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WO2013188975A1 - Dispersion aqueuse à base de paraffine - Google Patents

Dispersion aqueuse à base de paraffine Download PDF

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Publication number
WO2013188975A1
WO2013188975A1 PCT/CA2013/050471 CA2013050471W WO2013188975A1 WO 2013188975 A1 WO2013188975 A1 WO 2013188975A1 CA 2013050471 W CA2013050471 W CA 2013050471W WO 2013188975 A1 WO2013188975 A1 WO 2013188975A1
Authority
WO
WIPO (PCT)
Prior art keywords
wax
gypsum
parts
vinyl acetate
ethylene
Prior art date
Application number
PCT/CA2013/050471
Other languages
English (en)
Inventor
Laurence Anthony Sinnige
Maria Racota
Jan COCQUYT
Patrick HAERENS
Original Assignee
Walker Industries Holdings Limited
Govi Nv
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Walker Industries Holdings Limited, Govi Nv filed Critical Walker Industries Holdings Limited
Publication of WO2013188975A1 publication Critical patent/WO2013188975A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00612—Uses not provided for elsewhere in C04B2111/00 as one or more layers of a layered structure
    • C04B2111/0062—Gypsum-paper board like materials

Definitions

  • This invention relates to aqueous wax dispersions and their use to impart water- repellent properties to gypsum products, such as gypsum blocks, gypsum wallboards or gypsum panels.
  • diethylenetriaminepentacetic acid are used to optimize the setting behavior of the slurry.
  • Dispersing agents such as lignin sulfonates, naphthalene sulfonates or sulfonated melamine polycondensates, can be added to increase the fluidity of the gypsum slurry. Fluidity means the ability of the gypsum slurry to flow and is important in order to have a smooth production process and to maintain the dimensions of the gypsum boards.
  • Foaming agents are used to control the density of the board through the incorporation of air.
  • Starch is mainly used to improve the bond between the paper liner and the gypsum core in a gypsum board.
  • the gypsum slurry may contain many other chemicals in addition to the ones listed above.
  • Gypsum products absorb water. This not only leads to visual defects but also to a dramatic loss of the strength of the product. It is a well-known practice to add hydrophobic agents to the gypsum slurry. Asphalt emulsions, metallic soaps and resin-based products have been used. Polysiloxane based systems are known as relatively effective hydrophobing agents. However, they are prone to large fluctuations in price and availability. In addition, their handling and use is difficult and they give rise to defoaming problems, increased emissions and silica buildup in dryers and on equipment. [0005] Suitable hydrocarbon wax dispersions are known to provide water-repellent properties to gypsum products.
  • paraffin wax based dispersed phase is normally melted before dispersion in water. Strictly speaking, only above the melting temperature of the dispersed phase, when this phase is in the liquid state, can paraffin wax dispersions also be referred to as paraffin wax emulsion. However, the term paraffin emulsion is often used in the art even though the temperature may be below the melting point.
  • Paraffin wax dispersions used as hydrophobing agents for gypsum products such as gypsum wallboards, often also contain a polar wax-like component in addition to paraffin.
  • polar compounds described in literature are oxidated paraffins as described in US Patent No. 4042409, polyolefin maleic anhydride graft polymers as described in US Patent No. 6890976 B1 , mixtures of longchain fatty acids and longchain fatty esters as described in CA2226246, resins like a colophonium resin as described in EP1907480 B1 , or a styrene - maleic anhydride resin as described in US Patent No.
  • paraffin wax dispersions described in the literature contain a film-forming substance or polymer in addition to the paraffin and a polar wax-like component.
  • film forming polymers described in the prior art include acrylates as in US4042409 or cellulose derivatives as in US2006283356 A1 and more commonly polyvinyl alcohol as in US6890976 B1 , US5437722 A, US6946504 B2, and WO9809925 A1 which may be combined with a crosslinking agent as in US4094694 A.
  • montan wax An essential ingredient in many conventional hydrocarbon wax dispersions is montan wax.
  • montan wax is a crude natural product that contains a variety of components. The composition of montan wax varies over time and also by the geographic region of the mine from which it originates. This leads to variable hydrophobing characteristics of the hydrocarbon wax dispersion containing the montan wax. 2.
  • conventional hydrocarbon wax dispersions are usually based on relatively expensive synthetic or refined hydrocarbon wax.
  • Synthetic hydrocarbon waxes are usually made with the well-known Fisher Tropsch process. Refined hydrocarbon waxes are obtained in base oil refineries by extensive de-oiling or through hydrocracking. The oil content of refined waxes is typically below 3%, measured with ASTM D721 :
  • paraffin slack wax is obtained from base oil refineries using the solvent extraction principle, contains between 3 and 50% oil and is considerably cheaper than refined or synthetic hydrocarbon wax.
  • the use of paraffin slack wax in conventional hydrocarbon wax dispersions has been known to lead to drastically reduced hydrophobing effect in the resulting gypsum products. 3.
  • Polyvinyl alcohol (PVA) can also be used to enhance the performance of
