CN103756396B - Preparation method for mixed wax capable of enhancing smoothness of coating - Google Patents
Preparation method for mixed wax capable of enhancing smoothness of coating Download PDFInfo
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- CN103756396B CN103756396B CN201310730682.7A CN201310730682A CN103756396B CN 103756396 B CN103756396 B CN 103756396B CN 201310730682 A CN201310730682 A CN 201310730682A CN 103756396 B CN103756396 B CN 103756396B
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Abstract
The invention provides a preparation method of mixed wax capable of enhancing smoothness of a coating. The preparation method comprises the following steps: in a reaction kettle, adding a certain amount of dispersant, imitator, and polyethylene (PE) wax/hexafluoropropene trimer/silicyl vinyl unsaturated silane; heating to reaction temperature, thus obtaining surface-grafted PE wax powder after reaction; then, mixing the PE wax powder with polytetrafluoroethylene (PTFE) powder; and grinding and crushing the mixture in a flour mill to obtain the mixed wax provided by the invention. PE wax spheres are surface-modified through the hexafluoropropylene trimer and the hydrolytic silicyl vinyl unsaturated silane, so that the compatibility of the PE wax spheres with PTFE is improved. Meanwhile, the hexafluoropropene trimer and the hydrolytic silicyl vinyl unsaturated silane are polymerized to form a net structure with branch chains, thereby improving binding force of the PE wax powder with the PTFE micro powder in blending. The mixed wax can be widely applied to various water-based paints or alcohol soluble paints.
Description
Technical field
The present invention relates to a kind of preparation method of blended wax, particularly a kind of preparation method strengthening the blended wax of the smooth performance of coating.
Background technology
Tetrafluoroethylene wax is added into polymer coating, can improvement table top or transmit the non-wettability of adhesion article travelling belt, and easily sticky article do not stick containing wax coating.Tetrafluoroethylene wax is added into mineral oil or synthetic oil, as viscosifying agent, prepares special oil.Because tetrafluoroethylene wax has the characteristic of high-low temperature resistant, anticorrosive and low friction, the grease of thus institute's multiviscosisty is also correspondingly provided with these valuable performances, can be applicable to the special occasions of environment harshness.
In the preparation of coating material, generally add wax with 0.01-10% concentration.Generally PE wax, PTFE wax, PP wax, amide waxe, FT paraffin, montanin wax, natural wax, coarse-grain and microcrystalline wax, polyethylene and ethylene copolymers, Isosorbide Dinitrate and metallocenes wax, with their blend same, add these wax with the form of thin slice, particle, powder, dispersion, emulsion or powder compounds, conventional type of service is the fine powder powder that granularity is at most 4 μm.Use these waxes to reach following effect in coating material: better scratch-resistant, better wear resistance, the better dispersion of pigment, better pigment stability, the improvement of sedimentation tendency, the improvement of pigment redispersion, for the active orientation material of effect pigment, effective delustring, gratifying sense of touch, the improvement of oilness, the improvement of metal mark, reach effective introducing of effect pigment, the impact of rheological property, better adhesion inhibiting properties, better sand milling, degassed additive in powder coating, for increasing the additive of powder coating output.
These wax additives can be used for all coating systems, as low solid, Medium Solids, high solid, solvent-based coating material, moisture or rare coating material, powder coating material, physical dryness coating system, chemosetting coating material and radiation curable coating material can be released, as UV coating material by water.
CN 1429257 provides the purposes of wax mixture for improvement of coating material performance, this wax mixture comprises homopolymer or the multipolymer of C2-C18 alpha-olefin a) prepared by metallocene catalyst, with the degradation wax of the same relative high chain length manufacture of polyolefins from being produced by metallocene catalyst, with as auxiliary agent, one or more are selected from other following wax: b) PE wax, c) PTFE wax, d) PP wax, e) amide waxe, f) FT paraffin, g) montanin wax, h) natural wax, i) coarse-grain and microcrystalline wax, j) polar polyolefin waxes, or k) Isosorbide Dinitrate, 1) polymeric amide, m) polyolefine, n) PTFE, o) wetting agent, p) silicate.
