CN105771789B - A kind of phosphate-based quaternary cationics and its synthetic method - Google Patents
A kind of phosphate-based quaternary cationics and its synthetic method Download PDFInfo
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- CN105771789B CN105771789B CN201610171064.7A CN201610171064A CN105771789B CN 105771789 B CN105771789 B CN 105771789B CN 201610171064 A CN201610171064 A CN 201610171064A CN 105771789 B CN105771789 B CN 105771789B
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- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 66
- 239000010452 phosphate Substances 0.000 title claims abstract description 66
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 62
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 35
- 238000010189 synthetic method Methods 0.000 title claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims abstract description 6
- 239000003093 cationic surfactant Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 150000003512 tertiary amines Chemical class 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005292 vacuum distillation Methods 0.000 claims description 10
- 239000005457 ice water Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 8
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001350 alkyl halides Chemical class 0.000 claims description 6
- -1 chlorine di-phosphate ester Chemical class 0.000 claims description 6
- LGTLXDJOAJDFLR-UHFFFAOYSA-N diethyl chlorophosphate Chemical compound CCOP(Cl)(=O)OCC LGTLXDJOAJDFLR-UHFFFAOYSA-N 0.000 claims description 6
- 208000006278 hypochromic anemia Diseases 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- HXBZCHYDLURWIZ-UHFFFAOYSA-N diphenyl hydrogen phosphate;hydrochloride Chemical compound Cl.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 HXBZCHYDLURWIZ-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical class CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 2
- KOFZTCSTGIWCQG-UHFFFAOYSA-N 1-bromotetradecane Chemical class CCCCCCCCCCCCCCBr KOFZTCSTGIWCQG-UHFFFAOYSA-N 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 2
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical class CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 239000003995 emulsifying agent Substances 0.000 abstract description 3
- 231100000584 environmental toxicity Toxicity 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 abstract description 2
- 229910052791 calcium Inorganic materials 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000000344 soap Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 11
- 230000002194 synthesizing effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 150000003222 pyridines Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- MOULNFHEXIVCEW-UHFFFAOYSA-M azanium;potassium;dihydroxide Chemical compound [NH4+].[OH-].[OH-].[K+] MOULNFHEXIVCEW-UHFFFAOYSA-M 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 125000002270 phosphoric acid ester group Chemical group 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Classifications
-
- 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
- C09K23/14—Derivatives of phosphoric acid
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/11—Esters of phosphoric acids with hydroxyalkyl compounds without further substituents on alkyl
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/12—Esters of phosphoric acids with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The present invention relates to cationic surfactant field, and in particular to a kind of phosphate-based quaternary cationics and its synthetic method.The present invention provides a kind of phosphate-based quaternary cationics, contains phosphate-based and quaternary ammonium salt group in its structure.The present invention is synthesized using two steps, and synthesis technique is simple, and product separating-purifying is easy, the recyclable recycling of the organic solvent used.The product of synthesis has very high surface-active, and biological degradability is good, and eco-toxicity is low, dispersion of calcium soap is excellent.It in addition, the emulsifiability of product is good, can use separately as emulsifying agent, can also be compounded with the chemicals with special applications performance, while this product also has good bactericidal action.
Description
Technical field
The present invention relates to cationic surfactant field, and in particular to lives on a kind of phosphate-based quaternary ammonium salt cationic surface
Property agent and its synthetic method.
Background technology
Phosphate ester surfactant is the surfactant of phosphoric acid ester group or phosphate ester salt group in molecular structure
It is referred to as, is that one kind has premium properties, the surfactant being widely used.Its premium properties mainly includes good emulsification
Property, antistatic behaviour, eco-toxicity are low and biological degradability is good etc..
Quaternary cationics is fast-growth, had wide range of applications, a kind of work of surface of function admirable
Property agent, all it is the study hotspot of surfactant field all the time.Quaternary ammonium salt cationic surfactant is due to hydrophilic group
It is positively charged, there is stronger suction-operated to bacterium of the cell membrane with negative electrical charge, diffusion effect enters cell membrane, then
Cell interior is further penetrated through, is passivated desmoenzyme, it is protein-modified, play bactericidal action so as to kill bacterium.In addition, season
Ammonium salt cationic surfactant is also used as softening agent, dispersant, wetting agent and emulsifying agent etc..
At present, the research of phosphate base class surfactant is mainly also anionic and nonionic, but relevant is contained
The report of the quaternary cationics of phosphate-based structure is seldom, traces it to its cause and may is that synthesis technique need
Research and perfect, the problems such as purification of products is difficult, complicated, therefore, it is necessary to the quaternary ammonium salt sun containing phosphate-based structure from
The synthetic method of sub- surfactant is studied.
