USOO9404221B2
`
`(12) United States Patent
`Hagiopol et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 9.404,221 B2
`Aug. 2, 2016
`
`(54) COMPOSITIONS THAT INCLUDE
`HYDROPHOBIZNGAGENTS AND
`STABILIZERS AND METHODS FOR MAKING
`AND USING SAME
`
`(71) Applicant: Georgia-Pacific Chemicals LLC,
`Altanta, GA (US)
`(72) Inventors: Cornel Hagiopol, Lilburn, GA (US);
`Adam K. Sniady, Lilburn, GA (US);
`David F. Townsend, Grayson, GA (US);
`Bobby L. Williamson, Conyers, GA
`(US)
`(73) Assignee: Georgia-Pacific Chemicals LLC,
`Atlanta, GA (US)
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 4 days.
`(21) Appl. No.: 14/135,459
`
`(*) Notice:
`
`(22) Filed:
`
`Dec. 19, 2013
`
`(65)
`
`Prior Publication Data
`US 2014/0202647 A1
`Jul. 24, 2014
`
`Related U.S. Application Data
`(60) Provisional application No. 61/756,197, filed on Jan.
`24, 2013.
`
`(51) Int. Cl.
`D2 IIH 2L/6
`COSL 97/02
`C08L 61/06
`COSL 97/OO
`CO4B 24/38
`COSL 91/06
`(52) U.S. Cl.
`CPC .............. D2IH 21/16 (2013.01); C04B 24/383
`
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`
`(2013.01); C08L 61/06 (2013.01); C08L91/06
`(2013.01); C08L97/005 (2013.01); C08L97/02
`(2013.01)
`
`(58) Field of Classification Search
`CPC .......... C08L91/06; C08L97/02: C08L 61/06
`USPC .......................................................... 152/165
`See application file for complete search history.
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`
`
`4,193,814 A * 3/1980 Shen ........................ 106,123.12
`6,113,729 A * 9/2000 Chiu ............................. 156,296
`6,291,558 B1* 9/2001 Raskin et al. ................... 524, 13
`6,576, 175 B1* 6/2003 Roos ..................
`... 264,109
`2005/0011621 A1
`1/2005 Westermarket al. ..
`... 162/9
`2005. O197441 A1* 9, 2005 Shibutani et al. ......
`524/459
`2006/0030629 A1* 2/2006 Wantling et al. ................ 516.38
`2006/0243323 A1* 1 1/2006 Wantling et al. ...
`137,87.01
`2006/0264519 A1* 11/2006 Eckert et al. .................... 516,41
`2007/0245931 A1* 10/2007 Wantling ...................... 106,778
`2009.0114123 A1* 5, 2009 Clark et al. .
`... 106,164.01
`2009/0272292 A1* 1 1/2009 Wantling ................... 106.162.5
`2011/0245381 A1* 10, 2011 Winterowd et al. ............ 524/14
`2012/0263963 A1* 10/2012 Mahoney et al. .
`428,484.1
`2014/0202647 A1* 7/2014 Hagiopol et al. .......... 162,164.6
`* cited by examiner
`Primary Examiner — Michael A Salvitti
`(74) Attorney, Agent, or Firm — Ram W. Sabnis
`(57)
`ABSTRACT
`Compositions that include hydrophobizing agents and stabi
`lizers and methods for making and using same are provided.
`In at least one specific embodiment, a composition can
`include about 40 wt.% to about 60 wt % lignosulfonic acid or
`a salt thereof, about 1 wt % to about 20 wt % of a hydropho
`bizing agent, and about 20 wt % to about 59 wt % of a liquid
`medium, where all weight percents are based on the com
`bined weight of the lignosulfonic acid or salt thereof, the
`hydrophobizing agent, and the liquid medium.
`
`20 Claims, No Drawings
`
`EX. 1029
`APPLE INC. / Page 1 of 27
`
`

`

`1.
`COMPOSITIONS THAT INCLUDE
`HYDROPHOBIZNGAGENTS AND
`STABILIZERS AND METHODS FOR MAKING
`AND USING SAME
`
`CROSS-REFERENCE TO RELATED
`APPLICATION
`
`This application claims priority to U.S. Provisional Patent
`Application having Ser. No. 61/756,197, filed Jan. 24, 2013,
`which is incorporated by reference herein.
