Method for preparing sizing agent

Abstract

The invention relates to the field of papermaking. In particular, the invention relates to a method for preparing a sizing agent, and the sizing agent prepared according to the method. The method can reduce the viscosity of the reaction system and / or realize toluene-free operation.

Description

Technical Field

[0001] The present invention relates to the field of papermaking. In particular, the present invention relates to a method for preparing a sizing agent and a sizing agent prepared according to the method. The method of the present invention can reduce the viscosity of the reaction system and / or achieve toluene-free operation. Background Art

[0002] Paper is formed by the entanglement of materials including plant cellulose. Plant cellulose has hydroxyl groups, which gives the paper a certain degree of hydrophilicity. Plant cellulose also entangles to form a pore structure, which has a capillary effect, which gives the paper a certain degree of fluid (such as water, oil, ink, juice, etc.) permeability. Therefore, the surface of the paper usually needs to be treated to improve the performance. In the papermaking process, the surface of the paper can be treated by applying a sizing agent. The sizing agent can form a protective coating (for example, on the surface of the paper or the surface of the cellulose) after being applied and dried, reducing the direct contact between the paper and the fluid, so that the paper has improved mechanical strength and reduced fluid permeability. Depending on the pH value, the sizing agent can be divided into an acidic sizing agent, a neutral sizing agent and an alkaline sizing agent. In recent years, neutral sizing papermaking has become more and more popular in the papermaking industry because it can meet increasingly stringent environmental protection requirements and can give the paper good performance.

[0003] A commonly used neutral sizing agent is Alkyl Ketene Dimer (AKD), which has a history of application of more than 50 years. AKD is a waxy solid at room temperature. AKD can be used as both an internal sizing agent and a surface sizing agent. AKD is usually represented by the following structure:

[0004] Among them, each R a , R b , R c and R d The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbon. It is found that each R in the above ketene dimer a , R b , R c and R d The radicals may be not only saturated hydrocarbon radicals but also unsaturated hydrocarbon radicals (eg alkenyl radicals derived from oleic acid). Ketene dimers with unsaturated hydrocarbon radicals are still referred to as AKD (alkyl ketene dimer) for the sake of convention.

[0005] The four-membered lactone ring in the AKD molecule can react with the hydroxyl groups on cellulose to form an ester bond, thereby being positioned on cellulose. a , R b, R c and R d One or more of the above) produces a hydrophobic effect on the fiber surface and covers part of the pore structure, thereby giving the paper hydrophobicity and anti-permeability. The schematic diagram of the reaction between AKD and cellulose is shown below:

[0006]

[0007] A typical method for preparing AKD includes the steps of adding fatty acid chlorides (FACl) and triethylamine (TEA) to a reactor. In the above preparation process, with the formation of triethylamine hydrochloride (TEA·HCl) as a byproduct, the viscosity of the reaction increases, which leads to a series of problems such as difficult stirring, increased energy consumption, and poor heat dissipation. At the same time, in the industry, it is often necessary to add inert solvents such as toluene to reduce the adverse effects of high viscosity. With the improvement of environmental awareness, further requirements have been put forward for reducing the amount of toluene used.

[0008] Currently, there is still a continuous demand in the art for a method for preparing a sizing agent (especially AKD) that can achieve reduced viscosity. Summary of the invention

[0009] The preparation method of AKD is well known in the art. For example, AKD is usually produced from carboxylic acid substances through three steps of acylation, dehydrochlorination and dimerization. An exemplary synthesis process of AKD is shown below.

[0010]

[0011] In the AKD represented by structural formula (IV),

[0012] R a The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbon;

[0013] R b The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbon;

[0014] R c The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 a hydrocarbon group; and

[0015] R d The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C30 Hydrocarbon.

[0016] For R a , R b , R c or R d Any one of the C1-C 30 The hydrocarbon group is preferably C 10 -C 20 Hydrocarbyl, more preferably C 13 -C 17 Hydrocarbon, such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , C 25 , C 26 , C 27 , C 28 , C 29 , C 30 For R a , R b , R c or R d In any of the above, the hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group; preferably an alkyl group.

