WO2017075848A1 - 环保烷基烯酮二聚体乳化剂的制备方法 - Google Patents

环保烷基烯酮二聚体乳化剂的制备方法 Download PDF

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WO2017075848A1
WO2017075848A1 PCT/CN2015/095049 CN2015095049W WO2017075848A1 WO 2017075848 A1 WO2017075848 A1 WO 2017075848A1 CN 2015095049 W CN2015095049 W CN 2015095049W WO 2017075848 A1 WO2017075848 A1 WO 2017075848A1
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temperature
sorbitan trioleate
alkyl ketene
emulsifier
catalyst
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PCT/CN2015/095049
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French (fr)
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王利伟
胡小雷
王瑛
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江苏四新界面剂科技有限公司
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Publication of WO2017075848A1 publication Critical patent/WO2017075848A1/zh

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    • 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

Definitions

  • the invention relates to the technical field of functional fine chemicals, in particular to the preparation technology of alkyl ketene dimer emulsifiers.
  • the alkyl ketene dimer is an unsaturated lactone.
  • the product is a water-insoluble waxy solid with a melting point of about 50 ° C.
  • the emulsion is commonly used in the manufacture of pulp neutral sizing.
  • Neutral sizing is widely used in the papermaking industry for its advantages of improving the strength, durability and quality of paper, reducing energy consumption, reducing emissions of waste water, and reducing corrosion of equipment such as acid sizing.
  • the alkyl ketene dimer is difficult to emulsify, and it is required to be equipped with a high-speed shear emulsifier, a homogenizer, and the like for emulsification.
  • the object of the present invention is to provide a preparation method of an alkyl ketene dimer emulsifier which is environmentally friendly, excellent in performance and inexpensive.
  • the technical proposal of the invention is: placing sorbitan trioleate in a stainless steel reaction vessel, placing a catalyst, heating and heating, dehydrating at 120 ° C, dehydrating for 30 minutes, after the dehydration is completed, heating the material to 150 ° C, starting Passing ethylene oxide, the reaction is carried out at a temperature of 160-180 ° C. After the addition of ethylene oxide for 30 minutes, the cooling water is introduced to reduce the temperature of the mixed system to 80 ° C. Under the condition of adding acetic acid for neutralization reaction, and then continue to cool down to the temperature of the system ⁇ 70 ° C discharge, that is, the alkyl ketene dimer emulsifier - polyoxyethylene (25) sorbitan trioleate.
  • the invention has simple production process, rich raw material sorbitan trioleate and renewable, excellent emulsification performance and good biodegradability, and is a kind of green environmental protection product.
  • the alkyl ketene dimer emulsion emulsified by it has blue light and the particle size of the emulsion is finer. It is a yellow transparent liquid having a saponification value of 76-86 mgKOH/g, an acid value of ⁇ 2 mgKOH/g, and a hydroxyl value of 30-50 mgKOH/g.
  • the emulsifier is environmentally friendly, has low production cost, and has superior performance.
  • the alkyl ketene dimer emulsion emulsified by the emulsifier has blue light, and the particle size of the emulsion is finer.
  • composition of the oleic acid in the sorbitan trioleate of the present invention is: C 18 : 1 component ⁇ 75%, C 18 : 2 component ⁇ 13 %, C 18 : 0 component ⁇ 12%
  • the other components are ⁇ 1%; the sorbitan trioleate is a yellow transparent liquid, the saponification value is 170-185 mgKOH/g, the acid value is ⁇ 15 mgKOH/g, and the hydroxyl value is 60-80 mgKOH/g.
  • the polyoxyethylene (25) sorbitan trioleate produced by this specification of sorbitan trioleate is stable between batches.
  • the mass ratio of the sorbitan trioleate to ethylene oxide is 1:1.15, which produces the HLB value of the polyoxyethylene (25) sorbitan trioleate (hydrophilic-lipophilic balance)
  • the value is 11, which corresponds to the HLB value (hydrophilic-lipophilic balance) of the emulsifier required for emulsifying the alkyl ketene dimer.
