CN107602755A - A kind of acrylic emulsion and its synthetic method of PVDF fluorocarbon powder paints - Google Patents

A kind of acrylic emulsion and its synthetic method of PVDF fluorocarbon powder paints Download PDF

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Publication number
CN107602755A
CN107602755A CN201710778188.6A CN201710778188A CN107602755A CN 107602755 A CN107602755 A CN 107602755A CN 201710778188 A CN201710778188 A CN 201710778188A CN 107602755 A CN107602755 A CN 107602755A
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China
Prior art keywords
monomer
acrylic emulsion
powder paints
pvdf fluorocarbon
fluorocarbon powder
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CN201710778188.6A
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Chinese (zh)
Inventor
游东升
赵军
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Guangdong East New Materials Co Ltd
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Guangdong East New Materials Co Ltd
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Priority to CN201710778188.6A priority Critical patent/CN107602755A/en
Publication of CN107602755A publication Critical patent/CN107602755A/en
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Abstract

A kind of acrylic emulsion and its synthetic method for PVDF fluorocarbon powder paints, including monomer, the monomer includes at least one methacrylate monomers and at least one acrylate monomer, also include a kind of the functional compound monomer and the feature anti-yellowing additives of resistance to baking of the carbon-carbon double bonds that free radical addition polymerization can be carried out with the methacrylate monomers and acrylate monomer, its preparation process is:First deionized water and appropriate initiator are mixed and are warming up to certain temperature, then formula ratio monomer and appropriate initiator mixed liquor is added dropwise and is incubated a period of time, add remaining initiator and be incubated a period of time, then the resistance to baking anti-yellowing additives of feature are added and are incubated a period of time, discharged after certain temperature is cooled to, acrylic emulsion is made.The acrylic resin that the application provides has resistance to baking, can effectively improve the performance of PVDF fluorocarbon coatings, its final film is had more stability.