  • the present invention provides an aqueous dispersion, for addition to an aqueous gypsum slurry comprising:
  • the invention provides a gypsum slurry composition for use in making a water-resistant gypsum product comprising:
  • hydrocarbon wax having a melting point of 40-80°C and iii) a copolymer of ethylene and vinyl acetate in an amount of 1 to 200 parts per 100 parts of said hydrocarbon wax ii)
  • the present invention provides a wax dispersion for imparting water repellency to gypsum products comprising various components.
  • a wax dispersion for imparting water repellency to gypsum products comprising various components.
  • an aqueous dispersion for use in making gypsum products containing a hydrocarbon wax and a copolymer of ethylene and vinyl acetate (EVA).
  • EVA ethylene and vinyl acetate
  • the copolymer of ethylene and vinyl acetate contains between 1 and 50% polyvinylacetate.
  • the copolymer of ethylene and vinyl acetate is present in an amount of about 1 to 200 parts, by weight, per 100 parts of said hydrocarbon wax. In another embodiment, the amount is 1 to 50 parts, by weight, per 100 parts of said hydrocarbon wax.
  • hydrocarbon wax has a melting point of 40-80°C.
  • hydrocarbon waxes are suitable including, for example, paraffin slack wax, refined paraffin wax, Fisher Tropsch wax, polyethylene wax or mixtures thereof.
  • Copolymers of ethylene and vinyl acetate have been found to have a relatively good compatibility with hydrocarbon wax.
  • the melting point of most available ethylene vinyl acetate copolymers lies in the range of 40-90°C, which is similar to most available paraffin waxes.
  • the copolymer melt index generally changes relative to the chain length. Lower melt indexes generally indicate longer polymer chains and more difficult dissolution into molten hydrocarbon wax dispersion.
  • the melt index of common ethylene vinyl acetate copolymers lies between 1 and 1000 g per 10 minutes.
  • the polarity of the copolymer of ethylene and vinyl acetate leads to a better affinity and a better adhesion to the gypsum air interface. Additionally, the EVA also has film forming properties.
  • EVA polymers examples include products under the brand name ElvaxTM, all produced by DuPont, or EvataneTM, produced by Arkema.
  • EvataneTM 28-420 which is a random copolymer of ethylene and vinyl acetate made by high-pressure radical polymerization process. This particular example has a vinyl acetate content of 27-29% wt, a melt index (190°C/2.16 kg) of 370-470 g/10 min and a melting point of 69°C.
  • One embodiment of the present invention consists of a formulation including water, paraffin, EVA and PVA wherein the PVA is dissolved in the water phase and provides strengthening properties to the gypsum product and the EVA is added to the paraffin wax phase and reduces the water uptake of the final gypsum product.
  • the PVA is in a concentration between about 0.01 and about 5% wt.
  • Another embodiment of the present invention consists of a formulation comprising EVA and paraffin slack wax, which is optionally combined with one or more refined hydrocarbon waxes.
  • the hydrocarbon wax fraction of the present EVA-containing hydrophobing dispersions for gypsum may consist partly or exclusively of paraffin slack wax, while still maintaining acceptable hydrophobing activity in the final gypsum product.
  • the aqueous dispersions described above may be added to an aqueous gypsum slurry.
  • the aqueous gypsum slurry may then be used to make gypsum products.
  • a gypsum composition used to make a water-resistant gypsum product comprising:
  • the copolymer of ethylene and vinyl acetate is in an amount of 1 to 50 parts per 100 parts of said hydrocarbon wax ii).
  • the copolymer of ethylene and vinyl acetate has a vinyl acetate content between 1 and 50% wt.
  • the gypsum products made from the gypsum compositions include wallboards, panels, blocks, and the like.
  • the aqueous gypsum slurry may include any combination of the following:
  • Various comparative samples were prepared using an emulsion composition as described in United States Patent 6890976, 'Wax emulsion formulation and gypsum composition containing same", incorporated herein by reference.
  • a base emulsion composition comprising a paraffin wax, polyethylene wax, a maleic anhydride graft polymer (Ceramer® 67 manufactured by Baker Petrolite) as well as ancillary dispersants and stabilizers (see Table 1 ), was prepared in combination with various levels of EVA and PVA according to Table 3.
  • Table 1 The Composition of the Base Emulsion
  • Stepan Chemicals, 5% The resulting mixture was set in the form of board panels 1 ⁇ 2" thickness and 12" X 12" diameter.
  • the boards were heated to dryness in a convection oven, cooled overnight to ambient temperature, cut down to 6" X 6" and weighed (initial wt).
  • the panels were then immersed in water for 2 hours and weighed again (final wt).
  • the percentage of water absorbed by these samples was calculated using the following formulation:
  • the change in fluidity was measured by mixing 4 parts emulsion, 54 parts water, 0.4 parts naphthalene sulfonate (dispersant) and 100 parts stucco. The resulting mixture was poured onto a glass plate and the diameter measured. The percent change relative to a control sample without emulsion was then calculated. As can be seen, a reduction in PVA results in a less negative impact on the fluidity. Complete removal of PVA results in a positive shift. This further allows for a reduction in the use of dispersant required in the emulsion.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

