CN101108324B - Emulsion of hyperstable latex capable of varying phase of circulation - Google Patents
Emulsion of hyperstable latex capable of varying phase of circulation Download PDFInfo
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- CN101108324B CN101108324B CN2007100259923A CN200710025992A CN101108324B CN 101108324 B CN101108324 B CN 101108324B CN 2007100259923 A CN2007100259923 A CN 2007100259923A CN 200710025992 A CN200710025992 A CN 200710025992A CN 101108324 B CN101108324 B CN 101108324B
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- emulsion
- emulsifying agent
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- calcium carbonate
- water
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- 239000000839 emulsion Substances 0.000 title claims abstract description 56
- 239000004816 latex Substances 0.000 title 1
- 229920000126 latex Polymers 0.000 title 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 31
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 31
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- -1 dope Substances 0.000 claims abstract description 8
- 239000012736 aqueous medium Substances 0.000 claims abstract description 5
- 239000008346 aqueous phase Substances 0.000 claims abstract description 4
- 239000003973 paint Substances 0.000 claims abstract description 4
- 239000003921 oil Substances 0.000 claims description 29
- 239000012071 phase Substances 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 15
- 239000002563 ionic surfactant Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 12
- 238000004945 emulsification Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000000295 fuel oil Substances 0.000 claims description 5
- 239000003905 agrochemical Substances 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011164 primary particle Substances 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 241001465754 Metazoa Species 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 239000002283 diesel fuel Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000003502 gasoline Substances 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 238000000034 method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000000084 colloidal system Substances 0.000 abstract description 2
- 239000000575 pesticide Substances 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 4
- 239000003795 chemical substances by application Substances 0.000 abstract 4
- 239000000446 fuel Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 3
- 239000005946 Cypermethrin Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 2
- 229960005424 cypermethrin Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007764 o/w emulsion Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- YCSMVPSDJIOXGN-UHFFFAOYSA-N CCCCCCCCCCCC[Na] Chemical compound CCCCCCCCCCCC[Na] YCSMVPSDJIOXGN-UHFFFAOYSA-N 0.000 description 1
- 241000594182 Sarcophaga sigma Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940126680 traditional chinese medicines Drugs 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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- Colloid Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
An super stable emulsion emulsifier which can make the circle direction change is provided, which belongs to surface activating agent and colloid field. The invention is composed of Nami calcium carbonate grains without modification and ion-typed surface activating agent The Nami calcium carbonate grains and the ion-typed surface activating agent take effect to each other in aqueous medium, whichchanges the surface humidity of the Nami grains at site and makes the Nami grains have surface activity, thus be able of collecting or adsorbing on oil or water interface, and make the emulsion stable; with changing the usage proportion of the Nami calcium carbonate grains (adding concentration is counted by emulsion aqueous phase weight as 0.5 per cent to 6 per cent) and the ion-typed surface activating agent (the using concentration is counted by emulsion aqueous phase volume as 1 multiply 10 to 6 to 0.5 mol L-1) to realize circle direction change, namely from oil in water (O/W) to water inoil (W/O), then change into oil in water (O/W). The emulsifier can be used in pesticide, paint, dope, oil production, fuel watering and multiple technology field.
Description
Technical field
The present invention relates to the emulsifying agent and the application thereof of a kind of overstable oil-in-water (O/W) or Water-In-Oil (W/O) emulsion, use this emulsifying agent can realize the circulation phase inversion of emulsion by the composition that changes emulsifying agent, belong to surfactant and colloid field, relate to agricultural chemicals, paint, coating, oil recovery, fuel oil and add a plurality of applied technical fields such as water.