CN 101469148 discloses a kind of fluorine-containing polymer dispersant for water paint.It is with vinylformic acid hexafluoro butyl ester, vinylformic acid, methyl methacrylate, for polymerization single polymerization monomer, Diisopropyl azodicarboxylate is initiator, and Virahol is solvent, and sodium hydroxide is neutralizing agent, adopt free radical polymerization process, prepare a kind of fluorine-containing polymer dispersant for water paint.The dispersion agent obtained can be suitable for pigment dyestuff and mineral dye, for the surface tension Be very effective reducing water, the mill base obtained after dispersion has that viscosity is low, concentration is high, bright in colour, the characteristic of good stability, and when being diluted with water to lower concentration, mill base also can not assemble, return thick phenomenon.
Existing known technology all has complicated components, and cost is high, and poor compatibility between high molecular polymer, mixes the shortcomings such as uneven, have impact on the result of use in full scale plant.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method strengthening the blended wax of the smooth performance of coating.
In a kettle., squeeze into pure water, stopper, add a certain amount of dispersion agent, initiator, polyethylene wax PE/ hexafluoropropylene trimer/silyl vinyl insatiable hunger silane, is warming up to temperature of reaction, question response terminates, dry closing bag, obtain the polyethylene wax powder of surface grafting, then mix with polytetrafluoroethylene PTFE powder, in pulverizing mill, grinding is broken, obtains product of the present invention.
The present invention introduces the hexafluoropropylene trimer C of a small amount of band double bond on the surface in polyethylene wax pellets
9f
18with Third monomer silyl vinyl insatiable hunger silane as comonomer, carry out surface modification, hydrolyzable silyl vinyl unsaturated silane facile hydrolysis in water, generate vinyl silanol, its vinyl and hexafluoropropylene trimer occur free-radical polymerized, and the product of generation has certain 3 D cross-linked reticulated structure.The consistency of PE/PTFE polymkeric substance can be improved.
The invention provides a kind of preparation method strengthening the blended wax of the smooth performance of coating, realized by following steps:
The preparation of step 1. aqueous phase
By weight, add 1000 parts of water in a kettle., 0.5-10 part emulsifying agent (preferably 2 parts), stirs;
Described emulsifying agent comprises anionic emulsifier, is any one in ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, cetyl benzenesulfonic acid sodium, B-53, Voranol EP 2001 sodium sulfate and paraffin sulfonate, Perfluorocaprylic Acid sylvite or ammonium salt and the pungent sulfonate sodium of perfluor alkane or ammonium salt.And nonionic emulsifier, be any one in Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene sorbitan alcohol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester.Preferred cetyl benzenesulfonic acid sodium.
The preparation of step 2. oil phase
By weight, by 100 parts of PE waxes, 3-10 part (preferably 3 parts) hexafluoropropylene trimer, 1-10 part (preferably 1 part) silyl vinyl insatiable hunger silane monomer mixes, then adds 0.05-1 part peroxide initiator (preferably 0.2 part), stirs;
Step 3. suspension polymerization
Being added in step 1 to be equipped with by the oil-phase solution prepared in step 2 beaker prepares in the reactor of aqueous phase, first slow rear fast carrying out stirs, then from 40-80 DEG C of (preferably 50 DEG C) temperature reaction 10-15h (preferred 10h), reaction terminates rear blowing, washing microballoon is limpid to water, obtains product;
The blended pulverizing of step 4.
Polyethylene wax powder 80-98 part step 3 being obtained surface grafting mixes with 2-20 part PTFE powder, and in pulverizing mill, grinding is broken, obtains product of the present invention.
The preferred Potassium Persulphate of described peroxide initiator, ammonium persulphate.
Described pulverizing mill can be used to preparation/mixed powder or other materials, and described equipment can comprise, without limitation, such as: multiple agitator, comprises revolving stirrer, and multiple pulverizing mill, comprise ball mill, electromagnetic ball grinding machine, disc flour mill, needle mill, high energy impact shredder, stream energy impact mill, reversal nozzle jet mill, fluidized bed jet mill, beater grinder, tumbling mill, mechanic diffusion handler, or impact mill.In described pulverizing mill, at a high speed and high strength can be employed or be applied on dry powder material, to realize high-shear or HI high impact is applied to dry powder material, preferably fluidized bed jet mill.
