CN1903419A - Polyoxyethylene chain three cation quaternary ammonium salt type surfactant and its sysnthesis method - Google Patents
Polyoxyethylene chain three cation quaternary ammonium salt type surfactant and its sysnthesis method Download PDFInfo
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- CN1903419A CN1903419A CNA2006100129338A CN200610012933A CN1903419A CN 1903419 A CN1903419 A CN 1903419A CN A2006100129338 A CNA2006100129338 A CN A2006100129338A CN 200610012933 A CN200610012933 A CN 200610012933A CN 1903419 A CN1903419 A CN 1903419A
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Abstract
A tricationic quaternary ammonium salt surfactant containing substituent polyoxyvinyl chain is prepared from substituent polyoxyvinyl ether, epoxy alkyl chloride and pentalkyl dienyl triamine, mixing them with solvent, acid binding agent, phase-transfer catalyst and composite catalyst, stirring, and two-step synthesizing.
Description
Technical field
The invention belongs to technical field of organic chemistry, particularly relate to and contain polyoxyethylene chain three cation quaternary ammonium salt type surfactant and synthetic method thereof.
Technical background
Three cation quaternary ammonium salt is a class novel surfactant of developing over past ten years, compare with single dication quaternary ammonium salt, owing to contain three quaternary ammonium functional group in its molecular structure, having shown excellent performance aspect foaming capacity and the reduction solution surface tension, be applied in a lot of fields gradually.Therefore the preparation of three cation quaternary ammonium salt type surfactant be applied to one of focus for current cationic surfactant research.
Preparation about three cation quaternary ammonium salt type surfactant at present mainly contains following several method:
Formerly method 1: with dodecyl methylamine, epoxychloropropane, dodecyl dimethyl tertiary amine is raw material, synthetic a series of methods that contain many alkyl multi-quaternary ammonium salt of a methylene imine base, dodecyl imido grpup, dimethyl imido grpup and dodecyl first class imido grpup between two dodecyl dimethyl quaternary ammonium salt groups respectively.This kind method can be synthesized polytype surfactant, but synthesis step is more, and conversion ratio is low, the cost height.(Tae-Seong?Kim，Toshiyuki?Kida，Yohji?Nakatsuji，and?IsaoIkeda.Preparation?and?Properties?of?Multiple?Ammonium?Salts?Quaternizedby?Epichlorohydri.Langmuir，1996，12：6304-6308)。
Formerly method 2: with bromododecane, pentamethyl-diethylenetriamine is raw material, by synthetic a series of mono-quaternaries, bi-quaternary ammonium salt, three quaternary ammonium salts that have a plurality of long-chains of quaterisation.Though this method can synthesize different types of quaternary ammonium salt, still, because its long-chain that contains is oil loving, water-soluble relatively poor, use is very restricted.(Kunio?Esumi，Kazuhiro?Taguma，Yoshifumi?Koide.AqueousProperties?of?Multichain?Quaternary?Cationic?Surfactants.Langmuir1996，12：4039-4041.)
Formerly method 3: with bromododecane, 3-chloro-1-propyl alcohol, methylamine, dodecyl dimethyl tertiary amine is raw material, the method for synthetic three long-chains, three quarternary ammonium salt compounds.This method divided for four steps carried out, each step reaction controlled condition strictness, and data shows: react abundant inadequately, cost is higher, is not suitable for suitability for industrialized production.Langmuir?R.Zana，H.Levy，D.Papoutsi，G.Beinert.Micellization?of?twotriquaternary?ammonium?surfactants?in?aqueous?solution.Langmuir，1995，11：3694-3698。
Formerly method 4: with the trihydroxy tertiary amine is primary raw material, by adding halide reagent, carries out hyperbranched reaction then and can generate the different multi-quaternary ammonium salt compound of the degree of polymerization.This method novelty, synthetic route is simple, can obtain different quaternary ammonium salts, but there is certain difficulty in the product separation, and it is water-soluble relatively poor in addition.(WOpatent?Num?00\39241，Cationic?Gemini?and?related?multiple?hydrophilic/hydrophobic?functional?compounds?and?their?use?as?surfactants.)
