CN104356154A - Preparation method of cationic trisiloxane surfactants - Google Patents
Preparation method of cationic trisiloxane surfactants Download PDFInfo
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- CN104356154A CN104356154A CN201410489676.1A CN201410489676A CN104356154A CN 104356154 A CN104356154 A CN 104356154A CN 201410489676 A CN201410489676 A CN 201410489676A CN 104356154 A CN104356154 A CN 104356154A
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- quaternary ammonium
- ammonium salt
- surfactant
- trisiloxane
- bromohexadecane
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Abstract
The invention discloses a preparation method of cationic trisiloxane surfactants. The preparation method comprises the following steps: (1) 1,1,1,3,5,5,5-heptamethyl trisiloxane and N,N-dimethyl ethanolamine which are used as raw materials react in the presence of a platinum catalyst at 100 DEG C for 1 h to synthesize a trisiloxane tertiaryamine intermediate (Me3SiO)2Si(Me)(OC2H4)NMe2; and (2) the trisiloxane tertiaryamine intermediate (Me3SiO)2Si(Me)(OC2H4)NMe2, bromoethane, chloropropene, bromododecane and bromohexadecane are used as raw materials to respectively synthesize bromoethane quaternary ammonium salt, chloropropene quaternary ammonium salt, bromododecane quaternary ammonium salt and bromohexadecane quaternary ammonium salt. After and before heating, surface tension of the synthesized four cationic surfactants changes little, and the four cationic surfactants are more resistant to acid-base. In addition, the four cationic surfactants have good surface tension.
Description
Technical field
The present invention relates to, specifically, relate to a kind of preparation method of positively charged ion trisiloxane surfactant.
Background technology
Tensio-active agent, as a kind of important fine chemicals, has purposes very widely.Its Application Areas relates to the other field of national economy gradually from daily chemical industries such as traditional washing composition, makeup, soap, the industries such as such as intermetallic composite coating, building, pharmacy, weaving, oil, the nearly cover every field of fine chemistry industry.Since twentieth century, human sciences strides forward with the rapid pace of making rapid progress, along with the continuous progress of science and technology and improving constantly of standard of living, therefore also increase year by year for the annual production of tensio-active agent and demand, this is that the research of its basic theory and the exploitation of new variety put forward higher requirement.Everything all has dual character, and scientific-technical progress brings life also to bring a large amount of problem of environmental pollutions easily simultaneously, and the tensio-active agent of the Sustainable development of development of new is the main flow of current era development.
Organic silicon surfactant is a kind of modified siloxane based on polyether modified silicon oil or polysiloxane.As a kind of novel green cats product, trisiloxane surfactant has the performance of more excellences compared with traditional hc-surfactant.The surface tension of water (can be reduced to 20mN/m by the interfacial tension that organic silicon surfactant effectively can not only reduce water-oil interface, and common hydrocarbon type tensio-active agent can only make surface tension reduce to about 30mN/m), because it can carry out wetting expansion on the surface of low-energy hydrophobic, there is the excellent properties being called as " super extended " or " super wettability ", these are all the character that conventional surfactant does not possess, or even other fluorine-containing or silicon-containing surfactant is difficult to match in excellence or beauty.The research of current most domestic is all non-ionic silicone surfactants, little to the silicone surfactant research of other types, the synthesis of more leisure opinion to positively charged ion trisiloxanes, the research of properties and application.Therefore really to accomplish that opening domestic market just needs the cationic trisiloxane surfactant of R and D.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, a kind of preparation method of positively charged ion trisiloxane surfactant is provided.
To achieve these goals, the present invention adopts following technical scheme:
A preparation method for positively charged ion trisiloxane surfactant, comprises the steps:
(1) with 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD
hm) and N, N-dimethylethanolamine (DMEA) be raw material, add platinum catalyst at 100 DEG C, react 1 hour synthesis trisiloxanes tertiary amine intermediate (Me
3siO)
2si (Me) (OC
2h
4) NMe
2;
(2) with trisiloxanes tertiary amine intermediate (Me
3siO)
2si (Me) (OC
2h
4) NMe
2be raw material respectively synthetic bromide ethane quaternary ammonium salt, propenyl chloride quaternary ammonium salt, bromododecane quaternary ammonium salt and bromohexadecane quaternary ammonium salt with monobromethane, propenyl chloride, bromododecane and bromohexadecane.