Technical background
As everyone knows, only can in certain time limit, keep stable, promptly have limited dynamic stability with the stable emulsion of conventional surfactants.This in essence emulsion is thermodynamic unstable system, between the storage life sedimentation, layering can take place, coalescent and final shared oil/water two-phase.The unstability of emulsion brings a series of problem for the application of emulsion.It is found that in recent years the appropriate nano particle of surface wettability can accumulate in oil/water termination, thus can stable emulsion.The contact angle that forms when nano particle and oil/water termination is during 90 ° of left and right sides, and nano particle almost is irreversible in the gathering (absorption) at interface, and the stable emulsion of nano particle has superstability thus, can maintain a long-term stability.Usually inorganic nanoparticles has stronger hydrophily, and they trend towards being dispersed in the water, is difficult for assembling in oil/water termination.Make them become good emulsion stabilizer, need carry out surface modification usually.But modification causes cost to increase considerably.The present invention uses the inorganic nano calcium carbonate granule of non-modified, by in aqueous medium, changing the surface wettability of nano particle on the spot with the interaction of ionic surfactant (parents' compound), thereby make it have surface-active, can assemble or be adsorbed on oil/water termination, become the stabilizing agent of emulsion.Can prepare multiple overstable emulsion with this nano particle/parents' compound compound emulsifying agent, both can be the O/W type, also can be w/o type, and can realize that by the ratio that changes nano particle/parents' compound circulation changes mutually.
Summary of the invention
The object of the present invention is to provide a kind of emulsifying agent of overstable emulsion.Can prepare multiple overstable O/W or w/o type emulsion with this emulsifying agent.Can realize that by the composition that changes emulsifying agent the circulation of emulsion changes mutually, promptly change w/o type into, change the O/W type again into from the O/W type.
Technical scheme of the present invention: a kind of emulsifying agent of the overstable emulsion of transformation mutually that can cause circulating, adopt the nano-calcium carbonate particles of non-modified, in aqueous medium and the alkyl carbon atoms number be that 10 to 18 ionic surfactant interacts, change the surface wettability of nano particle on the spot, make nano particle have surface-active, thereby can assemble or be adsorbed on oil/water termination, stable emulsion.
Realize that by the usage ratio that changes nano-calcium carbonate particles and ionic surfactant the circulation of emulsion changes mutually;
The primary particle diameter of used nano-calcium carbonate particles is 20-200nm, adds concentration and counts 0.5%-6% with emulsion water weight.
Ionic surfactant is selected C for use
10-C
18Straight or branched, saturated or unsaturated, contain or do not contain benzene ring structure, contain or do not contain polyoxyethylene groups, its hydrophilic group partly is a sulfate, sulfonate, carboxylate, amine salt or quaternary ammonium salt, working concentration counts 1 * 10 with emulsion water volume
-6～0.5mol L
-1
Ionic surfactant is preferably with lauryl sodium sulfate or softex kw.
Play the oil phase of the overstable emulsion of emulsification by this emulsifying agent and select mineral oil for use: gasoline, kerosene, diesel oil or heavy oil, or hydro carbons: alkane, cycloalkane or aromatic hydrocarbons, animals and plants oils, fatty acid ester, polar organic matter: C
5-C
20Fatty alcohol, aliphatic acid or fatty amine, the volume fraction of oil phase is 10%-80% in the emulsion.
The aqueous phase that is played the overstable emulsion of emulsification by this emulsifying agent contains or does not contain monovalence or multivalence electrolyte.
The preparation method of described emulsifying agent is with in the ultrasonic aqueous solution that is dispersed in ionic surfactant of nano-calcium carbonate particles.
Beneficial effect of the present invention: the invention provides the emulsifying agent and the application thereof of a kind of overstable oil-in-water (O/W) or Water-In-Oil (W/O) emulsion, emulsifying agent of the present invention is made up of the nano-calcium carbonate particles and the ionic surfactant of non-modified.Nano-calcium carbonate particles interacts at aqueous medium neutralize ions type surfactant, changes the surface wettability of nano particle on the spot, makes nano particle have surface-active, thereby can assemble or be adsorbed on oil/water termination, stable emulsion; (working concentration counts 1 * 10 with emulsion water volume by changing nano-calcium carbonate particles (add concentration and count 0.5%-6% with emulsion water weight) and ionic surfactant
-6～0.5mol L
-1) usage ratio realize that circulation changes mutually, promptly change Water-In-Oil (W/O) type into from oil-in-water (O/W) type, change oil-in-water (O/W) type again into.This kind emulsifying agent can be applied to agricultural chemicals, paint, coating, oil recovery, fuel oil and add a plurality of technical fields such as water.
