CN106349274A - Organic silicon quaternary ammonium surfactant and preparation method thereof - Google Patents
Organic silicon quaternary ammonium surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN106349274A CN106349274A CN201610733904.4A CN201610733904A CN106349274A CN 106349274 A CN106349274 A CN 106349274A CN 201610733904 A CN201610733904 A CN 201610733904A CN 106349274 A CN106349274 A CN 106349274A
- Authority
- CN
- China
- Prior art keywords
- quaternary ammonium
- preparation
- surfactant
- ammonium salt
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 229910052710 silicon Inorganic materials 0.000 title abstract description 18
- 239000010703 silicon Substances 0.000 title abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229940023462 paste product Drugs 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 51
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 36
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000005292 vacuum distillation Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 8
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VOVKNAOBZXBVMN-UHFFFAOYSA-N dichloro(3-chloropropyl)silicon Chemical compound ClCCC[Si](Cl)Cl VOVKNAOBZXBVMN-UHFFFAOYSA-N 0.000 claims description 5
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- PHOQVHQSTUBQQK-SQOUGZDYSA-N D-glucono-1,5-lactone Chemical compound OC[C@H]1OC(=O)[C@H](O)[C@@H](O)[C@@H]1O PHOQVHQSTUBQQK-SQOUGZDYSA-N 0.000 claims description 3
- 238000011938 amidation process Methods 0.000 claims description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 125000002252 acyl group Chemical group 0.000 claims 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 11
- 125000004442 acylamino group Chemical group 0.000 abstract 1
- -1 weaving Substances 0.000 description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000007789 sealing Methods 0.000 description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 10
- UIUXUFNYAYAMOE-UHFFFAOYSA-N methylsilane Chemical compound [SiH3]C UIUXUFNYAYAMOE-UHFFFAOYSA-N 0.000 description 9
- 238000006136 alcoholysis reaction Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 125000004494 ethyl ester group Chemical group 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an organic silicon quaternary ammonium surfactant and a preparation method of the organic silicon quaternary ammonium surfactant. The organic silicon quaternary ammonium surfactant is prepared by 1) preparing midbody of organic silicon; 2) preparing midbody of acylamino; 3) preparing organic silicon quaternary ammonium surfactant, and finally obtaining yellowish-brown paste product. The invention provides an economic and simple method for preparing the organic silicon quaternary ammonium surfactant; compared with the traditional surfactant, the surfactant has high surface activity, good water solubility and biological degradability; the surfactant is safe and environmental-friendly while remains the excellent characteristics of the organic silicon surfactant.
Description
Technical field
The present invention relates to a kind of organosilicone quaternary ammonium salt surfactant of function admirable and its system-Preparation Method, such surface
Activating agent can belong to field of fine chemical as household chemicalss, textile finshing agent etc..
Background technology
Organic silicon surfactant is as a kind of novel surfactant that organosilicon material grows up, and it removes has
Outside the general character of conventional surfactants, also have compared with the more preferable surface activity of conventional surfactants, moistening, spreading property and
The superior function such as nontoxic, harmless, efficient, safety and physiological inertia.In recent years, organic silicon surfactant is with its special performance
Cause the great interest of people, and obtain a wide range of applications in fields such as daily use chemicals, weaving, pesticide and oil fields.Organosilicon season
Ammonium salt is class Novel Cationic Surfactants, and it is while giving fabric excellent anti-bacterium capability moreover it is possible to make fabric possess
Good water absorption, absorption of perspiration, flexibility, flatness, resilience, static electricity resistance and pollution resistance.But silicone industry in China quaternary ammonium salt
In the research starting evening of surfactant, research is not still deep enough compared with abroad, mainly due to complicated process of preparation, operates
Condition has high demands, and environmental pollution is big, and power consumption is high, product purification difficult.Therefore, design synthesizing efficient, green from molecular structure
Color, environmental protection, low cost, high-quality organosilicone quaternary ammonium salt surfactant important in inhibiting in actual production.The present invention
One class amide based surfactants with cheap ester as Material synthesis, such surfactant has than general surfactant
Have more preferable biological degradability, water solublity and hydrolytic resistance, have simultaneously raw material be easy to get, low abnormal smells from the patient, nontoxic, environmental protection,
Low production cost, processing are simple, function admirable the features such as.
