CN105837739A - Method for preparing water-based fluorine-containing hydroxyl acrylic emulsion - Google Patents
Method for preparing water-based fluorine-containing hydroxyl acrylic emulsion Download PDFInfo
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- CN105837739A CN105837739A CN201610291364.9A CN201610291364A CN105837739A CN 105837739 A CN105837739 A CN 105837739A CN 201610291364 A CN201610291364 A CN 201610291364A CN 105837739 A CN105837739 A CN 105837739A
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- emulsion
- hydroxyl acrylic
- acrylic emulsion
- containing hydroxyl
- fluorine
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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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
-
- 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
-
- 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
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a method for preparing water-based fluorine-containing hydroxyl acrylic emulsion .The method comprises the steps of preparing pre-emulsion, adding a mixture of water and negative non-ionic emulsifier into a reaction still, increasing temperature to 80-85 DEG C, adding a primary initiator, then adding the prepared pre-emulsion and an initiator dropwise, and conducting heat insulation for half an hour to obtain core layer emulsion; adding a hydroxyl monomer, methyl methacrylate and butyl acrylate into a pre-emulsification tank to be evenly mixed, adding the prepared core layer emulsion dropwise for 1-3 h for continuous reaction, conducting heat insulation, and conducting discharging after cooling and ph value regulation .In this way, by introducing a fluoroacrylate monomer, a compound emulsifier and the core-shell technology to water-based hydroxyl acrylic emulsion for copolymerization, ultralow surface energy, ultrahigh paint film strength and extremely good weather resistance of an emulsion paint film are realized through the fluorine monomer.
Description
Technical field
The present invention relates to high molecular synthetic material field, particularly relate to the preparation method of a kind of aqueous fluorine-containing hydroxyl acrylic emulsion.
Background technology
Water paint refers to use water as the coating of solvent or disperse medium, has that protective is good and the advantage such as good corrosion resistance, and compared with oil paint, the production of water paint can save resource, and the pollution during producing and using is little, therefore applies more and more extensive.
Existing water-based hydroxyl acrylic emulsion is carboxylic monomer and adds acrylic ester monomer copolymerization and form, and there is also certain deficiency at aspects such as resistance to water, hardness and weatherabilities.
Summary of the invention
The technical problem that present invention mainly solves is to provide the preparation method of a kind of aqueous fluorine-containing hydroxyl acrylic emulsion, promotes resistance to water, hardness and weatherability.
For solving above-mentioned technical problem, the technical scheme that the present invention uses is: provides the preparation method of a kind of aqueous fluorine-containing hydroxyl acrylic emulsion, comprises the following steps:
80-100 part water and 5-10 part anionic and nonionic emulsifier mixture are added in pre-emulsification still, then it is sequentially added into 50-100 part fluorine monomer, 30-100 part methyl methacrylate, 70-120 part butyl acrylate and 10-20 part methacrylic acid and carries out pre-emulsification 20 minutes, obtain pre-emulsion；
Reactor adds water and 5-10 part anionic and nonionic emulsifier mixture of 200-300 part, is warmed up to 80-85 degree, put into initiator at the beginning of 1-3 part, then start to drip the pre-emulsion prepared and 2-4 part initiator；
Pre-emulsion dropping dropping in 1-3 hour is complete, and insulation prepares stratum nucleare emulsion half an hour；
In pre-emulsification tank, add the carboxylic monomer of 50-150 part, 40-70 part methyl methacrylate and 40-80 part butyl acrylate mix homogeneously, then instill the stratum nucleare emulsion prepared and continue reaction, time for adding 1-3 hour, be incubated 1 hour；
Above-mentioned part is parts by weight；
Cooling regulation ph value, to 7-9 discharging, prepares the aqueous fluorine-containing hydroxyl acrylic emulsion with nucleocapsid structure.
In a preferred embodiment of the present invention, described just initiator and initiator are ammonium persulfate solution.
In a preferred embodiment of the present invention, described anionic and nonionic emulsifier mixture is the mixture of anion emulsifier and nonionic emulsifier, described anion emulsifier uses one or more in dodecylbenzene sodium sulfonate, allyl alkylphenol ethoxylate ammonium sulfate and AESA, described nonionic emulsifier uses one or both in alkylphenol polyoxyethylene and phenyl polyoxyethylene ether, and the part by weight of described anion emulsifier and nonionic emulsifier is 1:1 ~ 3:1.
