A high-stability oil-in-water type high-carbon alcohol emulsion composition and preparation method thereof

Abstract

The invention discloses a high-stability oil-in-water high-carbon alcohol emulsion composition and a preparation method thereof, and belongs to the technical field of degassing agents used in papermaking processes. The invention is composed of the following components in weight percentage: 15-25% of high-carbon alcohol, 1-5% of nonionic emulsifier, 0.5-5% of anionic emulsifier, 1-3% of hydrophilic nanoparticles, 0.5-5% of thickener, and 60-80% of water; wherein the high-carbon alcohol is a fatty alcohol of C16-C28. The invention uses nonionic emulsifiers and anionic emulsifiers to prepare a 60%-70% oil-in-water emulsion with high carbon alcohols of C16-C28. On the basis of high content, the unstable oil phase is accelerated to migrate to the water phase by heating, and then the oil phase entering the water phase is adsorbed by adding hydrophilic nanoparticles. The oil-in-water emulsion composition prepared by the method has high stability, can be stably stored for more than 1 year, and the viscosity change range is small.

Description

Technical Field

[0001] The invention belongs to the technical field of degassing agents used in papermaking processes, and particularly relates to a high-stability oil-in-water type higher-carbon alcohol emulsion composition and a preparation method thereof. Background Art

[0002] Oil-in-water type high-carbon alcohol emulsion compositions have been widely used as degassing agents in papermaking processes. Such degassing agents generally have two defects. On the one hand, the viscosity of the product increases or even solidifies during storage, which makes the product inconvenient during use. On the other hand, the degassing performance of the product is greatly affected by the temperature of the use environment. In severe cases, the performance effects in winter and summer are completely different.

[0003] CN106075961A discloses an emulsion defoamer composed of fatty alcohol, organic hydrocarbon, water-soluble 2-acrylamide-2-methylpropanesulfonic acid homopolymer and / or salt, water-soluble alcohol and non-cationic surfactant. The product stabilizes the fatty alcohol emulsion and inhibits viscosity increase by introducing the water-soluble homopolymer. However, the product still cannot meet the storage period requirement of one year.

[0004] US5807502A discloses a dispersion composed of C10-C28 fatty alcohol, anionic surfactant, C6-C18 fatty diol polyoxyethylene ether and water. The stability of the product during storage is improved by C6-C18 fatty diol polyoxyethylene ether. The raw material of C6-C18 fatty diol polyoxyethylene ether is rare and expensive.

[0005] CN103628353A discloses a method for improving the stability of a fatty alcohol emulsion, wherein the fatty alcohol emulsion is strongly dispersed by a high-speed disperser so that the fatty alcohol particles are evenly dispersed in the water phase, and at the same time, in the preparation process, a high molecular weight polyacrylate dispersant and a high molecular weight polyacrylic acid thickener are used to synergistically act to achieve a good dispersion effect, thereby obtaining a defoamer product with good stability. This method has high requirements on production equipment.

[0006] CN103830937A discloses a method for preparing a stable natural fatty alcohol emulsion, which uses a two-step emulsification method to stabilize the natural fatty alcohol emulsion, wherein the natural fatty alcohol is emulsified and wrapped twice with a nonionic emulsifier, and the natural fatty alcohol is dispersed twice with a dispersant to prevent the aggregation of particles in the emulsion, thereby stabilizing the natural fatty alcohol emulsion, and the obtained natural fatty alcohol emulsion maintains good stability at a wide storage temperature. The emulsion prepared by this method cannot meet the requirement of a 1-year storage period.

[0007] Many researchers have studied and improved the storage stability of high-carbon alcohol emulsions, but they can only improve the product's stability period. Some foreign customers often require a storage period of 1 year or even longer, which is still difficult to meet. Summary of the invention

[0008] In view of the above-mentioned problems existing in the prior art, the technical problem to be solved by the present invention is to provide a high-stability water-in-oil type high-carbon alcohol emulsion composition, which can effectively solve the problem of increased viscosity during product storage; another technical problem to be solved by the present invention is to provide a method for preparing a high-stability water-in-oil type high-carbon alcohol emulsion composition, and the water-in-oil type emulsion composition prepared by the method has high stability, can be stably stored for more than one year, and the viscosity variation range is small.