Content of the invention
Object of the present invention is to provide a kind of organosilicone quaternary ammonium salt surfactant and preparation method thereof, system of the present invention
Standby surfactant has higher surface activity, preferable water solublity and biodegradation compared with conventional surfactant
Property, safe and environmentally friendly, remain the excellent characteristic of organic silicon surfactant simultaneously again.
For reaching above-mentioned purpose, the technical scheme is that
A kind of organosilicone quaternary ammonium salt surfactant, shown in structural formula such as formula (1):
In formula, r is ch3Or (ch3)3Sio, r1For hoch2conh(ch2)3Or hoch2(choh)4conh(ch2) or ho
(ch2)3conh(ch2)3Or ho (ch2)5conh(ch2)3；
A kind of preparation method of organosilicone quaternary ammonium salt surfactant, comprises the steps:
1) preparation of silicone intermediate: press the mol ratio of 1:4～6 using chloropropyl trichloro-silane and trim,ethylchlorosilane
Or added in reaction bulb using the mol ratio that 1:2～4 pressed by chloropropyl dichlorosilane and trim,ethylchlorosilane, then Deca respectively
Isopropanol and deionized water are reacted, and are then peeled off organic layer, and deionized water is washed till neutrality, plus anhydrous na2so4It is dried
Overnight, then vacuum distillation obtains silicone intermediate；
2) preparation of the intermediate of amide groups: using methyl glycollate, d- glucono-δ-lactone, gamma-butyrolacton and ε-
One of caprolactone carries out amidation process with 3- DIMAPA by the mol ratio of 1:1～1.2, and reaction end is used just own
Alkane or methanol and the multiple washed product of mixture of ethyl acetate, place in drying baker and are dried.
3) preparation of organosilicone quaternary ammonium salt surfactant: with benzyl alcohol as solvent, ki is catalyst, by step 2) preparation
Amide groups intermediate and step 1) silicone intermediate prepared by 1:1～3 mol ratio, in n2Protection is lower to react, reaction
After end, vacuum distillation removes solvent, and is repeatedly purified with the mixture of ether and acetone, obtains yellowish-brown paste product.
Described step 1) in 6h be stirred at room temperature, reaction end is cooled to room temperature.
Described step 2) in reaction temperature be 90～110 DEG C.
Described step 3) in n2Lower 90～100 DEG C of reaction 48h of protection.
The invention has the beneficial effects as follows: the invention provides a kind of economical and convenient prepares organosilicone quaternary ammonium salt surfactant
Method, this surfactant has higher surface activity, preferable water solublity and biology compared with conventional surfactant
Degradability, safe and environmentally friendly, remain the excellent characteristic of organic silicon surfactant simultaneously again.
Table 1 be test in embodiment 7 the measured cmc of glucose amide esters organosilicone quaternary ammonium salt surfactant and
γcmcTable.
Specific embodiment
Embodiment 1
A kind of organosilicone quaternary ammonium salt surfactant preparation method of the present embodiment, comprises the steps:
1) preparation of chloropropyl three-(trimethylsiloxy group) silane；
In the reaction bulb equipped with reflux condensing tube, add 8.47g (0.04mol) chloropropyl trichloro-silane and 26.06g
(0.24mol) trim,ethylchlorosilane, is stirred at room temperature down and is slowly added to 21.62g (0.36mol) isopropanol and carries out alcoholysis reaction, so
Deca 6.48g (0.36mol) deionized water more afterwards, is stirred at room temperature 6h, is cooled to room temperature, separates organic layer, deionized water
It is washed till neutrality, plus anhydrous na2so4It is dried overnight, vacuum distillation obtains chloropropyl three-(trimethylsiloxy group) silane.
