A polymer containing aldehyde groups and a method for preparing the same

Abstract

The present application relates to a kind of aldehyde group-containing polymer and its preparation method.The aldehyde group-containing polymer of the present application includes the structural unit derived from the reaction of furfural derivative with anhydride group with hydroxyl group, its aldehyde group density can be adjusted, raw material is simple to obtain, realizes the high-value utilization of olefin resources.The preparation method of the aldehyde group-containing polymer of the present application is simple, cost controllable, and little environmental pollution.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of polymer, and particularly relates to a polymer containing aldehyde group and a preparation method thereof. BACKGROUND

[0002] As confirmed by many research institutes, aldehyde group as an important functional group has rich reactivity and high reaction activity, and can participate in various chemical reactions even under mild environmental conditions. For example, aldehyde group can be converted into carboxylic acid through oxidation reaction, and form hydroxymethyl through reduction reaction; it can also react with alcohol to form acetal or hemiacetal, and react with amine to form Schiff base, etc. Therefore, aldehyde group compounds have wide and important applications in many fields such as organic synthesis, biological medicine, agriculture, textile industry and construction industry.

[0003] However, in the natural environment, aldehyde group-containing molecules are not common, and carbonyl compounds mainly exist in the form of ketones, esters, carboxylic acids, etc. More importantly, many common small molecule aldehyde compounds, such as formaldehyde, acetaldehyde, propylene aldehyde, croton aldehyde, etc., have significant volatility, toxicity, irritability, high biological permeability, and even carcinogenicity, and are prone to oxidation and other reactions under natural conditions to cause deterioration. Such physical and chemical properties to some extent limit the wide application of aldehyde compounds.

[0004] A possible solution is to use aldehyde group-containing polymers to replace small molecule aldehyde substances, so as to effectively overcome the above-mentioned deficiencies.

[0005] There are two conventional methods for synthesizing aldehyde group-containing polymers at present. One method is to use aldehyde group-containing vinyl monomers to self-polymerize or copolymerize with other vinyl monomers to prepare aldehyde group-containing polymers. For example, in Non-patent Literature 1, 4-hydroxybenzaldehyde and methacryloyl chloride are used as raw materials to synthesize a aldehyde group-containing vinyl monomer, i.e. p-formylphenyl methacrylate (FPMA), and then FPMA, methyl methacrylate and poly(ethylene glycol) methacrylate are used as polymerization monomers to synthesize a aldehyde group-containing terpolymer, which has both biological reactivity and biological inertness.

[0006] In Patent Literature 1, a vinyl monomer containing phosphorylcholine hydrophilic group is copolymerized with a vinyl monomer containing aldehyde group (methylacrolein) through simple solution radical polymerization to synthesize a phosphorylcholine polymer containing aldehyde group, and a biomimetic adhesive coating with a structure similar to extracellular membrane is prepared. However, aldehyde group-containing vinyl monomers such as propylene aldehyde, methylacrolein and butenyl aldehyde have strong suffocating irritating odor, high toxicity, and are difficult to be used in actual production. In addition, due to the difference in reactivity between the aldehyde group-containing monomer and other monomers, the aldehyde group content of the aldehyde group-containing polymer prepared by copolymerization is too low.

[0007] Another method is to modify the polymer with aldehyde groups to prepare aldehyde-containing polymers, such as oxidizing the primary hydroxyl groups on the polymer chain to aldehyde groups. However, this method produces aldehyde-containing polymers with low aldehyde content, small aldehyde density and poor water solubility, and requires a large amount of organic solvent during use, which does not meet the modern environmental protection concept.

[0008] To this end, the prior art has made some efforts. For example, a water-soluble aldehyde-containing polymer is prepared in Non-patent document 2 by adopting the process steps of polymerization first and then oxidation. In the first step, a polymer containing vicinal diol structure in the side chain is obtained by RAFT polymerization method, and in the second step, the vicinal diol is converted to aldehyde group by sodium periodate oxidation reaction, thereby obtaining an aldehyde-containing polymer with uniformly distributed aldehyde groups on the polymer chain.

[0009] A water-soluble polyaldehyde polymer tanning agent is prepared in Patent document 2 by adopting the process steps of homopolymerization first and then oxidation. In the first step, a linear polyhydroxyacrylate is synthesized by free radical homopolymerization reaction, and in the second step, the primary hydroxyl groups on the polymer chain are oxidized to aldehyde groups as much as possible by precisely controlling the oxidation conditions of 2,2,6,6-tetramethylpiperidine oxide (TEMPO) catalysis.

[0010] CITATIONS

[0011] Non-patent document 1: Kim et al., Covalently Assembled Bifunctional Copolymer Layers as a Matrix for Immobilization of Oligonucleotides. Bulletin of the Korean Chemical Society, 2012, 33(4): 1401;

[0012] Non-patent document 2: New Aldehyde-Functional Methacrylic Water-Soluble Polymers. Angewandte Chemie International Edition. 2021, 60, 12032;

[0013] Patent document 1: CN 108715644 A;

[0014] Patent document 2: CN 110041451 A. SUMMARY

[0015] PROBLEMS TO BE SOLVED BY THE INVENTION

[0016] The aldehyde group-containing vinyl monomers (e.g., propenal, methacrolein, butenal, and the like) used in the methods of Non-Patent Literature 1 and Patent Literature 1 all have a strong pungent odor, are highly toxic, and are difficult to use in actual production. In addition, due to the difference in reactivity between the aldehyde group-containing monomers and other monomers, the aldehyde group content of the aldehyde group-containing polymers prepared by copolymerization is too low.

[0017] The process of the methods of Non-Patent Literature 2 and Patent Literature 2 is complicated and requires precise control of the reaction conditions.

[0018] Therefore, there is still an urgent need to develop an aldehyde group-containing polymer having a high aldehyde group content, a large aldehyde group density, a simple preparation process, and good water solubility, and a method for preparing the same.

[0019] Solution to the problem

[0020] In view of the above problems, the present inventors have conducted long-term and in-depth research and found that the use of a furfural derivative having a hydroxyl group and a polymer having an anhydride group to react can solve the above problems.

[0021] Specifically, the present application solves the problems of the present application by the following solutions.