Formerly method 5: with 1-bromo-octadecane, tetramethyl second two ammoniums, 3-bromopropyl trimethylammonium bromide is raw material, has synthesized the octadecyl three cation quaternary ammonium salt type surfactant.This method synthetic route is simple, and mainly as structure directing agent, range of application is very little for three quaternary ammonium salts that synthesized.(Shaodian?Shen，Bozhi?Tian，Chengzhong?Yu，Songhai?Xie，Zhendong?Zhang，Bo?Tu，and?Dongyuan?Zhao.Synthesis?of?Highly?Ordered?Thermally?Stable?Cubic?MesostructuredZirconium?Oxophosphate?Templated?by?Tri-Headgroup?Quaternary?AmmoniumSurfactants.Chem.Mater，2003，15：4046-4051.)
Formerly method 6: with citric acid, senior fat tertiary amine and epoxy alkyl halide is raw material, and three's hybrid reaction can make citrate tri-long-chain alkyl three quaternary cationicses.This method only needs single step reaction, and low toxicity, still, this quaternary ammonium salt poorly water-soluble, the scope of application is greatly limited.(Chinese patent publication number: 1778459A on May 31st, 2006. citrate tri-long-chain alkyl three quaternary cationicses and preparation method).
In the technology of above-mentioned document and patent disclosure, major part is to introduce some hydroxyls, ester group in quaternary ammonium salt, this can make the water-soluble of them increase, but it is also smaller, produce precipitation when strong electrostatic interaction makes this mixed system concentration surpass CMC when they and anion surfactant are composite because between anion/cation or be separated, the concentration that some systems are separated even be lower than CMC particularly waits molar mixture.This phase behavior has hindered the practical application of this class mixed system.Therefore can improve the water-soluble of them widely if introduce polyoxyethylene group, they are carrying out can be good at overcoming the above problems when composite with anion surfactant.
Summary of the invention
The present invention is based on the problems referred to above, in quaternary ammonium salt, introduce and contain substituent polyoxyethylene chain, to improve the water-soluble of quaternary ammonium salt, solve them and carrying out the problem of long-chain lipophile when composite and water-soluble relatively poor and narrow application range, thereby propose that a kind of synthesis step is simple, reaction efficiency is high, the polyoxyethylene chain three cation quaternary ammonium salt and the synthetic method thereof of good water solubility and suitable suitability for industrialized production with anion surfactant.
The present invention relates to a kind of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant, its general formula is as follows:
Wherein: R
1, R
2, R
3Be that carbon number is 6～12 straight chained alkyl or alkyl phenolic group, R
4～R
8Be that carbon number is 1～2 straight chained alkyl, j, k, m are 5～10, and n is 1～3, and x, y are 2～4.
The present invention relates to a kind of synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant, with substituting group APEO, epoxy-1-alkyl chloride, five alkyl diene triamines is raw material, under coordinative solvent, acid binding agent, phase transfer catalyst, composite catalyst and uniform temperature and stirring condition, synthesize target product in two steps.With dodecyl APEO, epoxychloropropane, pentamethyl-diethylenetriamine is example, and its synthesis step is as follows:
The first step:
Second step:
M=8 in the formula.
Five alkyl diene, three aminated compounds that the present invention uses in the synthetic method of above-mentioned substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant are as the main framework of product structure; The epoxy alkyl chloride can be 1 substituent of the epoxyalkane of different chain length; The substituting group APEO can be alkyl polyoxyethylene ether or APES.