2) preparation of n- (3- dimethylamino-propyl) d- glucose amide ester；
7.12g (0.04mol) d- glucono-δ-lactone is added in the reaction bulb of 250ml, is filled with n2Sealing, plus
Enter 60ml methanol, add 4.08g (0.04mol) 3- DIMAPA, back flow reaction 8h, it is molten that reaction terminates revolving removing
Agent, adds multiple washed product at 60～65 DEG C of normal hexane, is then placed in being dried in vacuum drying oven.
3) preparation of organosilicone quaternary ammonium salt surfactant；
By 2.80g (0.01mol) step 2) n- (3- dimethylamino-propyl) the d- glucose amide ester prepared, 0.05g
(0.0003mol) ki and 30ml benzyl alcohol is added in 100ml reaction bulb, is filled with n2Sealing, is slowly added to 11.18g
(0.03mol) step 1) chloropropyl three-(trimethylsiloxy group) silane prepared, 90 DEG C of reaction 48h, reaction terminates vacuum distillation
Remove solvent, and repeatedly purified with the mixture of ether and acetone, dry yellowish-brown paste product.
Three-step reaction in the said method of the present embodiment, reaction scheme is as follows:
1) preparation of chloropropyl three-(trimethylsiloxy group) silane
2) amidation process
3) quaterisation
Above-mentioned prepared organosilicone quaternary ammonium salt surfactant is carried out with infrared spectrum and nuclear magnetic resonance, NMR characterizes, data is such as
Under.Understand that synthesized compound is consistent with the structure of target product by infrared spectrum and nmr spectrum.
Ftir (kbr, cm-1): 3251～3456 (- oh), 2890～2960 (c-h), 1654 (c=o), 1558 (n h),
1258,838,756 (si-me3), 1025～1135 (c-o, si-o).
1h nmr(cdcl3, ppm): 0.07 (s, 27h, si-ch3), 0.42～0.56 (t, 2h, si-ch2), 1.63～
1.80(m,2h,si-c-ch2-), 2.01～2.19 (t, 2h, n-c-ch2- c), 3.13 (s, 6h, n- (ch3)2), 3.22 (t, 2h,
n-c-c-ch2-), 3.39 (m, 4h, si-c-c-ch2-n-ch2-), 3.73 (s, 4h ,-(ch)4-), 4.11,4.31 (d, 2h ,-
ch2-), 4.57～4.69 (s, 5h ,-oh), 8.12 (s, h ,-nh-)
The present embodiment is prepared for a kind of method that economical and convenient prepares organosilicone quaternary ammonium salt surfactant, this surface activity
Agent has higher surface activity, preferable water solublity and biological degradability compared with conventional surfactant, not only safety but also ring
Protect, remain the excellent characteristic of organic silicon surfactant simultaneously again.
Embodiment 2
A kind of organosilicone quaternary ammonium salt surfactant preparation method of the present embodiment, comprises the steps:
1) preparation of chloropropyl two-(trimethylsiloxy group) methyl-monosilane；
In the reaction bulb equipped with reflux condensing tube, add 9.57g (0.05mol) chloropropyl dichlorosilane and
21.64g (0.20mol) trim,ethylchlorosilane, is stirred at room temperature down and is slowly added to 18.00g (0.30mol) isopropanol to carry out alcoholysis anti-
Should, then it is slowly added dropwise 5.40g (0.30mol) deionized water again, 6h is stirred at room temperature, be cooled to room temperature, separate organic layer, use
Deionized water is washed till neutrality, plus anhydrous na2so4It is dried overnight, vacuum distillation obtains chloropropyl two-(trimethylsiloxy group) methyl
Silane.
2) preparation of n- (3- dimethylamino-propyl) glycollic amide ester；
12.26g (0.12mol) 3- DIMAPA is added in the reaction bulb of 100ml, is filled with n2Sealing, 50
～70 DEG C of addition 9.01g (0.10mol) methyl glycollates, mixture reacts 8h at 100 DEG C, and reaction terminates to add methanol and acetic acid
The mixture of ethyl ester carries out recrystallization to crude product, places in vacuum drying oven and is dried.