[0022] [1] A polymer containing a structural unit A, a structural unit B, and a structural unit C, wherein

[0023] The structural unit A is at least one selected from the group consisting of the structural units represented by the following formulae (1) to (4):

[0024]

[0025] In structures (3) and (4), M + is a metal ion or an ammonium ion

[0026] The structural unit B is a structural unit derived from an olefin monomer;

[0027] The structural unit C is at least one selected from the group consisting of the structural units represented by the following formulae (5) and (6):

[0028]

[0029] In structure (6), M + is a metal ion or an ammonium ion

[0030] [2] The polymer according to [1], wherein the olefin monomer is at least one selected from the group consisting of mono-olefins or di-olefins having a carbon number of 2 to 20, styrene and derivatives thereof, and fused ring aromatic olefins;

[0031] Preferably, the olefin monomer is at least one selected from the group consisting of ethylene, propylene, isobutylene, butadiene, isoprene, cyclopentadiene, dicyclopentadiene, styrene and derivatives thereof, indene, benzofuran, benzothiophene;

[0032] Preferably, the olefin is derived from at least one of the following raw materials: a C4 fraction, a C5 fraction, a C8 fraction, a C9 fraction, an ethylene tar, a crude gasoline, a coal-to-olefin C4 or more byproduct fraction, a coal tar, a coal-derived oil,

[0033] Preferably, the C4 fraction is selected from the group consisting of a refinery C4, a naphtha cracking C4, and the crude gasoline is selected from the group consisting of an ether front gasoline, a catalytic cracking gasoline, a catalytic hydrogenation gasoline, a coking gasoline.

[0034] [3] The polymer according to [1], wherein the content of the structural unit A is 5 to 45 mol%, the content of the structural unit B is 30 to 70 mol%, and the content of the structural unit C is 1 to 35 mol%, based on the total number of moles of the structural units of the polymer.

[0035] Preferably, the content of the structural unit C is 1 to 50 mol%, preferably 10 to 45 mol%, based on the total number of moles of the structural unit A and the structural unit C.

[0036] [4] The polymer according to [1], wherein the aldehyde group content is 0.05 to 3 mmol·g -1 .

[0037] [5] A method for producing the polymer according to any one of [1] to [4], comprising the steps of:

[0038] (1) reacting a precursor polymer with 5-hydroxymethylfurfural, the precursor polymer containing a structural unit A represented by formula (1) and a structural unit B derived from an olefin monomer;

[0039] (2) optionally, subjecting the polymer obtained in step (1) to an ammonolysis and / or a neutralization reaction.

[0040] [6] The production method according to [5], wherein,

[0041] In step (1), the esterification reaction of the anhydride group in the structural unit represented by formula (1) with the hydroxyl group in 5-hydroxymethylfurfural is carried out in the presence of a catalyst; the catalyst is preferably an acid or a base, the base is preferably one or more selected from the group consisting of pyridine, 4-dimethylaminopyridine, triethylamine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene; the acid is preferably one or more selected from the group consisting of acetic acid, propionic acid, n-butyric acid, succinic acid, p-toluenesulfonic acid, hydrochloric acid, and sulfuric acid;

[0042] In step (1), the molar ratio of 5-hydroxymethylfurfural to the structural unit shown in formula (1) is (0.1-3):1, preferably (1-2):1;

[0043] In step (2), the polymer obtained in step (1) is contacted with ammonia to carry out the ammonolysis reaction and / or the polymer obtained in step (1) is contacted with a metal hydroxide or a metal carbonate to carry out the neutralization reaction.

[0044] [7] According to the preparation method described in [5], wherein,

[0045] In step (1), the precursor polymer is dispersed or dissolved in a solvent, and then 5-hydroxymethylfurfural is added to it to react the precursor polymer with 5-hydroxymethylfurfural.

[0046] Preferably, the solvent is one or more selected from ketone solvents, ester solvents, ether solvents, amide solvents, and sulfoxide solvents.

[0047] [8] According to the preparation method described in [6], the temperature of the esterification reaction in step (1) is 40 to 150°C and the time of the esterification reaction is 0.1 to 100 hours; the time of the ammonolysis reaction in step (2) is 0.1 to 30 minutes, preferably 1 to 10 minutes; the time of the neutralization reaction in step (2) is 0.1 to 30 minutes, preferably 1 to 10 minutes.

[0048] [9] The preparation method according to [5] further includes the following steps:

[0049] (1') The electron-accepting monomer and the olefin monomer undergo self-stabilizing precipitation polymerization to obtain the precursor polymer;

[0050] The electron-accepting monomer is maleic anhydride;

[0051] Preferably, at least one of the following is selected as the raw material for the olefin monomer: C4 fraction, C5 fraction, C8 fraction, C9 fraction, ethylene tar, crude gasoline, coal-to-olefins C4 and above by-product fraction, coal tar, and coal-to-oil.

[0052] The C4 fraction is preferably selected from refined oil C4 and naphtha cracking C4; the crude gasoline is preferably selected from pre-ether gasoline, catalytic cracking gasoline, catalytic hydrogenated gasoline, and coking gasoline.

[0053]

[10] Use of the polymer according to any one of [1] to [4] in paper sizing agents or wood adhesives.

[0054] The effects of the invention

[0055] The present invention has the following beneficial effects:

[0056] 1) The aldehyde-containing polymer of the present invention has adjustable aldehyde density and simple raw material acquisition, realizing high-value utilization of olefin resources;

[0057] 2) The preparation method of the aldehyde-containing polymer of the present invention is simple, cost-controllable, and environmentally friendly;

[0058] 3) The aldehyde-containing reagent used in the preparation method of the aldehyde-containing polymer of the present invention is 5-hydroxymethylfurfural (5-HMF), a biomass platform compound, which is environmentally friendly, broadens the application of 5-HMF, and is conducive to improving the production capacity of 5-HMF. Attached Figure Description

[0059] Figure 1 The polymer P obtained in Example 1 c1 Photos of the actual product;

[0060] Figure 2 The polymer P obtained in Example 1 b1 Infrared spectrum;

[0061] Figure 3 The polymer P obtained in Example 1 c1 Infrared spectrum;

[0062] Figure 4 The polymer P obtained in Example 7 b7 1H NMR spectrum ( 1 H-NMR);

[0063] Figure 5 The polymer P obtained in Example 7 c7 1H NMR spectrum ( 1 H-NMR);

[0064] Figure 6 The polymer P obtained in Example 10 b10 Photos of the actual product;

[0065] Figure 7 This is a graph showing the change of water contact angle over time as measured in the hydrophobicity test. Detailed Implementation

[0066] The present invention will now be described in detail. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.

[0067] <Terminology and Definitions>

[0068] In this specification, "self-stabilizing precipitation polymerization" refers to a polymerization method in which no emulsifier is used in the polymerization system and the polymerization product is suspended in the reaction medium.

[0069] In the present specification, "electron-accepting monomer" means a monomer having an electron-accepting group on a carbon-carbon double bond participating in a polymerization reaction.

[0070] In the present specification, "electron-donating monomer" means a monomer having an electron-donating group on a carbon-carbon double bond participating in a polymerization reaction.

[0071] In the present specification, "alkyl group" means a linear, branched, or cyclic alkyl group, unless otherwise explicitly stated.

[0072] In the present specification, a numerical range represented by "numerical value A to numerical value B" means a range including the end point numerical values A and B.

[0073] In the present specification, a numerical range represented by "above" or "below" means a range including the present numerical value.

[0074] In the present specification, the meaning represented by "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.

[0075] In the present specification, "optionally" or "optional" means that a certain substance, component, execution of a step, application of a condition, and the like is used or not used.

[0076] In the present specification, the unit names used are international standard unit names, and if not specifically stated, "%" used means a percentage by weight or mass.