[0009] In order to solve the above problems, the technical solution adopted by the present invention is as follows:

[0010] A high-stability oil-in-water high-carbon alcohol emulsion composition is composed of the following components in weight percentage: 15-25% of high-carbon alcohol, 1-5% of non-ionic emulsifier, 0.5-5% of anionic emulsifier, 1-3% of hydrophilic nanoparticles, 0.5-5% of thickener, and 60-80% of water; wherein the high-carbon alcohol is a C16-C28 fatty alcohol, and the anionic emulsifier is one or more of carboxylate, sulfonate, sulfate ester, and phosphate ester.

[0011] The nonionic surfactant is selected from one or more of nonylphenol polyoxyethylene (20) ether, stearyl alcohol polyoxyethylene (20) ether, stearic acid polyoxyethylene (20) ether, oleic acid polyoxyethylene (20) ether, castor oil polyoxyethylene (20) ether, sorbitan monostearate, sorbitan monooleate, sorbitan tristearate, sorbitan trioleate, ethylene glycol stearate, ethylene glycol laurate, propylene glycol oleate, propylene glycol stearate, glycerol monostearate, glycerol monolaurate, diethylene glycol monolaurate, pentaerythritol stearate, polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan tristearate, polyethylene glycol 4000 monooleate, and polyethylene glycol 2000 monolaurate.

[0012] The thickener is selected from hydroxyethyl cellulose, carboxymethyl cellulose, xanthan gum, polyacrylamide, and polyacrylic acid.

[0013] Preferably, the high-stability oil-in-water high-carbon alcohol emulsion composition is composed of the following components in weight percentage: 20-25% of high-carbon alcohol, 2-4% of non-ionic emulsifier, 1-3% of anionic emulsifier, 1-3% of hydrophilic nanoparticles, 0.5-5% of thickener, and 70-80% of water; wherein the high-carbon alcohol is selected from C18-C26 fatty alcohol; the non-ionic emulsifier is selected from fatty alcohol polyoxyethylene ether; the anionic emulsifier is selected from sulfonate; the hydrophilic nanoparticles are selected from silicon dioxide; and the thickener is selected from hydroxyethyl cellulose.

[0014] Preferably, the high-stability oil-in-water high-carbon alcohol emulsion composition is composed of the following components in weight percentage: 20% mono-C22 alcohol, 3% stearyl alcohol polyoxyethylene (20) ether, 1% sodium dodecylbenzene sulfonate, 3% hydrophilic nano-silica, 1% hydroxyethyl cellulose, and 72% water.

[0015] Preferably, the higher carbon alcohol is selected from any one of mono-C16 alcohol, mono-C18 alcohol, mono-C20 alcohol, mono-C22 alcohol, mono-C24 alcohol, mono-C26 alcohol, mono-C28 alcohol, C16-C18 mixed alcohol, C18-C26 mixed alcohol, C24-C28 mixed alcohol and C20-C28 mixed alcohol.

[0016] Preferably, the anionic emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl phosphate, and sodium dodecyl diphenyl ether disulfonate.

[0017] Preferably, the hydrophilic nanoparticles are selected from any one of calcium carbonate, silicon dioxide, aluminum oxide and kaolin, and have a particle size of no more than 300 nm.

[0018] A method for preparing a high-stability oil-in-water type higher carbon alcohol emulsion composition, comprising the following steps:

[0019] 1) Mix high carbon alcohol, nonionic emulsifier and anionic emulsifier, stir and heat to 85-100°C, and stir for 30 minutes;

[0020] 2) heating the first portion of water to 85-100° C. and slowly adding it to the mixture obtained in step 1), stirring and heat preservation for 30 minutes, passing the obtained mixture through a homogenizing device after heat preservation, and cooling it to room temperature;

[0021] 3) heating the mixture obtained in step 2) to 40-55° C., adding hydrophilic nanoparticles, stirring at the temperature for 30 min, adding the second portion of water, and cooling to room temperature;

[0022] 4) Adding a thickener to the mixture obtained in step 3) to obtain the target product.

