CN1135373A - Surfactant for emulsified-liquid film and preparation method thereof - Google Patents
Surfactant for emulsified-liquid film and preparation method thereof Download PDFInfo
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- CN1135373A CN1135373A CN95121437.3A CN95121437A CN1135373A CN 1135373 A CN1135373 A CN 1135373A CN 95121437 A CN95121437 A CN 95121437A CN 1135373 A CN1135373 A CN 1135373A
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- butyl rubber
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Abstract
The surfactant is prepared by using butyl rubber, whose molecular weight is 40-70 ten-thousand, as raw material. The technical steps are in turn: 1) thermal degradation whose temp. is 280-300 degree C and constant-temp. time is 40-90 min.; 2) adding non-polar dissolvant to dissolve; 3) thermal addition of reacting with maleic anhydride at constant temp. of 200-240 degree C for 8-12 hours; 4) aminating reaction by adding vinyl-amine kind compound. It has the advantage of simple process, saving energy, wide suitable range, good stability and less swelling.
Description
The present invention relates to liquid Membrane Separation Technique, specifically provide a kind of surfactant that is used for the application of liquid film separation industries and preparation method thereof.
In the world, liquid Membrane Separation Technique is risen gradually at the seventies.One of problem of most critical is to adopt a kind of desirable surfactant in liquid Membrane Separation Technique, and the at present domestic and international commercially available surfactant that is used for liquid Membrane Separation Technique all exists swelling ratio excessive, the breakage rate height, the shortcoming of condensate film stability difference, therefore, can not satisfy the requirement of commercial scale continuous operation.
External just locating pilot scale and with surfactant U.S. Pat 4,259 is being arranged, 189 disclosed ENJ-3029 and BP Brit, UK2,038,201 disclosed ECA-4360 to the liquid film of obtaining effect of commercial Application transition stage.According to the content of these two patent documentation records, these two kinds of surfactants are the polyamine analog derivative, and mean molecule quantity is about 2000, and its structural formula is as follows respectively:
ENJ-3029
M is about 40 in the formula, and mean molecule quantity is about 2000
N is about 40 in the formula, and mean molecule quantity is about 2000
Though above-mentioned two kinds of liquid films improve a lot than span-80 etc. with surfactant condensate film stability under higher temperature, their belong to low molecular range, still exist the shortcoming that swelling is excessive, the running condensate film stability is not good enough.
All unexposed its preparation method in above-mentioned and the immediate two pieces of documents of the present invention.
The objective of the invention is to overcome the shortcoming of background technology, create a kind of liquid film surfactant and preparation method thereof that can satisfy the commercial scale continuous service requirement.Start with from the selection of raw material, the setting of process route, with the composition that changes lipophilic group, hydrophilic group and molecular weight, molecular weight distribution, make surfactant of the present invention not only under multiple condition, can greatly reduce the swelling of liquid film, and breakage rate is low, condensate film stability is good.Preparation method's technology of the present invention is simple, easy to operate, equipment investment is few and energy-conservation, and raw material sources are abundant, and cheap, and product cost is low.
Purpose of the present invention can reach by following measure:
A kind of surfactant for emulsified-liquid film is characterized in that its effective ingredient is mainly the polyamine analog derivative of long chain hydrocarbon groups mono butonediimide, and its general structure is:
In the formula, R is the copolymer of isobutene and isoprene, and wherein the percentage by weight of isobutene component content is 97.5～98%, and the percentage by weight of isoprene component content is 2～2.5%; N is 2～10 integer, and its mean molecule quantity is 2000～10000, and molecular weight distributing index is greater than 3.
A kind of preparation method of polyamine class surfactant for emulsified-liquid film is characterized in that it in turn includes the following steps:
Step 1: molecular weight is the preparation of 2000～10000 cracking butyl rubber
A) molecular weight is that 40～700,000 butyl rubber is a raw material,
B) adopt far-infrared heating stove, N
2Carry out thermal degradation under the protection, its thermal degradation temperature is 280 ℃～300 ℃, and constant temperature time is 40～90 minutes, makes the cracking butyl rubber of the satisfied different condition needs that mean molecule quantity do not wait in 2000～10000 scopes;
Step 2: the preparation of the cracking butyl rubber glue of 30%～60% percentage by weight
Be right after step 1, add non-polar solven sulfonated kerosene or refined diesel oil or White Mineral Oil or atoleine while hot, be mixed with 30%～60% cracking butyl rubber glue, and filter while hot, remove residual little blob of viscose by the butyl rubber weight percent meter;
Step 3: hot adduction
To put into the reactor of sealing and band stirring through the butyl rubber glue after dissolving, the filtration, when being heated to 120 ℃～150 ℃, by the mol ratio of maleic anhydride/cracking butyl rubber is that 1.0～1.2/1 amount adds maleic anhydride, slowly be warming up to 200 ℃～240 ℃ then, and under this temperature constant temperature, stirring reaction 8～12 hours, make long chain hydrocarbon groups succinic anhydride solution;
Step 4: amination
Long chain hydrocarbon groups succinic anhydride solution is cooled to after the 60 ℃～room temperature with benzene or toluene by 1: 1～3 weight portion mixed dilutings, put into the reactor of the backflow of band stirring after the filtration, mol ratio by vinylamine compounds/long chain hydrocarbon groups succinic anhydride is that 1.0～1.2/1.0 adds the vinylamine compounds, carry out aminating reaction, added hot reflux two hours; After again its product being warming up to 130 ℃～150 ℃, to the water and solvent benzol or the toluene that eliminate in the mixed reactant, make surfactant for emulsified-liquid film through decompression distillation.
