WO2025130552A1 - 一种制备施胶剂的方法 - Google Patents

一种制备施胶剂的方法 Download PDF

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Publication number
WO2025130552A1
WO2025130552A1 PCT/CN2024/135484 CN2024135484W WO2025130552A1 WO 2025130552 A1 WO2025130552 A1 WO 2025130552A1 CN 2024135484 W CN2024135484 W CN 2024135484W WO 2025130552 A1 WO2025130552 A1 WO 2025130552A1
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Prior art keywords
tea
akd
total
facl
heel
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English (en)
French (fr)
Inventor
景荣宽
刘晨
李�灿
李逢阳
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Kemira Asia Co Ltd
Kemira Oyj
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Kemira Asia Co Ltd
Kemira Oyj
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Publication of WO2025130552A1 publication Critical patent/WO2025130552A1/zh
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/17—Ketenes, e.g. ketene dimers
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments

Definitions

  • the present invention relates to the field of papermaking, and in particular to a method for preparing a sizing agent.
  • the method of the present invention can reduce the viscosity of a reaction system and/or achieve toluene-free operation.
  • Paper is formed by the entanglement of materials including plant cellulose.
  • Plant cellulose has hydroxyl groups, which give 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 permeability to fluids (such as water, oil, ink, juice, etc.). Therefore, the surface of paper usually needs to be treated to improve the performance.
  • the surface of the paper can be treated by applying a sizing agent.
  • the sizing agent can be divided into acidic sizing agents, neutral sizing agents and alkaline sizing agents. In recent years, medium-alkaline sizing papermaking has become increasingly popular in the papermaking industry.
  • 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:
  • each Ra , Rb , Rc and Rd group is independently selected from hydrogen, optionally substituted, linear or branched C1 - C30 hydrocarbon groups at each occurrence. It has been found that each Ra , Rb , Rc and Rd group in the above ketene dimer can be not only a saturated hydrocarbon group, but also an unsaturated hydrocarbon group (e.g., an alkenyl group derived from oleic acid). Out of convention, ketene dimers with unsaturated hydrocarbon groups are still referred to as AKD (alkyl ketene dimer).
  • AKD alkyl ketene dimer
  • the four-membered lactone ring in the AKD molecule can react with the hydroxyl group on cellulose to form an ester bond, thereby being positioned on cellulose.
  • the hydrophobic long-chain groups of AKD i.e., one or more of Ra , Rb , Rc , and Rd ) produce a hydrophobic effect on the fiber surface and cover part of the pore structure, thereby giving the paper hydrophobicity and anti-permeability.
  • the reaction diagram of AKD and cellulose is shown below:
  • a typical method for preparing AKD includes the steps of adding fatty acid chlorides (FACl) and triethylamine (TEA) to a reactor.
  • FACl fatty acid chlorides
  • TAA triethylamine
  • 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.
  • inert solvents such as toluene are often added in industry 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.
  • a known method of reducing viscosity is to feed the residue of the sizing agent produced in an earlier batch (also called HEEL, which includes AKD and TEA ⁇ HCl, and optionally unreacted TEA) into the production of the next batch.
  • HEEL is beneficial to reduce the viscosity of the batch system, but still cannot completely eliminate the use of toluene.
  • 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.
  • the Ra group is independently selected at each occurrence from: hydrogen; an optionally substituted, straight or branched C1 - C30 hydrocarbon group;
  • the Rb group is independently selected at each occurrence from: hydrogen; an optionally substituted, straight or branched C1 - C30 hydrocarbon group;
  • the R c group is independently selected at each occurrence thereof from: hydrogen; an optionally substituted, straight or branched C 1 -C 30 hydrocarbon group; and,
  • the R d group is independently selected at each occurrence from: hydrogen; an optionally substituted, straight or branched C 1 -C 30 hydrocarbon group.
  • the C1 - C30 hydrocarbon group is preferably a C10 - C20 hydrocarbon group, more preferably a C13 - C17 hydrocarbon group, such as C1 , C2 , C3 , C4 , C5 , C6 , C7 , C8 , C9, C10 , C11 , C12, C13 , C14 , C15 , C16, C17 , C18 , C19 , C20 , C21 , C22 , C23 , C24 , C25 , C26 , C27 , C28 , C29 , or C30 hydrocarbon group.
  • the hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group; preferably, an alkyl group.
  • the R' group at each occurrence is independently selected from: hydrogen; an optionally substituted, linear or branched C 1 -C 30 hydrocarbon group; and/or
  • the R" group is independently selected at each occurrence from: hydrogen; an optionally substituted, straight or branched C1 - C30 hydrocarbon group.
  • the C1 - C30 hydrocarbon group is preferably a C10 - C20 hydrocarbon group, more preferably a C13 - C17 hydrocarbon group, such as C1 , C2 , C3 , C4 , C5 , C6 , C7 , C8 , C9 , C10 , C11 , C12, C13, C14 , C15 , C16 , C17 , C18 , C19 , C20 , C21 , C22 , C23, C24 , C25 , C26 , C27 , C28 , C29 , C30 hydrocarbon group.
  • the hydrocarbon group may be an alkyl, alkenyl, or alkynyl group; preferably an alkyl group.
  • the Ra group is independently selected at each occurrence from the group consisting of hydrogen; an optionally substituted, straight chain or branched C 1 -C 30 hydrocarbon group;
  • the Rb group is independently selected at each occurrence from the group consisting of hydrogen; an optionally substituted, straight chain or branched C 1 -C 30 hydrocarbon group;
  • the Rc group is independently selected at each occurrence from the group consisting of hydrogen; an optionally substituted, straight chain or branched C 1 -C 30 hydrocarbon group; and, the Rd group is independently selected at each occurrence from the group consisting of hydrogen; an optionally substituted, straight chain or branched C 1 -C 30 hydrocarbon group.
  • the C1 - C30 hydrocarbon group is preferably a C10 - C20 hydrocarbon group, more preferably a C13 - C17 hydrocarbon group, such as C1 , C2 , C3 , C4 , C5 , C6 , C7 , C8 , C9, C10 , C11 , C12, C13 , C14 , C15 , C16, C17 , C18 , C19 , C20 , C21 , C22 , C23 , C24 , C25 , C26 , C27 , C28 , C29 , or C30 hydrocarbon group.
