WO2014055494A1 - Alkali-soluble resin (asr) shell epoxy rdp exhibiting improved shelf stability - Google Patents
Alkali-soluble resin (asr) shell epoxy rdp exhibiting improved shelf stability Download PDFInfo
- Publication number
- WO2014055494A1 WO2014055494A1 PCT/US2013/062833 US2013062833W WO2014055494A1 WO 2014055494 A1 WO2014055494 A1 WO 2014055494A1 US 2013062833 W US2013062833 W US 2013062833W WO 2014055494 A1 WO2014055494 A1 WO 2014055494A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- epoxy resin
- dispersion
- polymer
- epoxy
- alkali soluble
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
Definitions
- the present invention relates to multilayer polymer particle redispersible polymer powders (RDP) comprising an epoxy resin layer and an outer layer of an alkali soluble polymer and having excellent shelf stability. More particularly, it relates to multilayer polymer particles comprising a major proportion of epoxy resins, a methacrylic acid containing alkali soluble polymer outer layer and a hydrophobic chain transfer agent or a high glass transition temperature colloidal stabilizer, as well as to methods of making the same.
- RDP multilayer polymer particle redispersible polymer powders
- RDPs prepared from emulsion polymers have been widely used in cement or hydraulic binder construction applications, e.g. cement containing tile adhesives, SLFC (self level flooring compounds) to improve mechanical properties of the cement or binder.
- RDPs comprising crosslinkable polymers have been used to improve chemical and stain resistance and reduce water permeation.
- epoxy resins are used in the repair of concrete and cement mortars to impart toughness, reduced water permeability, rapid setting, and chemical and stain resistance.
- a liquid epoxy dispersion and hardener may be admixed with the cement(s) as a dry powder in a three-part system; however, complicated use requirements e.g. order of mixing, short pot-life, and equipment contamination have limited use of the products to use only by professional contractors.
- An RDP epoxy would be easier to use than the three-part system.
- One possible approach would be to incorporate epoxy functional groups into emulsion polymers, however, this method results only in a low epoxy content; in addition, the epoxy functional addition polymerizable monomers, such as, glycidyl methacrylate (GMA) cost far more than conventional epoxy resins.
- GMA glycidyl methacrylate
- an epoxy RDP has been made by methods comprising mechanically dispersing Type 1 or liquid epoxy resin or from epoxy resin blends having a glass transition temperature (Tg) of ⁇ 40 °C, including PVOH as a primary dispersant in combination with a co-dispersant, to prepare aqueous epoxy resin dispersions, followed by using the epoxy dispersion to seed emulsion polymerization of acrylic monomers to introduce a high Tg acrylic shell onto the epoxy particles. Finally, the resultant dispersion was spray dried into epoxy powders that show 1 00 % redispersibility in aqueous alkali (NaOH).
- Tg glass transition temperature
- the resulting epoxy resin can be cured at high pH condition without amine hardener because the acrylic shell can be dissolved to trigger the curing reaction of epoxy resin in an alkaline environment. Nevertheless, in most end use applications, a 3 to 6 month shelf stability is critical. However, the prior epoxy RDP may lack sufficient shelf stability to enable utility to the end user.
- the present inventors have sought to solve the problem of achieving full redispersibility of an epoxy RDP powder in a cement environment.
- redispersible polymer powders comprise multilayer polymer particles of from 50 to 90 wt.%, preferably, from 60 to 85 wt.%, based on total polymer solids, of epoxy resin compositions, preferably a blend of two epoxy resins, having a calculated glass transition temperature (Tg) of from 0 to 40 °C, preferably from 5 to 35 °C, or, more preferably, from 10 to 35 °C, and from 10 to 50 wt.%, or, preferably, 25 to 50 wt.% based on epoxy solids, of an alkali soluble polymer shell around the epoxy resin, which polymer shell is the copolymerized product of from 10 to 50 wt.%, or, preferably, from 20 to 50 wt.% of methacrylic acid or its anhydride, based on total weight of monomers copolymerized to form the alkali soluble polymer shell, and the remainder of one or more
- the alkali soluble polymer shell comprises in copolymerized form from 0.1 to 10 wt.%, or, preferably, from 1 to 5 wt.% total, based on the total weight of ethylenically unsaturated monomers copolymerized to form the polymer shell, of one or more hydrophobic chain transfer agent, such as, for example, n-dodecyl mercaptan
- the redispersible polymer powder comprises from 3 to 25 wt.%, based on the total weight of epoxy resin, alkali soluble polymer and colloidal stabilizer solids, or, preferably, from 5 wt.% to 15 wt.% of one or a mixture of colloidal stabilizers having a Tg of 90 or more, or, more preferably, 120 or more, or, more preferably 140
- the colloidal stabilizer is chosen from polyvinyl alcohol or polyvinyl pyrrolidinone) or a copolymer thereof, or a mixture thereof; more preferably, the colloidal stabilizer is a polyvinyl pyrrolidinone) or its copolymer.
- the alkali soluble polymer that comprises the polymer shell of the multilayer polymer particle has a calculated Tg of 60°C or higher, preferably from 80 to 120 °C.
- the alkali soluble polymer of the multilayer polymer in any of items 1 , 2 or 3 has a weight average molecular weight of from 5 to 500 kg/mol, preferably, from 5 to 50 kg/mol.
- the present invention further comprises compositions comprising cement or hydraulic binder and the redispersible polymer powder composition as claimed in any one of items 1 to 4, above.
- the present invention comprises methods for making the water dispersible epoxy multilayer polymer powders of any of items 1 , 2, 3, 4, or 5 above, comprising, mechanically dispersing an epoxy resin in an aqueous medium to form an initial aqueous epoxy resin dispersion; charging the initial aqueous epoxy resin dispersion into a reaction vessel; providing in the reaction vessel an
- ethylenically unsaturated monomer mixture such as a monomer emulsion, comprising (i) from 10 to 50 wt.%, or, preferably, from 20 to 50 wt.% of methacrylic acid or its anhydride, based on total weight of ethylenically unsaturated monomers copolymerized to form the polymer shell, and (ii) the remainder of one or more copolymerizable ethylenically unsaturated monomers (iii) from 0 to 10 wt.%, based on the total weight of ethylenically unsaturated monomers copolymerized to form the polymer shell, or, preferably, from 1 to 5 wt.% of one or more chain transfer agent, and one or more addition polymerization catalyst, such as, for example, a free radical initiator or redox catalyst, and copolymerizing the monomer mixture in the presence of the initial aqueous epoxy resin dispersion to form an aqueous multi
- the unsaturated monomer mixture is selected so that the resulting alkali soluble polymer has a calculated glass transition temperature (calculated Tg) of 60 °C or higher, preferably, from 80 °C to 120 °C.
