CN1331585C - Surface activator from citrate three-long chain alkyl triple quaternary ammonium salt cation and preparation thereof - Google Patents
Surface activator from citrate three-long chain alkyl triple quaternary ammonium salt cation and preparation thereof Download PDFInfo
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- CN1331585C CN1331585C CNB2004100602816A CN200410060281A CN1331585C CN 1331585 C CN1331585 C CN 1331585C CN B2004100602816 A CNB2004100602816 A CN B2004100602816A CN 200410060281 A CN200410060281 A CN 200410060281A CN 1331585 C CN1331585 C CN 1331585C
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- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 title claims abstract description 13
- -1 quaternary ammonium salt cation Chemical class 0.000 title abstract description 10
- 239000012190 activator Substances 0.000 title 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 33
- 239000004593 Epoxy Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006065 biodegradation reaction Methods 0.000 abstract description 8
- 125000004185 ester group Chemical group 0.000 abstract description 5
- 150000003856 quaternary ammonium compounds Chemical class 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000032050 esterification Effects 0.000 abstract description 2
- 238000005886 esterification reaction Methods 0.000 abstract description 2
- BWZOPYPOZJBVLQ-UHFFFAOYSA-K aluminium glycinate Chemical compound O[Al+]O.NCC([O-])=O BWZOPYPOZJBVLQ-UHFFFAOYSA-K 0.000 abstract 1
- 150000002148 esters Chemical class 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 230000001954 sterilising effect Effects 0.000 abstract 1
- 238000004659 sterilization and disinfection Methods 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 235000015165 citric acid Nutrition 0.000 description 12
- 239000002253 acid Substances 0.000 description 10
- 150000001412 amines Chemical class 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000001816 cooling Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000005456 alcohol based solvent Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- GKIPXFAANLTWBM-UHFFFAOYSA-N epibromohydrin Chemical compound BrCC1CO1 GKIPXFAANLTWBM-UHFFFAOYSA-N 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000693 micelle Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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Abstract
The present invention relates to cationic surfactant containing citrate, three long chain alkyls and three quaternary salt cations, and a preparation method thereof. The cationic surfactant of the present invention is prepared from citric acid, high-grade fatty alamine and epoxy haloparaffin which are used as raw materials, and the raw material cost is low; the molecule of the cationic surfactant prepared through single step esterification and quaterisation has ester groups, three drainage alkyl chains and three quaternary ammonium salt cations and hydrophil hydroxyl groups. The cationic surfactant of the present invention has low toxicity and has the biodegradation capability simultaneously; simultaneously, the cationic surfactant of the present invention maintains inherent performance of quaternary ammonium compounds, such as flexibility, antistatic performance, sterilization performance, etc., and contains ester base groups; in addition, the dissolvability of the cationic surfactant can be improved through hydrophilic parts of the molecules of the quaternary ammonium compounds.
Description
Technical field
The present invention relates to a kind of cationic surfactant, relate more specifically to a kind of citrate tri-long-chain alkyl three quaternary cationicses.The invention still further relates to a kind of preparation method of these citrate tri-long-chain alkyl three quaternary cationicses simultaneously.
Background technology
Surfactant (or interfacial agent) is the material that can significantly reduce interfacial tension between surface tension of liquid or two-phase.Have surface-active material and be called amphipathic molecule, promptly contain hydrophilic in the molecule and two parts of oleophylic, oleophilic moiety is generally C
7-C
21Long alkyl chain, hydrophilic segment is generally water soluble group.In general, hydrophilic group makes molecule introduce water, and lipophilic group makes the molecule leaving water introduce oil, and these two kinds of groups lay respectively at the two ends of molecule, cause the asymmetric of molecule, so surfactant molecule is the molecule of a kind of not only hydrophilic but also oleophylic.Cationic surfactant, its hydrophilic radical partly is dissociated into cation when being dissolved in the water, and has and anion surfactant (fatty acid soaps) opposite configuration, to such an extent as to it also is known as invert soap (invert soap).Cationic surfactant is not only applicable to produce as common surface-active effects such as rinsing, emulsification, solubilisings, but also shows softening and anlistatig effect.