Description of drawings
The microphoto of the O/W type emulsion that Fig. 1 nano-calcium carbonate/CTAB is stable, oil phase is a normal octane, profit volume ratio 1: 1.(a) 1% nano-calcium carbonate+1 * 10
-6Mol L
-1CTAB, (b) 4% nano-calcium carbonate+1 * 10
-6Mol L
-1CTAB.
Figure 22 % nano-calcium carbonate+1 * 10
-5Mol L
-1The O/W type emulsion that CTAB is stable, oil phase is a toluene, profit volume ratio 1: 1.
The microphoto of the emulsion that Fig. 3 nano-calcium carbonate/SDS is stable.Oil phase is a toluene, oil/water volume ratio 1: 1.(a) 2% nano-calcium carbonate+1 * 10
-4Mol L
-1SDS, O/W type, (b) 2% nano-calcium carbonate+3 * 10
-3Mol L
-1SDS, w/o type, (c) 2% nano-calcium carbonate+0.1mol L
-1SDS, the O/W type.
The specific embodiment
In order to understand the present invention in depth, elaborate below in conjunction with embodiment.
Nano-calcium carbonate is sky, a Yixing power building materials chemical industry Co., Ltd product, content＞98%, average aggregated particle size＜3 μ m, average primary particle diameter 80-100nm.Lauryl sodium sulfate (SDS) is a U.S. Sigma company product, and purity＞99%, softex kw (CTAB) are chemical reagents corporation of traditional Chinese medicines group product, purity＞99%.
Embodiment 1
Under the room temperature, (50W 2min) is scattered in 10mL with the nano-calcium carbonate of 0.1g and 0.4g non-modified respectively and contains 1 * 10 with ultrasonic disperser
-6Mol L
-1In the CTAB aqueous solution, add the 10mL normal octane, with high-shear emulsion machine emulsification 3 minutes under 5000 rev/mins of rotating speeds.Obtain stable oil-in-water emulsion, liquid pearl size is bigger, and as seen naked eyes but reduce with the increase of concentrations of nanoparticles, Fig. 1 (a) and (b) be microphoto.
Embodiment 2
Under the room temperature, with ultrasonic disperser the nano-calcium carbonate of 0.2g non-modified is scattered in 10mL and contains 1 * 10
-5Mol L
-1In the CTAB aqueous solution, add 10mL toluene, with high-shear emulsion machine emulsification 3 minutes under 5000 rev/mins of rotating speeds.Obtain stable oil-in-water emulsion, liquid pearl size is bigger, and naked eyes as seen.Fig. 2 is a microphoto.
Embodiment 3
Under the room temperature, respectively the nano-calcium carbonate of 0.2g non-modified is scattered in the SDS aqueous solution of 10mL variable concentrations, adds 10mL toluene, with high-shear emulsion machine emulsification 3 minutes under 5000 rev/mins of rotating speeds with ultrasonic disperser.Obtain dissimilar emulsion.When SDS concentration less than 2.5 * 10
-3Mol L
-1, emulsion is the O/W type, when SDS concentration 2.5 * 10
-3～8 * 10
-3Mol L
-1The time, emulsion is w/o type, when SDS concentration greater than 8 * 10
-3Mol L
-1The time, emulsion changes the O/W type again into.Fig. 3 (a) (b) (c) is a microphoto.
Embodiment 4
Operation is with example 3, and SDS concentration is 0.1mol/L, is dissolved with the solid pesticide effective cypermethrin in the oil phase toluene, and content 50g cypermethrin/100g toluene obtains overstable O/W emulsion.
Above-mentioned overstable emulsion is gone through more than 1 year and is stored, and any coalescent wild effect does not take place.
Claims (8)
1. the preparation method of the emulsifying agent of the overstable emulsion that changes of causing circulating mutually, it is characterized in that adopting the nano-calcium carbonate particles of non-modified, in aqueous medium and the alkyl carbon atoms number be that 10 to 18 ionic surfactant interacts, change the surface wettability of nano particle on the spot, make nano particle have surface-active, thereby can assemble or be adsorbed on oil/water termination, stable emulsion;
Realize that by the usage ratio that changes nano-calcium carbonate particles and ionic surfactant the circulation of emulsion changes mutually;
The primary particle diameter of used nano-calcium carbonate particles is 20-200nm, adds concentration and counts 0.5%-6% with emulsion water weight;
Ionic surfactant is selected C for use
10-C
18Straight or branched, saturated or unsaturated, contain or do not contain benzene ring structure, contain or do not contain the ionic surfactant of polyoxyethylene groups, its hydrophilic group partly is a sulfate, sulfonate, carboxylate, amine salt or quaternary ammonium salt, working concentration counts 1 * 10 with emulsion water volume
-6～0.5mol L
-1
In the ultrasonic aqueous solution that is dispersed in ionic surfactant of nano-calcium carbonate particles.
