CN102174143A - Method for preparing fluorine-containing acrylate emulsion - Google Patents
Method for preparing fluorine-containing acrylate emulsion Download PDFInfo
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- CN102174143A CN102174143A CN 201110031522 CN201110031522A CN102174143A CN 102174143 A CN102174143 A CN 102174143A CN 201110031522 CN201110031522 CN 201110031522 CN 201110031522 A CN201110031522 A CN 201110031522A CN 102174143 A CN102174143 A CN 102174143A
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- acrylate
- acrylate emulsion
- fluorine
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Links
- 239000000839 emulsion Substances 0.000 title claims abstract description 180
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 16
- 229910052731 fluorine Inorganic materials 0.000 title abstract description 13
- 239000011737 fluorine Substances 0.000 title abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title abstract description 12
- 238000000034 method Methods 0.000 title abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 26
- -1 perfluoroalkyl ethyl acrylate Chemical compound 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 33
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 31
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 31
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 31
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 29
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 28
- 238000004945 emulsification Methods 0.000 claims description 23
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 22
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 22
- 238000009413 insulation Methods 0.000 claims description 19
- 238000009833 condensation Methods 0.000 claims description 18
- 230000005494 condensation Effects 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 16
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 15
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 15
- FSAJWMJJORKPKS-UHFFFAOYSA-N octadecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C=C FSAJWMJJORKPKS-UHFFFAOYSA-N 0.000 claims description 14
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 14
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 14
- 239000004160 Ammonium persulphate Substances 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 12
- 239000012874 anionic emulsifier Substances 0.000 claims description 12
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000007599 discharging Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 10
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 9
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 9
- 239000004159 Potassium persulphate Substances 0.000 claims description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 8
- 235000019394 potassium persulphate Nutrition 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 235000017550 sodium carbonate Nutrition 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 150000001282 organosilanes Chemical class 0.000 claims description 4
- UVAUHTUDFIJIDS-UHFFFAOYSA-N FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F Chemical compound FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F UVAUHTUDFIJIDS-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 2
- DIYRAAYFPDBELH-UHFFFAOYSA-N nonylbenzene;sodium Chemical compound [Na].CCCCCCCCCC1=CC=CC=C1 DIYRAAYFPDBELH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000306 component Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 19
- 239000003973 paint Substances 0.000 abstract description 13
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000032683 aging Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000004448 titration Methods 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000005336 cracking Methods 0.000 abstract 1
- 238000001514 detection method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 abstract 1
- 230000002940 repellent Effects 0.000 abstract 1
- 239000005871 repellent Substances 0.000 abstract 1
- 238000005201 scrubbing Methods 0.000 abstract 1
- 238000005187 foaming Methods 0.000 description 19
- 150000002148 esters Chemical class 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 230000003712 anti-aging effect Effects 0.000 description 9
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- FIGWTAOKQWILSW-UHFFFAOYSA-N CCCCCCCCCC(CC)=CC Chemical group CCCCCCCCCC(CC)=CC FIGWTAOKQWILSW-UHFFFAOYSA-N 0.000 description 5
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 239000002585 base Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- WUMYXTGZECPPNN-UHFFFAOYSA-M [Na+].C1(=CC=CC=C1)S(=O)(=O)[O-].C(CCCCCCCC)C1=C(C=CC=C1)O Chemical compound [Na+].C1(=CC=CC=C1)S(=O)(=O)[O-].C(CCCCCCCC)C1=C(C=CC=C1)O WUMYXTGZECPPNN-UHFFFAOYSA-M 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- YACCECLVHQLZQK-UHFFFAOYSA-N methoxyperoxyethane Chemical compound CCOOOC YACCECLVHQLZQK-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 description 1
- 101500021084 Locusta migratoria 5 kDa peptide Proteins 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing fluorine-containing acrylate emulsion. The fluorine-containing acrylate emulsion is prepared from perfluoroalkyl ethyl acrylate and acrylic monomers which are used as main materials, persulfate which is used as the initiator, and a compound emulsifier by adopting the semi-continuous titration polymerization process. The titration mode is adopted in the whole reaction process, the heat is preserved after finishing titrating, the reaction process is convenient to control, and the finally prepared fluorine-containing acrylate emulsion has excellent performance and high performance-price ratio, is environmental friendly and safe and can be cured at normal temperature to form a film. The detection on the emulsion paint prepared from the fluorine-containing acrylate emulsion shows that the emulsion paint can resist scrubbing of 10,000 times without changing, can resist both acid and base for 120 hours without blistering and powder falling in addition to slight loss of gloss and color and can resist ageing for 5,000 hours without blistering, stripping and cracking. The content of solid (the mass percent of non-volatile matters) in the fluorine-containing acrylate emulsion is more than 45%, and the water repellent angle of the coating of the fluorine-containing acrylate emulsion is more than 100 degrees.
