CN104379610A - Polymer dispersions having multimodal particle size distribution - Google Patents
Polymer dispersions having multimodal particle size distribution Download PDFInfo
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- CN104379610A CN104379610A CN201380033395.9A CN201380033395A CN104379610A CN 104379610 A CN104379610 A CN 104379610A CN 201380033395 A CN201380033395 A CN 201380033395A CN 104379610 A CN104379610 A CN 104379610A
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Abstract
An aqueous polymer dispersion having a multimodal particle size distribution IS produced by emulsion polymerization of a mixture comprising at least one free-radically polymerizable monomer and a stabilizer composition comprising at least two different stabilizers, wherein one of the stabilizers comprises a polyvinyl alcohol having acid groups attached to its polymer backbone.
Description
Technical field
The present invention relates to the polymeric dispersions with multimodal, especially bomodal size distribution.
Background of invention
There is the polymeric dispersions of multimodal, especially bomodal size distribution for multiple application, such as, as the binding agent being used for tackiness agent, paint vehicle and paper coating compositions.Multimodal polymer dispersion provides the advantage surmounting its unimodal counterpart, and described advantage is that they provide higher solid content usually, and this dispersion does not become too thickness or expansion.Such as, adopt unimodal polymerisation thing dispersion, be difficult to realize the solid content of 60 % by weight and there is no viscosity problem, and the stable multimodal dispersion with acceptable viscometric properties easily obtains with the solid content higher than 70 % by weight.This species diversity is important, because such as when binder formulation, higher binding agent solid content causes shorter setting time usually, and the brush of too high viscosity to said preparation is unfavorable.
At present, multimodal polymer dispersion is usually by obtaining to for the manufacture of adding one or more seed polymers (it is the product of easier polymerization process) in the monomer mixture of this polymeric dispersions.In the manufacture of multimodal polymer dispersion, use crystal seed example to be described in U.S. Patent number 6,852, in 81, wherein the letex polymerization of at least one ethylenically unsaturated monomer is carry out under the existence of the polymer beads crystal seed of 200 to 450 nanometers at least one tensio-active agent and diameter.Seed particles accounts for the 5-25 % by weight of monomer and crystal seed gross weight, and by mixing water dissolubility/fat-soluble system initiated polymerization.But this and other method based on crystal seed locks into needs the expensive problem with manufacturing seed polymer inconveniently in advance.
Avoid using a kind of alternative method of the manufacture multimodal polymer dispersion of seed polymer to be disclosed in U.S. Patent Application Publication No. 2005/0043463.The method comprises the letex polymerization of at least two kinds of ethylenically unsaturated monomers, wherein the initial charging of polymerization reactor comprises following mixture: (i) at least two kinds of polyvinyl alcohol, its mass difference at least 1.5 times, and it preferably has the degree of hydrolysis of at least 80% mole separately, (ii) at least one ionic comonomer, it is containing at least one α derived from the group of weak acid, β-monoene ethylenically unsaturated compounds.But, proved that this method is difficult to control and has been found that therefore suitability is limited in practice.
According to the present invention, have been found that now and can manufacture multimodal polymer dispersion by emulsion polymerization in a repeatable fashion and when not using crystal seed, described emulsion polymerization uses the stabiliser system comprising at least two kinds of different stablizers, wherein at least one of this stablizer comprises the sour modified polyvinyl alcohol usually with the degree of hydrolysis being less than or equal to 86% mole, optionally together with standard class polyvinyl alcohol and/or tensio-active agent.
Summary of the invention
On the one hand, the present invention relates to the aqueous polymer dispersion with multimodal size-grade distribution, described polymeric dispersions is obtained by the letex polymerization of the mixture of the monomer and stabiliser composition that comprise at least one free redical polymerization, described stabiliser composition comprises at least two kinds of different stablizers, and wherein one of this stablizer comprises the polyvinyl alcohol with the acid groups being connected to its polymer backbone.
Usually, the polyvinyl alcohol with the acid groups being connected to its polymer backbone has and is less than 86%, as being less than the degree of hydrolysis of 80% mole, and be present in this mixture with the amount of 0.2 to 2.0 % by weight of (one or more) total monomer weight in mixture.Acid groups comprises carboxylic acid and/or sulfonic acid group usually.
Usually, this stabiliser composition comprises the other stablizer of at least one, and it is selected from least one tensio-active agent, at least one protective colloid and composition thereof.Easily, the stabilizer package that described at least one is other does not substantially contain acid groups containing at least one and has the polyvinyl alcohol of the degree of hydrolysis of at least 86% mole.This is called standard class polyvinyl alcohol in this article.
In one embodiment, the other stabilizer package of described at least one is containing standard class polyvinyl alcohol, it can be made up of one or more polyvinyl alcohol, selects (one or more) viscosity of described polyvinyl alcohol to give the viscosity needed for final product.Suitable standard class polyvinyl alcohol has 4.8 to 5.8mPas's by 20 DEG C in 4 % by weight aqueous solution
viscosity, has 27 to 33mPas's with at 20 DEG C in 4 % by weight aqueous solution
the other standard class polyvinyl alcohol of viscosity combines.
Usually, this mixture also comprises Redox initiator systems, and this system comprises the oxygenant with the water solubility being less than or equal to 15 % by weight, as organo-peroxide, and preferred tertiary butylhydroperoxide.
Usually, the monomer of this at least one free redical polymerization comprises the vinyl ester of the carboxylic acid with maximum 20 carbon, preferred vinyl-acetic ester, and comprise in one embodiment based on the vinyl-acetic ester of 50 % by weight to 99 % by weight of total monomer weight in this mixture, the ethene of 1 % by weight to 40 % by weight and 0 % by weight to about additional comonomer of 10 % by weight.