`
`10
`
`BACKGROUND
`
`15
`
`1. Field
`Embodiments described generally relate to compositions
`of hydrophobizing agents and stabilizers and methods for
`making and using same.
`2. Description of the Related Art
`Various types of engineered lignocellulose composites,
`such as flakeboard, waferboard, particleboard, and oriented
`Strandboard are known and used in construction applications.
`These composite products are prepared by applying adhe
`sives to lignocellulosic particles, chips, or fibers and forming
`them into the desired composite through application of heat
`25
`and pressure. Small amounts of hydrophobizing agents, com
`monly applied as an emulsion, are used to improve the mois
`ture resistance of the lignocellulosic materials. Known emul
`sions include slack wax, fatty acid soaps, and non-ionic
`emulsifiers.
`These emulsions, however, have drawbacks. For example,
`these emulsions often include hydrophilic stabilizers that
`impart water to the lignocellulose materials, which can make
`production more difficult and interfere with the properties of
`the composite product. There can also be a lack of compat
`ibility between the emulsions and the adhesives used to bind
`the lignocellulosic materials, which can cause de-emulsifica
`tion and/or plugging of manufacturing lines.
`There is a need, therefore, for improved compositions con
`taining hydrophobizing agents and Stabilizers for use with
`composite lignocellulose products.
`
`30
`
`35
`
`40
`
`SUMMARY
`
`45
`
`Compositions that include hydrophobizing agents and sta
`bilizers, methods for making same, and uses for same in
`making composite products are provided. In at least one spe
`cific embodiment, a composition can include about 40 wt %
`to about 60 wt % lignosulfonic acid or a salt thereof, about 1
`wt % to about 20 wt % of a hydrophobizing agent, and about
`20 wt % to about 59 wt % of a liquid medium, where all
`weight percents are based on the combined weight of the
`lignoSulfonic acid or salt thereof, the hydrophobizing agent,
`and the liquid medium.
`In at least one specific embodiment, a method for making a
`composite product can include mixing a plurality of lignocel
`lulose Substrates, a binder, and a mixture comprising aligno
`Sulfonic acid or a salt thereof, a hydrophobizing agent, and a
`liquid medium to produce a resinated furnish. The mixture
`can include about 40 wt % to about 60 wt % of the lignosul
`fonic acid or salt thereof, about 1 wt % to about 20 wt % of the
`hydrophobizing agent, and about 20 wt % to about 59 wt % of
`the liquid medium, where all weight percents are based on the
`combined weight of the lignosulfonic acid or salt thereof, the
`hydrophobizing agent, and the liquid medium. The method
`can also include heating the resinated furnish to produce a
`composite product.
`
`50
`
`55
`
`60
`
`65
`
`US 9,404,221 B2
`
`2
`In at least one specific embodiment, a composite product
`can include an at least partially cured resinated furnish. Prior
`to curing, the resinated furnish can include a plurality of
`lignocellulose Substrates, a binder, and a mixture that can
`include lignoSulfonic acid or a salt thereof, a hydrophobizing
`agent, and a liquid medium. The mixture can include about 40
`wt % to about 60 wt % of the lignosulfonic acid or salt thereof,
`about 1 wt % to about 20 wt % of the hydrophobizing agent,
`and about 20 wt % to about 59 wt % of the liquid medium,
`where all weight percents are based on the combined weight
`of the lignosulfonic acid or salt thereof, the hydrophobizing
`agent, and the liquid medium.