The present invention compares with background technology has following advantage:
(1) surfactant of the present invention is a raw material with abundant, the cheap butyl rubber of originating, and by controlling the process conditions of preparation, make number-average molecular weight in 2000～10000 scopes, dispersion index is greater than 3 intermediate raw material cracking butyl rubber, add respectively different non-polar solvens with the vinylamine compounds amination prepare differently form, the series of products that can satisfy the different condition needs of different structure, thereby enlarged the scope of application.
(2) water insoluble, acetone of this product and ethanol, and be dissolved in organic solvents such as gasoline, kerosene, diesel oil, mineral oil, paraffin oil, n-hexane, therefore, particularly suitable prepares water-in-oil emulsion.In emulsion liquid membrane, this surfactant is not only a kind of emulsifying agent of function admirable, but also is effective film reinforcing agent.Under its effect, condensate film stability is good, breakage rate is low, swelling ratio is little.And splendid with all kinds of carrier compatibilities, can be widely used in acid, in, the alkalies film system.Surfactant molecule amount size, the relation of composition and condensate film stability and swelling sees attached list 1.
(3) preparation method of the present invention, technology is simple, easy to operate, and equipment investment is few and energy-conservation.
Subordinate list 1
| Sequence number | ?????????????I | ???????????????II | ????????????III | ????????????????????IV | ??????V | ????VI | ????VII | |||||||||
| ????Mn | ?9215 | ?9150 | ?8987 | ?5672 | ?5534 | ?5492 | ?4594 | ?4437 | ?4413 | ?7834 | ?7834 | ?7834 | ?7834 | ???ENJ-3029 | Orchid-113A | ???SPan-80 |
| ????D | ?2.61 | ?3.55 | ?6.32 | ?6.17 | ?4.68 | ?3.27 | ?5.46 | ?4.66 | ?2.34 | ?3.69 | ?3.69 | ?3.69 | ?3.69 | |||
| Surfactant hydrophilic group part | TEPA | Polyethylene polyamine | Triethylene tetramine | Polyethylene polyamine | Triethylene tetramine | TEPA | TEPA | Triethylene tetramine | Triethylene tetramine | Diethylenetriamine | Triethylene tetramine | TEPA | Polyethylene polyamine | |||
| Breakage rate (%) | ?0.10 | ?0.03 | ?0.04 | ?0.15 | ?0.17 | ?0.16 | ?0.38 | ?0.37 | ?0.89 | ?0.12 | ?0.05 | ?0.07 | ?0.04 | ????0.18 | ????0.23 | ????0.31 |
| Swelling ratio (%) | ?5.4 | ?3.7 | ?3.6 | ?7.0 | ?7.1 | ?6.8 | ?16.9 | ?17.5 | ?20.3 | ?6.7 | ?5.1 | ?5.6 | ?5.0 | ????31.3 | ????62.5 | ????92.3 |
| Remarks | Oil phase: 2.0% surfactant+98.0% kerosene; Interior water: contain 100.0ppm K 2Cr 2O 72MNaCl solution; Outer water: the aqueous solution that contains 1000.0ppmKCl; Oil internal ratio (Roi): 1: 1; Ratio of milk and water (Rew): 1: 5; Mixing speed: 240 rev/mins; Time: 60 minutes; Temperature: 25.0 ℃ | |||||||||||||||
Fig. 1 is a kind of surfactant for emulsified-liquid film preparation technology schematic flow sheet.