Usually, this mixture is not substantially containing seed polymer particle.
In one embodiment, this polymeric dispersions has the polymer solids content of at least 55 % by weight and comprises the first polymer beads of the mean diameter with 200 to 950 nanometers and be greater than described first polymer beads and have the second polymer beads of the mean diameter of 950 to 20,000 nanometer.
In other side, the present invention relates to the purposes of aqueous polymer dispersion described herein as binding agent in coating composition and tackiness agent.
Summary of drawings
Fig. 1 is the Photomicrograph of the bomodal size distribution of the polymeric dispersions of embodiment 1.
Embodiment describes in detail
Describe aqueous polymer dispersion, this dispersion is had multimodal size-grade distribution and is obtained by the letex polymerization of aqueous mixture, described aqueous mixture comprises the monomer of at least one free redical polymerization and comprises the stabiliser composition of at least two kinds of different stabilizers, and its at least one comprises the polyvinyl alcohol with the acid groups being connected to its polymer backbone.This aqueous polymerization mixture can substantially containing seed polymer particle, this means that this mixture contains and is less than 5 % by weight, is preferably less than 1 % by weight and most preferably not containing the seed polymer particle added.
Monomer
Aqueous polymerization mixture for the manufacture of this polymeric dispersions comprises the principal monomer of one or more free redical polymerizations.Suitable principal monomer is selected from (methyl) vinylformic acid C
1-C
20-alkyl ester, there is the vinyl ester of the carboxylic acid of maximum 20 carbon, there is vinyl-aromatic compounds, olefinically unsaturated nitriles, vinyl halide, the C of maximum 20 carbon
1-C
10the vinyl ether of alcohols, there is the C of 1 or 2 double bond
2-C
8the mixture of aliphatic hydrocarbon and these monomers.
Preferably (methyl) alkyl acrylate is (methyl) vinylformic acid C
1-C
10-alkyl ester, as methyl methacrylate, methyl acrylate, n-butyl acrylate, ethyl propenoate and 2-EHA.Also the mixture of (methyl) alkyl acrylate can be used.
Suitable C
1-C
20the example of the vinyl ester of carboxylic acid comprises vinyl-acetic ester, propionate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, 2 ethyl hexanoic acid vinyl acetate and tertiary ethylene carbonate, and vinyl-acetic ester is particularly preferred.
Suitable vinyl-aromatic compounds comprises Vinyl toluene, α-and p-vinyl toluene, α-butylstyrene, 4-n-butylstyrene, the positive decyl styrene of 4-, and preferred vinylbenzene.
The example of suitable nitrile comprises vinyl cyanide and methacrylonitrile.
Suitable vinyl halide comprises the alefinically unsaturated compounds of chloro-, fluoro-or bromo-replacement, as vinylchlorid and vinylidene chloride.
The example of vinyl ether is vinyl methyl ether and vinyl isobutyl ether, preferred C
1-C
4the vinyl ether of alcohols.
The suitable C with the double bond of an olefinic
2-C
8the example of aliphatic hydrocarbon comprises ethene and propylene, and has the C of the double bond of two olefinics
2-C
8the representative example of aliphatic hydrocarbon comprises divinyl, isoprene and chloroprene.
In one embodiment, this polymeric dispersions is obtained by the mixture of principal monomer of free redical polymerization of ethene of the nytril % by weight to 40 % by weight comprising 50 % by weight to 99 % by weight.
Except principal monomer discussed above, the aqueous polymerization mixture for the manufacture of this polymeric dispersions can comprise based on total monomer weight in this mixture maximum 10 % by weight auxiliary (one or more) comonomer.This type of additional comonomer can be those of the film that promotes better film or coating performance maybe can provide to have desirable properties by composition herein or coating.This type of desirable character can comprise the bounding force of the raising of such as effects on surface or substrate, improvement wet adhesion, better to scrubbing or the tolerance of removal that other type weathering or wearing and tearing cause, and the tolerance to film or coating cracking improved.Containing those of at least one polymerizable double bond and one or more additional functional moiety for the optional comonomer be mixed in the emulsion copolymers of composition herein.Suitable additional comonomer comprises unsaturated organic acid, unsaturated silane, glycidyl comonomer, urea groups comonomer, the comonomer with crosslinkable official energy, cross-linking comonomer and combination thereof.
The suitable additional comonomer comprising unsaturated organic acid comprises ethylenically unsaturated carboxylic acids and acid anhydrides thereof and acid amides, olefinic unsaturated sulfonic acid and the unsaturated phosphonic acids of olefinic.
Such as, this auxiliary monomer can comprise the unsaturated C of olefinic
3-C
8monocarboxylic acid and/or the unsaturated C of olefinic
4-C
8dicarboxylic acid, and its acid anhydrides or acid amides.The unsaturated C of suitable olefinic
3-C
8the example of monocarboxylic acid comprises vinylformic acid, methacrylic acid and β-crotonic acid.The unsaturated C of suitable olefinic
4-C
8the example of dicarboxylic acid comprises toxilic acid, fumaric acid, methylene-succinic acid and citraconic acid.
The example of suitable olefinic unsaturated sulfonic acid comprises those with 2-8 carbon atom, as vinyl sulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid, 2-acryloxy ethyl sulfonic acid and 2-methacryloxy ethyl sulfonic acid, 2-acryloxy-and 3-methacryloxy propanesulfonic acid.The example of the unsaturated phosphonic acids of suitable olefinic also comprises those with 2-8 carbon atom, as vinyl phosphonate and olefinic unsaturated polyester oxyethyl group alkyl ether phosphate.