3) preparation of organosilicone quaternary ammonium salt surfactant；
By 3.20g (0.02mol) step 2) n- (3- dimethylamino-propyl) the glycollic amide ester prepared, 0.03g
(0.0002mol) ki and 30ml benzyl alcohol is added in 100ml reaction bulb, is filled with n2Sealing, is slowly added to 5.98g
(0.02mol) step 1) chloropropyl two-(trimethylsiloxy group) methyl-monosilane prepared, 90 DEG C of reaction 48h, reaction terminates decompression
Solvent is distilled off, and is repeatedly purified with the mixture of ether and acetone, dry yellowish-brown paste product.
The present embodiment is prepared for a kind of method that economical and convenient prepares organosilicone quaternary ammonium salt surfactant, this surface activity
Agent has higher surface activity, preferable water solublity and biological degradability compared with conventional surfactant, not only safety but also ring
Protect, remain the excellent characteristic of organic silicon surfactant simultaneously again.
Embodiment 3
The present embodiment as described in Example 1, except that the rate of charge of raw material, specifically comprises the following steps that
1) preparation of chloropropyl three-(trimethylsiloxy group) silane；
In the reaction bulb equipped with reflux condensing tube, add 8.47g (0.04mol) chloropropyl trichloro-silane and 21.64g
(0.20mol) trim,ethylchlorosilane, is stirred at room temperature down and is slowly added to 18.00g (0.30mol) isopropanol and carries out alcoholysis reaction, so
Deca 5.40g (0.30mol) deionized water more afterwards, is stirred at room temperature 6h, is cooled to room temperature, separates organic layer, deionized water
It is washed till neutrality, plus anhydrous na2so4It is dried overnight, vacuum distillation obtains chloropropyl three-(trimethylsiloxy group) silane.
2) preparation of n- (3- dimethylamino-propyl) γ-butanol carboxylic acid amide esters；
11.24g (0.11mol) 3- DIMAPA is added in the reaction bulb of 100ml, is filled with n2Sealing, 50
～70 DEG C of addition 8.61g (0.10mol) gamma-butyrolactons, mixture reacts 8h at 100 DEG C, and reaction terminates to add methanol and acetic acid
The mixture of ethyl ester carries out recrystallization to crude product, places in vacuum drying oven and is dried.
3) preparation of organosilicone quaternary ammonium salt surfactant；
By 1.88g (0.01mol) step 2) n- (3- dimethylamino-propyl) γ-butanol carboxylic acid amide esters of preparing, 0.03g
(0.0002mol) ki and 30ml benzyl alcohol is added in 100ml reaction bulb, is filled with n2Sealing, is slowly added to 7.45g
(0.02mol) step 1) chloropropyl three-(trimethylsiloxy group) silane prepared, 95 DEG C of reaction 48h, reaction terminates vacuum distillation
Remove solvent, and repeatedly purified with the mixture of ether and acetone, dry yellowish-brown paste product.
The present embodiment is prepared for a kind of method that economical and convenient prepares organosilicone quaternary ammonium salt surfactant, this surface activity
Agent has higher surface activity, preferable water solublity and biological degradability compared with conventional surfactant, not only safety but also ring
Protect, remain the excellent characteristic of organic silicon surfactant simultaneously again.
Embodiment 4
The present embodiment as described in Example 2, except that the rate of charge of raw material, specifically comprises the following steps that
1) preparation of chloropropyl two-(trimethylsiloxy group) methyl-monosilane；
In the reaction bulb equipped with reflux condensing tube, add 9.57g (0.05mol) chloropropyl dichlorosilane and
10.82g (0.10mol) trim,ethylchlorosilane, is stirred at room temperature down and is slowly added to 9.00g (0.15mol) isopropanol to carry out alcoholysis anti-
Should, then it is slowly added dropwise 2.70g (0.15mol) deionized water again, 6h is stirred at room temperature, be cooled to room temperature, separate organic layer, use
Deionized water is washed till neutrality, plus anhydrous na2so4It is dried overnight, vacuum distillation obtains chloropropyl two-(trimethylsiloxy group) methyl
Silane.