[0077] In the present specification, "preferred embodiments", "embodiments", and the like referred to mean that the specific elements (for example, features, structures, properties, and / or characteristics) described in relation to the embodiments are included in at least one of the embodiments described herein, and can or can not be present in other embodiments. In addition, it should be understood that the elements can be combined in various embodiments in any suitable manner.

[0078] <Polymers>

[0079] An object of the present application is to provide a polymer containing structural unit A, structural unit B, and structural unit C, wherein

[0080] The structural unit A is at least one selected from the group consisting of structural units represented by the following formulae (1) to (4):

[0081]

[0082] In structures (3) and (4), M + is a metal ion or an ammonium ion

[0083] The structural unit B is a structural unit derived from an olefin monomer;

[0084] The structural unit C is at least one of the structural units represented by the following formula (5) and formula (6):

[0085]

[0086] In structure (6), M + is a metal ion or an ammonium ion

[0087] The polymer of the present application is an aldehyde group-containing polymer. In some embodiments, the aldehyde group content of the polymer of the present application is 0.05 to 3 mmol.g -1 , preferably 0.1 to 2.5 mmol.g -1 , more preferably 0.15 to 2 mmol.g -1 , still for example 0.18 to 1.4 mmol.g -1 , 0.3 mmol.g -1 , 0.4 mmol.g -1 , 0.5 mmol.g -1 , 0.6 mmol.g -1 , 0.7 mmol.g -1 , 0.8 mmol.g -1 , 0.9 mmol.g -1 , 1.0 mmol.g -1 , 1.1 mmol.g -1 , 1.2 mmol.g -1 , 1.3 mmol.g -1 , etc.

[0088] In some embodiments, the polymer of the present application consists of the structural unit A, the structural unit B and the structural unit C, and thus can be considered as a terpolymer.

[0089] Each of the structural units in the polymer of the present application is described in detail below, respectively.

[0090] Building block A

[0091] The structural unit A is at least one of the structural units having an anhydride group, an amic acid group, an amic acid salt or a carboxylic acid salt represented by the above formula (1) to formula (4). Specifically, the one represented by formula (1) is a structural unit having a maleic anhydride group, the one represented by formula (2) is a structural unit having a maleic amic acid group, the one represented by formula (3) is a structural unit having a maleic amic acid metal salt, ammonium salt, and the one represented by formula (4) is a structural unit having a maleic acid metal ion salt.

[0092] In some embodiments, the structural unit A comprises a structural unit represented by formula (1).

[0093] In some embodiments, the structural unit A comprises at least one of the structural units represented by formula (2) to formula (4). The structural units represented by formula (2) to formula (4) can impart sufficient water solubility to the polymer. Therefore, in these embodiments, the polymer of the present application has good water solubility, has excellent solubility in water, and can avoid the use of organic solvents in subsequent application processes, which is economic, environmentally friendly and green and safe;

[0094] In some embodiments, the structural unit A comprises a structural unit represented by formula (2).

[0095] In some embodiments, the structural unit A comprises a structural unit represented by formula (3).

[0096] In some embodiments, the structural unit A comprises a structural unit represented by formula (4).

[0097] In some embodiments, the content of the structural unit A is 5 to 45 mol%, preferably 10 to 30 mol%, based on the total number of moles of the structural units in the polymer.

[0098] In some embodiments, the metal ion represented by M is one or more selected from alkali metal ions and alkaline earth metal ions, preferably one or more selected from lithium ions, sodium ions, potassium ions, calcium ions, magnesium ions, and more preferably sodium ions.

[0099] Building block B

[0100] The structural unit B is a structural unit derived from an olefin monomer, specifically, the structural unit B is a structural unit formed by polymerization (e.g., chain polymerization) of an olefin monomer.

[0101] In some embodiments, the olefin monomer is at least one selected from mono-olefins or di-olefins having 2 to 20 carbon atoms, styrene and derivatives thereof, and fused ring aromatic olefins.

[0102] Preferably, the olefin monomer is at least one selected from ethylene, propylene, isobutylene, butadiene, isoprene, cyclopentadiene, dicyclopentadiene, styrene and derivatives thereof, indene, benzofuran, and benzothiophene.

[0103] Preferably, the olefin is derived from at least one of the following raw materials: carbon four fraction (including refinery C4, naphtha cracking C4), carbon five fraction, carbon eight fraction, carbon nine fraction, ethylene tar, crude gasoline (crude gasoline is at least one selected from ether front gasoline, catalytic cracking gasoline, catalytic hydrogenation gasoline, coking gasoline), coal-to-olefin C4 and above byproduct fraction, coal tar, coal oil.

[0104] In some embodiments, the content of the structural unit B is 30 to 70 mol%, preferably 40 to 60 mol%, based on the total moles of the structural units in the polymer.

[0105] Building block C

[0106] The structural unit C is at least one selected from the group consisting of structural units containing an aldehyde group represented by formula (5) and formula (6). The metal ion represented by M can be selected from those described above for the structural unit A.

[0107] In some embodiments, the content of the structural unit C is 1 to 35 mol%, preferably 5 to 30 mol%, more preferably 10 to 25 mol%, based on the total moles of the structural units in the polymer.

[0108] In some embodiments, the content of the structural unit C is 1 to 50 mol%, preferably 10 to 45 mol%, based on the total moles of the structural units A and C.

[0109] Further building blocks

[0110] The polymer of the present application can also contain other structural units, for example, structural units derived from one or more monomers of a vinyl ether-based monomer, a vinyl ester-based monomer.

[0111] In some embodiments, the content of the other structural units is 10 mol% or less, preferably 5 mol% or less, for example, 2 to 4 mol%, or the like, based on the total moles of the structural units in the polymer.

[0112] <Method for producing the polymer>

[0113] An object of the present application is to provide a method for producing the polymer of the present application, which comprises the following steps:

[0114] (1) reacting a precursor polymer containing a structural unit A represented by formula (1) and a structural unit B derived from an olefin monomer with 5-hydroxymethylfurfural;

[0115] (2) optionally, subjecting the polymer obtained in step (1) to an ammonolysis reaction and / or a neutralization reaction.

[0116] In some embodiments, the method for producing the present application further comprises the following steps:

[0117] (1') subjecting an electron-withdrawing monomer to a self-stabilizing precipitation polymerization with an olefin monomer, thereby obtaining the precursor polymer; wherein the electron-withdrawing monomer is maleic anhydride.

[0118] The following details the individual steps of the method for producing the present application.

[0119] Step (1')

[0120] Step (1') is a step of preparing a precursor polymer by self-stabilizing precipitation polymerization, specifically, subjecting an electron-accepting monomer to self-stabilizing precipitation polymerization with an olefin monomer, thereby obtaining the precursor polymer.

[0121] The self-stabilizing precipitation polymerization of the electron-accepting monomer with the olefin monomer can be performed in a conventional manner, for example, by the manner described in patent document CN 113563152 A, patent document CN 115926024 A, patent document CN 117417481 A.