  • the hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group; preferably, an alkyl group.
  • triethylamine hydrochloride N(CH 2 CH 3 ) 3 ⁇ HCl
  • triethylamine hydrochloride N(CH 2 CH 3 ) 3 ⁇ HCl
  • the raw material of formula (II) is generally referred to as fatty acid chlorides (FACl), which undergo dehydrochlorination under the action of triethylamine (TEA). Accordingly, for the purpose of convenience of description only, the raw material of formula (I) in the above reaction 1 is referred to herein as fatty acid (FA), whether it is saturated or unsaturated.
  • FACl fatty acid chlorides
  • TAA triethylamine
  • a typical step of the AKD preparation method involves contacting TEA and FACl to carry out a reaction, and its reaction formula can also be written as follows. 2FACl+2TEA ⁇ AKD+2TEA ⁇ HCl.
  • the present invention surprisingly found that by pre-adding the first part of the total TEA to a HEEL-containing reaction system to obtain a HEEL-containing reaction system with pre-added TEA, and then adding the remaining second part of the total TEA and FACl to the HEEL-containing reaction system with pre-added TEA for reaction, the viscosity of the reaction system can be significantly reduced, allowing the preparation of AKD without solvent (such as toluene).
  • FIG. 1 shows the viscosity of the reaction systems of Examples 1-4.
  • FIG. 2 shows the viscosity of the reaction systems of Examples 6-8.
  • the present invention provides a method for preparing a sizing agent, comprising the following steps:
  • the weight percentage of the first part in the total TEA is not greater than 90% of the total TEA.
  • the weight percentage of the first part of TEA in the total TEA is: 100% ⁇ the ratio of the weight of the first part of TEA to the sum of the weight of the first part of TEA and the weight of the remaining second part of TEA.
  • the HEEL-containing reaction system of the present invention comprises any raw materials/intermediates/products involved in the production of the sizing agent, such as FA, TEA, FACl, alkyl ketene, AKD, TEA ⁇ HCl, or a combination thereof.
  • the HEEL-containing reaction system of the present invention comprises FACl, TEA, AKD, TEA ⁇ HCl, or a combination thereof.
  • the HEEL described herein refers to any mixture comprising AKD and TEA ⁇ HCl.
  • the HEEL further comprises TEA or other components.
  • the HEEL described herein may be fresh or recycled.
  • the HEEL described herein is part of a reaction mixture of an earlier batch of sizing agent production, which comprises AKD and TEA ⁇ HCl, preferably also comprising unreacted TEA.
  • the AKD and TEA ⁇ HCl in the HEEL may be present in any ratio.
  • the weight ratio of AKD and TEA ⁇ HCl is 1:1 to 10:1, preferably 3:1 to 6:1.
  • the AKD, TEA ⁇ HCl and TEA (if present) in the HEEL may be present in any ratio.
  • the weight ratio of AKD, TEA ⁇ HCl and TEA (if present) is 1:1:5 to 10:1:1, preferably 3:1:1 to 6:1:1.
  • the reaction mixture of the present invention comprises FA, TEA, FACl, alkyl ketene, AKD, TEA ⁇ HCl, or a combination thereof.
  • the reaction mixture of the present invention refers to a mixture of the reaction (2FACl+2TEA ⁇ AKD+2TEA ⁇ HCl).
  • the HEEL-containing reaction system described herein further comprises FA, TEA, FACl, alkyl ketene, AKD, TEA ⁇ HCl, or a combination thereof in addition to HEEL.
  • the HEEL-containing reaction system described herein does not contain other components in addition to HEEL.
  • any of the raw materials described herein, such as FA, TEA, FACl, alkyl ketene, AKD and/or TEA ⁇ HCl, may be either fresh or recycled.
  • the fatty acyl chloride (FACl) described herein is a compound having structural formula (II):
  • the R' group is independently selected at each occurrence from: hydrogen; an optionally substituted, linear or branched C 1 -C 30 hydrocarbon group; and/or
  • the R" group is independently selected at each occurrence from: hydrogen; an optionally substituted, straight or branched C1 - C30 hydrocarbon group.
  • the C1 - C30 hydrocarbon group is preferably a C10 - C20 hydrocarbon group, more preferably a C13 - C17 hydrocarbon group, such as C1 , C2 , C3 , C4 , C5 , C6 , C7 , C8 , C9 , C10 , C11 , C12, C13, C14 , C15, C16 , C17 , C18 , C19 , C20 , C21 , C22 , C23, C24 , C25 , C26 , C27 , C28 , C29 , C30 hydrocarbon group.
  • the hydrocarbon group may be an alkyl, alkenyl, or alkynyl group; preferably an alkyl group.
  • the fatty acyl chloride (FACl) described herein can be a mixture of two or more fatty acyl chlorides.
  • the AKD described herein can be a mixture of two or more AKDs.
  • the fatty acids described herein can be a mixture of two or more fatty acids.
  • the fatty acyl chlorides, fatty acids and AKD described herein can have the same or different alkyl moieties.
  • the addition (preferably simultaneous addition) of FACl and the second portion of TEA occurs between 50°C and 70°C, such as 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C, 60°C, 61°C, 62°C, 63°C, 64°C, 65°C, 66°C, 67°C, 68°C, 69°C, 70°C; preferably, between 52°C and 68°C; more preferably, between 52°C and 65°C.
  • the weight percentage of the first part to the total TEA is no more than 90% of the total TEA, such as between greater than 0% and 90%, such as 90%, 89%, 88%, 87%, 86%, 85%, 84%, 83%, 82%, 81%, 80%, 79%, 78%, 77%, 76%, 75%, 74%, 73%, 72%, 71%, 70%, 69%, 68%, 67%, 66%, 65%, 64%, 63%, 62%, 61%, 60%, 59%, 58%, 57%, 56%, 55%, 54%, 53%, 52%, 51%, 50%.
  • the addition (preferably simultaneous addition) of FACl and the second portion of TEA occurs between 52°C and 68°C.
