CN104829641B - A kind of fluorine-containing organic silicon monomer and preparation method thereof - Google Patents
A kind of fluorine-containing organic silicon monomer and preparation method thereof Download PDFInfo
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- CN104829641B CN104829641B CN201510242341.4A CN201510242341A CN104829641B CN 104829641 B CN104829641 B CN 104829641B CN 201510242341 A CN201510242341 A CN 201510242341A CN 104829641 B CN104829641 B CN 104829641B
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- 239000000178 monomer Substances 0.000 title claims abstract description 41
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 38
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011737 fluorine Substances 0.000 title claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 29
- 239000010703 silicon Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 56
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- IGFROWMWDMZLTQ-UHFFFAOYSA-N 1,1,1-trifluoronon-2-ene Chemical group CCCCCCC=CC(F)(F)F IGFROWMWDMZLTQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 34
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 22
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 claims description 13
- 229910001641 magnesium iodide Inorganic materials 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- NMTAKLAVCOXDCJ-UHFFFAOYSA-N 1-fluoro-1-iodohexane Chemical class CCCCCC(F)I NMTAKLAVCOXDCJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 4
- 239000004210 ether based solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 239000012295 chemical reaction liquid Substances 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- -1 2 propyl group magnesium iodides Chemical class 0.000 abstract description 33
- 229920001296 polysiloxane Polymers 0.000 abstract description 22
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 abstract description 21
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 230000001186 cumulative effect Effects 0.000 abstract description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 6
- 230000001988 toxicity Effects 0.000 abstract description 5
- 231100000419 toxicity Toxicity 0.000 abstract description 5
- 239000005046 Chlorosilane Substances 0.000 abstract description 3
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 125000005010 perfluoroalkyl group Chemical group 0.000 abstract description 3
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical class CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 abstract 2
- ANOOTOPTCJRUPK-UHFFFAOYSA-N 1-iodohexane Chemical compound CCCCCCI ANOOTOPTCJRUPK-UHFFFAOYSA-N 0.000 abstract 1
- 238000007259 addition reaction Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000010992 reflux Methods 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 8
- 230000002940 repellent Effects 0.000 description 8
- 239000005871 repellent Substances 0.000 description 8
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000376 reactant Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000008236 heating water Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 235000016709 nutrition Nutrition 0.000 description 2
- 230000035764 nutrition Effects 0.000 description 2
- 230000002688 persistence Effects 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical class FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- 229910018540 Si C Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- TWJVNKMWXNTSAP-UHFFFAOYSA-N azanium;hydroxide;hydrochloride Chemical class [NH4+].O.[Cl-] TWJVNKMWXNTSAP-UHFFFAOYSA-N 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- Silicon Polymers (AREA)
Abstract
The invention discloses a kind of fluorine-containing organic silicon monomer and preparation method thereof.Using 30 trifluoro hexyl propylene and the iodohexane of ten trifluoro 1 as initiation material, 1 is synthesized by single electron transfer addition reaction, 3 two (ten trifluoro hexyls) 2 iodopropanes, by 1,3 two (ten trifluoro hexyls) 2 iodopropanes and metal reactive magnesium, prepare 1, react to obtain substituted chlorosilane containing fluoroalkyl with tetrachloro silicane after 3 two (ten trifluoro hexyls) 2 propyl group magnesium iodides, double [1,3 two (ten trifluoro hexyls) isopropyl] dichlorosilane products are obtained by rectifying.Perfluoroalkyl is short fluoroalkyl in product molecule structure, and carbon chain lengths are equal to 6, not difficult degradation, without cumulative toxicity, is a kind of environmentally friendly monomer for synthesizing fluorinated polysiloxane.The fluorine-containing organic silicon monomer of the present invention prepares that reaction condition is gentle, simple process, and raw material are easy to get, and are easy to industrialized production and popularization and application.
Description
Technical field
The present invention relates to the preparation of organic compound, and in particular to a kind of fluorine-containing organic silicon monomer and preparation method thereof, category
In fluorine material and Field of Fine Chemicals.
