CN105061640B - Fluorine-containing emulsifier as well as anionic fluorine-containing emulsion prepared based on emulsifier and method - Google Patents
Fluorine-containing emulsifier as well as anionic fluorine-containing emulsion prepared based on emulsifier and method Download PDFInfo
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- CN105061640B CN105061640B CN201510434013.4A CN201510434013A CN105061640B CN 105061640 B CN105061640 B CN 105061640B CN 201510434013 A CN201510434013 A CN 201510434013A CN 105061640 B CN105061640 B CN 105061640B
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 81
- 239000011737 fluorine Substances 0.000 title claims abstract description 81
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000003995 emulsifying agent Substances 0.000 title claims abstract description 54
- 239000000839 emulsion Substances 0.000 title claims abstract description 45
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 18
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000004816 latex Substances 0.000 claims description 33
- 229920000126 latex Polymers 0.000 claims description 33
- 238000006116 polymerization reaction Methods 0.000 claims description 27
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 11
- 230000032050 esterification Effects 0.000 claims description 10
- 238000005886 esterification reaction Methods 0.000 claims description 10
- 229920000570 polyether Polymers 0.000 claims description 10
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 230000033228 biological regulation Effects 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- LZRIYTFPVMKAIR-UHFFFAOYSA-N 1-fluoroheptan-1-ol Chemical compound CCCCCCC(O)F LZRIYTFPVMKAIR-UHFFFAOYSA-N 0.000 claims description 5
- LFNVRNWBMJBTKZ-UHFFFAOYSA-N 1-fluorohexan-1-ol Chemical compound CCCCCC(O)F LFNVRNWBMJBTKZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- 235000019394 potassium persulphate Nutrition 0.000 claims description 5
- 150000002221 fluorine Chemical class 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N n-Butanol Substances CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 3
- -1 2,2,3,4,4,4-hexafluoro-n-butyl Chemical group 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 210000000481 breast Anatomy 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 238000007599 discharging Methods 0.000 abstract description 7
- 239000003960 organic solvent Substances 0.000 abstract description 7
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000004321 preservation Methods 0.000 abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract 1
- 239000002612 dispersion medium Substances 0.000 abstract 1
- 238000010008 shearing Methods 0.000 abstract 1
- 125000000542 sulfonic acid group Chemical group 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 4
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical group C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- LVFXLZRISXUAIL-UHFFFAOYSA-N 2,2,3,4,4,4-hexafluorobutan-1-ol Chemical compound OCC(F)(F)C(F)C(F)(F)F LVFXLZRISXUAIL-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229950000845 politef Drugs 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The present invention discloses a fluorine-containing emulsifier as well as anionic fluorine-containing emulsion prepared based on the emulsifier and a method, and belongs to the technical field of fine chemical preparation. Fluorocarbon emulsion containing a sulfonic acid group consists of the following raw materials: fluorine-containing acrylate, butyl acrylate, styrene, acrylic acid or 2-acrylamide-2-methylpropane sulfonic acid, an emulsifier, an initiator and water. The preparation comprises: carrying out high speed shearing on all types of the raw materials (wherein 70% of the water is added, and the remaining 30% of the water is kept for later use) for 30 minutes, taking the remaining 30% of water and 5% of the pre-emulsion after obtaining pre-emulsion, raising the temperature of the water and the pre-emulsion to 50-80 DEG C under stirring, and starting to carry out heat preservation; and starting to dropwise add the remaining pre-emulsion after carrying out the heat preservation for 30 minutes, enabling the remaining pre-emulsion to react for 5-25 hours, cooling the remaining pre-emulsion to the room temperature, and discharging the cooled pre-emulsion, thereby preparing the anionic fluorine-containing emulsion . According to the present invention, the emulsifier in the emulsion directly reacts with a polymeric monomer, thereby avoiding a migration problem of a conventional emulsifier; and meanwhile the water is used as a dispersion medium, so that no organic solvent is contained, resources are saved, and environment-friendly requirements are satisfied..
Description
Technical field
The invention belongs to Field of Fine Chemicals, relate to a kind of emulsion and preparation method thereof, be specifically related to one
Fluorine-containing emulsifier and the anionic fluorine-containing latex prepared based on this emulsifying agent and method.