Wherein five alkyl diene, three aminated compounds molecular formula are:
X, y=2～4 in the following formula, R
4～R
8Straight chained alkyl for carbon number 1～2
Wherein epoxy alkyl chloride molecular formula is:
n＝1～3
Wherein the APES molecular formula is:
R is the straight chained alkyl of carbon number 6-12 in the following formula, m=5～10
Wherein the alkyl polyoxyethylene ether molecular formula is:
R is the straight chained alkyl of carbon number 6～12 in the following formula, m=5～10
The present invention is in the synthetic method of above-mentioned substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant, the solvent of described first step reaction is benzene, toluene, n-hexane or cyclohexane etc., the solvent of second step reaction is an isopropyl alcohol, N, dinethylformamide, n-butanol or normal propyl alcohol etc.; Described acid binding agent is potash, sodium carbonate, potassium hydroxide or sodium hydroxide powder or their aqueous solution; Described phase transfer catalyst is quaternary ammonium salts such as TBAB, tetraethylammonium bromide, DTAB etc.; Composite catalyst is inorganic acid and phase transfer catalysis (PTC) agent composition, and wherein inorganic acid is hydrochloric acid or hydrobromic acid; The temperature of described two-step reaction is the reflux temperature of reactant liquor; Described target product is the three cation quaternary ammonium salt type surfactant that contains three substituting group polyoxyethylene chains.The raw material of described method can synthesize three three cation quaternary ammonium salt type surfactants that long-chain is different as if the substituting group polyoxyethylene ether mixture with different long-chains.On the other hand, described method can be synthesized disubstituted polyoxyethylene chain dication quaternary surfactant if adopt two (uncle) amine as raw material.
Advantage of the present invention is: (1) equipment is simple; (2) volatility of raw material is little; (3) reaction temperature is low; (4) the synthetic route step is few, and is easy to operate; (5) reaction control easily, post processing is easy; (6) cost is low; (7) pollution-free; (8) reaction gained target product has good characteristics such as polarity is strong, good water solubility, surface-active height.
The specific embodiment
The present invention is further described as follows in conjunction with the embodiments:
Embodiment 1
With 34.0g C
7Alkyl polyoxyethylene ether (EO=5), the 1.0g TBAB, 13.0g Anhydrous potassium carbonate powder, the 50ml n-hexane adds in the reactor, under agitation, is warmed up to 80 ℃, and beginning slowly drips the epoxychloropropane of 30ml, dropwises in about 50～60min.Be warming up to reflux temperature then, stirring reaction 6.0～7.0 hours.Cool to room temperature, the solids removed by filtration material is washed this liquid with massive laundering, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 4.0g pentamethyl-diethylenetriamine in reactor, add the 50ml isopropyl alcohol, under agitation, show slightly acid with concentrated hydrochloric acid regulator solution pH value, be warmed up to 60 ℃, beginning slowly drips goes up step gained transparency liquid 35ml, dropwises in about 60min.Continue to be warming up to backflow, stirring reaction 40～45 hours.In the course of reaction, keep the pH value and show slightly acid.After reaction stopped, the decompression distillation reactant mixture can obtain containing the faint yellow suspension of tiny solid particle, add excessive acetone, left standstill after stirring evenly 2.0 hours, filter, filter cake washs 2～3 times with acetone, and drying gets 30.3g white fine particle shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 6.65 * 10
-3N/m)
Embodiment 2
With 35.0g C
8Alkyl polyoxyethylene ether (EO=5), 1.0g DTAB, contain 13.0g Carbon Dioxide saturated aqueous solution of sodium and 50ml toluene and add in the reactor, under agitation, be warmed up to reflux temperature, beginning slowly drips the epoxychloropropane of 30ml, dropwise in about 50～60min, continued stirring reaction 6.0～7.0 hours.Cool to room temperature is got supernatant liquid after the layering, wash this liquid with massive laundering, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 4.0g pentamethyl-diethylenetriamine in reactor, add 50ml N, dinethylformamide, after stirring, show slightly acid, be warmed up to 80 ℃ with concentrated hydrochloric acid regulator solution pH value, beginning slowly drips goes up step gained transparency liquid 35ml, dropwises in about 60min.Continue to be warming up to backflow, stirring reaction 40～45 hours.In the course of reaction,, the pH value is maintained show slightly acid with concentrated hydrochloric acid regulation system pH value.After reaction stopped, the decompression distillation reactant mixture can obtain containing the faint yellow suspension of tiny solid particle, adds excessive acetone, leaves standstill after stirring evenly 2.0 hours, filtered, and filter cake is with acetone washing 2～3 times, and drying must 30.5g off-white powder shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 6.90 * 10
-3N/m).