[0023] Preferably, the first portion of water is used in an amount of 5-30%, so that the emulsion content before adding the hydrophilic nanoparticles is 60-70%, and the second portion of water is used in an amount of the balance of water.

[0024] The method for preparing the high-stability oil-in-water high-carbon alcohol emulsion composition prepares the high-stability oil-in-water high-carbon alcohol emulsion composition.

[0025] The high-stability oil-in-water type higher carbon alcohol emulsion composition is used as a degassing agent used in papermaking technology.

[0026] Compared with the prior art, the present invention has the following beneficial effects:

[0027] (1) The present invention uses a nonionic emulsifier and an anionic emulsifier to prepare a 60% to 70% oil-in-water emulsion with a high carbon alcohol of C16 to C28, and heats the formed oil-in-water emulsion to 40 to 55° C. By preparing a high content and heating the emulsion, the unstable oil phase is accelerated to migrate to the water phase, and then hydrophilic nanoparticles are added to absorb the oil phase into the water phase, thereby forming a highly stable oil-in-water emulsion. The oil-in-water emulsion composition prepared by the method has high stability, can be stably stored for more than one year, and has a small viscosity change range;

[0028] (2) The raw materials of the present invention are easily available, the raw material cost is low, the requirements for production equipment are low, and the production process is easy to operate. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical scheme and advantages of the present invention clearer, the present invention is further described below in conjunction with specific embodiments. In the following embodiments, unless otherwise specified, the technical means used are conventional means well known to those skilled in the art.

[0030] Example 1

[0031] A method for preparing a high-stability oil-in-water type higher carbon alcohol emulsion composition, comprising the following steps:

[0032] 1) Mix 20 parts of C22 alcohol, 3 parts of stearyl alcohol polyoxyethylene (20) ether and 1 part of sodium dodecylbenzene sulfonate, stir and heat to 95°C, and keep stirring for 30 minutes;

[0033] 2) 15 parts of water were heated to 90° C. and slowly added to the mixture obtained in step 1), stirred at the temperature for 30 minutes, passed through a homogenizer, and cooled to room temperature;

[0034] 3) heating the mixture obtained in step 2) to 50° C., adding 3 parts of nano-silicon dioxide (particle size of 150 nm), stirring at the temperature for 30 minutes, adding 57 parts of water, and cooling to room temperature;

[0035] 4) Add 1 part of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product.

[0036] Example 2

[0037] A method for preparing a high-stability oil-in-water type higher carbon alcohol emulsion composition, comprising the following steps:

[0038] 1) 15 parts of C18-C26 mixed alcohol, 2 parts of sorbitan monooleate, 3 parts of polyoxyethylene (20) sorbitan monooleate and 5 parts of sodium dodecyl diphenyl ether disulfonate were mixed and stirred, heated to 100° C., and stirred for 30 minutes;

[0039] 2) 15 parts of water were heated to 95° C. and slowly added to the mixture obtained in step 1), stirred at the temperature for 30 minutes, passed through a homogenizer, and cooled to room temperature;

[0040] 3) heating the mixture obtained in step 2) to 45° C., adding 1 part of nano calcium carbonate (particle size of 300 nm), stirring at the temperature for 30 min, adding 54 parts of water, and cooling to room temperature;

[0041] 4) Add 5 parts of polyacrylamide to the mixture obtained in step 3) to obtain the target product.

