CN103721582A - Preparation method of microemulsion for forming nano emulsion with high stability in situ - Google Patents
Preparation method of microemulsion for forming nano emulsion with high stability in situ Download PDFInfo
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- CN103721582A CN103721582A CN201210393477.1A CN201210393477A CN103721582A CN 103721582 A CN103721582 A CN 103721582A CN 201210393477 A CN201210393477 A CN 201210393477A CN 103721582 A CN103721582 A CN 103721582A
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Abstract
The invention relates to a preparation method of a microemulsion for forming a nano emulsion with high stability in situ, and belongs to the technical field of nano emulsion preparation. The method is characterized by at least comprising the following steps: respectively weighing the following components in 100 parts by weight: 45-76 parts of oil phase, 19-45 parts of nonionic surfactant, 0-2.5 parts of inorganic salt, 0.1-2 parts of cationic surfactant and the balance of water, subsequently dissolving the weighed cationic surfactant and the inorganic salt into water so as to obtain water phase, further uniformly mixing the weighed oil phase and the nonionic surfactant with the prepared water phase, adding into a flask so as to obtain the microemulsion which can be prepared into the nano emulsion with high stability in situ. The invention provides the method for preparing the microemulsion for forming the nano emulsion with high stability in situ, and the microemulsion is low in cost and is not easy to cause phenomena such as layering when being put into high and low environment.
Description
Technical field
The invention belongs to nanoemulsions preparing technical field.Relate to the preparation method of microemulsion that a kind of original position forms the nanoemulsions of high stability.
Background technology
Nanoemulsions is all widely used in fields such as oil exploitation, medicine, food, building energy conservation, concrete water-saving maintenance, agricultural, papermaking, wood-based plate, special cermacis, light industrys.
Inventor once applied for < < multifunctional drilling fluid additive and preparation method thereof and application > > before this, nanoemulsions in this patent has good lubricated texts, but in high and low temperature environment, place after a period of time, easily there is the phenomenons such as layering, lose original effect.
Summary of the invention
The preparation method who the invention provides that a kind of cost is low, places the microemulsion of the nanoemulsions that a kind of original position that is difficult for occurring the phenomenons such as layering forms high stability in high and low temperature environment.
The object of the present invention is achieved like this, a kind of original position forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: at least comprise: oil phase, nonionic surface active agent, inorganic salts, cationic surfactant, in 100 weight portions, take respectively following component: oil phase 45-76 part, nonionic surface active agent 19-45 part, inorganic salts 0-2.5 part, cationic surfactant 0.1-2 part, surplus is water; Then the cationic surfactant taking is dissolved in water together with inorganic salts, obtains water; Again the oil phase taking, non-ionic surface active agent and the water that makes are mixed, and add in beaker, with the rotating speed of 150-500 rev/min, stir after 10-40 minute at normal temperatures standingly, obtain can original position forming the microemulsion of the nanoemulsions of high stability.
Under 70 ° of C, to utilize above-mentioned microemulsion is diluted to water content for 70wt%, original position formation aqueous phase content is the nanoemulsions of 70 parts, translucent blueing light, narrow diameter distribution, the polydispersion factor is less than 0.2, and particle diameter is distributed between 50nm-200nm.
Described speed of agitator is 200-300 rev/min.
Described oil phase is alkane, that is: the mixture of linear paraffin or n-alkane and isoparaffin; Described linear paraffin is decane, n-dodecane, n-tetradecane or hexadecane; Described n-alkane and the mixture of isoparaffin are atoleine or white oil.
Described non-ionic surface active agent is that polyethenoxy ether class non-ionic surface active agent and polyol ester class non-ionic surface active agent are by weight the mixture of 44:56; Described polyethenoxy ether class non-ionic surface active agent is Span20, Span40, Span60 or Span65; Described polyol ester class non-ionic surface active agent Tween20, Tween40, Tween60, Tween65 or Tween80.
Described inorganic salts are the mixture of sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt or these five kinds of any part by weight of inorganic salts.
Described cationic surfactant is that alkyl trimethyl ammonium bromide or alkyl trimethyl ammonium chloride are DTAB, TTAB, CTAB, DTAC, one of TTAC; Described pair of alkyl chain cationic surfactant is DDAB, DODAC, one of DODAB.
Described oil phase is 45 parts of 45 parts of white oils or atoleines preferably, and preferred non-ionic surface active agent is the mixture of 26.4 parts of Span80 and 33.6 parts of Tween80, and cationic surfactant is 2 parts of CTAB.
Described inorganic salts are NaCl, NaBr, KCl, KBr, Na
2s0
4, K
2s0
4, MgCl
2, MgBr
2, CaCl
2, MgS0
4, AlCl
3.