At present, the surfactant that a class is referred to as the new structure of geminal surfactant (Gemini surfactants) has caused people's extensive concern, and this geminal surfactant is made up of two hydrophobic chains, two hydrophilic groups and an interval group.Group couples together two hydrophobic groups at the position near polar group at interval.Assemble in solution about this class surfactant in the research of behavior and find that this geminal surfactant is compared with corresponding conventional surfactant, and many unique distinctions are arranged on performance.It has good surface-active, with common surfactant good synergistic is arranged.Although twin cationic surfactant (Gemini surfactants) has many good performances,, be difficult for applying because of its biological degradability is lower.Therefore, the research of inserting in the molecule about the group that will have biodegradable functional group (as introducing hydroxyl and introduce ester group in molecule in alkyl group) is carried out energetically.In addition, also have at present and in surfactant molecule, introduce many hydrophobic groups, surface property and the physical and chemical performance of many hydrophilic radicals to improve surfactant, but, in surfactant molecule, introduce in many hydrophobic groups, many hydrophilic radicals the method with the surface property that improves surfactant, still do not relate to cationic surfactant, and the cost of existing preparation surfactant is higher.
Summary of the invention
The object of the present invention is to provide a kind of citrate tri-long-chain alkyl three quaternary cationicses.
The present invention also aims to provide a kind of preparation method of these citrate tri-long-chain alkyl three quaternary cationicses simultaneously.
In order to achieve the above object, technical program of the present invention lies in adopting a kind of citrate tri-long-chain alkyl three quaternary cationicses, its general formula is as follows:
R wherein
1, R
2Be C
1-C
4Alkyl, R
3Be C
7-C
21The alkyl or the alkenyl of straight or branched, A is CH
2CH (OH) (CH
2)
n, n is the integer of 0-3, X is a halogen atom.
Described R
1, R
2Preferred C
1-C
2Alkyl.
R
3Preferred C
8-C
18The alkyl or the alkenyl of straight or branched.
Simultaneously, technical program of the present invention also lies in adopting a kind of method for preparing cationic surfactant, it is a raw material with citric acid, senior fat tertiary amine and epoxy halogenated alkane, be reaction 8-20 hour under 70-120 ℃ the condition in temperature, can obtain citrate tri-long-chain alkyl three quaternary cationicses.
The general formula of described epoxy halogenated alkane is:
Wherein, n is the integer of 0-3, and X is a halogen atom.
The mol ratio of described senior fat tertiary amine and citric acid is 3.0-3.3: 1.
The mol ratio of described epoxy halogenated alkane and citric acid is 3.0-3.3: 1.
Above-mentioned raw materials can react in reaction dissolvent.
Described reaction dissolvent can be water, methyl alcohol, ethanol, 1-propyl alcohol, 1-butanols, 2-propyl alcohol, ethylene glycol, propane diols, glycerine.
The consumption of reaction dissolvent is the 10-100% of reactant gross weight.
Also can not use reaction dissolvent among the preparation method of the present invention.
Cationic surfactant of the present invention is with citric acid, senior fat tertiary amine and epoxy halogenated alkane are that raw material prepares, cost of material is lower, by having ester group in the prepared cationic surfactant molecule of step esterification and a quaterisation, three hydrophobic alkyl chains, three quaternary ammonium salt cationics and hydrophilic hydroxyl, the present invention has the hypotoxic while, has the biodegradable ability that is easy to, also keep the intrinsic performance of quaternary ammonium compound simultaneously, it is flexibility, antistatic behaviour, bactericidal properties etc., comprise ester group again, and, by the hydrophilic segment in this compound molecule, can improve its solubility in water.
The preparation process of cationic surfactant of the present invention, shown in following reaction equation 1:
[reaction equation 1]
R wherein
1, R
2Be C
1-C
4Alkyl, R
3Be C
7-C
21The alkyl or the alkenyl of straight or branched, A is CH
2CH (OH) (CH
2)
n, n is the integer of 0-3, X is a halogen atom.
In the superincumbent reaction equation, when citric acid, long-chain fat tertiary amine, when the epoxy halogenated alkane reacts, epoxy halogenated alkane and citric acid reactions generate the alkyl derivative with ester group, and take on catalyst by tertiary amine, this product again with reactive tertiary amine, generate quaternary ammonium compound.
Description of drawings
Fig. 1 is for being the infrared spectrogram of the prepared cationic surfactant of raw material with citric acid, epoxychloropropane and dodecyl dimethyl tertiary amine among the present invention;
Fig. 2 is the surface tension and the concentration relationship curve of the represented cationic surfactant of Fig. 1;
Fig. 3 is the surface tension and the logc relation curve of the represented cationic surfactant of Fig. 1.