The content of the invention
It is an object of the present invention to provide a kind of phosphate-based quaternary cationics, contain phosphate in its structure
Base and quaternary ammonium salt group.
It is a further object to provide the synthetic method of above-mentioned phosphate-based quaternary cationics.
A kind of phosphate-based quaternary cationics, chemical structural formula are as follows：
；
Wherein, n=8,10,12,14；R is ethyl or phenyl；X is Cl or Br.
A kind of synthetic method of phosphate-based quaternary cationics, comprises the following steps：
（a）Chlorine di-phosphate ester, organic solvent A and acid binding agent are added in the reactor of inert atmosphere, is placed in ice-water bath,
Stirring, N methyldiethanol amine is added, the reaction time is 3~6h, when the content for measuring unhindered amina is less than 0.2%, is terminated anti-
Should, organic solvent is removed in vacuum distillation, is filtered, is obtained phosphate-based tertiary amine；
（b）Phosphate-based tertiary amine, alkyl halide and organic solvent B are added into reactor, stirs, is warming up to 70~100 DEG C,
20~45h of back flow reaction, stop reaction, be evaporated under reduced pressure and remove organic solvent B, then recrystallized with ether, finally obtain institute
State phosphate-based quaternary ammonium salt sun.
Further, the step（1）In chlorine di-phosphate ester for diethyl chloro-phosphate, in diphenyl phosphate chloride one
Kind.
Further, the step（1）In organic solvent A be toluene, dimethylbenzene, dichloromethane, in tetrahydrofuran
It is at least one.
Further, the step（1）In acid binding agent for triethylamine, pyridine, sodium carbonate, potassium carbonate, sodium hydroxide, hydrogen
At least one of potassium oxide.
Further, the step（1）In chlorine di-phosphate ester and N methyldiethanol amine mol ratio be 2.0~2.1：
1。
Further, the step（2）In alkyl halide for 1- chloros octane, 1- bromooctanes, 1- chloros decane, 1- bromines
For one kind in decane, Dodecyl Bromide, 1- bromotetradecanes.
Further, the step（2）In phosphate-based tertiary amine and alkyl halide mol ratio be 1：1~1.2.
Further, the step（2）In organic solvent B be ethanol, isopropanol, at least one of acetone.
The present invention has the advantages that：
（1）The present invention is synthesized using two steps, and synthesis technique is simple, and product separating-purifying is easy, and the organic solvent used can
Recycling.
（2）The product that the present invention synthesizes has very high surface-active, and biological degradability is good, and eco-toxicity is low, calcium soap point
It is excellent to dissipate power.
（3）The product emulsifiability that the present invention synthesizes is good, can be used separately as emulsifying agent, also can with special applications
The chemicals of performance is compounded, while this product also has good bactericidal action.
Embodiment
With reference to embodiment, the present invention will be described in detail.Embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
（1）34.5g diethyl chloro-phosphates, 100mL toluene and 6.67g triethylamines are added into the reactor of inflated with nitrogen, is put
In ice-water bath, stirring, 11.92gN- methyl diethanolamines, 3~6h of reaction being added, the content for measuring unhindered amina is less than 0.2%,
Terminate reaction, organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）19.6g phosphate-based tertiary amine, 9.7g1- bromooctanes and 60mL ethanol are added into reactor, is stirred, heating
To 78 DEG C, back flow reaction 30h, stop reaction, be evaporated under reduced pressure and remove organic solvent, then recrystallized with ether, finally obtained
Described phosphate-based quaternary cationics.
Embodiment 2
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
（1）34.5g diethyl chloro-phosphates, 110mL toluene and 5g pyridines are added into the reactor of inflated with nitrogen, is placed in frozen water
In bath, stirring, 11.92gN- methyl diethanolamines, 3~6h of reaction are added, the content for measuring unhindered amina is less than 0.2%, terminates anti-
Should, organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）19.6g phosphate-based tertiary amine, 7.45g1- chloros octane and 80mL acetone are added into reactor, is stirred, is risen
Temperature stops reaction to 82 DEG C, back flow reaction 32h, is evaporated under reduced pressure and removes organic solvent, then is recrystallized with ether, finally
To described phosphate-based quaternary cationics.
Embodiment 3
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
It is placed in ice-water bath, stirs, add 11.92gN- methyl diethanolamines, 3~6h of reaction, measures the content of unhindered amina
Less than 0.2%, terminate reaction, organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）19.6g phosphate-based tertiary amine, 11.09g1- bromodecanes and 60mL isopropanols are added into reactor, is stirred,
85 DEG C, back flow reaction 34h are warming up to, stops reaction, is evaporated under reduced pressure and removes organic solvent, then is recrystallized with ether, finally
Obtain described phosphate-based quaternary cationics.
