistant polymer.

[0072] In a fifth aspect, the present invention provides a use of the hydrolysis-resistant polymer described in the first aspect as a cross-linking agent for a carboxyl-containing resin.

[0073] In the present invention, the carboxyl group-containing resin may be polyacrylic acid resin (PAA resin) or waterborne polyurethane resin (PU resin).

[0074] Without violating the common sense in the art, the above-mentioned preferred conditions can be arbitrarily combined to obtain the preferred embodiments of the present invention.

[0075] The reagents and raw materials used in the present invention are commercially available.

[0076] Compared with the prior art, the present invention has at least the following beneficial effects:

[0077] The anti-hydrolysis polymer has a glass transition temperature of -8 to -20 DEG C, has better toughness, the viscosity of the anti-hydrolysis polymer solution is less than or equal to 60 mPa s at 25 DEG C, has smaller viscosity and good storage stability, can be stored for at least 7 days at 50 DEG C, the viscosity increase amount is less than or equal to 6 mPa s when stored in an oven at 50 DEG C for 7 days, preferably the viscosity increase amount is less than or equal to 3 mPa s when stored in an oven at 50 DEG C for 7 days, no VOC is generated in the preparation process of the anti-hydrolysis polymer, which meets the environmental protection development requirements, the anti-hydrolysis polymer can improve the toughness and anti-hydrolysis property of the carboxyl-containing resin as a crosslinking agent of the carboxyl-containing resin, the crosslinking degree of the crosslinked resin prepared by using the prepared anti-hydrolysis polymer as a crosslinking agent is greater than or equal to 89%, the elongation at break is greater than or equal to 58%, and the tensile strength is greater than or equal to 802 MPa. DETAILED DESCRIPTION

[0078] In order to facilitate the understanding of the present application, the present application lists the following examples. It should be understood by those skilled in the art that the examples are only used to help understand the present application and should not be regarded as a specific limitation on the present application.

[0079] The reagents or instruments used are not marked with the manufacturer, and are all conventional products that can be purchased through a regular channel.

[0080] Some raw materials and equipment used in the following examples and comparative examples and tests are as follows:

[0081] Methyl methacrylate, isobutyl acrylate, isopropenyl oxazoline, isoprene, dodecyl mercaptan, ammonium persulfate, sodium dodecyl sulfate, PAA resin (average Mv ~ 450000) are all purchased from Titan Science and Technology Exploration Platform;

[0082] Butadiene: purchased from Shanghai Jun Ding Gas Sales Co., Ltd.;

[0083] pH meter: Mettler Toledo, model SevenExcellence S400-Micro;

[0084] DSC instrument: Mettler Toledo, model DSC 3+;

[0085] Rotational viscometer: Shanghai Precision Instruments and Meters Co., Ltd., model SNB-1;

[0086] Gel permeation chromatography (GPC): Agilent, model 1260Infinity II;

[0087] Universal tensile machine: Fudler Instruments Technology (Shanghai) Co., Ltd., model FL-P.

[0088] Example 1

[0089] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The raw materials for preparing the hydrolysis-resistant polymer solution include a polymer monomer, a chain transfer agent (dodecyl mercaptan), an emulsifier (sodium lauryl sulfate), an initiator (ammonium persulfate), a pH adjuster (ammonia water, concentration of 25 wt%), and deionized water.

[0090] The polymerizable monomers include the following components by mass percentage: 20% of an acrylic acid ester compound (methyl methacrylate), 40% of an oxazoline-containing olefin compound (isopropenyl oxazoline), and 40% of a conjugated diene (butadiene);

[0091] Based on the total mass of the polymerized monomers being 100%, the mass of the chain transfer agent is 0.2%, the mass of the emulsifier is 2%, the mass of the initiator is 0.4%, and the mass of the pH adjuster is 1%.

[0092] The mass ratio of the above-mentioned polymerization monomer and deionized water is 1:1.