Compared with prior art, the present invention has following beneficial effect: four kinds of cationic surfactant monobromethane quaternary ammonium salts of the present invention's synthesis, propenyl chloride quaternary ammonium salt, bromododecane quaternary ammonium salt and bromohexadecane quaternary ammonium salt, heating front and rear surfaces tension variation is less, more acid and alkali-resistance, organic silicon surfactant difference similar with it is compared also not quite with stability to hydrolysis under weak basic condition neutral, but under highly basic or acidic conditions, the stability to hydrolysis of four kinds of products is obviously better than similar organic silicon surfactant, namely the novel cation organosilicon quaternary ammonium salt synthesized has wider pH to be suitable for value.In addition, four kinds of cationic surfactants of synthesis have good surface tension.
Embodiment
Embodiment 1: the preparation of target product
By 1,1,1,3,5,5,5-heptamethyltrisiloxane (MD
hm) and N, N-dimethylethanolamine (DMEA) be raw material, add platinum catalyst at 100 DEG C, react 1 hour synthesis trisiloxanes tertiary amine intermediate (Me
3siO)
2si (Me) (OC
2h
4) NMe
2;
With trisiloxanes tertiary amine intermediate (Me
3siO)
2si (Me) (OC
2h
4) NMe
2be raw material respectively synthetic bromide ethane quaternary ammonium salt, propenyl chloride quaternary ammonium salt, bromododecane quaternary ammonium salt and bromohexadecane quaternary ammonium salt with monobromethane, propenyl chloride, bromododecane and bromohexadecane; Raw material is positioned in there-necked flask, adds magnetic rotor, install thermometer and prolong, start reaction.Consumption and the reaction conditions of each material are as shown in table 1.
Table 1
Embodiment 2: product purification and Structural Identification
Adopt dissolution with solvents crude product to carry out recrystallization, decompress filter obtains white crystal, and at 60 DEG C, vacuum-drying 4h obtains dry purified product, and fast sealing product prevents product hydrolytic spoilage, adopts nucleus magnetic hydrogen spectrum method to characterize its structure.In the reaction of synthetic intermediate, by online infrared monitoring reaction process.Former DMEA and MD can be real-time monitored
hthe corresponding group content change of M, resultant (Me
3siO)
2si (Me) (OC
2h
4) N (CH
3)
2the change of corresponding group content, each functional group vibrational wave number is as table 2.
Table 2, each functional group vibrational wave number
| Wave number/cm-1 | Ownership |
| 3492.1 | -OH stretching vibration ν (-OH) |
| 2157 | Si-H stretching vibration ν (Si-H) |
| 1462，1477 | Methyl symmetrical deformation vibration δ (-CH3) |
| 1059 | Si-O stretching vibration ν (Si-O) |
| 925.26 | Si-H formation vibration δ (Si-H) |
| 839 | Si-CH3 formation vibration δ (Si-C) |
When adding reactant MD
hhydroxyl charateristic avsorption band corresponding to M, DMEA and MD
hsilicon hydrogen charateristic avsorption band corresponding to M all correspondingly decreases, and the intensity of absorption peak reduces gradually, but it is slower to underspeed.In view of DMEA is as the first raw material added in reaction system, we obtain the infrared spectrogram before and after the reaction of its pure compound, and the charateristic avsorption band obtaining DMEA is positioned at 3492cm
-1the oh group collection of illustrative plates of left and right changes in time.As seen from the above analysis, initial time, the transformation efficiency of DMEA is 0, and the intensity of absorption peak is maximum, and after adding catalyzer, hydroxyl characteristic of correspondence absorption peak declines rapidly, and reaction is carried out fast, and experiment can be observed a large amount of bubble and emerged.After reaction for some time, speed of reaction starts to decline, and gradually will tend towards stability.Along with the increase in reaction times, the charateristic avsorption band of Si-O key increases to some extent.Due to raw material MD
hsi-O key is natively there is, so the increase that we observe the concentration of Si-O key does not have raw material MD in M
hthe change that M and DMEA participates in the charateristic avsorption band of reaction is so obvious, but also can find out that with the change of raw material be corresponding.