In a preferred embodiment of the present invention, described fluorine monomer uses one or more in trifluoroethyl methacrylate, hexafluorobutyl acrylate and methacrylic acid octafluoro pentyl ester.
In a preferred embodiment of the present invention, described carboxylic monomer uses one or more in 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate and hy-droxybutyl.
The invention has the beneficial effects as follows: the preparation method of a kind of aqueous fluorine-containing hydroxyl acrylic emulsion that the present invention points out, in water-based hydroxyl acrylic emulsion, introduce fluoro-acrylate monomer carry out graft copolymerization, increase substantially water-fast weatherability and the hardness of paint film, copolymerization is carried out by introducing fluoro-acrylate monomer and compound emulsifying agent and nucleocapsid technique in water-based hydroxyl acrylic emulsion, fluorine monomer gives the ultralow surface of emulsion paint film can, the weatherability that the paint film of superelevation is strong and splendid, owing to carboxylic monomer belongs to hydrophilic monomer, and fluorinated acrylate is strong-hydrophobicity monomer, it is difficult to common emulsifying and the difficult point of polymerization stability difference so existing, and technical scheme is taked compound emulsifying agent and hud polymerization technique thus is solved above difficult point, it is made that stable aqueous fluorine-containing hydroxyl acrylic emulsion.
Detailed description of the invention
Technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, all other embodiments that those of ordinary skill in the art are obtained under not making creative work premise, broadly fall into the scope of protection of the invention.
The embodiment of the present invention includes:
The preparation method of a kind of aqueous fluorine-containing hydroxyl acrylic emulsion, comprises the following steps:
100kg water and 10kg anionic and nonionic emulsifier mixture are added in pre-emulsification still, then it is sequentially added into 100kg methacrylic acid octafluoro pentyl ester, 80kg methyl methacrylate, 90kg butyl acrylate and 15kg methacrylic acid and carries out pre-emulsification 20 minutes, obtain pre-emulsion；
Reactor adds water and the 8kg anionic and nonionic emulsifier mixture of 250kg, it is warmed up to 80-85 degree, put into 2kg ammonium persulfate solution, then start to drip the pre-emulsion prepared and 3kg ammonium persulfate solution, described anionic and nonionic emulsifier mixture is the mixture of anion emulsifier and nonionic emulsifier, described anion emulsifier uses AESA, described nonionic emulsifier uses phenyl polyoxyethylene ether, and the part by weight of described anion emulsifier and nonionic emulsifier is 2:1；
It is complete that pre-emulsion drips dropping in 2.5 hours, and insulation prepares stratum nucleare emulsion half an hour；
In pre-emulsification tank, add 120kg hy-droxybutyl, 60kg methyl methacrylate and 70kg butyl acrylate mix homogeneously, then instill the stratum nucleare emulsion prepared and continue reaction, time for adding 3 hours, be incubated 1 hour；
Cooling regulation ph value, to 8 dischargings, prepares the aqueous fluorine-containing hydroxyl acrylic emulsion with nucleocapsid structure.
In sum, the preparation method of a kind of aqueous fluorine-containing hydroxyl acrylic emulsion that the present invention points out, carry out copolymerization by introducing fluoro-acrylate monomer and compound emulsifying agent and nucleocapsid technique in water-based hydroxyl acrylic emulsion, fluorine monomer give the ultralow surface of emulsion paint film can, the strong and splendid weatherability of the paint film of superelevation.
The foregoing is only embodiments of the invention; not thereby the scope of the claims of the present invention is limited; every equivalent structure utilizing description of the invention content to be made or equivalence flow process conversion; or directly or indirectly it is used in other relevant technical field, the most in like manner it is included in the scope of patent protection of the present invention.
