CN101812164B - Fluosilicate-containing amphipathic segmented copolymer and preparation method and aqueous emulsion thereof - Google Patents
Fluosilicate-containing amphipathic segmented copolymer and preparation method and aqueous emulsion thereof Download PDFInfo
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- CN101812164B CN101812164B CN2010101615787A CN201010161578A CN101812164B CN 101812164 B CN101812164 B CN 101812164B CN 2010101615787 A CN2010101615787 A CN 2010101615787A CN 201010161578 A CN201010161578 A CN 201010161578A CN 101812164 B CN101812164 B CN 101812164B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 229920001577 copolymer Polymers 0.000 title abstract description 35
- 239000000839 emulsion Substances 0.000 title abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 48
- 229920000570 polyether Polymers 0.000 claims abstract description 46
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 34
- -1 (meth) acrylic acid alkyl fluoride Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 68
- ZHPNWZCWUUJAJC-UHFFFAOYSA-N fluorosilicon Chemical compound [Si]F ZHPNWZCWUUJAJC-UHFFFAOYSA-N 0.000 claims description 63
- 229920000642 polymer Polymers 0.000 claims description 63
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 47
- 229910052757 nitrogen Inorganic materials 0.000 claims description 34
- 239000007788 liquid Substances 0.000 claims description 31
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 20
- 238000002390 rotary evaporation Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- 230000008014 freezing Effects 0.000 claims description 17
- 238000007710 freezing Methods 0.000 claims description 17
- 238000006392 deoxygenation reaction Methods 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 16
- 238000004945 emulsification Methods 0.000 claims description 16
- 238000010792 warming Methods 0.000 claims description 16
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical group Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 12
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229920006395 saturated elastomer Polymers 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 229910021575 Iron(II) bromide Inorganic materials 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229940046149 ferrous bromide Drugs 0.000 claims description 3
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 239000010813 municipal solid waste Substances 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 7
- 239000010985 leather Substances 0.000 abstract description 2
- 239000000123 paper Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000007822 coupling agent Substances 0.000 abstract 1
- 230000001804 emulsifying effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 239000004753 textile Substances 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 11
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 6
- QTKPMCIBUROOGY-UHFFFAOYSA-N 2,2,2-trifluoroethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(F)(F)F QTKPMCIBUROOGY-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- SPTAJTRODSJRMF-UHFFFAOYSA-N n,n-dimethylheptadecan-1-amine;hydrochloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCC[NH+](C)C SPTAJTRODSJRMF-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229920000151 polyglycol Polymers 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- PDSVZUAJOIQXRK-UHFFFAOYSA-N trimethyl(octadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)C PDSVZUAJOIQXRK-UHFFFAOYSA-N 0.000 description 3
- LZFWKAISMPFBFI-UHFFFAOYSA-M [Cl-].N.C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C Chemical compound [Cl-].N.C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C LZFWKAISMPFBFI-UHFFFAOYSA-M 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229910021332 silicide Inorganic materials 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- WWSNLNXXISONLQ-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Cl(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Cl(C)(C)C WWSNLNXXISONLQ-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- IKCHUGFGDDICSD-UHFFFAOYSA-N [Br+].[Cl+].C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C Chemical compound [Br+].[Cl+].C(CCCCCCCCCCCCCCCCC)[N+](C)(C)C IKCHUGFGDDICSD-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Silicon Polymers (AREA)
- Polyethers (AREA)
Abstract
The invention discloses a fluosilicate-containing amphipathic segmented copolymer and a preparation method and an aqueous emulsion thereof. The fluosilicate-containing amphipathic segmented copolymer comprises the following components in part by weight: 100 parts single/dual-bromine terminated polyether, 0.1 to 30 parts of (meth) acrylic acid alkyl fluoride, 0.1 to 30 parts of organosilane coupling agent containing end-reaction dual-bond, 0.1 to 50 parts of catalyst, 0.1 to 50 parts of coordinating agent and 1 to 500 parts of organic solvent, and the above components are heated and reacted to obtain the fluosilicate-containing amphipathic segmented copolymer at the temperature of 30 to 150 DEG C. The aqueous emulsion of the fluosilicate-containing amphipathic segmented copolymer is obtained through the high-shearing emulsifying reaction of 100 parts of water, 1 to 80 parts of amphipathic segmented copolymer and 0 to 5 parts of emulsifier at the atmospheric temperature. The aqueous emulsion of the fluosilicate-containing amphipathic segmented copolymer has good stability and high surface activity, and can be applicable to the fields such as paint, paper, textile, leather arrangement agent and the like.