Except described acid or replace described acid, also likely use its salt, preferably its basic metal or ammonium salt, particularly preferably its sodium salt, such as the sodium salt of vinyl sulfonic acid and 2-acryamidopropanesulfonic acid.
The unsaturated silane that can be used as additional comonomer can meet structural formula I usually:
Wherein R represents at ω-undersaturated organic group of position olefinic, and R
1, R
2and R
3, it is identical or different, represents group-OZ, and Z represents the uncle that hydrogen or optional alkoxy replace or secondary alkyl or carboxyl groups.The unsaturated silane compound of the suitable formula I radicals R preferably wherein in this formula represents the ω-unsaturated chain thiazolinyl of 2 to 10 carbon atoms, particularly 2 to 4 carbon atoms, or those of the ω-esters of unsaturated carboxylic acids formed by the unsaturated carboxylic acid of maximum 4 carbon atoms and the alcohol with Si group of maximum 6 carbon atoms.Suitable radicals R
1, R
2, R
3preferably group-OZ; Z represents the uncle of maximum 10 carbon atoms, preferably maximum 4 carbon atoms and/or secondary alkyl; or the alkyl group of the preferably alkoxy replacement of maximum 3 carbon atoms, or the carboxyl groups of maximum 6 carbon atoms, preferably maximum 3 carbon atoms, or hydrogen.Most preferred unsaturated silane comonomer is vinyl trialkyl oxysilane.
The example of the silane compound of preferred formula I comprises γ-methacryloxypropyl three (2-methoxy ethoxy) silane, vinyl methoxy silane, vinyltriethoxysilane, methylvinyldiethoxysilane alcohol, vinylethoxysilane glycol, allyltriethoxysilane, vinyl tripropoxy silane, vinyl silane triisopropoxide, vinyltributoxysilane, vinyltriacetoxy silane, trimethylammonium ethylene glycol vinyl silane, γ-methacryloxypropyl trimethylammonium ethylene glycol silane, γ-acryloxypropyl triethoxyl silane and γ-methacryloxypropyl trimethoxy silane.
It is epoxy functionalized to give this emulsion copolymers that glycidyl compound also can be used as optional additional comonomer.The example of suitable glycidyl optional comonomer comprises glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether and vinyl glycidyl ether.
The optional comonomer of another type comprises ring-type urea groups comonomer.The film that the known imparting of ring-type urea groups comonomer is formed by the multipolymer containing these comonomers or coating are with the wet adhesion character improved.Ring-type urea-based compound and promote that the purposes of comonomer is disclosed in U.S. Patent number 4,104,220 as wet adhesion; 4,111,877; 4,219,454; 4,319,032; 4,599,417 and 5,208, in 285.The disclosure of all these United States Patent (USP)s is incorporated to herein through this incorporated.
The optional comonomer of another type comprises the comonomer with crosslinkable official energy, as the N-methylol amide of N hydroxymethyl acrylamide, N-methylol methacrylamide, N-methylol allyl carbamate, N-methylol maleimide, N-methylol maleinamic acid and aromatic ethylene yl carboxylic acid, as N-methylol-p-vinyl benzamide.The N-methylol ester of N-ethanol (methyl) acrylamide, N-propyl alcohol (methyl) acrylamide, N-methylol (methyl) acrylamide or N-methylol allyl carbamate or N-alkyl oxide or Mannich base, acrylamidoglycolic acid and/or its salt, acrylamido methoxy menthyl acetate or N-(2,2-dimethoxy-1-hydroxyethyl) acrylamide.
The another kind of comonomer being suitable for preparing emulsion polymer used herein comprises cross-linking monomer, belongs to unsaturated and the comonomer therefore with crosslinked action as having polyenoid.Example comprises Phthalic acid, diallyl ester, diallyl maleate, triallyl cyanurate, tetraallyloxyethane, Vinylstyrene, dimethacrylate fourth-Isosorbide-5-Nitrae-diol ester, TEGDMA, vinyl hexanediacetate, (methyl) allyl acrylate, Vinyl crotonate, methylene-bisacrylamide, hexanediol diacrylate, diacrylate pentaerythritol ester and Viscoat 295.
Stablizer
Except above-mentioned monomer, the aqueous polymerization mixture for the manufacture of this polymeric dispersions comprises two or more different stablizers.At least one of these stablizers comprises the acid groups having and be connected to its polymer backbone, as the polyvinyl alcohol of carboxylic acid and/or sulfonic acid group.Usually, this polyvinyl alcohol containing acid groups has and is less than 86%, as being less than the degree of hydrolysis of 80% mole, and with based on (one or more) total monomer weight in mixture 0.2 to 2.0 % by weight amount be present in this mixture.An example of the commercially available polyvinyl alcohol containing acid groups is Kuraray Poval
tMkL-506, it is the polyvinyl alcohol containing hydroxy-acid group, have the degree of hydrolysis of 74-80 % by mole and 5.2-6.2mPas according to DIN 53015 in 4% aqueous solution at 20 DEG C
viscosity.
Usually, this stabiliser composition comprises one or more other stablizers, and it is selected from protective colloid, anionic and/or nonionic surface active agent and composition thereof.Usually, other (one or more) stablizer with based on (one or more) total monomer weight in described mixture 0.5 to 15 % by weight amount be present in this aqueous polymerization mixture.