2) preparation of n- (3- dimethylamino-propyl) ε-hexanol carboxylic acid amide esters；
12.26g (0.12mol) 3- DIMAPA is added in the reaction bulb of 100ml, is filled with n2Sealing, 50
～70 DEG C of addition 11.41g (0.10mol) 6-caprolactones, mixture reacts 8h at 110 DEG C, and reaction terminates to add methanol and acetic acid
The mixture of ethyl ester carries out recrystallization to crude product, places in vacuum drying oven and is dried.
3) preparation of organosilicone quaternary ammonium salt surfactant；
By 2.16g (0.01mol) step 2) n- (3- dimethylamino-propyl) ε-hexanol carboxylic acid amide esters of preparing, 0.03g
(0.0003mol) ki and 30ml benzyl alcohol is added in 100ml reaction bulb, is filled with n2Sealing, is slowly added to 8.96g
(0.03mol) step 1) chloropropyl two-(trimethylsiloxy group) methyl-monosilane prepared, 95 DEG C of reaction 48h, reaction terminates decompression
Solvent is distilled off, and is repeatedly purified with the mixture of ether and acetone, dry yellowish-brown paste product.
The present embodiment is prepared for a kind of method that economical and convenient prepares organosilicone quaternary ammonium salt surfactant, this surface activity
Agent has higher surface activity, preferable water solublity and biological degradability compared with conventional surfactant, not only safety but also ring
Protect, remain the excellent characteristic of organic silicon surfactant simultaneously again.
Embodiment 5
The present embodiment as described in Example 1, except that the rate of charge of raw material, specifically comprises the following steps that
1) preparation of chloropropyl three-(trimethylsiloxy group) silane；
In the reaction bulb equipped with reflux condensing tube, add 12.72g (0.06mol) chloropropyl trichloro-silane and 26.07g
(0.24mol) trim,ethylchlorosilane, is stirred at room temperature down and is slowly added to 21.62g (0.36mol) isopropanol and carries out alcoholysis reaction, so
Deca 6.48g (0.36mol) deionized water more afterwards, is stirred at room temperature 6h, is cooled to room temperature, separates organic layer, deionized water
It is washed till neutrality, plus anhydrous na2so4It is dried overnight, vacuum distillation obtains chloropropyl three-(trimethylsiloxy group) silane.
2) preparation of n- (3- dimethylamino-propyl) glycollic amide ester；
10.22g (0.10mol) 3- DIMAPA is added in the reaction bulb of 100ml, is filled with n2Sealing, 50
～70 DEG C of addition 9.01g (0.10mol) methyl glycollates, mixture reacts 8h at 100 DEG C, and reaction terminates to add methanol and acetic acid
The mixture of ethyl ester carries out recrystallization to crude product, places in vacuum drying oven and is dried.
3) preparation of organosilicone quaternary ammonium salt surfactant；
By 3.20g (0.02mol) step 2) n- (3- dimethylamino-propyl) the glycollic amide ester prepared, 0.03g
(0.0002mol) ki and 30ml benzyl alcohol is added in 100ml reaction bulb, is filled with n2Sealing, is slowly added to 7.46g
(0.02mol) step 1) chloropropyl three-(trimethylsiloxy group) silane prepared, 100 DEG C of reaction 48h, reaction terminates decompression and steams
Evaporate removing solvent, and repeatedly purified with the mixture of ether and acetone, dry yellowish-brown paste product.
The present embodiment is prepared for a kind of method that economical and convenient prepares organosilicone quaternary ammonium salt surfactant, this surface activity
Agent has higher surface activity, preferable water solublity and biological degradability compared with conventional surfactant, not only safety but also ring
Protect, remain the excellent characteristic of organic silicon surfactant simultaneously again.