[0122] By using maleic anhydride as the electron-accepting monomer, a structural unit represented by formula (1) is introduced into the precursor polymer.

[0123] The olefin monomer used in step (1') can be selected from those described above for the structural unit B of the polymer of the present application.

[0124] In some embodiments, at least one of carbon four fraction (containing refinery C4, naphtha cracking C4), carbon five fraction, carbon eight fraction, carbon nine fraction, ethylene tar, crude gasoline (crude gasoline is selected from ether front gasoline, catalytic cracking gasoline, catalytic hydrogenation gasoline, coking gasoline), coal-to-olefin C4 and above byproduct fraction, coal tar, coal oil is used as the raw material of the olefin monomer.

[0125] Step (1)

[0126] In step (1), the precursor polymer is reacted with 5-hydroxymethylfurfural, thereby converting at least a portion of the structural unit represented by formula (1) in the precursor polymer into a structural unit represented by formula (5).

[0127] In some embodiments, in step (1), the anhydride group in the structural unit represented by formula (1) is subjected to esterification reaction with the hydroxyl group in 5-hydroxymethylfurfural in the presence of a catalyst.

[0128] In some embodiments, the catalyst is an acid or a base. The base is preferably one or more selected from pyridine, 4-dimethylaminopyridine, triethylamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene; the acid is preferably one or more selected from acetic acid, propionic acid, n-butyric acid, succinic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid.

[0129] In some embodiments, the total esterification rate of the structural unit represented by formula (1) after the esterification reaction is 1-70 mol%, preferably 2-55 mol%, more preferably 10-50 mol%.

[0130] Herein, the "esterification rate" refers to the molar ratio of the total amount of the structural unit represented by formula (5) in the polymer after the esterification reaction to the total amount of the structural unit represented by formula (1) in the precursor polymer.

[0131] The esterification rate is affected by various factors, such as the type and amount of catalyst, the feed ratio, the reaction temperature, and the reaction time.

[0132] In some embodiments, the amount of catalyst used is 0.1 to 10% relative to the mass of 5-hydroxymethylfurfural.

[0133] In some embodiments, in step (1), the molar ratio of 5-hydroxymethylfurfural to the anhydride group in the structural unit represented by formula (1) is (0.1 to 3): 1, preferably (1 to 2): 1.

[0134] In some embodiments, the temperature of the esterification reaction in step (1) is 40 to 150°C.

[0135] In some embodiments, the time of the esterification reaction in step (1) is 1 to 100 hours.

[0136] In more specific embodiments, in step (1), the precursor polymer is dispersed or dissolved in a solvent, and then 5-hydroxymethylfurfural is added thereto to allow the precursor polymer to react with 5-hydroxymethylfurfural.

[0137] Preferably, the solvent is one or more selected from the group consisting of ketone solvents, ester solvents, ether solvents, amide solvents, and sulfoxide solvents. Among them, the ketone solvents include, but are not limited to, acetone, butanone, cyclohexanone, methyl isobutyl ketone, methyl isopropyl ketone, and the like; the ester solvents include, but are not limited to, ethyl formate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl butyrate, ethyl benzoate, and the like; the ether solvents include, but are not limited to, tetrahydrofuran, dioxane, 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 isoamyl ether, methyl tert-amyl ether, methyl cyclopentyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and the like; the amide solvents include, but are not limited to, dimethylformamide, dimethylacetamide, and the like; and the sulfoxide solvents are, for example, dimethyl sulfoxide, and the like.

[0138] In some embodiments, the mass ratio of the precursor polymer to the solvent is 1:(1 to 30).

[0139] In some embodiments, the 5-hydroxymethylfurfural used in the present application is biologically derived 5-hydroxymethylfurfural, i.e., 5-hydroxymethylfurfural prepared using biomass as a raw material.

[0140] As the biomass for producing 5-hydroxymethylfurfural, cellulose, glucose, fructose (e.g., crude fructose, purified fructose, polyfructose, fructose syrup, etc.), and the like can be exemplified.

[0141] Step (2)

[0142] Step (2) is an optional step. In step (2), the polymer obtained in step (1) is subjected to an amination reaction and / or a neutralization reaction. In the amination reaction, anhydride groups react with ammonia (NH3) to form amide acid groups and / or amide acid ammonium salt groups. By this amination reaction, the structural unit represented by formula (1) in the polymer is converted into the structural unit represented by formula (2) and / or formula (3). In the neutralization reaction, carboxyl groups (-COOH) and / or anhydride groups react with a base to form carboxylate salts, and anhydride groups react with a base to form amide acid salts. By this neutralization reaction, the structural unit represented by formula (1) in the polymer is converted into the structural unit represented by formula (3) and / or formula (4), and the structural unit represented by formula (5) is converted into the structural unit represented by formula (6).

[0143] In step (2), the amination reaction alone, the neutralization reaction alone, or both the amination and the neutralization reaction can be performed. In the embodiment in which both reactions are performed, the order of the amination reaction and the neutralization reaction is not particularly limited.

[0144] In some embodiments, the polymer obtained in step (1) is contacted with ammonia gas to perform the amination reaction, and the neutralization reaction is optionally performed after the amination reaction. From the viewpoint of facilitating the progress of the amination reaction, it is preferable to use ammonia gas (ammonia-containing gas) having a high purity, for example, ammonia gas having an ammonia content of 95% by volume or more, preferably 98% by volume or more, more preferably 99% by volume or more, for example, 100% by volume.

[0145] In some embodiments, the time for the amination reaction in step (2) is 0.1 to 30 minutes, preferably 1 to 10 minutes.

[0146] In some embodiments, the polymer obtained in step (1) is contacted with an aqueous alkali solution to perform the neutralization reaction, and the amination reaction is optionally performed after the neutralization reaction. From the viewpoint of facilitating the progress of the neutralization reaction, the alkali in the aqueous alkali solution is one or more selected from the group consisting of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, and potassium bicarbonate. Preferably, the concentration of the aqueous alkali solution is 0.01 to 5 mol / L, preferably 0.1 to 1.5 mol / L, more preferably 0.2 to 1.2 mol / L.

[0147] In some embodiments, the temperature for the neutralization reaction is 20 to 80°C.

[0148] In some embodiments, the time for the neutralization reaction is 1 to 60 minutes.

[0149] Further steps

[0150] In some embodiments, the preparation method of the present application further comprises a post-treatment step. Specifically, after step (1) or step (2) (if present), the resulting polymer is separated from the reaction system, and optionally subjected to purification, drying, etc.

[0151] The post-treatment step of the present application is not particularly limited, and suitable methods known in the art can be used.

[0152] <Use>

[0153] It is an object of the present application to provide the use of the polymer of the present application for paper sizing agent.

[0154] It is an object of the present application to provide the use of the polymer of the present application for wood adhesive.