[0093] The preparation method of the above-mentioned anti-hydrolysis polymer solution is as follows: under an inert gas atmosphere, deionized water, an emulsifier and an initiator are first added to a polymerization reaction kettle, stirred thoroughly, dissolved and mixed evenly, and then the temperature is raised to 70°C, and then the evenly mixed acrylic acid ester compound, oxazoline-containing olefin compound and conjugated diene are added dropwise thereto at a dropping rate of 0.55g / min. After the addition is completed, the temperature is raised to 80°C and the reaction is carried out at a constant temperature for 8 hours. After the reaction time is completed, a pH adjuster is added to obtain the anti-hydrolysis polymer solution.

[0094] The cross-linked resin was prepared by the following method: PAA resin and the above-mentioned anti-hydrolysis polymer solution were mixed in a mass ratio of 10:1, stirred and mixed evenly, poured into a drying mold and filled completely, first kept at a constant temperature of 60°C for 4 hours, and then transferred to a 120°C oven at a constant temperature for 2 hours to complete drying to obtain the cross-linked resin.

[0095] Example 2

[0096] This example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. This example differs from Example 1 in that the polymerizable monomers comprise the following components, by mass percentage: 10% of an acrylate compound (methyl methacrylate), 45% of an oxazoline-containing olefin compound (isopropenyloxazoline), and 45% of a conjugated diene (butadiene). Other conditions are the same as those in Example 1.

[0097] Example 3

[0098] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and embodiment 1 is that the polymerizable monomer comprises the following components by mass percentage: 30% of an acrylate compound (methyl methacrylate), 35% of an oxazoline-containing olefin compound (isopropenyl oxazoline), and 35% of a conjugated diene (butadiene);

[0099] Based on the total weight of the polymerized monomers as 100%, the weight of the chain transfer agent is 0.3%, the weight of the emulsifier is 4%, the weight of the initiator is 0.1%, and the weight of the pH adjuster is 1%. Other conditions are the same as those in Example 1.

[0100] Example 4

[0101] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the mass percentage of the oxazoline-containing olefin compound (isopropenyl oxazoline) in the polymerization monomer is adjusted to 35% and the mass percentage of the conjugated diene (butadiene) is adjusted to 45%. Other conditions are the same as those in Example 1.

[0102] Example 5

[0103] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the mass percentage of the oxazoline-containing olefin compound (isopropenyl oxazoline) in the polymerization monomer is adjusted to 45% and the mass percentage of the conjugated diene (butadiene) is adjusted to 35%. Other conditions are the same as those in Example 1.

[0104] Example 6

[0105] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the mass percentage of the oxazoline-containing olefin compound (isopropenyl oxazoline) in the polymerization monomer is adjusted to 30% and the mass percentage of the conjugated diene (butadiene) is adjusted to 50%. Other conditions are the same as those in Example 1.

[0106] Example 7

[0107] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the mass percentage of the oxazoline-containing olefin compound (isopropenyl oxazoline) in the polymerization monomer is adjusted to 50% and the mass percentage of the conjugated diene (butadiene) is adjusted to 30%. Other conditions are the same as those in Example 1.

[0108] Example 8

[0109] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the acrylic acid ester compound (methyl methacrylate) is replaced with an acrylic acid ester compound (isobutyl acrylate) of the same mass, and other conditions are the same as those in Example 1.

[0110] Example 9

[0111] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the acrylic acid ester compound (methyl methacrylate) is replaced with an acrylic acid ester compound of the same mass (methyl methacrylate and isobutyl acrylate in a mass ratio of 1:1). Other conditions are the same as those in Example 1.

[0112] Example 10

[0113] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the conjugated diene (butadiene) is replaced with a conjugated diene (isoprene) of the same mass, and other conditions are the same as those in Example 1.

[0114] Example 11

[0115] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the oxazoline-containing olefinic compound (isopropenyl oxazoline) is replaced with an oxazoline-containing olefinic compound (vinyl oxazoline) of the same mass, and the other conditions are the same as those in Example 1.

[0116] Example 12

[0117] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and embodiment 1 is that the mass of the chain transfer agent is adjusted to 0.5% based on the total mass of the polymerized monomers as 100%, and other conditions are the same as those in embodiment 1.

[0118] Example 13

[0119] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and embodiment 1 is that the mass of the chain transfer agent is adjusted to 0.8% based on the total mass of the polymerized monomers as 100%. Other conditions are the same as those in embodiment 1.