[0017] In any of the structural formulas I, II and / or III, the R' group is independently selected at each occurrence from: hydrogen; an optionally substituted, straight or branched C1-C 30 Hydrocarbyl; and / or

[0018] The R" group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbon.

[0019] For any of R' or R", the C1-C 30 The hydrocarbon group is preferably C 10 -C 20 Hydrocarbyl, more preferably C 13 -C 17 Hydrocarbon, such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , C 25 , C 26 , C 27 , C 28 , C 29 , C 30 For either R' or R", the hydrocarbyl group may be an alkyl group, an alkenyl group, or an alkynyl group; preferably an alkyl group.

[0020] Formula (III-1) enone is to use enone of formula (III-2) The same steps were used to synthesize R a The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbon; R b The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbon; R c The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbyl; and, R d The group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 For R a , R b , R c or R d Any one of the C1-C 30 The hydrocarbon group is preferably C 10 -C 20 Hydrocarbyl, more preferably C 13 -C 17 Hydrocarbon, such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C20 , C 21 , C 22 , C 23 , C 24 , C 25 , C 26 , C 27 , C 28 , C 29 , C 30 For R a , R b , R c or R d In any of the above, the hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group; preferably an alkyl group.

[0021] In the acylation step, (a) PCI3, (b) SOCl2 and (c) COCl2 + DMF are three commonly used acylation methods. The method (c) using COCl2 and DMF is currently the most commonly used acylation method, in which phosgene (COCl2) is used as an acylating agent and dimethylformamide (DMF) is used as a catalyst.

[0022] In the dehydrochlorination step, for the purpose of cost saving, triethylamine hydrochloride (N(CH2CH3)3·HCl) is usually regenerated into triethylamine and then recycled.

[0023] In the above reaction 2, the raw material of formula (II) is usually called fatty acid chlorides (FACl), which undergoes dehydrochlorination under the action of triethylamine (TEA).

[0024] Therefore, a typical step of the AKD preparation method involves contacting TEA and FACl to react, and its reaction formula can also be written as follows:

[0025] 2FACl+2TEA→AKD+2TEA·HCl

[0026] The byproduct TEA·HCl produced in the reaction crystallizes. As the crystallization progresses, the viscosity of the reaction mixture increases, and the energy consumption required for stirring increases accordingly.

[0027] The present invention has been found that by adding one or more amphoteric polymers before, after or simultaneously with the addition of TEA, the crystallization behavior of TEA·HCl can be influenced, the crystal size in the reaction mixture can be reduced, and the viscosity of the reaction mixture can be reduced. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The relationship between the reaction time and the viscosity of the reaction mixture in the blank control group is shown.

[0029] Figure 2 The relationship between the reaction time and the viscosity of the reaction mixture with the addition of the polymer is shown.

[0030] Figure 3 The relationship between the reaction time and the viscosity of the reaction mixture with the addition of the polymer is shown.

[0031] Figure 4 The crystal sizes of triethylamine hydrochloride in the blank control and with different concentrations of ethylene acrylic acid copolymer added are shown.

[0032] Figure 5 The precipitation of triethylamine hydrochloride crystals after centrifugation with the addition of different concentrations of ethylene acrylic acid copolymer is shown. DETAILED DESCRIPTION

[0033] In some embodiments of the present invention, the present invention provides a method for preparing a sizing agent, wherein:

[0034] The method comprises the steps of contacting triethylamine (TEA) and fatty acid chloride (FACl), and

[0035] The method further comprises adding one or more amphiphilic polymers before, after or simultaneously with the addition of TEA, wherein the amphiphilic polymer is a polymer comprising repeating units containing hydrophobic groups and repeating units containing hydrophilic groups.

[0036] In one aspect of the present invention, the reaction mixture of the present invention comprises one or more of TEA, FACl, alkyl ketene, AKD and / or TEA·HCl. The reaction mixture of the present invention refers to a mixture of reaction 2 (2FACl+2TEA→AKD+2TEA·HCl).