[0155] Examples

[0156] The embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will understand that the following examples are only for illustration of the present application and should not be regarded as limiting the scope of the present application. The specific conditions are not specified in the examples, and the conventional conditions or the conditions recommended by the manufacturer are used. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be obtained by purchase.

[0157] The raw materials used in the following examples are described as follows:

[0158] Styrene-maleic anhydride linear copolymer (SMA): Mn = 45000 g·mol -1 , and the MAH unit content is about 50%. Synthesis method: 10 g of styrene, 10 g of maleic anhydride, 0.2 g of azobisisobutyronitrile, and 180 g of isopentyl acetate were added to a reaction bottle, and nitrogen was passed for 15 min. After reaction at 70°C for 6 h, centrifugation, washing, and drying were performed.

[0159] Isobutylene-maleic anhydride linear copolymer (IB-MA): purchased from Shanghai Adamas Reagent Co., Ltd., CAS No.: 6426-80-2, Item No.: 121947BC

[0160] Propylene-maleic anhydride linear copolymer (PP-MA): Synthesis method: 3 g of propylene, 10 g of maleic anhydride, 0.2 g of azobisisobutyronitrile, and 120 g of isopentyl acetate were added to a reaction kettle, and nitrogen was passed for 15 min. After reaction at 70°C for 6 h, centrifugation, washing, and drying were performed.

[0161] Dephenolized phenol-formaldehyde resin: synthesis method: 20 g of dephenolized phenol, 10 g of formaldehyde, 0.2 g of azobisisobutyronitrile, 180 g of isopropyl acetate were put into a reaction bottle, and nitrogen was passed for 15 min. After reaction at 70 °C for 6 h, centrifugation, washing and drying were performed.

[0162] C5 fraction-styrene-maleic anhydride linear copolymer (C5-MA): synthesis method: 5 g of C5 fraction, 5 g of styrene, 10 g of maleic anhydride, 0.2 g of azobisisobutyronitrile, 180 g of isopropyl acetate were put into a reaction bottle, and nitrogen was passed for 15 min. After reaction at 70 °C for 6 h, centrifugation, washing and drying were performed.

[0163] C9 fraction-styrene-maleic anhydride linear copolymer (C9-MA): synthesis method: 5 g of C9 fraction, 5 g of styrene, 10 g of maleic anhydride, 0.2 g of azobisisobutyronitrile, 180 g of isopropyl acetate were put into a reaction bottle, and nitrogen was passed for 15 min. After reaction at 70 °C for 6 h, centrifugation, washing and drying were performed.

[0164] 5-hydroxymethylfurfural (5-HMF): purchased from Shanghai Aldrin Company, CAS No.: 67-47-0, Item No.: H106324-25g

[0165] 4-dimethylaminopyridine (DMAP): purchased from Bailingwei J&K, CAS No.: 1122-58-3, Item No.: 117147

[0166] triethylamine (TEA): purchased from Bailingwei J&K, CAS No.: 121-44-8, Item No.: 959833

[0167] sodium hydroxide (NaOH): purchased from Shanghai Titan Science and Technology Co., Ltd., CAS No.: 1310-73-2, Item No.: 01410952

[0168] Test method

[0169] Esterification rate:

[0170] The esterification rate was calculated by integrating the area of the hydrogen spectrum, a was the peak of aldehyde hydrogen, located at 9.5 ppm, b was the peak of aromatic hydrogen on the benzene ring, located at 5.8-7.6 ppm, and the results of two double bond hydrogens in the structure of 5-hydroxymethylfurfural at 6.7, 7.5 ppm were deducted. The calculation formula is:

[0171]

[0172] Aldehyde group content:

[0173] The aldehyde group content was calculated by mass method, w0 was the mass of the polymer precursor, w1 was the mass of the polymer after introducing 5-hydroxymethylfurfural. The calculation formula is:

[0174]

[0175] Example 1

[0176] Take 3g of styrene-maleic anhydride linear copolymer (SMA, Mn = 45000g·mol⁻¹) -1 A mixture of 26 g of butanone (MEK), 1.89 g of 5-HMF, and 0.06 g of DMAP was placed in a 50 mL single-necked flask and stirred for 0.5 h to obtain a pale yellow, clear, and transparent solution. The reaction was carried out at 70 °C for 24 h. After the reaction was complete, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer precipitated. After centrifugation, washing, and repeated dissolution and precipitation three times, and drying, a pure aldehyde-containing terpolymer (P) based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester was obtained. b1 Nuclear magnetic resonance (NMR) spectroscopy analysis revealed that, based on maleic anhydride units, the esterification rate was 25%, and the aldehyde content of the polymer was 1.07 mmol·g. -1 .

[0177] Take 1g of the prepared polymer P b1 High-purity ammonia gas was introduced into a 100 mL beaker for 10 min to obtain an aldehyde-containing water-soluble terpolymer (P) based on the structure of maleic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester. c1 ).

[0178] Figure 1 The copolymer P is shown c1 The actual photo shows a pale yellow powder.

[0179] Figure 2 and Figure 3 Polymer P is shown respectively b1 and copolymer P c1 The infrared spectrum. (From) Figure 2 and Figure 3 It can be determined that it is located at 1775 and 1850 cm. -1 The anhydride peak at 1680 cm⁻¹ completely disappeared, and the peak at 1680 cm⁻¹ was located there. -1 The aldehyde peak at 1555 cm⁻¹ was retained, and new peaks were added at 1555 and 1660 cm⁻¹. -1 The amide peak at that location.

[0180] Example 2

[0181] Take 3g of styrene-maleic anhydride linear copolymer (SMA, Mn = 45000g·mol⁻¹) -1, MAH unit content of about 50%), 26 g butanone, 1.89 g 5-HMF, 0.06 g DMAP in a 50 mL single-necked flask, stirring for 0.5 h to obtain a light yellow clear transparent solution. Reaction at 120 °C for 24 h. After the reaction, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer precipitated and settled. After centrifugation, washing, and repeated dissolution and precipitation three times, the pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b2 ) was obtained after drying. According to the analysis by nuclear magnetic resonance hydrogen spectrum, the esterification rate was 19% based on the maleic anhydride unit, and the aldehyde group content of the polymer was 0.84 mmol·g -1 .

[0182] Take 1 g of the prepared polymer P b2 , and introduce high-purity ammonia gas into the 100 mL beaker for 10 min to obtain an aldehyde group-containing water-soluble terpolymer based on maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester structure (P c2 ).

[0183] Example 3

[0184] Take 3 g of a styrene-maleic anhydride linear copolymer (SMA, Mn = 45000 g·mol -1 , MAH unit content of about 50%), 26 g butanone, 1.89 g 5-HMF, 0.06 g DMAP in a 50 mL single-necked flask, stirring for 0.5 h to obtain a light yellow clear transparent solution. Reaction at 120 °C for 24 h. After the reaction, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer precipitated and settled. After centrifugation, washing, and repeated dissolution and precipitation three times, the pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b3 ) was obtained after drying. According to the analysis by nuclear magnetic resonance hydrogen spectrum, the esterification rate was 19% based on the maleic anhydride unit, and the aldehyde group content of the polymer was 0.84 mmol·g -1 .