[0120] Example 14

[0121] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and embodiment 1 is that the mass of the chain transfer agent is adjusted to 0.05% based on the total mass of the polymerized monomers as 100%, and other conditions are the same as those in embodiment 1.

[0122] Example 15

[0123] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and embodiment 1 is that the mass of the chain transfer agent is adjusted to 5% based on the total mass of the polymerized monomers as 100%, and other conditions are the same as those in embodiment 1.

[0124] Example 16

[0125] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the chain transfer agent (dodecyl mercaptan) is replaced with a chain transfer agent of the same mass (α-benzyloxystyrene), and other conditions are the same as those in Example 1.

[0126] Example 17

[0127] This embodiment provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this embodiment and Example 1 is that the chain transfer agent (dodecyl mercaptan) is replaced with a chain transfer agent of the same mass (allyl alcohol), and other conditions are the same as those in Example 1.

[0128] Comparative Example 1

[0129] This comparative example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between the comparative example and Example 1 is that the polymerization monomer includes the following components by mass percentage: 40% of an acrylate compound (methyl methacrylate), 30% of an oxazoline-containing olefin compound (isopropenyl oxazoline), and 30% of a conjugated diene (butadiene). Other conditions are the same as those in Example 1.

[0130] Comparative Example 2

[0131] This comparative example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between it and Example 1 is that the mass percentage of the oxazoline-containing olefin compound (isopropenyl oxazoline) in the polymerization monomer is adjusted to 10% and the mass percentage of the conjugated diene (butadiene) is adjusted to 70%. Other conditions are the same as in Example 1.

[0132] Comparative Example 3

[0133] This comparative example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between it and Example 1 is that the mass percentage of the oxazoline-containing olefin compound (isopropenyl oxazoline) in the polymerization monomer is adjusted to 70% and the mass percentage of the conjugated diene (butadiene) is adjusted to 10%. Other conditions are the same as in Example 1.

[0134] Comparative Example 4

[0135] This comparative example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between the comparative example and Example 1 is that no oxazoline-containing olefin compound (isopropenyl oxazoline) is added to the polymerization monomer, the mass percentage of the conjugated diene (butadiene) is adjusted to 80%, and the other conditions are the same as those in Example 1.

[0136] Comparative Example 5

[0137] This comparative example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between it and Example 1 is that no conjugated diene (butadiene) is added to the polymerization monomer, the mass percentage of the oxazoline-containing olefin compound (isopropenyl oxazoline) is adjusted to 80%, and the other conditions are the same as those in Example 1.

[0138] Comparative Example 6

[0139] This comparative example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this comparative example and Example 1 is that no chain transfer agent (dodecyl mercaptan) is added to the raw materials for preparing the hydrolysis-resistant polymer solution, and other conditions are the same as those in Example 1.

[0140] Comparative Example 7

[0141] This comparative example provides a hydrolysis-resistant polymer solution, a preparation method thereof, and a cross-linked resin. The difference between this comparative example and Example 1 is that no pH regulator (ammonia water, concentration of 25 wt%) is added to the raw materials for preparing the hydrolysis-resistant polymer solution, and other conditions are the same as those in Example 1.

[0142] The following performance tests were performed on the hydrolysis-resistant polymer solutions provided in Examples 1 to 17 and Comparative Examples 1 to 7.

[0143] (1) pH determination: pH meter is used for testing, according to GB / T 9724-2007;

[0144] (2) Viscosity test: Tested using a rotational viscometer in accordance with GB / T 2794-2013;

[0145] (3) Glass transition temperature (Tg) test: The hydrolysis-resistant polymer solution was dried and then tested using a DSC instrument in accordance with GB / T 2794-2013;

[0146] (4) Number average molecular weight test: The hydrolysis-resistant polymer solution was dried and then tested using gel permeation chromatography according to GB / T 2794-2013;

[0147] (5) Stability test: Take 50g of the anti-hydrolysis polymer solution and place it in a clean, sealed bottle. Keep it in a constant temperature oven at 50℃ for 7 days. After 7 days, take it out and check whether the anti-hydrolysis polymer solution shows any stratification or turbidity, as well as the change in viscosity. If there is no stratification or turbidity, and the viscosity increase is ≤6mPa·s, it means that its stability is good.