[0037] In one embodiment, the fatty acyl chloride (FACl) described herein is a compound having structural formula (II):

[0038]

[0039] in,

[0040] The R' group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbyl; and / or

[0041] The R" group is independently selected at each occurrence from: hydrogen; optionally substituted, straight or branched C1-C 30 Hydrocarbon.

[0042] For any of R' or R", the C1-C 30 The hydrocarbon group is preferably C 10 -C20 Hydrocarbyl, more preferably C 13 -C 17 Hydrocarbon, such as C1, C2, C3, C4, C5, C6, C7, C8, C9, C 10 , C 11 , C 12 , C 13 , C 14 , C 15 , C 16 , C 17 , C 18 , C 19 , C 20 , C 21 , C 22 , C 23 , C 24 , C 25 , C 26 , C 27 , C 28 , C 29 , C 30 For either R' or R", the hydrocarbyl group may be an alkyl group, an alkenyl group, or an alkynyl group; preferably an alkyl group.

[0043] In one aspect of the present invention, the fatty acid chloride (FACl) described herein may be a mixture of two or more fatty acid chlorides. Similarly, the AKD described herein may be a mixture of two or more AKDs.

[0044] In one aspect of the present invention, the amphiphilic polymer is a polymer comprising both repeating units containing hydrophobic groups and repeating units containing hydrophilic groups. The polymer of the present invention may be a homopolymer, a copolymer, a block copolymer, and the like.

[0045] In one aspect of the invention, the repeating unit containing hydrophobic group includes the repeating unit derived from olefin, styrene and / or unsaturated ester. In one embodiment, the monomer for providing the repeating unit containing hydrophobic group is called hydrophobic monomer. Hydrophobic monomer described herein can be ethylene, propylene, vinyl chloride, styrene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate and / or propyl methacrylate etc. The repeating unit containing hydrophobic group described herein can include the repeating unit derived from ethylene, propylene, vinyl chloride, styrene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate and / or propyl methacrylate.

[0046] In one aspect of the invention, the repeating unit containing hydrophilic groups includes repeating units containing carboxylic acid, carboxylate, sulfonic acid, and / or sulfonate groups. In one embodiment, the monomer for providing the repeating unit containing hydrophilic groups is called hydrophilic monomer. Hydrophilic monomers described herein can be acrylic acid, acrylate (e.g., metal or alkali metal salts, such as Na, K, Ca, Mg salts), allyl sulfonic acid, allyl sulfonate (e.g., metal or alkali metal salts, such as Na, K, Ca, Mg salts). The repeating unit containing hydrophilic groups described herein can include repeating units derived from acrylic acid, acrylate (e.g., metal or alkali metal salts, such as Na, K, Ca, Mg salts), allyl sulfonic acid, allyl sulfonate (e.g., metal or alkali metal salts, such as Na, K, Ca, Mg salts).

[0047] In one aspect of the present invention, the amphoteric polymer comprises ethylene acrylic acid copolymer (EAA).

[0048] In one embodiment, the ethylene acrylic acid copolymer (EAA) has the following structural formula (1):

[0049]

[0050] in:

[0051] x is an integer ranging from 10 to 100,000; and

[0052] y is an integer ranging from 10 to 100,000.

[0053] In one embodiment, x can be any integer selected from the range, for example, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000, or a sub-range consisting of any two of these values.

[0054] In one embodiment, y can be any integer selected from the range, for example, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000, or a sub-range consisting of any two of these values.

[0055] In one aspect of the present invention, the amphoteric polymer comprises poly(methyl methacrylate-co-methacrylic acid) (Poly(methyl methacrylate-co-methacrylic acid, P(MMA-co-MAA)).

[0056] In one embodiment, poly(methylmethacrylate-co-methacrylic acid) (Poly(methylmethacrylate-co-methacrylic acid, P(MMA-co-MAA)) has the following structural formula (2):

[0057]

[0058] in:

[0059] a is an integer ranging from 10 to 100,000; and,

[0060] b is an integer ranging from 10 to 100,000.

[0061] In one embodiment, a can be any integer selected from the range, for example, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000, or a sub-range consisting of any two of these values.

[0062] In one embodiment, b can be any integer selected from the range, for example, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000, or a sub-range consisting of any two of these values.