[0185] Take 1 g of the prepared polymer P b3 , and introduce high-purity ammonia gas into the 100 mL beaker for 10 min to obtain an aldehyde group-containing water-soluble terpolymer based on maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester structure (P c3 ).

[0186] Example 4

[0187] Take 3 g of a styrene-maleic anhydride linear copolymer (SMA, Mn = 45000 g·mol-1 , 26 g butanone, 1.89 g 5-HMF in a 50 mL single-necked flask, stirring for 0.5 h to obtain a light yellow clear transparent solution. The reaction was carried out at 70 °C for 24 h. After the reaction was completed, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer precipitated and settled. After centrifugation, washing, and repeated dissolution and precipitation three times, the pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b4 ) was obtained after drying. According to the analysis by nuclear magnetic resonance hydrogen spectrum, the esterification rate was 9% and the aldehyde group content was 0.42 mmol·g -1 .

[0188] 1 g of the prepared polymer P b4 was taken in a 100 mL beaker, and high-purity ammonia gas was introduced thereinto for 10 min to obtain an aldehyde group-containing water-soluble terpolymer based on maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester structure (P c4 ).

[0189] Example 5

[0190] 3 g of a styrene-maleic anhydride linear copolymer (SMA, Mn = 45000 g·mol -1 , MAH unit content about 50%), 26 g butanone, 1.89 g 5-HMF, 0.3 g TEA in a 50 mL single-necked flask, stirring for 0.5 h to obtain a light yellow clear transparent solution. The reaction was carried out at 70 °C for 24 h. After the reaction was completed, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer precipitated and settled. After centrifugation, washing, and repeated dissolution and precipitation three times, the pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b5 ) was obtained after drying. According to the analysis by nuclear magnetic resonance hydrogen spectrum, the esterification rate was 28% and the aldehyde group content was 1.18 mmol·g -1 .

[0191] 1 g of the prepared polymer P b5 was taken in a 100 mL beaker, and high-purity ammonia gas was introduced thereinto for 10 min to obtain an aldehyde group-containing water-soluble terpolymer based on maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester structure (P c5 ).

[0192] Example 6

[0193] 3 g of a styrene-maleic anhydride linear copolymer (SMA, Mn = 45000 g·mol -1, MAH unit content of about 50%), 26 g butanone, 0.189 g 5-HMF, 0.06 g TEA in a 50 mL single-necked flask, stirring for 0.5 h to obtain a light yellow clear transparent solution. Reaction at 70°C for 24 h. After the reaction, the reaction solution was poured into 200 mL of methyl tert-butyl ether, the polymer precipitated and settled, and repeated three times by centrifugation, washing, and dissolution, precipitation, and dried to obtain pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b6 ) with a esterification rate of 4% and an aldehyde group content of 0.20 mmol·g -1 .

[0194] Take 1 g of the prepared polymer P b6 , and pass high-purity ammonia gas into it for 10 min in a 100 mL beaker to obtain an aldehyde group-containing water-soluble terpolymer based on maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester structure (P c6 ).

[0195] Example 7

[0196] Take 3 g of a styrene-maleic anhydride linear copolymer (SMA, Mn= 45000 g·mol -1 , MAH unit content of about 50%), 26 g butanone, 5.67 g 5-HMF, 0.06 g TEA in a 50 mL single-necked flask, stirring for 0.5 h to obtain a light yellow clear transparent solution. Reaction at 70°C for 24 h. After the reaction, the reaction solution was poured into 200 mL of methyl tert-butyl ether, the polymer precipitated and settled, and repeated three times by centrifugation, washing, and dissolution, precipitation, and dried to obtain pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b7 ) with a esterification rate of 55% and an aldehyde group content of 2.03 mmol·g -1 .

[0197] Take 1 g of the prepared polymer P b7 , and pass high-purity ammonia gas into it for 10 min in a 100 mL beaker to obtain an aldehyde group-containing water-soluble terpolymer based on maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester structure (P c7 ).

[0198] Figure 4 and Figure 5 show the nuclear magnetic resonance hydrogen spectrum of the copolymer P b7 and the copolymer P c7 , respectively. From theFigure 4 and Figure 5 It can be seen that the peak of aldehyde hydrogen at 9.5 ppm is retained, and the peak of aromatic hydrogen on the benzene ring at 5.8-7.6 ppm remains unchanged.

[0199] Example 8

[0200] Take 1.5 g of styrene-maleic anhydride linear copolymer (SMA, Mn = 45000 g·mol -1 , MAH unit content is about 50%), 26 g of butanone, 1.89 g of 5-HMF, 0.06 g of TEA in a 50 mL single-necked flask, stir for 0.5 h to obtain a light yellow clear transparent solution. React at 70℃ for 24 h. After the reaction is completed, pour the reaction solution into 200 mL of methyl tert-butyl ether, and the polymer precipitates. After repeated centrifugation, washing, and dissolution, precipitation three times, and drying, the pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b8 ) is obtained. It can be seen from the nuclear magnetic resonance hydrogen spectrum analysis that the esterification rate is 13% and the aldehyde group content is 0.60 mmol·g -1 .

[0201] Take 1 g of the prepared polymer P b8 , and pass high-purity ammonia gas into it for 10 min in a 100 mL beaker to obtain an aldehyde group-containing water-soluble terpolymer based on maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester structure (P c8 ).

[0202] Example 9

[0203] Take 6 g of styrene-maleic anhydride linear copolymer (SMA, Mn = 45000 g·mol -1 , MAH unit content is about 50%), 26 g of butanone, 5.67 g of 5-HMF, 0.06 g of TEA in a 50 mL single-necked flask, stir for 0.5 h to obtain a light yellow clear transparent solution. React at 70℃ for 24 h. After the reaction is completed, pour the reaction solution into 200 mL of methyl tert-butyl ether, and the polymer precipitates. After repeated centrifugation, washing, and dissolution, precipitation three times, and drying, the pure aldehyde group-containing terpolymer based on maleic anhydride, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester (P b9 ) is obtained. It can be seen from the nuclear magnetic resonance hydrogen spectrum analysis that the esterification rate is 30% and the aldehyde group content is 1.25 mmol·g -1 .

[0204] Take 1 g of the prepared polymer P b9In a 100 mL beaker, high-purity ammonia gas was introduced for 10 min to obtain an aldehyde group-containing water-soluble terpolymer (P c9 ) based on the structure of maleamic acid, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester.

