CN106237924B - A kind of functional fluoropolymer surfactant and its preparation method and application - Google Patents
A kind of functional fluoropolymer surfactant and its preparation method and application Download PDFInfo
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- CN106237924B CN106237924B CN201610819509.8A CN201610819509A CN106237924B CN 106237924 B CN106237924 B CN 106237924B CN 201610819509 A CN201610819509 A CN 201610819509A CN 106237924 B CN106237924 B CN 106237924B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000004094 surface-active agent Substances 0.000 title claims description 34
- 229920002313 fluoropolymer Polymers 0.000 title description 3
- 239000004811 fluoropolymer Substances 0.000 title description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 24
- 239000010703 silicon Substances 0.000 claims abstract description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims abstract description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 p-trifluoromethyl phenyl Group Chemical group 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 21
- 125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000428 triblock copolymer Polymers 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 abstract description 10
- 230000003213 activating effect Effects 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 6
- 229920001577 copolymer Polymers 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004945 emulsification Methods 0.000 abstract description 3
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000002202 Polyethylene glycol Substances 0.000 abstract 1
- 229920001223 polyethylene glycol Polymers 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 36
- 239000003921 oil Substances 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 238000013019 agitation Methods 0.000 description 12
- 229920002545 silicone oil Polymers 0.000 description 11
- 238000004364 calculation method Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920001400 block copolymer Polymers 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 9
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 9
- 229920000570 polyether Polymers 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 150000003384 small molecules Chemical class 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229920001296 polysiloxane Polymers 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- JJRDHFIVAPVZJN-UHFFFAOYSA-N cyclotrisiloxane Chemical compound O1[SiH2]O[SiH2]O[SiH2]1 JJRDHFIVAPVZJN-UHFFFAOYSA-N 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000002537 cosmetic Substances 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 125000001165 hydrophobic group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 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
- C09K23/007—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses function surface activating agent of a kind of new structure and its preparation method and application.The preparation method includes the poly- methyl fluorine alkyl siloxanes by n-BuLi active controllably synthesis end group silicon hydrogen under the facilitation of glycol dimethyl ether, then the polyethylene glycol of poly- methyl fluorine alkyl siloxanes and both-end vinyl is copolymerized by hydrosilylation, obtains three block structure copolymer.Method preparation technology provided by the invention is easy, reaction condition is gentle, combined coefficient is high；The function surface activating agent of acquisition, there is good emulsification and stablize microlayer model effect.
Description
Technical field
The present invention relates to compound synthesis field, more particularly to a kind of novel fluorine surfactant and preparation method thereof and
Using.
Background technology
Speciality polymer surfactant is primarily referred to as the surfactant of siliceous, fluorine etc..Except with general small molecule table
Outside all features of face activating agent, speciality polymer surfactant Yin Qigao relative molecular mass and molecular structure and have
Some unique performances.
The hydrophobic group of siliceous high molecular surfactant is polymethyl silicane chain, hydrophilic group be one on siloxane chain or
Multiple polar groups.Hydrophobic group skeleton silica chain has good compliance, and surrounding is covered by methyl or other alkyl, therefore
Molecular-chain polarr very little, it is in a liquid state under normal temperature, there is very high surface-active in water or nonaqueous solvents.Nonionic is organic
Performance, most widely used one kind in polymeric silicon surfactant, wherein again mostly important with polyether silicone.This kind of polyethers changes
Property silicone oil is formed by connecting by the very big polyether segment of performance difference with polysiloxanes segment by chemical bond.Hydrophilic polyether chain
Section assigns its water solubility, and hydrophobic PolydimethylsiloxaneChain Chain section then assigns its low surface tension.In polyether segment molecule
Ratio it is bigger, copolymer water solubility it is better.Therefore, as a kind of high molecular surfactant, polyether silicone is in many
The performance of aspect is that general high molecular surfactant even pure siloxane is incomparable.It had both had the production of traditional siloxane class
The excellent properties such as the high-low temperature resistant of product, anti-aging, hydrophobic, electric insulation, low surface tension, while have what polyether segment provided again
Lubrication, soft effect, the special nature such as good spreadability and emulsion stability.Polyether modified silicon oil has been widely used as poly- ammonia
Ester foam foam stabilizer, cosmetics, coating additive, textile auxiliary, chemical additives, paper grade (stock) softening agent, oil field chemical etc..