Description
Technical field
The present invention relates to a kind of preparation method of emulsion, particularly a kind of preparation method of fluorinated acrylate emulsion.
Background technology
Pure-acrylic emulsion, organosilicon crylic acid latex occupy critical role in the emulsion production field, existing pure-acrylic emulsion, organosilicon crylic acid latex are in resistance to chemical attack, and aspects such as automatically cleaning also can't meet the demands.And fluorinated acrylate emulsion is because the bond energy of its C-F key is big, more stable, and the F atom combines firmly with the C atom, and it is very tight in the outer arrangement of carbochain skeleton, prevent the exposure of C atom and C chain effectively, more can embody remarkable water repellency, resistance to acids and bases, self-cleaning and weathering resistance.Aqueous fluorine-containing coating with the fluorine-containing emulsion preparation has low surface energy, the weathering resistance of excellence and the feature of contamination resistance.Ptfe emulsion PTFE and polyvinylidene difluoride (PVDF) emulsion PVDF be because of its second-order transition temperature height in the market, can not film forming under the normal temperature, need high temperature sintering, and therefore use and be restricted in paint field.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of fluorinated acrylate emulsion.This method reaction process is easy to control, does not need high temperature sintering, and normal temperature is the energy film-forming down, and the final fluorinated acrylate emulsion that obtains had both had the characteristic of fluorine, had kept the excellent properties of ACRYLIC EMULSION again.
Technical solution of the present invention is:
A kind of preparation method of fluorinated acrylate emulsion is as follows according to parts by weight meter step:
1. prepare pre-emulsification emulsion
(1) with distilled water 54-60 part, anionic emulsifier 1.0-1.7 part, nonionic emulsifying agent 2.0-4.0 part is mixed, Acrylic Acid Monomer 65.8-73.5 part that slow adding has stirred, emulsification 5-20min makes pre-emulsion I;
(2) in parts by weight, with distilled water 45-64 part, anionic emulsifier 1.0-1.7 part, nonionic emulsifying agent 2.0-3.0 part is mixed, Acrylic Acid Monomer 49-63 part that slow adding has stirred, perfluor alkyl ethide acrylate 5-31 part, emulsification 5-30min makes the pre-emulsion II;
2. preparation seed emulsion
With distilled water 48-60 part, anionic emulsifier 0.4-0.8 part, nonionic emulsifying agent 0.8-1.5 part, sodium bicarbonate or yellow soda ash 0.3-1.5 part, the 17%-25% of pre-emulsion I total amount mixes, and 200-280r/min stirs down, logical nitrogen, open water of condensation, be warming up to 65-75 ℃, add initiator 0.15-0.75 part, described initiator is a persulphate, reaction 3-10min obtains seed emulsion;
3. dropping mode adds monomer
When blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, in 1.0-3.0h, drip off, drip the mixing solutions of 0.3-0.9 part initiator and 18 parts of distilled water, described initiator is a persulphate, dropwises at 1.1-3.1h, and temperature is controlled at 72 ℃～90 ℃;
4. dropwising back insulation 1-2h, emulsion is cooled to 30-40 ℃, filters discharging, transfer PH to 7-8, make fluorinated acrylate emulsion with 3-8 part alkali neutralizing agent.
The structural formula of above-mentioned perfluor alkyl ethide acrylate is (CH2=CHCOOCH2CH2(CF2) nF), wherein n is 6-18 even number.
Above-mentioned emulsifying agent is made up of anionic emulsifier and nonionic emulsifying agent, wherein the weight ratio of anionic emulsifier and nonionic emulsifying agent is 1.6:1-2.5:1, described nonionic emulsifying agent is a fatty alcohol-polyoxyethylene ether, TX-10 polyoxyethylene octylphenol ether or NP-10 polyoxyethylene nonylphenol ether, anionic emulsifier is the mixture of sodium lauryl sulphate (SDS) or sodium lauryl sulphate and component A, according to sodium lauryl sulphate 68-72% in the weight ratio mixture, component A 28-32%, described component A are perfluoro butyl potassium sulfonate or perfluor nonyl benzene sodium sulfonate.