  • the weight percentage of the first part to the total TEA is between 10% and 90% of the total TEA.
  • the addition (preferably simultaneous addition) of FACl and the second part of TEA in step (2) occurs between 52°C and 68°C, more preferably between 52°C and 65°C.
  • FACl and/or a second portion of TEA are added at the same or different rates in step (2).
  • FACl is added at a rate of 5 ml/min to 20 ml/min, preferably at a rate of 6 ml/min to 16 ml/min.
  • TEA is added at a rate of 1 ml/min to 10 ml/min, preferably at a rate of 4 ml/min to 8 ml/min.
  • the viscosity of the reaction system is less than 250cp, less than 240cp, less than 230cp, less than 220cp, less than 210cp, less than 200cp, less than 190cp, less than 180cp, less than 170cp, less than 160cp, less than 150cp, less than 140cp, less than 130cp, less than 120cp, less than 110cp, less than 100cp, and less than 90cp.
  • the viscosity of the reaction system is less than 250cp, less than 240cp, less than 230cp, less than 220cp, less than 210cp, less than 200cp, less than 190cp, less than 180cp, less than 170cp, less than 160cp, less than 150cp, less than 140cp, less than 130cp, less than 120cp, less than 110cp, less than 100cp, or less than 90cp.
  • the ratio of the total moles of the first and second TEA to the moles of FACl is 0.95: 1 to 2: 1, preferably 1.4: 1 to 1.75: 1. In one aspect of the invention, the ratio of the total weight of the first and second TEA to the weight of FACl is 1: 3 to 2: 3, preferably 1: 1.7 to 1: 2.1.
  • 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.
  • 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.
  • the present invention relates to a method for preparing a sizing agent under toluene-free conditions, comprising the following steps:
  • the weight percentage of the first part in the total TEA is not greater than 90% of the total TEA.
  • 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), comprising the following steps:
  • the weight percentage of the first part in the total TEA is not greater than 90% of the total TEA.
  • 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.
  • 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 C 1 -C 2 , C 1 -C 3, or C 1 -C 6. As used herein, a specified range refers to each member of the range as an independent species of alkyl group.
  • C 1 -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 an independent species description.
  • C 1 -C 4 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 being described as an independent species.
  • C 0 -C n alkyl When C 0 -C n alkyl is used herein in conjunction with another group, such as (C 3 -C 7 cycloalkyl)C 0 -C 4 alkyl or -C 0 -C 4 alkyl(C 3 -C 7 cycloalkyl), the indicated group, in this case cycloalkyl, is either directly bonded by a single covalent bond (C 0 alkyl) or connected by an alkyl chain (in this case 1, 2, 3 or 4 carbon atoms). Alkyl groups may also be connected via other groups such as heteroatoms, such as in -OC 0 -C 4 alkyl(C 3 -C 7 cycloalkyl).
  • alkyl examples 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.
  • the alkyl group is optionally substituted as described above.
  • 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.
  • a specified range refers to each member of the range as an independent species of alkenyl group, as described above for the alkyl portion.
  • C1-C30 alkenyl refers to a straight or branched alkenyl 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 an independent species description.
  • alkenyl include, but are not limited to, ethenyl and propenyl.
  • alkenyl groups are optionally substituted as described above.
  • 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.
  • a specified range refers to each member of the range as an independent species of alkynyl group, as described above for the alkyl portion.
  • C1-C30 alkynyl refers to a straight or branched chain alkynyl 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 an independent species description.
  • 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.
  • alkynyl group is optionally substituted as described above.
  • Hydrocarbyl is a branched or straight chain saturated, unsaturated aliphatic group.
  • the hydrocarbyl can be an alkyl, alkenyl, or alkynyl.
  • a specified range refers to each member of the range as an independent group.
  • C1 - C30 hydrocarbyl refers to a hydrocarbyl 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 an independent species description.
  • the temperature described herein refers to degrees Celsius.
  • the concentration/content/amount/number of portions described herein may be the concentration/content/amount/number of portions expressed in terms of weight, volume, mole, weight/volume, or volume/weight.
  • Adding as described herein refers to adding by any means.
  • the second part TEA and FACl herein can be added at the same time or at different times.
  • the second part TEA and FACl herein can be added at the same rate or at different rates.
  • the sum of the first portion TEA and the (remaining) second portion TEA may be referred to as the total TEA.
  • the sum of the first portion TEA weight and the (remaining) second portion TEA weight may be referred to as the total TEA weight.
  • Total TEA as described herein refers to the total amount of TEA to be used, for example, the total amount of TEA to be used calculated based on FACl. Compared with FACl, the amount can be insufficient, equal or excessive. Those skilled in the art can determine the total amount of reasonable TEA, because the reaction of TEA with FACl to prepare AKD is a reaction known in the art. Generally, those skilled in the art use weight as a unit for feeding and monitoring in this reaction, because the reaction is not actually carried out in a stoichiometric manner.
  • the weight percentage of the first portion TEA is 100% x the ratio of the first portion TEA weight to the sum of the first portion TEA weight and the remaining second portion TEA weight, and may be referred to as an X value or an X range.
  • HEEL can be used at about 5wt% to 40wt% of the reaction mixture of the earlier batch of sizing agent production, preferably between 5wt% and 20wt%. In one embodiment, the amount of HEEL is 5wt% to 40wt% of the total reaction system.
  • the process described herein can be carried out in a continuous manner or a batch manner, preferably a batch manner.
  • reaction mixture and “reaction system” are used interchangeably.
  • first portion of TEA refers to the portion of TEA that is intended to be pre-added to the HEEL-containing reaction system.
  • Example 1 (control group): without first part TEA
  • the system temperature was kept at 60-62 degrees during the addition, and the temperature was kept at 60 degrees for 1 hour after the addition was completed.
  • the viscosity of the reaction system was monitored by a Heimerson online viscometer during the entire reaction process (Figure 1), and the final viscosity of the system was 973cP. After separation, a light yellow AKD product is obtained with a purity higher than 85% (in compliance with the implementation standard: GB/T 27565-2011).
  • Example 2 The first part of TEA accounts for 70% by weight of TEA
  • the system temperature was kept at 60-62 degrees during the addition, and the mixture was kept warm at 60 degrees for 1 hour after the addition was completed.