`
`DETAILED DESCRIPTION
`
`It has been Surprisingly and unexpectedly discovered that
`compositions or mixtures that include hydrophobizing or siz
`ing agents, stabilizers, and liquid mediums can beformed that
`contain a high concentration of the stabilizer. These mixtures
`can be in the form of an emulsion, Suspension, dispersion,
`and/or solution. It has been Surprisingly found that the stabi
`lizer can be present in the composition in an amount of about
`30 wt % or more, about 40 wt % or more, or about 50 wt % or
`more, based on the combined weight of the stabilizer, the
`hydrophobizing agent, and the liquid medium. The stabilizer
`can be or include one or more lignoSulfonic acids and/or one
`or more salts thereof. The stabilizer or lignosulfonic acid
`and/or the salt thereof can be present in the mixture in an
`amount from a low of about 30 wt %, about 35 wt %, about 37
`wt %, about 40%, or about 45 wt %, to a high of about 50%,
`about 55%, about 60%, about 65%, or about 70%, based on
`the combined weight of the lignosulfonic acid or salt thereof,
`the hydrophobizing agent, and the liquid medium. In another
`example, the lignoSulfonic acid and/or salt thereof can be
`present in the mixture in an amount of about 35 wt % to about
`42 wt %, about 39 wt % to about 44 wt %, about 42 wt % to
`about 48 wt %, about 46 wt % to about 52 wt %, about 45 wt
`% to about 55 wt %, about 50 wt % to about 57 wt %, or about
`55 to about 68 wt %, based on the combined weight of the
`lignoSulfonic acid or salt thereof, the hydrophobizing agent,
`and the liquid medium. In yet another example, the lignoSul
`fonic acid and/or one or more salts thereof can be present in
`the mixture in an amount of at least 30 wt %, at least 35 wt %,
`at least 40% wit, at least 45 wt %, or at least 50 wt % to about
`55 wt %, about 57 wt %, about 60 wt %, about 63 wt %, or
`about 65 wt %, based on the combined weight of the ligno
`Sulfonic acid or salt thereof, the hydrophobizing agent, and
`the liquid medium.
`The mixture of the hydrophobizing agent and the stabilizer
`can be used as a sizing agent for making composite lignocel
`lulose products. The high concentration of stabilizer in the
`mixture can provide colloidal stability for the preparation of
`Such emulsion, Suspension, dispersion, and/or Solution while
`providing the necessary Surface activity to ensure effective
`deposition of the one or more hydrophobizing agents onto the
`Surface of lignocellulose Substrates. The high concentration
`of stabilizer in the mixture can also reduce or lower the
`concentration of the liquid medium, e.g., water, that can be
`combined with the hydrophobizing agent and the stabilizer to
`produce the mixture. Reducing the liquid medium content in
`the composite lignocellulose product can lower the manufac
`turing costs. For example, the reduced presence of the liquid
`medium can correlate to less energy input needed to cure the
`resins to produce the composite products.
`The mixture of the hydrophobizing agent and the lignoSul
`fonic acid or salt thereof can include at least about 0.5 wt.% to
`about 30 wt % of the hydrophobizing agent, based on the
`
`EX. 1029
`APPLE INC. / Page 2 of 27
`
`

`

`US 9,404,221 B2
`
`10
`
`3
`combined weight of the lignosulfonic acid or salt thereof, the
`hydrophobizing agent, and the liquid medium. For example,
`the emulsion can include the hydrophobizing agent in an
`amount from a low of 0.5 wt %, about 0.7 wt %, about 1 wt %,
`about 3 wt %, about 6 wt %, about 9 wt %, or about 12 wt %
`to a high of about 15 wt %, about 20 wt %, about 23 wt %, or
`about 25 wt %, based on the combined weight of the ligno
`Sulfonic acid or salt thereof, the hydrophobizing agent, and
`the liquid medium. In another example, the hydrophobizing
`agent can be present in the mixture in an amount from about
`0.6 wt % to about 3 wt %, about 1.3 wt % to about 5.5 wt %,
`about 5 wt % to about 8 wt %, about 1 wt % to about 10 wt %,
`about 7 wt.% to about 12 wt %, about 9 wt % to about 16 wit
`%, about 14 wt % to about 17 wt %, about 15 wt % to about
`18 wt %, about 19 wt % to about 25 wt %, or about 25 wt %
`15
`to about 30 wt %, based on the combined weight of the
`lignoSulfonic acid or salt thereof, the hydrophobizing agent,
`and the liquid medium.