Embodiment 3
With 36.0g C
9Alkyl polyoxyethylene ether (EO=5), the 1.0g tetraethylammonium bromide, 17.0g potassium hydroxide powder, 50ml n-hexane add in the reactor, under agitation, and the temperature rising reflux temperature, beginning slowly drips the epoxychloropropane of 30ml, dropwises in about 50～60min.Continued stirring reaction then 6.0～7.0 hours.Cool to room temperature removes by filter the solid matter in the solution, washs this liquid with massive laundering then, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 4.0g pentamethyl-diethylenetriamine in reactor, add the 50ml n-butanol, under agitation, show slightly acid with concentrated hydrochloric acid regulator solution pH value, be warmed up to 90 ℃, beginning slowly drips goes up step gained transparency liquid 35ml, dropwises in about 60min.Continue to be warming up to backflow, stirring reaction 40～45 hours.In the course of reaction,, it is maintained show slightly acid with concentrated hydrochloric acid regulation system pH value.After reaction stopped, the decompression distillation reactant mixture can obtain containing the faint yellow suspension of tiny solid particle, adds excessive acetone, leaves standstill after stirring evenly 2.0 hours, filtered, and filter cake is with acetone washing 2～3 times, and drying must 34.0g off-white powder shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 6.53 * 10
-3N/m)
Embodiment 4
With 35.0g C
8Alkyl polyoxyethylene ether (EO=5), 1.0g dodecyl dimethyl ammonium bromide, 50% the aqueous solution that contains 17.0g potassium hydroxide, the 50ml n-hexane adds in the reactor, under agitation, be warmed up to reflux temperature, beginning slowly drips the epoxychloropropane of 30ml, dropwise in about 50～60min, continued stirring reaction 6.0～7.0 hours.Cool to room temperature is got supernatant liquid after the layering, wash this liquid with massive laundering, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 4.0g pentamethyl-diethylenetriamine in reactor, add the 50ml normal propyl alcohol, under agitation, show slightly acid with concentrated hydrochloric acid regulator solution pH value, be warmed up to 80 ℃, beginning slowly drips goes up step gained transparency liquid 35ml, dropwises in about 60min.Continue to be warming up to backflow, stirring reaction 40～45 hours.In the course of reaction,, it is maintained show slightly acid with concentrated hydrochloric acid regulation system pH value.After reaction stopped, the decompression distillation reactant mixture can obtain containing the faint yellow suspension of tiny solid particle, adds excessive acetone, leaves standstill after stirring evenly 2.0 hours, filtered, and filter cake is with acetone washing 2～3 times, and drying must 29.0g off-white powder shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 6.0 * 10
-3N/m)
Embodiment 5
With 40.0g NPE (EO=5), 1.0g DTAB, 15.0g 50% the aqueous solution of NaOH, 50ml benzene adds in the reactor, under agitation, be warming up to reflux temperature, beginning slowly drips the epoxychloropropane of 30ml, dropwise in about 50～60min, continued stirring reaction then 7.0～8.0 hours.Cool to room temperature is got supernatant liquid after the layering, wash this liquid with massive laundering, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 4.0g pentamethyl-diethylenetriamine in reactor, add 50ml N, dinethylformamide, after stirring, show slightly acid, be warmed up to 80 ℃ with concentrated hydrochloric acid regulator solution pH value, beginning slowly drips goes up step gained transparency liquid 35ml, dropwises in about 60min.Be warming up to backflow, stirring reaction 45～50 hours.In the course of reaction, maintain with concentrated hydrochloric acid regulation system pH value and to show slightly acid.After reaction stopped, the decompression distillation reactant mixture can obtain containing the faint yellow suspension of tiny solid particle, adds excessive acetone, leaves standstill after stirring evenly 2.0 hours, filtered, and filter cake is with acetone washing 2～3 times, and drying must 31.5g off-white powder shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 7.60 * 10
-3N/m)
Embodiment 6
With 35.0g C