- the ethylenically unsaturated monomer mixture is added by gradual addition to the reaction vessel containing the initial aqueous epoxy resin dispersion; however, some or all of the monomer mixture can be combined with the aqueous medium comprising epoxy resin or with the initial aqueous epoxy resin dispersion at any time prior to or during copolymerizing.
- filler(s) includes, in the alternative, one filler and two or more fillers.
- aqueous means water or a mixture of water and up to 50 wt.%, preferably, up to 10 wt.%, or, more preferably, 5 wt.% or less of water miscible solvent(s), based on the total weight of water and the one or more solvent.
- the particle size distribution was measured using a CoulterTM LS 13-320 laser diffraction particle size analyzer (Beckman Coulter, Brea, CA) per manufacturer's recommended procedures via laser scattering.
- the scattering light from particles through laser scattering and polarization intensity differential scattering is collected as a function of angle, and subsequently converted to a particle size distribution.
- the phrase "average particle size” means volume-average particle size as determined by laser diffraction according to ISO 13320-2009 using a Coulter Counter particle size and count analyzers.
- the term "based on polymer solids" means the epoxy resin composition and the alkali soluble polymer when referring to the multilayer polymer particle.
- the term "calculated Tg" refers to the glass transition temperature of a (co)polymer as determined by the Fox equation, using temperature values in degrees Kelvin:
- Tg ⁇ poiymer is the Tg of the copolymer
- wf is the weight-fraction of monomer "i” in the (co)polymer
- Tg is the glass transition temperature of a homopolymer made from monomer "i” and the summation is over all monomers "i”.
- epoxy glass transition temperature (Tg) or "epoxy resin calculated glass transition temperature (calculated Tg)” for a blend of epoxy resins is determined by the epoxy composition, and is predicted by the Fox equation where "w” is the wt.% of solid epoxy resin in the blend (Tg is calculated in degrees Kelvin):
- glass transition temperature or “Tg” refers to a calculated Tg.
- the concept of a "glass transition temperature (Tg) of a mixture of colloidal stabilizers” is a weighted average of each colloidal stabilizer in the mixture; thus, for example, a mixture of 50 wt.%, the weights based on the total weight of colloidal stabilizers, of a colloidal stabilizer having a Tg of 80 °C and 50 wt.% of a colloidal stabilizer having a Tg of 160 would give a mixture of colloidal stabilizers having a Tg of 120 .
- molecular weight refers to the weight average molecular weight as measured by gel permeation
- multilayer polymer particle refers to polymer particles having two or more layers associated with one another including by chemical grafting, encapsulation, and physical adsorption (physiadsorption).
- polymer refers, in the alternative, to a polymer made from one or more different monomer, such as a copolymer, a terpolymer, a tetrapolymer, a pentapolymer etc., and may be any of a random, block, graft, sequential or gradient polymer.
- polymer includes copolymers and polymers within its scope.
- total RDP weight refers to polymer, colloidal stabilizer, and any additive solids in the RDP powder.
- the present invention enables improved shelf life for epoxy powder particles for use in cement.
- the epoxy resin in the multilayer polymer particle of the present invention is present at a very high concentration of 50 wt.% or higher, preferably, 65 wt.% or greater, still more preferably, 75 wt.% or greater and can be present at a concentration of 85 wt.% or greater and up to 90 wt.% or less based on total epoxy RDP particle weight. Shelf stability for such epoxy powder compositions is not expected where the glass transition temperature (Tg) of the epoxy resin ranges from 0 to 40 °C. Lower Tg epoxy resins are desirable because they diffuse more quickly as a binder and because they are film forming even room temperature or below.
- Tg glass transition temperature
- the shelf life of the redispersible polymer powder of the present invention can be extended to greater than 3 months shelf life in the case of a low Tg or liquid epoxy resin, even greater than 6 months.
- blends of solid and liquid epoxy resins can be used to fine tune the glass transition temperature of the epoxy to the desired or preferred range, thereby maximizing film formation, storage stability and redispersibility.
- Suitable epoxy resins for use in the present invention include aliphatic, araliphatic and aromatic epoxy compounds which are polyglycidyl ethers of a polyol, such as a hydroxyl-functional oligomer.
- Such epoxy resins have at least 2 glycidyl groups and are the reaction products of a polyol, such as a glycol, or a hydroxyl-functional oligomer, with an epihalohydrin, such as epichlorohydrin.
- Such preparations are well known in the art (see for example US-A-5,1 1 8,729, columns 4-7 and "Epoxy resins" by Pham, H.Q. and Marks, M.J. in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag, Weinheim, 2005).
- suitable polyols include polyhydric phenols and polyhydric alcohols.
- monomeric polyols are resorcinol, catechol, hydroquinone, bisphenol, bisphenol A, bisphenol AP (1 , 1 -bis(4-hydroxylphenyl)-1 - phenyl ethane), bisphenol F, bisphenol K, tetrabromobisphenol A, tetra- methylbiphenol, tetramethyl-tetrabromobiphenol, tetramethyl tribromobiphenol, tetrachlorobisphenol A, 4,4'- sulfonyldiphenol, 4,4- oxydiphenol, 4,4'- dihydroxybenzophenone, 9,9'- bis(4-hydroxyphenyl)fluorine, 4,4'-dihydroxybiphenyl, and 4, 4'-dihydroxy-a-methylstilbene.
- hydroxyl-functional oligomers include phenol-formaldehyde novolak resins, alkyl substituted phenol-formaldehyde resins, phenol-hydroxybenzaldehyde resins, cresol-hydroxybenzaldehyde resins, dicyclopentadiene-phenol resins, and dicyclopentadiene-substituted phenol resins.
- Suitable polyols for making the epoxy reasin can be substituted, if desired, with one or more non-interfering substituents, such as halogen atoms, ether radicals, lower alkyls and the like.
- An oligomeric or polymeric compound such as a phenol- formaldehyde novolac may be used as the polyhydroxy compound.
- the polyol used to prepare the epoxy resin is an aromatic dihydroxy compound, such as bisphenol A and/or bisphenol F.
- epoxy resins for use in the present invention include the diglycidyl ether of bisphenol A, such as the be condensates of bisphenol A and epichlorohydrin or methylepichlorohydrin; the diglycidyl ether of bisphenol F that generally contain the condensates of a mixture of bisglycidyloxyphenylmethanes ("Bisphenol F-type resins"); a mixed diglycidyl ether of bisphenol A and F; the diglycidyl ether of a phenol-formaldehyde novolak; and modified epoxy resins such as epoxy resins, e.g.