`In one or more embodiments, the hydrophobizing agent
`can include a single hydrophobizing agent. In one or more
`embodiments, the hydrophobizing agent can be or include
`two or more different hydrophobizing agents. If the hydro
`phobizing agent includes two different hydrophobizing
`agents, i.e., a first hydrophobizing agent and a second hydro
`phobizing agent, the first and second hydrophobizing agents
`can be present in any amount with respect to one another. For
`example, the first and second hydrophobizing agents can be
`present in a weight ratio of about 99:1, about 90:10, about
`80:20, about 70:30, about 60:40, about 50:50, about 40:60,
`about 30:70, about 20:80, about 10:90, or about 1:99. In
`another example, if the hydrophobizing agent includes a first
`hydrophobizing agent and a second hydrophobizing agent,
`the mixture can have a hydrophobizing agent composition
`that includes the first hydrophobizing agent in an amount
`from about 1 wt % to about 99 wt % and conversely about 99
`wt % to about 1 wt % of the second hydrophobizing agent,
`based on the combined weight of the first and second hydro
`phobizing agents. In another example, the amount of the first
`hydrophobizing agent can be from a low of about 5 wt %,
`about 10 wt %, about 15 wt %, about 20 wt %, about 25 wt %
`40
`about 30 wt %, about 35 wt %, about 40 wt %, or about 45 wt
`% to a high of about 60 wt %, about 65 wt %, about 70 wt %,
`about 75 wt %, about 80 wt %, about 85 wt %, about 90 wt %,
`or about 95 wt %, based on the combined weight of the first
`and second hydrophobizing agents. In another example, if
`three or more hydrophobizing agents are present, then the
`three or more hydrophobizing agents can be present in any
`ratio with respect to one another.
`If two or more hydrophobizing agents are present in the
`mixture, the two or more hydrophobizing agents can be com
`50
`bined with one another as a solid, a liquid, or as a combination
`of Solid and liquid. If solid, the hydrophobizing agent can be
`heated to its melting point and introduced into the mixing tank
`or heated within the mixing tank to provide the hydrophobi
`Zing agent in liquid form. The mixture of hydrophobizing
`agents can be agitated to achieve a homogeneous product.
`Mixing blades, impellers, magnetic stir bars, shear agitation,
`or other mechanical means can be used to mix the hydropho
`bizing agents. In another example, in-line mixing through a
`mixing tube can, for example, also be used to achieve the final
`product. In another example, ultrasonic Sound waves can be
`used to mix, blend, or otherwise combine the hydrophobizing
`agents.
`The mixture of the hydrophobizing agent and lignoSulfonic
`acid or salt thereof can have a liquid medium content from a
`low of about 18 wt %, about 20 wt %, or about 25 wt % to a
`high of about 35 wt %, about 40 wt %, or about 59 wt %, based
`
`30
`
`4
`on the combined weight of the lignoSulfonic acid or salt, the
`hydrophobizing agent, and the liquid medium. For example,
`the mixture of the hydrophobizing agent and the lignoSul
`fonic acid or salt thereof can have a liquid medium content or
`water concentration of about 59 wt % or less, about 45 wt %
`or less, about 40 wt % or less, about 35 wt % or less, about 30
`wt % or less, or about 25 wt % or less, based on the combined
`weight of the lignoSulfonic acid or salt, the hydrophobizing
`agent, and the liquid medium. In other example, the mixture
`of the hydrophobizing agent and the lignoSulfonic acid or salt
`thereof can have a liquid medium content of about 15 wt % to
`about 25 wt %, about 20 wt % to about 30 wt %, about 20 wit
`% to about 59 wt %, about 25 wt % to about 35 wt %, about
`27 wt % to about 40 wt %, about 33 wt % to about 43 wt %,
`about 37 wt.% to about 49 wt %, about 45 wt % to about 56 wit
`%, or about 45 wt.% to about 59 wt %, based on the combined
`weight of the lignoSulfonic acid or salt, the hydrophobizing
`agent, and the liquid medium.
`The viscosity of the mixture of the hydrophobizing agent
`and the lignosulfonic acid or salt thereof can vary widely. For
`example, the viscosity of the mixture of the hydrophobizing
`agent and the lignoSulfonic acid or salt thereof can be from a
`low of about 1 centipoise (“cP”), about 100 cB. about 250cP.
`about 500 cB, or about 700 cF to a high of about 1,000 cP.