Description

A kind of acrylic emulsion and its synthetic method of PVDF fluorocarbon powder paints
Technical field
The application is to be related to a kind of acrylic emulsion of PVDF fluorocarbon powder paints, belongs to high polymer material technology neck Domain.
Background technology
The manufacture method of PVDF fluorocarbon powder paints has many kinds, and wherein emulsion seasoning is a kind of safe and environment-friendly, energy-conservation Production method.This method requires that acrylic emulsion film has excellent resistance to baking.At present, in the polymerization of emulsion all Emulsifying agent is added, so that its stable system and nucleation, but the addition of emulsifying agent can influence the resistance to baking of emulsion polymer, The apparent effect of the PVDF fluorine carbon dusts of white can greatly be influenceed.
The content of the invention
It is an object of the invention to provide a kind of acrylic emulsion for PVDF fluorocarbon powder paints, not only with excellent Good resistance to baking, and the performance of PVDF fluorocarbon powder paints can be improved, ensure the excellent apparent effect of its film.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of acrylic emulsion of PVDF fluorocarbon powder paints, including monomer, the monomer include at least one methyl Acrylate monomer and at least one acrylate monomer, in addition to the feature anti-yellowing additives of resistance to baking, the feature are resistance to Toast anti-yellowing additives and be selected from the compound of phosphorous heat stabilizer and antioxidant and the heat of the rare earth of (/ or) containing sulfonic group The compound of stabilizer and antioxidant.
Further, the monomer is synthesized by copolyreaction, and the copolyreaction is reacted for emulsifier-free emulsion polymerization.
Further, by mass percentage:Methacrylate monomers account for 55~75%, and acrylate monomer accounts for 20~ 50%, the resistance to baking anti-yellowing additives of feature account for 1~3%.
Further, the methacrylate monomers are selected from methyl methacrylate, EMA, metering system At least one of sour N-butyl.
Further, the acrylate monomer is selected from least one of ethyl acrylate, n-butyl acrylate.
Further, the initiator used in the copolyreaction is selected from potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, persulfuric acid Salt-sodium hydrogensulfite, hydrogen peroxide-ferrous sulfate, hydrogen peroxide-rongalite, hydrogen peroxide-ascorbic acid or water-soluble even At least one of nitrogen class initiator.
Further, the dosage of the initiator is calculated as accounting for the 0.01~10% of monomer total amount according to mass percent.
Further, the monomer also includes functional compound monomer, the functional compound monomer can with it is described Methacrylate monomers and acrylate monomer carry out copolyreaction.
Further, the functional compound monomer is unsaturated carboxylic acid monomer, and the functional compound monomer is according to matter Measure accounting of the percentages in the monomer and be no more than 2%.
Further, a kind of synthetic method for the acrylic emulsion for preparing PVDF fluorocarbon powder paints as described above, Specific steps include:
(1) according to weight fraction meter, 20~40 parts of deionized waters and appropriate initiator are first added in reaction vessel, and rise Temperature is to 60~80 DEG C;
(2) while monomer and appropriate initiator solution is added dropwise, is added dropwise 3~6 hours;
(3) 1.5~5.0 hours are incubated;
(4) remaining initiator is added, then is incubated 1~3 hour;
(5) 95 DEG C are then heated to, adds the feature anti-yellowing additives of resistance to baking, is incubated 2 hours;
(6) 40 DEG C of dischargings are cooled to, the acrylic emulsion is made.
Further, nertralizer can be added before acrylic emulsion discharging, adjusts its pH value, the nertralizer is basic species Matter, including inorganic base, organic base and amine substance.
Further, the nertralizer is selected from ammoniacal liquor, potassium hydroxide, sodium hydroxide, monoethanolamine, diethanol amine, three ethanol At least one of amine, N methyldiethanol amine, N, N- dimethylethanolamines, triethylamine.
Compared with prior art, the present invention has the advantages that:
1. the glass transition temperature of acrylic emulsion dry film provided by the invention is 48~62 DEG C, weight average molecular weight is 11000~160000, for PVDF fluorocarbon powder paints, excellent effect;2. acrylic resin provided by the invention has excellent Resistance to baking, coating xanthochromia because of caused by baking can be significantly inhibited;3. any breast is not added in building-up process of the present invention Agent, production cost is not only reduced, reduced environmental pollution, may be omitted with the last handling processes such as emulsion breaker, obtained micelle Show cleaning, it is dispersed, emulsion property is preferable.
Embodiment
The application is made with reference to embodiment further in detail, intactly to illustrate;It is unreceipted specific in the following example The experimental method of condition, generally according to normal condition or according to the condition proposed by manufacturer.
Embodiment 1
A kind of acrylic emulsion of PVDF fluorocarbon powder paints, including monomer, the monomer include at least one methyl Acrylate monomer and at least one acrylate monomer, in addition to the feature anti-yellowing additives of resistance to baking, the feature are resistance to Toast anti-yellowing additives and be selected from the compound of phosphorous heat stabilizer and antioxidant and the heat of the rare earth of (/ or) containing sulfonic group The compound of stabilizer and antioxidant.
The monomer is synthesized by copolyreaction, and the copolyreaction is reacted for emulsifier-free emulsion polymerization.
By mass percentage:Methacrylate monomers account for 55~75%, and acrylate monomer accounts for 20~50%, function Property it is resistance to baking anti-yellowing additives account for 1~3%.
The methacrylate monomers are selected from methyl methacrylate, EMA, the positive fourth of methacrylic acid At least one of ester.
The acrylate monomer is selected from least one of ethyl acrylate, n-butyl acrylate.
Initiator used in the copolyreaction is selected from potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, persulfate-sulfurous Sour hydrogen sodium, hydrogen peroxide-ferrous sulfate, hydrogen peroxide-rongalite, hydrogen peroxide-ascorbic acid or water-soluble azo class are drawn Send out at least one of agent.
The dosage of the initiator is calculated as accounting for the 0.01~10% of monomer total amount according to mass percent.
A kind of synthetic method for the acrylic emulsion for preparing PVDF fluorocarbon powder paints as described above, specific steps bag Include:
(1) according to weight fraction meter, 20~40 parts of deionized waters and appropriate initiator are first added in reaction vessel, and rise Temperature is to 60~80 DEG C;