Embodiment 6
The present embodiment as described in Example 2, except that the rate of charge of raw material, specifically comprises the following steps that
1) preparation of chloropropyl two-(trimethylsiloxy group) methyl-monosilane；
In the reaction bulb equipped with reflux condensing tube, add 7.66g (0.04mol) chloropropyl dichlorosilane and
13.04g (0.12mol) trim,ethylchlorosilane, is stirred at room temperature down and is slowly added to 10.81g (0.18mol) isopropanol to carry out alcoholysis anti-
Should, then it is slowly added dropwise 3.24g (0.18mol) deionized water again, 6h is stirred at room temperature, be cooled to room temperature, separate organic layer, use
Deionized water is washed till neutrality, plus anhydrous na2so4It is dried overnight, vacuum distillation obtains chloropropyl two-(trimethylsiloxy group) methyl
Silane.
2) preparation of n- (3- dimethylamino-propyl) γ-butanol carboxylic acid amide esters；
10.22g (0.10mol) 3- DIMAPA is added in the reaction bulb of 100ml, is filled with n2Sealing, 50
～70 DEG C of addition 8.61g (0.10mol) gamma-butyrolactons, mixture reacts 8h at 100 DEG C, and reaction terminates to add methanol and acetic acid
The mixture of ethyl ester carries out recrystallization to crude product, places in vacuum drying oven and is dried.
3) preparation of organosilicone quaternary ammonium salt surfactant；
By 1.88g (0.01mol) step 2) n- (3- dimethylamino-propyl) γ-butanol carboxylic acid amide esters of preparing, 0.03g
(0.0002mol) ki and 30ml benzyl alcohol is added in 100ml reaction bulb, is filled with n2Sealing, is slowly added to 5.98g
(0.02mol) step 1) chloropropyl two-(trimethylsiloxy group) methyl-monosilane prepared, 100 DEG C of reaction 48h, reaction end subtracts
Pressure is distilled off solvent, and is repeatedly purified with the mixture of ether and acetone, dry yellowish-brown paste product.
The present embodiment is prepared for a kind of method that economical and convenient prepares organosilicone quaternary ammonium salt surfactant, this surface activity
Agent has higher surface activity, preferable water solublity and biological degradability compared with conventional surfactant, not only safety but also ring
Protect, remain the excellent characteristic of organic silicon surfactant simultaneously again.
Embodiment 7
The present embodiment is by the glucose amide preparing in embodiment 1 esters organosilicon quaternary ammonium salt surfactant formulatory
Become a series of testing sample solution of variable concentrations, its dense critical micelle concentration (cmc) is surveyed using sessile drop method and critical micell is dense
Surface tension γ under degreecmc.
Cmc and γ of the measured glucose amide esters organosilicone quaternary ammonium salt surfactant of experimentcmcAs shown in table 1,
The synthesized relatively conventional organosilicon quaternary ammonium salt surface activity of glucose amide esters organosilicone quaternary ammonium salt surfactant is described
Agent has relatively low cmc and surface tension.
Table 1
| Title | cmc | γcmc |
| Organosilicone quaternary ammonium salt surfactant | 12.0mmol/l | 21.9mn/m |
Claims (5)
1. a kind of organosilicone quaternary ammonium salt surfactant is it is characterised in that structural formula such as formula (1) is shown:
In formula, r is ch3Or (ch3)3Sio, r1For hoch2conh(ch2)3Or hoch2(choh)4conh(ch2) or ho (ch2)3conh(ch2)3Or ho (ch2)5conh(ch2)3.