And general fluoro containing polymerses surfactant is mainly hydrogen partial or all fluorine atoms in hydrocarbon chain hydrophobic grouping
Substituted high molecular surfactant, its performance are different from traditional hydrocarbon family macromolecule surfactant and containing polymeric silicons
Surfactant.Fluoro containing polymerses surfactant has high surface, high heat resistance, high chemical stability and hated
Water, the characteristic for hating oil.Due to having good antifouling effect in an atmosphere with extremely low surface energy, fluoro containing polymerses surfactant
Fruit.
Present invention incorporates the advantage of siliceous high molecular surfactant and fluoro containing polymerses surfactant, with efficient
Hydrosilylation has synthesized the block copolymer of fluorinated polysiloxane and polyethers, and the copolymer is as the existing biography of surfactant
The compliant characteristic, anti-aging property etc. for siloxane backbone of uniting, the water and oil repellence with fluoro containing polymerses surfactant is special again
Property.There is extensive potential using value in numerous areas such as cosmetics, coating, chemical additives.
The content of the invention
The present invention provides a kind of functional fluoropolymer surfactant and its synthetic method and the application in microlayer model.
In one embodiment, the present invention provides a kind of formula (1)Table
Face activating agent, wherein, n=16-64, m=10-40, R are fluorine-containing organo-functional group.
In one embodiment, R is trifluoropropyl group, p-trifluoromethyl phenyl group or to fluorobenzene in formula (1)
Base group.
In one embodiment, there is provided a kind of method of the surfactant of formula (1), it comprises the following steps：
A. the poly- methyl fluorine alkyl siloxanes of formula (2) end group silicon hydrogen；
B. prepare Si―H addition reaction with scheme (1) and prepare triblock copolymer,
In one embodiment, the poly- methyl fluorine alkyl siloxanes of formula (2) end group silicon hydrogen are prepared by scheme (2)：
,
X can be 3,4 and 5 wherein in formula (3).
In one embodiment, spent glycol dimethyl ether triggers polymerization in scheme (2), by the amount control of glycol dimethyl ether
Polymerization speed processed, reaction temperature is at 40-100 DEG C.
In one embodiment, scheme (2) controls reactive polymeric degree by n-BuLi amount.
In one embodiment, scheme (1) selects tetrahydrofuran as the solvent, -15h of heating reflux reaction 1.
In one embodiment, the application of surfactant of the invention in microlayer model is prepared.
In the present invention, function surface activating agent is by the way that the fluorinated polysiloxane of hydrophobic low-surface-energy and hydrophilic are gathered
It is prepared by the copolymer that ethylene glycol synthesizes block structure with efficient hydrosilylation, the preparation method is simple efficiently,
It is safely controllable.The surfactant of the present invention is a kind of nonionic function surface activating agent, can be applied to prepare emulsion and steady
Determine microlayer model.
Brief description of the drawings
In order to illustrate more clearly of the technical scheme in the embodiment of the present application, will use below required in embodiment
Accompanying drawing is briefly described, it should be apparent that, drawings in the following description are only some embodiments described in the application, right
For those of ordinary skill in the art, on the premise of not paying creative work, it can also be obtained according to these accompanying drawings
Its accompanying drawing.
Fig. 1 is the photo of the microlayer model prepared by surfactant of the present invention；With
Fig. 2 is that microlayer model prepared by surfactant of the present invention places the photo after 24h.
Embodiment
In order that art technology field personnel more fully understand the technical scheme in the application, below in conjunction with following knot
Closing embodiment, the invention will be further described, it is clear that and described embodiment is only some embodiments of the present application, without
It is whole embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not before creative work is made
The all other embodiment obtained is put, should all belong to the scope of the application protection.
Embodiment 1
50g methyl trifluoro propyls cyclotrisiloxane and 4.14mL glycol dimethyl ethers are weighed in 100mL single port bottles, machinery
Stirring, 40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 8.35mLn-BuLi of nitrogen protection-1) start to trigger and gather
Close, after polymerisation 3h, add dimethylchlorosilane end-blocking, LiCl is filtered to remove after 2h, absolute ethyl alcohol washing removes small molecule
Impurity, the fluorosilicon oil of silicon hydrogen must be held after drying, it is 2500gmol to measure molecular weight by gel permeation chromatography-1。
Weigh the 10g molecular weight 2500gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking fluorosilicon oil in 50mL single port bottle, add
Enter 10mL THF as solvent, add 1g molecular weight 440gmol-1End-vinyl PEG is anti-with Karstedt catalysts
Should, electromagnetic agitation is uniform, and 50 DEG C of constant temperature oil bath backflow, nitrogen protection, removing solvent obtains block copolymer FSH- after reacting 12h
PEG-FSH, the molecular weight as obtained by theoretical calculation are 5440gmol-1, polymer is triblock polymer, wherein fluorosilicon oil two
End, 2500*2=5000, and interlude PEG is 440, therefore molecular weight is 5440.