  • the viscosity of the reaction system was monitored by a Heimerson online viscometer during the entire reaction process (Figure 1), and the final viscosity of the system was 155.1 cP. After separation, a light yellow AKD product was obtained with a purity of more than 85% (in compliance with the implementation standard: GB/T 27565-2011).
  • Example 3 The weight ratio of the first part TEA to the total TEA is 6.4%
  • the system temperature was kept at 60-62 degrees during the addition, and the mixture was kept warm at 60 degrees for 1 hour after the addition was completed.
  • the viscosity of the reaction system was monitored by a Heimerson online viscometer during the entire reaction process (Figure 1), and the final viscosity of the system was 715 cP. After separation, a light yellow AKD product was obtained with a purity of more than 85% (in compliance with the implementation standard: GB/T 27565-2011).
  • Example 5 The weight ratio of the first part TEA to the total TEA (146.1 g) is 1.4%
  • Example 6 The weight ratio of the first part TEA to the total TEA is 21%
  • Example 7 The weight ratio of the first part TEA to the total TEA is 21%
  • Example 8 (control group): The weight ratio of the first part TEA to the total TEA is 100%

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Abstract

本发明涉及造纸领域。特别地，本发明涉及一种制备施胶剂的方法。本发明方法包括以下步骤：(1)预添加总TEA的第一部分TEA至含HEEL反应体系以得到预添加TEA的含HEEL反应体系；以及，(2)向预添加TEA的含HEEL反应体系添加总TEA的剩余的第二部分TEA和FACl以进行反应，其中第一部分占总TEA的重量百分比不大于总TEA的90％。本发明方法能够降低反应体系的粘度，和/或实现无甲苯操作。

Description

一种制备施胶剂的方法 技术领域
本发明涉及造纸领域。特别地，本发明涉及一种制备施胶剂的方法。本发明方法能够降低反应体系的粘度，和/或实现无甲苯操作。
背景技术
纸张是由包含植物纤维素的材料相互缠绕形成。植物纤维素具有羟基，这赋予纸张一定程度的亲水性。植物纤维素还缠绕形成孔结构，所述孔结构具有毛细作用，这赋予纸张一定程度的流体(例如水、油、油墨、果汁等)渗透性。因此，纸张表面通常需要处理以改善性能。在造纸过程中，可通过施加施胶剂(a sizing agent)来对纸张表面进行处理。根据pH值的不同，施胶剂可分为酸性施胶剂、中性施胶剂和碱性施胶剂。近年来，中碱性施胶造纸越来越受到造纸业的欢迎。
一种常用的中性施胶剂是烷基烯酮二聚体(Alkyl Ketene Dimer，简称AKD)，其具有超过50年的应用历史。AKD在常温下为蜡状固体。AKD既能作为浆内施胶剂使用，又能作为表面施胶剂使用。AKD通常用以下结构表示：
其中各Ra、Rb、Rc和Rd基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基。研究发现，上述烯酮二聚体中的各Ra、Rb、Rc和Rd基团不仅可以是饱和烃基，还可以是不饱和烃基(例如源自油酸的烯基)。出于惯例，具有不饱和烃基的烯酮二聚体仍然称为AKD(烷基烯酮二聚体)。
AKD分子中的四元内酯环能和纤维素上的羟基反应形成酯键，从而被定位在纤维素上。AKD的疏水性长链基团(即Ra、Rb、Rc和Rd中的一个或多个)在纤维表面产生疏水作用并覆盖部分孔结构，从而赋予纸张疏水性和抗渗透性。AKD与纤维素的反应示意图如下所示：
制备AKD的一个典型方法包括向反应器中添加脂肪酰氯(fatty acid chlorides，简称FACl)和三乙胺(triethylamine，简称TEA)的步骤。在上述制备过程中，随着副产物三乙胺盐酸盐(triethylamine hydrochloride，简称TEA·HCl)的形成，所述反应中的粘度增加，从而引发搅拌困难、耗能增多、散热不佳等一系列问题。很多情况下，工业上往往需要加入甲苯等惰性溶剂以减轻高粘度的不利影响。随着环保意识的提高，也对甲苯用量的降低提出了进一步的要求。
一种已知的降低粘度的方法是将较早前批次生产施胶剂的残余物(也称为HEEL，其包括AKD和TEA·HCl、和任选的未反应的TEA)投入到下一批次的生产中。所述HEEL有利于降低该批次体系的粘度，但仍然不能完全免除甲苯的使用。
目前，本领域对能实现降低粘度的施胶剂(尤其是AKD)制备方法以及无甲苯的制备方法仍存在持续需求。
发明内容
AKD的制备方法是本领域所公知的。例如，AKD通常以羧酸类物质为原料，通过酰化、脱氯化氢和二聚三个步骤生成。AKD的示例性合成过程如下所示。
(反应1)
(反应2)
(反应3)
在结构式(IV)所示的AKD中，
Ra基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；
Rb基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；
Rc基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；和，
Rd基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基。