Background technology
The good film-forming property of acrylic acid ester emulsion, application property are good, film is alkaline-resisting, colour retention is good, pollution-free,
It has been used widely.But its stain resistance, weatherability, thermostability, oil resistivity etc. are the most unsatisfactory,
Therefore also need to acrylic acid ester emulsion further optimize.
Fluoropolymer due to have high surface, high heat-resistant stability, high chemical inertness, hydrophobicity and
" the three-hypers two is hated " performance of oil repellency and be used widely.At present, the preparation method of common fluorine-containing latex
Mainly have several under several: (1) is the homopolymerization or altogether of monomer under conventional emulsifier/fluorine-containing emulsifier acts on jointly
Poly-；(2) homopolymerization of monomer or copolymerization under conventional emulsifier/organic solvent effect；(3) politef
Emulsion and the simple blend of conventional emulsions；But in above method, its final products all contain conventional emulsifier
Or (with) organic solvent, this is to fluorine-containing latex product surface performance and environmentally undesirable.And add polymerizable and contain
Fluorine surfactant becomes the preparation method that fluorine-containing latex is new, but this type of fluorine-containing surfactant is with poly-ammonia at present
Ester type is main, and it is organic solvent to be used in building-up process, and severe reaction conditions.
Summary of the invention
In order to overcome the defect of above-mentioned prior art, it is an object of the invention to provide a kind of anionic fluorine-containing
Emulsion and preparation method thereof, the method is simple to operate, without organic solvent, environmental protection, through the party's legal system
Anionic fluorine-containing latex stable performance, excellent.
The present invention is to be achieved through the following technical solutions:
The invention discloses a kind of fluorine-containing emulsifier, this fluorine-containing emulsifier is by maleic anhydride and allyl polyether
In molar ratio after 1:1 esterification, then carry out preparing after esterification with fluorine-containing alcohol 1:1 in molar ratio, knot
Structure is as follows:
Wherein, RfFor C4H3F6、C5H3F8、C6H4F9Or C7H3F12, n is the integer more than 2.
The relative molecular weight of described allyl polyether is 2000.
Described fluorine-containing alcohol be 2,2,3,4,4,4-hexafluoro-n-butyl alcohol, 2,2,3,3,4,4,5,5-octafluoro-1-amylalcohol,
1H, 1H, 2H, 2H-nine fluoro-1-hexanol or 1H, the fluoro-1-heptanol of 1H, 7H-12.
The invention also discloses the preparation method of a kind of anionic fluorine-containing latex, comprise the following steps:
1) polymerizable raw material monomer, fluorine-containing emulsifier, initiator and water are taken；Polymerization monomer includes: fluorine-containing third
Olefin(e) acid ester, butyl acrylate, styrene and acrylic acid or 2-acrylamide-2-methyl propane sulfonic；
Wherein, acrylic acid or 2-acrylamide-2-methyl propane sulfonic and fluorinated acrylate, butyl acrylate and
Cinnamic mol ratio is (0.02～0.4): (0.2～1.0): 1.0:1.0；
Fluorine-containing emulsifier accounts for the 0.5%～5% of polymerization monomer gross mass；Initiator accounts for polymerization monomer gross mass
0.1%～2%；Water accounts for the 200%～300% of polymerization monomer gross mass；
2) after polymerizable raw material monomer, fluorine-containing emulsifier, initiator and part water being mixed, at high speed shear
Reason 30min, obtains pre-emulsion；Part water accounts for the 70% of water gross mass；
3) take and be warming up under the pre-emulsion of pre-emulsion gross mass 5% and the water of remainder, stirring
After 50～80 DEG C, it is incubated 30min, then drips remaining pre-emulsion, react 5～25h, regulate reactant
Be pH value be 7～8, be cooled to room temperature, prepare anionic fluorine-containing latex.
Described fluorine-containing emulsifier is by after maleic anhydride and allyl polyether 1:1 esterification in molar ratio,
Preparing carry out esterification again with fluorine-containing alcohol 1:1 in molar ratio after, structure is as follows:
Wherein, RfFor C4H3F6、C5H3F8、C6H4F9Or C7H3F12, n is the integer more than 2.