8Alkyl polyoxyethylene ether (EO=5), 1.0g DTAB, 15.0g sodium hydroxide powder, 50ml toluene adds in the reactor, after mixing, is warmed up to 60 ℃, beginning slowly drips epoxy-1-chlorobutane of 37ml, dropwises in about 50～60min.Be warming up to backflow then, stirring reaction 6.0～7.0 hours.Cool to room temperature, suction filtration are removed the solid matter in the solution, wash this liquid with massive laundering then, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 4.0g pentamethyl-diethylenetriamine in reactor, add 50ml N, dinethylformamide, after stirring, show slightly acid, be warmed up to 80 ℃ with concentrated hydrochloric acid regulator solution pH value, beginning slowly drips goes up step gained transparency liquid 35ml, dropwises in about 60min.Be warming up to backflow then, stirring reaction 40～47 hours.In the course of reaction,, it is maintained show slightly acid with concentrated hydrochloric acid regulation system pH value.After reaction stopped, the decompression distillation reactant mixture can obtain containing the faint yellow suspension of tiny solid particle, adds excessive acetone, leaves standstill after stirring evenly 2.0 hours, filtered, and filter cake is with acetone washing 2～3 times, and drying must 33.5g off-white powder shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 6.10 * 10
-3N/m)
Embodiment 7
With 35.0g C
7～C
9The mixture of alkyl polyoxyethylene ether (EO=5), 1.0g DTAB, the saturated aqueous solution that contains the 13.0g natrium carbonicum calcinatum, the 50ml n-hexane adds in the reactor, after mixing, be warmed up to 60 ℃, begin epoxy-1-chlorobutane of slow Dropwise 35 ml, dropwise in about 50～60min.Be warming up to backflow then, stirring reaction 6.0～7.0 hours.Cool to room temperature is got supernatant liquid after the layering, wash this liquid with massive laundering, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 4.0g pentamethyl-diethylenetriamine in reactor, add the 50ml isopropyl alcohol, after stirring, show slightly acid with concentrated hydrochloric acid regulator solution pH value, be warmed up to 80 ℃, beginning slowly drips goes up step gained transparency liquid 35ml, dropwises in about 60min.Be warming up to backflow, stirring reaction 40～45 hours.In the course of reaction, maintain with concentrated hydrochloric acid regulation system pH value and to show slightly acid.After reaction stopped, gained liquid was reacted in decompression distillation, can obtain containing the faint yellow suspension of tiny solid particle, add excessive acetone, left standstill after stirring evenly 2.0 hours, filter, filter cake washs 2～3 times with acetone, and drying gets 32.0g off-white powder shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 6.15 * 10
-3N/m)
Embodiment 8
With 35.0g C
8Alkyl polyoxyethylene ether (EO=5), 1.0g dodecyl dimethyl ammonium bromide, 50% the aqueous solution that contains 17.0g potassium hydroxide, the 50ml n-hexane adds in the reactor, after mixing, be warmed up to reflux temperature, beginning slowly drips the epoxychloropropane of 30ml, dropwises in about 50～60min.Be warming up to backflow then, stirring reaction 6.0～7.0 hours.Cool to room temperature is got supernatant liquid after the layering, wash this liquid with massive laundering, and decompression distillation again gets transparency liquid, collects stand-by.
Get the 3.0g tetramethylethylenediamine in reactor, add the 50ml normal propyl alcohol, after stirring, show slightly acid with concentrated hydrochloric acid regulator solution pH value, be warmed up to 80 ℃, beginning slowly drips goes up step gained transparency liquid 25ml, dropwises in about 60min.Be warming up to backflow then, stirring reaction 20～25 hours.In the course of reaction, maintain with concentrated hydrochloric acid regulation system pH value and to show slightly acid.After reaction stopped, gained liquid was reacted in decompression distillation, can obtain containing the faint yellow suspension of tiny solid particle, add excessive acetone, left standstill after stirring evenly 2.0 hours, filter, filter cake washs 2～3 times with acetone, and drying gets 21.0g off-white powder shape solid product.(surface-active: its concentration is 1.0 * 10
-4The surface tension of the aqueous solution of g/ml is reduced to 9.0 * 10
-3N/m)
Claims (10)
1. substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant, its general formula is as follows:
Wherein: R
1, R
2, R
3Be that carbon number is 6～12 straight chained alkyl or alkyl phenolic group, R
4～R
8Be that carbon number is 1～2 straight chained alkyl, j, k, m are 5～10, and n is 1～3, and x, y are 2～4.
2. the synthetic method that is used for the described substituting group polyoxyethylene of claim 1 chain three cation quaternary ammonium salt type surfactant, it is characterized in that with substituting group APEO, epoxy-1-alkyl chloride, the basic diene triamine of five first (second) be raw material, under coordinative solvent, acid binding agent, phase transfer catalyst, composite catalyst and uniform temperature and stirring condition, synthesize target product in two steps.
3. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2, the used raw material substituting group APEO of its method is alkyl polyoxyethylene ether and APES.
4. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2, first step reaction solvent for use is in its method: benzene, toluene, n-hexane or cyclohexane; Second step reaction solvent for use is: isopropyl alcohol, N, dinethylformamide or n-butanol.
5. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2, the acid binding agent in its method are potash, sodium carbonate, potassium hydroxide or sodium hydroxide powder or their aqueous solution.
6. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2, the phase transfer catalyst in its method are quaternary ammonium salt, as TBAB, tetraethylammonium bromide or DTAB quaternary ammonium salt.
7. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2, the composite catalyst in its method are the mixture of inorganic acid and phase transfer catalyst, and wherein inorganic acid is hydrochloric acid or hydrobromic acid.
8. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2, the temperature of the two-step reaction described in its method is the reflux temperature of reactant liquor.
9. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2, substituting group polyoxyethylene ether mixture with different chains in its method is a raw material, can prepare three three substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactants that long-chain is different.
10. the synthetic method of substituting group polyoxyethylene chain three cation quaternary ammonium salt type surfactant as claimed in claim 2 in its method, if adopt two (uncle) amine as raw material, can be prepared disubstituted polyoxyethylene chain dication quaternary surfactant.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185614B (en) * | 2007-11-30 | 2010-05-19 | 华南理工大学 | Modified polyhydroxy cation quaternary ammonium salt thickening soft finishing agent and preparation and application thereof |
| CN102666640A (en) * | 2009-11-17 | 2012-09-12 | 陶氏环球技术有限责任公司 | Amine adducts |
| CN102702209A (en) * | 2012-05-17 | 2012-10-03 | 太原理工大学 | Quaternary cationic quaternary ammnonium and preparation method thereof |
| CN104870521B (en) * | 2012-12-28 | 2017-03-29 | 花王株式会社 | Quarternary ammonium salt compound |
| CN109400871A (en) * | 2018-11-28 | 2019-03-01 | 湖南华腾制药有限公司 | The quaternary ammonium salt and preparation method thereof of three arm polyglycol ether of monodisperse octadecyl |
| CN114702396A (en) * | 2022-05-10 | 2022-07-05 | 浙江鹿达科技有限公司 | Preparation method of PEG-6 glycerol polyoxyethylene ether quaternary ammonium salt |
| CN115594854A (en) * | 2022-10-18 | 2023-01-13 | 扬州工业职业技术学院（Cn） | Silicon-containing degradable surfactant and preparation method thereof |
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2006
- 2006-07-07 CN CNB2006100129338A patent/CN100415355C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101185614B (en) * | 2007-11-30 | 2010-05-19 | 华南理工大学 | Modified polyhydroxy cation quaternary ammonium salt thickening soft finishing agent and preparation and application thereof |
| CN102666640A (en) * | 2009-11-17 | 2012-09-12 | 陶氏环球技术有限责任公司 | Amine adducts |
| CN102702209A (en) * | 2012-05-17 | 2012-10-03 | 太原理工大学 | Quaternary cationic quaternary ammnonium and preparation method thereof |
| CN102702209B (en) * | 2012-05-17 | 2015-06-03 | 太原理工大学 | Quaternary cationic quaternary ammnonium and preparation method thereof |
| CN104870521B (en) * | 2012-12-28 | 2017-03-29 | 花王株式会社 | Quarternary ammonium salt compound |
| CN109400871A (en) * | 2018-11-28 | 2019-03-01 | 湖南华腾制药有限公司 | The quaternary ammonium salt and preparation method thereof of three arm polyglycol ether of monodisperse octadecyl |
| CN114702396A (en) * | 2022-05-10 | 2022-07-05 | 浙江鹿达科技有限公司 | Preparation method of PEG-6 glycerol polyoxyethylene ether quaternary ammonium salt |
| CN115594854A (en) * | 2022-10-18 | 2023-01-13 | 扬州工业职业技术学院（Cn） | Silicon-containing degradable surfactant and preparation method thereof |
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