One or more the protective colloid being suitable for use as other (one or more) stablizer comprises polyvinyl alcohol, Polyvinylpyrolidone (PVP), methylcellulose gum, hydroxyethyl-and propyl cellulose and Xylo-Mucine, gelatin, casein, starch, Sudan Gum-arabic, hydroxyethylamyle and sodiun alginate.Preferred protective colloid is polyvinyl alcohol.Be suitable for use as the polyvinyl alcohol of other stablizer substantially not containing acid groups, and there is the degree of hydrolysis of at least 86 moles.These standard class polyvinyl alcohol have selects to mate final viscosity needed for this dispersion
viscosity.Easily, these standard classes comprise the mixture of at least two kinds of polyvinyl alcohol to regulate the viscosity of this polymeric dispersions.In one embodiment, the stabilizer package that at least one is other is lower containing having
the polyvinyl alcohol (being such as 4.8 to 5.8mPas at 20 DEG C in 4 % by weight aqueous solution) of viscosity number and have higher
the polyvinyl alcohol (being such as 27 to 33mPas at 20 DEG C in 4 % by weight aqueous solution) of viscosity number.
It is C that suitable aniorfic surfactant comprises chain length
12-C
20the sodium salt of straight-chain aliphatic carboxylic acid, sylvite and ammonium salt, hydroxyl octodecane sodium sulfonate, chain length is C
12-C
20the sodium salt of hydroxy fatty acid, sylvite and ammonium salt, and their sulfonation and/or acetylizad product, alkyl-sulphate, and trolamine salt form, alkyl (C
10-C
20) sulfonate, alkyl (C
10-C
20) arylsulphonate, dimethyl-dialkyl (C
8-C
18) ammonium chloride and their sulfonated products, with chain length C
4-C
16an alkali metal salt of sulfosuccinic ester of aliphatics saturated monohydroxy alcohol, be C with chain length
10-C
12the sulfo-succinic acid 4-ester (disodium salt) of polyglycol ether of aliphatic monobasic alcohol, with the sulfo-succinic acid 4-ester (disodium salt) of polyethylene glycol nonylphenyl ether, sulfo-succinic acid dicyclohexyl ester (sodium salt), lignosulfonic acid and calcium, magnesium, sodium and ammonium salt, resinous acid, the resinous acid of hydrogenation and dehydrogenation and their an alkali metal salt, (myristalated phenyl ether) sodium disulfonate and Sodium Lauryl Sulphate BP/USP, or ethoxylation bay ether sodium sulfate.Also likely use the mixture of ionic emulsifying agent.
Suitable nonionic surface active agent comprises acyl group, alkyl, oil base and alkaryl ethoxylate.Example comprise the list of ethoxylation-, two-and three-alkylphenol (EO degree: 3 to 50, alkyl substituent: C
4to C
12) and ethoxylized fatty alcohol (EO degree: 3 to 80; Alkyl: C
8to C
36), especially C
12-C
14fatty alcohol ethoxylate, C
13-C
15-oxo process alcohol ethoxylate, C
16-C
18fatty alcohol ethoxylate, C
1-10oxo process alcohol ethoxylate, C
1-3the polyethylene oxide ether of oxo process alcohol ethoxylate, the polyethylene oxide polyoxyethylene-sorbitan mono-oleate with ethylene oxide group, the oxyethane with the minimum ethylene oxide content of 10 % by weight and the multipolymer of propylene oxide, the polyethylene oxide ether of oleyl alcohol and nonyl phenol.Specially suitable is the polyethylene oxide ether of fatty alcohol, especially C
12-C
14those of-fatty alcohol.
Polymerization process
Required polymeric dispersions is obtained by the free-radical emulsion polymerization of aqueous polymerization mixture above-mentioned under the existence of one or more radical initiators.
The preferred radical initiator used when being polymerized and starting is Redox initiator systems, it comprises the oxygenant with the water solubility being less than or equal to 15 % by weight, because these oxygenants are found to produce the polymeric dispersions having less polymer beads and reunite, and therefore produce the comparatively low viscosity of final polymeric dispersions, and more spherical particle.The example of this type of oxygenant comprises organo-peroxide, as benzoyl peroxide, lauryl peroxide, tert-butyl peroxide, azo isobutyronitrile and tertbutyl peroxide.Preferred oxygenant is tertbutyl peroxide.An alkali metal salt of oxygen base methyl-sulfinic acid, hydroxyl amine salt, dialkyldithiocarbamacompositions sodium, sodium bisulfite, ammonium bisulfite, V-Brite B, di-isopropyl xanthate disulphide, xitix, tartrate and saccharosonic acid can be used as reductive agent.
Usually, Oxidizing and Reducing Agents is separately before polymerization to load in this reaction mixture to about 0.5 % by weight, more preferably about 0.025 % by weight to about amount of 0.2 % by weight to about 1.0 % by weight, preferably approximately 0.02 % by weight based on about 0.01 % by weight of comonomer gross weight.Usually, in this Redox initiator systems, oxygenant is 10:1 to 1:10 to the mol ratio of reductive agent.
Redox initiator systems used herein optionally can also comprise the catalytic metal salt of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium or cobalt.These catalytic salts can use when having or do not have metal chelating agent with the content of about 0.1 to about 100ppm.Preferred use iron or cobalt.
This polymerization can use any known polymerization reactor system, as intermittent type, ring system, continous way or compact cascade type reactor assembly with one, two or more stage carries out.
Polymerization temperature is typically about 20 DEG C to about 150 DEG C, more preferably about 50 DEG C to about 120 DEG C.In the appropriate case, polymerization is usually at pressure, and preferably approximately 2 carries out to the pressure of about 100 bar to about 150 bar, more preferably about 5.