The relative molecular weight of described allyl polyether is 2000.Described fluorine-containing alcohol is 2,2,3,4,4,4-hexafluoro-1-
Butanol, 2,2,3,3,4,4,5,5-octafluoro-1-amylalcohol, 1H, 1H, 2H, 2H-nine fluoro-1-hexanol or 1H, 1H, 7H-12
Fluoro-1-heptanol.Described initiator is Ammonium persulfate. or potassium peroxydisulfate.
Use and sodium hydroxide, potassium hydroxide, ammonia or triethylamine regulate reaction system pH to 7～8.
Invention additionally discloses and adopt the anionic fluorine-containing latex prepared with the aforedescribed process.
Compared with prior art, the present invention has a following useful technique effect:
Fluorine-containing emulsifier disclosed by the invention, is to use Organic fluoride alcohol to be esterified with allyl polyether with maleic anhydride
Product reacts, the nonionic reactivity fluorine-containing emulsifier prepared, and this fluorine-containing emulsifier can be by regulation
The length of fluorine-containing alcohol segment, changes the surface behavior of fluorocarbon surfactant.
Anionic fluorine-containing latex preparation method disclosed by the invention, with the addition of above-mentioned new non-ionic type anti-
Answering property fluorine-containing emulsifier, this fluorine-containing emulsifier can directly be polymerized monomer reaction, it is to avoid conventional emulsifier
" migration " problem, meanwhile, using water as disperse medium, without organic solvent, economize on resources, meet
Environmental requirement.
Through the anionic fluorine-containing latex stable performance, excellent that the inventive method prepares.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, described in the present invention
Explain rather than limit.
The fluorine-containing emulsifier of the present invention be maleic anhydride with allyl polyether (relative molecular mass=2000) with
Mol ratio 1:1 esterification after, then with fluorine-containing alcohol (2,2,3,4,4,4-hexafluoros-n-butyl alcohol, 2,2,3,3,4,4,5,5-octafluoros
-1-amylalcohol, 1H, the one in 1H, 2H, 2H-nine fluoro-1-hexanol, the fluoro-1-heptanol of 1H, 1H, 7H-12) to rub
You are esterified than 1:1, the reactive fluorine-containing emulsifier obtained.
Molecular structure is as follows:
Wherein :-RfFor :-C4H3F6、-C5H3F8、-C6H4F9、-C7H3F12In one.
The preparation method of a kind of anionic fluorine-containing latex, comprises the following steps:
1) raw material is taken: fluorinated acrylate, butyl acrylate, styrene, acrylic acid or 2-acrylamide
-2-methyl propane sulfonic acid, emulsifying agent, initiator and water.
Wherein, polymerization monomeric fluoro acrylate, butyl acrylate, styrene, acrylic acid or 2-acryloyl
The mol ratio of amine-2-methyl propane sulfonic acid is 0.2-1.0: 1.0: 1.0: 0.02-0.4；It is total that emulsifying agent accounts for polymerization monomer
The 0.5%～5% of quality；Initiator accounts for the 0.1%～2% of polymerization monomer gross mass；Water accounts for the polymerization total matter of monomer
The 200%～300% of amount.
2) by above-mentioned all kinds raw material (wherein: water adds 70%, remaining 30% standby), container is added
High speed is sheared 30 minutes, obtains pre-emulsion.
3) in the dry there-necked flask of belt stirrer, condenser and Dropping funnel, remaining 30% water is added
Pre-emulsion with 5%, is warming up to 50 DEG C-80 DEG C under stirring, start insulation；Start after being incubated 30 minutes to drip
Add remaining pre-emulsion, react 5h-25h, use in sodium hydroxide, potassium hydroxide, ammonia, triethylamine
A kind of regulation pH to 7～8, be cooled to room temperature discharging, prepare anionic fluorine-containing latex.
Described emulsifying agent is maleic anhydride with allyl polyether (relative molecular mass=2000) with mol ratio 1:1
After esterification, then with fluorine-containing alcohol (2,2,3,4,4,4-hexafluoros-n-butyl alcohol, 2,2,3,3,4,4,5,5-octafluoro-1-amylalcohols,
One in 1H, 1H, 2H, 2H-nine fluoro-1-hexanol, the fluoro-1-heptanol of 1H, 1H, 7H-12) with mol ratio 1:1
Esterification, the reactive fluorine-containing emulsifier obtained.