Described hydrolyzable silyl group vinyl insatiable hunger silane is vinyltrimethoxy silane, vinyl methyl diethoxy silane, vinyl methyl dimethoxysilane, vinyltriethoxysilane and vinyl ethyl diethoxy silane, (methyl) acryloxypropyl Trimethoxy silane, (methyl) acryloxypropyl triethoxyl silane, Y-(methyl) acryloxypropyl organoalkoxysilane, the alkoxysilylalkyl Vinyl Ethers such as trimethoxy-silylpropyl Vinyl Ether and triethoxysilylpropyltetrasulfide Vinyl Ether, any one in trimethoxysilyl vinyl and triethoxysilyl vinyl.
Beneficial effect of the present invention:
Polyethylene wax spheroid, through hexafluoropropylene trimer and hydrolyzable silyl group vinyl insatiable hunger silane modified surface, improves the consistency with tetrafluoroethylene, can contact fully being pulverized and mixed in process, dispersion evenly.Hexafluoropropylene trimer and hydrolyzable silyl group vinyl insatiable hunger polymerizable silane form branched reticulated structure simultaneously, are conducive to the bonding force in blended middle raising and ptfe micropowder; For in water-based or alcohol dissolubility (polar solvent system) coating system, the slipping of coating can be increased substantially, due to can be compatible with acrylic resin, urethane resin, Synolac, epoxy resin, Vinylite, nitrocellulose resin etc., so can be widely used in all kinds water-borne coatings or alcohol soluble paint.
Embodiment
Following examples are only further illustrate the present invention, are not restriction the scope of protection of the invention.
The invention provides a kind of preparation method strengthening the blended wax of the smooth performance of coating, realized by following steps:
Embodiment 1
The preparation of step 1. aqueous phase
By weight, add 1000 parts of water in a kettle., 2 parts of cetyl benzenesulfonic acid sodium, stir.
The preparation of step 2. oil phase
By weight, by 100 parts of PE waxes, 3 parts of hexafluoropropylene trimers, the mixing of 1 part of silyl vinyl insatiable hunger silane monomer, then add 0.2 part of peroxide initiator, stir.
Step 3. suspension polymerization
Being added in step 1 to be equipped with by the oil-phase solution prepared in step 2 beaker prepares in the reactor of aqueous phase, and first slow rear fast carrying out stirs, and then from 50 DEG C of reaction 10h, reaction terminates rear blowing, and washing microballoon is limpid to water, obtains product.
The blended pulverizing of step 4.
The polyethylene wax powder 90 parts of steps 3 being obtained surface grafting mixes with 10 parts of PTFE powders, and weight grinds fragmentation in fluidized bed jet mill, obtains product.Be numbered SX-1.
Embodiment 2
The polyethylene wax powder 80 parts of steps 3 being obtained surface grafting mixes with 20 parts of PTFE powders, and weight grinds fragmentation in fluidized bed jet mill, obtains product.Be numbered SX-2.
Embodiment 3
The polyethylene wax powder 98 parts of steps 3 being obtained surface grafting mixes with 2 parts of PTFE powders, and weight grinds fragmentation in fluidized bed jet mill, obtains product.Be numbered SX-3.
Embodiment 4
In step 2, hydrolyzable silyl group vinyl insatiable hunger silane monomer selects vinyltrimethoxy silane, the other the same as in Example 1.Products obtained therefrom is numbered SX-4.
Embodiment 5
In step 2, hydrolyzable silyl group vinyl insatiable hunger silane monomer selects vinyl methyl diethoxy silane, the other the same as in Example 2.Products obtained therefrom is numbered SX-5.
Embodiment 6
In step 2, hydrolyzable silyl group vinyl insatiable hunger silane monomer selects vinyl methyl dimethoxysilane, the other the same as in Example 3.Products obtained therefrom is numbered SX-6.
Embodiment 7
In step 2, hydrolyzable silyl group vinyl insatiable hunger silane monomer selects (methyl) acryloxypropyl Trimethoxy silane, the other the same as in Example 1.Products obtained therefrom is numbered SX-7.
Embodiment 8
In step 2, hydrolyzable silyl group vinyl insatiable hunger silane monomer selects trimethoxysilyl vinyl, the other the same as in Example 1.Products obtained therefrom is numbered SX-8.
Embodiment 9
In step 2, hydrolyzable silyl group vinyl insatiable hunger silane monomer selects trimethoxy-silylpropyl Vinyl Ether, the other the same as in Example 1.Products obtained therefrom is numbered SX-9.