[0063] In one aspect of the present invention, the amphoteric polymer comprises ethylene methacrylic acid copolymer (EMAA).

[0064] In one embodiment, the ethylene methacrylic acid copolymer (EMAA) has the following structural formula (3):

[0065] in:

[0066] c is an integer ranging from 10 to 100,000; and,

[0067] d is an integer ranging from 10 to 100,000.

[0068] In one embodiment, c can be any integer selected from the range, for example, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000, or a sub-range consisting of any two of these values.

[0069] In one embodiment, d can be any integer selected from the range, for example, 10, 50, 100, 200, 300, 400, 500, 600, 700, 800, 900, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000, or a sub-range consisting of any two of these values.

[0070] In one aspect of the invention, the weight ratio of the hydrophilic monomer to the hydrophobic monomer is 80 / 20 to 5 / 95, for example, 75 / 25, 70 / 30, 65 / 35, 60 / 40, 55 / 45, 50 / 50, 45 / 55, 40 / 60, 35 / 65, 30 / 70, 25 / 75, 20 / 80, 15 / 85, 10 / 90, and subranges consisting of any two of these values.

[0071] In one aspect of the invention, the melt index of the amphoteric polymer is from 1 g / 10 min to 200 g / 10 min, for example, from 5 g / 10 min, 10 g / 10 min, 15 g / 10 min, 20 g / 10 min, 25 g / 10 min, 30 g / 10 min, 35 g / 10 min, 40 g / 10 min, 45 g / 10 min, 50 g / 10 min, 55 g / 10 min, 60 g / 10 min, 65 g / 10 min, 70 g / 10 min, 75 g / 10 min, 80 g / 10 min, 85 g / 10 min, 90 g / 10 min, 95 g / 10 g / 10min, 170 g / 10min, 175 g / 10min, 180 g / 10min, 185 g / 10min or 190 g / 10min, or a sub-range consisting of any two of these values.

[0072] In one aspect of the invention, the molecular weight of the amphoteric polymer is 500Da to 1,000,000Da, preferably 5,000Da to 100,000Da. The molecular weight of the amphoteric polymer can be, for example, 500Da, 1,000Da, 5,000Da, 10,000Da, 15,000Da, 20,000Da, 25,000Da, 30,000Da, 35,000Da, 40,000Da, 45,000Da, 50,000Da, 55,000Da, 60,000Da, 65,000Da, 70,000Da, 75,000Da, 80,000Da, 85,000Da, 90,000Da, 100,000Da , 110,000 Da, 120,000 Da, 130,000 Da, 140,000 Da, 150,000 Da, 160,000 Da, 170,000 Da, 180,000 Da, 190,000 Da, 200,000 Da, 300,000 Da, 400,000 Da, 500,000 Da, 600,000 Da, 700,000 Da, 800,000 Da, 900,000 Da, or 1,000,000 Da, or a subrange consisting of any two of these values.

[0073] In one aspect of the invention, the amphoteric polymer is linear or branched.

[0074] In one aspect of the invention, the amphoteric polymer is added before, after or simultaneously with the addition of TEA, preferably simultaneously with TEA.

[0075] In one aspect of the present invention, the amount of the amphoteric polymer added is 50-20,000 ppm, for example, 50 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm, 500 ppm, 550 ppm, 600 ppm, 650 ppm, 700 ppm, 750 ppm, 800 ppm, 850 ppm, 900 ppm, 950 ppm, 1,000 ppm, 1,100 ppm, 1,150 ppm, 1,200 ppm, 1,250 ppm, 1,300 ppm, 1,350 ppm, 1,400 ppm, 1,450 ppm, 1,500 ppm, 1,550 ppm, 1,5 ppm, 18,000 ppm, 19,000 ppm, or 20,000 ppm, or a subrange consisting of any two of these values. In one aspect of the invention, the amount of the amphoteric polymer added is calculated based on the weight of the reaction mixture.

[0076] The method of the present invention can reduce the viscosity of the reaction mixture. The reduced viscosity of the reaction mixture reduces the energy consumption required for stirring. At the same time, the reduced viscosity of the reaction mixture also enables the production of sizing agents (such as AKD) under conditions / operations without solvents such as toluene.