- epoxy resins modified with an epoxy functional surfactants, such as, for example, epoxy functional nonionic or epoxy functional anionic surfactant, and/or poly(alkylene glycol) epoxide, typically poly(propylene glycol) epoxide or poly(ethylene glycol) epoxide.
- the epoxy resin can be and desirably is free of sulfur.
- One suitable epoxy resin is a linear, non-cross-linked polymer of bisphenol A and epichlorohydrin having terminal epoxide groups.
- a specific example of a suitable epoxy resin which may be employed herein is D.E.R. 664U, a solid epoxy resin of medium molecular weight, which is the solid reaction product of epichlorohydrin and bisphenol A, having a softening point of 100 to ⁇ ⁇ 0°C (The Dow Chemical Company, Midland, Ml).
- mechanically dispersing epoxy resin into an aqueous medium to form the initial epoxy resin dispersion may comprise providing the epoxy resin in a softened state, such as, for example, by heating it to a temperature higher than its Tg, if needed, and combining it with an aqueous phase under shear.
- the shear serves to break the epoxy resin into particles as it disperses those particles into the aqueous phase.
- an aqueous phase and an organic phase are combined with shearing, such as by feeding them through a high shear mixer that disperses one phase into the other. This may form a high internal phase emulsion.
- High internal phase emulsions generally have a greater than 74 volume % internal phase dispersed within a continuous phase where volume percent is relative to the total emulsion volume.
- the epoxy resin and aqueous phase can be fed into a high shear mixer to produce a dispersion. If a high internal phase dispersion of epoxy resin in aqueous phase is produced, it can be diluted down with additional aqueous phase if desired to, for example, reduce viscosity of the dispersion.
- a particularly desirable benefit of mechanical dispersion is that it can produce dispersions with dispersed particles having a highly uniform particle size (narrow particle size distribution) that can be two ⁇ or less, or, preferably, one ⁇ or less.
- the epoxy resin particles in the initial epoxy resin dispersion desirably have a particle size of 5 ⁇ or less, preferably, 2 ⁇ or less, or, more preferably 1 ⁇ or less, or, yet more preferably 750 nm or less. Generally, smaller particles require higher shear to form.
- Suitable shearing methods include extrusion and melt kneading in a known manner including, for example, in a kneader, a Banbury mixer, single-screw extruder, or a multi-screw extruder.
- a preferred melt-kneading machine is, for example, a multi screw extruder having two or more screws, to which a kneading block can be added at any position of the screws.
- an extruder may be provided with a first material-supplying inlet, such as for the epoxy resin, a second material-supplying inlet, such as for and any dispersant, and, further, if desired, third and forth material-supplying inlets in this order from the upstream to the downstream along the flow direction of a material to be kneaded. Further, a vacuum vent may be added.
- Preferred shearing devices include a multi screw extruder having two or more screws for continuous processing, and rotor stator mixer and pressurized high shear device for batch processing.
- Mechanically dispersing the epoxy resin into the aqueous phase can comprise a batch, semi-continuous or continuous process.
- Batch processes include preparing the epoxy resin dispersion in a single container by adding the aqueous phase and epoxy resin together while mixing. It is common to add the epoxy resin to the aqueous phase while mixing, however both the aqueous phase and epoxy resin can be added together to the vessel while mixing or the epoxy resin can be added first and the aqueous phase added while mixing. It is also possible to add the epoxy resin and aqueous phase together without mixing and, once the two components have been combined, then mix them together to form a dispersion.
- a continuous shearing method comprises mixing both aqueous phase and epoxy resin in a continuous stream to produce the initial epoxy resin dispersion, such as in a multi-screw extruder.
- Suitable epoxy resins having a Tg of 40 °C or lower, especially those with a Tg of 35 °C or lower, 30 °C or lower are more readily softened for forming the initial epoxy resin dispersion without requiring further heating or softening of any other kind. This avoids the cost and complexity of applying heat to soften the epoxy resin.
- such epoxy resins can be blends of low and higher molecular weight epoxy resins as well as epoxy resins that are liquid at ambient temperature.
- the aqueous phase is preferably water.
- the epoxy resin can contain plasticizers to help them flow, for example, fugitive plasticizer, non-fugitive plasticizer, a combination of fugitive and non-fugitive plasticizer.
- plasticizers for example, fugitive plasticizer, non-fugitive plasticizer, a combination of fugitive and non-fugitive plasticizer.
- the epoxy resin is free of plasticizer.
- the initial epoxy resin dispersion is formed in the absence of any organic solvent which means that it contains less than 1 000 ppm, or preferably, less than 500 ppm of such a solvent.
- Organic solvents exclude fugitive plasticizers and monomers.
- a dispersing agent may be used to prepare the initial epoxy resin dispersion.
- the dispersing agent can be added to the epoxy resin or directly to the aqueous phase prior to dispersing the epoxy resin, or added to the initial epoxy dispersion as the epoxy resin and aqueous phase are being mixed.
- Suitable dispersing agents for stabilizing the initial epoxy resin dispersion include any colloidal stabilizers taught above with regard to the epoxy RDP, such as, for example, polyvinyl alcohol (PVOH).
- Suitable amounts of dispersing agent in the initial epoxy resin dispersion are 1 5 wt.% or less, preferably, from 4 to 10 wt.% based on total epoxy resin weight.
- the alkali soluble polymer shell around the epoxy resin in the multilayer polymer particle RDP of the present invention may prevent the epoxy resin from diffusing from one particle to another, thereby precluding irreversible agglomeration of particles.
- the multilayer polymer particles can contain a low concentration of shell (and, hence, much higher concentration of epoxy resin).
- the alkali soluble polymer shell also releases the epoxy when the epoxy is desired for use as a binder in a cementitious (or other alkaline) formulation because the alkali soluble shell dissolves upon dispersing the RDP particles of the present invention into an aqueous alkali composition.
- the monomers used to make the alkali soluble polymer are selected so as to form an alkali soluble polymer shell having a calculated glass transition temperature (Tg) of 60°C or higher, preferably 75 or higher, still more preferably 90 or higher, even more preferably 100 or higher, or up to 120 °C. It is desirable for the alkali soluble polymer shell to have a higher Tg to resist irreversible agglomeration of particles during isolation of the epoxy RDP particles, particularly in the presence of components such as dispersing agents that might plasticize the alkali soluble polymer shell.