Embodiment 2
50g methyl trifluoro propyls cyclotrisiloxane and 10.3mL glycol dimethyl ethers are weighed in 100mL single port bottles, machinery
Stirring, 40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 2.09mLn-BuLi of nitrogen protection-1) start to trigger and gather
Close, after polymerisation 3h, add dimethylchlorosilane end-blocking, LiCl is filtered to remove after 2h, absolute ethyl alcohol washing removes small molecule
Impurity, the fluorosilicon oil of silicon hydrogen must be held after drying, it is 10000gmol to measure molecular weight by gel permeation chromatography-1。
Weigh the 10g molecular weight 10000gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking fluorosilicon oil in 50mL single port bottle,
10mL THF is added as solvent, adds 0.9g molecular weight 1800gmol-1End-vinyl PEG, urged with Karstedt catalyst
Change reaction, electromagnetic agitation is uniform, 50 DEG C of constant temperature oil bath backflow, nitrogen protection, and removing solvent after reaction 12h obtains block copolymer
FSH-PEG-FSH, the molecular weight as obtained by theoretical calculation are 21800gmol-1。
Embodiment 3
50g methyl trifluoro propyls cyclotrisiloxane and 4.14mL glycol dimethyl ethers are weighed in 100mL single port bottles, machinery
Stirring, 40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 8.35mLn-BuLi of nitrogen protection-1) start to trigger and gather
Close, after polymerisation 3h, add dimethylchlorosilane end-blocking, LiCl is filtered to remove after 2h, absolute ethyl alcohol washing removes small molecule
Impurity, the fluorosilicon oil of silicon hydrogen must be held after drying, it is 2500gmol to measure molecular weight by gel permeation chromatography-1。
Weigh the 10g molecular weight 2500gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking fluorosilicon oil in 50mL single port bottle, add
Enter 10mL THF as solvent, add 3.6g molecular weight 1800gmol-1End-vinyl PEG, with Karstedt catalysts
Reaction, electromagnetic agitation is uniform, and 50 DEG C of constant temperature oil bath backflow, nitrogen protection, removing solvent obtains block copolymer after reacting 12h
FSH-PEG-FSH, the molecular weight as obtained by theoretical calculation are 6800gmol-1。
Embodiment 4
50g methyl trifluoros phenyl ring siloxane and 3.16mL glycol dimethyl ethers are weighed in 100mL single port bottles, machinery stirs
Mix, 40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 6.38mLn-BuLi of nitrogen protection-1) start to trigger and gather
Close, after polymerisation 3h, add dimethylchlorosilane end-blocking, LiCl is filtered to remove after 2h, absolute ethyl alcohol washing removes small molecule
Impurity, the p-trifluoromethyl phenyl silicone oil TFPSH of silicon hydrogen must be held after drying, measuring molecular weight by gel permeation chromatography is
3200gmol-1。
Weigh the 10g molecular weight 3200gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking p-trifluoromethyl phenyl silicone oil in
50mL single port bottle, 10mL THF is added as solvent, adds 0.69g molecular weight 440gmol-1End-vinyl PEG, with
Karstedt catalysts react, and electromagnetic agitation is uniform, 50 DEG C of constant temperature oil bath backflow, nitrogen protection, are removed after reacting 12h
Solvent obtains block copolymer TFPSH-PEG-TFPSH, and the molecular weight as obtained by theoretical calculation is 6840gmol-1。
Embodiment 5
50g methyl trifluoros phenyl ring siloxane and 7.9mL glycol dimethyl ethers are weighed in 100mL single port bottles, machinery stirs
Mix, 40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 1.60mLn-BuLi of nitrogen protection-1) start to trigger and gather
Close, after polymerisation 3h, add dimethylchlorosilane end-blocking, LiCl is filtered to remove after 2h, absolute ethyl alcohol washing removes small molecule
Impurity, the p-trifluoromethyl phenyl silicone oil TFPSH of silicon hydrogen must be held after drying, measuring molecular weight by gel permeation chromatography is
12800gmol-1。
Weigh the 10g molecular weight 12800gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking fluorosilicon oil in 50mL single port bottle,
10mL THF is added as solvent, adds 0.7g molecular weight 1800gmol-1End-vinyl PEG, urged with Karstedt catalyst
Change reaction, electromagnetic agitation is uniform, 50 DEG C of constant temperature oil bath backflow, nitrogen protection, and removing solvent after reaction 12h obtains block copolymer
TFPSH-PEG-TFPSH, the molecular weight as obtained by theoretical calculation are 27400gmol-1。
Embodiment 6
50g trifluoromethyls cyclotrisiloxane and 7.9mL glycol dimethyl ethers are weighed in 100mL single port bottles, machinery