La présente invention concerne une dispersion aqueuse comprenant de l'eau, une paraffine hydrocarbonée et un copolymère d'éthylène et d'acétate de vinyle, une composition de gypse contenant ladite dispersion aqueuse et l'utilisation de la dispersion aqueuse ou de la composition de gypse pour produire des produits de gypse hydrofuges.
PCT/CA2013/050471 2012-06-19 2013-06-19 Dispersion aqueuse à base de paraffine WO2013188975A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261661716P 2012-06-19 2012-06-19
US61/661,716 2012-06-19

Publications (1)

Publication Number Publication Date
WO2013188975A1 true WO2013188975A1 (fr) 2013-12-27

Family

ID=49767983

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CA2013/050471 WO2013188975A1 (fr) 2012-06-19 2013-06-19 Dispersion aqueuse à base de paraffine

Country Status (1)

Country Link
WO (1) WO2013188975A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0669377A1 (fr) * 1994-02-25 1995-08-30 Bakor Inc. Compositions de plâtre résistant à l'eau et émulsion pour les préparer
WO2011130337A1 (fr) * 2010-04-13 2011-10-20 T.I.P. Traditional Industries Intellectual Property Ltd. Substitut de cire de montan pour produits de gypse

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0669377A1 (fr) * 1994-02-25 1995-08-30 Bakor Inc. Compositions de plâtre résistant à l'eau et émulsion pour les préparer
WO2011130337A1 (fr) * 2010-04-13 2011-10-20 T.I.P. Traditional Industries Intellectual Property Ltd. Substitut de cire de montan pour produits de gypse

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