Above-mentioned persulphate is ammonium persulphate or Potassium Persulphate.
Above-mentioned acrylic monomer is in methacrylic acid, vinylformic acid, methyl methacrylate, butyl acrylate, octadecyl acrylate, Propylene glycol monoacrylate, the N hydroxymethyl acrylamide at least two kinds.
Above-mentioned after Acrylic Acid Monomer 65.8-73.5 part that slowly adding has stirred, add perfluor alkyl ethide acrylate 10-15 part and carry out pre-emulsification.
Above-mentioned alkali neutralizing agent is sodium bicarbonate aqueous solution, aqueous sodium carbonate, ammoniacal liquor or the 2-amino-2-methyl-1-propanol aqueous solution.
Above-mentioned acrylic monomer is three kinds or four kinds in methacrylic acid, vinylformic acid, methyl methacrylate, butyl acrylate, octadecyl acrylate, Propylene glycol monoacrylate, the N hydroxymethyl acrylamide.
The above-mentioned organosilane monomer that in pre-emulsion, also adds the 0.1-10 of parts by weight.
Above-mentioned organosilane monomer is vinyltrimethoxy silane, vinyltriethoxysilane or γ-(methacryloxypropyl) propyl group methyl dimethoxysilane.
The present invention adopts perfluor alkyl ethide acrylate and acrylic monomer to carry out copolymerization mode to prepare fluorinated acrylate emulsion.The fluorinated acrylate emulsion that obtains had both had the characteristic of fluorine, had kept the excellent properties of ACRYLIC EMULSION again; Use the perfluor alkyl ethide acrylate monomer to carry out polymerization, can be connected on fluorochemical monomer on the polymkeric substance like this; Demonstrate fully chemical resistant properties and the uvioresistant and the antioxidant property of the excellence of C-F key; Owing to add N hydroxymethyl acrylamide fluorine monomer is alternately arranged in multipolymer, make the polymer formation reticulated structure, make molecular weight distribution comparatively even, improved the weathering resistance of polymkeric substance: entire reaction course adopts the dropping mode, dropwise the back insulation, the convenient control of reaction process, the final fluorinated acrylate emulsion excellent performance that obtains, adopt cloudy, non-ionic composite emulsifying agent, make the fluorine-containing emulsion that makes more stable; With water is medium, and environmental protection, safety, cost performance height, normal temperature down can film-formings.Emulsion is mixed with emulsion paint detects, No. 10000 no changes of washability, acidproof 120h is non-foaming, dry linting not, allows slight loss of gloss and variable color; Alkaline-resisting 120h is non-foaming, and dry linting does not allow slight loss of gloss and variable color, and anti-aging test 5000h is non-foaming, do not peel off, flawless, and solids content (mass fraction of non-volatile matter) is greater than 45%, films to refuse the water angle and can reach more than 100 °.
Embodiment
Embodiment 1
1. prepare pre-emulsion I: distilled water 54g, sodium lauryl sulphate 1.4g, TX-10 polyoxyethylene octylphenol ether 4.0g are mixed, methyl methacrylate 36.4g, butyl acrylate 28.6g, methacrylic acid 0.9g that slow adding has stirred, with mulser emulsification 20min, get pre-emulsion I 125.3g.
Preparation pre-emulsion II: distilled water 54g, sodium lauryl sulphate 1.4g, TX-10 polyoxyethylene octylphenol ether 3.0g are mixed, methyl methacrylate 31.7g, butyl acrylate 18.5g, methacrylic acid 0.6g that slow adding has stirred, N hydroxymethyl acrylamide 0.15 g, basic ethyl propylene acid esters 15 g of perfluor get pre-emulsion II 124.35g with mulser emulsification 15min.
2. preparation seed emulsion: get distilled water 48.7g, sodium lauryl sulphate 0.6g, TX-10 polyoxyethylene octylphenol ether 1.5g, yellow soda ash 1.5g, pre-emulsion I 25.8g are in four-hole boiling flask, open and stir 260r/min, logical nitrogen, open water of condensation, be warming up to 75 ℃, add ammonium persulphate 0.45g, reaction 8min gets seed emulsion 78.55g.
3. drip: when blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 1.0h, the other end drips the mixed solution of 0.5g ammonium persulphate and 18g distilled water, speed control 1.1h dropwises, and controlled temperature is at 85 ℃～90 ℃.