Embodiment 10
Polyethylene wax powder does not carry out grafting, only carries out the blended of step 4, does not carry out the reaction of step 1-3, the other the same as in Example 1.Products obtained therefrom is numbered SX-10.
Embodiment 11
Micro mist wax is used for the object of delustring and slip to the introducing in nitrocellulose Standard Varnish: by dissolver, then uses framework applicator to be drawn to (60 μm of wet-film thickness) on sheet glass downwards the NC varnish neutralization of 2wt% micro mist wax introducing 98wt% by dispersion.After drying, gloss is measured.
By means of framework applicator, varnish is coated to (in each case at least two plates) on glass (60 μm of wet-film thickness).Thereafter plate is stored 24 hours in an oven at 50 DEG C.In the case, plate is placed, have coating thereon with loading 500g weight.Thereafter, adhesion behavior is evaluated.
Gloss (60 ° of angles) | Slide | Blocking characteristics | |
NC varnish is without wax | 143 | 0.48 | Sizable |
SX-1 | 41 | 0.13 | Nothing |
SX-2 | 23 | 0.11 | Nothing |
SX-3 | 48 | 0.21 | Trace |
SX-4 | 44 | 0.18 | Nothing |
SX-5 | 29 | 0.21 | Nothing |
SX-6 | 59 | 0.23 | Trace |
SX-7 | 18 | 0.11 | Nothing |
SX-8 | 22 | 0.17 | Nothing |
SX-9 | 19 | 0.19 | Nothing |
SX-10 | 108 | 0.31 | Some |
Claims (1)
1. strengthen a preparation method for the blended wax of the smooth performance of coating, it is characterized in that comprising the following steps:
The preparation of step 1. aqueous phase
By weight, add 1000 parts of water in a kettle., 0.5-10 part emulsifying agent, stirs;
Described emulsifying agent comprises anionic emulsifier, is any one in ammonium lauryl sulfate, Sodium dodecylbenzene sulfonate, cetyl benzenesulfonic acid sodium, B-53, Voranol EP 2001 sodium sulfate, paraffin sulfonate, Perfluorocaprylic Acid sylvite, ammonium salt of perfluorooctanoic acid; Or nonionic emulsifier, be any one in Voranol EP 2001, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkylallyl ether, polyoxyethylene sorbitan alcohol fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerol fatty acid ester;
The preparation of step 2. oil phase
By weight, by 100 parts of PE waxes, 3-10 part hexafluoropropylene trimer, 1-10 part silyl vinyl insatiable hunger silane monomer mixes, then adds 0.05-1 part peroxide initiator, stirs;
Step 3. suspension polymerization
By weight, be added in step 1 to be equipped with by the oil-phase solution prepared and prepare in the reactor of aqueous phase in step 2 beaker, first slow rear fast carrying out stirs, then 40-80 DEG C of reaction 10-15h, and reaction terminates rear blowing, and washing microballoon is limpid to water, obtains product;
The blended pulverizing of step 4.
By weight, the polyethylene wax powder of surface grafting 80-98 part step 3 obtained mixes with 2-20 part PTFE powder, and in pulverizing mill, grinding is broken, obtains this product.
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CN104031346B (en) * | 2014-06-20 | 2016-08-17 | 浙江衢州万能达科技有限公司 | A kind of modified polypropylene waxes and the compositions of politef |
CN104031347A (en) * | 2014-06-20 | 2014-09-10 | 浙江衢州万能达科技有限公司 | Modified polyamide wax and polytetrafluoroethylene composition |
CN104109378B (en) * | 2014-06-20 | 2017-08-22 | 浙江衢州万能达科技有限公司 | A kind of composition of nylon 46 and polytetrafluoroethylene (PTFE) |
CN104356313B (en) * | 2014-11-19 | 2017-05-31 | 广东华兹卜新材料科技有限公司 | A kind of aqueous alkide resin and preparation method thereof |
CN106752270A (en) * | 2016-12-30 | 2017-05-31 | 安徽真信涂料有限公司 | A kind of special delustring micro mist wax of valve protective coating |
CN110240824B (en) * | 2018-03-09 | 2021-08-17 | 衢州市中通化工有限公司 | Preparation method of composite wax composition |
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US20110105647A1 (en) * | 2009-10-30 | 2011-05-05 | Rust-Oleum Corporation | Countertop Coating |
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