对于Ra、Rb、Rc或Rd中的任一者，所述C1-C30烃基优选C10-C20烃基，更优选C13-C17烃基，例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20、C21、C22、C23、C24、C25、C26、C27、C28、C29、C30烃基。对于Ra、Rb、Rc或Rd中的任一者，所述烃基可以是烷基、烯基、或炔基；优选烷基。
在结构式I、II和/或III的任一者中，R’基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；和/或
R”基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基。
对于R’或R”中的任一者，所述C1-C30烃基优选C10-C20烃基，更优选C13-C17烃基，例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20、C21、C22、C23、C24、C25、C26、C27、C28、C29、C30烃基。对于R’或R”中的任一者，所述烃基可以是烷基、烯基、或炔基；优选烷基。
式(III-1)烯酮是采用与式(III-2)烯酮相同的步骤合成的。Ra基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；Rb基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；Rc基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；和，Rd基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基。对于Ra、Rb、Rc或Rd中的任一者，所述C1-C30烃基优选C10-C20烃基，更优选C13-C17烃基，例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20、C21、C22、C23、C24、C25、C26、C27、C28、C29、C30烃基。对于Ra、Rb、Rc或Rd中的任一者，所述烃基可以是烷基、烯基、或炔基；优选烷基。
酰化步骤中，(a)PCl3、(b)SOCl2和(c)COCl2+DMF是三种常用的酰化手段。使用COCl2和DMF的手段(c)是目前最常用的酰化手段，其中光气(COCl2)是用作酰化剂，而二甲基甲酰胺(DMF)是用作催化剂。
在脱氯化氢步骤中，出于节约成本的目的，三乙胺盐酸盐(N(CH2CH3)3·HCl)通常经再生为三乙胺后循环使用。
在上述反应2中，式(II)的原料通常称为脂肪酰氯(fatty acid chlorides，简称FACl)，其在三乙胺(triethylamine，简称TEA)作用下经历脱氯化氢。相应地，仅为描述方便的目的，在上述反应1中式(I)的原料在本文中称为脂肪酸(fatty acid，简称FA)，无论其是饱和的还是不饱和的。
因此，AKD制备方法的一个典型步骤涉及将TEA和FACl接触以进行反应，其反应式还可以写成如下形式。
2FACl+2TEA→AKD+2TEA·HCl。
本发明令人惊奇地发现，通过先预添加总TEA的第一部分TEA至含HEEL反应体系以得到预添加TEA的含HEEL反应体系，然后再向预添加TEA的含HEEL反应体系添加总TEA的剩余的第二部分TEA和FACl以进行反应，能够显著降低反应体系的粘度，允许实现无溶剂(如甲苯)制备AKD。
附图说明
图1示出了实例1-4反应体系的粘度。
图2示出了实例6-8反应体系的粘度。
具体实施方式
在本发明的一些实施方案中，本发明提供一种制备施胶剂的方法，包括以下步骤：
(1)预添加总TEA的第一部分TEA至含HEEL反应体系以得到预添加TEA的含HEEL反应体系；以及，
(2)向预添加TEA的含HEEL反应体系添加总TEA的剩余的第二部分TEA和FACl以进行反应；
其中第一部分占总TEA的重量百分比不大于总TEA的90％。第一部分TEA占总TEA的重量百分比为：100％×第一部分TEA的重量与第一部分TEA的重量和剩余的第二部分TEA的重量之和的比值。
在本发明的一个方面，本发明的含HEEL反应体系包含生产所述施胶剂涉及的任何原料/中间体/产物，例如FA、TEA、FACl、烷基烯酮、AKD、TEA·HCl、或其组合。在一种优选实施方式中，本发明的含HEEL反应体系包含FACl、TEA、AKD、TEA·HCl、或其组合。
在一种实施方式中，本文所述HEEL是指任何包含AKD和TEA·HCl的混合物。任选的，所述HEEL还包含TEA或其他组分。本文所述HEEL既可以是新鲜的，也可以是回收的。在一种实施方式中，本文所述HEEL是较早前批次生产施胶剂的反应混合物的一部分，其包括AKD和TEA·HCl，优选还包括未反应的TEA。
在一种实施方式中，在所述HEEL中的所述AKD和TEA·HCl可以以任何比例存在。在一种实施方式中，所述AKD和TEA·HCl的重量比例为1:1至10:1，优选地3:1至6:1。
在另一种实施方式中，在所述HEEL中的所述AKD、TEA·HCl和TEA(如果存在)可以以任何比例存在。在还有另一种实施方式中，所述AKD、TEA·HCl和TEA(如果存在)的重量比例为1:1:5至10:1:1，优选地3:1:1至6:1:1。
在本发明的一个方面，本发明的反应混合物包含FA、TEA、FACl、烷基烯酮、AKD、TEA·HCl、或其组合。在一种实施方式中，本发明所述反应混合物是指反应(2FACl+2TEA→AKD+2TEA·HCl)的混合物。
在一种实施方式中，本文所述含HEEL反应体系除HEEL之外还包含FA、TEA、FACl、烷基烯酮、AKD、TEA·HCl、或其组合。在另一种实施方式中，本文所述含HEEL反应体系除HEEL之外不含其他组分。
本文所述任何原料，例如FA、TEA、FACl、烷基烯酮、AKD和/或TEA·HCl，既可以是新鲜的，也可以是回收的。
在一种实施方式中，本文所述脂肪酰氯(FACl)是具有结构式(II)的化合物：
其中，
R’基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基；和/或
R”基团在其每一次出现时独立地选自：氢；任选取代的、直链或支链C1-C30烃基。
对于R’或R”中的任一者，所述C1-C30烃基优选C10-C20烃基，更优选C13-C17烃基，例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14、C15、C16、C17、C18、C19、C20、C21、C22、C23、C24、C25、C26、C27、C28、C29、C30烃基。对于R’或R”中的任一者，所述烃基可以是烷基、烯基、或炔基；优选烷基。