  • the catalyst is sodium hydroxide or potassium hydroxide, and the two catalysts have good catalytic effect, and react with sorbitan trioleate to form water, which does not pollute the environment.
  • the catalyst is added in an amount of from 0.32% to 0.45% by mass of the sorbitan trioleate.
  • the small amount of catalyst will cause slow reaction, long production time and economical cost; the large amount of catalyst will easily saponify with sorbitan trioleate to form sodium oleate, which will produce by-product oil after passing through ethylene oxide.
  • the acid polyoxyethylene ester has a large amount of by-products which is disadvantageous for the emulsified alkyl ketene dimer.
  • the catalyst is added in an amount of from 0.32% to 0.45% of the mass of the sorbitan trioleate.
  • the amount of the acetic acid is the same as the amount of the catalyst, so that the product is kept neutral, which is more favorable for the storage stability of the product.
  • the selected sorbitan trioleate has a yellow transparent liquid, a saponification value of 174 mgKOH/g, an acid value of 10 mgKOH/g, a hydroxyl value of 71 mgKOH/g, and a oleic acid component of: C 18 :1 component 79%. , C 18 : 2 components 9%, C 18 : 0 component 11.5%, and other components 0.5%.
  • sorbitan trioleate 500 kg was placed in a stainless steel reaction vessel, 2 kg of catalyst sodium hydroxide was placed, heated to heat, dehydrated at 120 ° C, dehydrated for 30 minutes, after dehydration was completed, the temperature was raised to 150 ° C, and began.
  • the reaction was carried out by introducing ethylene oxide, the reaction temperature was controlled at 160 ° C, and after 575 kg of ethylene oxide was added, the temperature was kept for 30 minutes, cooled to 80 ° C by cooling water, neutralized with 3 kg of acetic acid, and kept for 30 minutes, then Continue to cool down to 70 ° C discharge.
  • the product was a yellow transparent liquid having a saponification value of 81 mgKOH/g, an acid value of 1 mgKOH/g, and a hydroxyl value of 41 mgKOH/g.
  • the alkyl ketene dimer is subjected to reverse phase emulsification with the emulsifier, and the emulsifier is used in an amount of one-half the mass of the alkyl ketene dimer to obtain a blue alkyl ketene having a solid content of 30%.
  • the dimer emulsion was measured by a laser particle size analyzer to have a particle size of 0.5 ⁇ m.
  • the selected sorbitan trioleate has a yellow transparent liquid, a saponification value of 177 mgKOH/g, an acid value of 11 mgKOH/g, a hydroxyl value of 68 mgKOH/g, and a oleic acid component of: C 18 :1 component 81%. , C 18 : 2 components 10%, C 18 : 0 component 8.4%, and other components 0.6%.
  • the product was a yellow transparent liquid having a saponification value of 82 mgKOH/g, an acid value of 0.9 mgKOH/g, and a hydroxyl value of 39 mgKOH/g.
  • the alkyl ketene dimer is subjected to reverse phase emulsification with the emulsifier, and the emulsifier is used in an amount of one-half the mass of the alkyl ketene dimer to obtain a blue alkyl ketene having a solid content of 30%.
  • the dimer emulsion was measured by a laser particle size analyzer to have a particle size of 0.6 ⁇ m.
  • the selected sorbitan trioleate has a yellow transparent liquid, a saponification value of 180 mgKOH/g, an acid value of 11 mgKOH/g, a hydroxyl value of 62 mgKOH/g, and a oleic acid component of C 18 :1 component 82%. , C 18 : 2 components 11%, C 18 : 0 component 6.6%, and other components 0.4%.
  • the product was a yellow transparent liquid having a saponification value of 84 mgKOH/g, an acid value of 1 mgKOH/g, and a hydroxyl value of 36 mgKOH/g.
  • the alkyl ketene dimer is subjected to reverse phase emulsification with the emulsifier, and the emulsifier is used in an amount of one-half the mass of the alkyl ketene dimer to obtain a blue alkyl ketene having a solid content of 30%.
  • the dimer emulsion was measured by a laser particle size analyzer to have a particle size of 0.6 ⁇ m.
  • the above three methods can produce polyoxyethylene (25) sorbitan trioleate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

环保烷基烯酮二聚体乳化剂的制备方法，涉及功能性精细化学品技术领域，将山梨糖醇酐三油酸酯和催化剂置于不锈钢反应釜内，加热至120℃进行脱水后，升温物料至150℃，通入环氧乙烷，在反应体系的温度为160～180℃的条件下进行反应，加完环氧乙烷后保温30分钟后通入冷却水，使混合体系的温度降至80℃，保温条件下加入乙酸进行中和反应，然后降温、放料，即得烷基烯酮二聚体乳化剂，本发明生产工艺简单，山梨糖醇酐三油酸酯可再生，产品乳化性能优越，生物降解性好，是一类绿色环保产品。