4. insulation: after dropwising, insulation 2h, emulsion is cooled to 30 ℃, closes nitrogen, water of condensation, filter discharging, add 5% sodium bicarbonate 3g, transfer PH to 7.9, get fluorinated acrylate emulsion 305.0g, the mass fraction that records non-volatile matter is 50%, and filming and refusing the water angle is 110 °.
This emulsion is mixed with emulsion paint detects, No. 11000 no changes of washability; Non-foaming, not dry linting and the variable color of acidproof 120h; Alkaline-resisting 120h is non-foaming, not dry linting and variable color; Anti-aging test 5000h no change.
Embodiment 2
1. prepare pre-emulsion I: distilled water 60g, sodium lauryl sulphate 1.2g, NP-10 polyoxyethylene nonylphenol ether 2.4g are mixed, methyl methacrylate 38.4g, butyl acrylate 28.6g, vinylformic acid 0.9g that slow adding has stirred, octadecyl acrylate 4g, with mulser emulsification 5min, get pre-emulsion I 135.5g.
Preparation pre-emulsion II: distilled water 54g, sodium lauryl sulphate 1.2g, perfluor nonyl phenol benzene sulfonic acid sodium salt 0.5g, NP-10 fatty alcohol-polyoxyethylene ether 2.2g are mixed, methyl methacrylate 33.7g, butyl acrylate 22.5g, vinylformic acid 0.7g that slow adding has stirred, octadecyl acrylate 2g, the basic ethyl propylene acid esters 31 of perfluor, with mulser emulsification 25min, get pre-emulsion II 148.25g.
2. preparation seed emulsion: get distilled water 60.0g, sodium lauryl sulphate 0.6g, NP-10 polyoxyethylene nonylphenol ether 1.2g, sodium bicarbonate 0.8g, pre-emulsion I 26.75g are in four-hole boiling flask, open and stir 200r/min, logical nitrogen, open water of condensation, when being warming up to 72 ℃, add Potassium Persulphate 0.75g, reaction 10min gets seed emulsion 90.1g.
3. drip: when blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 1.5h, the other end drips the mixed solution of 0.85g Potassium Persulphate and 18g distilled water, speed control 1.6h dropwises, and controlled temperature is at 75 ℃～85 ℃.
4. insulation: after dropwising, insulation 1.5h, emulsion is cooled to 35 ℃, closes nitrogen, water of condensation, filter discharging, add 26% ammoniacal liquor 5g, transfer PH to 8.0, get fluorinated acrylate emulsion 335.0g, the mass fraction that records non-volatile matter is 47.2%, and filming and refusing the water angle is 118 °.
This emulsion is mixed with emulsion paint detects, No. 10100 no changes of washability; Non-foaming, not dry linting and the variable color of acidproof 120h; Alkaline-resisting 120h is non-foaming, not dry linting and variable color; Anti-aging test 5500h no change.
Embodiment 3
1. prepare pre-emulsion I: distilled water 60g, sodium lauryl sulphate 1.2g, NP-10 polyoxyethylene nonylphenol ether 2.4g are mixed, methyl methacrylate 38.4g, butyl acrylate 28.6g, vinylformic acid 0.9g that slow adding has stirred, perfluor nonyl ethyl propylene acid esters 15g, with mulser emulsification 10min, get pre-emulsion 146.5g.
Preparation pre-emulsion II: distilled water 64g, sodium lauryl sulphate 1.2g, perfluoro butyl potassium sulfonate 0.5g, NP-10 polyoxyethylene nonylphenol ether 2.4g are mixed, methyl methacrylate 33.7g, butyl acrylate 22.5g, vinylformic acid 0.7g that slow adding has stirred, octadecyl acrylate 6g, the basic ethyl propylene acid esters of perfluor 16g, perfluor nonyl ethyl propylene acid esters 15g, with mulser emulsification 5min, get pre-emulsion 147.25g.
2. preparation seed emulsion: get distilled water 60.0g, sodium lauryl sulphate 0.6g, NP-10 polyoxyethylene nonylphenol ether 1.2g, sodium bicarbonate 0.8g, pre-emulsion I 26.75g are in four-hole boiling flask, open and stir 280r/min, logical nitrogen, open water of condensation, be warming up to 72 ℃, add Potassium Persulphate 0.75g, reaction 5min gets seed emulsion 90.1g.
3. drip: when blue light appears in emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 1.5h, the other end drips the mixed solution of 0.85g Potassium Persulphate and 18g distilled water, and 1.6h dropwises, and temperature is controlled at 75 ℃～85 ℃.