Description
Technical field
The present invention relates to the polymer materials field, particularly amphipathic nature block polymer of a kind of fluorine silicon and preparation method thereof and water miscible liquid.
Background technology
The silicon-fluorine polymer thing has the advantage of organosilicon and organo-fluorine polymer, and particularly water-based silicon-fluorine polymer thing with water is solvent, and is environmentally friendly, is a new focus in polymer materials field.But, at present the aqueous silicon fluoro polymkeric substance generally is to be the random copolymers that raw material is made with organic fluorine monomer, organosilane monomer and the vinylformic acid and the ester thereof that contain reactive double bond, because that the fluorine silicon group distributes is scattered, be entangled with mutually between macromolecular chain, a lot of fluorine silicon groups are difficult to arrive the material layer surface of required processing after the film forming, thereby have weakened the effect of fluorine silicon group.
Summary of the invention
The objective of the invention is to overcome the shortcoming that exists in the prior art, the amphipathic nature block polymer of a kind of stable performance, fluorine silicon that surfactivity is high is provided.
Another object of the present invention is to provide a kind of preparation method of amphipathic nature block polymer of above-mentioned fluorine silicon.
A further object of the present invention is to provide a kind of water miscible liquid of amphipathic nature block polymer of above-mentioned fluorine silicon.
Purpose of the present invention is achieved through the following technical solutions:
A kind of amphipathic nature block polymer of fluorine silicon comprises following components in part by mass:
100 parts of list/pair bromine terminated polyether
0.1～30 part of (methyl) vinylformic acid fluorinated alkyl esters
Contain 0.1～30 part of organo silane coupling agent holding reactive double bond
0.1～50 part of catalyzer
0.1～50 part of coordination agent
1～500 part of organic solvent.
Described list/pair bromine terminated polyether, adopt following method to prepare: the compd A (structural formula 1) of 100 mass parts and the saturated hydrogen bromide-acetum of 200 mass parts are mixed, 50 ℃ are stirred 5h down, and 90 ℃ of rotary evaporation 2h of Rotary Evaporators use 10mmol/L NaHCO
3The pH value of reaction solution is transferred to 7, again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains list/pair bromine terminated polyether.
The structural formula of described compd A is a formula 1:
In the formula 1, R be H or-CH
3, 0≤m≤400,0≤n≤400, m, n can not be 0 simultaneously.
Described (methyl) vinylformic acid fluorinated alkyl esters, structural formula is a formula 2:
In the formula 2, R '=H, F or-CH
3, R
fThe expression carbonatoms is that hydrogen atom in 1～12 the alkyl is by the part or all of metathetical Polyfluoroalkyl of fluorine atom.
The described organo silane coupling agent of holding reactive double bond that contains, structural formula is a formula 3:
CH
2＝CR
1-(COOCH
2CH
2CH
2)
i-Si(OR
2)
3
Formula 3
In the formula 3, R
1Be H or-CH
3, R
2Be-CH
3,-C
2H
5,-C
2H
4OCH
3,-OC (CH
3)
3Or-COCH
3, i=0 or 1.
Described catalyzer is the lower valency metal halide, preferred cuprous bromide, ferrous bromide.
Described coordination agent can be: (1) dipyridyl or derivatives thereof, and as 2,2 '-dipyridyl; (2) straight-chain paraffin of many nitrogen is as pentamethyl-diethylenetriamine (PMDETA); (3) triphenylphosphine.