[0148] The test results are shown in Table 1.

[0149] The cross-linked resins provided in Examples 1 to 17 and Comparative Examples 1 to 7 were subjected to the following performance tests.

[0150] (1) Hydrolysis resistance test: Weigh about 2 g of cross-linked resin and record the weight as W1. Wrap it completely with a 200-mesh filter and place it in water for reflux dissolution for 24 h. Weigh the weight of the dried film after dissolution and record it as W2. Calculate its cross-linking degree H: H = W2 / W1 × 100%.

[0151] (2) Elongation at break and tensile strength test: The elongation at break and tensile strength of the cross-linked resins and PAA resins provided in Examples 1 to 17 and Comparative Examples 1 to 6 were tested with reference to GB / T 528-2009.

[0152] The test results are shown in Table 1 and Table 2.

[0153] Table 1

[0154]

[0155] In Table 1, “ / ” means that the test was not performed.

[0156] Table 2

[0157]

[0158]

[0159] In Table 2, “ / ” means that the test was not performed.

[0160] As can be seen from the test results in Tables 1 and 2, the viscosity of the hydrolysis-resistant polymer solutions provided in Examples 1 to 17 is ≤60 mPa·s, and the viscosity increase after being kept in an oven at 50°C for 7 days is ≤6 mPa·s, indicating good stability. The cross-linked resin obtained has a cross-linking degree ≥89%, an elongation at break ≥58%, and a tensile strength ≥802 MPa, which improves the hydrolysis resistance and toughness of the carboxyl-containing resin and extends its service life.

[0161] It can be seen from Examples 1 and 4 to 7 that the mass ratio of the oxazoline-containing olefin compound to the conjugated diene is preferably (0.7 to 1.3):1, and the stability of the hydrolysis-resistant polymer solution prepared is better.

[0162] As can be seen from Example 1 and Examples 12-15, the anti-hydrolysis polymer prepared by the present application has better effects on improving the properties of the carboxyl-containing resin, by controlling the mass percentage of the chain transfer agent in a specific range, preferably 0.5%-0.8% based on the total mass of the polymerized monomers.

[0163] Compared with Example 1, if the content of the acrylate compound is too high (Comparative Example 1), the stability of the anti-hydrolysis polymer solution prepared is decreased, and the crosslinking degree and mechanical properties of the crosslinked resin prepared are decreased, thus it can be seen that the anti-hydrolysis polymer prepared by controlling the mass percentage of the acrylate compound in a specific range has better effects on improving the anti-hydrolysis and toughness of the carboxyl-containing resin.

[0164] Compared with Example 1, if the mass ratio of the oxazoline group-containing olefin compound and the conjugated diene is too low (Comparative Example 2), the anti-hydrolysis and toughness of the crosslinked resin are both decreased, because the crosslinking degree of the anti-hydrolysis polymer prepared with the carboxyl-containing resin is insufficient, and a good network structure cannot be formed, and the performance is insufficiently improved; if the mass ratio of the oxazoline group-containing olefin compound and the conjugated diene is too high (Comparative Example 3), the content of the conjugated diene is too low, and the elongation at break of the crosslinked resin prepared is not ideal, i.e., the toughness is insufficiently improved; thus it can be seen that the anti-hydrolysis polymer prepared by controlling the mass percentage of the mass ratio of the oxazoline group-containing olefin compound and the conjugated diene in a specific range has better effects on improving the anti-hydrolysis and toughness of the carboxyl-containing resin.

[0165] Compared with Example 1, if the oxazoline group-containing olefin compound is not added (Comparative Example 4), the anti-hydrolysis and toughness of the crosslinked resin prepared are both greatly decreased; if the conjugated diene is not added (Comparative Example 5), the toughness of the crosslinked resin prepared is greatly decreased.

[0166] Compared with Example 1, if the chain transfer agent is not added (Comparative Example 6), the molecular weight of the anti-hydrolysis polymer prepared is obviously increased, the viscosity of the anti-hydrolysis polymer solution is also increased, the stability is decreased, the applicability is reduced, and the effects of the anti-hydrolysis and toughness of the crosslinked resin prepared are decreased.

