WO2021203555A1 - 一种脂肪醇乳液消泡剂的制备方法 - Google Patents

一种脂肪醇乳液消泡剂的制备方法 Download PDF

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WO2021203555A1
WO2021203555A1 PCT/CN2020/097379 CN2020097379W WO2021203555A1 WO 2021203555 A1 WO2021203555 A1 WO 2021203555A1 CN 2020097379 W CN2020097379 W CN 2020097379W WO 2021203555 A1 WO2021203555 A1 WO 2021203555A1
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fatty alcohol
defoamer
water
parts
emulsion
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PCT/CN2020/097379
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English (en)
French (fr)
Inventor
刘姝
张琳
徐晓雅
曹添
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江苏四新科技应用研究所股份有限公司
南京绿界新材料研究院有限公司
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Publication of WO2021203555A1 publication Critical patent/WO2021203555A1/zh

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    • 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
    • D21H21/06—Paper forming aids
    • D21H21/12—Defoamers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D19/00—Degasification of liquids
    • B01D19/02—Foam dispersion or prevention
    • B01D19/04—Foam dispersion or prevention by addition of chemical substances

Definitions

  • the invention relates to a preparation method of a fatty alcohol emulsion defoamer.
  • the defoamer is a fine chemical additive. Therefore, the present invention belongs to the technical field of fine chemicals.
  • the papermaking process is roughly divided into three parts: pulp preparation, papermaking, and rewinding. Among them, the processes in the papermaking section all need to remove the gas in the white water.
  • the white water mainly contains fine fibers, fillers, coatings and dissolved wood components, as well as added sizing materials, wet strength agents, preservatives, etc.
  • Now white water is generally closed in circulation, and it is easy to produce bubbles. The existence of these bubbles has a great impact on the paper. Decrease the operating efficiency of the pump and increase energy consumption.
  • CN106075961A introduces a water-soluble homopolymer-stable fatty alcohol emulsion defoamer and its preparation method.
  • the method of adding water-soluble homopolymer can make the emulsion phase separate less and inhibit gelation and thickening. It solves the phenomenon of phase separation of the fatty alcohol emulsion to generate gel mass and thickening during storage.
  • the product has poor anti-foaming performance and does not have a good market advantage.
  • CN107059474A introduces a high-carbon alcohol defoaming agent, which is composed of rice bran wax, wax, alkane or vegetable oil, surfactant, bactericide, and water, and rice bran wax is the active component of the defoaming agent.
  • Rice bran wax has a large amount of hexacosanol, octacosanol, triacontanol and corresponding alcohol esters, and has a better anti-foaming effect.
  • CN109432830A introduces a method for preparing high-carbon alcohol bulk high-temperature defoamer, which uses high-carbon alcohol , Mineral oil, fatty alcohol polyether polyol, and polyether modified silicone oil are used as emulsified products to obtain emulsion A, which is mixed with emulsion B made of microcrystalline wax, and stirred at above 180°C to obtain the final emulsion.
  • the emulsification method adopts the method of mixing the active substance and the emulsion separately to make the emulsification more fully, but the emulsion product has higher viscosity, poor dispersibility, and easier to cream; CN107137959B separately prepares separate emulsified fatty alcohol emulsion and oil Emulsion, paraffin emulsion, and finally the three emulsions are compounded into the final emulsion to improve the stability of the emulsion, but the anti-foaming performance of the product needs to be further improved.
  • two types of long-chain fatty alcohols with different carbon chains are compounded and used to improve the foam suppression performance of the defoamer; in the preparation process, the fatty alcohol and paraffin are separately emulsified into emulsions and then compounded into the final defoamer emulsion. It avoids the problem of excessive emulsification during the emulsification process, which leads to poor product stability; in the process of separate emulsification of fatty alcohols, the fatty alcohols and ethers are compounded and the fatty alcohols are emulsified by the water phase method to make the emulsification more complete and at the same time eliminate The foam suppression performance has been improved.
  • the preparation method of a fatty alcohol emulsion defoamer of the present invention is as follows:
  • fatty alcohol emulsion M Mix fatty alcohol A and ether B to 55°C ⁇ 70°C, stir evenly, and cool to room temperature for later use; mix water G1 with thickener F1, and then add non-ionic surfactant D1, then add anionic surfactant E1, mix and heat up to 50 ⁇ 70°C; add the mixture of fatty alcohol A and ether B to it and continue to stir, then add water G2 at 70 ⁇ 85°C, and then pass through high-speed shearing equipment Further emulsify, cool to room temperature, add water G3 and stir evenly;
  • paraffin wax emulsion N mix paraffin wax C, non-ionic surfactant D2, anionic surfactant E2, heat up to 70 ⁇ 85°C, slowly add 70 ⁇ 85°C water G4 to the above mixture, pass through high speed The shearing equipment is further emulsified, cooled to room temperature, water G5 and thickener F2 are added and stirred evenly;
  • the fatty alcohol emulsion defoamer of the present invention is composed of the following components:
  • the amount of fatty alcohol accounts for 15-30% of the total mass of the defoamer.