[0042] Example 3

[0043] A method for preparing a high-stability oil-in-water type higher carbon alcohol emulsion composition, comprising the following steps:

[0044] 1) Mix 15 parts of C16 alcohol, 1 part of glycerol monostearate, 2 parts of oleic acid polyoxyethylene (20) ether and 0.5 parts of sodium lauryl sulfate, stir and heat to 90°C, and keep stirring for 30 minutes;

[0045] 2) 10 parts of water were heated to 85° C. and slowly added to the mixture obtained in step 1), stirred at the temperature for 30 minutes, passed through a homogenizer, and cooled to room temperature;

[0046] 3) heating the mixture obtained in step 2) to 55° C., adding 1 part of nano calcium carbonate (particle size of 150 nm), stirring at the temperature for 30 minutes, adding 70 parts of water, and cooling to room temperature;

[0047] 4) Add 0.5 parts of carboxymethyl cellulose to the mixture obtained in step 3) to obtain the target product.

[0048] Example 4

[0049] A method for preparing a high-stability oil-in-water type higher carbon alcohol emulsion composition, comprising the following steps:

[0050] 1) Mix 25 parts of C24-C28 mixed alcohol, 1 part of polyethylene glycol 2000 monolaurate and 5 parts of sodium lauryl phosphate, stir and heat to 85°C, and keep stirring for 30 minutes;

[0051] 2) Heat 20 parts of water to 95° C. and slowly add it to the mixture obtained in step 1), keep warm and stir for 30 minutes, pass through a homogenizer, and cool to room temperature;

[0052] 3) heating the mixture obtained in step 2) to 40° C., adding 3 parts of nano-alumina (particle size of 100 nm), stirring at the temperature for 30 minutes, adding 44 parts of water, and cooling to room temperature;

[0053] 4) Add 2 parts of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product.

[0054] The specific components and proportions of Examples 1-4 are shown in Table 1 below.

[0055] Table 1 Specific components and proportions of Examples 1-4

[0056]

[0057]

[0058] Comparative Example 1

[0059] The preparation method of the oil-in-water type high-carbon alcohol emulsion composition comprises the following steps:

[0060] 1) Mix 20 parts of C22 alcohol, 3 parts of stearyl alcohol polyoxyethylene (20) ether and 1 part of sodium dodecylbenzene sulfonate, stir and heat to 95°C, and keep stirring for 30 minutes;

[0061] 2) 15 parts of water were heated to 90° C. and slowly added to the mixture obtained in step 1), stirred at this temperature for 30 minutes, and then passed through a homogenizing device;

[0062] 3) adding 3 parts of nano-silicon dioxide (particle size of 150 nm) to the mixture obtained in step 2), stirring at 90° C. for 30 min, adding 57 parts of water, and cooling to room temperature;

[0063] 4) Add 1 part of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product with a viscosity of 487 mPa.s.

[0064] Comparative Example 2

[0065] The preparation method of the oil-in-water type high-carbon alcohol emulsion composition comprises the following steps:

[0066] 1) 20 parts of C22 alcohol, 3 parts of stearyl alcohol polyoxyethylene (20) ether, 1 part of sodium dodecylbenzene sulfonate and 3 parts of nano silicon dioxide (particle size of 150 nm) were mixed and heated to 95° C. and stirred for 30 minutes;

[0067] 2) 15 parts of water were heated to 90° C. and slowly added to the mixture obtained in step 1), stirred at this temperature for 30 minutes, and then passed through a homogenizing device;

[0068] 3) adding 57 parts of water to the mixture obtained in step 2) and cooling to room temperature;

[0069] 4) Add 1 part of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product with a viscosity of 379 mPa.s.

[0070] Comparative Example 3

[0071] The preparation method of the oil-in-water type high-carbon alcohol emulsion composition comprises the following steps:

[0072] 1) Mix 20 parts of C22 alcohol, 3 parts of stearyl alcohol polyoxyethylene (20) ether and 1 part of sodium dodecylbenzene sulfonate, stir and heat to 95°C, and keep stirring for 30 minutes;

[0073] 2) 35 parts of water were heated to 90° C. and slowly added to the mixture obtained in step 1), stirred at the temperature for 30 minutes, passed through a homogenizer, and cooled to room temperature;

[0074] 3) heating the mixture obtained in step 2) to 50° C., adding 3 parts of nano-silicon dioxide (particle size of 150 nm), stirring at the temperature for 30 minutes, adding 37 parts of water, and cooling to room temperature;

[0075] 4) Add 1 part of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product with a viscosity of 425 mPa.s.