4. insulation: after dropwising, insulation 1.5h, emulsion is cooled to 40 ℃, closes nitrogen, water of condensation, filter discharging, add 5% sodium bicarbonate 8g, transfer PH to 8.0, get fluorinated acrylate emulsion 343.0g, the mass fraction that records non-volatile matter is 45.6%, and filming and refusing the water angle is 105 °.
This emulsion is mixed with emulsion paint detects, No. 10000 no changes of washability, non-foaming, not dry linting, the nondiscoloration of acidproof 120h; Alkaline-resisting 120h is non-foaming, not dry linting, nondiscoloration; Anti-aging test 5000h no change.
Embodiment 4
1. prepare pre-emulsion I: distilled water 58g, sodium lauryl sulphate 1.5g, fatty alcohol-polyoxyethylene ether 2.6g are mixed, methyl methacrylate 39g, butyl acrylate 26g, methacrylic acid 0.7g that slow adding has stirred, octadecyl acrylate 4.3g, perfluor nonyl ethyl propylene acid esters 10g, with mulser emulsification 10min, get pre-emulsion I 142.1g.
Preparation pre-emulsion II: distilled water 50g, sodium lauryl sulphate 1.6g, fatty alcohol-polyoxyethylene ether 2.2g are mixed, methyl methacrylate 32g, butyl acrylate 16g, methacrylic acid 0.6g that slow adding has stirred, Propylene glycol monoacrylate 1.2g, perfluoro capryl ethyl propylene acid esters 5g, with mulser emulsification 30min, get pre-emulsion II 108.6g.
2. preparation seed emulsion: get distilled water 55g, sodium lauryl sulphate 0.7g, fatty alcohol-polyoxyethylene ether 1.0g, sodium bicarbonate 1.0g, pre-emulsion I 33g are in four-hole boiling flask, open and stir 240r/min, logical nitrogen, open water of condensation, when being warming up to 75 ℃, add ammonium persulphate 0.65g, reaction 3min gets seed emulsion 91.35g.
3. drip: when blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 3h, the other end drips 0.36 g ammonium persulphate and 18g distilled water mixing solutions, speed control 3.1h dropwises, and controlled temperature is at 75 ℃～85 ℃.
4. insulation: after dropwising, insulation 1h, emulsion is cooled to 38 ℃, close nitrogen, water of condensation, filter discharging, the aqueous solution 3g of 2-amino-2-methyl-1-propanol 95%, transfer PH to 7.6, get fluorinated acrylate emulsion 306g, the mass fraction that records non-volatile matter is 45.6%, and filming and refusing the water angle is 108 °.
This emulsion is mixed with emulsion paint detects, No. 10000 no changes of washability; Non-foaming, not dry linting and the variable color of acidproof 160h; Alkaline-resisting 160h is non-foaming, not dry linting and variable color; Anti-aging test 5000h no change.
Embodiment 5
1. prepare pre-emulsion I: distilled water 58g, sodium lauryl sulphate 1.7g, fatty alcohol-polyoxyethylene ether 2.6g are mixed, methyl methacrylate 38.9g, butyl acrylate 26g, methacrylic acid 0.7g that slow adding has stirred, octadecyl acrylate 4.3g, vinyltrimethoxy silane 0.1g, with mulser emulsification 10min, get pre-emulsion I 132.1g.
Preparation pre-emulsion II: distilled water 50g, sodium lauryl sulphate 1.6g, fatty alcohol-polyoxyethylene ether 2.2g are mixed, methyl methacrylate 32g, butyl acrylate 16g, methacrylic acid 0.6g that slow adding has stirred, Propylene glycol monoacrylate 1.2g, perfluoro capryl ethyl propylene acid esters 5g, with mulser emulsification 10min, get pre-emulsion II 108.6g.
2. seed emulsion: get distilled water 55g, sodium lauryl sulphate 0.7g, fatty alcohol-polyoxyethylene ether 1.0g, sodium bicarbonate 1.0g, pre-emulsion I 33g are in four-hole boiling flask, open and stir 240r/min, logical nitrogen, when opening water of condensation and being warming up to 75 ℃, add ammonium persulphate 0.65g, reaction 7min gets seed emulsion 91.35g.
3. drip: when blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 3h, the other end drips 0.36g ammonium persulphate and 18g distilled water mixing solutions, speed control 3.1h dropwises, and controlled temperature is at 75 ℃～85 ℃.