  • the structural formula of the ethers of the present invention is: R 1 -OR 2 , wherein R 1 and R 2 are saturated alkane groups of C10 ⁇ C18, specifically selected from the group consisting of decyl ether, lauryl ether, hexadecyl ether, and octadecyl ether. One or more. Ethers account for 1 to 5% of the total mass of the defoamer.
  • the paraffin in the present invention is selected from microcrystalline paraffin and liquid paraffin.
  • the amount of paraffin wax accounts for 5-10% of the total mass of the defoamer.
  • the non-ionic surfactants of the present invention are divided into two categories
  • Nonionic surfactant D1 is an ester, formed by esterification of C12 ⁇ C18 fatty acids and C2 ⁇ C6 mono-to-tetrahydric alcohols, specifically selected from sorbitan monolaurate (Span20), sorbitan Alcohol monopalmitate (Span40), sorbitan monostearate (Span60), glyceryl tristearate, sorbitan monooleate, glyceryl monostearate, glycerol pentaerythritol stearate
  • One or more of ester ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monostearate, and diethylene glycol distearate, non-ionic surface active
  • the dosage of agent D1 accounts for 0.5-3% of the total defoamer.
  • the structure of the nonionic surfactant D2 is R-O-(EO)n-H, where R is a C12-C14 alkyl group, n is an integer of 10-20, and the amount of D2 accounts for 1 to 4% of the total defoamer.
  • the anionic surfactant of the present invention is selected from one or more of alkyl sulfonate, alkyl diphenyl ether disulfonate, alkylphenol polyoxyethylene ether phosphate salt, fatty alcohol polyoxyethylene ether sulfate Species, specifically selected from one or more of sodium lauryl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl phosphate, sodium dodecyl diphenyl ether disulfonate.
  • the amount of anionic surfactant accounts for 0.03-0.1% of the total defoamer.
  • the anionic surfactant is divided into two parts, E1 and E2.
  • the thickener of the present invention is selected from one or more of xanthan gum, guar gum, xanthan gum, hydroxymethyl cellulose, hydroxyethyl cellulose, methyl cellulose, polyacrylic acid, and polyacrylamide
  • the thickener is preferably xanthan gum.
  • the amount of thickener accounts for 0.02% to 0.1% of the total defoamer.
  • the thickener is divided into two parts, F1 and F2.
  • the water in the present invention is deionized water, the amount of which accounts for 60-75% of the total defoamer, the water is used in 5 parts, the amount of water G1 is 10.6-17% of the total mass of the defoamer, and the amount of water G2 accounts for the amount of defoamer.
  • the amount of water G3 accounts for 20 to 32% of the total mass of the defoamer, the amount of water G4 accounts for 6 to 15% of the total mass of the defoamer, and the amount of water G5 accounts for the total mass of the defoamer Of 8-20%.
  • paraffin emulsion N1 mix 6 parts of microcrystalline paraffin, 3.4 parts of polyoxyethylene laureth (20), and 0.01 part of sodium dodecyl benzene sulfonate, heat up to 70°C, and set 7.095 parts of 70°C Add water slowly to the above mixture, further emulsify through high-speed shearing equipment, cool to room temperature, add 11.82 parts of water and 0.02 parts of guar gum and stir evenly;
  • paraffin emulsion N2 Preparation of paraffin emulsion N2: mix 6.37 parts of liquid paraffin, 1 part of tetradecyl alcohol polyoxyethylene ether (10), and 0.02 parts of sodium lauryl phosphate, heat up to 85°C, add 7 parts of water at 85°C Slowly add to the above mixture, further emulsify by high-speed shearing equipment, cool to room temperature, add 10 parts of water and 0.0125 parts of xanthan gum and stir evenly;
  • paraffin emulsion N3 mix 5 parts of liquid paraffin, 1 part of polyoxyethylene laureth (15), and 0.04 part of sodium dodecyl benzene sulfonate, heat up to 80 °C, and add 15 parts of 80 °C Water is slowly added to the above mixture, further emulsified by high-speed shearing equipment, cooled to room temperature, 18.1 parts of water and 0.028 parts of xanthan gum are added and stirred evenly;
  • paraffin emulsion N4 Preparation of paraffin emulsion N4: mix 10 parts of microcrystalline paraffin, 1.8 parts of polyoxyethylene laureth (20), and 0.02 parts of sodium dodecyl benzene sulfonate, heat to 75°C, and 13.02 parts of 80°C Add water slowly to the above mixture, further emulsify through high-speed shearing equipment, cool to room temperature, add 11 parts of water and 0.012 parts of methyl cellulose and stir evenly;
  • paraffin wax emulsion N5 mix 8 parts of liquid paraffin, 0.7 parts of tetradecyl alcohol polyoxyethylene ether (10), and 0.01 part of sodium lauryl diphenyl ether disulfonate, heat up to 80°C, and set 9 Part of 85°C water is slowly added to the above mixture, further emulsified by high-speed shearing equipment, cooled to room temperature, 20 parts of water and 0.008 parts of methyl cellulose are added and stirred evenly;