Described organic solvent comprises toluene, 1,4-dioxane or butanone.
A kind of preparation method of amphipathic nature block polymer of fluorine silicon, comprise the steps: list/pair bromine terminated polyether 100 mass parts, (methyl) vinylformic acid fluorinated alkyl esters 0.1～30 mass parts, contain organo silane coupling agent 0.1～30 mass parts, coordination agent 0.1～50 mass parts and organic solvent 1～500 mass parts of holding reactive double bond and mix, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 30～150 ℃ then, add catalyzer 0.1～50 mass parts, react 1.5～25h, make the amphipathic nature block polymer of fluorine silicon.
Described cryosel bath is freezing to be: add 20～40 mass parts CaCl in 100 mass parts trash ices
26H
2O stirs, and temperature is-4～-10 ℃.
A kind of water miscible liquid of amphipathic nature block polymer of fluorine silicon, be with the amphipathic nature block polymer of the above-mentioned fluorine silicon of the water of 100 mass parts, 1～80 mass parts and the emulsifying agent of 0～5 mass parts, high speed shear emulsification at normal temperatures obtains the water miscible liquid of the amphipathic nature block polymer of fluorine silicon.
Described emulsifying agent comprises the quaternary cationics that contains chain alkyl and/or has the nonionogenic tenside of polyoxyethylene segment.The preferred cetyl trimethyl chlorine of the quaternary cationics of described chain alkyl (bromine) is changed one or more mixtures of amine and octadecyl trimethylammonium chlorine (bromine) change amine; The described nonionogenic tenside preferred alkyl that has the polyoxyethylene segment is that 4～18 chain alkyl polyoxyethylene groups ether and alkyl are one or more mixtures of 4～20 alkylphenol-polyethenoxy base ether.
The amphipathic nature block polymer of fluorine silicon provided by the invention focuses on molecular chain one end with the fluorine silicon group on the one hand, obtains the multipolymer of compound with regular structure, thereby improves the probability that the fluorine silicon group arrives the material layer surface, gives full play to the effect of fluorine silicon; Segmented copolymer of the present invention on the other hand comprises hydrophilic and hydrophobic two kinds of segments simultaneously, has unique microcosmic and divides phase behavior and macroscopical amphiphilic nature.
The present invention compared with prior art has following advantage and effect:
(1) fluorine silicon amphipathic nature block polymer of the present invention, compound with regular structure, fluorine silicon helps giving full play to the effect of fluorine silicon at molecular chain one end; Because comprise hydrophilic and hydrophobic two kinds of segments simultaneously, can increase the dispersion concentration of fluorine-silicon copolymer thing in water greatly, thereby can prepare water miscible liquid again.
(2) preparation method of the present invention is simple.
(3) water miscible liquid of fluorine silicon amphipathic nature block polymer of the present invention has good stability, and performances such as surfactivity height can be applied in fields such as coating, paper, fabric, leather finishing composition.
Embodiment
Below in conjunction with embodiment the present invention is done further detailed description, but embodiments of the present invention are not limited thereto.
Among the following embodiment, viscosity is pressed GB/T 15357-1994 and is measured; Surface tension is pressed GB11985-89 and is measured.
Embodiment 1
Table 1: the amphipathic nature block polymer of fluorine silicon and water miscible liquid performance
In the table 1:
The preparation method of the amphipathic nature block polymer 1 of fluorine silicon: single bromine terminated polyether 100g, trifluoroethyl methacrylate 20g, Alpha-Methyl vinyltriethoxysilane 20g, 2,2 '-dipyridyl 4g and butanone 150g mix,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 100 ℃ then, add cuprous bromide 10g, react 5h, obtain the amphipathic nature block polymer 1 of fluorine silicon.Wherein single bromine terminated polyether, make according to following method: with 100 mass parts structures suc as formula (1) (R=H wherein, m=180, n=0) Biao Shi compd A, hydrogen bromide-acetum that 200 mass parts are saturated mix, 50 ℃ are stirred 5h down, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, single bromine terminated polyether.The preparation method of the water miscible liquid of segmented copolymer 1: the amphipathic nature block polymer 40g of water 100g, above-mentioned fluorine silicon, and the polyoxyethylene nonylphenol ether of 3g (EO=40), high speed shear emulsification under the normal temperature.