4. insulation: after dropwising, insulation 1h, emulsion is cooled to 40 ℃, closes nitrogen, water of condensation, filter discharging, add 5% sodium bicarbonate, 8 g, transfer PH to 7.6, get fluorinated acrylate emulsion 298.0g, the mass fraction that records non-volatile matter is 46.6%, and filming and refusing the water angle is 108 °.
This emulsion is mixed with emulsion paint detects, No. 10000 no changes of washability; Non-foaming, not dry linting and the variable color of acidproof 126h; Alkaline-resisting 126h is non-foaming, not dry linting and variable color; Anti-aging test 5000h no change.
Embodiment 6
1. pre-emulsion I: distilled water 58g, sodium lauryl sulphate 1.5g, fatty alcohol-polyoxyethylene ether 2.6g are mixed, methyl methacrylate 39g, butyl acrylate 26g, methacrylic acid 0.7g that slow adding has stirred, octadecyl acrylate 4.3g, vinyltriethoxysilane 5g, usefulness mulser emulsification 10min get pre-emulsion I 134.6g.
Pre-emulsion II: distilled water 50g, sodium lauryl sulphate 1.6g, fatty alcohol-polyoxyethylene ether 2.2g are mixed, methyl methacrylate 32g, butyl acrylate 16g, methacrylic acid 0.6g that slow adding has stirred, Propylene glycol monoacrylate 1.2g, vinyltriethoxysilane 2.5g, perfluoro capryl ethyl propylene acid esters 5g, with mulser emulsification 30min, get pre-emulsion II 111.1g.
2. seed emulsion: get distilled water 55g, sodium lauryl sulphate 0.7g, fatty alcohol-polyoxyethylene ether 1.0g, sodium bicarbonate 1.0g, pre-emulsion I 33g are in four-hole boiling flask, open and stir 240r/min, logical nitrogen, open water of condensation, when being warming up to 75 ℃, add ammonium persulphate 0.65g, reaction 10min gets seed emulsion 91.35g.
3. drip: when blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 3h, the other end drips 0.36g ammonium persulphate and 18g distilled water mixing solutions, speed control 3.1h, and controlled temperature is at 75 ℃～85 ℃.
4. insulation: after dropwising, insulation 1h, emulsion is cooled to 40 ℃, closes nitrogen, water of condensation, filter discharging, add 5% aqueous sodium carbonate 6g, transfer PH to 7.6, get fluorinated acrylate emulsion 302.0g, the mass fraction that records non-volatile matter is 48.6%, and filming and refusing the water angle is 112 °.
This emulsion is mixed with emulsion paint detects, No. 12000 no changes of washability; Non-foaming, not dry linting and the variable color of acidproof 168h; Alkaline-resisting 168h is non-foaming, not dry linting and variable color; Anti-aging test 5600h no change.
Embodiment 7
1. prepare pre-emulsion I: distilled water 60g, sodium lauryl sulphate 1.2g, NP-10 polyoxyethylene nonylphenol ether 2.4g are mixed, methyl methacrylate 38.4g, butyl acrylate 28.6g, vinylformic acid 0.9g that slow adding has stirred, octadecyl acrylate 4g, γ-(methacryloxypropyl) propyl group methyl dimethoxy oxygen base silicon 5g, with mulser emulsification 5min, get pre-emulsion I 140.5g.
Preparation pre-emulsion II: with distilled water 54g, sodium lauryl sulphate 1.2g, NP-10 polyoxyethylene nonylphenol ether 2.4g, perfluor nonyl phenol benzene sulfonic acid sodium salt 0.5g mixes, methyl methacrylate 33.7g, butyl acrylate 22.5g, vinylformic acid 0.7g that slow adding has stirred, octadecyl acrylate 2g, γ-(methacryloxypropyl) propyl group methyl dimethoxy oxygen base silicon 5g, the basic ethyl propylene acid esters of perfluor 16g, perfluor nonyl ethyl propylene acid esters 15g, with mulser emulsification 30min, get pre-emulsion II 153.25g.
2. preparation seed emulsion: get distilled water 60.0g, sodium lauryl sulphate 0.6g, NP-10 polyoxyethylene nonylphenol ether 1.2g, sodium bicarbonate 0.8g, pre-emulsion I 28.1g are in four-hole boiling flask, open and stir 200r/min, logical nitrogen, open water of condensation, when being warming up to 72 ℃, add Potassium Persulphate 0.75g, reaction 6min gets seed emulsion 91.45g.
3. drip: when blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 1.5h, the other end drips the mixed solution of 0.85g Potassium Persulphate and 18g distilled water, speed control 1.6h dropwises, and temperature is controlled at 75 ℃～85 ℃.