  • paraffin emulsion N6 Preparation of paraffin emulsion N6: mix 9 parts of microcrystalline paraffin, 4 parts of tridecanol polyoxyethylene ether (20), and 0.03 parts of sodium lauryl sulfate. The temperature is raised to 75°C, and 6 parts of 80°C Slowly add water to the above mixture, further emulsify by high-speed shearing equipment, cool to room temperature, add 8 parts of water and 0.03 parts of polyacrylamide and stir evenly;
  • paraffin wax emulsion N7 mix 6 parts of microcrystalline paraffin, 3.4 parts of polyoxyethylene laureth (20), and 0.01 part of sodium dodecyl benzene sulfonate, heat up to 70°C, and set 7.095 parts of 70°C Add water slowly to the above mixture, further emulsify through high-speed shearing equipment, cool to room temperature, add 11.82 parts of water and 0.02 parts of guar gum and stir evenly;
  • fatty alcohol emulsion M8 Mix 30 parts of C28 fatty alcohol and 1 part of octadecyl ether, heat up to 70°C, stir evenly, and cool to room temperature for later use; mix 12.5 of water with 0.0375g of xanthan gum, and then add 1.5 1 part of sorbitol monooleate, then add 0.06 part of sodium lauryl sulfate, mix and heat up to 70°C; add the mixture of mixed fatty alcohol and stearyl ether to it and continue to stir, then add 5.2 parts of water at 85°C , And then further emulsify by high-speed shearing equipment, cool to room temperature, add 25.3 parts of water and stir evenly;
  • paraffin emulsion N8 mix 6.37 parts of liquid paraffin, 1 part of tetradecyl alcohol polyoxyethylene ether (10), and 0.02 parts of sodium lauryl phosphate, heat up to 85°C, and add 7 parts of 85°C water Slowly add to the above mixture, further emulsify by high-speed shearing equipment, cool to room temperature, add 10 parts of water and 0.0125 parts of xanthan gum and stir evenly;
  • fatty alcohol emulsion M9 Preparation of fatty alcohol emulsion M9: mix 10 parts of C22 and 6.5 parts of C26 mixed fatty alcohols, heat up to 55°C, stir evenly, cool to room temperature for later use; mix 17 parts of water with 0.042 parts of carboxymethyl cellulose, and then add 2.33 parts of ethylene glycol monostearate, then add 0.06 parts of sodium lauryl diphenyl ether disulfonate, mix uniformly and raise the temperature to 60°C; add the mixed fatty alcohol to it and continue to stir, then add 4.9 parts of 80°C The water is further emulsified by high-speed shearing equipment, cooled to room temperature, and 20 parts of water are added and stirred evenly;
  • paraffin wax emulsion N9 mix 5 parts of liquid paraffin, 1 part of polyoxyethylene laureth (15), and 0.04 part of sodium dodecylbenzene sulfonate, heat to 80°C, and add 15 parts of 80°C Water is slowly added to the above mixture, further emulsified by high-speed shearing equipment, cooled to room temperature, 18.1 parts of water and 0.028 parts of xanthan gum are added and stirred evenly;
  • paraffin emulsion N10 mix 10 parts of microcrystalline paraffin, 1.8 parts of polyoxyethylene laureth (20), and 0.02 parts of sodium dodecyl benzene sulfonate, heat to 75°C, and 13.02 parts of 80°C Add water slowly to the above mixture, further emulsify through high-speed shearing equipment, cool to room temperature, add 11 parts of water and 0.012 parts of methyl cellulose and stir evenly;
  • paraffin emulsion N12 Preparation of paraffin emulsion N12: mix 9 parts of microcrystalline paraffin, 4 parts of tridecyl alcohol polyoxyethylene ether (20), and 0.03 parts of sodium lauryl sulfate. The temperature is increased to 75°C, and the high-speed shearing equipment is used to further Emulsify, cool to room temperature, add 14 parts of water and 0.03 parts of polyacrylamide and stir evenly;
  • the emulsions prepared in the above examples and comparative examples were placed at 5°C, 25°C, and 40°C to perform a viscosity tracking test for 6 months.
  • the specific test method of viscosity adopts NDJ-8 digital display viscometer, 2# rotor, and the test is carried out under the condition of 6rpm.
  • the specific situation is shown in Table 1 below (the viscosity unit is mPa.s, "—" means that the emulsion becomes a paste and cannot flow):
  • the viscosity change range is small, and it shows good storage stability.
  • the viscosity of fatty alcohol emulsions prepared in Comparative Examples 1-6 increased to varying degrees at 6 months.
  • the performance of the defoamer is measured by the cyclic bubbling method. Add 600ml of white water to the circulatory bubbling equipment and heat it to the required temperature, turn on the flow pump, and circulate to the foam volume of 300ml at a flow rate of 8/L min, and add 6ul of defoaming It records the change of foam volume with time. In the same time, the smaller the volume, the better the foam suppression performance; the longer the time for the foam to reach 300ml again, the better the foam suppression performance.
  • the fatty alcohol emulsion prepared by the invention exhibits good antifoaming properties at 30°C and 55°C.

