CN104403471A - Polyacrylic acid emulsion hydrophobic coating material with low fluorine content and preparation method thereof - Google Patents
Polyacrylic acid emulsion hydrophobic coating material with low fluorine content and preparation method thereof Download PDFInfo
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- CN104403471A CN104403471A CN201410460554.XA CN201410460554A CN104403471A CN 104403471 A CN104403471 A CN 104403471A CN 201410460554 A CN201410460554 A CN 201410460554A CN 104403471 A CN104403471 A CN 104403471A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
Abstract
The invention provides a polyacrylic acid emulsion hydrophobic coating material with low fluorine content and a preparation method thereof. The coating comprises 30-50 wt.% of core-shell structure fluorinated polyacrylate resin, 0.6-3 wt.% of an emulsifier and 47-69.4% of water. The preparation method uses a core-shell polymerization method to prepare acrylate emulsion with surface containing fluorine, and uses the transfer characteristic of the fluoride-containing group to prepare the hydrophobic coating through the control of film forming conditions. Control on film forming conditions mainly includes film-forming temperature, heating rate and film-forming agent. By controlling the film forming conditions, in the premise of low fluorine content, control of surface migration of fluorine can reduce the surface energy and improve the hydrophobicity of the coating surface. The method can effectively reduce the usage amount of the fluorine-containing monomer, reduce synthesis cost, save energy and protect the environment, and has important application prospect.
Description
Technical field
The present invention relates to a kind of polyacrylate emulsion hydrophobic coating material and preparation method thereof, relate to a kind of low fluorine content polyacrylate emulsion hydrophobic coating material and preparation method thereof.
Background technology
In recent years, fluorocarbon coating becomes the focus that vast researcher is paid close attention to because of characteristics such as its good anticorrosion, antifouling, super weather-proof, chemical-resistant reagent, sticking power, water-absorbents, and is widely used in the high-technology fields such as aerospace, boats and ships, bridge, vehicle.Along with the enhancing of people's environmental consciousness, various countries are to VOC(volatile organic compounds) containing quantitative limitation increasingly stringent, the use of traditional solvent-borne type fluorocarbon coating is more and more restricted.Therefore, aqueous fluorocarbon coating has become the new direction of coating worker research, and wherein fluorinated acrylate emulsion combines the excellent properties of conventional acrylic emulsion and fluorine-containing latex, is subject to the favor of people.At present, researchist has invented the method for the fluoroacrylic resin coating having prepared better performances.CN1730502A take ethylenically unsaturated monomers as major ingredient, under the acting in conjunction of buffer reagent and emulsifying agent, seed emulsion is prepared by redox initiator, then semi-continuous polymerzation technique is adopted to prepare microemulsion of fluorin containing crylic acid of self-crosslink at normal temperatures, the film of this emulsion had both had good hydrophobicity, there is again suitable wetting ability, the self-cleaning function of film can be realized, belong to double environmental protection type macromolecular material.VDF/TEF/HFP copolymer emulsion and polyacrylate dispersion split are then prepared aqueous fluorocarbon coating by CN1566234A, and this coating, when solidification value 120 ~ 130 DEG C, has excellent resistance to soiling and weathering resistance.In addition the method preparing fluoroacrylic resin coating is all proposed in the patent such as CN1322775A, CN102617783A.
But there is the large problem of fluorochemical monomer consumption more in these methods.Aqueous fluorocarbon coating is divided into three kinds: fluorine-containing propene acids, FEVE and PVDF, and wherein PVDF fluorine content is the highest, general >50%, FEVE>15%, and fluorine-containing propene acids Oil repellent is minimum, but also more than 10%.In the general fluorocarbon coating used of current enterprise product, fluorine content is 17-35%.This not only makes synthesis cost increase, and unfavorable to protection of the environment, there is potential threat to physical environment.
Prepare fluorine-containing core-shell acrylic-resin emulsion in patent CN100451042C, owing to only having shell structure fluorine-containing, therefore reduce the consumption of fluorochemical monomer from source, but the Oil repellent in system has been still relatively high.In the application of reality, in order to meet different Environment space requirements, need the content reducing fluorine on this basis further.
Summary of the invention
An object of the present invention is to provide a kind of low fluorine content polyacrylate emulsion hydrophobic coating material.
Two of object of the present invention is the preparation method providing this coated material.