`about 3,250 cP, about 4,500 cP. about 5,000 cP, or about
`10,000 cB at a temperature of about 25° C. In another
`example, the mixture of the hydrophobizing agent and the
`lignoSulfonic acid or salt thereof can have a viscosity from
`about 10 cp to about 125 cP, about 20 cP to about 75 cP, about
`75 cP to about 125 cP, about 260 cP to about 460 cP, about 725
`cP to about 1,100 cP, about 4,100 cp to about 8,600 cP, about
`8,600 cP to about 9,200 cP, or about 7,900 cP to about 9,990
`cP at a temperature of about 25°C. In another example, the
`mixture of the hydrophobizing agent and the lignoSulfonic
`acid or salt thereof can have a viscosity from about 1 c to
`about 450 cP, about 450 cP to about 1,205, about 6,250 cp to
`about 7,550 cP, about 6,550 cP to about 8,250 cP. about 7,250
`cP to about 9,100 cP, about 8,100 cP to about 9,600 cP, or
`about 6,600 cB to about 8.200 cBata temperature of about 25°
`C. The Viscosity can be measured using a Brookfield viscom
`eter. For example, the BrookfieldViscometer can be equipped
`with a small sample adapter Such a 10 mL adapter and the
`appropriate spindle to maximize torque such as a spindle no.
`31.
`The mixture can also include one or more inorganic bases.
`Illustrative inorganic bases can be or include, but are not
`limited to, potassium hydroxide, sodium hydroxide, calcium
`hydroxide, magnesium hydroxide, or any mixture or combi
`nation thereof. The inorganic base can be present in the mix
`ture in an amount from about a low of about 0.1 wt %, about
`0.3 wt %, about 0.5 wt %, about 0.8 wt %, or about 1 wt % to
`a high of about 4 wt %, about 5 wt %, or about 6 wt %, based
`on the combined weight of the lignoSulfonic acid or salt, the
`hydrophobizing agent, the inorganic base, and the liquid
`medium. In another example, the inorganic base can be from
`about 0.2 wt % to about 0.4 wt %, about 0.5 wt % to about 0.7
`wt %, about 1.0 wt % to about 1.6 wt %, about 2.4 wt % to
`about 4.0 wt %, or about 3.2 wt % to about 5.8wt %, based on
`the combined weight of the lignosulfonic acid or salt, the
`hydrophobizing agent, the inorganic base, and the liquid
`medium.
`The pH of the mixture can be from a low of about 1, about
`2, about 3, about 4, about 5, about 6, about 7 to a high of about
`8, about 9, about 10, about 11, about 12, or about 13. In
`another example, the pH of the mixture of the hydrophobizing
`agent and the lignoSulfonic acid or salt thereof can have a pH
`from about 1 to about 2, about 2 to about 3, about 3 to about
`
`25
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`EX. 1029
`APPLE INC. / Page 3 of 27
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`

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`US 9,404,221 B2
`
`5
`4, about 4 to about 5, about 5 to about 6, about 6 to about 7,
`about 7 to about 8, about 8 to about 9, about 9 to about 10,
`about 10 to about 11, about 11 to about 12, or about 12 to
`about 13.
`The mixture can include one or more additives. Illustrative 5
`additives can include, but are not limited to, Surfactants, dis
`persants, corrosion inhibitors, dyes, fungicides, insecticides,
`or any mixture thereof. Illustrative surfactant can include, but
`are not limited to, dioctyldimethylammonium chloride, dide
`cyldimethylammonium chloride, dicocodimethylammonium 10
`chloride, cocobenzyldimethylammonium chloride, coco
`(fractionated)benzyldimethylammonium chloride, octadecyl
`trimethylammonium chloride, dioctadecyl dimethylammo
`nium chloride, dihexadecyl dimethylammonium chloride,
`di(hydrogenated tallow)dimethylammonium chloride, di(hy- 15
`drogenated tallow)benzylmethylammonium chloride, (hy
`drogenated tallow)benzyldimethylammonium chloride, dio
`leyldimethylammonium
`chloride,
`and
`di(ethylene
`hexadecanecarboxylate)dimethylammonium chloride, alky
`lphenol, ethoxilated, ethoxilated fatty acids, ethoxylated fatty 20
`alcohols, salts offatty acids, ethylene oxide-propylene oxide
`block copolymers, or any mixture thereof.
`The dispersant, if present, can include non-surface active
`polymers or Surface-active Substances added to improve the
`separation of particles and/or to inhibit settling or clumping. 25
`The dispersant can be cationic, anionic, non-ionic, or ampho
`teric. The dispersant can include natural starches and deriva
`tized starches. Suitable starch dispersants can include, but are
`not limited to, hydroxyethyl-, hydroxypropyl-, methylhy
`droxypropyl- and ethythydroxyethylcellulose, methyl- and 30
`carboxymethylcellulose, gelatin, starch, guar gum, Xanthan
`gum, polyvinyl alcohol, and mixtures thereof. The starch
`dispersant can include nano-starches. Such nano-starches can
`include those sold by Ecosynthetix, Inc. Derivatized starches
`can be obtained by reacting natural starches with cationizing 35
`agents, such as glycidyltrimethylammonium chloride or
`3-chloro-2-hydroxypropyltrimethylammonium
`chloride.