[0077] In one aspect of the present invention, the present invention relates to a method for preparing a sizing agent under toluene-free conditions, wherein:

[0078] The method comprises the steps of contacting triethylamine (TEA) and fatty acid chloride (FACl), and

[0079] The method further comprises adding one or more amphiphilic polymers before, after or simultaneously with the addition of TEA, wherein the amphiphilic polymer is a polymer comprising repeating units containing hydrophobic groups and repeating units containing hydrophilic groups.

[0080] In one aspect of the present invention, the present invention relates to a method for reducing the viscosity of a sizing agent preparation process (e.g., reducing the viscosity of a reaction mixture), wherein:

[0081] The sizing agent preparation process comprises the steps of contacting triethylamine (TEA) and fatty acid chloride (FACl), and

[0082] The method further comprises adding one or more amphiphilic polymers before, after or simultaneously with the addition of TEA, wherein the amphiphilic polymer is a polymer comprising repeating units containing hydrophobic groups and repeating units containing hydrophilic groups.

[0083] As used herein, the term "substituted" means that any one or more hydrogens on the designated atom or group is replaced with a moiety selected from the indicated group, provided that the normal valency of the designated atom is not exceeded.

[0084] "Alkyl" is a branched or straight chain saturated aliphatic hydrocarbon group. In one embodiment, the alkyl group contains 1 to about 20 carbon atoms, more typically 1 to about 12 carbon atoms, 1 to about 6 carbon atoms, or 1 to about 4 carbon atoms. In one embodiment, the alkyl group contains 1 to about 8 carbon atoms. In certain embodiments, the alkyl group is C1-C2, C1-C3, or C1-C6. As used herein, a specified range refers to each member of the range as an independent species of alkyl group. For example, as used herein, the term C1-C 30 Alkyl refers to a straight or branched chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms and is intended to refer to each of these as a separate species description. For example, as used herein, the term C1-C4 alkyl refers to a straight or branched chain alkyl group having 1, 2, 3 or 4 carbon atoms and is intended to refer to each of these as a separate species description. When C0-C n When alkyl is used in conjunction with another group in this article, for example (C3-C7 cycloalkyl)C0-C4 alkyl or -C0-C4 alkyl (C3-C7 cycloalkyl), the indicated group - in this case cycloalkyl, or directly bonded by a single covalent bond (C0 alkyl) or connected by an alkyl chain (in this case 1, 2, 3 or 4 carbon atoms). Alkyl can also be connected via other groups such as heteroatoms, such as in -O-C0-C4 alkyl (C3-C7 cycloalkyl). Examples of alkyl include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, n-hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl and 2,3-dimethylbutyl. In one embodiment, the alkyl group is optionally substituted as described above.

[0085] "Alkenyl" is a branched or straight chain aliphatic hydrocarbon group having one or more carbon-carbon double bonds, which may occur at a stable point along the chain. Non-limiting examples are C2-C8 alkenyl, C2-C6 alkenyl, and C2-C4 alkenyl. As used herein, a specified range refers to each member of the range as an independent species of alkenyl group, as described above for the alkyl portion. For example, as used herein, the term C1-C 30 Alkenyl refers to a straight or branched alkenyl group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms and is intended to refer to each of these as an independent species description. Examples of alkenyl include but are not limited to vinyl and propenyl. In one embodiment, the alkenyl group is optionally substituted as described above.

[0086] "Alkynyl" is a branched or straight chain aliphatic hydrocarbon group having one or more carbon-carbon triple bonds, which may occur at any stable point along the chain, such as C2-C8 alkynyl or C2-C6 alkynyl. As used herein, a specified range refers to each member of the range as a separate species of alkynyl group, as described above for the alkyl portion. For example, as used herein, the term C1-C8 30 Alkynyl refers to a straight or branched alkynyl group with 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms and is intended to refer to each of these as an independent species description. The example of alkynyl includes but is not limited to ethynyl, propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl and 5-hexynyl. In one embodiment, the alkynyl group is optionally substituted as described above.