Below will the invention will be further described by embodiment and accompanying drawing:
Step 1: the preparation of cracking butyl rubber
With commercially available Japanese 268 butyl rubbers is raw material, is cut into film, and its thickness is advisable to be not more than 0.5cm, takes by weighing 1000 grams and is tiled in equably in the stainless steel pallet, then pallet is placed airtight far-infrared heating stove, N
2Protection is warming up to 200 ℃ down, and at this moment butyl rubber begins expanded--fusing--separates, and opens exhaust blower and in time the gas that produces is discharged.Continue to be warming up to 280 ℃～300 ℃, the temperature-rise period time is about 30 minutes, butyl rubber begins cracking, in 280 ℃～300 ℃ temperature range, constant temperature 40～90 minutes, the centre can be opened fire door and be stirred, when the flowability of glue obviously increases, the control constant temperature time can make the cracking butyl rubber of different molecular weight with the prolongation of the rising of cracking temperature and constant temperature time, and the relation of its cracking temperature, constant temperature time and molecular weight and molecular weight distribution is tabulated by table 2 and provided.
Step 2:
Adding sulfonated kerosene or non-polar solvens such as refined diesel oil or White Mineral Oil or atoleine while hot by the consumption in the table 2, to prepare percentage by weight respectively be 30%～60% cracking butyl rubber glue, and then filter, remove residual little blob of viscose while hot.
Step 3: hot adduction
The butyl rubber glue that takes by weighing after dissolving, filtration is put into the reactor of sealing and band stirring, add maleic anhydride by listed process conditions in the table 2 when being heated to 120 ℃～150 ℃, be warming up to the hot adduction temperature of each embodiment then respectively, and under this temperature constant temperature, stir by the required reaction time stoichiometric number of each embodiment and hour make long chain hydrocarbon groups succinic anhydride solution.
Step 4: amination
Long chain hydrocarbon groups succinic anhydride solution is cooled to 60 ℃ to room temperature, press consumption adding benzene or dilution with toluene in the table 2, put into the four-hole refluxing reactor that band stirs after the filtration, press consumption and title adding vinylamine compounds in the table 2 again, make its aminating reaction through heating, backflow, the amination temperature and time of each embodiment is provided by table 2.Remove water and solvent benzol or the toluene that dereaction generates with water knockout drum at last.After most solvents and water are removed, be warming up to 130 ℃～150 ℃, decompression distillation eliminates water and solvent in the reactant, and products therefrom is and mainly contains the surfactant for emulsified-liquid film that effective constituent is the long chain hydrocarbon groups mono butonediimide.
Subordinate list 2
| Sequence number | ????1 | ????2 | ????3 | ????4 | ????5 | ????6 | ????7 | ????8 | ????9 |
| The cracking time, divide | ????40 | ????50 | ????55 | ????60 | ????65 | ????70 | ????75 | ????80 | ????90 |
| Cracking temperature; ℃ | ????295～300 | ?290～295 | ?295～300 | ?290～295 | ?295～300 | ?280～285 | ?290～295 | 285～290 | 280～285 |
| Number-average molecular weight Mn | ????9340 | ????8978 | ????7834 | ????6266 | ????5680 | ????4512 | ????3808 | ????3410 | ????2410 |
| Dispersion index D | ????2.67 | ????4.50 | ????3.69 | ????3.72 | ????6.17 | ????5.46 | ????4.67 | ????3.62 | ????2.56 |
| The cracking butyl rubber, gram | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 | ????100 |
| Sulfonated kerosene, gram | ????240 | ????70 | |||||||
| Refined diesel oil, gram | ????100 | ????100 | |||||||
| White Mineral Oil, gram | ????150 | ????100 | |||||||
| Atoleine, gram | ????100 | ????200 | ????65 | ||||||
| Maleic anhydride, gram | ????1.2 | ????1.1 | ????1.5 | ????1.7 | ????1.9 | ????2.2 | ????2.8 | ????2.9 | ????4.5 |
| Hot adduction temperature ℃ | ????230～240 | ?230～240 | ?200～220 | ?200～210 | ?210～220 | ?230～240 | ?230～240 | ?230～240 | ?230～240 |
| The hot adduction time, hour | ????8 | ????10 | ????12 | ????10 | ????8 | ????9 | ????8 | ????9 | ????12 |
| Benzene, gram | ????500 | ????600 | ????300 | ????300 | |||||
| Toluene, gram | ????200 | ????400 | ????500 | ????300 | ????600 | ||||
| Diethylenetriamine, gram | ????1.8 | ????2.3 | |||||||
| Triethylene four, amine, gram | ????2.5 | ????4.3 | ????6.7 | ||||||
| TEPA, gram | ????2.3 | ????5.4 | |||||||
| Polyethylene polyamine, gram | ????2.5 | ????4.5 | |||||||
| The amination time, hour | ????4 | ????3 | ????4 | ????4 | ????3.5 | ????4 | ????3 | ????3 | ????3.5 |
Claims (5)
1, a kind of surfactant for emulsified-liquid film is characterized in that its effective ingredient is mainly the polyamine analog derivative of long chain hydrocarbon groups mono butonediimide, and its general structure is:
In the formula, R is isobutene and isoprene copolymer, and wherein the percentage by weight of isobutene component content is 97.5～98%, and the percentage by weight of isoprene component content is 2～2.5%; N is 2～10 integer; Its mean molecule quantity is 2000～10000, and molecular weight distributing index is greater than 3.