[0076] Comparative Example 4

[0077] The preparation method of the oil-in-water type high-carbon alcohol emulsion composition comprises the following steps:

[0078] 1) Mix 20 parts of C22 alcohol, 3 parts of stearyl alcohol polyoxyethylene (20) ether and 1 part of sodium dodecylbenzene sulfonate, stir and heat to 95°C, and keep stirring for 30 minutes;

[0079] 2) 15 parts of water were heated to 90° C. and slowly added to the mixture obtained in step 1), stirred at the temperature for 30 minutes, passed through a homogenizer, and cooled to room temperature;

[0080] 3) adding 3 parts of nano-silicon dioxide (particle size of 150 nm) to step 2), stirring at room temperature for 30 minutes, and then adding 57 parts of water;

[0081] 4) Add 1 part of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product with a viscosity of 447 mPa.s.

[0082] Comparative Example 5

[0083] The preparation method of the oil-in-water type high-carbon alcohol emulsion composition comprises the following steps:

[0084] 1) Mix 20 parts of C22 alcohol, 3 parts of stearyl alcohol polyoxyethylene (20) ether and 1 part of sodium dodecylbenzene sulfonate, stir and heat to 95°C, and keep stirring for 30 minutes;

[0085] 2) 15 parts of water were heated to 90° C. and slowly added to the mixture obtained in step 1), stirred at the temperature for 30 minutes, passed through a homogenizer, and cooled to room temperature;

[0086] 3) heating the mixture obtained in step 2) to 50° C., adding 2 parts of stearyl alcohol polyoxyethylene (20) ether and 1 part of sodium dodecylbenzene sulfonate, stirring at the temperature for 30 minutes, adding 57 parts of water, and cooling to room temperature;

[0087] 4) Add 1 part of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product with a viscosity of 796 mPa.s.

[0088] Comparative Example 6

[0089] The preparation method of the oil-in-water type high-carbon alcohol emulsion composition comprises the following steps:

[0090] 1) Mix 20 parts of C22 alcohol and 4 parts of nano-silicon dioxide (particle size 150 nm), heat to 95°C, and keep stirring for 30 minutes;

[0091] 2) 15 parts of water were heated to 90° C. and slowly added to the mixture obtained in step 1), stirred at the temperature for 30 minutes, passed through a homogenizer, and cooled to room temperature;

[0092] 3) heating the mixture obtained in step 2) to 50° C., adding 3 parts of nano-silicon dioxide (particle size of 150 nm), stirring at the temperature for 30 minutes, adding 57 parts of water, and cooling to room temperature;

[0093] 4) Add 1 part of hydroxyethyl cellulose to the mixture obtained in step 3) to obtain the target product with a viscosity of 521 mPa.s.

[0094] Example 5

[0095] The performance tests of the products prepared in the above embodiments and comparative examples are as follows:

[0096] The product was placed at 25°C for 12 months and the viscosity was followed up. The viscosity test instrument was Brookfield DV2T, and the test conditions were 2# rotor, 6rpm. The specific results are shown in Table 2.

[0097] Table 2 Storage stability test results (unit: mPa.s)

[0098] product Initial viscosity 2 weeks 1 month 3 months 6 months 12 months Example 1 439 476 442 396 413 484 Example 2 574 592 596 613 578 581 Example 3 382 378 393 401 406 397 Example 4 486 501 492 480 517 510 Comparative Example 1 487 258 52 (layered) - - - Comparative Example 2 379 178 67 (layered) - - - Comparative Example 3 425 576 1215 3786 ＞5000 - Comparative Example 4 447 782 2147 4292 ＞5000 - Comparative Example 5 796 1267 3761 ＞5000 - - Comparative Example 6 521 83 (layered) - - - -

[0099] From the viscosity tracking results in Table 2, it can be seen that the product prepared in the present application can be stably stored for 12 months.