Fluoro-containing group due to its surface energy low, in solution or solid solution, have the characteristic to surface transport, as long as motor capacity is enough to overcome the resistance that molecular chain internal friction produces, then the system of low fluorine content still can reach the hydrophobic property similar to high fluorine content.The present invention adopts the method for hud polymerization to prepare a kind of acrylic ester emulsion of low fluorochemical monomer consumption, by changing filming condition, controlling the surface transport of fluorine element, thus realizing the hydrophobicity of coatingsurface.
In order to achieve the above object, the present invention adopts following technical scheme:
A kind of low fluorine content polyacrylate emulsion hydrophobic coating material, is characterized in that the composition of this coated material and mass percentage are:
The fluorine-containing polyacrylic resin 30 ~ 50% of nucleocapsid structure;
Emulsifying agent 0.6 ~ 3%;
Water 47 ~ 69.4%;
The fluorine-containing polyacrylic resin of described nucleocapsid structure after polymerization, forms stratum nucleare with acrylic ester monomer, it is coated with the shell formed by acrylate containing fluorine monomer and acrylic ester monomer copolymerization, the mass percentage of wherein said stratum nucleare is 50% ~ 80%, and all the other are shell; In the monomer of described formation shell, acrylate containing fluorine monomer accounts for 3 ~ 20% of shell total monomer mole number.
Above-mentioned acrylate containing fluorine monomer is: Hexafluorobutyl mathacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or perfluor alkyl ethide methacrylic ester.
Above-mentioned acrylic ester monomer is at least one in methyl methacrylate, methyl acrylate, butyl methacrylate, Tert-butyl Methacrylate, butyl acrylate, tert-butyl acrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate and Propylene glycol monoacrylate.
Above-mentioned emulsifying agent is: at least one in span 20, OP-10, sodium lauryl sulphate, ethoxylated alkyl sulfate and the O/W such as fatty alcohol and ethylene oxide condensate type emulsifying agent.
The preparation method of above-mentioned low fluorine content polyacrylate emulsion hydrophobic coating material, adopts emulsion polymerization, it is characterized in that the concrete steps of the method are:
A. the part in nuclear layer monomer is formed emulsion as seed monomer and emulsifying agent, initiator ammonium persulfate and water at 75 ± 2 DEG C of isothermal reaction 30 ± 5min, the wherein mass ratio (30 ~ 50) of seed monomer and water: 100, emulsifying agent is the 2-6% of seed monomer quality, and initiator is 0.05 ~ 0.2% of seed monomer quality;
B. in step a gained emulsion, drip remaining nuclear layer monomer, and be incubated 60 ± 10min;
C. continue to drip shell monomers and initiator ammonium persulfate in step b gained emulsion, after dropwising, be warming up to 80 ± 2 DEG C and continue reaction 1.5 ~ 2 hours, be cooled to room temperature, filter and regulate ph value of emulsion 7 ~ 7.5 after removing filter residue, obtaining low fluorine content polyacrylate emulsion hydrophobic coating material; Wherein initiator is 0.05 ~ 0.2% of shell monomers quality.
The film of above-mentioned low fluorine content polyacrylate emulsion hydrophobic coating material, is characterized in that the concrete steps of the method are: be first diluted to solid content 5 ~ 20% by adding film coalescence aid in low fluorine content polyacrylate emulsion hydrophobic coating material; Constant temperature process 10 ~ 12 hours within the scope of second-order transition temperature Tg ~ Tg+20 DEG C that is warming up to shell fluorinated acrylate resin again.
The film of above-mentioned low fluorine content polyacrylate emulsion hydrophobic coating material, is characterized in that the concrete steps of the method are: be first diluted to solid content 5 ~ 20% by adding film coalescence aid in low fluorine content polyacrylate emulsion hydrophobic coating material; The first second-order transition temperature Tg of intensification shell fluorinated acrylate resin, then in 0.5-2.0 hour, be warming up to Tg ~ Tg+20 DEG C, then constant temperature 5 ~ 7 hours;
Above-mentioned film coalescence aid is propylene glycol monomethyl ether, dipropylene or 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate.
The present invention adopts the method for core-shell emulsion polymerization to prepare low acrylate containing fluorine emulsion, effectively improves the utilization ratio of fluorochemical monomer, reduces material cost; Meanwhile, in film process, by being controlled to the filming condition such as film temperature, temperature rise rate, promote that fluorine element is to surface transport, improves coatingsurface hydrophobicity further.The acrylic resin coating prepared by the method, when fluorine content is lower, can realizes surface contact angle and be greater than 100 °, and gained coating transparent, densification there is certain mechanical strength.The method is simple to operation, cost is low, have certain practicality.
Accompanying drawing explanation
Fig. 1. be the contact angle photo of invention coating sample in embodiment three.