Background technology
The radius of fluorine atom is small, electronegativity is high, and C-F bond polarization rates are very low, so being coagulated between the polymer molecule containing carbon-fluorine bond
Poly- power is smaller, and the surface energy of polymer is very low, and this assigns characteristic of its surface to the difficult wetting of the liquid such as water, oil, difficult attachment, existing
The surface tension for having the polymer containing carbon-fluorine bond of hydrophobic oil resistant is generally 20mN/m, it is considered that surface tension is less than 20mN/m
Liquid be high surface liquid.Current most widely used fluoropolymer is fluorine-contaninig polyacrylate and fluorine-containing poly- silicon
Oxygen alkane, both fluoropolymers are prepared using the monomer containing perfluoro capryl mostly, and perfluoro capryl therein is due to rigidity
Sawtooth chain structure, and have certain crystallinity and shielding completely, the effect of protection main polymer chain can be played.In silicon-fluorine polymer thing
In, the polysiloxanes performance with perfluoro capryl side chain protrudes, the fluorosilicon oil surface tension as little as 18mN/m.
However, the Long carbon chain fluorochemical monomer (carbochain >=8) being commonly used easy oxidative degradation life in natural environment
Into corresponding perfluorocarboxylic acid or sulfonyl compound, as perfluoro octyl sulfonic acid salt compound (Perfluorooctane sulphonate,
PFOS) and the environmental contaminants such as perfluoro caprylic acid (Perfluorooctanoic acid, PFOA), they are to be most difficult to degraded at present
Organic pollution, and exist to health and seriously endanger.PFOS has high lasting stability, can be in environment, human body and animal
It is enriched with tissue, therefore 2009《Convention of Stockholm》It is controlled that PFOS is classified as newly-increased persistence organic pollutant (POPs)
Material.Data shows that the PFOS concentration in high nutrition level animal is higher than low nutrition level animal, illustrates that biomagnification exists
Have an effect.
Unlike Long carbon chain fluoroalkyl monomer, the carboxylic acid or sulfonyl compound of perfluoroalkyl carbon chain lengths≤6 (PFBS,
Perfluorobutane Sulfonate) do not have bioaccumulation.For example, Minnesota Mining and Manufacturing Company is on perfluorochemical biology
Cumulative system research report points out that the perfluoro butyl sulfonic acid fluorocarbon chain that they research and develop is short, long-pending without obvious persistence and biology
Tired property, short time can excrete with human metabolism, and its nontoxic degradable thing, although perfluoro butyl sulfonic acid fluorine system
The surface energy of row product far above perfluoro capryl product, refuse anti-performance and can not show a candle to long fluorocarbon chain product, but the achievement in research is led
The PFOS substitutes exploitation upsurge of fluorine-containing auxiliary agent research field.Found during the surface tension for analyzing fluorine-containing alkyl polymer, with
The reduction of perfluoroalkyl side base carbon chain lengths, the surface tension of polymer gradually rises, and water and oil repellant performance reduces, because
Following 2 points of deficiencies be present in the perfluoroalkyl chain of carbon chain atom number≤6：(1) short fluoroalkyl does not have crystallinity, can not formed surely
Fixed liquid crystal structure arrangement, it is difficult to make-CF3High density, stable alignment are in outermost surface；(2) synthesized by short fluoroalkyl monomer
Polymer Oil repellent it is often relatively low, it is difficult to reach the effect of the complete shielded polymer main chain of fluorine atom and polymer film.It is positive because
In this way, the application of short fluoroalkylation material is restricted.
The content of the invention
It is an object of the invention to provide a kind of fluorine-containing organic silicon monomer；Its perfluoroalkyl carbon chain lengths included is equal to 6, no
With cumulative toxicity, without refractory organicses；And dichlorosilane monomer contains multiple ten trifluoros hexyls, monomer Oil repellent is very
Height, particularly there is as little as 18.7mN/m surface tension.
To achieve the above object of the invention, the technical solution adopted by the present invention is：A kind of fluorine-containing organic silicon monomer, it is double
[1,3- bis- (ten trifluoro hexyls) isopropyl] dichlorosilane.With following chemical constitution：
The perfluoroalkyl carbon chain lengths of the fluorine-containing organic silicon monomer of the present invention are equal to 6, without cumulative toxicity, without difficulty
Degradability, and monomer Oil repellent is very high；There is the advantages of environment-friendly and high surface simultaneously.