[0087] "Hydrocarbyl" is a branched or straight chain saturated or unsaturated aliphatic group. The hydrocarbyl group may be an alkyl, alkenyl, or alkynyl group. As used herein, a specified range refers to each member of the range as an independent group. For example, as used herein, the term C1-C 30 Hydrocarbyl refers to hydrocarbyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 carbon atoms and is intended to refer to each of these as being described as a separate species.

[0088] The temperature described herein refers to degrees Celsius. As required, the concentration / content / amount / number of portions described herein may be the concentration / content / amount / number of portions expressed in terms of mass, volume, mole, mass / volume, or volume / mass.

[0089] The molecular weight described herein may be a number average molecular weight or a weight average molecular weight.

[0090] The process described herein can be carried out in a continuous mode or a batch mode, preferably in a continuous mode.

[0091] The technical scheme of the present invention is now described in conjunction with specific embodiments. It should be understood that the following embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. Unless otherwise specified, the reagents described in this embodiment are all commercially available. Specific embodiments

[0093] Example 1 (control group)

[0094] Before feeding, the reactor was evacuated and replaced with nitrogen three times, 100g of AKD wax powder (n-C16 alkyl AKD: n-C18 alkyl AKD = 60: 40, Kemira, FennoWax 1840 TF) was added into the reactor, stirring was started, and heating was performed until melting, and then 151g of triethylamine (analytical grade, Shanghai Lingfeng Chemical Reagent Co., Ltd.) was added. After AKD and TEA were evenly mixed, 405g of acyl chloride (industrial grade, n-C16 alkanoyl chloride: n-C18 alkanoyl chloride = 60: 40, Aladdin) was added dropwise at a rate of 8ml / min, and the system temperature was maintained at 55°C during the addition. After the addition was completed, the temperature was kept for half an hour. The viscosity of the reaction system was monitored by a Heimerson online viscometer during the entire reaction process. The relationship between time and viscosity is shown in the following figure. Figure 1 As shown, the final viscosity was 1517 cp.

[0095] Example 2

[0096] Before adding the materials, the reactor was evacuated and replaced with nitrogen three times. 100 g of AKD wax powder (n-C16 alkyl AKD: n-C18 alkyl AKD = 60:40, Kemira, FennoWax 1840 TF) was added to the reactor, stirred, heated to melt, and then 151 g of triethylamine (analytical grade, Shanghai Lingfeng Chemical Reagent Co., Ltd.) was added. After AKD and TEA were evenly mixed, 1000 ppm of ethylene acrylic acid copolymer (Mw molecular weight ∼45,000 Da, McLean, its structure is as shown in formula (1), wherein x is 1,400 and y is 75) was added. After stirring for 10 minutes, 405 g of acyl chloride (industrial grade, n-C16 alkanoyl chloride: n-C18 alkanoyl chloride = 60:40, Aladdin) was added dropwise at a rate of 8 ml / min. The system temperature was kept at 55°C during the addition. After the addition was completed, the temperature was kept for half an hour. The viscosity of the reaction system was monitored by a Heimerson online viscometer during the entire reaction process. The relationship between time and viscosity is shown in the following figure: Figure 2 As shown, the final viscosity was reduced to 922 cp, showing a viscosity reduction of about 40% compared to the control group.

[0097] Example 3

[0098] Before adding the materials, the reactor was evacuated and replaced with nitrogen three times. 100 g of AKD wax powder (n-C16 alkyl AKD: n-C18 alkyl AKD = 60:40, Kemira, FennoWax 1840 TF) was added into the reactor, stirred, heated to melt, and then 151 g of triethylamine (analytical grade, Shanghai Lingfeng Chemical Reagent Co., Ltd.) was added. After AKD and TEA were evenly mixed, 1000 ppm of poly (methyl methacrylate-co-methylacrylic acid) (Mw molecular weight of ~34,000 Da, McLean, its structure is as shown in formula (2), wherein a is 300 and b is 60) was added. After stirring for 10 minutes, 405 g of acyl chloride (industrial grade, n-C16 alkanoyl chloride: n-C18 alkanoyl chloride = 60:40, Aladdin) was added dropwise at a rate of 8 ml / min. The system temperature was kept at 55°C during the addition. After the addition was completed, the temperature was kept for half an hour. The viscosity of the reaction system was monitored by a Heimerson online viscometer during the entire reaction process. The relationship between time and viscosity is shown in the following figure: Figure 3 As shown, the final viscosity was reduced to 470 cp, showing a viscosity reduction of about 70% compared to the control group.