Above-mentioned accompanying drawing only is the explanation to a preferred embodiment of the present invention, to explain the present invention better.
The specific embodiment
For helping the understanding of the present invention, preferred embodiment is described below, still, below the embodiment that provided only be in order to explain the present invention better, and the present invention is not subjected to the restriction of following embodiment.
The epoxychloropropane (0.6 mole) and the 103.6 gram octyl dimethyl tertiary amines (0.660 mole, excessive 10%) of 38.4 gram citric acids (0.2 mole), 55.5 grams are placed the four neck flasks that mechanical agitator, thermometer and condenser are housed simultaneously.Then, be added to the 2-propyl alcohol solvents (reaction-ure mixture 25%) of 49.4 grams in this reactor and reaction 15 hours under 80 ℃ temperature.After the reaction, the productive rate that calculates product from remaining amine content and acid content surpasses 95%, and amine value and acid number are measured with the Chinese Industrial Standards (CIS) analytical method.When this product being dissolved in acetone and cooling off, will form paste.Separate two-phase then, liquids recovery recycles, and product is removed solvent, puts into drier and is dried to constant weight, weigh final products.Repeat to be dissolved in acetone, cooling, decant program more than twice.Then, with the product drying of gained, just obtain the pure cationic surfactant of paste.Adopt drop-volume method to measure the critical micelle concentration CMC value of product in the aqueous solution; The nitrogen content value is to represent with the ratio of the nitrogen content that calculates according to molecular formula with nitrogenous gram number in the product of the constant weight of Kjeldahl mensuration; Use the efficient liquid phase chromatographic analysis product, after microcomputer is tried to achieve each peak area with the product data integrate, try to achieve product content with normalization method; Estimate the final biodegradability of this cationic surfactant by closing bottle test.The physico-chemical property of embodiment 1 and biodegradability evaluation result are listed in the table one.
Embodiment 2
The citric acid (0.2 mole) of 38.4 grams, the epoxychloropropane (0.6 mole) and the 140.6 gram dodecyl dimethyl tertiary amines (0.660 mole, excessive 10%) of 55.5 grams are placed the four neck flasks that mechanical agitator, thermometer and condenser are housed simultaneously.Then, be added in this reactor with (reaction-ure mixture 25%) in the alcohol solvents of 60 grams and reaction 20 hours under 85 ℃ temperature.After the reaction, the productive rate that calculates product from remaining amine content and acid content surpasses 95%, and amine value and acid number are measured with the Chinese Industrial Standards (CIS) analytical method.When this product being dissolved in acetone and cooling off, will form paste.Separate two-phase then, liquids recovery recycles, and product is removed solvent, puts into drier and is dried to constant weight, weigh final products.Repeat to be dissolved in acetone, cooling, decant program more than twice.Then, with the product drying of gained, just obtain the pure cationic surfactant of paste.Measure the CMC value of product with the identical method of embodiment 1, nitrogen content, purity is estimated the final biodegradability of this cationic surfactant.The physico-chemical property of embodiment 2 and biodegradability evaluation result are listed in the table one.
Embodiment 3
The citric acid that contains the crystallization water (0.2 mole) of 42 grams, the epoxy bromopropane (0.6 mole) and the 140.6 gram dodecyl dimethyl tertiary amines (0.660 mole, excessive 10%) of 82.2 grams are placed the four neck flasks that mechanical agitator, thermometer and condenser are housed simultaneously.Then, be added in this reactor with (reaction-ure mixture 25%) in the 1-propyl alcohol solvents of 59.5 grams and reaction 12 hours under 90 ℃ temperature.After the reaction, the productive rate that calculates product from remaining amine content and acid content surpasses 95%, and amine value and acid number are measured with the Chinese Industrial Standards (CIS) analytical method.When this product being dissolved in acetone and cooling off, will form paste.Handle products therefrom with embodiment 1 identical method,, just obtain the pure cationic surfactant of paste the product drying of gained.And measure the CMC value of product with the identical method of embodiment 1, and nitrogen content, purity is estimated the final biodegradability of this cationic surfactant.The physico-chemical property of embodiment 3 and biodegradability evaluation result are listed in the table one.