Described initiator is the one in Ammonium persulfate., potassium peroxydisulfate.
Embodiment 1
A kind of anionic fluorine-containing latex, its raw material components and consumption are as follows:
Fluorinated acrylate, butyl acrylate, styrene, acrylic acid, emulsifying agent (-RfFor :-C4H3F6O)、
Ammonium persulfate. and water；Wherein: fluorinated acrylate, butyl acrylate, styrene, acrylic acid mol ratio
It is 0.7: 1.0: 1.0: 0.02；Emulsifying agent (-RfFor :-C4H3F6O) the 1.0% of polymerization monomer gross mass is accounted for；
Ammonium persulfate. accounts for the 0.2% of polymerization monomer gross mass；Water accounts for the 220% of polymerization monomer gross mass.
The preparation technology of this anionic fluorine-containing latex:
By above-mentioned all kinds raw material (wherein: water adds 70%, remaining 30% standby), add in container high
Speed is sheared 30 minutes, obtains pre-emulsion.Dry three mouthfuls of burnings at belt stirrer, condenser and Dropping funnel
Add in Ping and be warming up to 52 DEG C under remaining 30% water and the pre-emulsion of 5%, stirring, start insulation；Insulation
Start to drip remaining pre-emulsion after 30 minutes, react 13h, use sodium hydroxide regulation pH to 7～8,
It is cooled to room temperature discharging, prepares anionic fluorine-containing latex.
Embodiment 2
A kind of anionic fluorine-containing latex, its raw material components and consumption are as follows:
Fluorinated acrylate, butyl acrylate, styrene, 2-acrylamide-2-methyl propane sulfonic, emulsifying agent
(-RfFor :-C4H3F6O), Ammonium persulfate. and water；Wherein: fluorinated acrylate, butyl acrylate, benzene
Ethylene, the mol ratio of 2-acrylamide-2-methyl propane sulfonic are 0.5: 1.0: 1.0: 0.4；Emulsifying agent (-Rf
For :-C4H3F6O) the 2.2% of polymerization monomer gross mass is accounted for；Ammonium persulfate. accounts for the 1.1% of polymerization monomer gross mass；
Water accounts for the 230% of polymerization monomer gross mass.
The preparation technology of this anionic fluorine-containing latex:
By above-mentioned all kinds raw material (wherein: water adds 70%, remaining 30% standby), add in container high
Speed is sheared 30 minutes, obtains pre-emulsion.Dry three mouthfuls of burnings at belt stirrer, condenser and Dropping funnel
Add in Ping and be warming up to 60 DEG C under remaining 30% water and the pre-emulsion of 5%, stirring, start insulation；Insulation
Start to drip remaining pre-emulsion after 30 minutes, react 19h, use potassium hydroxide regulation pH to 7～8,
It is cooled to room temperature discharging, prepares anionic fluorine-containing latex.
Embodiment 3
A kind of anionic fluorine-containing latex, its raw material components and consumption are as follows:
Fluorinated acrylate, butyl acrylate, styrene, 2-acrylamide-2-methyl propane sulfonic, emulsifying agent
(-RfFor :-C5H3F8O), potassium peroxydisulfate and water；Wherein: fluorinated acrylate, butyl acrylate, benzene
Ethylene, the mol ratio of 2-acrylamide-2-methyl propane sulfonic are 1.0: 1.0: 1.0: 0.13；Emulsifying agent (-Rf
For :-C5H3F8O) the 2.6% of polymerization monomer gross mass is accounted for；Ammonium persulfate. accounts for the 0.4% of polymerization monomer gross mass；
Water accounts for the 245% of polymerization monomer gross mass.
The preparation technology of this anionic fluorine-containing latex:
By above-mentioned all kinds raw material (wherein: water adds 70%, remaining 30% standby), add in container high
Speed is sheared 30 minutes, obtains pre-emulsion.Dry three mouthfuls of burnings at belt stirrer, condenser and Dropping funnel
Add in Ping and be warming up to 68 DEG C under remaining 30% water and the pre-emulsion of 5%, stirring, start insulation；Insulation
Start to drip remaining pre-emulsion after 30 minutes, react 11h, use ammonia regulation pH to 7～8, be cooled to
Room temperature discharging, prepares anionic fluorine-containing latex.