2. the preparation method of emulsifying agent according to claim 1 is characterized in that ionic surfactant selects lauryl sodium sulfate or softex kw for use.
3. the preparation method of emulsifying agent according to claim 1 is characterized in that the oil phase that is played the overstable emulsion of emulsification by this emulsifying agent selects gasoline, kerosene, diesel oil or heavy oil for use, and the volume fraction of oil phase is 10%-80% in the emulsion.
4. the preparation method of emulsifying agent according to claim 1 is characterized in that the oil phase that is played the overstable emulsion of emulsification by this emulsifying agent selects alkane, cycloalkane or aromatic hydrocarbons for use, and the volume fraction of oil phase is 10%-80% in the emulsion.
5. the preparation method of emulsifying agent according to claim 1 is characterized in that the oil phase that is played the overstable emulsion of emulsification by this emulsifying agent selects animals and plants oils or fatty acid ester for use, and the volume fraction of oil phase is 10%-80% in the emulsion.
6. the preparation method of emulsifying agent according to claim 1 is characterized in that the oil phase that is played the overstable emulsion of emulsification by this emulsifying agent selects C for use
5-C
20Fatty alcohol, C
5-C
20Aliphatic acid or C
5-C
20Fatty amine, the volume fraction of oil phase is 10%-80% in the emulsion.
7. the preparation method of emulsifying agent according to claim 1 is characterized in that the aqueous phase that is played the overstable emulsion of emulsification by this emulsifying agent contains or do not contain monovalence or multivalence electrolyte.
8. the application of the emulsifying agent of the described method preparation of claim 1 is characterized in that this kind emulsifying agent is applied to agricultural chemicals, paint, coating, oil recovery and fuel oil and adds the water technical field.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100259923A CN101108324B (en) | 2007-08-13 | 2007-08-13 | Emulsion of hyperstable latex capable of varying phase of circulation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100259923A CN101108324B (en) | 2007-08-13 | 2007-08-13 | Emulsion of hyperstable latex capable of varying phase of circulation |
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| Publication Number | Publication Date |
|---|---|
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| CN101108324B true CN101108324B (en) | 2010-08-25 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735787A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Nano material-based water-based oil field injection agent and preparation method thereof |
| CN102728252B (en) * | 2011-04-02 | 2014-04-16 | 中国石油化工股份有限公司 | Method for preparing multiple emulsions from layered active particles |
| CN103432958B (en) * | 2013-08-22 | 2014-11-05 | 郑四荣 | Calcium carbonate surface-active agent |
| CA2936670A1 (en) * | 2013-12-13 | 2015-06-18 | Nestec S.A. | Emulsions stabilized by particles of an edible inorganic salt |
| CN104437231B (en) * | 2014-11-10 | 2016-09-28 | 江南大学 | A kind of surface active nanoparticles with switch property |
| CN105727824B (en) * | 2016-01-27 | 2018-01-02 | 江南大学 | A kind of stimulating responsive surfactant granules using pH as trigger mechanism |
| CN105802591A (en) * | 2016-04-12 | 2016-07-27 | 西南石油大学 | Reversible emulsification material and emulsion phase inversion induction technology thereof |
| CN105754572A (en) * | 2016-05-12 | 2016-07-13 | 河南正佳能源环保股份有限公司 | Method for preparing soluble nano oil-displacing agent |
| CN108479630B (en) * | 2018-03-14 | 2020-01-21 | 江南大学 | Ultra-low concentration type efficient composite emulsifier |
| CN113136194B (en) * | 2021-04-26 | 2023-05-02 | 中国石油大学(华东) | Emulsion based on nanocellulose and preparation method and application thereof |
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