The preparation method of segmented copolymer 2: single bromine terminated polyether 100g, α-fluorate acrylic acid octafluoro pentyl ester 20g, vinyltrimethoxy silane 10g, pentamethyl-diethylenetriamine 3g and toluene 100g mix,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 90 ℃ then, add cuprous bromide 10g, react 8h, obtain the amphipathic nature block polymer 1 of fluorine silicon.The preparation method of wherein single bromine end capped polyether is identical with the preparation method of single bromine end capped polyether in the segmented copolymer 1.The preparation method of the water miscible liquid of segmented copolymer 2: the amphipathic nature block polymer 45g of water 100g, above-mentioned fluorine silicon, and the cetyl trimethyl ammonia chloride of 3g, high speed shear emulsification under the normal temperature.
The preparation method of segmented copolymer 3: single bromine terminated polyether 100g, methacrylic acid ten difluoro heptyl ester 18g, vinyltri-t-butylperoxy silane 2g, 2,2 '-dipyridyl 4g and butanone 100g mix,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 100 ℃ then, add cuprous bromide 10g, react 6h, obtain the amphipathic nature block polymer 3 of fluorine silicon.The preparation method of wherein single bromine end capped polyether is identical with the preparation method of single bromine end capped polyether in the segmented copolymer 1.The preparation method of the water miscible liquid of segmented copolymer 3: the amphipathic nature block polymer 42g of water 100g, above-mentioned fluorine silicon, and the octadecyl trimethylammonium amine bromide of 3g, high speed shear emulsification under the normal temperature.
The preparation method of segmented copolymer 4: single bromine terminated polyether 100g, methacrylic acid hexafluoro butyl ester 6g, acryloxy propyl trimethoxy silicane 4g, pentamethyl-diethylenetriamine 8g and 1,4-dioxane 400g mixes,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 85 ℃ then, add cuprous bromide 10g, react 5h, obtain the amphipathic nature block polymer 4 of fluorine silicon.The preparation method of wherein single bromine end capped polyether is identical with the preparation method of single bromine end capped polyether in the segmented copolymer 1.The preparation method of the water miscible liquid of segmented copolymer 4: the amphipathic nature block polymer 41g of water 100g, above-mentioned fluorine silicon, and the hexadecyl trimethyl ammonium bromide of 3g, high speed shear emulsification under the normal temperature.
The segmented copolymer of the present invention that provides from table 1 and the performance of water miscible liquid: 1. same polyether can prepare the amphipathic nature block polymer of fluorine silicon with different fluorochemicals and polymerizable organosilicon; 2. the water miscible liquid surface tension of Zhi Bei segmented copolymer is relevant with the fluorine silicone content, and the fluorine silicone content is high more, and the surface tension of water miscible liquid is more little.Table 1 data have demonstrated fully technique effect of the present invention.