In the typical polymerization program relating to such as vinyl acetate copolymer dispersion, this vinyl-acetic ester, stabilising system and other comonomer any can be polymerized with under the existence of initiator at the stablizer of specifying in water-bearing media under the pressure of the highest about 120 bar.Aqueous reaction mixture in aggregation container can remain on the pH of about 2 to about 7 by suitable buffer reagent under.
Combine several polymeric composition, namely the mode of stabilising system, comonomer, initiator system component etc. can extensively change.Usually, the water-bearing media containing at least part of stabilising system can be initially in aggregation container and be formed, and other polymeric composition various joins in container subsequently.
Comonomer can continuously, increasingly join in this aggregation container, or joins in this aggregation container as the single charge of the whole amount of comonomer to be used.Comonomer can use with pure monomer form, or can use with pre-mixing emulsion form.When it is present, can be pumped in this aggregation container as the ethene of comonomer and to keep wherein at suitable pressures.
The Redox initiator systems of whole amount is likely included in when being polymerized and starting in the initial charging sending into this reactor.But preferably, a part of initiator is included in initial charging when starting, remainder after initiated polymerization with one or more step or add continuously.In a preferred embodiment, the first Redox initiator systems is used for initial charging when being polymerized and starting, and it comprises the oxygenant with the water solubility being less than or equal to 15 % by weight.This reaction is carried out continuously by the second initiator system subsequently, and described second initiator system can be identical or different with the first Redox initiator systems.This second initiator system can be Redox initiator systems or thermal initiator system.In preferred embodiments, this reaction continues to carry out by different initiator systems, and described different initiator system can be the thermal initiator system comprising the oxygenant with the water solubility being greater than 15 % by weight.The example of this type of oxygenant is hydrogen peroxide, the persulphate of ammonium, sodium or potassium, peroxydisulfate or water-soluble azo amidine.
As mentioned above, this polymerization is carried out when not using seed latex usually.
When polymerization was complete, aftertreatment that is further, preferably chemistry can be carried out subsequently, especially use redox catalyst, such as the combination of above-mentioned Oxidizing and Reducing Agents, to reduce the content of remaining unreacted monomer on product.In addition, residual monomer can be removed in a known way, such as, by physics demonomerization, namely distills removal, especially by vapor distillation, or by using rare gas element stripping.It is one of physics and chemistry method that one especially effectively combines, and residual monomer can be reduced to low-down content (<1000ppm, preferred <100ppm) by it.
The characteristic of polymeric dispersions
The polymeric dispersions obtained by method of the present invention comprises the polymer beads with multimodal size-grade distribution.In one particular embodiment, this polymeric dispersions comprise there are 200 to 950 nanometers, the first polymer beads of the mean diameter that is generally 350 to 800 nanometers and be greater than described first polymer beads and have 950 to 20,000 nanometer, be generally 1, second polymer beads of the mean diameter of 500 to 10,000 nanometer.This first polymer beads exists with the amount of 10 to 90 of polymer solids % by weight usually, and the second polymer beads exists with the amount of 90 to 10 of polymer solids % by weight usually.
Multipolymer aqueous dispersion prepared herein usually have at least 55 % by weight solid content and adopt Brookfield viscometer to record under 20rpm be less than 40,000, be preferably less than the viscosity at 25 DEG C of 5,000mPas.
The purposes of polymeric dispersions
Copolymer dispersion described herein can be formulated in the coating for multiple material, described multiple material such as paper, timber, concrete, metal, glass, pottery, plastics, gypsum, roofing substrate, if bituminous coating, roofing felt, polyurathamc thermal insulation material, polymer roof film and masonry substrate are as brick, clinker brick and concrete layer, comprise external buildings encasing system as EIFS (exterior wall isolation finishing systems).This substrate comprise mopping in advance, prime, scribble undercoat, wearing and tearing or the substrate of weathering.The method comprises makes the surface of substrate contact to form coating with latex coating composition; And this coating dry is with this coating of hardening.Film contained widely in term used herein " coating ", and (such as thickness is the layer of 0.02 to 5 millimeter, paint as made or ink formulations formed) and thicker layer, the thick bead (such as thickness is the bead of 5 to 50 millimeters or larger, as formed in use spackling or material) of such as material.Term " coating " comprises continuously and the layer of patterning further.This aqueous coating composition can be administered on this material by multiple technologies known in the art, and described technology such as curtain coating, sponge, brush, cylinder, mop, air are assisted or Airless spraying, electrostatic spraying, caulking gun, ink-jet etc.In one particular embodiment, this copolymer dispersion can be formulated as inside or outside, timber or exterior wall paint vehicle.
Copolymer dispersion described herein can also be used as binder material, for inorganic materials as glass wool, mineral wool, glass fibre, the textiles be made up of natural fiber (as cellulosic fibre) or synthon and nonwoven material, described synthon include but not limited to one or more of polyester, polyethylene, polypropylene and polyvinyl alcohol, or thickness fiber, or these arbitrary combination.This polymeric dispersions is included in the manufacture of building products as other purposes of binding agent, as chip board, particle board and cardboard, and in the manufacture of isolated material, comprises paper fibre or plastic optical fibre.Another use field is as the binding agent for glass fibre, and it is such as reinforced plastics watt, mould and as isolated material, or as vitrified bond.