4. insulation: after dropwising, insulation 1.5h, emulsion is cooled to 40 ℃, close nitrogen, water of condensation, filter discharging, the aqueous solution 3g of 2-amino-2-methyl-1-propanol 95%, transfer PH to 8.0, get fluorinated acrylate emulsion 349.0g, the mass fraction that records non-volatile matter is 49.8%, and filming and refusing the water angle is 121 °.
This emulsion is mixed with emulsion paint detects, washability 16000h no change; Non-foaming, not dry linting and the variable color of acidproof 192h; Alkaline-resisting 192h is non-foaming, not dry linting and variable color; Anti-aging test 6000h no change.
Acrylic monomer among the foregoing description 1-embodiment 7 is three kinds or four kinds in methacrylic acid, vinylformic acid, methyl methacrylate, butyl acrylate, octadecyl acrylate, Propylene glycol monoacrylate, the N hydroxymethyl acrylamide, at least two kinds of replacements in available methacrylic acid, vinylformic acid, methyl methacrylate, butyl acrylate, octadecyl acrylate, Propylene glycol monoacrylate, the N hydroxymethyl acrylamide; The carbon fluorine chain number of the perfluor basic ethyl propylene acid esters of above-mentioned example 1 to the example 7 is 6, the carbon fluorine chain number of perfluoro capryl ethyl propylene acid esters is 8, the carbon fluorine chain number of perfluor nonyl ethyl propylene acid esters is 10, can also be that 12,14,16 or 18 perfluor alkyl ethide acrylate is replaced with carbon fluorine chain, simultaneously can also be with the perfluor alkyl ethide methacrylic ester replacement of corresponding carbon fluorine chain number.
Contrast: example
1. prepare pre-emulsion I: distilled water 60g, sodium lauryl sulphate 1.0g, fatty alcohol-polyoxyethylene ether 2.0g are mixed, methyl methacrylate 40.4g, butyl acrylate 32.1g, methacrylic acid 0.9g that slow adding has stirred, with mulser emulsification 10min, get pre-emulsion I 136.4g.
Preparation pre-emulsion II: distilled water 45.7g, sodium lauryl sulphate 1.0g, fatty alcohol-polyoxyethylene ether 2.0g are mixed, methyl methacrylate 35.7g, butyl acrylate 22g, methacrylic acid 0.6g that slow adding has stirred, N hydroxymethyl acrylamide 0.04g, with mulser emulsification 30min, get pre-emulsion II 107.04g.
2. preparation seed emulsion: get distilled water 51.0g, sodium lauryl sulphate 0.4g, fatty alcohol-polyoxyethylene ether 0.8g, sodium bicarbonate 0.32g, pre-emulsion I 23.8g open and stir 240r/min in four-hole boiling flask, and logical nitrogen is opened water of condensation.When being warming up to 65 ℃, add ammonium persulphate 0.15g, reaction 3min gets seed emulsion 76.47g.
3. drip: when blue light appears in seed emulsion, begin to drip residue pre-emulsion I and pre-emulsion II, dropwise through 2h, the other end drips the mixed solution of 0.36 g ammonium persulphate and 18g distilled water, speed control 2.1h dropwises, and temperature is controlled at 72 ℃～82 ℃.
4. insulation: after dropwising, insulation 1h, emulsion is cooled to 40 ℃, closes nitrogen, water of condensation, filter discharging, add 5% sodium bicarbonate 8g, transfer PH to 7.6, get acrylic ester emulsion 298.0g, the mass fraction that records non-volatile matter is 46%, and filming and refusing the water angle is 65 °.
This emulsion is mixed with emulsion paint detects, washability 6000h no change; Non-foaming, not dry linting and the variable color of acidproof 96h; Alkaline-resisting 96h is non-foaming, not dry linting and variable color; Anti-aging test 2600h no change.
Record among the standard GB 20623-2006 " coating emulsion ", emulsion is mixed with the emulsion paint washability 200 times, water-fast 48h, acidproof, alkaline-resisting 48 hours, ageing-resistant 600 hours.Testing data is all above this standard after testing, and the filming of fluorinated acrylate emulsion preparation made from the foregoing description 1-embodiment 7 has excellent water repellency, resistance to acids and bases, self-cleaning and weathering resistance.