The invention also discloses the preparation method of above-mentioned fluorine-containing organic silicon monomer, including following preparation process：
(1) by weight, 200~500 parts of trifluoro hexyl propylene of 3- ten and 300~600 part ten are put into the reactor
Three fluoro- 1- iodohexanes, are heated to 75~95 DEG C；Then under nitrogen protection, 5~20 parts of azo initiators, stirring reaction are added
30~48 hours；After reaction terminates, rectifying, it is 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes to take 106~107 DEG C of cuts；
(2) by weight, 3 parts of magnesium chips and 3~100 parts of ether solvents are put into the reactor, and nitrogen protection is lower to heat
To 20~60 DEG C；Then 20~120 parts of 1,3- bis- (ten trifluoro hexyls) -2- iodine third are added dropwise with the speed of 30~120 drops/minute
Alkane；Continue reaction 30 minutes~10 hours after being added dropwise to complete, obtain the suspension of 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide
Liquid；
(3) by the RMgBr 1 in step (1), the regulation of (ten trifluoro the hexyls) -2- propyl group magnesium iodides of 3- bis- suspension temperature
To -15~0 DEG C；
By weight, 4~16 parts of tetrachloro silicanes and 10~100 parts of anhydrous ether solvents are put into the reactor, are mixed
Mixed liquor is obtained, regulation mixeding liquid temperature is -15~0 DEG C；Then under nitrogen protection, dripped with the speed of 10~30 drops/minute
Add 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension that the temperature is -15~0 DEG C；Continue after being added dropwise to complete anti-
Answer 2~24 hours, obtain the fluorine-containing organic silicon monomer.
Preferably, in addition to purification, specially reaction terminate to add 10~50 parts of saturated ammonium chloride water in backward reaction solution
Solution；Then reacting liquid temperature is adjusted to room temperature；Then reaction solution is filtered, filtrate collects 142~143 through distillation, rectification under vacuum
DEG C cut, as described fluorine-containing organic silicon monomer；
The vapo(u)rizing temperature is 30~50 DEG C, and vacuum is 10~20mmHg；Rectification under vacuum temperature is 140~150 DEG C, very
Reciprocal of duty cycle is 1~2mmHg.
In above-mentioned technical proposal, in step (1), azo initiator is azodiisobutyronitrile.
Preferably, in step (1), during stirring reaction, every 8~12 hours plus 2~3 parts of azo initiators.Be advantageous to original
The abundant reaction of material, increases operation rate.
In above-mentioned technical proposal, the ether solvent in step (2) is consistent with the ether solvent in step (3)；The ethers
Solvent is the mixture of any one or any two kinds in ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane.The ether of step (3)
Class solvent passes through Non-aqueous processing before using.
In above-mentioned technical proposal, when ether solvent is any two kinds in ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane,
In described any two kinds of mixture, the mass ratio of two kinds of solvents is 1: 1.
In preferable technical scheme, in step (3), by 1,3- bis- (ten trifluoro hexyls) -2- propyl group iodate in step (2)
Magnesium suspension temperature is adjusted to -5~0 DEG C；It is -5~0 DEG C to adjust mixeding liquid temperature.
In above-mentioned technical proposal, in step (3), reacting liquid temperature is adjusted to room temperature by the way of heating up naturally.
The present invention using the trifluoro hexyl propylene of 3- ten and 13 fluoro- 1- iodohexanes as initiation material, by single electron transfer plus
Into reaction (Single Electron Transfer, SET) synthesis 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes；Again by 1,3-
Two (ten trifluoro hexyls) -2- iodopropanes react in the presence of magnesium metal is prepared into 1,3- bis- (ten trifluoro hexyls) -2- propyl iodides
Change magnesium；Finally by (ten trifluoro the hexyls) -2- propyl group magnesium iodides of 1,3- bis- and double [1,3- bis- (ten trifluoros of tetrachloro silicane reaction generation
Hexyl) isopropyl] dichlorosilane crude product, post-processed by rectifying, collect 142~143 DEG C of cut and obtain Polyfluoroalkyl two
Chlorosilane, i.e., double [1,3- bis- (ten trifluoro hexyls) isopropyl] dichlorosilanes.
Reaction equation is as follows：
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：
1. present invention firstly discloses a kind of fluorine-containing organic silicon monomer；Its perfluoroalkyl carbon chain lengths included is equal to 6, no
With cumulative toxicity, without refractory organicses, and dichlorosilane monomer contains multiple ten trifluoros hexyls, and monomer Oil repellent is very
It is high；Overcome Long carbon chain fluoroalkyl organosilicon material in the prior art and cumulative toxicity, difficult degradation and migration, short carbon chain fluorine be present
The defects of alkyl organic material surface energy is high.