[0100] In summary, Example 1 of the present invention is the optimal embodiment, in which high carbon alcohol is prepared into a 60% to 70% high-content oil-in-water emulsion using a nonionic emulsifier and an anionic emulsifier, and the formed oil-in-water emulsion is heated to 40 to 55°C. By preparing a high content and heating the emulsion, the migration of the oil phase to the water phase is accelerated, and then the oil phase is adsorbed into the water phase by adding hydrophilic nanoparticles, thereby forming a high-stability oil-in-water emulsion.

[0101] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and variations. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A method for preparing a high-stability oil-in-water type higher carbon alcohol emulsion composition, characterized in that: The high-stability oil-in-water type high-carbon alcohol emulsion composition is composed of the following components in weight percentage: 15-25% of high-carbon alcohol, 1-5% of nonionic emulsifier, 0.5-5% of anionic emulsifier, 1-3% of hydrophilic nanoparticles, 0.5-5% of thickener, and 60-80% of water; specifically comprising the following steps: 1) Mix high carbon alcohol, nonionic emulsifier and anionic emulsifier, stir and heat to 85-100℃, and keep stirring for 30 minutes; 2) heating the first part of water to 85-100° C. and slowly adding it to the mixture obtained in step 1), wherein the amount of the first part of water is 5-30%, so that the emulsion content before adding the hydrophilic nanoparticles is 60-70%, and stirring for 30 minutes at the same temperature. After the temperature is maintained, passing the obtained mixture through a homogenizing device and cooling it to room temperature; 3) heating the mixture obtained in step 2) to 40-55° C., adding hydrophilic nanoparticles, stirring at the temperature for 30 min, adding the remaining amount of water and cooling to room temperature; 4) adding a thickener to the mixture obtained in step 3) to obtain the target product; The anionic emulsifier is selected from one or more of sodium dodecyl sulfate, sodium dodecylbenzene sulfonate, sodium dodecyl phosphate, and sodium dodecyl diphenyl ether disulfonate; The hydrophilic nanoparticles are selected from any one of calcium carbonate, silicon dioxide, aluminum oxide, and kaolin, and have a particle size of no more than 300 nm; The high carbon alcohol is selected from any one of mono-C16 alcohol, mono-C18 alcohol, mono-C20 alcohol, mono-C22 alcohol, mono-C24 alcohol, mono-C26 alcohol, mono-C28 alcohol, C16-C18 mixed alcohol, C18-C26 mixed alcohol, C24-C28 mixed alcohol, and C20-C28 mixed alcohol.

2. The method for preparing the high-stability oil-in-water higher alcohol emulsion composition according to claim 1, characterized in that: The high-stability oil-in-water high-carbon alcohol emulsion composition is composed of the following components in weight percentage: 20-25% of high-carbon alcohol, 2-4% of nonionic emulsifier, 1-3% of anionic emulsifier, 1-3% of hydrophilic nanoparticles, 0.5-5% of thickener, and 70-80% of water; wherein the high-carbon alcohol is selected from C18-C26 fatty alcohol; the nonionic emulsifier is selected from fatty alcohol polyoxyethylene ether; the anionic emulsifier is selected from sulfonate; the hydrophilic nanoparticles are selected from silicon dioxide; and the thickener is selected from hydroxyethyl cellulose.

3. The method for preparing the high-stability oil-in-water higher alcohol emulsion composition according to claim 1, characterized in that: The high-stability oil-in-water high-carbon alcohol emulsion composition is composed of the following components in weight percentage: 20% of mono-C22 alcohol, 3% of stearyl alcohol polyoxyethylene (20) ether, 1% of sodium dodecylbenzene sulfonate, 3% of hydrophilic nano-silica, 1% of hydroxyethyl cellulose, and 72% of water.

4. The method for preparing the high-stability oil-in-water higher carbon alcohol emulsion composition according to any one of claims 1 to 3 is used to prepare a high-stability oil-in-water higher carbon alcohol emulsion composition.

5. Use of the high-stability oil-in-water higher alcohol emulsion composition according to claim 4 as a degassing agent used in papermaking process.

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