Embodiment 4
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
（1）34.5g diethyl chloro-phosphates, 110mL dimethylbenzene and 2.8g sodium hydroxides are added into the reactor of inflated with nitrogen,
It is placed in ice-water bath, stirs, add 11.92gN- methyl diethanolamines, 3~6h of reaction, the content for measuring unhindered amina is less than
0.2%, terminate reaction, organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）19.6g phosphate-based tertiary amine, 8.85g1- chloros decane and 70mL isopropanols are added into reactor, is stirred,
90 DEG C, back flow reaction 35h are warming up to, stops reaction, is evaporated under reduced pressure and removes organic solvent, then is recrystallized with ether, finally
Obtain described phosphate-based quaternary cationics.
Embodiment 5
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
（1）34.5g diethyl chloro-phosphates, 120mL toluene, 4g triethylamines and 1.8g hydrogen are added into the reactor of inflated with nitrogen
Potassium oxide, it is placed in ice-water bath, stirs, add 11.92gN- methyl diethanolamines, 3~6h of reaction, measures the content of unhindered amina
Less than 0.2%, terminate reaction, organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）19.6g phosphate-based tertiary amine, 12.5g1- bromododecanes and 80mL isopropanols are added into reactor, is stirred
Mix, be warming up to 92 DEG C, back flow reaction 36h, stop reaction, be evaporated under reduced pressure and remove organic solvent, then recrystallized with ether, most
Described phosphate-based quaternary cationics is obtained afterwards.
Embodiment 6
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
（1）53.73g diphenyl phosphate chlorides, 120mL dichloromethane and the second of 7.2g tri- are added into the reactor of inflated with nitrogen
Amine, it is placed in ice-water bath, stirs, add 11.92gN- methyl diethanolamines, 3~6h of reaction, the content for measuring unhindered amina is less than
0.2%, terminate reaction, organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）27.57g phosphate-based tertiary amine, 11.1g1- bromodecanes and 90mL ethanol are added into reactor, is stirred, is risen
Temperature stops reaction to 95 DEG C, back flow reaction 35h, is evaporated under reduced pressure and removes organic solvent, then is recrystallized with ether, finally
To described phosphate-based quaternary cationics.
Embodiment 7
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
（1）53.73g diphenyl phosphate chlorides, 130mL dichloromethane and 5.6g pyridines are added into the reactor of inflated with nitrogen,
It is placed in ice-water bath, stirs, add 11.92gN- methyl diethanolamines, 3~6h of reaction, the content for measuring unhindered amina is less than
0.2%, terminate reaction, organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）27.57g phosphate-based tertiary amine, 12.6g1- bromododecanes and 100mL ethanol are added into reactor, is stirred
Mix, be warming up to 98 DEG C, back flow reaction 40h, stop reaction, be evaporated under reduced pressure and remove organic solvent, then recrystallized with ether, most
Described phosphate-based quaternary cationics is obtained afterwards.
Embodiment 8
Exemplified by synthesizing the following phosphate quaternary cationics of chemical structural formula, specific synthetic method
For：
（1）Added into the reactor of inflated with nitrogen 53.73g diphenyl phosphate chlorides, 120mL tetrahydrofurans, 3.2g pyridines and
4.2g potassium carbonate, is placed in ice-water bath, stirring, adds 11.92gN- methyl diethanolamines, 3~6h of reaction, measures unhindered amina
Content is less than 0.2%, terminates reaction, and organic solvent is removed in vacuum distillation, is filtered, is obtained the phosphate-based tertiary amine of target product.
（2）27.57g phosphate-based tertiary amine, 13.92g1- bromotetradecanes and 110mL isopropanols are added into reactor,
Stirring, 100 DEG C, back flow reaction 42h are warming up to, stop reaction, be evaporated under reduced pressure and remove organic solvent, then tied again with ether
Crystalline substance, finally obtain the phosphate-based quaternary cationics of target product.
Emulsifiability is tested：
Each portion of sample aqueous solution of mass fraction 1% is prepared at 25 DEG C, takes the solution 25ml of preparation to pour into respectively
In 100ml graduated cylinders（With plug）, then 20ml mineral oil is added into graduated cylinder, observation, most postscript are stood after being aggressively shaken 25 times
Each mixed liquor separates the time used in 10ml water under record, and it is longer to separate the time of 10ml water, represents that emulsifiability is better, otherwise compared with
Difference.
Each product emulsifiability compares：
Note embodiment 1, embodiment 3, embodiment 5, embodiment 6, embodiment 7, the sintetics of embodiment 8 be respectively A, B,
C, D, E, F, each product emulsifiability are as shown in table 1.