Stirring, 40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 1.60mLn-BuLi of nitrogen protection-1) start to trigger and gather
Close, after polymerisation 3h, add dimethylchlorosilane end-blocking, LiCl is filtered to remove after 2h, absolute ethyl alcohol washing removes small molecule
Impurity, the p-trifluoromethyl phenyl silicone oil TFPSH of silicon hydrogen must be held after drying, measuring molecular weight by gel permeation chromatography is
3200gmol-1。
Weigh the 10g molecular weight 3200gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking p-trifluoromethyl phenyl silicone oil in
50mL single port bottle, 10mL THF is added as solvent, adds 2.8g molecular weight 1800gmol-1End-vinyl PEG, with
Karstedt catalysts react, and electromagnetic agitation is uniform, 50 DEG C of constant temperature oil bath backflow, nitrogen protection, are removed after reacting 12h
Solvent obtains block copolymer TFPSH-PEG-TFPSH, and the molecular weight as obtained by theoretical calculation is 8200gmol-1。
Embodiment 7
50g p-fluorophenyls cyclosiloxane and 4.2mL glycol dimethyl ethers are weighed in 100mL single port bottles, mechanical agitation, 40
DEG C constant temperature oil bath, lower hexane solution (the 2.4mol L for adding 8.46mL n-BuLi of nitrogen protection-1) start to trigger polymerization, gather
After closing reaction 3h, dimethylchlorosilane end-blocking is added, LiCl is filtered to remove after 2h, absolute ethyl alcohol washing removes small molecular weight impurity,
The p-fluorophenyl silicone oil FPSH of silicon hydrogen must be held after drying, it is 2500gmol to measure molecular weight by gel permeation chromatography-1。
Weigh the 10g molecular weight 2500gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking p-fluorophenyl silicone oil in 50mL list
Mouth bottle, adds 10mL THF as solvent, adds 1g molecular weight 440gmol-1End-vinyl PEG, with Karstedt catalyst
Catalytic reaction, electromagnetic agitation is uniform, and 50 DEG C of constant temperature oil bath backflow, nitrogen protection, removing solvent obtains block copolymerization after reacting 12h
Thing FPSH-PEG-FPSH, the molecular weight as obtained by theoretical calculation are 5440gmol-1。
Embodiment 8
50g p-fluorophenyls cyclosiloxane and 10.3mL glycol dimethyl ethers are weighed in 100mL single port bottles, mechanical agitation,
40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 2.09mL n-BuLi of nitrogen protection-1) start to trigger polymerization,
After polymerisation 3h, dimethylchlorosilane end-blocking is added, LiCl is filtered to remove after 2h, it is miscellaneous that absolute ethyl alcohol washing removes small molecule
Matter, the p-fluorophenyl silicone oil FPSH of silicon hydrogen must be held after drying, it is 10000gmol to measure molecular weight by gel permeation chromatography-1。
Weigh the 10g molecular weight 10000gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking fluorosilicon oil in 50mL single port bottle,
10mL THF is added as solvent, adds 0.9g molecular weight 1800gmol-1End-vinyl PEG, urged with Karstedt catalyst
Change reaction, electromagnetic agitation is uniform, 50 DEG C of constant temperature oil bath backflow, nitrogen protection, and removing solvent after reaction 12h obtains block copolymer
FPSH-PEG-FPSH, the molecular weight as obtained by theoretical calculation are 21800gmol-1。
Embodiment 9
50g p-fluorophenyls cyclosiloxane and 4.14mL glycol dimethyl ethers are weighed in 100mL single port bottles, mechanical agitation,
40 DEG C of constant temperature oil baths, lower hexane solution (the 2.4mol L for adding 8.35mL n-BuLi of nitrogen protection-1) start to trigger polymerization,
After polymerisation 3h, dimethylchlorosilane end-blocking is added, LiCl is filtered to remove after 2h, it is miscellaneous that absolute ethyl alcohol washing removes small molecule
Matter, the p-fluorophenyl silicone oil FPSH of silicon hydrogen must be held after drying, the molecular weight as obtained by theoretical calculation is 2500gmol-1。
Weigh the 10g molecular weight 2500gmol of above-mentioned synthesis-1End silicon hydrogen end-blocking p-fluorophenyl silicone oil FPSH in 50mL
Single port bottle, add 10mL THF as solvent, add 3.6g molecular weight 1800gmol-1End-vinyl PEG, with
Karstedt catalysts react, and electromagnetic agitation is uniform, 50 DEG C of constant temperature oil bath backflow, nitrogen protection, are removed after reacting 12h
Solvent obtains block copolymer FPSH-PEG-FPSH, and the molecular weight as obtained by theoretical calculation is 6800gmol-1。
Embodiment 10
Using FSH-PEG-FSH prepared by embodiment 1 as surfactant, drop is prepared using microfluidic chip technology.