The Another Application field of this copolymer dispersion is for preparing tackiness agent, and this tackiness agent is for the porous that bonds, non-porous and half perforated substrate.Specific examples comprises for the substrate of viscose fibre element as the tackiness agent (as described in timber particularly solid wood or the material derived from timber) of timber, and for engineering materials, such as facing, clamping plate, veneer sheet, gummed laminated material, closely knit improved wood, composition board or wood fiber material, as porous, hard or intermediate density wood-fiber board, or scribble the ornamental wood-fiber board of plastics.Other example comprises the tackiness agent of preparation for the paper that bonds, cardboard, corrugated cardboard, foam, cement, leather, textiles and dipping laminating material.Other application is the tackiness agent for building trade, as floor, wall or top ceiling tackiness agent, or is used as household pad pasting or carpet backing tackiness agent.
More specifically describe the present invention now with reference to accompanying drawing and following non-limiting examples, wherein adopt following testing method and polymerization procedure.
The measurement of size-grade distribution
Use the Mastersizer Microplus laser-diffractometer from Malvern to carry out size-grade distribution (PSD) to measure.Use " Polydisperse Mie " model evaluation scattering data that Malvern provides.This model uses according to following hypothesis: the specific refractory power of the polymkeric substance of dispersion is assumed to 1.456.All granularities are with reference to the peak maximum of volume (quality) averaged curve.Granularity provides in units of micron.Particle fraction ratio is by the calculated by peak area of PSD curve.
Except diffractometry, by the differential-interference contrast microscope production microphotograph from Leitz to evaluate the form of particle.
Viscosity measurement
Brookfield RVT viscometer is used under 20rpm, to measure viscosity at the temperature of 23 DEG C.Each measurement is provided to the test main shaft measured for these.
Polymerization process
In order to be polymerized, use circle tube glass container, this container is equipped with anchor stirrer, heating/cooling bath, feed entrance and electronic temperature controller.
Use 37 parts of deionized waters to prepare aqueous phase, wherein following polyethylenes alcohol dissolves 1 hour at 90 DEG C:
Kuraray Poval
tMkL-506-is described above;
S-PVOH-1-have 86.5-89 % by mole of degree of hydrolysis and according to DIN 53015 at 20 DEG C in 4% aqueous solution 4.8-5.8mPas
the standard class polyvinyl alcohol of viscosity; With
S-PVOH-2-have 86.5-89 % by mole of degree of hydrolysis and according to DIN 53015 at 20 DEG C in 4% aqueous solution 27-33mPas
the standard class polyvinyl alcohol of viscosity.
After polyvinyl alcohol dissolution, solution is made to be cooled to room temperature.Before the polymerization, at room temperature add second aqueous solution, described second aqueous solution contains the commercially available nonionic surface active agent (having the mixture of the ethoxylated linear fatty alcohol of the average degree of ethoxylation of 30) of 0.95 part (activity) in 25.3 parts of deionized waters, 0.8 part of formic acid (90%) and the 30ppm in water (activity) ferric chloride hexahydrate (III).The pH of the aqueous phase of combination is about 3.4+/-0.1.
5 parts of the vinyl-acetic ester of total 100 parts are joined in the aqueous phase of this combination, and mixture is heated to 60 DEG C, now add initial initiator solvent according to the information provided in each embodiment.Then this temperature of reaction is made to be increased to 72 DEG C.After 30 minutes, add 95 parts of remaining vinyl-acetic esters gradually through the time periods of 4 hours, and to feed in raw material the superoxol of the 0.375 active part be added in abreast in 7 parts of deionized waters with vinyl-acetic ester through 4.25 hours.At the end of monomer adds, temperature of reaction be increased to 78 DEG C and keep 1 hour at this value.Make this batch of material cool subsequently, and process so that demonomerization at 60 DEG C with tertbutyl peroxide and sodium sulfoxylate formaldehyde.Finally, with sodium hydroxide solution, emulsion is adjusted to pH 4 to obtain the product that solid content is 57+/-1%.
Embodiment 1
In order to prepare this aqueous phase, use 1.1 parts of S-PVOH-1,0.47 part of S-PVOH-2 and 0.95 part of Poval KL-506.Initial initiator solution is made up of part Sodium Pyrosulfite of 0.05 in 0.8 part of water and 0.05 active part tertbutyl peroxide (70%) in 1.2 parts of water.
The viscosity of gained emulsion is 2,520mPas (main shaft 3) under the solid content of 57.0%.
This PSD shows the different particle fraction of two kinds of the maximum value with dw=0.58 micron (40%) and dw=3.60 micron (60%) place.The Photomicrograph display of this PSD in FIG.Find that the second particle fraction is by granulometric composition that is roughly spherical, that do not reunite to a great extent.
Embodiment 2
Repeat embodiment 1, but initial initiator solution is made up of part Sodium Pyrosulfite of 0.025 in 0.8 part of water and 0.025 active part tertbutyl peroxide (70%) in 1.2 parts of water.
The viscosity of gained emulsion is 3,225mPas (main shaft 3) under the solid content of 57.2%.
This PSD shows the different particle fraction of two kinds of the maximum value with dw=0.58 micron (35%) and dw=6.63 micron (65%) place.Find that the second particle fraction is by granulometric composition that is roughly spherical, that do not reunite to a great extent.
Embodiment 3
Repeat embodiment 1, but initial initiator solution is made up of part Sodium Pyrosulfite of 0.08 in 0.8 part of water and 0.075 active part tertbutyl peroxide (70%) in 1.2 parts of water.
The viscosity of gained emulsion is 3,100mPas (main shaft 3) under the solid content of 57.2%.
This PSD shows the different particle fraction of two kinds of the maximum value with dw=0.31 micron (48%) and dw=3.09 micron (48%) place.The 3rd less mark has the maximum value of dw=16.57 (4%).Find that the second particle fraction is by granulometric composition that is roughly spherical, that do not reunite to a great extent.