Embodiment 4
The citric acid (0.2 mole) of 38.4 grams, the epoxy bromopropane (0.6 mole) and the 159 gram myristyl dimethyl tertiary amines (0.660 mole, excessive 10%) of 82.2 grams are placed the four neck flasks that mechanical agitator, thermometer and condenser are housed simultaneously.Then, be added in this reactor with (reaction-ure mixture 25%) in the 2-propyl alcohol solvents of 68 grams and reaction 20 hours under 85 ℃ temperature.After the reaction, the productive rate that calculates product from remaining amine content and acid content surpasses 95%, and amine value and acid number are measured with the Chinese Industrial Standards (CIS) analytical method.When this product being dissolved in acetone and cooling off, will form paste.Handle products therefrom with embodiment 1 identical method,, just obtain the pure cationic surfactant of paste the product drying of gained.And measure the CMC value of product with the identical method of embodiment 1, and nitrogen content, purity is estimated the final biodegradability of this cationic surfactant.The physico-chemical property of embodiment 4 and biodegradability evaluation result are listed in the table one.
The citric acid (0.2 mole) of 38.4 grams, the epoxychloropropane (0.6 mole) and the 196 gram octadecyl dimethyl tertiary amines (0.660 mole, excessive 10%) of 55.5 grams are placed the four neck flasks that mechanical agitator, thermometer and condenser are housed simultaneously.Then, be added in this reactor with (reaction-ure mixture 25%) in the 1-propyl alcohol solvents of 73 grams and reaction 20 hours under 95 ℃ temperature.After the reaction, the productive rate that calculates product from remaining amine content and acid content surpasses 95%, and amine value and acid number are measured with the Chinese Industrial Standards (CIS) analytical method.When this product being dissolved in acetone and cooling off, will form paste.Handle products therefrom with embodiment 1 identical method,, just obtain the pure cationic surfactant of paste the product drying of gained.And measure the CMC value of product with the identical method of embodiment 1, and nitrogen content, purity is estimated the final biodegradability of this cationic surfactant.The physico-chemical property of embodiment 5 and biodegradability evaluation result are listed in the table one.
Test case
The ultimate biodegradation ability assessment
The ultimate biodegradation ability is a kind of test of estimating the degree of sample complete biodegradable Cheng Shui and carbon dioxide, and its mensuration is to determine by closing bottle test (Closed Bottle Test) whether sample has 60% or be higher than in two weeks that 60% sample can rise by biodegradation 28 days in-test when it begins to decompose.Carry out with cationic surfactant prepared among the embodiment 1 to embodiment 5, dimethyl dialkyl ammonium chloride and two alkyl bi-quaternary ammonium salt.Two alkyl bi-quaternary ammonium salts are the represented compound of comparative structure formula 1.
The comparative structure formula
The ultimate biodegradation ability the results are shown in following table 1.The conventional cationic surfactant and the ultimate biodegradation ability of two alkyl bi-quaternary ammonium salts are lower than GB 60%, because of rather than be easy to biodegradable.On the other hand, the ultimate biodegradation ability of the cationic surfactant that embodiment 1 to embodiment 5 is prepared all is higher than 60%, show the prepared cationic surfactant of the present invention be easy to biodegradable.
Table 1 embodiment physico-chemical property and biodegradability evaluation result
| Embodiment | Molecular formula | Molecular weight | Critical micelle concentration (mol/L) | Nitrogen content (%) | Purity (%) | Biodegradation value (%) |
| Embodiment 1 | C 45H 92N 3O 10Cl 3 | 940.5 | 3.5×10 -4 | 98.30 | 96.88 | 76 |
| Embodiment 2 | C 57H 116N 3O 10Cl 3 | 1108.5 | 3.3×10 -4 | 98.70 | 97.58 | 74 |
| Embodiment 3 | C 57H 116N 3O 10Br 3 | 1242 | 2.3×10 -4 | 98.47 | 96.77 | 71 |
| Embodiment 4 | C 63H 128N 3O 10Br 3 | 1326 | 1.1×10 -4 | 98.62 | 97.62 | 69 |
| Embodiment 5 | C 75H 152N 3O 10Cl 3 | 1360.5 | 2.6×10 -4 | 97.98 | 96.73 | 65 |
| Dialkyl dimethyl ammonium chloride | - | - | - | - | - | 53 |
| Two alkyl bi-quaternary ammonium salts | - | - | - | - | - | 47 |
It should be noted last that: the present invention can summarize with other the concrete form without prejudice to spirit of the present invention or principal character.Therefore, no matter from which point, above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that: still can make amendment or be equal to replacement the present invention, and not breaking away from any modification or partial replacement of the spirit and scope of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (9)
1, a kind of citrate tri-long-chain alkyl three quaternary cationicses, its general formula is as follows:
R wherein
1, R
2Be C
1-C
4Alkyl, R
3Be C
7-C
21The alkyl or the alkenyl of straight or branched, A is CH
2CH (OH) (CH
2)
n, n is the integer of 0-3, X is a halogen atom.