- Tg glass transition temperature
- the alkali soluble polymer shell comprises the copolymerization product of 5 or more wt.% and up to 50 wt.%, preferably 10 wt.% or more, or, more preferably, 15 wt.% or more, and yet more preferably, 20 wt.% or more of monomers selected from methacrylic acid and anhydride monomers, based on the total weight of monomers polymerized to form the alkali soluble polymer shell, with the remainder one or more copolymerizable ethylenically unsaturated monomers.
- concentrations of carboxylic acid or anhydride monomer range further below about 50 wt.%, the alkali soluble polymer will comprise the reaction product of some hydrophilic
- hydrophilic monomers may comprise hydroxyalkyl esters of a carboxylic acid or (meth)acrylamide. Useful amounts of such hydrophilic monomers may range from zero to 30 wt.% based on the total weight of monomers polymerized to form the alkali soluble polymer shell, or, preferably from 5 to 20 wt.%.
- the remaining copolymerizable ethylenically unsaturated monomers used to form the alkali soluble polymer shell are desirably chosen from alkyl methacrylates, such as, for example, 2-ethylhexyl methacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and fatty alkyl methacrylates, such as lauryl methacrylate.
- Such monomers may comprise 30 to 95 wt.% of monomers, based on the total weight of monomers polymerized to form the alkali soluble polymer shell.
- the copolymerizable ethylenically unsaturated monomers can further comprise up to 25 wt.%, preferably up to 10 wt.%, based on the total weight of monomers used to make the copolymer, of one or more other nonionic monomers, such as vinyl aromatic monomers like styrene or alkyl substituted styrene; and alkyl acrylates may be copolymerized in to the alkali soluble polymer.
- the nonionic monomers comprise hard hydrophobic monomers, such as vinyl aromatic to improve the shell stability.
- all of the ethylenically unsaturated monomer mixture can be combined with the already formed initial aqueous epoxy resin dispersion before or during their polymerization.
- all of the ethylenically unsaturated monomer mixture is added by gradual addition, e.g. metering it, into the reaction vessel containing the initial aqueous epoxy resin dispersion.
- Such monomers, including the carboxylic acid or anhydride monomers may be added during or prior to addition of an addition polymerization catalyst, preferably in a separate feed.
- Suitable chain transfer agents for use in the polymerization methods of the present invention may include any mercaptans.
- the preferred hydrophobic chain transfer agents or making the redispersible polymer powders of the present invention may be C 6 to Ci 8 alkyl, cycloalkyl or alkylaryl group containing thiols or mercaptans, or, preferably, C 8 or higher alkyl, cycloalkyl or alkylaryl group containing thiols or mercaptans, such as, for example, n-dodecyl mercaptan a fatty thiol. More preferably, such C 8 or higher alkyl, cycloalkyl or alkylaryl group containing chain transfer agents having a single sulfur atom.
- the chain transfer agent can be mixed into a monomer emulsion or can be separately added into the epoxy dispersion and the monomer emulsion is fed separately.
- the chain transfer agents can be charged or metered by gradual addition, preferably, added in one shot.
- the ethylenically unsaturated monomer mixture of the alkali soluble polymer shell of the present invention is polymerized by conventional emulsion polymerization.
- Addition polymerization catalysts are fed into the reaction vessel before, during or after addition of the unsaturated monomers, with stirring and, optionally, with heating.
- Suitable catalysts include thermal and/or redox triggered free radical initiators, preferably that are water soluble.
- thermally triggered initiators include peracid salts, such as alkali metal persulfate salts, such as, for example, sodium persulfate; or ammonium persulfate.
- Suitable redox initiators include combinations of oxidizing agents (such as persulfate salt and organic peroxides) and reducing agents (such as sodium formaldehyde sulfoxylate) and a redox catalyst such an iron (II) sulfate.
- the conditions that result in free radical polymerization to make the alkali soluble polymer shell depend on the type of free radical initiator added and are known to the ordinary skilled artisan. Depending on the initiation temperature of the initiator and the ambient temperature of the mixture, thermally triggered initiators may require heating the monomer mixture.
- the amount of free radical initiator is generally 0.01 wt.% or more, preferably 0.1 wt.% or more while at the same time is generally 2 wt.% or less, based on the total weight of ethylenically unsaturated monomers used to make the alkali soluble polymer shell.
- the total polymerization time may range from 1 to 6 hours, preferably up to 4 hours and may include one monomer feed, or two or more monomer feeds which can be sequential feeds, overlapping in time or simultaneous to one another.
- the resulting dispersion comprising multilayer polymer particles having an alkali soluble polymer shell is a dispersion of the present invention.
- the weight-average molecular weight of the alkali soluble polymer shell may range from 2,500 grams per mole (g/mol) to 500,000 g/mol or less, or 250,000 g/mol or less, or, preferably, 5,000 g/mol or more, or, preferably, 50,000 g/mol or less.
- An excessively high molecular weight can causes a viscosity buildup at and alkaline pH, thereby leading to handling problems.
- the alkali soluble polymer shell comprises copolymers of methacrylic acid and methyl methacrylate.
- concentration of methacrylic acid and methyl methacrylate is the concentration of methacrylic acid.
- copolymerized methacrylic acid 10 wt.% or more, preferably 1 5 wt.% or more preferably 20 wt.% or more while at the same time desirably being 50 wt.% or less.
- the balance of the copolymer is copolymerized methyl methacrylate.
- the alkali soluble shell is primarily located around the surface of the epoxy RDP particles and as such efficiently protects the epoxy resin within the particles.
- the concentration of alkali soluble shell can be equal to or less than the concentration of epoxy resin and still preclude irreversible agglomeration of the epoxy RDP particles.
- the concentration of the alkali soluble shell may range less than 50 wt.%, , and at the same time should range 1 0 wt.% or more, or, preferably, 15 wt.% or more, or, still more preferably 20 wt.% or more relative to the total weight of the epoxy resins in the multilayer polymer particle RDP.
- Removing the aqueous phase and isolate the resulting RDP particles can be done any number of ways including freeze drying or spray drying (atomization), or a combination of both, preferably by spray drying.
- freeze drying or spray drying atomization
- spray drying atomization
- Such removing of the aqueous phase is conventional in the art and is as described, for example, in US
- drying the aqueous admixture comprises spray drying.
- Spray drying can be carried out in customary spray drying plants, with atomization being carried out by means of single- fluid, two- fluid or multifluid nozzles or a rotary disc atomizer.
- air, nitrogen or nitrogen enriched air may be employed as the drying gas, the inlet temperature of the drying gas generally not exceeding 200 °C, preferably from 1 10°C to 1 80 , more preferably from 140 °C to 170 °C.