The microemulsion outward appearance that original position prepared by the present invention forms high-stability nano emulsion is transparent or semitransparent liquid, narrow diameter distribution, there is good long-time stability, high-temperature stability, low-temperature stability, control strip electric weight easily, meet environmental protection and every industrial requirements, be easy to transportation, the nanoemulsions that utilizes this microemulsion can original position to form good stability, can place for a long time.
Accompanying drawing explanation
Below in conjunction with embodiment and accompanying drawing, the invention will be further described:
Accompanying drawing 1 is the microemulsion that adds the CTAB of variable concentrations in the present invention, the particle diameter distribution map of the nanoemulsions obtaining after original position dilution.
Accompanying drawing 2 is the different microemulsions that add different cationic surfactants to prepare in the present invention, the particle diameter distribution map of the nanoemulsions obtaining after original position dilution.
The specific embodiment
Embodiment 1
In 100 weight portions, get 76 parts of white oils, 8.36 parts of Span80,10.64 parts of Tween80,0.1 part of CTAB, 5 parts of water, wherein Span80 and Tween80 are totally 19 parts, and both weight ratios are 11:14.Then be placed in reactor and mix together, the rotating speed stirring with 500 revs/min under normal temperature can be made into microemulsion for 10 minutes.
In example, nonionic surface active agent used is all purchased from Chemical Reagent Co., Ltd., Sinopharm Group (No. 52, Ningbo road, Shanghai City postcode 200002), and cationic surfactant is all liked Sha (Tianjin) Chemical Co., Ltd. (CBD International Building, No. 16, East, Yongan, Chaoyang District, Beijing City 1509 postcodes 100022) purchased from Alpha.
The particle diameter of the nanoemulsions that after microemulsion high-temperature stability, long-time stability, low-temperature stability and the dilution of the original position synthesis of nano emulsion that by the following method prepared by investigation respectively, original position forms distributes:
1. stability measurement:
Long-time stability: the long-time static placement of product, observe outward appearance, note whether occurring layering clearly, if product is placed half a year, above outward appearance is unchanged, without obvious layering and sedimentation phenomenon.
High-temperature stability: sample is placed in 70 ° of C insulating boxs to 5 hours, observes outward appearance, whether layering or sedimentation, if product was placed at 70 ℃ after 4-5 hour, outward appearance is unchanged,, without obvious layering and sedimentation phenomenon, illustrates that emulsion high-temperature stability is good.
Low-temperature stability: sample is placed on to refrigerator freezing layer (approximately-17 ° of C), observes outward appearance, whether layering or sedimentation, if product is placed on freezing 1-2 hour at-15 to-20 ℃, outward appearance is unchanged,, without obvious layering and sedimentation phenomenon, illustrates that emulsion low-temperature stability is good.
2. grain diameter measurement:
After microemulsion is diluted to aqueous phase content in the process constantly stirring is 70wt% water, during dilution, temperature maintains 70 ° of C.
Get proper amount of nano emulsion and in measuring element, dilute general 500 times, be then placed in BI-200SM dynamic light scattering, the particle diameter of measuring emulsion distributes, and the particle diameter of emulsion distributes narrower, and average grain diameter is less, and the stability of emulsion is better.
Result is as shown in the table:
Embodiment 2
In 100 weight portions, get 45 parts of atoleines, 19.8 parts of Span80,25.2 parts of Tween80,2 parts of CTAB and 8 parts of water, wherein Span80 and Tween80 are totally 45 parts, both weight ratios are 11:14(0.7857).2 parts of CTAB are dissolved in 8 parts of water, obtain water; Again 45 parts of atoleines, 19.8 parts of Span80 and 25.2 parts of Tween80 are mixed in reactor with the water making, under normal temperature, with 300 revs/min, stir and within 15 minutes, can be made into microemulsion.
By method described in embodiment 1, detect, result is as follows:
| Product appearance | Transparent translucent |
| Long-time stability | Place not layering in 1 month |
| High-temperature stability | Stable |
| Low-temperature stability | Stable |
| Outside the rear nanoemulsions of dilution | The micro-blueing light of milky |
| See | |
| Nanoemulsions initial particle | 74.5nm |
| Nanoemulsions stability | Place not layering in 1 month |
Embodiment 3
In 100 weight portions, get 76 parts of white oils, 8.36 parts of Span80,10.64 parts of Tween80,1 part of DODMAC, 4 parts of water, wherein Span80 and Tween80 are totally 19 parts, and both weight ratios are 11:14.Then be placed in reactor and mix together, the rotating speed stirring with 150 revs/min under normal temperature can be made into microemulsion for 40 minutes.