Description

环保烷基烯酮二聚体乳化剂的制备方法 技术领域
本发明涉及功能性精细化学品技术领域，尤其涉及烷基烯酮二聚体乳化剂的制备技术。
背景技术
烷基烯酮二聚体是一种不饱和内酯，产品是不溶于水的蜡状固体，熔点为50℃左右，其乳液常用于制造纸浆中性施胶。中性施胶以其提高纸张的强度，耐久性和质量，降低能耗，减少排放废水污染，减少设备腐蚀等酸性施胶所无法比拟的优点，在造纸行业大范围推广及应用。但是烷基烯酮二聚体较难乳化，乳化时需要配备高速剪切乳化机，均质机等设备。
发明内容
本发明目的是提供一种环保、性能优、价格便宜的烷基烯酮二聚体乳化剂的制备方法。
本发明的技术方案是：将山梨糖醇酐三油酸酯置于不锈钢反应釜内，置入催化剂，加热升温，120℃进行脱水，脱水30分钟，脱水完毕后，升温物料至150℃，开始通入环氧乙烷，在反应体系的温度为160～180℃的条件下进行反应，加完环氧乙烷后保温30分钟后通入冷却水，使混合体系的温度降至80℃，保温条件下加入乙酸进行中和反应，然后继续降温至体系的温度≤70℃放料，即得烷基烯酮二聚体乳化剂——聚氧乙烯(25)山梨糖醇酐三油酸酯。
本发明生产工艺简单，原料山梨糖醇酐三油酸酯丰富且可再生，产品乳化性能优越，生物降解性好，是一类绿色环保产品。制备乳液时无需配备高速剪切乳化机，均质机等设备，只要常规搅拌釜即可，使用极其方便，经其乳化的烷基烯酮二聚体乳液带蓝光，乳液粒径更细小，产品为黄色透明液体，皂化值为76-86mgKOH/g,酸值<2mgKOH/g，羟值为30-50mgKOH/g。该乳化剂绿色环保，生产成本低，且性能优越，经其乳化的烷基烯酮二聚体乳液带蓝光，乳液粒径更细小。
进一步地，本发明所述山梨糖醇酐三油酸酯中油酸的成分为：C18：1组分≥75％，C18：2组分≤13％，C18：0组分≤12％，其它组分≤1％；山梨糖醇酐三油酸酯为黄色透明液体，皂化值为170～185mgKOH/g，酸值<15mgKOH/g，羟值为60～80mgKOH/g。此规格的山梨糖醇酐三油酸酯生产出的聚氧乙烯(25)山梨糖醇酐三油酸酯批次间稳定好。
所述山梨糖醇酐三油酸酯与环氧乙烷的混合质量比为1∶1.15，此比例生产聚氧乙烯(25)山梨糖醇酐三油酸酯的HLB值(亲水亲油平衡值)为11，符合乳化烷基烯酮二聚体所需乳化剂的HLB值(亲水亲油平衡值)。
所述催化剂为氢氧化钠或氢氧化钾，这两种催化剂催化效果好，与山梨糖醇酐三油酸酯反应生成水，不会对环境产生污染。
所述催化剂的加入量为山梨糖醇酐三油酸酯质量的0.32％～0.45％。催化剂量少会造成反应缓慢，生产时间较长，经济上不划算；催化剂量大容易与山梨糖醇酐三油酸酯发生皂化反应，生成油酸钠，通环氧乙烷后生成副产物油酸聚氧乙烯酯，副产物量多对乳化烷基烯酮二聚体不利。催化剂加入量为山梨糖醇酐三油酸酯质量的0.32％～0.45％最佳。
所述乙酸用量与催化剂用量为相同的摩尔数，这样使产品保持中性，更有利于产品的保存稳定性。
具体实施方式
实施例1：
选用的山梨糖醇酐三油酸酯外观为黄色透明液体，皂化值为174mgKOH/g,酸值10mgKOH/g，羟值为71mgKOH/g，油酸的成分为：C18：1组分79％，C18：2组分9％，C18：0组分11.5％，其它组分0.5％。
将500千克山梨糖醇酐三油酸酯置于不锈钢反应釜内，置入催化剂氢氧化钠2千克，加热升温，120℃进行脱水，脱水30分钟，脱水完毕后，升温物料至150℃，开始通入环氧乙烷进行反应，反应温度控制160℃，待575千克环氧乙烷加完后保温30分钟，通冷却水降温至80℃，置入乙酸3千克中和，保温30分钟，然后继续降温至70℃放料。
产品为黄色透明液体，皂化值为81mgKOH/g,酸值1mgKOH/g，羟值为41mgKOH/g。
对烷基烯酮二聚体用此乳化剂进行反相乳化，乳化剂的用量为烷基烯酮二聚体质量的二分之一，制得固含量为30％的带蓝光烷基烯酮二聚体乳液，激光粒度仪测得乳液的粒径为0.5微米。
实施例2：
选用的山梨糖醇酐三油酸酯外观为黄色透明液体，皂化值为177mgKOH/g,酸值11mgKOH/g，羟值为68mgKOH/g，油酸的成分为：C18：1组分81％，C18：2组分10％，C18：0组分8.4％，其它组分0.6％。
将1400千克山梨糖醇酐三油酸酯置于不锈钢反应釜内，置入催化剂氢氧化钾4.5千克，加热升温，120℃进行脱水，脱水30分钟，脱水完毕后，升温物料至150℃，开始通入环氧乙烷进行反应，反应温度控制180℃，待1610千克环氧乙烷加完后保温30分钟，通冷却水降温至80℃，置入乙酸4.82千克中和，保温30分钟，然后继续降温至65℃放料。
产品为黄色透明液体，皂化值为82mgKOH/g,酸值0.9mgKOH/g，羟值为39mgKOH/g。
对烷基烯酮二聚体用此乳化剂进行反相乳化，乳化剂的用量为烷基烯酮二聚体质量的二分之一，制得固含量为30％的带蓝光烷基烯酮二聚体乳液，激光粒度仪测得乳液的粒径为0.6微米。
实施例3：
选用的山梨糖醇酐三油酸酯外观为黄色透明液体，皂化值为180mgKOH/g,酸值11mgKOH/g，羟值为62mgKOH/g，油酸的成分为：C18：1组分82％，C18：2组分11％，C18：0组分6.6％，其它组分0.4％。
将1860千克山梨糖醇酐三油酸酯置于不锈钢反应釜内，置入催化剂氢氧化钠6千克，加热升温，120℃进行脱水，脱水30分钟，脱水完毕后，升温物料至150℃，开始通入环氧乙烷进行反应，反应温度控制175℃，待2140千克环氧乙烷加完后保温30分钟，通冷却水降温至80℃，置入乙酸9千克中和，保温30分钟，然后继续降温至60℃放料。
产品为黄色透明液体，皂化值为84mgKOH/g,酸值1mgKOH/g，羟值为36mgKOH/g。
对烷基烯酮二聚体用此乳化剂进行反相乳化，乳化剂的用量为烷基烯酮二聚体质量的二分之一，制得固含量为30％的带蓝光烷基烯酮二聚体乳液，激光粒度仪测得乳液的粒径为0.6微米。
以上三种方式均能制得聚氧乙烯(25)山梨糖醇酐三油酸酯。