- the outlet temperature may generally be from 30 to 100 °C, preferably from 50 ⁇ ⁇ to 80 °C, depending on the plant, the Tg of the resin and the desired degree of drying.
- the viscosity of the feed to be spray-dried may be adjusted via the solids content so that a value of less than 1 000 mPas (Brookfield viscosity at 20 rpm and 23 ), preferably less than 250 mPas, is obtained.
- the solids content of the admixture to be spray-dried may generally be from 25% to 60% by weight, preferably from 35% to 50% by weight, based on the total weight of the dispersion.
- Anti-caking agent can be added in any manner including mixing in with the dispersion prior to spray drying or mixing with the dispersion while spray drying by, for example, blowing into to a chamber with the dispersion.
- a colloidal stabilizer or a dispersing agent can be added while feeding and polymerizing the ethylenically unsaturated monomer mixture, while removing the aqueous phase from the multilayer polymer particle RDP particles, or both.
- Colloidal stabilizer added when spray drying should facilitate redispersion of the RDP particles when the RDP particles are added to an aqueous medium. It is particularly desirable to add a colloidal stabilizer to the RDP particles during the spray drying process.
- a colloidal stabilizer is present in the RDP of the present invention and may include one or more of cellulosic thickeners, such as hydroxypropyl cellulose, or hydroxyethyl methyl cellulose; polymers of methyl vinyl ether, water soluble copolymers of ethylenically unsaturated carboxylic acids, such as (meth) acrylic acid or its salts, or preferably a polyvinyl pyrrolidinone), including its copolymers, a polyvinyl alcohol (PVOH), a partially hydrolyzed PVOH, or any mixture of colloidal stabilizers containing at least 25 wt.% of polyvinyl pyrrolidinone), based on the total weight of colloidal stabilizers.
- cellulosic thickeners such as hydroxypropyl cellulose, or hydroxyethyl methyl cellulose
- Surfactants can be useful as an additive in the RDP of the present invention to facilitate redispersing of the epoxy particles in an aqueous solution.
- Suitable surfactants such as, for example, anionic, cationic and/or nonionic surfactants may be used in place of at least part of a colloidal stabilizer.
- Surfactants containing ethylene oxide groups range in amounts of less than 5 wt.%, based on the total weight of colloidal stabilizer plus surfactant because such surfactants can interfere with the protective nature of the alkali soluble shell.
- Suitable amounts of the colloidal stabilizer may range 2 wt.% or more, or, preferably, 5 wt.% or more, or, still more preferably, 7 wt.% or more, and can be present at a concentration of 10 wt.% or more, or up to 25 wt.% or less, or, preferably 20 wt.% or less, or, more preferably, 1 5 wt.% or less based on the total RDP polymer weight including the colloidal stabilizer, and any other additives.
- the desired concentration of colloidal stabilizers added during the spray drying process may range from 5 to 15 wt.% relative to total epoxy resin and alkali soluble polymer solids.
- the epoxy RDP of the present invention desirably includes one or more anti- caking agent to improve powder flowability.
- Anti-caking agents may be used when spray drying the polymer aqueous dispersion to isolate the multilayer polymer particles. Accordingly, the anti-caking agent can be added in any manner including mixing in with the dispersion prior to spray drying or mixing with the dispersion while spray drying by, for example, blowing into to a chamber with the dispersion.
- Suitable anti-caking agents include mineral filler such as calcium carbonate, kaolin, barium sulphate, titanium oxide, talc, hydrated alumina, bentonite, calcium sulphoaluminate and silica.
- the RDP can be free of anti-caking agent, but generally contains 0.5 wt.% or more, or, preferably 2 wt.% or more, or, more preferably 5 wt.% or more relative to total RDP weight.
- the molar ratio of M 2+ ions to the carboxyl acid groups in the alkali soluble polymer shell is from 10 to 200 mole %, preferably, from 25 to 100 mole %.
- the multilayer polymer particle water redispersible powder (RDP) of the present invention can be dispersed in an aqueous medium to form a dispersion of fine particles, which is also a dispersion of the present invention.
- an aqueous medium preferably water
- the pH of the dispersion formed may fall in a pH range of 9-13 where the base comprises a cationic species, such as ammonia or NaOH or a base. Cement provides sufficient alkalinity for redispersion of the RDP of the present invention.
- the multilayer polymer particle RDP of the present invention is particularly useful for formulating with cementitious components to form epoxy modified cement.
- the RDP can be dry blended with cement to make a dry mix to which water can be added in use.
- Dispersions of multilayer polymer particles that fall within the scope of the present invention include the dispersion of multilayer polymer particles comprising an alkali soluble shell prior to removing the aqueous phase that is formed during the method of the present invention.
- EXAMPLES The present invention will be illustrated below by the following non- limiting examples.
- Example 1 Batch Dispersion.
- the reactor was sealed and heated to 100 °C, and after reaching the temperature the mixture was stirred for 10 minutes to allow sufficient mixing of the epoxy resin and PVOH solution together at ⁇ 1 830 rpm.
- water was added using a HPLC pump at the rate of 1 .4 ml/min for 20 min. The water addition rate was increased to 14 mL/min for 4 min while the heating mantle was removed and the Parr reactor was cooled by air and water.
- the reactor was cooled down to 50 °C in water bath while stirring. The resultant dispersion was collected by filtration through a 190 ⁇ filter and had a 40-45% solids content.
- Epoxy Dispersions were prepared using a KWP (KRUPP WERNER & PFLEIDERER Ramsey, NJ) ZSK25 extruder (60 L/D rotating at 450 rpm) according to the following procedure with the formulation components shown in Table 1 , below.
- the solid epoxy resin (D.E.R. 669E (9-type solid bisphenol-A epoxy resin,
- IA initial aqueous stream
- melt polymer blend was then emulsified in the presence of water in the extruder.
- a co-dispersant E-SPERSE 100 PEO (14) di- and tristyrenated Phenol ammonium sulfate (Ethox Chemicals, LLC Greenville, SC)
- E-SPERSE 100 PEO (14) di- and tristyrenated Phenol ammonium sulfate (Ethox Chemicals, LLC Greenville, SC)
- the emulsion phase was then conveyed forward to the dilution and cooling zone of the extruder where additional water was added to form the aqueous dispersions having solid level levels of less than 60 weight percent.
- the properties of each of the dispersion components were measured, and are reported in Table 1 .
- the initial water and liquid co- dispersants like E-SPERSE 100, and dilution water were all supplied by ISCO dual syringe pumps (500 ml).