Embodiment 2
Table 2: the segmented copolymer and the water miscible liquid performance (II) of fluorine-containing, silicon
| 2 | Two bromine end capped polyethers 2 | Trifluoroethyl methacrylate | The acryloxy propyl trimethoxy silicane | Stable transparent water emulsion | 5.4 | 27.67 |
| 3 | Single bromine end capped polyether 1 | Trifluoroethyl methacrylate | The acryloxy propyl trimethoxy silicane | Stable transparent water emulsion | 5.8 | 27.65 |
| 4 | Single bromine end capped polyether 2 | α-fluorate acrylic acid octafluoro pentyl ester | Vinyltri-t-butylperoxy silane | Stable transparent water emulsion | 5.7 | 27.75 |
In the table 2:
The preparation method of segmented copolymer 1: two bromine terminated polyether 100g, methacrylic acid hexafluoro butyl ester 20g, Alpha-Methyl vinyltrimethoxy silane 5g, 2,2 '-dipyridyl 3g and butanone 200g mix,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 100 ℃ then, add cuprous bromide 10g, react 5h, obtain the amphipathic nature block polymer 1 of fluorine silicon.Wherein two bromine terminated polyether, make as follows: with 100 mass parts structures suc as formula (1) (R=H wherein, m=150, n=0) Biao Shi compd A, hydrogen bromide-acetum that 200 mass parts are saturated mix, 50 ℃ are stirred 5h down, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains two bromine terminated polyether.The preparation method of the water miscible liquid of segmented copolymer 1: the amphipathic nature block polymer 40g of water 100g, above-mentioned fluorine silicon, and the cetyl trimethyl ammonia chloride of 3g, high speed shear emulsification under the normal temperature.
The preparation method of segmented copolymer 2: two bromine terminated polyether 100g, trifluoroethyl methacrylate 15g, acryloxy propyl trimethoxy silicane 2g, pentamethyl-diethylenetriamine 3g and toluene 100g mix,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 90 ℃ then, add cuprous bromide 10g, react 8h, obtain the amphipathic nature block polymer 2 of fluorine silicon.The preparation method of wherein two bromine end capped polyethers is identical with the preparation method of two bromine end capped polyethers in the segmented copolymer 1, distinguish the structural formula that only is compd A suc as formula (1) (R=H wherein, m=130, n=0).The preparation method of the water miscible liquid of segmented copolymer 2: the amphipathic nature block polymer 40g of water 100g, above-mentioned fluorine silicon, and the cetyl trimethyl ammonia chloride of 3g, high speed shear emulsification under the normal temperature.
The preparation method of segmented copolymer 3: single bromine terminated polyether 100g, trifluoroethyl methacrylate 18g, acryloxy propyl trimethoxy silicane 5g, 2,2 '-dipyridyl 4g and butanone 100g mix,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 100 ℃ then, add cuprous bromide 10g, react 6h, obtain the amphipathic nature block polymer 3 of fluorine silicon.The preparation method of two bromine end capped polyethers is identical in the preparation method of wherein single bromine end capped polyether and the segmented copolymer 1, and the structural formula that difference only is compd A is suc as formula (1) (R=-CH wherein
3, m=120, n=130).The preparation method of the water miscible liquid of segmented copolymer 3: the amphipathic nature block polymer 35g of water 100g, above-mentioned fluorine silicon, and the octadecyl trimethylammonium ammonia chloride of 3g, high speed shear emulsification under the normal temperature.
The preparation method of segmented copolymer 4: two bromine terminated polyether 100g, α-fluorate acrylic acid octafluoro pentyl ester 20g, vinyltri-t-butylperoxy silane 5g, pentamethyl-diethylenetriamine 8g and 1,4-dioxane 400g mixes,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 85 ℃ then, add cuprous bromide 10g, react 5h, obtain the amphipathic nature block polymer 4 of fluorine silicon.The preparation method of two bromine end capped polyethers is identical in the preparation method of wherein single bromine end capped polyether and the segmented copolymer 1, and the structural formula that difference only is compd A is suc as formula (1) (R=-CH wherein
3, m=140, n=100).The preparation method of the water miscible liquid of segmented copolymer 4: the amphipathic nature block polymer 40g of water 100g, above-mentioned fluorine silicon, and the cetyl trimethyl ammonia chloride of 3g, high speed shear emulsification under the normal temperature.
The segmented copolymer of the present invention that provides from table 2 and the performance of water miscible liquid thereof: 1. same polyether can prepare the amphipathic nature block polymer of fluorine silicon with different fluorochemicals and silicide polymerization; Different polyethers can prepare the amphipathic nature block polymer of fluorine silicon with identical fluorochemical and silicide polymerization; 2. the water miscible liquid performance of Zhi Bei segmented copolymer is similar, and good stability, surface tension are big.Table 2 data have demonstrated fully technique effect of the present invention.