Embodiment 4
Repeat embodiment 1, but initial initiator solution is made up of part Sodium Pyrosulfite of 0.08 in 0.8 part of water and 0.054 active part hydrogen peroxide (35%) in 1.2 parts of water.
The viscosity of gained emulsion is 12,300mPas (main shaft 5) under the solid content of 57.0%.Product expression goes out the flowing of swollen property.
This PSD shows two kinds of particle fraction of the maximum value with dw=0.27 micron (25%) and dw=1.95 micron (75%) place.This second particle fraction that shows microphotograph contain signal portion aspheric, reunite particle.
Comparative example 1
Repeat embodiment 1, but use 2.05 parts of S-PVOH-1 and 0.47 part S-PVOH-2, and do not use Poval KL-506.
The viscosity of gained emulsion is 10,800mPas (main shaft 5) under the solid content of 56.1%.
This PSD only shows a kind of particle fraction of the maximum value with dw=1.44 micron place.
Claims (31)
1. there is the aqueous polymer dispersion of multimodal size-grade distribution, described polymeric dispersions is obtained by the letex polymerization of the mixture of the monomer and stabiliser composition that comprise at least one free redical polymerization, described stabiliser composition comprises at least two kinds of different stablizers, and wherein one of this stablizer comprises the polyvinyl alcohol with the acid groups being connected to its polymer backbone.
2. the polymeric dispersions of claim 1, the wherein said polyvinyl alcohol with the acid groups being connected to its polymer backbone has and is less than 86%, is preferably less than or equal to the degree of hydrolysis of 80% mole.
3. the polymeric dispersions of claim 1 or claim 2, the wherein said polyvinyl alcohol with the acid groups being connected to its polymer backbone with based on one or more total monomer weights in described mixture 0.2 to 2.0 % by weight amount be present in described mixture.
4. the polymeric dispersions of aforementioned any one of claim, wherein this stabiliser composition comprises the other stablizer of at least one, and it is selected from least one tensio-active agent, at least one protective colloid and composition thereof.
5. the polymeric dispersions of claim 4, the stabilizer package that wherein this at least one is other does not contain the polyvinyl alcohol of acid groups substantially containing at least one.
6. the polymeric dispersions of claim 4 or claim 5, the stabilizer package that wherein this at least one is other has the polyvinyl alcohol of the degree of hydrolysis of at least 86% mole containing at least one.
7. the polymeric dispersions of claim 5 or claim 6, the stabilizer package that wherein this at least one is other is containing at least two kinds of polyvinyl alcohol, and described polyvinyl alcohol has different separately at 20 DEG C in 4 % by weight aqueous solution
viscosity number.
8. the polymeric dispersions of claim 7, has 4.8 to 5.8mPas's at the stabilizer package that wherein this at least one is other is contained in 20 DEG C in 4 % by weight aqueous solution
the polyvinyl alcohol of viscosity number, and in 4 % by weight aqueous solution, have 27 to 33mPas's at 20 DEG C
the other polyvinyl alcohol of viscosity number.
9. the polymeric dispersions of any one of claim 4 to 8, the stablizer that wherein this at least one is other also comprises aniorfic surfactant.
10. the polymeric dispersions of any one of claim 4 to 9, the stablizer that wherein this at least one is other with based on one or more total monomer weights in described mixture 0.5 to 15 % by weight amount be present in described mixture.
The polymeric dispersions of 11. aforementioned any one of claim, wherein this mixture is also containing Redox initiator systems, and described Redox initiator systems comprises the oxygenant with the water solubility being less than or equal to 15 % by weight.
The polymeric dispersions of 12. claims 12, wherein said oxidant package contains organo-peroxide, preferred tertiary butylhydroperoxide.
The polymeric dispersions of 13. claims 11 or claim 12, wherein said Redox initiator systems with based on one or more total monomer weights in described mixture 0.01 to 0.25 % by weight amount be present in described mixture.
The polymeric dispersions of 14. aforementioned any one of claim, the monomer of wherein said at least one free redical polymerization is selected from (methyl) vinylformic acid C
1-C
20-alkyl ester, there is the vinyl ester of the carboxylic acid of maximum 20 carbon, there is vinyl-aromatic compounds, olefinically unsaturated nitriles, vinyl halide, the C of maximum 20 carbon
1-C
10the vinyl ether of alcohols, there is the C of 1 or 2 double bond
2-C
8the mixture of aliphatic hydrocarbon or these monomers.
The polymeric dispersions of 15. aforementioned any one of claim, the monomer of wherein said at least one free redical polymerization comprises the vinyl ester of the carboxylic acid with maximum 20 carbon.
The polymeric dispersions of 16. claims 15, wherein this vinyl ester comprises vinyl-acetic ester.
The polymeric dispersions of 17. claims 15 or claim 16, the monomer of wherein said at least one free redical polymerization comprises ethene further.
The polymeric dispersions of 18. aforementioned any one of claim, wherein mixture comprises based on the vinyl-acetic ester of 50 % by weight to 99 % by weight of total monomer weight in this mixture, the ethene of 1 % by weight to 40 % by weight and 0 % by weight to about additional comonomer of 10 % by weight.
The polymeric dispersions of 19. aforementioned any one of claim, and comprise the first polymer beads of the mean diameter with 200 to 950 nanometers and be greater than described first polymer beads and there is the second polymer beads of the mean diameter of 950 to 20,000 nanometer.
The polymeric dispersions of 20. aforementioned any one of claim, and there is the polymer solids content of at least 55 % by weight.