`Non-ionic dispersants can include, but are not limited to,
`ethoxylated fatty alcohols, fatty acids, alkyl phenols, fatty
`acid amides, ethoxylated or non-ethoxylated glycerol esters, 40
`sorbitan esters of fatty acids, and mixtures thereof. Suitable
`cationic dispersants can include nitrogen-containing com
`pounds such as quaternary ammonium compounds, salts of
`tertiary amines, water-soluble nitrogen-containing epichloro
`hydrin resins, cationic polyurethanes, polyamidoamines, 45
`poly-amideamine-epichlorohydrin copolymers, dimethy
`lamine-epichlorohydrin copolymers, dimethylamine-ethyl
`enediamine-epichlorohydrin copolymers, ammonia-ethyl
`enendichloride copolymers, homopolymers and copolymers
`of diallyldimethylammonium chloride, dialkyl-aminoalkyl 50
`acrylates, methacrylates and acrylamides (e.g., dimethylami
`noethyl acrylates and methacrylates), cationic polymers (e.g.,
`polyacrylamide, polyethyleneimine, polyamidoamine and
`poly(diallyldimethyl ammonium chloride)) and mixtures
`thereof. Suitable anionic dispersants can include, but are not 55
`limited to, phosphated, Sulphonated and carboxylated lignin
`or polysaccharides, anionic polyurethanes, naphthalene Sul
`tanates, and vinyl addition polymers formed from monomers
`with anionic groups (e.g., acrylic acid, methacylic acid,
`maleic acid, itaconic acid, crotonic acid, vinylsulfonic acid, 60
`Sulfonated styrene and phosphates of hydroxyalkyl acrylates,
`and methacrylates). The weight ratio of the hydrophobizing
`agent to the dispersant to can be from a low of about 0.1 wt %,
`about 1 wt %, about 0.1 wt %, about 5 wt %, or about 7 wt %,
`to a high of about 15 wt %, about 18 wt %, or about 20 wt %. 65
`In another example, the dispersant can be present in the mix
`ture in an amount from about a low of about 0.1 wt %, about
`
`6
`5 wt %, about 7 wt %, or about 10 wt % to a high of about 18
`wt %, about 22 wt %, or about 30 wt %, based on the com
`bined weight of the lignosulfonic acid or salt, the hydropho
`bizing agent, the dispersant, and the water. In another
`example, the dispersant can be from about 0.2 wt % to about
`0.4 wt %, about 1 wt % to about 7 wt %, about 10 wt % to
`about 16 wt %, or about 20 wt % to about 25 wt %, based on
`the combined weight of the lignosulfonic acid or salt, the
`hydrophobizing agent, the inorganic base, and the water.
`The mixture of the hydrophobizing agent and the lignoSul
`fonic acid or salt thereof can have a non-volatile material or
`“solids' content from a low of about 20 wt %, about 40 wt %,
`about 50 wt %, or about 65 wt % to a high of about 75 wt %,
`about 80 wt %, about 85 wt %, about 95 wt %, or about 99.9
`wt %, based on the combined weight of the lignosulfonic acid
`or salt thereof, the hydrophobizing agent, and the liquid
`medium. In other example, the emulsion can have a solids
`content of about 20 wt % to about 59 wt %, about 40 wt % to
`about 60 wt %, about 60 wt % to about 80 wt %, about 80 wit
`% to about 95 wt %, about 25 wt % to about 75 wt %, about
`60 wt % to about 90 wt %, or about 75 wt % to about 85 wt %,
`based on the combined weight of the lignosulfonic acid or
`salt, the hydrophobizing agent, and the liquid medium. In
`another example, the emulsion can have a solids content of at
`least 20 wt %, at least 33 wt %, at least 41 wt %, at least 50 wit
`%, at least 55 wt %, or at least 62 wt %, based on the combined
`weight of the lignoSulfonic acid or salt, the hydrophobizing
`agent, and the liquid medium.