Embodiment 3
With the 100g polyoxyethylene glycol (structure is seen formula (1), R=H wherein, m=400, n=0), hydrogen bromide-acetum that 200g is saturated mixes, 50 ℃ are stirred 5h, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO down
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, two bromine terminated polyether.
(structure is seen formula (2), R '=H wherein, R with the two end capped polyoxyethylene glycol of bromine of 100g, 0.1g vinylformic acid trifluoro ethyl ester
f=-CF
3), 0.1g vinyltrimethoxy silane (CH
2=CHSi (OCH
3)
3), 0.1g 2,2 '-dipyridyl and 500 mass parts butanone mix ,-10 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 30 ℃ then, add 0.1g cuprous bromide reaction 25h, obtain the amphipathic nature block polymer of fluorine silicon.
The amphipathic nature block polymer 1g of the fluorine silicon that adding 100g distilled water and above-mentioned reaction obtain in the high speed shear mulser, high speed shear emulsification obtains the translucent emulsion with blue-fluorescence.This water miscible liquid viscosity is 4.7mPaS, and surface tension is 25.02N/m.
Embodiment 4
(structure is seen formula (1), wherein R=CH with the 100g poly glycol monomethyl ether
3, m=400, n=0), hydrogen bromide-acetum that 200g is saturated mixes, 50 ℃ are stirred 5h, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO down
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains single bromine end-blocking poly glycol monomethyl ether.
(structure is seen formula (1), R '=F wherein, R with the single bromine end-blocking of 100g poly glycol monomethyl ether, 30g α-fluorate acrylic acid trifluoro ethyl ester
f=-CF
3) and 30g vinyltriethoxysilane (CH
2=CHSi (OC
2H
5)
3), 50g pentamethyl-diethylenetriamine (PMDETA) and 500 mass parts butanone mix, it is freezing that-9 ℃ of cryosels are bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 150 ℃ then, add 50g cuprous bromide reaction 1.5h, obtain the amphipathic nature block polymer of fluorine silicon.
The amphipathic nature block polymer 80g of the fluorine silicon that adding 100g distilled water and above-mentioned reaction obtain in the high speed shear mulser, cetyl trimethyl ammonia chloride 1.33g, high speed shear emulsification obtains the translucent emulsion with blue-fluorescence.This water miscible liquid viscosity is 2.7mPaS, and surface tension is 20.92N/m.
Embodiment 5
With the 100g polypropylene glycol (structure is seen formula (1), R=H wherein, m=0, n=400), hydrogen bromide-acetum that 200g is saturated mixes, 50 ℃ are stirred 5h, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO down
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains two bromine end capped polyethers.
With the two end capped polypropylene glycols of bromine of 100g, (structure is seen formula (1), wherein R '=CH to 5.0g α-Jia Jibingxisuan hexafluoro butyl ester
3, R
f=-C
3HF
6), 5.0g Alpha-Methyl vinyltrimethoxy silane (CH
2=C (CH
3) Si (OCH
3)
3), 1g triphenylphosphine and 500 mass parts toluene mix, it is freezing that-6 ℃ of cryosels are bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 30 ℃ then, add 1g ferrous bromide reaction 25h, obtain the amphipathic nature block polymer of fluorine silicon.
The amphipathic nature block polymer 70g of the fluorine silicon that adding 100g distilled water and above-mentioned reaction obtain in the high speed shear mulser, octadecyl trimethylammonium amine bromide 2g, high speed shear emulsification obtains the translucent emulsion with blue-fluorescence.This water miscible liquid viscosity is 5.5mPaS, and surface tension is 24.18N/m;
Embodiment 6
(structure is seen formula (1), wherein R=CH with 100g polypropylene glycol monomethyl ether
3, m=0, n=400), hydrogen bromide-acetum that 200g is saturated mixes, 50 ℃ are stirred 5h, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO down
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains single bromine end-blocking polypropylene glycol monomethyl ether.