By method described in embodiment 1, detect, result is as follows:
Embodiment 4
In 100 weight portions, get 45 parts of atoleines, 19.8 parts of Span80,25.2 parts of Tween80,2.5 parts of NaCl, 2 parts of CTAB and 5.5 parts of water, wherein Span80 and Tween80 are totally 45 parts, both weight ratios are 11:14(0.7857).2.5 parts of NaCl and 2 parts of CTAB are dissolved in 5.5 parts of water, obtain water; Again 45 parts of atoleines, 19.8 parts of Span80 and 25.2 parts of Tween80 are mixed in reactor with the water making, under normal temperature, with 250 revs/min, stir and within 20 minutes, can be made into microemulsion.
By method described in embodiment 1, detect, result is as follows:
Embodiment 5
In 100 weight portions, get 76 parts of atoleines, 8.36 parts of Span80,10.64 parts of Tween80,1.5 parts of CaCl
2, 1 part of NaCl, 1 part of CTAB and 5.5 parts of water, wherein Span80 and Tween80 are totally 45 parts, both weight ratios are 11:14(0.7857).By 1.5 parts of CaCl
2with 1 part of NaCl
2, 1 part of CTAB is dissolved in 5.5 parts of water, obtains water; Again 45 parts of atoleines, 8.36 parts of Span80 and 10.64 parts of Tween80 are mixed in reactor with the water making, under normal temperature, with 300 revs/min, stir and within 15 minutes, can be made into microemulsion.
By method described in embodiment 1, detect, result is as follows:
Embodiment 6
In 100 weight portions, get 60 parts of atoleines, 13.2 parts of Span80,16.8 parts of Tween80,1 part of DTAB and 9 parts of water, wherein Span80 and Tween80 are totally 30 parts, both weight ratios are 11:14(0.7857).1 part of CTAB is dissolved in 9 parts of water, obtains water; Again 60 parts of atoleines, 13.2 parts of Span80 and 16.8 parts of Tween80 are mixed in reactor with the water making, under normal temperature, with 350 revs/min, stir and within 25 minutes, can be made into microemulsion.
By method described in embodiment 1, detect, result is as follows:
Inorganic salts of the present invention are the mixture of sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt or these five kinds of any part by weight of inorganic salts.The preferred NaCl of described inorganic salts, NaBr, KCl, KBr, Na
2s0
4, K
2s0
4, MgCl
2, MgBr
2, CaCl
2, MgS0
4, AlCl
3.Described cationic surfactant is DTAB, TTAB, and CTAB, DTAC, TTAC, DDAB, DODAC, DODAB mono-all can.
The part that the present embodiment does not describe in detail and english abbreviation belong to the common practise of the industry, can search on the net, here not narration one by one.
Claims (9)
1. an original position forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: at least comprise: oil phase, nonionic surface active agent, inorganic salts, cationic surfactant, in 100 weight portions, take respectively following component: oil phase 45-76 part, nonionic surface active agent 19-45 part, inorganic salts 0-2.5 part, cationic surfactant 0.1-2 part, surplus is water; Then the cationic surfactant taking is dissolved in water together with inorganic salts, obtains water; Again the oil phase taking, non-ionic surface active agent and the water that makes are mixed, and add in beaker, with the rotating speed of 150-500 rev/min, stir after 10-40 minute at normal temperatures standingly, obtain can original position forming the microemulsion of the nanoemulsions of high stability.
2. a kind of original position according to claim 1 forms the microemulsion preparation method of the nanoemulsions of high stability, it is characterized in that: under 70 ° of C, utilization is diluted to water content for 70wt% by above-mentioned microemulsion, original position formation aqueous phase content is the nanoemulsions of 70 parts, translucent blueing light, narrow diameter distribution, the polydispersion factor is less than 0.2, and particle diameter is distributed between 50nm-200nm.
3. a kind of original position according to claim 1 forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: described speed of agitator is 200-300 rev/min.
4. a kind of original position according to claim 1 forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: described oil phase is alkane, that is: the mixture of linear paraffin or n-alkane and isoparaffin; Described linear paraffin is decane, n-dodecane, n-tetradecane or hexadecane; Described n-alkane and the mixture of isoparaffin are atoleine or white oil.
5. a kind of original position according to claim 1 forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: described non-ionic surface active agent is polyethenoxy ether class non-ionic surface active agent and the polyol ester class non-ionic surface active agent mixture of 44:56 by weight; Described polyethenoxy ether class non-ionic surface active agent is Span20, Span40, Span60 or Span65; Described polyol ester class non-ionic surface active agent Tween20, Tween40, Tween60, Tween65 or Tween80.