2. as claimed in claim 1 a kind of preparation method of organosilicone quaternary ammonium salt surfactant it is characterised in that include as
Lower step:
1) preparation of silicone intermediate: by the mol ratio of 1:4～6 or adopted using chloropropyl trichloro-silane and trim,ethylchlorosilane
Added in reaction bulb with the mol ratio that chloropropyl dichlorosilane and trim,ethylchlorosilane press 1:2～4, then Deca isopropyl respectively
Alcohol and deionized water are reacted, and are then peeled off organic layer, and deionized water is washed till neutrality, plus anhydrous na2so4It is dried overnight,
Vacuum distillation obtains silicone intermediate again；
2) preparation of the intermediate of amide groups: using methyl glycollate, d- glucono-δ-lactone, gamma-butyrolacton and ε-oneself in
One of ester and 3- DIMAPA carry out amidation process by the mol ratio of 1:1～1.2, reaction end normal hexane or
Methanol and the multiple washed product of mixture of ethyl acetate, place in drying baker and are dried.
3) preparation of organosilicone quaternary ammonium salt surfactant: with benzyl alcohol as solvent, ki is catalyst, by step 2) acyl prepared
Amido intermediate and step 1) silicone intermediate prepared by 1:1～3 mol ratio, in n2Protection is lower to react, and reaction terminates
Vacuum distillation removes solvent afterwards, and is repeatedly purified with the mixture of ether and acetone, obtains yellowish-brown paste product.
3. as claimed in claim 2 a kind of preparation method of organosilicone quaternary ammonium salt surfactant it is characterised in that described
Step 1) in 6h be stirred at room temperature, reaction end is cooled to room temperature.
4. as claimed in claim 2 a kind of preparation method of organosilicone quaternary ammonium salt surfactant it is characterised in that described
Step 2) in reaction temperature be 90～110 DEG C.
5. as claimed in claim 2 a kind of preparation method of organosilicone quaternary ammonium salt surfactant it is characterised in that described
Step 3) in n2Lower 90～100 DEG C of reaction 48h of protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610733904.4A CN106349274A (en) | 2016-08-25 | 2016-08-25 | Organic silicon quaternary ammonium surfactant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610733904.4A CN106349274A (en) | 2016-08-25 | 2016-08-25 | Organic silicon quaternary ammonium surfactant and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106349274A true CN106349274A (en) | 2017-01-25 |
Family
ID=57854770
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610733904.4A Pending CN106349274A (en) | 2016-08-25 | 2016-08-25 | Organic silicon quaternary ammonium surfactant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106349274A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948068A (en) * | 2018-07-23 | 2018-12-07 | 皖西学院 | The preparation method of alkyl imidazoline organosilicon quaternary ammonium salt |
| CN109837760A (en) * | 2019-03-08 | 2019-06-04 | 新昌县高纤纺织有限公司 | Environment-friendly type composite fabric finishing agent and preparation method thereof |
| CN111072716A (en) * | 2020-01-06 | 2020-04-28 | 江西蓝星星火有机硅有限公司 | Preparation method of tetramethyl tetravinylcyclotetrasiloxane |
| CN113698444A (en) * | 2021-08-25 | 2021-11-26 | 太和县芮欣生物科技有限公司 | Cationic alkyl glycoside quaternary ammonium salt surfactant and preparation process thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788487A (en) * | 2015-05-11 | 2015-07-22 | 九江学院 | Hydrolysis resistant Si-C-Si type cation organosilicon surfactant |
-
2016
- 2016-08-25 CN CN201610733904.4A patent/CN106349274A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788487A (en) * | 2015-05-11 | 2015-07-22 | 九江学院 | Hydrolysis resistant Si-C-Si type cation organosilicon surfactant |
Non-Patent Citations (3)
| Title |
|---|
| FU HAN等: ""Synthesis and Characterization of a Quaternized Glucosamide-Based Trisiloxane Surfactant"", 《J. SURFACT. DETERG.》 * |