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  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

本发明提供了一种脂肪醇乳液消泡剂的制备方法，引入不同碳链的两类长链脂肪醇复配使用，提高消泡剂的抑泡性能；制备过程中将脂肪醇和石蜡分别单独乳化成乳液后再复配成最终消泡剂乳液，避免了乳化过程中乳化物过多，导致产品稳定性差的问题；脂肪醇单独乳化过程中，将脂肪醇和醚类物质复配后采用了水相法乳化脂肪醇，使得脂肪醇乳化更完全的同时消抑泡性能得到了提升。

Description

一种脂肪醇乳液消泡剂的制备方法 技术领域
本发明涉及一种脂肪醇乳液消泡剂的制备方法，消泡剂是精细化学品添加剂，因此，本发明属于精细化学品技术领域。
背景技术
在造纸工艺中大致分为三部分：备浆、抄纸、复卷。其中在抄纸工段中的工序都需要除去白水中的气体，同时，白水主要含有细小纤维、填料、涂料和溶解了的木材成分，以及添加的胶料、湿强剂、防腐剂等。现在白水一般都是封闭循环，很容易产生气泡，这些气泡的存在对纸张有很大的影响，使施胶度差，纸面出现斑点、透光点和小孔，甚至引起断纸，且容易使泵的运行效率下降，增加能耗。
而脂肪醇乳液消泡剂在抄纸白水中的应用已经很成熟，国内外的研究人员对脂肪醇乳液消泡剂有很多的研究，主要是针对稳定性以及消抑泡性能。CN106075961A中介绍了一种水溶性均聚物稳定的脂肪醇乳液消泡剂及其制备方法，采用添加水溶性均聚物的方式，使乳液相分离较少，且抑制胶化和增粘。解决了脂肪醇乳液在储存时出现乳液相分离生成凝胶块及增稠现象。但该产品的消抑泡性能较差，不具备很好的市场优势。
CN107059474A中介绍了一种高碳醇消泡剂，由米糠蜡、蜡、烷烃或植物油脂、表面活性剂、杀菌剂、水组成，其中米糠蜡是消泡剂的活性成分。米糠蜡有大量的二十六醇、二十八醇、三十醇及对应的 醇酯，消抑泡效果较好。但该产品的成分过于复杂，对乳化工艺要求较高且粘度变化大，容易发生结膏的现象；CN109432830A中介绍了一种高碳醇本体高温消泡剂的制备方法，采用了将高碳醇，矿物油，脂肪醇聚醚多元醇，聚醚改性硅油作为被乳化物得到乳液A，与微晶蜡制成的乳液B进行乳液复配，并在180℃以上进行搅拌得到最终的乳液。其中乳化方法采用了活性物与乳化物分别混合的方法，使乳化更充分，但该乳液产品粘度较大，分散性较差，且较易结膏；CN107137959B中分别制备单独乳化脂肪醇乳液、油脂乳液、石蜡乳液，最后将三种乳液复配制成最终乳液，提高乳液的稳定性，但是产品的消抑泡性能还需要进一步提高。
本发明人发现在脂肪醇乳液的乳化过程中，被乳化物过多，除了脂肪醇之外还有蜡及油脂等其他组分，使得乳化工艺复杂，降温困难，导致产品稳定性较差。本发明人通过一种简单的制备工艺，将脂肪醇乳液消泡剂的稳定性提高。
发明内容
本发明中引入不同碳链的两类长链脂肪醇复配使用，提高消泡剂的抑泡性能；制备过程中将脂肪醇和石蜡分别单独乳化成乳液后再复配成最终消泡剂乳液，避免了乳化过程中乳化物过多，导致产品稳定性差的问题；脂肪醇单独乳化过程中，将脂肪醇和醚类物质复配后采用了水相法乳化脂肪醇，使其乳化更完全的同时消抑泡性能得到了提升。
本发明所述的一种脂肪醇乳液消泡剂的制备方法如下：
(1)脂肪醇乳液M制备：将脂肪醇A和醚类B混合升温至55℃～70℃搅拌均匀，冷却至室温备用；将水G1与增稠剂F1混合，再加入非离子表面活性剂D1，再加入阴离子表面活性剂E1，混合均匀升温至50～70℃；向其中加入脂肪醇A和醚类B的混合物继续搅拌，再加入70～85℃的水G2，然后通过高速剪切设备进一步乳化，冷却至室温，加入水G3搅拌均匀；
(2)石蜡乳液N的制备：将石蜡C、非离子表面活性剂D2、阴离子表面活性剂E2混合，升温至70～85℃，将70～85℃的水G4缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入水G5及增稠剂F2搅拌均匀；
(3)将脂肪醇乳液M、石蜡乳液N在常温下混合均匀，即可得本发明所述的消泡剂。
本发明所述的一种脂肪醇乳液消泡剂，由以下组分组成：
A、脂肪醇
本发明所述脂肪醇为C18～C22脂肪醇和C24～C30脂肪醇的混合物，其中C18～C22脂肪醇和C24～C30脂肪醇的质量比为：C18～C22脂肪醇：C24～C30脂肪醇＝4:1～2:1。脂肪醇用量占消泡剂总质量的15～30％。
B、醚类
本发明所述醚类的结构式为：R 1-O-R 2，其中R 1和R 2为C10～C18的饱和烷烃基，具体选自癸醚，十二醚，十六醚，十八醚中的一种或多种。 醚类占消泡剂总质量的1～5％。
C、石蜡
本发明所述石蜡选自微晶石蜡、液体石蜡。石蜡用量占消泡剂总质量的5～10％。
D、非离子表面活性剂
本发明所述非离子表面活性剂分为两类