It is and existing 2. the silicon nuclear structure of fluorine-containing organic silicon monomer disclosed by the invention has up to four ten trifluoro hexyls
Short fluoroalkyl organosilicon product is compared, and product Oil repellent is high, it is possible to provide lower surface tension；Polyfluoroalkyl dense accumulation, can
More complete fluoroalkyl shielding action is provided；There is the advantages of environment-friendly and high surface simultaneously.
3. the perfluoroalkyl carbon chain lengths of fluorine-containing organic silicon monomer disclosed by the invention are 6, Polyfluoroalkyl prepared therefrom
The surface tension test of polysiloxanes is 18.7mN/m, and (carbon chain lengths are with the existing polysiloxanes with perfluoro capryl side chain
8) performance is suitable, overcomes prior art and thinks that the Polyfluoroalkyl carbon chain lengths of polysiloxanes side chain are short, surface tension is high
Technology prejudice.
4. fluorine-containing organic silicon monomer disclosed by the invention can be as the monomer for preparing Polyfluoroalkyl polysiloxanes, it prepares work
Skill is easy, and raw material are easy to get, and are suitable for industrialized production, it is possible to provide the fluorine environment-friendly, surface energy is low and combination property is superior
Silicon materials, application prospect are wide.
Brief description of the drawings
Fig. 1 is the infrared absorption curve collection of illustrative plates of the fluorine-containing organic silicon monomer of embodiment one；
Fig. 2 is the fluorine nmr collection of illustrative plates of the fluorine-containing organic silicon monomer of embodiment one；
Fig. 3 is Polyfluoroalkyl polysiloxane film in embodiment two to water contact angle test chart.
Embodiment
With reference to embodiment, accompanying drawing, the invention will be further described：
Embodiment one
In the four-hole boiling flask for being equipped with reflux condensing tube, mechanical agitation and heater, put into 400 grams of trifluoros of 3- ten oneself
Base propylene and 500 gram of 13 fluoro- 1- iodohexane, mixture are heated to 88 DEG C, and nitrogen protection is lower to add 10 grams of initiator azos two
Isobutyronitrile, reactant mixture stirring reaction 48 hours at 88 DEG C, during which divide 3 times and added azodiisobutyronitrile every 12 hours,
Add 2 grams of azodiisobutyronitriles every time.After reaction terminates, stop reaction, rectifying (temperature is 150 DEG C, vacuum 2mmHg) obtains
It is product 1 to 106~107 DEG C of cuts, 3- bis- (ten trifluoro hexyls) -2- iodopropanes, yield is up to 97.0%.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, 2.9 grams of magnesium chips and 50 grams are added
Anhydrous tetrahydro furan, nitrogen is imported, starts to stir using magnetic stirring apparatus, and pass through constant pressure to 30 DEG C with heating water bath system
69.2 grams of 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are slowly added dropwise in dropping funel, and rate of addition control is 60 drops/minute.Add
Reaction is further continued for after complete and obtains within 6 hours the suspension that 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodides are suspended in tetrahydrofuran.
The suspension that above-mentioned 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodides are suspended in tetrahydrofuran is pre-cooled
It is standby to -1 DEG C.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, add 8.6 grams of tetrachloro silicanes and
50 grams of anhydrous tetrahydro furan, nitrogen is imported, and system temperature is down to -1 DEG C with sub-cooled bath, then be slowly added dropwise above-mentioned cold
But extremely -1 DEG C 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodides, rate of addition control is 20 drops/minute, is continued after adding
Stirring reaction 24 hours, temperature control is at -1 DEG C in whole course of reaction.
Reaction terminate after, by 5.3 grams of chloride leaches in 14.7 grams of distilled water, be made into mass concentration be 26.5% 20
Gram saturated aqueous ammonium chloride.Saturated aqueous ammonium chloride is added in reaction solution after being quenched reaction, reaction solution is risen naturally
Greenhouse temperature, filter, filtrate is first distilled except solvent, and vapo(u)rizing temperature is 40 DEG C, vacuum 20mmHg, distill to no liquid distillate for
Only.Then by reactant mixture rectification under vacuum, rectification temperature is 150 DEG C, vacuum 2mmHg, and 142~143 DEG C of collection evaporates
It is double [1,3- bis- (the ten trifluoro hexyls) isopropyl] dichlorosilanes of Polyfluoroalkyl dichlorosilane product to divide, and obtains product 55.1
Gram, yield 75.6%, product purity is measured as 96.7% by gas-chromatography.