Claims (6)

  1. 环保烷基烯酮二聚体乳化剂的制备方法，其特征在于：将山梨糖醇酐三油酸酯置于不锈钢反应釜内，置入催化剂，加热升温，120℃进行脱水，脱水30分钟，脱水完毕后，升温物料至150℃，开始通入环氧乙烷，在反应体系的温度为160～180℃的条件下进行反应，加完环氧乙烷后保温30分钟后通入冷却水，使混合体系的温度降至80℃，保温条件下加入乙酸进行中和反应，然后继续降温至体系的温度≤70℃放料，即得烷基烯酮二聚体乳化剂。
  2. 根据权利要求1所述的制备方法，其特征在于：所述山梨糖醇酐三油酸酯中油酸的成分为：C18：1组分≥75％，C18：2组分≤13％，C18：0组分≤12％，其它组分≤1％；山梨糖醇酐三油酸酯为黄色透明液体，皂化值为170～185mgKOH/g，酸值<15mgKOH/g，羟值为60～80mgKOH/g。
  3. 根据权利要求1或2所述的制备方法，其特征在于：所述山梨糖醇酐三油酸酯与环氧乙烷的混合质量比为1∶1.15。
  4. 根据权利要求1所述的制备方法，其特征在于：所述催化剂为氢氧化钠或氢氧化钾。
  5. 根据权利要求1或4所述的制备方法，其特征在于：所述催化剂的加入量为山梨糖醇酐三油酸酯质量的0.32％～0.45％。
  6. 根据权利要求1所述的制备方法，其特征在于：所述乙酸用量与催化剂用量为相同的摩尔数。
PCT/CN2015/095049 2015-11-03 2015-11-19 环保烷基烯酮二聚体乳化剂的制备方法 WO2017075848A1 (zh)

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