Four kinds of product nucleus magnetic hydrogen spectrum structural characterizations and analysis: positively charged ion trisiloxane surfactant recrystallisation solvent is selected as table 3.
Table 3
Organosilicon quaternary ammonium salt molecular formula (R=C
2h
5, C
3h
5, C
12h
25, C
16h
33; X=Cl, Br)
Hydrogen nuclear magnetic resonance spectroscopy can demonstrate dissimilar hydrogen contained in different quaternary ammonium salt intuitively, by observing displacement and the area of each type hydrogen, can judge whether synthetic is target product.This experiment solvent for use be neon for chloroform (CDC13), internal standard substance is tetramethylsilane (TMS).The chemical shiftsum peak area of propenyl chloride quaternary surfactant is as table 4, the chemical shiftsum peak area of monobromethane quaternary surfactant is as table 5, the chemical shiftsum peak area of bromododecane quaternary surfactant is as table 6, and the chemical shiftsum peak area of bromohexadecane quaternary surfactant is as table 7.
Table 4
Table 5
Table 6
Table 7
Conclusion: we can observe and obtain distinctive group on different quaternary ammonium salt by data results, in four kinds of synthetic products, all do not observe the nuclear magnetic resonance peak of Si-H, this illustrative experiment has finally synthesized target product monobromethane quaternary ammonium salt, propenyl chloride quaternary ammonium salt, bromododecane quaternary ammonium salt and bromohexadecane quaternary ammonium salt.
Embodiment 3: steady-state fluorescence measures the CMC value of product
The basic reason that tensio-active agent can produce the effects such as solubilising, washing, wetting, emulsification, flocculation and dispersion is the formation of micella, and micelle-forming concentration is also weigh an extremely important physical quantity of tensio-active agent surfactivity and application.Can there is noticeable change in the character of surfactant soln, according to this feature, find the concentration during catastrophe point changed to be exactly the CMC value of tensio-active agent near micelle-forming concentration.Fluorescence probe method first Application gives the credit to the people such as Turro in the mensuration of CMC value, and research draws system aggregation number of micelle N being less than to 100, and we can say that the mensuration of probe fluorescence emission spectra is still more accurate.
Experimental procedure is as follows: four kinds of different positively charged ion trisiloxane surfactant aqueous solution of preparation different concns, magnetic stirrer over night, carries out fluorometric investigation.
1. get the pyrene-ethanolic soln of 10 μ L in sample bottle with microsyringe, wait for that ethanol volatilization is dry;
2. weigh the surfactant soln that 5g sample is configured to 10g/L, stir;
3. weigh sample in sample bottle by desired concn, keep pyrene-alcohol concn to be constant;
4. at room temperature stir and spend the night, carry out test and obtain fluorescence data.
Interpretation: pyrene has five fluorescence peaks, and the fluorescence intensity I at peak 1 (being about 373nm)
1with the fluorescence intensity I at peak 3 (being about 384nm)
3ratio I
1/ I
3value is the strong polarity depending on solvent, and after therefore can being solubilized into micella with pyrene, residing for pyrene, the change of polarity environment causes I
1/ I
3the sudden change (catastrophe point is exactly micelle-forming concentration) of value measures the micelle-forming concentration of synthetic product.
Take pyrene as fluorescent probe, the CMC value recording monobromethane quaternary ammonium salt, propenyl chloride quaternary ammonium salt, bromododecane quaternary ammonium salt and bromohexadecane quaternary ammonium salt when pyrene-alcohol concn is constant is respectively 0.3g/L, 0.03g/L, 1.00 × 10
-3g/L, 6.00 × 10
-4g/L.For ionogenic surfactant, along with carbochain increases, the CMC value of its aqueous solution can decrease.Can infer thus, the formation of synthesized organosilicon quaternary ammonium salt surfactant micelle mainly relies on long alkyl chain.When alkyl chain length is shorter, association is more weak, needs higher surfactant concentration to form micella.Consult pertinent literature, compare with hydrocarbon-surfactant of the same type, can illustrate that the formation of the unpromising micella of heptamethyltrisiloxane end provides effect, further demonstrate heptamethyltrisiloxane end neither hydrophilic also not oleophylic, but its superior spreading property effectively can lower surface tension.