Referring to accompanying drawing 1, for the infrared of double [1,3- bis- (ten trifluoro hexyls) isopropyl] dichlorosilanes manufactured in the present embodiment
Collection of illustrative plates, in absorption curve, in 2964.4cm-1The absworption peak at place is-CH2- middle C-H strong symmetrical stretching vibration causes,
2881.0cm-1, stretching vibration that 1245.1cm-1 is Si-C and-CH- flexural vibrations cause, 1458.2cm-1For-CH2Middle C-H
Weak asymmetrical deformation vibration cause, 1200.7cm-1For-CF2Middle C-F flexural vibrations absworption peak, in 625.5cm-1Place occurs
The characteristic feature absworption peaks of Si-Cl keys.In addition, 3411.8cm-1The absworption peak at place is probably due to double [1,3- bis- (ten trifluoros
Hexyl) isopropyl] Si-OH absorbs dichlorosilane caused by hydrolysis on a small quantity with moisture in air reaction during infrared test
Peak.
Referring to accompanying drawing 2, for the fluorine core of double [1,3- bis- (ten trifluoro hexyls) isopropyl] dichlorosilanes manufactured in the present embodiment
Magnetic resonance collection of illustrative plates.Product19F NMR(δ)：-81.01(-CF3), -116.39 (- CF2), -122.13 (- CF2), -123.15 (-
CF2), -123.64 (- CF2), -126.39 (- CF2)。
Infrared spectrum and fluorine nuclear-magnetism characterization result illustrate to have obtained double [1,3- bis- (the ten trifluoro hexyls) isopropyls of target product
Base] dichlorosilane.
Cohydrolysis-equilibrium polycondensation prepares Polyfluoroalkyl polysiloxanes
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, 60 grams of water are sequentially added,
200ml dichloromethane, in 10 DEG C, by 36.5g double [1,3- bis- (ten trifluoro hexyls) isopropyl] dichlorosilane, 6.3 grams of dimethyl
It is added dropwise after dichlorosilane and 2.7 grams of trim,ethylchlorosilanes are well mixed by constant pressure funnel, drips off within 1.5 hours, drip
Reaction solution is continued into reaction 2 hours in room temperature after finishing.Reaction solution is poured into separatory funnel, divides sub-cloud sour water, with mass concentration
Washed 3 times for 5% sodium hydrate aqueous solution, use 40 grams of sodium hydrate aqueous solutions every time, be then washed with deionized 5 times,
Use 60 grams of deionized waters every time.Finally reaction solution is dried, revolving removes methylene chloride, obtains 45 grams of cohydrolysis product.
Above-mentioned 45 grams of cohydrolysis products and 0.5 gram of trifluoro are added in the three-necked flask equipped with reflux condensing tube and thermometer
Methanesulfonic acid, after leading to nitrogen, it is heated to 78~80 DEG C and reacts 6 hours.After reaction terminates, 2 grams of concentrated ammonia liquors, neutralization reaction are added
1 hour.Then reaction solution is diluted with 50 grams of n-hexanes, be washed with deionized 5 times, use 20 grams of deionized waters every time.Most
Reaction solution is dried afterwards, revolving removes solvent, and finally the stripping low-boiling-point substance under the conditions of 160 DEG C and 1mmHg, is obtained transparent, sticky
Liquid Polyfluoroalkyl polysiloxanes.Product weighs 38 grams, yield 90.0%.
It is 51.72% to measure product Oil repellent by elementary analysis, and the surface tension of liquid Polyfluoroalkyl polysiloxanes is tested
For 19.3mN/m.Above-mentioned 1 gram of Polyfluoroalkyl silicone product is taken, is dissolved in 9 grams of benzotrifluorides and forms homogeneous solution, revolving
Spin-coating film on painting machine, then flint dry 1 hour at 170 DEG C, obtained Polyfluoroalkyl polysiloxane film are cooled to room temperature
Afterwards, it is 137.9 ° to water contact angle to measure Polyfluoroalkyl polysiloxane film.Illustrate to be gathered by Polyfluoroalkyl prepared by monomer of the present invention
Silicone surfactant is excellent.
Embodiment two
1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are prepared according to embodiment one.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, 3.1 grams of magnesium chips and 55 grams are added
Absolute ether, import nitrogen, start to stir using magnetic stirring apparatus, and dripped by constant pressure to 30 DEG C with heating water bath system
69.2 grams of 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are added dropwise in liquid funnel, add within 15 minutes totally 1 hour.It is further continued for after adding anti-
Answer 6 hours to obtain 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension.