非离子表面活性剂D1为一种酯类，由C12～C18的脂肪酸和C2～C6的一元至四元醇酯化形成，具体选自失水山梨醇单月桂酸酯(Span20)、失水山梨醇单棕榈酸酯(Span40)、失水山梨醇单硬脂酸酯(Span60)、三硬脂酸甘油酯、失水山梨醇单油酸酯、单硬脂酸甘油酯、季戊四醇硬脂酸甘油酯、乙二醇单硬脂酸酯、乙二醇二硬脂酸酯、二乙二醇单硬脂酸酯、二乙二醇二硬脂酸酯中一种或多种，非离子表面活性剂D1的用量占消泡剂总量的0.5～3％。
非离子表面活性剂D2的结构为R-O-(EO)n-H,其中R为C12～C14烷基，n为10～20整数，D2的用量占消泡剂总量的1～4％。
E、阴离子表面活性剂
本发明所述阴离子表面活性剂选自烷基磺酸盐、烷基二苯醚二磺酸盐、烷基酚聚氧乙烯醚磷酸酯盐、脂肪醇聚氧乙烯醚硫酸盐中一种或多种，具体的选自十二烷基硫酸钠、十二烷基苯磺酸钠、十二烷基磷酸钠、十二烷基二苯醚二磺酸钠中的一种或多种。阴离子表面活性剂用量占消泡剂总量的0.03～0.1％，阴离子表面活性剂分为两部分E1和E2使用，E1和E2的质量比为E1：E2＝1.5:1～3:1。
F、增稠剂
本发明所述增稠剂选自汉生胶、瓜尔胶、黄原胶、羟甲基纤维素、羟乙基纤维素、甲基纤维素、聚丙烯酸、聚丙烯酸酰胺中的一种或多种，增稠剂优选黄原胶，增稠剂用量占消泡剂总量的0.02％～0.1％，增稠剂分为两部分F1和F2使用，F1和F2的质量比为F1：F2＝1.5:1～3:1。
G、水
本发明所述水为去离子水，用量占消泡剂总量的60～75％，水分为5部分使用，水G1的用量消泡剂总质量的10.6～17％、水G2的用量占消泡剂总质量的4.4～7％、水G3的用量占消泡剂总质量20～32％、水G4用量占消泡剂总质量的6～15％、水G5的用量占消泡剂总质量的8～20％。
具体实施方式
实施例1
(1)脂肪醇乳液M1制备：将16份脂肪醇(C18：C28＝3:1)和4.27份的十二醚混合升温至55℃搅拌均匀，冷却至室温备用；将10.6份水与0.06份的瓜尔胶混合，加入1.7份的失水山梨醇单硬脂酸酯，再加入0.025份的十二烷基苯磺酸钠，混合均匀升温至50℃；向其中加入混合脂肪醇和十二醚的混合物继续搅拌，再加入7份70℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入32份水搅拌均匀；
(2)石蜡乳液N1的制备：将6份微晶石蜡、3.4份月桂醇聚氧乙烯醚(20)、0.01份十二烷基苯磺酸钠混合，升温至70℃，将7.095份70℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入11.82份水及0.02份瓜尔胶搅拌均匀；
(3)将脂肪醇乳液M1、石蜡乳液N1在常温下混合均匀，即可得本发明消泡剂。
实施例2
(1)脂肪醇乳液M2制备：将30份脂肪醇(C24：C28＝4:1)和1份的十八醚混合升温至70℃搅拌均匀，冷却至室温备用；将12.5的水与0.0375g的黄原胶混合，再加入1.5份失水山梨醇单油酸酯，再加入0.06份十二烷基硫酸钠，混合均匀升温至70℃；向其中加入混合物脂肪醇和十八醚的混合物继续搅拌，再加入5.2份85℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入25.3份水搅拌均匀；
(2)石蜡乳液N2的制备：将6.37份液体石蜡、1份十四醇聚氧乙烯醚(10)、0.02份十二烷基磷酸钠混合，升温至85℃，将7份85℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入10份水及0.0125份黄原胶搅拌均匀；
(3)将脂肪醇乳液M2、石蜡乳液N2在常温下混合均匀，即可得本发明消泡剂。
实施例3
(1)脂肪醇乳液M3制备：将15份脂肪醇(C22：C26＝2:1)和 1.5份的十六醚混合升温至55℃搅拌均匀，冷却至室温备用；将17份水与0.042份羧甲基纤维素混合，再加入2.33份的乙二醇单硬脂酸酯，再加入0.06份十二烷基二苯醚二磺酸钠，混合均匀升温至60℃；向其中加入混合脂肪醇和十六醚的混合物继续搅拌，再加入4.9份80℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入20份水搅拌均匀；
(2)石蜡乳液N3的制备：将5份液体石蜡、1份月桂醇聚氧乙烯醚(15)、0.04份十二烷基苯磺酸钠混合，升温至80℃，将15份80℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入18.1份水及0.028份黄原胶搅拌均匀；
(3)将脂肪醇乳液M3、石蜡乳液N3在常温下混合均匀，即可得本发明消泡剂。
实施例4