Fig. 2. film-forming temperature is on the impact of coating contact angle.
Fig. 3. temperature rise rate is on the impact of coating contact angle.
Fig. 4. film coalescence aid is on the impact of coating contact angle.
Fig. 5. be the contact angle photo of invention coating sample in embodiment seven.
Fig. 6. be the contact angle photo of invention coating sample in embodiment eight.
Embodiment
Below in conjunction with embodiment, further detailed description is done to the present invention, but embodiments of the present invention are not limited thereto.
embodiment one:low fluorine-containing emulsion preparation
Stirring is being housed, the good seed monomer 4.00g methyl methacrylate of pre-emulsification and ammonium persulfate aqueous solution is added in the there-necked flask of reflux condensing tube, nuclear layer monomer 18.00g methyl methacrylate is dripped after 75 DEG C of isothermal reaction 30min, 1h dropwises, continue to drip shell monomers 1.60g dodecafluoroheptyl methacrylate after insulation 1h, 9.30g butyl acrylate and 7.90g methyl methacrylate, drip ammonium persulfate aqueous solution simultaneously, 1h dropwise and a little on carry agitator, be warming up to 80 DEG C and continue reaction 2h, be cooled to room temperature, filter and regulate ph value of emulsion about 7 with ammoniacal liquor after removing filter residue, obtain stable fluorine-containing emulsion.
Adopt ethoxylated alkyl sulfate (AES)/fatty alcohol and ethylene oxide condensate (AEO-3) to be compound emulsifying agent during synthesis, its mass ratio is AES:AEO-3=1:2, and emulsifying agent total amount is 1.20g.
In the present embodiment, nuclear layer monomer methyl methacrylate also can part replace with other monomers, and other monomers comprise the mixture of one or more monomers in methyl acrylate, ethyl propenoate, butyl acrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate.The total consumption of nuclear layer monomer is 22.0g.Its effect is substantially identical with alone poly-polymethacrylic acid methyl ester.
In the present embodiment, change shell monomers total amount and ratio, the low fluorine content ACRYLIC EMULSION of different fluorine content can be obtained.
embodiment two:low fluorine-containing emulsion preparation
The present embodiment is substantially identical with embodiment one, and difference is that shell fluorochemical monomer adopts Hexafluorobutyl mathacrylate.All monomer consumptions are constant.Namely stirring is being housed, the good seed monomer 4.00g methyl methacrylate of pre-emulsification and ammonium persulfate aqueous solution is added in the there-necked flask of reflux condensing tube, nuclear layer monomer 18.00g methyl methacrylate is dripped after 75 DEG C of isothermal reaction 30min, 1h dropwises, continue to drip shell monomers 1.60g Hexafluorobutyl mathacrylate after insulation 1h, 9.30g butyl acrylate and 7.90g methyl methacrylate, drip ammonium persulfate aqueous solution simultaneously, 1h dropwise and a little on carry agitator, be warming up to 80 DEG C and continue reaction 2h, be cooled to room temperature, filter and regulate ph value of emulsion about 7 with ammoniacal liquor after removing filter residue, obtain stable fluorine-containing emulsion.
Adopt ethoxylated alkyl sulfate (AES)/fatty alcohol and ethylene oxide condensate (AEO-3) to be compound emulsifying agent during synthesis, its mass ratio is AES:AEO-3=1:2, and emulsifying agent total amount is 1.20g.
In the present embodiment, nuclear layer monomer methyl methacrylate also can part replace with other monomers, and other monomers comprise the mixture of one or more monomers in methyl acrylate, ethyl propenoate, butyl acrylate, β-dimethyl-aminoethylmethacrylate, butyl methacrylate, vinylbenzene.The total consumption of nuclear layer monomer is 22.0g.Its effect is substantially identical with alone poly-polymethacrylic acid methyl ester.
In the present embodiment, change shell monomers total amount and ratio, the low fluorine content ACRYLIC EMULSION of different fluorine content can be obtained.
embodiment three:constant temperature film forming
It is 15% that emulsion is first diluted to solid content with deionized water by the emulsion in embodiment one, then on the clean sheet glass of process, applies uniform emulsion film.Put into baking oven, under 50 DEG C of conditions, leave standstill 12h, take out and be cooled to room temperature, be i.e. the acrylic resin hydrophobic coating of obtained low fluorine content, contact angle is 101.8 °, and as shown in Figure 1, wherein the consumption of fluorochemical monomer is only 4% of monomer total amount to contact angle photo.DSC test result shows, and this resin Tg is 41.2 DEG C, raises film-forming temperature, and molecular motion aggravates, and-CF group increases to the speed of surface transport, and film coated surface can reduce, and contact angle increases.