(2) while monomer and appropriate initiator solution is added dropwise, is added dropwise 3~6 hours;
(3) 1.5~5.0 hours are incubated;
(4) remaining initiator is added, then is incubated 1~3 hour;
(5) 95 DEG C are then heated to, adds the feature anti-yellowing additives of resistance to baking, is incubated 2 hours;
(6) 40 DEG C of dischargings are cooled to, the acrylic emulsion is made.
Nertralizer can be added before acrylic emulsion discharging, adjusts its pH value, the nertralizer is alkaline matter, including Inorganic base, organic base and amine substance.
The nertralizer is selected from ammoniacal liquor, potassium hydroxide, sodium hydroxide, monoethanolamine, diethanol amine, triethanolamine, N- first At least one of base diethanol amine, N, N- dimethylethanolamines, triethylamine.
The amount of the appropriate initiator for referring to, by concrete technology requirement, be added can make the deionized water or the list Body is fully reacted with the initiator, and the initiator is divided into be added three times, and for the first time and second of amount added is that it reacts institute The minimum needed, is for the third time remaining amount.
The present embodiment specific formula parameter is as follows:
The mass parts of methyl methacrylate 60, the mass parts of ethyl acrylate 39.5, containing the resistance to baking yellowing-resistant of Phosphorus feature 0.5 part of auxiliary agent;Initiator uses potassium peroxydisulfate, and dosage is 0.5 mass parts;Using deionized water as polymer solvent, make reaction The solid content of system is 36%;
Embodiment 2
The acrylic emulsion is prepared by the method for embodiment 1, the monomer also includes functional compound monomer, the work( Energy property compound monomer can carry out copolyreaction with the methacrylate monomers and acrylate monomer.The feature Compound monomer is unsaturated carboxylic acid monomer, the functional compound monomer accounting in the monomer according to mass percent meter Than no more than 2%.
Its specific formula parameter is as follows:
The mass parts of methyl methacrylate 63, the mass parts of ethyl acrylate 36, the functional compound is preferably methyl Acrylic acid, its dosage are 0.65 mass parts, containing resistance to 0.35 part of the anti-yellowing additives of baking of Phosphorus feature;Initiator uses persulfuric acid Sodium, dosage are 0.5 mass parts;Using deionized water as polymer solvent, the solid content for making reaction system is 33%;
Embodiment 3
The acrylic emulsion is prepared by the method for embodiment 1, its specific formula parameter is as follows:
The mass parts of methyl methacrylate 68, the mass parts of ethyl acrylate 31.5, the resistance to baking of the feature of terres rares containing sulphur 0.5 part of anti-yellowing additives;Initiator uses potassium peroxydisulfate, and dosage is 0.5 mass parts;Using deionized water as polymer solvent, The solid content for making reaction system is 30%;
Embodiment 4
The acrylic emulsion is prepared by the method for embodiment 1, its specific formula parameter is as follows:
The mass parts of methyl methacrylate 75, the mass parts of ethyl acrylate 15, the mass parts of butyl acrylate 10 are dilute containing sulphur Resistance to 0.3 part of the anti-yellowing additives of baking of great soil group feature;Initiator uses potassium peroxydisulfate, and dosage is 0.5 mass parts;Use deionization For water as polymer solvent, the solid content for making reaction system is 30%;
Comparative example 1
The acrylic emulsion is prepared by prior art, its specific formula parameter is as follows:
The mass parts of methyl methacrylate 60, the mass parts of ethyl acrylate 39.5, initiator use potassium peroxydisulfate, and dosage is 0.5 mass parts;Using deionized water as polymer solvent, the solid content for making reaction system is 36%;
Comparative example 2
The acrylic emulsion is prepared by prior art, its specific formula parameter is as follows:
The mass parts of methyl methacrylate 68, the mass parts of ethyl acrylate 31.5, initiator use potassium peroxydisulfate, and dosage is 0.5 mass parts;Using deionized water as polymer solvent, the solid content for making reaction system is 30%;
After tested, embodiment 1-4 and comparative example 1-2 design parameters and effect are as follows:
* resistance to baking:The 0.4mm thickness aluminium sheets of formed objects are taken, it is clean with ethanol, area identical navicular is converted into, Then embodiment 1~4 identical in quality and comparative example acrylic emulsion are respectively dropped into, gently shakes up that to sprawl into area roughly the same Film layer, after drying, toast 20 minutes as in 245 DEG C of baking ovens, takes out cold, visual observations of drying in the air:
1 grade:Water-white homogeneous transparent, free from admixture
2 grades:It is water-white transparent, show micro- Huang at indivedual points once in a while
3 grades:It is water-white transparent, have more at show micro- Huang
4 grades:Film is transparent, shows micro- Huang on the whole
5 grades:Film yellow
As from the foregoing:
1st, in prior art, the compound of phosphorous heat stabilizer and antioxidant is added and/or containing sulfonic group The heat stabilizer of rare earth and the compound of antioxidant, by the present invention the preparation-obtained acrylic resin of synthetic method, In resistance to baking rank by original 3 grades of liftings to 1 grade or 2 grades, it was demonstrated that the propylene prepared by using the synthetic method of the present invention Acid has more preferable resistance to cooking performance, is more beneficial for the apparent effect of the PVDF fluorocarbon powder paints of the light color such as white, silver color.
2nd, in prior art, the compound of phosphorous heat stabilizer and antioxidant is added and/or containing sulfonic group The heat stabilizer of rare earth and the compound of antioxidant, the acrylic resin being prepared by the synthetic method of the present invention, its glass Glass transition temperature is bigger than the glass transition temperature range of prior art between 48~62 DEG C, those skilled in the art It can voluntarily select appropriate compound to be synthesized according to specific needs, obtain under required glass transition temperature, resistance to baking The property high acrylic resin of rank.
It should be noted that:The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations;Although reference The present invention is described in detail previous embodiment, it will be understood by those within the art that:It still can be right Technical scheme described in foregoing embodiments is modified, or carries out equivalent substitution to which part technical characteristic;And this A little modifications are replaced, and the essence of appropriate technical solution is departed from the protection domain of various embodiments of the present invention technical scheme.