(structure is seen formula (1), R '=H wherein, R with the single bromine end-blocking of 100g poly glycol monomethyl ether, 30g vinylformic acid hexafluoro butyl ester
f=-C
3HF
6) and 10g vinyltri-t-butylperoxy silane (CH
2=CHSi (OOC (CH
3)
3)
3), 50g 2,2 '-dipyridyl and 500 mass parts 1, the 4-dioxane mixes ,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 150 ℃ then, add 50g cuprous bromide reaction 1.5h, obtain the amphipathic nature block polymer of fluorine silicon.
The amphipathic nature block polymer 40g of the fluorine silicon that adding 100g distilled water and above-mentioned reaction obtain in the high speed shear mulser, the emulsification of octadecyl trimethylammonium ammonia chloride high speed shear obtains the white emulsion with blue-fluorescence.This water miscible liquid viscosity is 5.1mPaS, and surface tension is 23.91N/m.
Embodiment 7
With the 100g polyethers (structure is seen formula (1), R=H wherein, m=400, n=400), hydrogen bromide-acetum that 200g is saturated mixes, 50 ℃ are stirred 5h, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO down
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains two bromine end capped polyethers.
(structure is seen formula (1), R '=F wherein, R with the two bromine end capped polyethers of 100g, 10g α-fluorate acrylic acid octafluoro pentyl ester
f=-C
4HF
8) and 2g acryloxy propyl trimethoxy silicane (CH
2=CH (COOCH
2CH
2CH
2) Si (OCH
3)
3), 1g pentamethyl-diethylenetriamine (PMDETA) and 500 mass parts butanone mix, it is freezing that-4 ℃ of cryosels are bathed, and vacuumizes, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 30 ℃ then, add 1g cuprous bromide reaction 25h, obtain the amphipathic nature block polymer of fluorine silicon.
The amphipathic nature block polymer 30g of the fluorine silicon that adding 100g distilled water and above-mentioned reaction obtain in the high speed shear mulser, octadecyl trimethylammonium amine bromide 0.2g, the emulsification of polyoxyethylene nonylphenol ether (EO=40) 0.3g high speed shear obtains the translucent emulsion with blue-fluorescence.This water miscible liquid viscosity is 4.3mPaS, and surface tension is 23.83N/m.
Embodiment 8
(structure is seen formula (1), wherein R=CH with the 100g polyethers
3, m=400, n=400), hydrogen bromide-acetum that 200g is saturated mixes, 50 ℃ are stirred 5h, 90 ℃ of rotary evaporation 2h of Rotary Evaporators, product 10mmol/L NaHCO down
3Adjust pH to 7 is again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains single bromine end capped polyether.
With the two bromine end capped polyethers of 100g, (structure is seen formula (1), wherein R '=CH to 10g α-fluorate acrylic acid octafluoro pentyl ester
3, R
f=-C
4HF
8), 30g Alpha-Methyl vinyltriethoxysilane (CH
2=C (CH
3) Si (OC
2H
5)
3), 1g 2,2 '-dipyridyl and 500 mass parts butanone mix ,-4 ℃ of cryosels are bathed freezing, vacuumize, drum nitrogen 3 times is with deoxygenation; Under nitrogen protection, be warming up to 30 ℃ then, add 1g cuprous bromide reaction 25h, obtain the amphipathic nature block polymer of fluorine silicon.
The amphipathic nature block polymer 20g of the fluorine silicon that adding 100g distilled water and above-mentioned reaction obtain in the high speed shear mulser, polyoxyethylene nonylphenol ether (EO=40) 1.0g, high speed shear emulsification obtains the transparent aqueous solution with blue-fluorescence.This water miscible liquid viscosity is 6.2mPaS, and surface tension is 23.27N/m.