Above-mentioned 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension is cooled to -3 DEG C, it is standby.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, 12.9 grams of tetrachloro silicanes are added
With 55 grams of absolute ether, nitrogen is imported, and system temperature is down to -3 DEG C with sub-cooled bath, then is added dropwise and above-mentioned is cooled to -3
DEG C 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension, be added dropwise within about 2 hours, continue stirring reaction after adding
20 hours, temperature should be all controlled at -3 DEG C in whole course of reaction.
Reaction terminate after, by 5.3 grams of chloride leaches in 14.7 grams of distilled water, be made into mass concentration be 26.5% 20
Gram saturated aqueous ammonium chloride.Saturated aqueous ammonium chloride is added in reaction solution after being quenched reaction, reaction solution is risen naturally
Greenhouse temperature, filter, filtrate is first distilled except solvent, and vapo(u)rizing temperature is 30 DEG C, vacuum 20mmHg, distill to no liquid distillate for
Only.Then by reactant mixture rectification under vacuum, rectification temperature is 150 DEG C, vacuum 2mmHg, and 142~143 DEG C of collection evaporates
Point, double [1,3- bis- (ten trifluoro hexyls) isopropyl] 43.6 grams of the dichlorosilanes of Polyfluoroalkyl dichlorosilane product are obtained, yield is
59.8%, product purity is measured as 94.2% by gas-chromatography.
Cohydrolysis-equilibrium polycondensation prepares Polyfluoroalkyl polysiloxanes
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, 60 grams of water are sequentially added,
200ml dichloromethane, in 5 DEG C, by 36.5g double [1,3- bis- (ten trifluoro hexyls) isopropyl] dichlorosilane, 4.2 grams of dimethyl two
It is added dropwise, is dripped off within 2 hours, after being added dropwise by constant pressure funnel after chlorosilane and 2.5 grams of trim,ethylchlorosilanes are well mixed
Reaction solution is warming up to room temperature and continues reaction 6 hours.Reaction solution is poured into separatory funnel, divides sub-cloud sour water, with mass concentration
Washed 3 times for 5% sodium hydrate aqueous solution, use 40 grams of sodium hydrate aqueous solutions every time, be then washed with deionized 5 times,
Use 60 grams of deionized waters every time.Finally reaction solution is dried, revolving removes methylene chloride, obtains 41 grams of cohydrolysis product.
Above-mentioned 41 grams of cohydrolysis products and 0.4 gram of trifluoro are added in the three-necked flask equipped with reflux condensing tube and thermometer
Methanesulfonic acid, after leading to nitrogen, it is heated to 80 DEG C and reacts 8 hours.After reaction terminates, 2 grams of concentrated ammonia liquors are added, neutralization reaction 2 is small
When.Then reaction solution is diluted with 50 grams of n-hexanes, be washed with deionized 5 times, use 20 grams of deionized waters every time.Finally will
Reaction solution is dried, and revolving removes solvent, and finally the stripping low-boiling-point substance under the conditions of 160 DEG C and 1mmHg, obtains transparent, sticky liquid
Shape Polyfluoroalkyl polysiloxanes.Product weighs 35 grams, yield 77.8%.
It is 54.66% to measure product Oil repellent by elementary analysis, takes above-mentioned 1 gram of Polyfluoroalkyl silicone product, is dissolved
Homogeneous solution is formed in 9 grams of toluene, the spin-coating film on spin coater, then flint dry 1 hour at 170 DEG C, is obtained
After Polyfluoroalkyl polysiloxane film is cooled to room temperature, it is 140.5 ° to water contact angle to measure Polyfluoroalkyl polysiloxane film；Accompanying drawing 3
It is Polyfluoroalkyl polysiloxane film to water contact angle test chart, contact angle test result shows that product has very superior water repellent
Performance.
The surface tension test for measuring liquid Polyfluoroalkyl polysiloxanes is 18.7mN/m；Carbochain in the monomer of the present invention
It is short, the low surface tension suitable with existing Long carbon chain product (polysiloxanes with perfluoro capryl side chain) is still achieved, is taken
Obtained unexpected effect.The molecular structure such as following formula for the Polyfluoroalkyl polysiloxanes being prepared：
Embodiment three
1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are prepared according to embodiment one.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, 3.5 grams of magnesium chips and 60 grams are added
Absolute ether, import nitrogen, start to stir using magnetic stirring apparatus, and dripped by constant pressure to 30 DEG C with heating water bath system
69.5 grams of 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are added dropwise in liquid funnel, add within totally 1 hour.Reaction 6 hours is further continued for after adding
Obtain 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension.