Each product emulsifiability of table 1 compares
Illustrated by the experimental result of table 1, synthesized product has good emulsifiability.
Embodiment described above only expresses embodiments of the present invention, and its description is more specific and detailed, but can not
Therefore the limitation to the scope of the claims of the present invention is interpreted as, as long as the skill obtained using the form of equivalent substitution or equivalent transformation
Art scheme, it all should fall within the scope and spirit of the invention.
Claims (9)
1. a kind of phosphate-based quaternary cationics, it is characterised in that chemical structural formula is as follows：
；
Wherein, n=8,10,12,14；R is ethyl or phenyl；X is Cl or Br.
A kind of 2. synthetic method of phosphate-based quaternary cationics described in claim 1, it is characterised in that
Comprise the following steps：
(1) chlorine di-phosphate ester, organic solvent A and acid binding agent are added in the reactor of inert atmosphere, is placed in ice-water bath, stirs
To mix, add N methyldiethanol amine, the reaction time is 3~6h, when the content for measuring unhindered amina is less than 0.2%, terminates reaction,
Organic solvent is removed in vacuum distillation, is filtered, is obtained phosphate-based tertiary amine；
(2) phosphate-based tertiary amine, alkyl halide and organic solvent B are added into reactor, is stirred, is warming up to 70~100 DEG C, backflow
20~45h is reacted, stops reaction, is evaporated under reduced pressure and removes organic solvent B, then is recrystallized with ether, finally obtains the phosphorus
Acid esters based quaternary ammonium salt cationic surfactant.
3. a kind of synthetic method of phosphate-based quaternary cationics according to claim 2, its feature
It is：Chlorine di-phosphate ester in the step (1) is diethyl chloro-phosphate, one kind in diphenyl phosphate chloride.
4. a kind of synthetic method of phosphate-based quaternary cationics according to claim 2, its feature
It is：Organic solvent A in the step (1) is at least one of toluene, dimethylbenzene, dichloromethane, tetrahydrofuran.
5. a kind of synthetic method of phosphate-based quaternary cationics according to claim 2, its feature
It is：Acid binding agent in the step (1) is triethylamine, in pyridine, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide extremely
Few one kind.
6. a kind of synthetic method of phosphate-based quaternary cationics according to claim 2, its feature
It is：The mol ratio of chlorine di-phosphate ester and N methyldiethanol amine in the step (1) is 2.0~2.1：1.
7. a kind of synthetic method of phosphate-based quaternary cationics according to claim 2, its feature
It is：Alkyl halide in the step (2) is 1- chloros octane, 1- bromooctanes, 1- chloros decane, 1- bromodecanes, 1- bromines
For one kind in dodecane, 1- bromotetradecanes.
8. a kind of synthetic method of phosphate-based quaternary cationics according to claim 2, its feature
It is：The mol ratio of phosphate-based tertiary amine and alkyl halide in the step (2) is 1：1~1.2.
9. a kind of synthetic method of phosphate-based quaternary cationics according to claim 2, its feature
It is：Organic solvent B in the step (2) is at least one of ethanol, isopropanol, acetone.
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| CN101575299A (en) * | 2009-06-18 | 2009-11-11 | 江南大学 | Method for synthesizing dual-long-chain ester based quaternary ammonium salt |
| CN102962005A (en) * | 2012-11-27 | 2013-03-13 | 中国日用化学工业研究院 | Ethoxylated trimester-group quaternary ammonium salt and preparation method thereof |
| CN103191671A (en) * | 2013-04-17 | 2013-07-10 | 重庆理工大学 | Trimeric quaternary ammonium salt type cationic surface active agent and preparation method thereof |
| CN103599730A (en) * | 2013-11-25 | 2014-02-26 | 齐齐哈尔大学 | Quaternary ammonium salt cationic surface active agent and preparation method thereof |
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| CN101575299A (en) * | 2009-06-18 | 2009-11-11 | 江南大学 | Method for synthesizing dual-long-chain ester based quaternary ammonium salt |
| CN102962005A (en) * | 2012-11-27 | 2013-03-13 | 中国日用化学工业研究院 | Ethoxylated trimester-group quaternary ammonium salt and preparation method thereof |
| CN103191671A (en) * | 2013-04-17 | 2013-07-10 | 重庆理工大学 | Trimeric quaternary ammonium salt type cationic surface active agent and preparation method thereof |
| CN103599730A (en) * | 2013-11-25 | 2014-02-26 | 齐齐哈尔大学 | Quaternary ammonium salt cationic surface active agent and preparation method thereof |
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