在本发明的一个方面，本文所述脂肪酰氯(FACl)可以是两种或更多种脂肪酰氯的混合物。类似地，本文所述AKD可以是两种或更多种AKD的混合物。本文所述脂肪酸可以是两种或更多种脂肪酸的混合物。本文所述脂肪酰氯、脂肪酸和AKD可以具有相同或不同的烃基部分。
在本发明的一个方面，添加(优选同时添加)FACl和第二部分TEA发生在50℃至70℃之间，如51℃、52℃、53℃、54℃、55℃、56℃、57℃、58℃、59℃、60℃、61℃、62℃、63℃、64℃、65℃、66℃、67℃、68℃、69℃、70℃；优选地，发生在52℃至68℃之间；更优选地发生在52℃至65℃之间。
在本发明的一个方面，第一部分占总TEA的重量百分比不大于总TEA的90％，比如在大于0％至90％之间，如90％、89％、88％、87％、86％、85％、84％、83％、82％、81％、80％、79％、78％、77％、76％、75％、74％、73％、72％、71％、70％、69％、68％、67％、66％、65％、64％、63％、62％、61％、60％、59％、58％、57％、56％、55％、54％、53％、52％、51％、50％、49％、48％、47％、46％、45％、44％、43％、42％、41％、40％、39％、38％、37％、36％、35％、34％、33％、32％、31％、30％、29％、28％、27％、26％、25％、24％、23％、22％、21％、20％、19％、18％、17％、16％、15％、14％、13％、12％、11％、10％、9％、8％、7％、6％、5％、4％、3％、2％、1％；或介于上述任意两个值之间，优选地在10％至90％之间。
在一种优选的实施方式中，添加(优选同时添加)FACl和第二部分TEA发生在52℃至68℃之间。
在本发明的一个方面，第一部分占总TEA的重量百分比在总TEA的10％至90％之间。在一种优选的实施方式中，步骤(2)中添加(优选同时添加)FACl和第二部分TEA发生在52℃至68℃之间，更优选在52℃至65℃之间。
在本发明的一个方面，步骤(2)中以相同或不同的速率添加FACl和/或第二部分TEA。在一些实施方案中，添加FACl的速率为5ml/min至20ml/min，优选地所述速率为6ml/min至16ml/min。在一些实施方案中，添加TEA的速率为1ml/min至10ml/min，优选地所述速率为4ml/min至8ml/min。
在本发明的一个方面，在反应过程中，反应体系的粘度小于250cp、小于240cp、小于230cp、小于220cp、小于210cp、小于200cp、小于190cp、小于180cp、小于170cp、小于160cp、小于150cp、小于140cp、小于130cp、小于120cp、小于110cp、小于100cp、小于90cp。
在本发明的一个方面，反应过程停止时，反应体系的粘度小于250cp、小于240cp、小于230cp、小于220cp、小于210cp、小于200cp、小于190cp、小于180cp、小于170cp、小于160cp、小于150cp、小于140cp、小于130cp、小于120cp、小于110cp、小于100cp、小于90cp。
在本发明的一个方面，第一部分TEA和第二部分TEA的总摩尔数与FACl的摩尔数之比为0.95:1至2:1，优选地为1.4:1至1.75:1。在本发明的一个方面，第一部分TEA和第二部分TEA的总重量与FACl的重量之比为1:3至2:3，优选地为1:1.7至1:2.1。
本发明所述方法能够降低的反应混合物粘度。降低的反应混合物粘度使得搅拌所需的能耗减少。同时，降低的反应混合物粘度还实现了在无甲苯等溶剂的条件/操作下生产施胶剂(例如AKD)。
在本发明的一个方面，本发明涉及一种无甲苯条件下制备施胶剂的方法，包括以下步骤：
(1)预添加总TEA的第一部分TEA至含HEEL反应体系以得到预添加TEA的含HEEL反应体系；以及，
(2)向预添加TEA的含HEEL反应体系添加总TEA的剩余的第二部分TEA和FACl以进行反应；
其中第一部分占总TEA的重量百分比不大于总TEA的90％。
在本发明的一个方面，本发明涉及一种降低施胶剂制备过程的粘度(例如降低反应混合物的粘度)的方法，包括以下步骤：
(1)预添加总TEA的第一部分TEA至含HEEL反应体系以得到预添加TEA的含HEEL反应体系；以及，
(2)向预添加TEA的含HEEL反应体系添加总TEA的剩余的第二部分TEA和FACl以进行反应；
其中第一部分占总TEA的重量百分比不大于总TEA的90％。
在本文中，术语“取代的”指所指定的原子或基团上的任何一个或多个氢被选自所指示基团的部分所代替，前提条件是不超过所指定的原子的正常价。
“烷基”为支链或直链饱和脂族烃基团。在一个实施方案中，烷基含1至约20个碳原子，更通常1至约12个碳原子、1至约6个碳原子或1至约4个碳原子。在一个实施方案中，烷基含1至约8个碳原子。在某些实施方案中，烷基为C1-C2、C1-C3或C1-C6。如本文所用，指定的范围指所述范围的每一个成员作为独立的种类的烷基基团。例如，如本文所用，术语C1-C30烷基指具有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个碳原子的直链或支链烷基基团并意在指这些中的每一者作为独立的种类描述。例如，如本文所用，术语C1-C4烷基指具有1、2、3或4个碳原子的直链或支链烷基基团并意在指这些中的每一者作为独立的种类描述。当C0-Cn烷基在本文中结合另一基团使用时，例如(C3-C7环烷基)C0-C4烷基或-C0-C4烷基(C3-C7环烷基)，所指示的基团——在此情况下环烷基，或通过单一共价键(C0烷基)直接键合或通过烷基链(在此情况下1、2、3或4个碳原子)连接。烷基也可经由其它基团如杂原子连接，如在-O-C0-C4烷基(C3-C7环烷基)中。烷基的实例包括但不限于甲基、乙基、正-丙基、异丙基、正-丁基、异丁基、仲-丁基、叔-丁基、正-戊基、异戊基、叔-戊基、新戊基、正-己基、2-甲基戊基、3-甲基戊基、2,2-二甲基丁基和2,3-二甲基丁基。在一个实施方案中，烷基基团任选地被如上所述取代。
“烯基”为具有一个或多个碳-碳双键的支链或直链脂族烃基团，所述双键可发生在沿链的稳定点处。非限制性实例有C2-C8烯基、C2-C6烯基和C2-C4烯基。如本文所用，指定的范围指所述范围的每一个成员作为独立的种类的烯基基团，如上面针对烷基部分所述。例如，如本文所用，术语C1-C30烯基指具有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个碳原子的直链或支链烯基基团并意在指这些中的每一者作为独立的种类描述。烯基的实例包括但不限于乙烯基和丙烯基。在一个实施方案中，烯基基团任选地被如上所述取代。