The FC-7500 solution and secondary water of 2%FSH-PEG-FSH mass concentrations are separately added into different syringes, respectively with 300 μ l/s
Imported with 900 μ l/s flow velocity in microchannel, carry out the emulsion that emulsification forms Water-In-Oil.Directly collected with silicone tube in the port of export
Emulsion.The stability and uniform particle diameter of drop are formed with micro- sem observation.
Fig. 1 results are shown can emulsify to be formed using embodiment 1FSH-PEG-FSH as surfactant, water phase and an oil phase
Emulsion and uniform particle diameter, illustrating that FSH-PEG-FSH can be enriched with water-oil interface reduces interfacial tension, stable aqueous phase droplets,
Therefore, FSH-PEG-FSH may be used as surfactant and have good emulsification.
Fig. 2 results display gained drop does not merge after placing 24h, i.e., drop has good stability, explanation
FSH-PEG-FSH has stable microlayer model effect well as surfactant.
It should be understood that the present invention disclosed is not limited only to specific method, scheme and the material of description, because these
Equal alterable.It will also be understood that purpose of the terminology used here just for the sake of the specific embodiment scheme of description, rather than
It is intended to limit the scope of the present invention, the scope of the present invention is limited solely by appended claim.
Those skilled in the art, which will also be appreciated that or be able to confirm that, uses no more than normal experiment, institute herein
The many equivalents for the specific embodiment of the invention stated.These equivalents are also contained in appended claim.
Claims (8)
- A kind of 1. formula (1)Surfactant, Wherein, n=16-64, m=10-40, and R are fluorine-containing organo-functional group, and wherein R is trifluoropropyl group, p-trifluoromethyl phenyl Group or p-fluorophenyl group.
- A kind of 2. method for the surfactant for preparing claim 1, it is characterised in that comprise the following steps：A. the poly- methyl fluorine alkyl siloxanes of formula (2) end group silicon hydrogen；B. prepare Si―H addition reaction with scheme (1) and prepare triblock copolymer,
- 3. methods described according to claim 2, it is characterised in that the poly- methyl fluorine alkyl siloxanes of formula (2) end group silicon hydrogen lead to Cross scheme (2) preparation：Formula (3),X can be 3,4 and 5 wherein in formula (3).
- 4. methods described according to claim 2, it is characterised in that spent glycol dimethyl ether triggers polymerization in scheme (1), by second The amount control polymerization speed of glycol dimethyl ether, reaction temperature is at 40-100 DEG C.
- 5. methods described according to claim 3, it is characterised in that scheme (2) controls reactive polymeric degree by n-BuLi amount.
- 6. methods described according to claim 2, it is characterised in that scheme (1), as solvent, is heated to reflux from tetrahydrofuran React 1-15h.
- 7. application of the surfactant of claim 1 in microlayer model is prepared.
- 8. application of the surfactant prepared according to any described methods of claim 2-6 in microlayer model is prepared.
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| CN102993225A (en) * | 2012-09-28 | 2013-03-27 | 山东农业大学 | Preparation method of anti-hydrolysis organosilane surfactant |
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| CN1974633A (en) * | 2006-11-28 | 2007-06-06 | 苏州大学 | Fluoric alkoxyl propyl methyl silicone oil and its prepn process |
| CN102993225A (en) * | 2012-09-28 | 2013-03-27 | 山东农业大学 | Preparation method of anti-hydrolysis organosilane surfactant |
| CN103394293A (en) * | 2013-07-22 | 2013-11-20 | 东华大学 | Preparation method for hydrophilia polyvinylidene fluoride hollow fiber membrane |
| WO2015038454A1 (en) * | 2013-09-16 | 2015-03-19 | Honeywell International Inc. | Poly fluorine-containing siloxane coatings |
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