Embodiment 4
A kind of anionic fluorine-containing latex, its raw material components and consumption are as follows:
Fluorinated acrylate, butyl acrylate, styrene, 2-acrylamide-2-methyl propane sulfonic, emulsifying agent
(-RfFor :-C6H4F9O), potassium peroxydisulfate and water；Wherein: fluorinated acrylate, butyl acrylate, benzene
Ethylene, the mol ratio of 2-acrylamide-2-methyl propane sulfonic are 0.8: 1.0: 1.0: 0.22；Emulsifying agent (-Rf
For :-C6H4F9O) the 1.7% of polymerization monomer gross mass is accounted for；Ammonium persulfate. accounts for the 1.4% of polymerization monomer gross mass；
Water accounts for the 200% of polymerization monomer gross mass.
The preparation technology of this anionic fluorine-containing latex:
By above-mentioned all kinds raw material (wherein: water adds 70%, remaining 30% standby), add in container high
Speed is sheared 30 minutes, obtains pre-emulsion.Dry three mouthfuls of burnings at belt stirrer, condenser and Dropping funnel
Add in Ping and be warming up to 72 DEG C under remaining 30% water and the pre-emulsion of 5%, stirring, start insulation；Insulation
Start to drip remaining pre-emulsion after 30 minutes, react 7h, use triethylamine regulation pH to 7～8, cooling
To room temperature discharging, prepare anionic fluorine-containing latex.
Embodiment 5
A kind of anionic fluorine-containing latex, its raw material components and consumption are as follows:
Fluorinated acrylate, butyl acrylate, styrene, acrylic acid, emulsifying agent (-RfFor :-C7H3F12O)、
Ammonium persulfate. and water；Wherein: fluorinated acrylate, butyl acrylate, styrene, acrylic acid mol ratio
It is 0.3: 1.0: 1.0: 0.35；Emulsifying agent (-RfFor :-C7H3F12O) the 0.7% of polymerization monomer gross mass is accounted for；
Ammonium persulfate. accounts for the 0.9% of polymerization monomer gross mass；Water accounts for the 300% of polymerization monomer gross mass.
The preparation technology of this anionic fluorine-containing latex:
By above-mentioned all kinds raw material (wherein: water adds 70%, remaining 30% standby), add in container high
Speed is sheared 30 minutes, obtains pre-emulsion.Dry three mouthfuls of burnings at belt stirrer, condenser and Dropping funnel
Add in Ping and be warming up to 78 DEG C under remaining 30% water and the pre-emulsion of 5%, stirring, start insulation；Insulation
Start to drip remaining pre-emulsion after 30 minutes, react 6h, use sodium hydroxide regulation pH to 7～8, cold
But to room temperature discharging, anionic fluorine-containing latex is prepared.
In sum, use Organic fluoride alcohol and maleic anhydride to react with allyl polyether esterification products, prepare
Reactive fluorine-containing emulsifier, by regulating the length of fluorine-containing alcohol segment, changes the surface of fluorocarbon surfactant
Behavior.By be polymerized monomer, initiator and water react prepare excellent in stability anionic fluorine-containing latex.
Emulsifying agent in this emulsion directly be polymerized monomer reaction, it is to avoid " migration " problem of conventional emulsifier；
Meanwhile, using water as disperse medium, without organic solvent, economize on resources, meet environmental requirement.
Claims (7)
1. a fluorine-containing emulsifier, it is characterised in that this fluorine-containing emulsifier is by maleic anhydride and pi-allyl
After polyethers 1:1 esterification in molar ratio, then carry out preparing after esterification with fluorine-containing alcohol 1:1 in molar ratio,
Structure is as follows:
Wherein, RfFor C4H3F6、C5H3F8、C6H4F9Or C7H3F12, n is the integer more than 2.
Fluorine-containing emulsifier the most according to claim 1, it is characterised in that described allyl polyether
Relative molecular weight is 2000.