embodiment four:constant temperature film forming
The present embodiment is substantially identical with embodiment three, and difference changes over film temperature to be respectively 20 DEG C, 30 DEG C, 40 DEG C, 60 DEG C and 70 DEG C.As shown in Figure 2, gained coating contact angle is all lower than embodiment one.When film-forming temperature is lower than polymer Tg, fluorine element motor capacity is not enough, and the fluorine element quantity migrating to surface is few, and surface contact angle is little, and coating hydrophobicity reduces; When film-forming temperature is greater than 50 DEG C, i.e. (T-Tg) >10 DEG C, velocity ratio-CF the group of coating curing reaction is fast to the speed of surface transport, still have part-CF group not have enough time to move to the surface of film when the cross-linked network of film is formed, thus cause the contact angle of film to decline.Therefore, the acid coated hydrophobic performance of the fluorine-containing propene prepared by this embodiment is not as embodiment three.
embodiment five:alternating temperature film forming
The present embodiment is substantially identical with embodiment three, difference is the mode adopting alternating temperature film forming, starting temperature is regulated to be 50 DEG C, terminal temperature is 60 DEG C, temperature rise rate is controlled by the method changing the heating-up time (0.5,1.0,1.5 and 2.0h), after temperature-rise period terminates, then at 60 DEG C constant temperature 6h until sample parches.Experimental result shows: when the heating-up time is 2.0h, and gained coating contact angle is 104.7 °, and hydrophobicity comparatively embodiment three has lifting.Meanwhile, along with the quickening of temperature rise rate, latex film surface contact angle and reducing, hydrophobicity reduces, as shown in Figure 3.
embodiment six:the impact of film coalescence aid
The present embodiment is substantially identical with embodiment three, and difference in system, adds appropriate propylene glycol monomethyl ether before film forming.After adding propylene glycol monomethyl ether, coating contact angle has increase, and as shown in Figure 4, when the addition of propylene glycol monomethyl ether is 2% of monomer mass, gained coating contact angle is 104.2 °, and comparatively embodiment three slightly promotes.
embodiment seven:constant temperature film forming
It is 15% that emulsion is first diluted to solid content with deionized water by the emulsion in embodiment two, then on the clean sheet glass of process, applies uniform emulsion film.Put into baking oven, under 50 DEG C of conditions, leave standstill 12h, take out and be cooled to room temperature, be i.e. the acrylic resin hydrophobic coating of obtained low fluorine content, this coating contact angle is 97 °, and as shown in Figure 5, hydrophobicity is not as good as embodiment three.
embodiment eight:constant temperature film forming
The present embodiment is substantially identical with embodiment seven, and difference is that to change over film temperature be 30 DEG C.Contact angle test result shows, and gained coating contact angle is 91 °, and as shown in Figure 6, hydrophobicity is not as good as embodiment seven.
embodiment nine:alternating temperature film forming
The present embodiment is substantially identical with embodiment seven, difference is the mode adopting alternating temperature film forming, starting temperature is regulated to be 50 DEG C, terminal temperature is 70 DEG C, temperature rise rate is controlled by the method changing the heating-up time (0.5,1.0,1.5 and 2.0h), after temperature-rise period terminates, then at 70 DEG C constant temperature 6h until sample parches.Along with the quickening of temperature rise rate, latex film surface contact angle and reducing, hydrophobicity reduces.
embodiment ten:the impact of film coalescence aid
The present embodiment is substantially identical with embodiment eight, and difference in system, adds propylene glycol monomethyl ether before film forming, and the addition of propylene glycol monomethyl ether is 2% of monomer mass, and gained coating contact angle is 94.3 °, and comparatively embodiment eight has lifting.
Claims (8)
1. a low fluorine content polyacrylate emulsion hydrophobic coating material, is characterized in that the composition of this coated material and mass percentage are:
The fluorine-containing polyacrylic resin 30 ~ 50% of nucleocapsid structure;
Emulsifying agent 0.6 ~ 3%;
Water 47 ~ 69.4%;
The fluorine-containing polyacrylic resin of described nucleocapsid structure after polymerization, forms stratum nucleare with acrylic ester monomer, it is coated with the shell formed by acrylate containing fluorine monomer and acrylic ester monomer copolymerization, the mass percentage of wherein said stratum nucleare is 50% ~ 80%, and all the other are shell; In the monomer of described formation shell, acrylate containing fluorine monomer accounts for 3 ~ 20% of shell total monomer mole number.