Claims (10)
1. the preparation method of a fluorinated acrylate emulsion is characterized in that according to parts by weight meter step as follows:
(1) the pre-emulsification emulsion of preparation
(1.1) with distilled water 54-60 part, anionic emulsifier 1.0-1.7 part, nonionic emulsifying agent 2.0-4.0 part is mixed, Acrylic Acid Monomer 65.8-73.5 part that slow adding has stirred, emulsification 5-20min makes pre-emulsion I;
(1.2) in parts by weight, with distilled water 45-64 part, anionic emulsifier 1.0-1.7 part, nonionic emulsifying agent 2.0-3.0 part is mixed, Acrylic Acid Monomer 49-63 part that slow adding has stirred, perfluor alkyl ethide acrylate 5-31 part, emulsification 5-30min makes the pre-emulsion II;
(2) preparation seed emulsion
With distilled water 48-60 part, anionic emulsifier 0.4-0.8 part, nonionic emulsifying agent 0.8-1.5 part, sodium bicarbonate or yellow soda ash 0.3-1.5 part, the 17%-25% of pre-emulsion I total amount mixes, and 200-280r/min stirs down, logical nitrogen, open water of condensation, be warming up to 65-75 ℃, add initiator 0.15-0.75 part, described initiator is a persulphate, reaction 3-10min makes seed emulsion;
(3) dropping mode adds monomer
When blue light appears in seed emulsion, begin to drip remaining pre-emulsion I and pre-emulsion II, in 1.0-3.0h, drip off, drip the mixing solutions of 0.3-0.9 part initiator and 18 distillation moisture content, described initiator is a persulphate, dropwise at 1.1-3.1h, temperature is controlled at 72 ℃～90 ℃;
(4) dropwising back insulation 1-2h, emulsion is cooled to 30-40 ℃, filters discharging, transfer PH to 7-8, obtain fluorinated acrylate emulsion with 3-8 part alkali neutralizing agent.
2. the preparation method of fluorinated acrylate emulsion according to claim 1, it is characterized in that: the structural formula of perfluor alkyl ethide acrylate is (CH2=CHCOOCH2CH2(CF2) nF), wherein n is 6-18 even number.
3. the preparation method of fluorinated acrylate emulsion according to claim 1, it is characterized in that: emulsifying agent is made up of anionic emulsifier and nonionic emulsifying agent, wherein the weight ratio of anionic emulsifier and nonionic emulsifying agent is 1.6:1-2.5:1, described nonionic emulsifying agent is a fatty alcohol-polyoxyethylene ether, polyoxyethylene octylphenol ether or polyoxyethylene nonylphenol ether, anionic emulsifier is the mixture of sodium lauryl sulphate or sodium lauryl sulphate and component A, according to sodium lauryl sulphate 68-72% in the weight percent meter mixture, component A 28-32%, described component A are perfluoro butyl potassium sulfonate or perfluor nonyl benzene sodium sulfonate.
4. the preparation method of fluorinated acrylate emulsion according to claim 1, it is characterized in that: described persulphate is ammonium persulphate or Potassium Persulphate.
5. the preparation method of fluorinated acrylate emulsion according to claim 1 is characterized in that: acrylic monomer is in methacrylic acid, vinylformic acid, methyl methacrylate, butyl acrylate, octadecyl acrylate, Propylene glycol monoacrylate, the N hydroxymethyl acrylamide at least two kinds.
6. the preparation method of fluorinated acrylate emulsion according to claim 1 is characterized in that: behind the Acrylic Acid Monomer that slowly adding has stirred, add 10-15 part perfluor alkyl ethide acrylate.
7. the preparation method of fluorinated acrylate emulsion according to claim 1, it is characterized in that: described alkali neutralizing agent is sodium bicarbonate aqueous solution, aqueous sodium carbonate, ammoniacal liquor or the 2-amino-2-methyl-1-propanol aqueous solution.
8. the preparation method of fluorinated acrylate emulsion according to claim 5 is characterized in that: described acrylic monomer is that acrylic monomer is in methacrylic acid, vinylformic acid, methyl methacrylate, butyl acrylate, octadecyl acrylate, Propylene glycol monoacrylate, the N hydroxymethyl acrylamide three kinds or four kinds.
9. the preparation method of fluorinated acrylate emulsion according to claim 1 is characterized in that: also add the organosilane monomer that parts by weight are 0.1-10 part in pre-emulsion.
10. the preparation method of fluorinated acrylate emulsion according to claim 9, it is characterized in that: described organosilane monomer is a vinyltrimethoxy silane, vinyltriethoxysilane or γ-(methacryloxypropyl) propyl group methyl dimethoxysilane.
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