Claims (10)
1. the amphipathic nature block polymer of a fluorine silicon, it is characterized in that: by following components in part by mass is that feedstock production obtains:
2. the amphipathic nature block polymer of fluorine silicon according to claim 1, it is characterized in that: described list/pair bromine terminated polyether, adopt following method to prepare: the compd A of 100 mass parts and the saturated hydrogen bromide-acetum of 200 mass parts are mixed, 50 ℃ are stirred 5h down, 90 ℃ of rotary evaporation 2h of Rotary Evaporators use 10mmol/L NaHCO
3The pH value of reaction solution is transferred to 7, again with distilled water and CH
2Cl
2Extract 5 times, stay CH
2Cl
2Place layer solution, 90 ℃ of Rotary Evaporators is rotary evaporation 2h once more, obtains list/pair bromine terminated polyether; The structural formula of described compd A is a formula 1:
Formula 1
In the formula 1, R be H or-CH
3, 0≤m≤400,0≤n≤400, m, n can not be 0 simultaneously.
3. the amphipathic nature block polymer of fluorine silicon according to claim 1, it is characterized in that: the structural formula of described (methyl) vinylformic acid fluorinated alkyl esters is a formula 2:
Formula 2
In the formula 2, R '=H, F or-CH
3, R
fThe expression carbonatoms is that hydrogen atom in 1～12 the alkyl is by the part or all of metathetical Polyfluoroalkyl of fluorine atom.
4. the amphipathic nature block polymer of fluorine silicon according to claim 1 is characterized in that: the described organo silane coupling agent of holding reactive double bond that contains, and structural formula is a formula 3:
CH
2＝CR
1-(COOCH
2CH
2CH
2)i-Si(OR
2)
3
Formula 3
In the formula 3, R
1Be H or-CH
3, R
2Be-CH
3,-C
2H
5,-C
2H
4OCH
3,-OC (CH
3)
3Or-COCH
3, i=0 or 1.
5. the amphipathic nature block polymer of fluorine silicon according to claim 1, it is characterized in that: described catalyzer is cuprous bromide or ferrous bromide.
6. the amphipathic nature block polymer of fluorine silicon according to claim 1, it is characterized in that: described coordination agent is the straight-chain paraffin or the triphenylphosphine of dipyridyl, many nitrogen; Described organic solvent comprises toluene, 1,4-dioxane or butanone.
7. the preparation method of the amphipathic nature block polymer of the described fluorine silicon of claim 1, it is characterized in that comprising the steps: list/pair bromine terminated polyether 100 mass parts, (methyl) vinylformic acid fluorinated alkyl esters 0.1～30 mass parts, contain organo silane coupling agent 0.1～30 mass parts, coordination agent 0.1～50 mass parts and organic solvent 1～500 mass parts of holding reactive double bond and mix, it is freezing that cryosel is bathed, and vacuumizes, drum nitrogen 3～5 times is with deoxygenation; Under nitrogen protection, be warming up to 30～150 ℃ then, add catalyzer 0.1～50 mass parts, react 1.5～25h, make the amphipathic nature block polymer of fluorine silicon.
8. the preparation method of the amphipathic nature block polymer of fluorine silicon according to claim 7 is characterized in that: described cryosel is bathed and freezingly is: add 20～40 mass parts CaCl in 100 mass parts trash ices
26H
2O stirs, and temperature is-4～-10 ℃.
9. the water miscible liquid of the amphipathic nature block polymer of a fluorine silicon, it is characterized in that: be the amphipathic nature block polymer of the described fluorine silicon of claim 1 of the water of 100 mass parts, 1～80 mass parts and the emulsifying agent of 0～5 mass parts, high speed shear emulsification at normal temperatures obtains the water miscible liquid of the amphipathic nature block polymer of fluorine silicon.
10. the water miscible liquid of the amphipathic nature block polymer of fluorine silicon according to claim 9, it is characterized in that: described emulsifying agent comprises the quaternary cationics that contains chain alkyl and/or has the nonionogenic tenside of polyoxyethylene segment.
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