[0099] Example 4

[0100] The crystal size of triethylamine hydrochloride (analytical grade, MacLean) decreases with the increase of the addition amount of ethylene acrylic acid copolymer.

[0101] Several groups of experiments were performed under the following conditions.

[0102] 4-1: Add 1 g of triethylamine hydrochloride to 2 ml of ethanol and 2 ml of n-hexane (control group);

[0103] 4-2: 1 g of triethylamine hydrochloride and 100 ppm of ethylene acrylic acid copolymer (acrylic acid 15 wt%, Macklin, its structure is as shown in Formula I) were added to 2 ml of ethanol and 2 ml of n-hexane (100 ppm group);

[0104] 4-3: 1 g of triethylamine hydrochloride and 500 ppm of ethylene acrylic acid copolymer were added to 2 ml of ethanol and 2 ml of n-hexane (500 ppm group);

[0105] 4-4: 1 g of triethylamine hydrochloride and 1000 ppm of ethylene acrylic acid copolymer were added to 2 ml of ethanol and 2 ml of n-hexane (1000 ppm group).

[0106] The specific operation steps are as follows: 1g triethylamine hydrochloride is dissolved in 2ml ethanol, and then 2ml n-hexane is added; triethylamine hydrochloride begins to precipitate, and then stands for 5 minutes. The polymer is dissolved in n-hexane and added together with n-hexane.

[0107] Use a pipette to take 0.5 ml of the above solution and drop it evenly on the glass slide. After the solvent evaporates, use a microscope to take microscopic photos of each group at the same scale, such as Figure 4 As shown. Figure 4 It can be seen that the crystal size of triethylamine hydrochloride decreases with the increase of the amount of ethylene acrylic acid copolymer added, which indicates the reduced viscosity of the reaction mixture in the AKD preparation process.

[0108] Example 5

[0109] The crystal size of TEA·HCl (analytical grade, MacLean) decreases with the increase of the amount of ethylene acrylic acid copolymer added

[0110] Several groups of experiments were performed under the following conditions.

[0111] 5-1: Add 1 g of triethylamine hydrochloride to 2 ml of ethanol and 2 ml of n-hexane (control group);

[0112] 5-2: 1 g of triethylamine hydrochloride and 50 ppm of ethylene acrylic acid copolymer were added to 2 ml of ethanol and 2 ml of n-hexane (50 ppm group);

[0113] 5-3: 1 g of triethylamine hydrochloride and 100 ppm of ethylene acrylic acid copolymer were added to 2 ml of ethanol and 2 ml of n-hexane (100 ppm group);

[0114] 5-4: 1 g of triethylamine hydrochloride and 500 ppm of ethylene acrylic acid copolymer were added to 2 ml of ethanol and 2 ml of n-hexane (500 ppm group);

[0115] 5-5: 1 g of triethylamine hydrochloride and 1000 ppm of ethylene acrylic acid copolymer were added to 2 ml of ethanol and 2 ml of n-hexane (1000 ppm group).

[0116] The specific operation steps are as follows: 1g of triethylamine hydrochloride is dissolved in 2ml of ethanol, and then 2ml of n-hexane is added; triethylamine hydrochloride begins to precipitate, and then it is left to stand for 5 minutes. The polymer is dissolved in n-hexane and added together with the n-hexane.

[0117] Each tube was centrifuged under the same conditions (4000 rpm, 10 min). Figure 5 As shown. Figure 5 It can be seen that the more ethylene acrylic acid copolymer is added, the denser the precipitate in the centrifuge tube is, which indicates that the crystal size of TEA·HCl is smaller. This suggests a reduced viscosity in the reaction mixture during the preparation of AKD.