“炔基”为具有一个或多个碳-碳三键的支链或直链脂族烃基团，所述三键可发生在沿链的任何稳定点处，例如C2-C8炔基或C2-C6炔基。如本文所用，指定的范围指所述范围的每一个成员作为独立的种类的炔基基团，如上面针对烷基部分所述。例如，如本文所用，术语C1-C30炔基指具有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个碳原子的直链或支链炔基基团并意在指这些中的每一者作为独立的种类描述。炔基的实例包括但不限于乙炔基、丙炔基、1-丁炔基、2-丁炔基、3-丁炔基、1-戊炔基、2-戊炔基、3-戊炔基、4-戊炔基、1-己炔基、2-己炔基、3-己炔基、4-己炔基和5-己炔基。在一个实施方案中，炔基基团任选地被如上所述取代。
“烃基”为支链或直链饱和、不饱和脂族基团。所述烃基可以是烷基、烯基、或炔基。如本文所用，指定的范围指所述范围的每一个成员作为独立的基团。例如，如本文所用，术语C1-C30烃基指具有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个碳原子的烃基并意在指这些中的每一者作为独立的种类描述。
本文所述温度是指摄氏度。根据需要，本文所述浓度/含量/用量/份数可以是以重量、体积、摩尔、重量/体积、体积/重量表示的浓度/含量/用量/份数。
本文所述添加是指以任何手段添加。本文所述第二部分TEA和FACl可以同时添加或不同时添加。本文所述第二部分TEA和FACl可以以相同的速率添加或者以不同的速率添加。
在本文中，第一部分TEA和(剩余的)第二部分TEA之和可被称为总TEA。类似地，第一部分TEA重量和(剩余的)第二部分TEA重量之和可以称为总TEA重量。
本文所述总TEA是指要使用的全部量的TEA，例如基于FACl计算的要使用的全部量的TEA。与FACl相比，所述量可以是不足量、等量或过量。本领域技术人员能够确定合理的TEA的总量，因为TEA与FACl反应制备AKD是本领域已知的反应。通常，本领域技术人员在该反应中使用重量作为单位进行投料和监测，因为该反应实际上不是以化学计量的方式进行。
在本文中，第一部分TEA的重量百分比为100％×第一部分TEA重量与第一部分TEA重量和剩余第二部分TEA重量之和的比值，并且可被称为X值或X范围。
例如，在本发明中，HEEL可以以较早前批次生产施胶剂的反应混合物的量的约5wt％至40wt％使用，优选地为5wt％至20wt％之间。在一种实施方式中，HEEL的量占总反应体系的量为5wt％至40wt％。
本文所述方法可以以连续方式或间歇方式进行，优选间歇方式进行。
在本文中，术语“反应混合物”和“反应体系”可以互换使用。
在本文中，术语“第一部分TEA”是指想要预添加到含HEEL反应体系中的TEA部分。
现结合具体实例对本发明的技术方案进行描述。应理解，以下实例仅用于说明本发明而不用于限制本发明的范围。除非另有说明，本实例所述的试剂均是商业上可获得的。
具体实例
实例1(对照组)：无第一部分TEA
投料前，将反应器进行2-3次抽真空氮气置换，将40.6gAKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝60:40(wt％),Kemira,FennoWax1840TF)投入反应器内，开启搅拌，加热至熔融，后加入10.8g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)，混合均匀后，开始以13.8ml/min的速度滴加405g酰氯(n-C16酰氯:n-C18酰氯＝60:40(wt％)，Kemira)，同时以6.8ml/min的速度滴加219g三乙胺，保持滴加时体系温度为60-62度，滴加完成后在60度保温1小时。整个反应过程由海默生在线粘度计监测反应体系粘度(图1)，体系最终粘度为973cP。经分离得到淡黄色AKD产品，纯度高于85％(符合执行标准：GB/T 27565-2011)。
实例2：第一部分TEA占TEA的重量比70％
投料前，将反应器进行2-3次抽真空氮气置换，将40.6gAKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝60:40(wt％),Kemira,FennoWax1840TF)投入反应器内，开启搅拌，加热至熔融，后加入10.8g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)和153g的三乙胺(分析纯，上海凌峰化学试剂有限公司)，混合均匀后，开始以14.2ml/min的速度滴加400g酰氯,(n-C16酰氯:n-C18酰氯＝60:40(wt％)，Kemira)，同时以5.2ml/min的速度滴加66g三乙胺，保持滴加时体系温度为60-62度，滴加完成后在60度保温1小时。整个反应过程由海默生在线粘度计监测反应体系粘度(图1)，体系最终粘度为155.1cP。经分离得到淡黄色AKD产品，纯度高于85％(符合执行标准：GB/T 27565-2011)。
实例3：第一部分TEA占总TEA的重量比6.4％
投料前，将反应器进行2-3次抽真空氮气置换，将40.6g AKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝60:40(wt％),Kemira,FennoWax 1840 TF)投入反应器内，开启搅拌，加热至熔融，后加入10.8g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)和14g的三乙胺(分析纯，上海凌峰化学试剂有限公司)，混合均匀后，开始滴加400g酰氯(n-C16酰氯:n-C18酰氯＝60:40(wt％)，Kemira)和205g三乙胺，保持滴加时体系温度为60-62度，滴加完成后在60度保温1小时。整个反应过程由海默生在线粘度计监测反应体系粘度(图1)，体系最终粘度为228.3cP。经分离得到淡黄色AKD产品，纯度高于85％(符合执行标准：GB/T 27565-2011)。
实例4(对照组)：第一部分TEA与总TEA的重量比为100％投料前，将反应器进行2-3次抽真空氮气置换，将40.6g AKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝60:40(wt％),Kemira,FennoWax1840TF)投入反应器内，开启搅拌，加热至熔融，后加入10.8g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)和219g的三乙胺(分析纯，上海凌峰化学试剂有限公司)，混合均匀后，开始滴加400g酰氯(n-C16酰氯:n-C18酰氯＝60:40(wt％)，Kemira)保持滴加时体系温度为60-62度，滴加完成后在60度保温1小时。整个反应过程由海默生在线粘度计监测反应体系粘度(图1)，体系最终粘度为715cP。经分离得到淡黄色AKD产品，纯度高于85％(符合执行标准：GB/T 27565-2011)。
实例5：第一部分TEA与(146.1g)总TEA的重量比为1.4％