Above-mentioned 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension is cooled to -5 DEG C, it is standby.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, add 7.2 grams of tetrachloro silicanes and
48 grams of absolute ether, nitrogen is imported, and be transferred in low-temp reaction device makes system temperature be down to -5 DEG C with low temperature bath, then be added dropwise
Above-mentioned 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodides for being cooled to -5 DEG C, are added dropwise, continue to stir after adding for about 2 hours
Reaction 18 hours is mixed, temperature should be all controlled at -5 DEG C or so in whole course of reaction.
Reaction terminate after, by 5.3 grams of chloride leaches in 14.7 grams of distilled water, be made into mass concentration be 26.5% 20
Gram saturated aqueous ammonium chloride.Saturated aqueous ammonium chloride is added in reaction solution after being quenched reaction, reaction solution is risen naturally
Greenhouse temperature, filter, filtrate is first distilled except solvent, and vapo(u)rizing temperature is 30 DEG C, vacuum 20mmHg, distill to no liquid distillate for
Only.Then by reactant mixture rectification under vacuum, rectification temperature is 145 DEG C, vacuum 2mmHg, and 142~143 DEG C of collection evaporates
It is double [1,3- bis- (the ten trifluoro hexyls) isopropyl] dichlorosilanes of Polyfluoroalkyl dichlorosilane product to divide, and obtains product 38.9
Gram, yield 53.4%, product purity is measured as 94.7% by gas-chromatography.
Example IV
1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are prepared according to embodiment one.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, 3.5 grams of magnesium chips and 60 grams are added
Absolute ether, import nitrogen, start to stir using magnetic stirring apparatus, and dripped by constant pressure to 30 DEG C with heating water bath system
69.2 grams of 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are added dropwise in liquid funnel, add within totally 1.5 hours.It is small that reaction 6 is further continued for after adding
When obtain 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension.
Above-mentioned 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension is cooled to -15 DEG C, it is standby.
In the three-necked flask equipped with reflux condensing tube, thermometer and constant pressure funnel, add 6.4 grams of tetrachloro silicanes and
45 grams of absolute ether, nitrogen is imported, and system temperature is down to -15 DEG C with ice salt bath, then be added dropwise and above-mentioned be cooled to -15 DEG C
1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodides, are added dropwise for about 2 hours, continue stirring reaction after adding 24 hours, entirely
Temperature should be all controlled at -5 DEG C in course of reaction.
Reaction terminate after, by 5.3 grams of chloride leaches in 14.7 grams of distilled water, be made into mass concentration be 26.5% 20
Gram saturated aqueous ammonium chloride.Saturated aqueous ammonium chloride is added in reaction solution after being quenched reaction, reaction solution is risen naturally
Greenhouse temperature, filter, filtrate is first distilled except solvent, and vapo(u)rizing temperature is 30 DEG C, vacuum 20mmHg, distill to no liquid distillate for
Only.Then by reactant mixture rectification under vacuum, rectification temperature is 150 DEG C, vacuum 2mmHg, and the cut for collecting 142 DEG C is
Double [1,3- bis- (the ten trifluoro hexyls) isopropyl] dichlorosilanes of Polyfluoroalkyl dichlorosilane product, obtain 28.5 grams of product, yield
For 39.0%, product purity is measured as 91.4% by gas-chromatography.