2, surfactant for emulsified-liquid film according to claim 1, its best mean molecule quantity is 5000～10000.
3, a kind of preparation method of polyamine class surfactant for emulsified-liquid film is characterized in that it in turn includes the following steps:
Step 1: molecular weight is the preparation of 2000～10000 cracking butyl rubber
A) molecular weight is that 40～700,000 butyl rubber is a raw material,
B) adopt far-infrared heating stove, N
2Carry out thermal degradation under the protection, its thermal degradation temperature is 280 ℃～300 ℃, and constant temperature time is 40～90 minutes, makes the cracking butyl rubber of the satisfied different condition needs that molecular weight do not wait in 2000～10000 scopes;
Step 2: the preparation of the cracking butyl rubber glue of 30%～60% percentage by weight
Be right after step 1, add 30%～60% the cracking butyl rubber glue of non-plate solvent preparation while hot, and filter while hot, remove residual little blob of viscose by the butyl rubber weight percent meter;
Step 3: hot adduction
To put into the reactor of sealing and band stirring through the butyl rubber glue after dissolving, the filtration, when being heated to 120 ℃～150 ℃, mol ratio by maleic anhydride/cracking butyl rubber is the amount adding maleic anhydride of 1.0～1.2/l, slowly be warming up to 200 ℃～240 ℃ then, and under this temperature constant temperature, stirring reaction 8～12 hours, make long chain hydrocarbon groups succinic anhydride solution;
Step 4: amination
Long chain hydrocarbon groups succinic anhydride solution is cooled to after the 60 ℃～room temperature reactor of putting into the backflow that band stirs with benzene or toluene by 1: 1～3 weight portion mixed dilutings, after filtering, by vinylamine compounds/long chain hydrocarbon groups succinic anhydride is 1.0～1.2/～1.0 adding vinylamine compounds, carry out aminating reaction, back flow reaction 2 hours; After again its product being warming up to 130 ℃～150 ℃, to the water and solvent benzol or the toluene that eliminate in the mixed reactant, make surfactant for emulsified-liquid film through decompression distillation.
4, the preparation method of surfactant for emulsified-liquid film according to claim 3 is characterized in that the non-polar solven optimal selection that step 2 adopts is sulfonated kerosene or refined diesel oil or White Mineral Oil or atoleine.
5,, it is characterized in that the vinylamine compounds optimal selection that step 4 adopts is diethylenetriamine or triethylene tetramine or TEPA or polyethylene polyamine according to the preparation method of claim 3,4 described surfactant for emulsified-liquid film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95121437A CN1064271C (en) | 1995-12-28 | 1995-12-28 | Surfactant for emulsified-liquid film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95121437A CN1064271C (en) | 1995-12-28 | 1995-12-28 | Surfactant for emulsified-liquid film and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1135373A true CN1135373A (en) | 1996-11-13 |
| CN1064271C CN1064271C (en) | 2001-04-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN95121437A Expired - Fee Related CN1064271C (en) | 1995-12-28 | 1995-12-28 | Surfactant for emulsified-liquid film and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090986C (en) * | 1997-03-21 | 2002-09-18 | 英特卫普有限公司 | Natural surfactant with amines and ethoxylated alcohol |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1248643B (en) * | 1959-03-30 | 1967-08-31 | The Lubrizol Corporation, Cleveland, Ohio (V. St. A.) | Process for the preparation of oil-soluble aylated amines |
| NL124842C (en) * | 1959-08-24 | |||
| US3272746A (en) * | 1965-11-22 | 1966-09-13 | Lubrizol Corp | Lubricating composition containing an acylated nitrogen compound |
| US4259189A (en) * | 1978-01-19 | 1981-03-31 | Exxon Research And Engineering Co. | Novel liquid membrane formulations |
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1995
- 1995-12-28 CN CN95121437A patent/CN1064271C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1090986C (en) * | 1997-03-21 | 2002-09-18 | 英特卫普有限公司 | Natural surfactant with amines and ethoxylated alcohol |
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| CN1064271C (en) | 2001-04-11 |
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