(1)脂肪醇乳液M4制备：将15份脂肪醇(C19：C30＝2:1)和1份的癸醚混合升温至65℃搅拌均匀，冷却至室温备用；将16.2份水与0.018份甲基纤维素混合，再加入0.5份二乙二醇单硬脂酸酯，再加入0.03份十二烷基磷酸钠，混合均匀升温至55℃；向其中加入混合脂肪醇和癸醚的混合物继续搅拌，再加入6.4份75℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入25份水搅拌均匀；
(2)石蜡乳液N4的制备：将10份微晶石蜡、1.8份月桂醇聚氧乙烯醚(20)、0.02份十二烷基苯磺酸钠混合，升温至75℃，将 13.02份80℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入11份的水及0.012份甲基纤维素搅拌均匀；
(3)将脂肪醇乳液M4、石蜡乳液N4在常温下混合均匀，即可得本发明消泡剂。
实施例5
(1)脂肪醇乳液M5制备：将16份脂肪醇(C21：C24＝3:1)和5份的十二醚混合升温至65℃搅拌均匀，冷却至室温备用；将14.5份的水与0.012份黄原胶混合，再加入0.8份三硬脂酸甘油酯，再加入0.02份十二烷基苯磺酸钠，混合均匀升温至65℃；向其中加入混合物脂肪醇和十二醚的混合物继续搅拌，再加入4.4份80℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入21.55份水搅拌均匀；
(2)石蜡乳液N5的制备：将8份液体石蜡、0.7份十四醇聚氧乙烯醚(10)、0.01份十二烷基二苯醚二磺酸钠混合，升温至80℃，将9份85℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入20份水和0.008份甲基纤维素搅拌均匀；
(3)将脂肪醇乳液M5、石蜡乳液N5在常温下混合均匀，即可得本发明消泡剂。
实施例6
(1)脂肪醇乳液M6制备：将20.82份脂肪醇(C20：C29＝2.6:1)、1份的十八醚和2份的十二醚混合升温至60℃搅拌均匀，冷却至室温备用；将13.2份的水与0.07份羟乙基纤维素混合，再加入1份乙二 醇二硬脂酸酯、2份单硬脂酸甘油酯，再加入0.05份十二烷基苯磺酸钠，混合均匀升温至60℃；向其中加入混合脂肪醇和十八醚的混合物继续搅拌，再加入5.8份80℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入27份的水搅拌均匀；
(2)石蜡乳液N6的制备：将9份微晶石蜡、4份十三醇聚氧乙烯醚(20)、0.03份十二烷基硫酸钠混合，升温至75℃，将6份80℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入8份的水及0.03份聚丙烯酰胺搅拌均匀；
(3)将脂肪醇乳液M6、石蜡乳液N6在常温下混合均匀，即可得本发明消泡剂。
对比例1
(1)脂肪醇乳液M7制备：将16份C18脂肪醇和4.27份的十二醚混合升温至55℃搅拌均匀，冷却至室温备用；将10.6份水与0.06份的瓜尔胶混合，加入1.7份的失水山梨醇单硬脂酸酯，再加入0.025份的十二烷基苯磺酸钠，混合均匀升温至50℃；向其中加入混合脂肪醇和十二醚的混合物继续搅拌，再加入7份70℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入32份水搅拌均匀；
(2)石蜡乳液N7的制备：将6份微晶石蜡、3.4份月桂醇聚氧乙烯醚(20)、0.01份十二烷基苯磺酸钠混合，升温至70℃，将7.095份70℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入11.82份水及0.02份瓜尔胶搅拌均匀；
(3)将脂肪醇乳液M7、石蜡乳液N7在常温下混合均匀，即可 得本发明消泡剂。
对比例2
(1)脂肪醇乳液M8制备：将30份C28脂肪醇和1份的十八醚混合升温至70℃搅拌均匀，冷却至室温备用；将12.5的水与0.0375g的黄原胶混合，再加入1.5份失水山梨醇单油酸酯，再加入0.06份十二烷基硫酸钠，混合均匀升温至70℃；向其中加入混合脂肪醇和十八醚的混合物继续搅拌，再加入5.2份85℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入25.3份水搅拌均匀；
(2)石蜡乳液N8的制备：将6.37份液体石蜡、1份十四醇聚氧乙烯醚(10)、0.02份十二烷基磷酸钠混合，升温至85℃，将7份85℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入10份水及0.0125份黄原胶搅拌均匀；
(3)将脂肪醇乳液M8、石蜡乳液N8在常温下混合均匀，即可得本发明消泡剂。
对比例3