6. a kind of original position according to claim 1 forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: described inorganic salts are the mixture of sodium salt, sylvite, magnesium salts, calcium salt, aluminium salt or these five kinds of any part by weight of inorganic salts.
7. a kind of original position according to claim 1 forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: described cationic surfactant is that alkyl trimethyl ammonium bromide or alkyl trimethyl ammonium chloride are DTAB, TTAB, CTAB, DTAC, one of TTAC; Described pair of alkyl chain cationic surfactant is DDAB, DODAC, one of DODAB.
8. a kind of original position according to claim 1 forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: described oil phase is 45 parts of 45 parts of white oils or atoleines, non-ionic surface active agent is the mixture of 26.4 parts of Span80 and 33.6 parts of Tween80, and cationic surfactant is 2 parts of CTAB.
9. a kind of original position according to claim 1 forms nanoemulsions and the microemulsion preparation method of high stability, it is characterized in that: described inorganic salts are NaCl, NaBr, KCl, KBr, Na
2s0
4, K
2s0
4, MgCl
2, MgBr
2, CaCl
2, MgS0
4, AlCl
3.
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Cited By (7)
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| CN105038735A (en) * | 2015-06-03 | 2015-11-11 | 中国海洋石油总公司 | Environment-friendly microemulsion capable of being dispersed into nano liquid drops in situ and preparation method thereof |
| CN108114617A (en) * | 2017-12-13 | 2018-06-05 | 中国石油大学(北京) | A kind of small particle super low concentration nano-emulsion composition and preparation method thereof |
| CN109233788A (en) * | 2018-10-31 | 2019-01-18 | 重庆地质矿产研究院 | Nano-emulsion cleanup additive for unconventional gas reservoir fracturing and preparation method thereof |
| CN109467108A (en) * | 2019-01-06 | 2019-03-15 | 中盐金坛盐化有限责任公司 | A kind of preparation method of nano level superfine sodium chloride |
| CN109773207A (en) * | 2019-02-01 | 2019-05-21 | 山东青年政治学院 | Using the method for nano oil-in-water emulsion preparation branch-like gold nano grain |
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| CN101721930A (en) * | 2009-12-15 | 2010-06-09 | 山东大学 | Low-energy preparation method of positive electricity nanometer emulsion |
| CN102698622A (en) * | 2012-06-20 | 2012-10-03 | 山东大学 | Micro-emulsion for forming nano-emulsion in situ and preparation method of micro-emulsion |
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Patent Citations (2)
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| CN101721930A (en) * | 2009-12-15 | 2010-06-09 | 山东大学 | Low-energy preparation method of positive electricity nanometer emulsion |
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| CN105038735A (en) * | 2015-06-03 | 2015-11-11 | 中国海洋石油总公司 | Environment-friendly microemulsion capable of being dispersed into nano liquid drops in situ and preparation method thereof |
| CN108114617A (en) * | 2017-12-13 | 2018-06-05 | 中国石油大学(北京) | A kind of small particle super low concentration nano-emulsion composition and preparation method thereof |
| US10800892B2 (en) | 2017-12-13 | 2020-10-13 | China University Of Petroleum-Beijing | Composition of nano-emulsion having small particle size and ultra-low concentration and a preparation method thereof |
| CN109233788A (en) * | 2018-10-31 | 2019-01-18 | 重庆地质矿产研究院 | Nano-emulsion cleanup additive for unconventional gas reservoir fracturing and preparation method thereof |
| CN109467108A (en) * | 2019-01-06 | 2019-03-15 | 中盐金坛盐化有限责任公司 | A kind of preparation method of nano level superfine sodium chloride |
| CN109467108B (en) * | 2019-01-06 | 2020-12-01 | 中盐金坛盐化有限责任公司 | Preparation method of nano-grade superfine sodium chloride |
| CN109773207A (en) * | 2019-02-01 | 2019-05-21 | 山东青年政治学院 | Using the method for nano oil-in-water emulsion preparation branch-like gold nano grain |
| CN111892117A (en) * | 2020-08-07 | 2020-11-06 | 吉林大学 | Microemulsion for solubilizing chlorinated hydrocarbon pollutants in underground environment and preparation method thereof |
| CN114832865A (en) * | 2022-06-15 | 2022-08-02 | 中国石油大学(华东) | Preparation method of molybdenum-based microemulsion catalyst applied to hydrocracking |
| CN114832865B (en) * | 2022-06-15 | 2023-08-22 | 中国石油大学(华东) | Preparation method of molybdenum-based microemulsion catalyst applied to hydrocracking |
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