[0205] Example 10

[0206] 2 g of isobutylene-maleic anhydride linear copolymer (IB-MA, Mn = 6600 g·mol -1 , MAH unit content is about 50%), 17 g of N,N-dimethylformamide, 1.26 g of 5-HMF, and 0.04 g of DMAP were taken in a 48 mL single-necked flask, stirred for 0.5 h to obtain a light yellow clear transparent solution. The reaction was carried out at 65°C for 24 h. After the reaction was completed, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer was precipitated and settled. After repeated centrifugation, washing, and dissolution and precipitation for three times, the pure aldehyde group-containing terpolymer (P b10 ) based on maleic anhydride, isobutylene, and maleic acid mono(5-hydroxymethylfurfural) ester was obtained after drying. According to the analysis by nuclear magnetic resonance hydrogen spectrum, the esterification rate was 10% based on the maleic anhydride unit, and the aldehyde group content was 0.46 mmol·g -1 .

[0207] 1 g of the prepared polymer P b10 was taken, and high-purity ammonia gas was introduced for 10 min in a 100 mL beaker to obtain an aldehyde group-containing water-soluble terpolymer (P c10 ) based on the structure of maleamic acid, isobutylene, and maleic acid mono(5-hydroxymethylfurfural) ester.

[0208] Figure 6 A physical photograph of the prepared copolymer P b10 is shown, which is a yellow liquid.

[0209] Example 11

[0210] 2 g of propylene-maleic anhydride linear copolymer (PP-MA), 17 g of butanone, 1.26 g of 5-HMF, and 0.04 g of DMAP were taken in a 48 mL single-necked flask, stirred for 0.5 h to obtain a light yellow clear transparent solution. The reaction was carried out at 65°C for 24 h. After the reaction was completed, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer was precipitated and settled. After repeated centrifugation, washing, and dissolution and precipitation for three times, the pure aldehyde group-containing terpolymer (P b11 ) based on maleic anhydride, propylene, and maleic acid mono(5-hydroxymethylfurfural) ester was obtained after drying. According to the analysis by nuclear magnetic resonance hydrogen spectrum, the esterification rate was 22% based on the maleic anhydride unit, and the aldehyde group content was 0.96 mmol·g -1 .

[0211] Take 1 g of the prepared polymer P b11 In a 100 mL beaker, high-purity ammonia gas was introduced for 10 min to obtain an aldehyde group-containing water-soluble terpolymer (P c11 ) based on the structure of maleamic acid, propylene, and maleic acid mono(5-hydroxymethylfurfural) ester.

[0212] Example 12

[0213] Take 2 g of the dephenolated creosote oil-maleic anhydride linear copolymer (DPPO-MA), 17 g of butanone, 1.26 g of 5-HMF, and 0.04 g of DMAP in a 48 mL single-necked flask, stir for 0.5 h to obtain a light yellow clear transparent solution. React at 65°C for 24 h. After the reaction is completed, pour the reaction solution into 200 mL of methyl tert-butyl ether, and the polymer precipitates. Repeat the centrifugation, washing, and dissolution and precipitation three times, and then dry to obtain a pure aldehyde group-containing terpolymer (P b12 ) based on maleic anhydride, dephenolated creosote oil monomer, and maleic acid mono(5-hydroxymethylfurfural) ester. According to the nuclear magnetic resonance hydrogen spectrum analysis, the esterification rate is 16% based on the maleic anhydride unit, and the aldehyde group content is 0.72 mmol·g -1 .

[0214] Take 1 g of the prepared polymer P b12 In a 100 mL beaker, high-purity ammonia gas was introduced for 10 min to obtain an aldehyde group-containing water-soluble terpolymer (P c12 ) based on the structure of maleamic acid, dephenolated creosote oil monomer, and maleic acid mono(5-hydroxymethylfurfural) ester.

[0215] Example 13

[0216] Take 2 g of the C5 fraction-styrene-maleic anhydride linear copolymer (C5-SMA), 17 g of butanone, 1.26 g of 5-HMF, and 0.04 g of DMAP in a 48 mL single-necked flask, stir for 0.5 h to obtain a light yellow clear transparent solution. React at 65°C for 24 h. After the reaction is completed, pour the reaction solution into 200 mL of methyl tert-butyl ether, and the polymer precipitates. Repeat the centrifugation, washing, and dissolution and precipitation three times, and then dry to obtain a pure aldehyde group-containing terpolymer (P b13 ) based on maleic anhydride, C5 fraction monomer, and styrene, and maleic acid mono(5-hydroxymethylfurfural) ester. According to the nuclear magnetic resonance hydrogen spectrum analysis, the esterification rate is 20% based on the maleic anhydride unit, and the aldehyde group content is 0.88 mmol·g -1 .

[0217] Take 1 g of the prepared polymer P b13High-purity ammonia gas was introduced into a 100 mL beaker for 10 min to obtain an aldehyde-containing water-soluble terpolymer (P) based on maleamic acid, C5 fraction monomers, and styrene and maleic acid mono(5-hydroxymethylfurfural) ester structure. c13 ).

[0218] Example 14

[0219] 2 g of C9 fraction-styrene-maleic anhydride linear copolymer (C9-SMA), 17 g of butanone, 1.26 g of 5-HMF, and 0.04 g of DMAP were placed in a 48 mL single-necked flask and stirred for 0.5 h to obtain a pale yellow, clear, and transparent solution. The reaction was carried out at 65 °C for 24 h. After the reaction was complete, the reaction solution was poured into 200 mL of methyl tert-butyl ether, and the polymer precipitated. After centrifugation, washing, and repeated dissolution and precipitation three times, and drying, a pure aldehyde-containing terpolymer (P) based on maleic anhydride, C9 fraction monomer, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester was obtained. b14 Nuclear magnetic resonance (NMR) 1H spectroscopy analysis revealed that, based on maleic anhydride units, the esterification rate was 20%, and the aldehyde content was 0.88 mmol·g. -1 .

[0220] Take 1g of the prepared polymer P b14 High-purity ammonia gas was introduced into a 100 mL beaker for 10 min to obtain an aldehyde-containing water-soluble terpolymer (P) based on maleamic acid, C9 fraction monomers, and styrene and maleic acid mono(5-hydroxymethylfurfural) ester structure. c14 ).

[0221] The types and amounts of raw materials, reaction conditions, esterification rates and aldehyde content in Examples 1 to 14 are listed in Table 1 below.

[0222] Table 1

[0223]

[0224] Example 15

[0225] Take 1g of polymer P prepared in Example 1 c1 In a 100 mL beaker, 10 mL of a 1 M NaOH aqueous solution was added, and the mixture was stirred at room temperature for 10 min to carry out a neutralization reaction, yielding an aldehyde-containing water-soluble terpolymer (P) based on the structure of sodium maleate, styrene, and maleic acid mono(5-hydroxymethylfurfural) ester. d1 ).

[0226] <Tests and Evaluations>

[0227] 1. Evaluation of hydrophobicity

[0228] Take 1 g of polymer P b7 and P c7 , respectively, dissolved in 199 g of distilled water to prepare a 0.5 wt% aqueous solution. The raw Xuan paper was immersed in the aqueous solution of polymer P b7 and P c7 for about 5 s, and then dried at room temperature after being taken out, and heat treated in an oven at 80℃ for 30 min to obtain the Xuan paper sized with polymer P b7 and P c7 .