| JINGLIN TAN等: ""Effect of hydrophobic chains on the aggregation behavior of cationic silicone surfactants in aqueous solution"", 《COLLOID POLYM SCI》 * |
| 梁维平 等: ""四硅氧烷Gemini咪唑表面活性剂的合成及表面性能"", 《高等学校化学学报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108948068A (en) * | 2018-07-23 | 2018-12-07 | 皖西学院 | The preparation method of alkyl imidazoline organosilicon quaternary ammonium salt |
| CN108948068B (en) * | 2018-07-23 | 2020-03-10 | 皖西学院 | Preparation method of alkyl imidazoline organosilicon quaternary ammonium salt |
| CN109837760A (en) * | 2019-03-08 | 2019-06-04 | 新昌县高纤纺织有限公司 | Environment-friendly type composite fabric finishing agent and preparation method thereof |
| CN111072716A (en) * | 2020-01-06 | 2020-04-28 | 江西蓝星星火有机硅有限公司 | Preparation method of tetramethyl tetravinylcyclotetrasiloxane |
| CN111072716B (en) * | 2020-01-06 | 2022-08-30 | 江西蓝星星火有机硅有限公司 | Preparation method of tetramethyl tetravinylcyclotetrasiloxane |
| CN113698444A (en) * | 2021-08-25 | 2021-11-26 | 太和县芮欣生物科技有限公司 | Cationic alkyl glycoside quaternary ammonium salt surfactant and preparation process thereof |
| CN113698444B (en) * | 2021-08-25 | 2024-05-03 | 东莞市妮特洗涤用品有限公司 | Cationic alkyl glycoside quaternary ammonium salt surfactant and preparation process thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106349274A (en) | Organic silicon quaternary ammonium surfactant and preparation method thereof | |
| CA2352436A1 (en) | Polymorphs of telmisartan, processes for preparing them and their use in the preparation of a pharmaceutical composition | |
| CN103059305B (en) | Preparation method of antibacterial hydrophobic complexing agent for polyester fibers | |
| CN110776972B (en) | Synthetic ester lubricating oil base oil based on green renewable resources | |
| CN106475005A (en) | A kind of cation type organic silicon Gemini surface active agent and preparation method thereof | |
| CN102250449A (en) | Process for synthesizing saturated polyester resin by using recycled terephthalic acid | |
| CN113512023B (en) | Crosslinking agent containing double-dynamic imine bond, self-repairing polymer and preparation method of self-repairing polymer | |
| CN113651723A (en) | Synthetic method, intermediate and application of 3- (3-hydroxyphenyl) -1, 1-dimethylurea | |
| CN110368987B (en) | Preparation method and application of tree-like loofah sponge supported ionic liquid catalyst | |
| EP3395808B1 (en) | Pseudo-ceramide compound and preparation method therefor | |
| JP2012513523A5 (en) | ||
| US5773629A (en) | Synthesis of (4S, 5R) -2, 4-diphenyl-5-carboxy-oxazoline derivative as taxol side-chain precursor | |
| CN113234113B (en) | Method for constructing 1, 2-cis-2-nitro-glucoside and galactose glucoside | |
| CN109879854A (en) | A kind of cyclobutane ketone compounds and preparation method thereof with antioxidation | |
| JP5615372B2 (en) | Polyurethane synthesis by self-condensation | |
| CN102050804A (en) | Methods for preparing docetaxel and intermediates thereof | |
| CN109438503B (en) | Organic silicon-chlorine flame retardant chloropropyl silicic acid trisilicon caged alcohol ester compound and preparation method thereof | |
| CN108070087B (en) | Preparation method of fluorine-containing polyether modified organic silicon polyol | |
| CN114394896A (en) | Glyceryl ester plasticizer, preparation method thereof and nontoxic environment-friendly polyvinyl chloride | |
| CN107629107B (en) | Synthetic method of ulipristal acetate | |
| CN115477595A (en) | Galanthamine intermediate compound | |
| CN107954873B (en) | Polysubstituted olefine acid ester derivative and preparation method thereof | |
| KR20080070500A (en) | Semisynthesis process for paclitaxel and docetaxel | |
| CN109503886B (en) | Flame-retardant charring agent silicic acid tetrasilicon caged alcohol ester compound and preparation method thereof | |
| CN105885017A (en) | Naphthalene tetracarboxylic diimide novel high-molecular polymer with triple bond |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170125 |
|
| RJ01 | Rejection of invention patent application after publication |