Embodiment 4: product hydrolytic stability measures
Trisiloxane surfactant is a kind of novel organosilicon tensio-active agent, because its special premium properties obtains the attention of domestic and international researcher.But polyether modified siloxane tensio-active agent has the shortcoming of facile hydrolysis, the rearrangement disproportionation reaction of siloxane bond can be there is and lose its surfactivity under acidity or property condition, thus in application, receiving limitation.The polar group that the research such as Retter finds to be positioned at quaternary trisiloxane surfactant micellar surface can protect Si-O key not by hydrolytic attack, thus can improve stability to hydrolysis.Experimental Research different pH values is on the impact of four kinds of its stability to hydrolysiies of product of synthesis.The hydrolysis main manifestations of trisiloxane surfactant is that the surface tension of its aqueous solution increases, and surfactivity reduces, and therefore judges its stability to hydrolysis by measuring its capillary change.
1 experiment reagent:
Monobromethane quaternary surfactant, propenyl chloride quaternary surfactant, bromododecane quaternary surfactant, bromohexadecane quaternary surfactant, non-ionic type trisiloxane surfactant, phosphoric acid and sodium bicarbonate.
.2 experimental procedure:
This experiment adopts to heat up carries out experimental study to accelerate hydrolysis rate method, compound concentration is all four kinds of different positively charged ion trisiloxane surfactant aqueous solution of 0.1%, add phosphoric acid or sodium bicarbonate adjust ph scope is 1-14, cool heat 30min at 50 DEG C after, constant temperature is to (25 ± 0.5) DEG C.Then measure the surface tension of solution by surface tension method, after leaving standstill for some time with this understanding, again measure its surface tension.
1, thermostat water bath regulates 50 DEG C, starts preheating;
2, take the target product of certain mass (about 3g), configuration concentration is massfraction is 1%, then getting 30g aqueous solution distilled water diluting, to obtain concentration to 300g be 0.1% aqueous solution.0.1% solution getting about 15ml, in beaker, adds acid-alkali accommodation pH value, measures its pH value with pH meter;
3, thermostat water bath heating 30min;
4, room temperature is cooled to, surface tension.
Result display monobromethane quaternary ammonium salt, propenyl chloride quaternary ammonium salt, bromododecane quaternary ammonium salt compare with it similar organic silicon surfactant difference also not quite neutral with stability to hydrolysis under weak basic condition with bromohexadecane quaternary ammonium salt, but under highly basic or acidic conditions, the stability to hydrolysis of four kinds of products is obviously better than similar organic silicon surfactant, and the novel cation organosilicon quaternary ammonium salt namely synthesized has wider pH to be suitable for value.
Claims (1)
1. a preparation method for positively charged ion trisiloxane surfactant, is characterized in that comprising the steps:
(1) with 1,1,1,3,5,5,5-heptamethyltrisiloxane and N, N-dimethylethanolamine for raw material, add platinum catalyst at 100 DEG C, react 1 hour synthesis trisiloxanes tertiary amine intermediate (Me
3siO)
2si (Me) (OC
2h
4) NMe
2;
(2) with trisiloxanes tertiary amine intermediate (Me
3siO)
2si (Me) (OC
2h
4) NMe
2be raw material respectively synthetic bromide ethane quaternary ammonium salt, propenyl chloride quaternary ammonium salt, bromododecane quaternary ammonium salt and bromohexadecane quaternary ammonium salt with monobromethane, propenyl chloride, bromododecane and bromohexadecane.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971662A (en) * | 2015-07-10 | 2015-10-14 | 广州大学 | Trisiloxane bola Gemini type super wetting agent, preparation method and applications thereof |
| CN105434190A (en) * | 2015-12-30 | 2016-03-30 | 广州星业科技股份有限公司 | Organic silicone surfactant, preparation method thereof and application thereof to cosmetics |
-
2014
- 2014-09-23 CN CN201410489676.1A patent/CN104356154A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971662A (en) * | 2015-07-10 | 2015-10-14 | 广州大学 | Trisiloxane bola Gemini type super wetting agent, preparation method and applications thereof |
| CN105434190A (en) * | 2015-12-30 | 2016-03-30 | 广州星业科技股份有限公司 | Organic silicone surfactant, preparation method thereof and application thereof to cosmetics |
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