Claims (5)
1. the preparation method of an aqueous fluorine-containing hydroxyl acrylic emulsion, it is characterised in that comprise the following steps:
80-100 part water and 5-10 part anionic and nonionic emulsifier mixture are added in pre-emulsification still, then it is sequentially added into 50-100 part fluorine monomer, 30-100 part methyl methacrylate, 70-120 part butyl acrylate and 10-20 part methacrylic acid and carries out pre-emulsification 20 minutes, obtain pre-emulsion；
Reactor adds water and 5-10 part anionic and nonionic emulsifier mixture of 200-300 part, is warmed up to 80-85 degree, put into initiator at the beginning of 1-3 part, then start to drip the pre-emulsion prepared and 2-4 part initiator；
Pre-emulsion dropping dropping in 1-3 hour is complete, and insulation prepares stratum nucleare emulsion half an hour；
In pre-emulsification tank, add the carboxylic monomer of 50-150 part, 40-70 part methyl methacrylate and 40-80 part butyl acrylate mix homogeneously, then instill the stratum nucleare emulsion prepared and continue reaction, time for adding 1-3 hour, be incubated 1 hour；
Above-mentioned part is parts by weight；
Cooling regulation ph value, to 7-9 discharging, prepares the aqueous fluorine-containing hydroxyl acrylic emulsion with nucleocapsid structure.
The preparation method of aqueous fluorine-containing hydroxyl acrylic emulsion the most according to claim 1, it is characterised in that described just initiator and initiator are ammonium persulfate solution.
The preparation method of aqueous fluorine-containing hydroxyl acrylic emulsion the most according to claim 1, it is characterized in that, described anionic and nonionic emulsifier mixture is the mixture of anion emulsifier and nonionic emulsifier, described anion emulsifier uses dodecylbenzene sodium sulfonate, one or more in allyl alkylphenol ethoxylate ammonium sulfate and AESA, described nonionic emulsifier uses one or both in alkylphenol polyoxyethylene and phenyl polyoxyethylene ether, the part by weight of described anion emulsifier and nonionic emulsifier is 1:1 ~ 3:1.
The preparation method of aqueous fluorine-containing hydroxyl acrylic emulsion the most according to claim 1, it is characterised in that described fluorine monomer uses one or more in trifluoroethyl methacrylate, hexafluorobutyl acrylate and methacrylic acid octafluoro pentyl ester.
The preparation method of aqueous fluorine-containing hydroxyl acrylic emulsion the most according to claim 1, it is characterised in that described carboxylic monomer uses one or more in 2-(Acryloyloxy)ethanol, hydroxyethyl methylacrylate, Hydroxypropyl acrylate and hy-droxybutyl.
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| CN201610291364.9A CN105837739A (en) | 2016-05-05 | 2016-05-05 | Method for preparing water-based fluorine-containing hydroxyl acrylic emulsion |
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| CN201610291364.9A CN105837739A (en) | 2016-05-05 | 2016-05-05 | Method for preparing water-based fluorine-containing hydroxyl acrylic emulsion |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056977A (en) * | 2017-05-22 | 2017-08-18 | 宁德师范学院 | The preparation method of aqueous cowboy's rubber cement covering hollow microsphere emulsion |
| CN107474182A (en) * | 2017-08-02 | 2017-12-15 | 李晖 | A kind of method that fluororesin is prepared using micro passage reaction |
| CN110885606A (en) * | 2019-11-19 | 2020-03-17 | 浙江天女集团制漆有限公司 | Water-based fluorocarbon metallic paint for high-reflection external wall and preparation method thereof |
| CN113880979A (en) * | 2021-10-29 | 2022-01-04 | 山东灵晓新材料有限公司 | High-water-retention acrylate back coating liquid and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107056977A (en) * | 2017-05-22 | 2017-08-18 | 宁德师范学院 | The preparation method of aqueous cowboy's rubber cement covering hollow microsphere emulsion |
| CN107474182A (en) * | 2017-08-02 | 2017-12-15 | 李晖 | A kind of method that fluororesin is prepared using micro passage reaction |
| CN110885606A (en) * | 2019-11-19 | 2020-03-17 | 浙江天女集团制漆有限公司 | Water-based fluorocarbon metallic paint for high-reflection external wall and preparation method thereof |
| CN113880979A (en) * | 2021-10-29 | 2022-01-04 | 山东灵晓新材料有限公司 | High-water-retention acrylate back coating liquid and preparation method thereof |
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Application publication date: 20160810 |