Claims (10)

1. a kind of acrylic emulsion of PVDF fluorocarbon powder paints, including monomer, the monomer includes at least one methyl-prop Olefin(e) acid ester monomer and at least one acrylate monomer, it is characterised in that:Also include the feature anti-yellowing additives of resistance to baking, it is described The resistance to baking anti-yellowing additives of feature are selected from the compound of phosphorous heat stabilizer and antioxidant and/or containing the dilute of sulfonic group The heat stabilizer of soil and the compound of antioxidant.
A kind of 2. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 1, it is characterised in that:The list Body is synthesized by copolyreaction, and the copolyreaction is reacted for emulsifier-free emulsion polymerization.
A kind of 3. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 2, it is characterised in that:According to matter Measuring percentages is:Methacrylate monomers account for 55~75%, and acrylate monomer accounts for 20~50%, and the resistance to baking of feature is anti- Yellowing additive accounts for 1~3%.
A kind of 4. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 3, it is characterised in that:The first Base acrylate monomer is selected from least one of methyl methacrylate, EMA, n-BMA.
A kind of 5. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 3, it is characterised in that:Described third Olefin(e) acid ester monomer is selected from least one of ethyl acrylate, n-butyl acrylate.
A kind of 6. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 5, it is characterised in that:It is described common Poly- reaction initiator used be selected from potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, persulphate-bisulphite sodium, hydrogen peroxide- At least one in ferrous sulfate, hydrogen peroxide-rongalite, hydrogen peroxide-ascorbic acid or water-soluble azo class initiator Kind.
A kind of 7. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 6, it is characterised in that:It is described to draw The dosage of hair agent is calculated as accounting for the 0.01~10% of monomer total amount according to mass percent.
A kind of 8. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 1, it is characterised in that:The list Body also includes functional compound monomer, and the functional compound monomer can be with the methacrylate monomers and propylene Acid ester monomer carries out copolyreaction.
A kind of 9. acrylic emulsion of PVDF fluorocarbon powder paints according to claim 8, it is characterised in that:The work( Energy property compound monomer is unsaturated carboxylic acid monomer, and the functional compound monomer is according to mass percent meter in the monomer Accounting be no more than 2%.
10. a kind of prepare such as a kind of acrylic emulsion of PVDF fluorocarbon powder paints according to any one of claims 1 to 9 Synthetic method, it is characterised in that:
Specific steps include:
(1) according to weight fraction meter, 20~40 parts of deionized waters and appropriate initiator are first added in reaction vessel, and be warming up to 60~80 DEG C;
(2) while monomer and the mixed solution of appropriate initiator is added dropwise, time for adding is 3~6 hours;
(3) 1.5~5.0 hours are incubated;
(4) remaining initiator is added, then is incubated 1~3 hour;
(5) 95 DEG C are then heated to, adds the feature anti-yellowing additives of resistance to baking, is incubated 2 hours;
(6) 40 DEG C of dischargings are cooled to, the acrylic emulsion is made.
CN201710778188.6A 2017-09-01 2017-09-01 A kind of acrylic emulsion and its synthetic method of PVDF fluorocarbon powder paints Pending CN107602755A (en)

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CN201710778188.6A CN107602755A (en) 2017-09-01 2017-09-01 A kind of acrylic emulsion and its synthetic method of PVDF fluorocarbon powder paints

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108752616A (en) * 2018-06-19 2018-11-06 界首市黑马渔具有限公司 A kind of outer painting methods of silica gel bionic fish bait

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Publication number Priority date Publication date Assignee Title
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CN104311722A (en) * 2014-11-06 2015-01-28 任婧 Acrylic resin used for fluorocarbon coatings
CN104497461A (en) * 2014-12-15 2015-04-08 上海锦湖日丽塑料有限公司 Heat-resistant scratch-resistant high-transmittance PMMA alloy resin composition and preparation method thereof
CN105524465A (en) * 2014-12-26 2016-04-27 比亚迪股份有限公司 Anti-yellowing composition, resin composition, metal-resin compound, preparation method and use of metal-resin compound and electronic product housing

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CN108752616A (en) * 2018-06-19 2018-11-06 界首市黑马渔具有限公司 A kind of outer painting methods of silica gel bionic fish bait

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