(1)脂肪醇乳液M9制备：将10份C22和6.5份C26的混合脂肪醇混合升温至55℃搅拌均匀，冷却至室温备用；将17份水与0.042份羧甲基纤维素混合，再加入2.33份的乙二醇单硬脂酸酯，再加入0.06份十二烷基二苯醚二磺酸钠，混合均匀升温至60℃；向其中加入混合脂肪醇继续搅拌，再加入4.9份80℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入20份水搅拌均匀；
(2)石蜡乳液N9的制备：将5份液体石蜡、1份月桂醇聚氧乙 烯醚(15)、0.04份十二烷基苯磺酸钠混合，升温至80℃，将15份80℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入18.1份水及0.028份黄原胶搅拌均匀；
(3)将脂肪醇乳液M9、石蜡乳液N9在常温下混合均匀，即可得本发明消泡剂。
对比例4
(1)脂肪醇乳液M10制备：将16.2份水与0.018份甲基纤维素混合，再加入0.5份二乙二醇单硬脂酸酯，再加入0.03份十二烷基磷酸钠，混合均匀升温至55℃；向其中依次加入15份脂肪醇(C19：C30＝2:1)、1份的癸醚继续搅拌，再加入6.4份75℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入25份水搅拌均匀；
(2)石蜡乳液N10的制备：将10份微晶石蜡、1.8份月桂醇聚氧乙烯醚(20)、0.02份十二烷基苯磺酸钠混合，升温至75℃，将13.02份80℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入11份的水及0.012份甲基纤维素搅拌均匀；
(3)将脂肪醇乳液M10、石蜡乳液N10在常温下混合均匀，即可得本发明消泡剂。
对比例5
(1)脂肪醇乳液M11制备：将16份脂肪醇(C21：C24＝3:1)和5份的十二醚混合升温至65℃搅拌均匀，冷却至室温备用；将18.9份的水与0.012份黄原胶混合，再加入0.8份三硬脂酸甘油酯，再加入0.02份十二烷基苯磺酸钠，混合均匀升温至65℃；向其中加入混 合物脂肪醇和十二醚的混合物继续搅拌，然后通过高速剪切设备进一步乳化，冷却至室温，加入21.55份水搅拌均匀；
(2)石蜡乳液N11的制备：将8份液体石蜡、0.7份十四醇聚氧乙烯醚(10)、0.01份十二烷基二苯醚二磺酸钠混合，升温至80℃，将9份85℃的水缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入20份水和0.008份甲基纤维素搅拌均匀；
(3)将脂肪醇乳液M11、石蜡乳液N11在常温下混合均匀，即可得本发明消泡剂。
对比例6
(1)脂肪醇乳液M12制备：将20.82份脂肪醇(C20：C29＝2.6:1)、1份的十八醚和2份的十二醚混合升温至60℃搅拌均匀，冷却至室温备用；将13.2份的水与0.07份羟乙基纤维素混合，再加入1份乙二醇二硬脂酸酯、2份单硬脂酸甘油酯，再加入0.05份十二烷基苯磺酸钠，混合均匀升温至60℃；向其中加入混合脂肪醇和十八醚的混合物继续搅拌，再加入5.8份80℃的水，然后通过高速剪切设备进一步乳化，冷却至室温，加入27份的水搅拌均匀；
(2)石蜡乳液N12的制备：将9份微晶石蜡、4份十三醇聚氧乙烯醚(20)、0.03份十二烷基硫酸钠混合，升温至75℃，通过高速剪切设备进一步乳化，冷却至室温，加入14份的水及0.03份聚丙烯酰胺搅拌均匀；
(3)将脂肪醇乳液M12、石蜡乳液N12在常温下混合均匀，即可得本发明消泡剂。
性能测试
1、乳液稳定性测试
将上述事例以及对比例制备出的乳液，分别放置在5℃、25℃、40℃下进行6个月粘度跟踪测试。粘度具体测试方法采用NDJ-8型数显粘度仪，2#转子，6rpm条件下进行测试。具体情况见下表1(粘度单位mPa.s，“—”表示乳液成膏体，无法流动)：
表1在不同储存温度下的乳液粘度变化。
Figure PCTCN2020097379-appb-000001
Figure PCTCN2020097379-appb-000002
从粘度跟踪数据可以看出，本发明制备的消泡剂在5℃、25℃、40℃条件下储存6个月，粘度变化幅度较小，显示出了良好的储存稳定性。而对比例1-6制备的脂肪醇乳液粘度在6个月时均有不同程度的增加。
2、消抑泡性能的测试方法：
消泡剂的性能采用循环鼓泡法测定，向循环鼓泡设备中加入600ml白水加热至所需温度，开启流量泵，在8/L min的流量下，循环至泡沫体积300ml，加入6ul消泡剂，记录泡沫体积随时间变化， 相同时间内，体积越小，消抑泡性能越好；泡沫重新达到300ml处的时间越长，则抑泡性能越好。
Figure PCTCN2020097379-appb-000003
Figure PCTCN2020097379-appb-000004
本发明制备的脂肪醇乳液在30℃、55℃下均表现出良好的消抑泡性能.