投料前，将反应器进行2-3次抽真空氮气置换，将40.6g AKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝5:95(wt％),Kemira,FennoWax 1895 TFE)投入反应器内，开启搅拌，加热至熔融，后加入10.8g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)和2.1g三乙胺(分析纯，上海凌峰化学试剂有限公司)，混合均匀后，降低体系温度为58度左右，混合物固化，搅拌困难，反应无法在此温度下进行。
实例6：第一部分TEA占总TEA的重量比21％
投料前，将反应器进行2-3次抽真空氮气置换，将69.4g AKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝5:95(wt％),Kemira,FennoWax 1895 TFE)投入反应器内，开启搅拌，加热至熔融，后加入35.3g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)和30.8g的三乙胺(分析纯，上海凌峰化学试剂有限公司)，混合均匀后，开始滴加405g酰氯(n-C16酰氯:n-C18酰氯＝5:95(wt％)，Kemira)和115.3g三乙胺，保持滴加时体系温度为58-60度，滴加完成后在63度保温半小时。整个反应过程由海默生在线粘度计监测反应体系粘度(图2)，体系最终粘度为106.6cP。经分离得到淡黄色AKD产品，纯度高于88％(符合执行标准：GB/T 27565-2011)。
实例7：第一部分TEA占总TEA的重量比21％
投料前，将反应器进行2-3次抽真空氮气置换，将69.4g AKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝5:95(wt％),Kemira,FennoWax 1895 TFE)投入反应器内，开启搅拌，加热至熔融，后加入35.3g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)和30.8g的三乙胺(分析纯，上海凌峰化学试剂有限公司)，混合均匀后，开始滴加405g酰氯(n-C16酰氯:n-C18酰氯＝5:95(wt％)，Kemira)和115.3g三乙胺，保持滴加时体系温度为62-64度，滴加完成后在63度保温半小时。整个反应过程由海默生在线粘度计监测反应体系粘度(图2)，体系最终粘度为120.5cP。经分离得到淡黄色AKD产品，纯度高于88％(符合执行标准：GB/T 27565-2011)。
实例8(对照组)：第一部分TEA与总TEA的重量比为100％
投料前，将反应器进行2-3次抽真空氮气置换，将69.4g AKD蜡粉(n-C16烷基AKD:n-C18烷基AKD＝5:95(wt％),Kemira,FennoWax 1895 TFE)投入反应器内，开启搅拌，加热至熔融，后加入35.3g三乙胺盐酸盐(99％，上海麦克林生化科技有限公司)和146.1g的三乙胺(分析纯，上海凌峰化学试剂有限公司)，混合均匀后，开始滴加405g酰氯(n-C16酰氯:n-C18酰氯＝5:95(wt％)，Kemira)，保持滴加时体系温度为62-64度，滴加完成后在63度保温半小时。整个反应过程由海默生在线粘度计监测反应体系粘度(图2)，体系最终粘度为262.8cP。经分离得到淡黄色AKD产品，纯度高于88％(符合执行标准：GB/T 27565-2011)。
本申请说明书中所阐述的机理仅为解释本发明，而不旨在以任何方式构成对本发明的限定。
应将前述实例和实施方式的描述视为说明而非限制本文所述发明。上述具体实施方式仅是本发明的具体方案，本发明的保护范围包括但不限于上述具体实施方式的方案。任何符合本发明所记载范围的实施方式以及任何所属技术领域的普通技术人员对其所做的适当变化或修饰，皆应落入本发明的保护范围。
如本文所用，术语“近似”、“约”、“基本上”以及类似术语旨在具有本公开内容所属主题的本领域技术人员普遍一致和接收使用的宽范围的含义。阅读本公开内容的本领域技术人员应理解的是，这些术语旨在实现对所述和所要求保护的某些特征进行描述，而没有将这些特征限制到所提供的精确数字范围。因此，这些术语应解读为表明所描述和要求保护的主题的非实质性或无关紧要的修改或变化被认为是在所附权利要求中所述的本发明的范围内。
如本文所用，“任选的”或“任选地”等旨在表示随后描述的事件或情况可能出现或者可能不出现，并且该描述包括所述事件或情况发生的实例及不发生的实例。除非另外说明，否则本文所用的不定冠词“一个”或“一种”及其相应的定冠词“该”表示至少一(个/种)，或者一(个/种)或多(个/种)。

Claims (12)

  1. 一种制备施胶剂的方法，包括以下步骤：
    (1)预添加总TEA的第一部分TEA至含HEEL反应体系以得到预添加TEA的含HEEL反应体系；以及，
    (2)向预添加TEA的含HEEL反应体系添加总TEA的剩余的第二部分TEA和FACl以进行反应；
    其中第一部分占总TEA的重量百分比不大于总TEA的90％。
  2. 根据权利要求1所述的方法，其中步骤(2)中添加第二部分TEA和FACl是在50℃至70℃之间进行，优选地，在52℃至68℃之间。
  3. 根据权利要求1或2所述的方法，其中第一部分占总TEA的重量百分比在总TEA的10％至90％之间。
  4. 根据前述权利要求中任一项所述的方法，其中步骤(2)添加第二部分TEA和FACl是在52℃至68℃之间进行，且第一部分占总TEA的重量百分比为总TEA的10％至90％。
  5. 根据前述权利要求中任一项所述的方法，其中步骤(2)中以相同或不同的速率添加FACl和第二部分TEA。
  6. 根据权利要求5所述的方法，其中添加FACl的速率为5ml/min至20ml/min，优选地所述速率为6ml/min至16ml/min。
  7. 根据权利要求5所述的方法，其中添加第二部分TEA的速率为1ml/min至10ml/min，优选地所述速率为4ml/min至8ml/min。
  8. 根据前述权利要求中任一项所述的方法，其中第一部分TEA和第二部分TEA的总重量与FACl的重量之比为1:3至2:3，优选地为1:1.7至1:2.1。
  9. 根据前述权利要求中任一项所述的方法，其中，所述含HEEL反应体系除HEEL之外还包含FA、TEA、FACl、烷基烯酮、AKD、TEA·HCl、或其组合。
  10. 根据前述权利要求中任一项所述的方法，其中所述施胶剂是烷基烯酮二聚体(AKD)。
  11. 根据前述权利要求中任一项所述的方法，其中在反应过程中，反应体系的粘度小于250cp，优选小于200cp，更优选小于150cp，最优选小于100cp。
  12. 根据前述权利要求中任一项所述的方法，其中反应过程停止时，反应体系的粘度小于250cp，优选小于200cp，更优选小于150cp，最优选小于100cp。
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