- the barrel temperature of the extruder was set to 100 °C. After the dispersion exited the extruder, it was further cooled and filtered via a 200 ⁇ mesh size filter.
- Particle size was measured on Beckman Coulter LS 1 3 320 Laser Light Diffraction Particle Size analyzer(Beckman Coulter, Inc. Brea, CA), using an epoxy resin model predetermined by the instrument software. Solid content analysis was performed on an Ohaus MB45 moisture analyzer (Ohaus Corporation, Parsippany, NJ).
- Dispersion F was made from dispersion D in Table 1 , above, in the same way as Dispersion E (Procedure A, above), except 1 3.2 grams of methyl methacrylate, 3.30 grams of methacrylic acid, 2.5 g of a 5.0 wt% aqueous solution of tert-butyl peroxide, and, separately, 2.5 g of 5.0 wt.% aqueous solution of sodium
- hydroxymethanesulfinate total 0.75 wt.% of each component relative to acrylic monomer weight
- Dispersion G was made from dispersion B in Table 1 , above, in the same way as Dispersion E (Procedure A, above), except 8.39 grams of methyl methacrylate, 2.10 grams of methacrylic acid, 2.5 g of a 3.1 5 wt.% aqueous solution of tert-butyl peroxide, and, separately, 2.5 g of 3.15 wt.% aqueous solution of sodium
- hydroxymethanesulfinate total 0.75 wt.% of each component relative to acrylic monomer weight
- Dispersion H was made from dispersion B in Table 1 , above, in the same way as Dispersion E (Procedure A, above), except 8.39 grams of methyl methacrylate, 2.10 grams of methacrylic acid, 0.105 gram of n-dodecyl mercaptan, 2.5 g of a 3.15 wt% aqueous solution of tert-butyl peroxide, and, separately, 2.5 g of 3.15 wt% aqueous solution of sodium hydroxymethanesulfinate (total 0.75 wt.% of each component relative to acrylic monomer weight) were used.
- Dispersion I was made from dispersion B in Table 1 , above, in the same way as Dispersion E (Procedure A, above), except 8.39 grams of methyl methacrylate, 2.10 grams of methacrylic acid, 0.210 gram of n-dodecyl mercaptan, 2.5 g of a 3.15 wt% aqueous solution of tert-butyl peroxide, and, separately, 2.5 g of 3.15 wt% aqueous solution of sodium hydroxymethanesulfinate (total 0.75 wt.% of each component relative to acrylic monomer weight) were used.
- Dispersion J was made from dispersion B in Table 1 , above, in the same way as Dispersion E (Procedure A, above), except 8.39 grams of methyl methacrylate, 2.10 grams of methacrylic acid, 0.210 gram of methyl 3-mercaptopropionate, 2.5 g of a 3.15 wt% aqueous solution of tert-butyl peroxide, and, separately, 2.5 g of 3.1 5 wt% aqueous solution of sodium hydroxymethanesulfinate (total 0.75 wt.% of each component relative to acrylic monomer weight) were used.
- Dispersion N was made from dispersion C in Table 1 , above, in the same way as Dispersion E (Procedure A, above), except 1 6.78 grams of methyl methacrylate, 4.20 grams of methacrylic acid, 2.5 g of a 6.3 wt% aqueous solution of tert-butyl peroxide, and, separately, 2.5 g of 6.3 wt% aqueous solution of sodium
- hydroxymethanesulfinate total 0.75 wt.% of each component relative to acrylic monomer weight
- Dispersion P was made from dispersion C in Table 1 , above, in the same way as Dispersion E (Procedure A, above), except 9.06 grams of methyl methacrylate, 3.52 grams of methacrylic acid, 0.503 gram of n-dodecyl mercaptan, 2.5 g of a 3.77 wt% aqueous solution of tert-butyl peroxide, and, separately, 2.5 g of 3.77 wt% aqueous solution of sodium hydroxymethanesulfinate (total 0.75 wt.% of each component relative to acrylic monomer weight) were used.
- Procedure B Using hybrid dispersion L in Table 2, below, as an example.
- 200 g of an aqueous epoxy dispersion (dispersion C in Table 1 , above) and 25 g of Dl water were added to a 500 ml_, 4-neck round bottom flask equipped with a mechanical stirrer, thermocouple, condenser and a stainless steel dip tube, stirred at 125 rpms, and warmed.
- the monomer emulsion (ME) indicated in Table 1 A was prepared by adding the ingredient listed below by mixing for 10 minutes with a stir bar.
- Dispersion K was made from dispersion C in Table 1 , above, in the same way as Dispersion L (Procedure B and Table 1 A, above), except using 66.7 wt.% of each the feeds listed in Table 1 A, above, based on the weight of each respective feed in Table 1 A.
- Dispersion M was made from dispersion C in Table 1 , above, in the same way as Dispersion L (Procedure B and Table 1 A, above), except using 166.7 wt.% of each of the feeds listed in Table 1 A, above, based on the weight of each respective feed in Table 1 A.
- Dispersion O was made from dispersion C in Table 1 , above, in the same way as Dispersion L (Procedure B and Table 1 A, above), except using 32.52 grams of MMA and 5.74 grams of MAA.
- Dispersion Q was made from dispersion C in Table 1 , above, in the same way as Dispersion L (Procedure B and Table 1 A, above), except replacing MAA with acrylic acid (AA).
- Dispersion R was made in the same way as Dispersion L (Procedure B and Table 1 A, above), except replacing the seed epoxy dispersion with 5.1 1 grams of MowiolTM 488 and 2.75 grams of E-Sperse 100 (60% active).
- Dispersion S was made in the same way as Dispersion L (Procedure B and Table 1 A, above), except replacing the seed epoxy dispersion with 5.1 1 grams of MowiolTM 488 and 2.75 grams of E-Sperse 1 00 (60% active) and without adding nDDM.
- Alkali Soluble Resin contains 78.5 wt.% PMMA and 20 wt.% PMAA, and 1 .5 wt.% ALMA, based on the total weight of monomers used to make the resin ; nDDm is n-dodecyl mercaptan.
- nDDM n-dodecyl mercaptan
- MMP Methyl 3-mercaptopropionate
- phr per hundred weight parts resin solids
- K, L, M and O there is 1 .5 wt .% ALMA in ASR shell, based on the total weight of monomers used to make the resin.
- Example 4 Spray Drying to make RDPs
- a two-fluid nozzle atomizer was equipped on a MOBILE MINORTM 2000 Model H spray dryer (GEA Niro, Denmark). The nitrogen pressure to nozzle atomizer was fixed at 1 bar with 50% flow which is equivalent to 6.0 kg/hour of air flow.