21. manufacture the method with the aqueous polymer dispersion of multimodal size-grade distribution, the method comprises the aqueous mixture that letex polymerization comprises the monomer of at least one free redical polymerization, at least one radical initiator and stabiliser composition, described stabiliser composition comprises at least two kinds of different stablizers, and wherein one of this stablizer comprises the polyvinyl alcohol with the acid groups being connected to its polymer backbone.
The method of 22. claims 21, the described polyvinyl alcohol wherein with the acid groups being connected to its polymer backbone has the degree of hydrolysis being less than 86%, being preferably less than or equal to 80% mole.
The method of 23. claims 21 or claim 22, the described polyvinyl alcohol wherein with the acid groups being connected to its polymer backbone with based on one or more total monomer weights in described mixture 0.2 to 2.0 % by weight amount be present in described mixture.
The method of 24. any one of claim 21 to 23, wherein this stabiliser composition comprises the other stablizer of at least one, and it is selected from least one tensio-active agent, at least one protective colloid and composition thereof.
The method of 25. claims 24, the stabilizer package that wherein this at least one is other does not contain the polyvinyl alcohol of acid groups substantially containing at least one.
The method of 26. any one of claim 21 to 25, wherein said aqueous mixture comprises Redox initiator systems, and this Redox initiator systems comprises the oxygenant with the water solubility being less than or equal to 15 % by weight.
The method of 27. claims 26, and comprise further:
A () provides initial charging in polyreaction region, this initially charging comprise water, at least partially described Redox initiator systems, the monomer of a part of at least one free redical polymerization and described stabiliser composition; With
B (), after initiated polymerization, adds the monomer of remaining at least one free redical polymerization and other initiator system in polyreaction region.
The method of 28. any one of claim 21 to 27, wherein said aqueous mixture is not substantially containing seed polymer particle.
The aqueous polymer dispersion of 29. any one of claim 1 to 20 is as the purposes of binding agent.
The aqueous polymer dispersion purposes in the coating composition of 30. any one of claim 1 to 20.
The purposes of aqueous polymer dispersion in tackiness agent of 31. any one of claim 1 to 20.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201261695640P | 2012-08-31 | 2012-08-31 | |
| US61/695,640 | 2012-08-31 | ||
| PCT/IB2013/002486 WO2014033545A1 (en) | 2012-08-31 | 2013-08-28 | Polymer dispersions having multimodal particle size distribution |
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| CN104379610A true CN104379610A (en) | 2015-02-25 |
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| CN201380033395.9A Pending CN104379610A (en) | 2012-08-31 | 2013-08-28 | Polymer dispersions having multimodal particle size distribution |
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| EP (1) | EP2890723A1 (en) |
| CN (1) | CN104379610A (en) |
| WO (1) | WO2014033545A1 (en) |
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| CN113429841B (en) * | 2021-06-22 | 2022-06-21 | 广东华润涂料有限公司 | Water-based coating composition for forming wall heat-insulating coating and wall reflection heat-insulating coating system containing heat-insulating coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6093766A (en) * | 1997-09-11 | 2000-07-25 | Clariant Gmbh | Process for preparing polyvinyl alcohol stabilized solvent- and plastifier-free polyvinyl ester dispersions |
| CN1594376A (en) * | 2003-08-13 | 2005-03-16 | 赛拉尼斯乳胶有限公司 | Preparation of multimodal polymer dispersions using polymeric stabilizers, and use thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US685281A (en) | 1900-01-29 | 1901-10-29 | Biddle Arthurs | Glass-machine. |
| US4111877A (en) | 1976-07-29 | 1978-09-05 | Air Products & Chemicals, Inc. | Allyl esters of n-alkyl-omega-(alkyleneureido) amic acids and their synthesis and use in aqueous emulsion polymer systems |
| US4104220A (en) | 1976-07-29 | 1978-08-01 | Air Products & Chemicals, Inc. | Alkenyl 1-(2-Aminoethyl) alkyleneureido succinamates, their synthesis, and use in aqueous emulsion polymer systems |
| US4219454A (en) | 1978-09-05 | 1980-08-26 | Air Products And Chemicals, Inc. | Vinyl acetate copolymer emulsions for paint |
| US4319032A (en) | 1980-06-06 | 1982-03-09 | Alcolac Inc. | Derivatives of aminoalkyl alkylene ureas |
| US4599417A (en) | 1984-11-05 | 1986-07-08 | Desoto, Inc. | Ureido-functional adhesion promoting amide monomers |
| US5208285A (en) | 1989-02-17 | 1993-05-04 | National Starch And Chemical Investment Holding Corporation | Vinyl acetate polymer with wet adhesion |
| JP4390992B2 (en) * | 2000-08-30 | 2009-12-24 | 日本合成化学工業株式会社 | Dispersing aid for suspension polymerization of vinyl compounds |
-
2013
- 2013-08-28 CN CN201380033395.9A patent/CN104379610A/en active Pending
- 2013-08-28 EP EP13801717.3A patent/EP2890723A1/en not_active Withdrawn
- 2013-08-28 WO PCT/IB2013/002486 patent/WO2014033545A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6093766A (en) * | 1997-09-11 | 2000-07-25 | Clariant Gmbh | Process for preparing polyvinyl alcohol stabilized solvent- and plastifier-free polyvinyl ester dispersions |
| CN1594376A (en) * | 2003-08-13 | 2005-03-16 | 赛拉尼斯乳胶有限公司 | Preparation of multimodal polymer dispersions using polymeric stabilizers, and use thereof |
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| WO2014033545A1 (en) | 2014-03-06 |
| EP2890723A1 (en) | 2015-07-08 |
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