2, citrate tri-long-chain alkyl three quaternary cationicses according to claim 1 is characterized in that: described R
1, R
2Be C
1-C
2Alkyl.
3, citrate tri-long-chain alkyl three quaternary cationicses according to claim 1 is characterized in that: R
3Be C
8-C
18The alkyl or the alkenyl of straight or branched.
4, a kind of preparation method of cationic surfactant as claimed in claim 1, it is characterized in that: with citric acid, senior fat tertiary amine and epoxy halogenated alkane is raw material, be reaction 8-20 hour under 70-120 ℃ the condition in temperature, can obtain citrate tri-long-chain alkyl three quaternary cationicses.
5, preparation method according to claim 4 is characterized in that: the general formula of described epoxy halogenated alkane is:
Wherein, n is the integer of 0-3, and X is a halogen atom.
6, preparation method according to claim 4 is characterized in that: the mol ratio of described senior fat tertiary amine and citric acid is 3.0-3.3: 1.
7, preparation method according to claim 4 is characterized in that: the mol ratio of described epoxy halogenated alkane and citric acid is 3.0-3.3: 1.
8, according to arbitrary described preparation method among the claim 4-7, it is characterized in that: above-mentioned raw materials reacts in reaction dissolvent.
9, preparation method according to claim 8 is characterized in that: described reaction dissolvent is a water, methyl alcohol, ethanol, 1-propyl alcohol, 1-butanols, 2-propyl alcohol, ethylene glycol, propane diols, glycerine.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105724A (en) * | 1993-10-28 | 1995-07-26 | 丁悠丹 | Oiling treating technology before raw silk weaving and treatment agent |
| WO2000061100A1 (en) * | 1999-04-12 | 2000-10-19 | Hans Schwarzkopf Gmbh & Co. Kg | Aqueous cosmetic preparation containing tartaric acid esters or citric acid esters of alkyl polyglucose, and vitamins |
| CN1411366A (en) * | 1999-12-17 | 2003-04-16 | 荷兰联合利华有限公司 | Hair treatment composition comprising cationic surfactants |
| WO2003075880A1 (en) * | 2002-03-11 | 2003-09-18 | Unilever Plc | Cosmetic compositions comprising citric acid triesters |
| CN1513592A (en) * | 2003-08-20 | 2004-07-21 | ���Խ��� | Citrate anionic surface active agent and its preparation method |
| US20040176266A1 (en) * | 1999-09-13 | 2004-09-09 | Klaus Kwetkat | Tenside composition containing gemini tensides and co-amphiphiles and production and use thereof |
| WO2004093835A1 (en) * | 2003-04-17 | 2004-11-04 | The Procter & Gamble Company | Hair conditioning compostion comprising polysorbates |
-
2004
- 2004-11-24 CN CNB2004100602816A patent/CN1331585C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1105724A (en) * | 1993-10-28 | 1995-07-26 | 丁悠丹 | Oiling treating technology before raw silk weaving and treatment agent |
| WO2000061100A1 (en) * | 1999-04-12 | 2000-10-19 | Hans Schwarzkopf Gmbh & Co. Kg | Aqueous cosmetic preparation containing tartaric acid esters or citric acid esters of alkyl polyglucose, and vitamins |
| US20040176266A1 (en) * | 1999-09-13 | 2004-09-09 | Klaus Kwetkat | Tenside composition containing gemini tensides and co-amphiphiles and production and use thereof |
| CN1411366A (en) * | 1999-12-17 | 2003-04-16 | 荷兰联合利华有限公司 | Hair treatment composition comprising cationic surfactants |
| WO2003075880A1 (en) * | 2002-03-11 | 2003-09-18 | Unilever Plc | Cosmetic compositions comprising citric acid triesters |
| WO2004093835A1 (en) * | 2003-04-17 | 2004-11-04 | The Procter & Gamble Company | Hair conditioning compostion comprising polysorbates |
| CN1513592A (en) * | 2003-08-20 | 2004-07-21 | ���Խ��� | Citrate anionic surface active agent and its preparation method |
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| CN1778459A (en) | 2006-05-31 |
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