- a glass jar was placed under the cyclone with the valve on the bottom of the cyclone open.
- Each of the aqueous dispersions from Table 2, above, (35-40 wt.% solid content) was pumped into the nozzle atomizer by an emulsion feed pump (from Cole-Parmar Instrument Company, Vernon Hills, IL). Where indicated in Table 3, below, additional polymer stabilizer like PVOH and polyvinylpyrrolidone (PVP) was mixed into the dispersion prior to spray drying.
- the multilayer polymer particle dispersion was atomized by high air pressure at the nozzle atomizer and dried inside the chamber, and the dry powder was collected in the glass jar attached on the cyclone.
- the resulting redispersible polymer powder has a mean particle size of 1 0 to 30 ⁇ .
- the test results for each redispersible polymer powder are listed in Table 3, below.
- Shelf Life Defined herein as the time when epoxy RDP remains >50 % redispersed (as defined below) at room temperature.
- An acceptable shelf life is at least 1 month and, preferably, 3 months or longer.
- Redispersibility The redispersibility of the RDP powders was evaluated by comparison of the particle size of the powder re-dispersed in water with the particle size of the original dispersion.
- the dry powder was dispersed into deionized water at 1 % solid and vortexed for 30 seconds twice, and 2-3 drops of 1 M NaOH solution was added to tune the pH of the redispersion to >1 0.
- the particle size of the redispersion was then measured by a Coulter LS 13 320 Laser Light Diffraction Particle Size analyzer.
- the redispersibility is defined as the volume percentage of particles below 1 ⁇ in the redispersion. For instance, if the redispersion shows 20 % particle below 1 ⁇ by volume, the redispersibility of this powder is 20 %.
- Example 1 6 See also Comparative Example 1 1 .
- the same polymer with 8.4 wt.% copolymerized methacrylic acid (28% acid in alkali soluble polymer present at 30 wt.% of the RDP) in Example 1 6 has approximately 4 months shelf life.
- copolymerized methacrylic acid 50% alkali soluble polymer with 20% copolymerized methacrylic acid
- PVP colloidal stabilizer in Example 14
- low Tg epoxy multilayer polymer particle RDP gave 2 months shelf life even without a hydrophobic chain transfer agent.
- Example 9 With a slightly higher Tg (22 °C) soft epoxy resin, as shown in Table 3, above, including the hydrophobic chain transfer agent even at 2 wt.% in the multilayer polymer particle RDP of the present invention greatly increases shelf life, as shown in Example 9 with 2% copolymerized nDDM and 6 months shelf life.
- Example 8 including some poly(vinylpyrrolidinone) colloidal stabilizer in the same polymer RDP increased shelf life to 12 months.
- a small amount of poly(vinylpyrrolidinone) colloidal stabilizer in the same polymer RDP increased shelf life to 2 months from less than one week with any other colloidal stabilizer in Comparative Examples 3, 5 and 6.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Epoxy Resins (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/432,098 US9758667B2 (en) | 2012-10-03 | 2013-10-01 | Alkali-soluble resin (ASR) shell epoxy RDP exhibiting improved shelf stability |
CN201380050138.6A CN104822734B (en) | 2012-10-03 | 2013-10-01 | Represent alkali soluble resins (ASR) the shell epoxy resin RDP of improved shelf stability |
EP13776669.7A EP2885343A1 (en) | 2012-10-03 | 2013-10-01 | Alkali-soluble resin (asr) shell epoxy rdp exhibiting improved shelf stability |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261709309P | 2012-10-03 | 2012-10-03 | |
US61/709,309 | 2012-10-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014055494A1 true WO2014055494A1 (en) | 2014-04-10 |
Family
ID=49354953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2013/062833 WO2014055494A1 (en) | 2012-10-03 | 2013-10-01 | Alkali-soluble resin (asr) shell epoxy rdp exhibiting improved shelf stability |
Country Status (4)
Country | Link |
---|---|
US (1) | US9758667B2 (en) |
EP (1) | EP2885343A1 (en) |
CN (1) | CN104822734B (en) |
WO (1) | WO2014055494A1 (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4123403A (en) | 1977-06-27 | 1978-10-31 | The Dow Chemical Company | Continuous process for preparing aqueous polymer microsuspensions |
US5118729A (en) | 1990-01-10 | 1992-06-02 | The Dow Chemical Company | Modified polyoxyethylene epoxy resin amphiphiles and stable aqueous epoxy dispersions thereof |
JPH07166031A (en) * | 1993-12-10 | 1995-06-27 | Mitsui Toatsu Chem Inc | One-pack curable aqueous emulsion composition |
US20010024644A1 (en) * | 2000-02-01 | 2001-09-27 | Klaus Kohlhammer | Crosslinkable polymer composition |
US20110160350A1 (en) | 2009-12-30 | 2011-06-30 | Roger Bergman | Redispersible polymer powders stabilized with protective colloid compositions |
WO2012177448A1 (en) * | 2011-06-23 | 2012-12-27 | Dow Global Technologies Llc | Water redispersible epoxy polymer powder and method for making the same |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4916171A (en) | 1984-07-25 | 1990-04-10 | Rohm And Haas Company | Polymers comprising alkali-insoluble core/alkali-soluble shell and copositions thereof |
CN1035059C (en) | 1984-07-25 | 1997-06-04 | 罗姆和哈斯公司 | Polymers and compositions comprised of alkali-insoluble core and alkali-soluble shell |
US4876313A (en) | 1986-08-29 | 1989-10-24 | Rohm And Haas Company | Grafted core-shell polymer compositions using polyfunctional compounds |
US5981627A (en) | 1989-08-02 | 1999-11-09 | National Starch And Chemical Investment Holding Corporation | Epoxy modified core-shell latices |
US5403894A (en) | 1991-07-11 | 1995-04-04 | Rohm And Haas Company | A redispersible core-shell polymer powder |
US5252704A (en) * | 1992-06-05 | 1993-10-12 | Air Products And Chemicals, Inc. | Redispersible polymer powders using polyvinyl pyrrolidone as a dispersing aid |
EP0654454A1 (en) | 1993-11-22 | 1995-05-24 | Rohm And Haas Company | A core-shell polymer powder |