Claims (8)
1. a kind of preparation method of fluorine-containing organic silicon monomer, it is characterised in that including following preparation process：
(1) by weight, 200~500 parts of trifluoro hexyl propylene of 3- ten are put into the reactor and 300~600 part 13 fluoro-
1- iodohexanes, it is heated to 75~95 DEG C；Then under nitrogen protection, 5~20 parts of azo initiators, stirring reaction 30~48 are added
Hour；After reaction terminates, rectifying, it is 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes to take 106~107 DEG C of cuts；
(2) by weight, 3 parts of magnesium chips and 3~100 parts of ether solvents are put into the reactor, and 20 are heated under nitrogen protection
~60 DEG C；Then 20~120 parts of 1,3- bis- (ten trifluoro hexyls) -2- iodopropanes are added dropwise with the speed of 30~120 drops/minute；Drop
Continue reaction 30 minutes~10 hours after adding into, obtain 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension；
(3) 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension temperatures in step (2) are adjusted to -15~0 DEG C；
By weight, 4~16 parts of tetrachloro silicanes and 10~100 parts of anhydrous ether solvents are put into the reactor, are uniformly mixed so as to obtain
Mixed liquor, regulation mixeding liquid temperature are -15~0 DEG C；Then under nitrogen protection, institute is added dropwise with the speed of 10~30 drops/minute
State 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension that temperature is -15~0 DEG C；Continue after being added dropwise to complete reaction 2~
24 hours, obtain the fluorine-containing organic silicon monomer；
The fluorine-containing organic silicon monomer has following chemical constitution：
2. the preparation method of fluorine-containing organic silicon monomer according to claim 1, it is characterised in that：Azo triggers in step (1)
Agent is azodiisobutyronitrile.
3. the preparation method of fluorine-containing organic silicon monomer according to claim 1, it is characterised in that：Stirring reaction in step (1)
When, every 8~12 hours plus 2~3 parts of azo initiators.
4. the preparation method of fluorine-containing organic silicon monomer according to claim 1, it is characterised in that：Ethers in step (2) is molten
Agent is consistent with the ether solvent in step (3)；The ether solvent is any in ether, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane
One or any two kinds of mixture.
5. the preparation method of fluorine-containing organic silicon monomer according to claim 4, it is characterised in that：Described any two kinds of mixing
In thing, the mass ratio of two kinds of solvents is 1: 1.
6. the preparation method of fluorine-containing organic silicon monomer according to claim 1, it is characterised in that：In step (3), by step
(2) 1,3- bis- (ten trifluoro hexyls) -2- propyl group magnesium iodide suspension temperatures in are adjusted to -5~0 DEG C；Adjust mixeding liquid temperature
For -5~0 DEG C.
7. the preparation method of fluorine-containing organic silicon monomer according to claim 1, it is characterised in that：Step (3) also includes purification
Step, specially reaction terminate to add 10~50 parts of saturated aqueous ammonium chlorides in backward reaction solution；Then regulation reaction liquid temperature
Spend to room temperature；Then reaction solution is filtered, filtrate is as described fluorine-containing through distillation, rectification under vacuum, the cut of 142~143 DEG C of collection
Organic silicon monomer；
The vapo(u)rizing temperature is 30~50 DEG C, and vacuum is 10~20mmHg；Rectification under vacuum temperature is 140~150 DEG C, vacuum
For 1~2mmHg.
8. the preparation method of fluorine-containing organic silicon monomer according to claim 7, it is characterised in that：By the way of heating up naturally
Reacting liquid temperature is adjusted to room temperature.
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| CN1141941A (en) * | 1995-06-05 | 1997-02-05 | Ppg工业公司 | Treatment of water-proof surface with integral bottom coating |
| CN102070662A (en) * | 2010-12-25 | 2011-05-25 | 锦州惠发天合化学有限公司 | Preparation method of fluorine-silicon surfactant |
| CN102219391A (en) * | 2011-03-28 | 2011-10-19 | 华南理工大学 | Method for forming super-hydrophobic coating on glass matrix |
| CN103044687A (en) * | 2012-12-21 | 2013-04-17 | 江苏美思德化学股份有限公司 | Fluorine contained organosilicon-polyether copolymer and preparation method thereof |
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1141941A (en) * | 1995-06-05 | 1997-02-05 | Ppg工业公司 | Treatment of water-proof surface with integral bottom coating |
| CN102070662A (en) * | 2010-12-25 | 2011-05-25 | 锦州惠发天合化学有限公司 | Preparation method of fluorine-silicon surfactant |
| CN102219391A (en) * | 2011-03-28 | 2011-10-19 | 华南理工大学 | Method for forming super-hydrophobic coating on glass matrix |
| CN103044687A (en) * | 2012-12-21 | 2013-04-17 | 江苏美思德化学股份有限公司 | Fluorine contained organosilicon-polyether copolymer and preparation method thereof |
| CN103865026A (en) * | 2014-03-18 | 2014-06-18 | 山东大学 | Preparation method of organic fluorosiloxane modified polyurethane emulsion containing short fluoroalkyl chain |
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