[0229] Contact angle test method: The treated Xuan paper was placed on a glass slide, and the water contact angle was tested using an OCA200 contact angle measuring instrument (purchased from Dataphysics Company, Germany). The injection volume for each test was 3 μL, and the syringe was raised after the water droplet was dropped on the surface of the paper, and the video recording mode was started to record the data within 300 s, with a sampling rate of 1 Hz, i.e. 1 sample per second.

[0230] Surprisingly, it was found that the polymer P c7 with furfural groups introduced therein could be used for paper sizing to achieve the surface hydrophobicity of the paper after low-temperature heat treatment. As shown in Figure 7 , the Xuan paper sized with P c7 with aldehyde groups introduced therein had a water contact angle within 5 min decreased from 114° to 72° and gradually stabilized, having obvious hydrophobic effect and waterproof effect. In contrast, the Xuan paper sized with P b7 had the water droplet absorbed into the paper within about 20 s, and did not have hydrophobic effect. The polymers containing amide acid structure reported in the literature for paper sizing generally have a heat treatment temperature of 120-160℃, and therefore, the aldehyde-containing polymer is expected to be used in the field of paper sizing agents, and to achieve a significant reduction in the heat treatment temperature.

[0231] Industrial applicability

[0232] The polymer of the present application can be widely used in industry as an aldehyde substance, for example, can be used in various fields such as organic synthesis, biomedicine, agriculture, textile industry, construction industry, etc., and in particular, can be used for paper sizing materials or wood adhesives.

Claims

1. A polymer, characterized in that, contains structural unit A, structural unit B, and structural unit C, wherein the structural unit A is at least one selected from the group consisting of structural units represented by the following formulae (1) to (4): wherein in structures (3) and (4), M + is a metal ion or an ammonium ion ; the structural unit B is a structural unit derived from an olefin monomer; the structural unit C is at least one selected from the group consisting of structural units represented by the following formulae (5) and (6): wherein in structure (6), M + is a metal ion or an ammonium ion .

2. The polymer of claim 1, wherein the olefin monomer is at least one selected from the group consisting of mono-olefins or di-olefins having 2 to 20 carbon atoms, styrene and derivatives thereof, and fused ring aromatic olefins.

3. The polymer of claim 2, wherein, the olefin monomer is at least one selected from the group consisting of ethylene, propylene, isobutylene, butadiene, isoprene, cyclopentadiene, dicyclopentadiene, styrene and derivatives thereof, indene, benzofuran, and benzothiophene.

4. The polymer of claim 2, wherein the olefin monomer is derived from at least one of the following raw materials: C4 fraction, C5 fraction, C8 fraction, C9 fraction, ethylene tar, crude gasoline, coal-to-olefin C4 or more by-product fraction, coal tar, coal-derived oil.

5. The polymer of claim 4, wherein the C4 fraction is selected from the group consisting of refinery C4, naphtha cracking C4, and the crude gasoline is selected from the group consisting of ether front gasoline, catalytic cracking gasoline, catalytic hydrogenation gasoline, and coking gasoline.

6. The polymer of claim 1, wherein the content of the structural unit A is 5 to 45 mol%, the content of the structural unit B is 30 to 70 mol%, and the content of the structural unit C is 1 to 35 mol%, based on the total moles of the structural units of the polymer.

7. The polymer of claim 6, wherein the content of the structural unit C is 1 to 50 mol%, based on the total moles of the structural unit A and the structural unit C.

8. The polymer of claim 7, wherein, the content of the structural unit C is 10 to 45 mol%, based on the total moles of the structural unit A and the structural unit C.

9. The polymer of claim 1, wherein, aldehyde group content of 0.05 to 3 mmol.g -1 .

10. The method of claim 1 to 9, wherein comprising the following steps: (1) reacting a precursor polymer with 5-hydroxymethylfurfural, the precursor polymer containing structural unit A represented by formula (1) and structural unit B derived from an olefin monomer; (2) optionally, subjecting the polymer obtained in step (1) to ammonolysis and / or neutralization reaction.

11. The production method according to claim 10, wherein in step (1), the esterification reaction of the anhydride group in the structural unit represented by formula (1) with the hydroxyl group in 5-hydroxymethylfurfural is performed in the presence of a catalyst; in step (1), the molar ratio of 5-hydroxymethylfurfural to the structural unit represented by formula (1) is (0.1 to 3): 1; in step (2), the polymer obtained in step (1) is contacted with ammonia gas to perform the ammonolysis reaction and / or the polymer obtained in step (1) is contacted with a metal hydroxide or a metal carbonate to perform the neutralization reaction.

12. The method of claim 11, wherein, the catalyst is an acid or a base.

13. The method of claim 12, wherein, the base is one or more selected from the group consisting of pyridine, 4-dimethylaminopyridine, triethylamine, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene; and the acid is one or more selected from the group consisting of acetic acid, propionic acid, n-butyric acid, succinic acid, p-toluenesulfonic acid, hydrochloric acid, and sulfuric acid.

14. The method of claim 11, wherein, in step (1), the molar ratio of 5-hydroxymethylfurfural to the structural unit represented by formula (1) is (1 to 2):

1.

15. The production method according to claim 10, wherein In step (1), the precursor polymer is dispersed or dissolved in a solvent, and then 5-hydroxymethylfurfural is added to the precursor polymer to react the precursor polymer with 5-hydroxymethylfurfural.

16. The method of claim 15, wherein, The solvent is one or more selected from ketone solvents, ester solvents, ether solvents, amide solvents, and sulfoxide solvents.

17. The method of claim 11, wherein, The temperature of the esterification reaction in step (1) is 40-150°C, and the time of the esterification reaction is 0.1-100 hours; the time of the ammonolysis reaction in step (2) is 0.1-30 minutes; and the time of the neutralization reaction in step (2) is 0.1-30 minutes.

18. The method of claim 17, wherein, The time of the ammonolysis reaction in step (2) is 1-10 minutes; and the time of the neutralization reaction in step (2) is 1-10 minutes.

19. The method of claim 10, wherein, Further comprising the following steps: (1') subjecting an electron-withdrawing monomer to self-stabilized precipitation polymerization with an olefin monomer to obtain the precursor polymer; The electron-withdrawing monomer is maleic anhydride.

20. The method of claim 19, wherein, At least one selected from carbon tetramer fraction, carbon pentamer fraction, carbon octamer fraction, carbon nonamer fraction, ethylene tar, crude gasoline, coal-to-olefin C4 and above byproduct fraction, coal tar, and coal-derived oil is used as a raw material of the olefin monomer.

21. The method of claim 20, wherein, The carbon tetramer fraction is selected from refinery C4 and naphtha cracking C4; and the crude gasoline is selected from ether front gasoline, catalytic cracking gasoline, catalytic hydrogenation gasoline, and coking gasoline.

22. Use of the polymer according to any one of claims 1-9 for paper sizing agents or wood adhesives.

Images