Claims (7)

  1. 一种脂肪醇乳液消泡剂的制备方法，其特征在于其包括的组分如下：
    A、脂肪醇，所述的脂肪醇为C18-C22脂肪醇和C24-C30脂肪醇的混合物，用量占占消泡剂总质量的15～30％；
    B、醚类，所述的醚类的结构式为：R 1-O-R2，其中R 1和R 2为C10～C18的饱和烷烃基，具体选自癸醚，十二醚，十六醚，十八醚中的一种或多种，用量占消泡剂总质量的1～5％；
    C、石蜡，所述石蜡选自微晶石蜡、液体石蜡，石蜡用量占消泡剂总质量的5～10％；
    D、非离子表面活性剂，所述的非离子表面活性剂分为两类D1和D2，其中非离子表面活性剂D1为一种酯类，由C12-C18的脂肪酸和C2～C6的一元至四元醇酯化形成，非离子表面活性剂D1的用量占消泡剂总量的0.5～3％；非离子表面活性剂D2的结构为R-O-(EO)n-H,其中R为C12～C14烷基，n为10-20整数，D2的用量占消泡剂总量的1～4％；
    E、阴离子表面活性剂，所述阴离子表面活性剂选自烷基磺酸盐、烷基二苯醚二磺酸盐、烷基酚聚氧乙烯醚磷酸酯盐、脂肪醇聚氧乙烯醚硫酸盐中一种或多种；阴离子表面活性剂用量占消泡剂总量的0.03～0.1％，阴离子表面活性剂分为两部分E1和E2使用；
    F、增稠剂，所述增稠剂选自汉生胶、瓜尔胶、黄原胶、羟甲基纤维素、羟乙基纤维素、甲基纤维素、聚丙烯酸、聚丙烯酸酰胺中的一 种或多种；增稠剂用量占消泡剂总量的0.02％～0.1％，增稠剂分为两部分F1和F2使用；
    G、水，所述水为去离子水，用量占消泡剂总量的60～75％，水分为5部分使用；
    一种脂肪醇乳液消泡剂的制备方法，具体步骤如下：
    (1)脂肪醇乳液M制备：将脂肪醇A和醚类B混合升温至55℃-70℃搅拌均匀，冷却至室温备用；将水G1与增稠剂F1混合，再加入非离子表面活性剂D1，再加入阴离子表面活性剂E1，混合均匀升温至50～70℃；向其中加入脂肪醇A和醚类B的混合物继续搅拌，再加入70-85℃的水G2，然后通过高速剪切设备进一步乳化，冷却至室温，加入水G3搅拌均匀；
    (2)石蜡乳液N的制备：将石蜡C、非离子表面活性剂D2、阴离子表面活性剂E2混合，升温至70～85℃，将70-85℃的水G4缓慢加入上述混合物中，通过高速剪切设备进一步乳化，冷却至室温，加入水G5及增稠剂F2搅拌均匀；
    (3)将脂肪醇乳液M、石蜡乳液N在常温下混合均匀，即可得本发明所述的消泡剂。
  2. 如权利要求1所述的一种脂肪醇乳液消泡剂的制备方法，其特征在于所述的C18-C22脂肪醇和C24-C30脂肪醇的质量比为：C18-C22脂肪醇：C24-C30脂肪醇＝4:1-2:1。
  3. 如权利要求1所述的一种脂肪醇乳液消泡剂的制备方法，其特征碍于所述的非离子表面活性剂D1选自失水山梨醇单月桂酸酯 (Span20)、失水山梨醇单棕榈酸酯(Span40)、失水山梨醇单硬脂酸酯(Span60)、三硬脂酸甘油酯、失水山梨醇单油酸酯、单硬脂酸甘油酯、季戊四醇硬脂酸甘油酯、乙二醇单硬脂酸酯、乙二醇二硬脂酸酯、二乙二醇单硬脂酸酯、二乙二醇二硬脂酸酯中一种或多种。
  4. 如权利要求1所述的一种脂肪醇乳液消泡剂的制备方法，其特征在于所述的阴离子表面活性剂选自十二烷基硫酸钠、十二烷基苯磺酸钠、十二烷基磷酸钠、十二烷基二苯醚二磺酸钠中的一种或多种。
  5. 如权利要求1所述的一种脂肪醇乳液消泡剂的制备方法，其特征在于所述的阴离子表面活性剂E1和E2的质量比为E1：E2＝1.5:1-3:1。
  6. 如权利要求1所述的一种脂肪醇乳液消泡剂的制备方法，其特征在于所述的增稠剂F1和F2的质量比为F1：F2＝1.5:1-3:1。
  7. 如权利要求1所述的一种脂肪醇乳液消泡剂的制备方法，其特征在于所述的水G1的用量消泡剂总质量的10.6-17％、水G2的用量占消泡剂总质量的4.4-7％、水G3的用量占消泡剂总质量20-32％、水G4用量占消泡剂总质量的6-15％、水G5的用量占消泡剂总质量的8-20％。
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