[0167] Compared with Example 1, if the pH regulator is not added (Comparative Example 7), the pH of the anti-hydrolysis polymer solution prepared is low, which leads to the instability of the anti-hydrolysis polymer solution, the viscosity is increased, and the applicability is reduced.

[0168] The applicant declares that the above description is only a specific embodiment of the present application, but the protection scope of the present application is not limited thereto, and it should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily thought of by those skilled in the art, and all fall within the protection scope and disclosure scope of the present application.

Claims

1. A hydrolysis-resistant polymer, characterized in that The raw materials for preparing the hydrolysis-resistant polymer include polymerization monomers, initiators, pH regulators and chain transfer agents; The polymerizable monomers include acrylate compounds, oxazoline-containing olefin compounds and conjugated dienes; based on the total mass of the polymerizable monomers as 100%, the mass percentage of the acrylate compounds in the polymerizable monomers is 10% to 30%, the mass percentage of the oxazoline-containing olefin compounds and conjugated dienes in the polymerizable monomers is 70% to 90%, and the mass ratio of the oxazoline-containing olefin compounds to the conjugated dienes is (0.4 to 2.5):

1.

2. The hydrolysis-resistant polymer according to claim 1, characterized in that The mass ratio of the oxazoline-containing olefin compound to the conjugated diene is (0.7-1.3):1; Preferably, the acrylate compound has a structure as shown in Formula I; In formula I, R1, R2, and R3 are each independently any one of hydrogen, methyl, or ethyl; R4 is a C1-C30 hydrocarbon group; Preferably, the acrylic ester compound includes any one of methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, n-octyl acrylate, n-octyl methacrylate, tridecyl acrylate, tridecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, stearyl acrylate, stearyl methacrylate, isobornyl acrylate, isobornyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, tert-butylcyclohexyl acrylate, tert-butylcyclohexyl methacrylate, cyclododecyl acrylate or cyclododecyl methacrylate, or a combination of at least two thereof.

3. The hydrolysis-resistant polymer according to claim 1 or 2, characterized in that The oxazoline-containing olefinic compound has a structure as shown in Formula II; In formula II, R5 is hydrogen or methyl; R6, R7, R8, and R9 are each independently any one of hydrogen, halogen, C1-C20 alkyl, C2-C20 alkenyl, C6-C20 aryl, C7-C32 arylalkyl, C1-C20 hydroxyalkyl, C1-C20 aminoalkyl, and C1-C20 haloalkyl; Preferably, the oxazoline-containing olefinic compounds include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-vinyl-4-ethyl-2-oxazoline, 2-vinyl-4,4-dimethyl-2-oxazoline, 2-vinyl-5,5-dimethyl-2-oxazoline, 2-vinyl-4,4,5,5-tetramethyl-2-oxazoline, 2-isopropenyl-2-oxazoline, Any one or a combination of at least two of oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-methyl-2-oxazoline, 2-isopropenyl-4-ethyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline, 2-isopropenyl-5,5-dimethyl-2-oxazoline or 2-isopropenyl-4,4,5,5-tetramethyl-2-oxazoline.