[0118] The mechanism described in the present application is only for explaining the present invention and is not intended to limit the present invention in any way.

[0119] The description of the foregoing embodiments and implementations should be regarded as illustrative rather than limiting the invention described herein. The above specific implementations are only specific schemes of the present invention, and the protection scope of the present invention includes but is not limited to the schemes of the above specific implementations. Any implementation that conforms to the scope of the present invention and any appropriate changes or modifications made to it by a person of ordinary skill in the art should fall within the protection scope of the present invention.

[0120] As used herein, the terms "approximately," "about," "substantially," and similar terms are intended to have the broad meanings generally agreed upon and accepted by those skilled in the art for use with the subject matter to which the present disclosure pertains. Those skilled in the art who read the present disclosure should understand that these terms are intended to describe certain features described and claimed without limiting these features to the precise numerical ranges provided. Therefore, these terms should be interpreted as indicating that insubstantial or inconsequential modifications or variations of the subject matter described and claimed are considered to be within the scope of the present invention as described in the appended claims.

[0121] As used herein, "optional" or "optionally" etc. are intended to indicate that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event or circumstance occurs and instances where it does not occur. Unless otherwise specified, the indefinite article "a" or "an" and the corresponding definite article "the" used herein mean at least one, or one or more.

Claims

1. A method for preparing a sizing agent, wherein: The method comprises the steps of contacting triethylamine (TEA) and fatty acid chloride (FACl), and The method further comprises adding one or more amphiphilic polymers before, after or simultaneously with the addition of TEA, wherein the amphiphilic polymer is a polymer comprising repeating units containing hydrophobic groups and repeating units containing hydrophilic groups.

2. The method according to claim 1, wherein the repeating unit containing a hydrophobic group comprises a repeating unit derived from an olefin, styrene and / or an unsaturated ester.

3. The method according to claim 1 or 2, wherein the repeating unit containing a hydrophilic group comprises a repeating unit containing a carboxylic acid, a carboxylate, a sulfonic acid, and / or a sulfonate group.

4. The method according to any one of claims 1 to 3, wherein the repeating units containing hydrophobic groups include repeating units derived from ethylene, propylene, vinyl chloride, styrene, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, and / or propyl methacrylate.

5. The method according to any one of claims 1 to 4, wherein the repeating unit containing a hydrophilic group comprises a repeating unit derived from acrylic acid, an acrylic acid salt (e.g., a metal or alkali metal salt, such as Na, K, Ca, Mg salt), allyl sulfonic acid, an allyl sulfonate (e.g., a metal or alkali metal salt, such as Na, K, Ca, Mg salt).

6. The method of any one of claims 1-5, wherein the amphoteric polymer comprises ethylene acrylic acid copolymer (EAA).

7. The method of any one of claims 1-6, wherein the amphoteric polymer comprises poly(methyl methacrylate-co-methacrylic acid) (Poly(methyl methacrylate-co-methacrylic acid, P(MMA-co-MAA)).

8. The method of any one of claims 1-7, wherein the amphoteric polymer comprises ethylene methacrylic acid copolymer (EMAA).

9. The method according to any one of claims 1 to 8, wherein the weight ratio of the hydrophilic monomer for providing the repeating unit containing the hydrophilic group to the hydrophobic monomer for providing the repeating unit containing the hydrophobic group is 80 / 20 to 5 / 95, preferably 70 / 30 to 30 / 70, more preferably 60 / 40-40 / 60.

10. The method according to any one of claims 1 to 9, wherein the molecular weight of the amphiphilic polymer is from 500 Da to 1,000,000 Da, preferably from 5,000 Da to 100,000 Da.

11. The method according to any one of claims 1 to 10, wherein the amphoteric polymer is added simultaneously with the addition of TEA.

12. The method according to any one of claims 1 to 11, wherein the amount of the amphoteric polymer added is 50 to 20,000 ppm, preferably 100 to 2,000 ppm.

13. The method according to any one of claims 1 to 12, wherein the sizing agent is alkyl ketene dimer (AKD).

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