Fluorine-containing emulsifier the most according to claim 1, it is characterised in that described fluorine-containing alcohol is
2,2,3,4,4,4-hexafluoro-n-butyl alcohol, 2,2,3,3,4,4,5,5-octafluoro-1-amylalcohol, 1H, 1H, 2H, 2H-nine fluoro-1-hexanol
Or the fluoro-1-heptanol of 1H, 1H, 7H-12.
4. use in claims 1 to 3 the fluorine-containing emulsifier described in any one to prepare the fluorine-containing breast of anionic
The method of liquid, it is characterised in that comprise the following steps:
1) polymerizable raw material monomer, fluorine-containing emulsifier, initiator and water are taken；Polymerization monomer includes: fluorine-containing third
Olefin(e) acid ester, butyl acrylate, styrene and acrylic acid or 2-acrylamide-2-methyl propane sulfonic；
Wherein, acrylic acid or 2-acrylamide-2-methyl propane sulfonic and fluorinated acrylate, butyl acrylate and
Cinnamic mol ratio is (0.02～0.4): (0.2～1.0): 1.0:1.0；
Fluorine-containing emulsifier accounts for the 0.5%～5% of polymerization monomer gross mass；Initiator accounts for polymerization monomer gross mass
0.1%～2%；Water accounts for the 200%～300% of polymerization monomer gross mass；
2) after polymerizable raw material monomer, fluorine-containing emulsifier, initiator and part water being mixed, at high speed shear
Reason 30min, obtains pre-emulsion；Part water accounts for the 70% of water gross mass；
3) take and be warming up under the pre-emulsion of pre-emulsion gross mass 5% and the water of remainder, stirring
After 50～80 DEG C, it is incubated 30min, then drips remaining pre-emulsion, react 5～25h, regulate reactant
Be pH value be 7～8, be cooled to room temperature, prepare anionic fluorine-containing latex.
The preparation method of anionic fluorine-containing latex the most according to claim 4, it is characterised in that
Described initiator is Ammonium persulfate. or potassium peroxydisulfate.
The preparation method of anionic fluorine-containing latex the most according to claim 4, it is characterised in that
Use sodium hydroxide, potassium hydroxide, ammonia or triethylamine regulation pH value of reaction system.
7. use in claim 4～6 the anionic fluorine-containing latex that the method described in any one prepares.
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| EP0825167A1 (en) * | 1996-01-30 | 1998-02-25 | Asahi Denka Kogyo Kabushiki Kaisha | Compounds and surfactants |
| US20030094223A1 (en) * | 1998-10-16 | 2003-05-22 | Clariant Gmbh | Explosives comprising modified copolymers of polyisobutylene and maleic anhydride as emulsifiers |
| CN1823094A (en) * | 2003-07-16 | 2006-08-23 | 大金工业株式会社 | Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent |
| CN103183795A (en) * | 2011-12-28 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Low air content polycarboxylic acid water reducer and preparation method thereof |
| CN103339216A (en) * | 2011-02-18 | 2013-10-02 | Agc清美化学股份有限公司 | Surfactant, composition including surfactant, use thereof, and fluorine-containing compound |
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| JP4226179B2 (en) * | 1999-12-24 | 2009-02-18 | 第一工業製薬株式会社 | Novel decomposable reactive emulsifier and polymer modification method using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0825167A1 (en) * | 1996-01-30 | 1998-02-25 | Asahi Denka Kogyo Kabushiki Kaisha | Compounds and surfactants |
| US20030094223A1 (en) * | 1998-10-16 | 2003-05-22 | Clariant Gmbh | Explosives comprising modified copolymers of polyisobutylene and maleic anhydride as emulsifiers |
| CN1823094A (en) * | 2003-07-16 | 2006-08-23 | 大金工业株式会社 | Method for producing fluorine-containing polymer, aqueous dispersion of fluorine-containing polymer, 2-acyloxycarboxylic acid derivative, and surface active agent |
| CN103339216A (en) * | 2011-02-18 | 2013-10-02 | Agc清美化学股份有限公司 | Surfactant, composition including surfactant, use thereof, and fluorine-containing compound |
| CN103183795A (en) * | 2011-12-28 | 2013-07-03 | 辽宁奥克化学股份有限公司 | Low air content polycarboxylic acid water reducer and preparation method thereof |
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