4. The hydrolysis-resistant polymer according to any one of claims 1 to 3, characterized in that The conjugated diene includes a cyclic conjugated diene and / or an acyclic conjugated diene; Preferably, the acyclic conjugated diene has a structure as shown in Formula III: In formula III, R 10 、R 11 、R 12 and R 13 Each is independently hydrogen or a C1-C4 alkyl group; Preferably, the acyclic conjugated diene comprises butadiene and / or isoprene; Preferably, the cyclic conjugated diene comprises cyclohexadiene and / or cyclooctadiene; Preferably, the initiator comprises a water-soluble polymerization initiator and / or an oil-soluble polymerization initiator; Preferably, the water-soluble polymerization initiator comprises a persulfate; Preferably, the persulfate comprises any one of lithium persulfate, potassium persulfate, sodium persulfate or ammonium persulfate, or a combination of at least two thereof; Preferably, the oil-soluble polymerization initiator comprises an organic peroxide; Preferably, the organic peroxide comprises any one of cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide, acetyl peroxide or diisopropylbenzene hydroperoxide, or a combination of at least two thereof; Preferably, the chain transfer agent comprises any one or a combination of at least two of alkyl mercaptan, xanthate compounds, phenolic compounds, allyl compounds, halogenated hydrocarbon compounds, vinyl ether, triphenylethane, pentaphenylethane, acrolein, methacrolein, thioglycolic acid, mercaptosuccinic acid, terpinolene or α-methylstyrene dimer; Preferably, the alkyl mercaptan includes any one or a combination of at least two of n-hexyl mercaptan, n-octyl mercaptan, tert-octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan or n-octadecyl mercaptan; Preferably, the xanthate compound comprises dimethyl xanthate disulfide and / or diisopropyl xanthate disulfide; Preferably, the phenolic compound includes 2,6-di-tert-butyl-4-methylphenol and / or styrenated phenol; Preferably, the allyl compound comprises allyl alcohol; Preferably, the halogenated hydrocarbon compound includes any one of dichloromethane, dibromomethane or tetrabromomethane, or a combination of at least two thereof; Preferably, the vinyl ether includes any one or a combination of at least two of α-benzyloxystyrene, α-benzyloxyacrylonitrile or α-benzyloxyacrylamide; Preferably, the pH adjuster comprises aqueous ammonia; Preferably, the mass of the initiator is 0.05% to 5% based on the total mass of the polymerized monomers as 100%; Preferably, based on 100% of the total mass of the polymerized monomers, the mass of the chain transfer agent is 0.05% to 5%.

5. The hydrolysis-resistant polymer according to any one of claims 1 to 4, characterized in that The raw materials for preparing the hydrolysis-resistant polymer also include a reducing agent and / or an emulsifier; Preferably, the reducing agent comprises any one or a combination of at least two of reducing inorganic acid salts, reducing carboxylic acids, reducing carboxylates, reducing sugar compounds or amine compounds; Preferably, the emulsifier comprises a surfactant; Preferably, the surfactant comprises an anionic surfactant and / or a nonionic surfactant; Preferably, the nonionic surfactant comprises any one or a combination of at least two of polyethylene glycol alkyl esters, polyethylene glycol alkylphenyl ethers or polyethylene glycol alkyl ethers; Preferably, the anionic surfactant includes any one or a combination of at least two of higher alcohol sulfate esters, aliphatic sulfates, alkylbenzene sulfonates, alkyldiphenyl oxide disulfonates, aliphatic sulfonates, aliphatic carboxylates, dehydroabietate or formalin condensates of naphthalenesulfonic acid; Preferably, the molar ratio of the reducing agent to the initiator is (0.1-1):1; Preferably, based on 100% of the total mass of the polymerized monomers, the mass of the emulsifier is 0.05% to 5%.

6. A hydrolysis-resistant polymer solution, characterized in that The hydrolysis-resistant polymer solution comprises the hydrolysis-resistant polymer according to any one of claims 1 to 5.

7. The hydrolysis-resistant polymer solution according to claim 6, characterized in that The solid content of the hydrolysis-resistant polymer solution is 40% to 55%; Preferably, the pH of the hydrolysis-resistant polymer solution is 7-9.

8. A method for preparing a hydrolysis-resistant polymer solution as claimed in claim 7, characterized in that: The preparation method comprises the following steps: mixing a polymerization monomer, an initiator, a pH regulator, a chain transfer agent, an optional reducing agent, an optional emulsifier and water, and reacting the mixture to obtain the hydrolysis-resistant polymer solution.

9. A method for preparing a hydrolysis-resistant polymer according to any one of claims 1 to 5, characterized in that: The preparation method comprises the following steps: drying the anti-hydrolysis polymer solution according to claim 6 or 7 or the anti-hydrolysis polymer solution prepared by the preparation method according to claim 8 to obtain the anti-hydrolysis polymer.

10. Use of the hydrolysis-resistant polymer according to any one of claims 1 to 5 as a cross-linking agent for carboxyl-containing resins.

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