2. low fluorine content polyacrylate emulsion hydrophobic coating material according to claim 1, is characterized in that described acrylate containing fluorine monomer is: Hexafluorobutyl mathacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, methacrylic acid ten trifluoro monooctyl ester or perfluor alkyl ethide methacrylic ester.
3. low fluorine content polyacrylate emulsion hydrophobic coating material according to claim 1, is characterized in that described acrylic ester monomer is at least one in methyl methacrylate, methyl acrylate, butyl methacrylate, Tert-butyl Methacrylate, butyl acrylate, tert-butyl acrylate, vinylformic acid, methacrylic acid, Hydroxyethyl acrylate and Propylene glycol monoacrylate.
4. low fluorine content polyacrylate emulsion hydrophobic coating material according to claim 1, is characterized in that described emulsifying agent is: at least one in span 20, OP-10, sodium lauryl sulphate, ethoxylated alkyl sulfate and the O/W such as fatty alcohol and ethylene oxide condensate type emulsifying agent.
5. the preparation method of the low fluorine content polyacrylate emulsion hydrophobic coating material according to claim 1,2 or 3, adopts emulsion polymerization, it is characterized in that the concrete steps of the method are:
A. the part in nuclear layer monomer is formed emulsion as seed monomer and emulsifying agent, initiator ammonium persulfate and water at 75 ± 2 DEG C of isothermal reaction 30 ± 5min, the wherein mass ratio (30 ~ 50) of seed monomer and water: 100, emulsifying agent is the 2-6% of seed monomer quality, and initiator is 0.05 ~ 0.2% of seed monomer quality;
B. in step a gained emulsion, drip remaining nuclear layer monomer, and be incubated 60 ± 10min;
C. continue to drip shell monomers and initiator ammonium persulfate in step b gained emulsion, after dropwising, be warming up to 80 ± 2 DEG C and continue reaction 1.5 ~ 2 hours, be cooled to room temperature, filter and regulate ph value of emulsion 7 ~ 7.5 after removing filter residue, obtaining low fluorine content polyacrylate emulsion hydrophobic coating material; Wherein initiator is 0.05 ~ 0.2% of shell monomers quality.
6. a film for low fluorine content polyacrylate emulsion hydrophobic coating material according to claim 1, is characterized in that the concrete steps of the method are: be first diluted to solid content 5 ~ 20% by adding film coalescence aid in low fluorine content polyacrylate emulsion hydrophobic coating material; Constant temperature process 10 ~ 12 hours within the scope of second-order transition temperature Tg ~ Tg+20 DEG C that is warming up to shell fluorinated acrylate resin again.
7. a film for low fluorine content polyacrylate emulsion hydrophobic coating material according to claim 1, is characterized in that the concrete steps of the method are: be first diluted to solid content 5 ~ 20% by adding film coalescence aid in low fluorine content polyacrylate emulsion hydrophobic coating material; The first second-order transition temperature Tg of intensification shell fluorinated acrylate resin, then in 0.5-2.0 hour, be warming up to Tg ~ Tg+20 DEG C, then constant temperature 5 ~ 7 hours.
8. the method according to claim 6 or 7, is characterized in that described film coalescence aid is propylene glycol monomethyl ether, dipropylene or 2,2,4-trimethylammonium-1,3-pentanediol mono isobutyrate.
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| CN111485430A (en) * | 2020-04-22 | 2020-08-04 | 浙江理工大学 | Fluorocarbon water-based paint and anti-bursting hydrophobic coating fabric |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105924585A (en) * | 2016-04-29 | 2016-09-07 | 永保化工（香港）有限公司 | Core-shell type fluorine-containing nanometer emulsion, and preparation method and application thereof |
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| CN111205387A (en) * | 2020-03-12 | 2020-05-29 | 广东巴德富新材料有限公司 | Zero-additive odor-free super stain-resistant acrylate emulsion and preparation method thereof |
| CN111485430A (en) * | 2020-04-22 | 2020-08-04 | 浙江理工大学 | Fluorocarbon water-based paint and anti-bursting hydrophobic coating fabric |
| CN115028781A (en) * | 2022-07-20 | 2022-09-09 | 山东恒泰纺织有限公司 | Liquid-like polymer nano emulsion and preparation method thereof |
| CN115028781B (en) * | 2022-07-20 | 2023-06-30 | 山东恒泰纺织有限公司 | Liquid-like polymer nano emulsion and preparation method thereof |
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