DE19502435A1 (en) | 1995-01-26 | 1996-08-01 | Elotex Ag | Chemical composition containing a) a copolymer based on styrene and / or alkyl (meth) acrylate and at least one further comonomer and b) a protective colloid, its aqueous polymer dispersion, process for its preparation and its use |
US5563187A (en) | 1995-02-16 | 1996-10-08 | Rohm And Haas Company | Grafted polymer composition |
FR2735134B1 (en) | 1995-06-09 | 1997-07-11 | Rhone Poulenc Chimie | WATER REDISPERSABLE POWDERS OF FILM-FORMING POLYMERS WITH CORE / BARK STRUCTURE |
US5942563A (en) | 1997-07-18 | 1999-08-24 | The Glidden Company | Aqueous dispersed acrylic-epoxy, branched epoxy protective coatings |
US6433061B1 (en) | 2000-10-24 | 2002-08-13 | Noveon Ip Holdings Corp. | Rheology modifying copolymer composition |
DE10253043A1 (en) * | 2002-11-14 | 2004-06-03 | Wacker Polymer Systems Gmbh & Co. Kg | Process for the recovery of residual ethylene in the production of vinyl ester-ethylene copolymers |
US6869982B2 (en) | 2002-11-27 | 2005-03-22 | Basell Poliolefine Italia S.P.A. | Irradiated, oxidized olefin polymer coupling agents |
DE10317882A1 (en) | 2003-04-17 | 2004-11-11 | Wacker Polymer Systems Gmbh & Co. Kg | Redispersion powder composition with setting accelerating effect |
WO2006094528A1 (en) | 2005-03-10 | 2006-09-14 | Wacker Polymer Systems Gmbh & Co. Kg | Non-efflorescing cementitious mortar compositions |
US8674039B2 (en) | 2009-02-02 | 2014-03-18 | Wacker Chemie Ag | Crosslinkable polymer powder composition which is redispersible in water |
DE102009000537A1 (en) | 2009-02-02 | 2010-08-05 | Wacker Chemie Ag | Crosslinkable, water-redispersible polymer powder composition |
FR2943665B1 (en) | 2009-03-27 | 2011-05-06 | Kerneos | SELF-LEVELING DENSE MORTAR WITH IMPROVED WEAR RESISTANCE |
DE102010041292A1 (en) | 2010-09-23 | 2012-03-29 | Wacker Chemie Ag | Flexible, waterproof roof coatings |
WO2013134208A1 (en) | 2012-03-09 | 2013-09-12 | Dow Global Technologies Llc | Carboxyl group containing acrylic rdp and dry mix cement formulations containing them |
BR112015013008B1 (en) | 2012-12-18 | 2021-09-14 | Dow Global Technologies Llc | WATER REDISPERSIBLE POLYMER POWDER, NON-CEMENTARY DRY MIXTURE FORMULATION, NON-CEMENTARY OUTER FINISH COMPOSITION, AND METHOD FOR FORMING A COATING ON A SURFACE WITH AN OUTER FINISH COMPOSITION |
-
2013
- 2013-10-01 US US14/432,098 patent/US9758667B2/en not_active Expired - Fee Related
- 2013-10-01 WO PCT/US2013/062833 patent/WO2014055494A1/en active Application Filing
- 2013-10-01 EP EP13776669.7A patent/EP2885343A1/en not_active Withdrawn
- 2013-10-01 CN CN201380050138.6A patent/CN104822734B/en not_active Expired - Fee Related
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4123403A (en) | 1977-06-27 | 1978-10-31 | The Dow Chemical Company | Continuous process for preparing aqueous polymer microsuspensions |
US5118729A (en) | 1990-01-10 | 1992-06-02 | The Dow Chemical Company | Modified polyoxyethylene epoxy resin amphiphiles and stable aqueous epoxy dispersions thereof |
JPH07166031A (en) * | 1993-12-10 | 1995-06-27 | Mitsui Toatsu Chem Inc | One-pack curable aqueous emulsion composition |
US20010024644A1 (en) * | 2000-02-01 | 2001-09-27 | Klaus Kohlhammer | Crosslinkable polymer composition |
US20110160350A1 (en) | 2009-12-30 | 2011-06-30 | Roger Bergman | Redispersible polymer powders stabilized with protective colloid compositions |
WO2012177448A1 (en) * | 2011-06-23 | 2012-12-27 | Dow Global Technologies Llc | Water redispersible epoxy polymer powder and method for making the same |
Non-Patent Citations (1)
Title |
---|
PHAM, H.Q.; MARKS, M.J.: "Ullmann's Encyclopedia of Industrial Chemistry", 2005, WILEY-VCH VERLAG |
Also Published As
Publication number | Publication date |
---|---|
CN104822734B (en) | 2017-06-20 |
CN104822734A (en) | 2015-08-05 |
US20160017140A1 (en) | 2016-01-21 |
EP2885343A1 (en) | 2015-06-24 |
US9758667B2 (en) | 2017-09-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9200155B2 (en) | Water redispersible epoxy polymer powder and method for making the same | |
EP2166028B1 (en) | Aqueous synthetic-resin emulsion for cement mortar admixture, re-emulsifiable powder for cement mortar admixture from aqueous synthetic-resin emulsion, and cement mortar admixture comprising the same | |
CA2778034C (en) | Redispersible epoxy powder by interfacial reaction | |
CA3032277C (en) | Ambient self-crosslinkable latex | |
WO2007060960A1 (en) | Re-emulsifiable resin powder, aqueous emulsion and adhesive composition using same | |
EP2537817B1 (en) | Redispersible epoxy powder | |
CN1107087C (en) | Aqueous emulsion composition | |
JP4541186B2 (en) | Liquid epoxy resin composition | |
US9574053B2 (en) | Alkali-soluble resin (ASR) shell epoxy RDP with divalent metal ions exhibiting improved powder redispersibility | |
EP2837608B1 (en) | Epoxy-multilayer polymer rdp geopolymer compositions and methods of making and using the same | |
JP5692626B2 (en) | Polymer emulsifier and polyolefin resin emulsion using the same | |
US9758667B2 (en) | Alkali-soluble resin (ASR) shell epoxy RDP exhibiting improved shelf stability | |
US10570272B2 (en) | Epoxy resin imbibed polymer particles | |
JP6874154B2 (en) | Vinyl chloride resin latex composition and its manufacturing method | |
CN106397656B (en) | A kind of preparation and application of water-based hydrophobic modified polymethyl hydrochlorate dispersant | |
JP3174199B2 (en) | Low viscosity epoxy resin composition and method for producing the same | |
JP5692625B2 (en) | Polymer emulsifier and polyolefin resin emulsion using the same | |
JP2005298646A (en) | Quick-drying aqueous resin composition, quick-drying coating resin using this and coating using this |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13776669 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013776669 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14432098 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112015006289 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 112015006289 Country of ref document: BR Kind code of ref document: A2 Effective date: 20150320 |