`As used herein, Solids content, as understood by those
`skilled in the art, can be measured by determining the weight
`loss upon heating a small sample, e.g., 1-5 grams of the
`mixture, to a suitable temperature, e.g., 125°C., and a time
`sufficient to remove the liquid therefrom. By measuring the
`weight of the sample before and after heating, the percent
`solids in the sample can be directly calculated or otherwise
`estimated.
`The mixture of the hydrophobizing agent and the lignoSul
`fonic acid or salt thereof can be prepared using any Suitable
`method or combination of methods. For example, the mixture
`of the hydrophobizing agent and the lignoSulfonic acid or salt
`thereof can be emulsified, Suspended, dispersed, and/or
`formed into a solution with a shear homogenizer, a Sonicator,
`and/or high pressure valve homogenizer (also known as a
`dynamic high pressure homogenizer). A shear homogenizer
`uses shear forces to emulsify the mixture and to reduce the
`particle size of the emulsion. A Sonicator uses sound or ultra
`Sound energy to emulsify the mixture and reduce the particle
`size of the emulsion. A high pressure valve homogenizer
`mixes the components and reduces the particle size by build
`ing up pressure on one side of a valve and then allowing the
`mixture to flow through a narrow, adjustable gap of the valve
`causing turbulent streams, and resulting in the mixing of
`components and a reduction of particle size. The mixture of
`the hydrophobizing agent and the lignoSulfonic acid or salt
`thereof can be mixed in a high pressure valve homogenizer at
`a pressure from a low of about 1.3 MPa, about 5 MPa, about
`10 MPa, or about 50 MPa, to a high of about 100 MPa, about
`150 MPa or about 207 MPa. In another example, the mixture
`of the hydrophobizing agent and the lignoSulfonic acid or salt
`thereof can be mixed in a high pressure valve homogenizer at
`a pressure from about 2 MPa to about 10 MPa, about 11 MPa
`to about 19 MPa, about 22 MPa to about 35 MPa, about 10
`MPa to about 45 MPa, about 12 MPa to about 150 MPa, or
`about 13 MPa to about 202 MPa.
`The hydrophobizing agent and the lignoSulfonic acid or
`salt thereof in the mixture can have a particle size from a low
`of about 25 nm, about 50 nm, about 75 nm or about 90 nm to
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`a high of about 200 nm, about 300 mm, about 2,000 nm, about
`3,000 nm, about 4,000 nm or about 5,000 nm. In another
`example, the mixture of the hydrophobizing agent and the
`lignoSulfonic acid or salt thereof can have particle size from
`about 30 nm to about 55 nm, about 66 nm to about 110 nm,
`about 50 nm to about 300 nm, about 100 nm to about 169 nm,
`about 149 nm to about 210 nm, about 200 nm to about 400
`nm, about 1,005 nm to about 1,755 nm, or about 2,200 nm to
`about 4.855 nm. The mixture of the hydrophobizing agent and
`the lignoSulfonic acid or salt thereof can have an average
`particle size from a low of about 80 nm, about 90 nm, about
`100 nm, about 120 nm, about 140 nm, about 160 nm, about
`180 nm, about 200 nm to a high of about 220 nm, about 250
`nm, about 300 nm, about 400 nm, about 500 nm, about 1,000
`nm, about 2,000 nm, about 3,000 nm, about 4,000 nm, or
`about 5,000 mm. In another example, the mixture of the
`hydrophobizing agent and the lignoSulfonic acid or salt
`thereof can have an average particle size from about 80 mm to
`about 175 nm, about 110 nm to about 170 nm, about 150 nm.
`to about 230 nm, about 280 nm to about 380 nm, about 150
`nm to about 190 nm, about 150 nm to about 2,000 nm, about
`160 nm to about 1,000 nm, about 800 nm to about 1,200 nm,
`about 2,000 nm to about 3,000 nm, or about 3,500 nm to about
`4,500 nm.
`The mixture of the hydrophobizing agent and the lignoSul
`fonic acid or salt thereof can be emulsified, Suspended, and/or
`dispersed at temperature from a low of about 10°C., about
`20° C., about 30° C., about 40°C., about 50° C. to a high of
`about 80°C., about 100° C., about 120° C., about 140°C., or
`about 160°C. In another example, the mixture of the hydro
`phobizing agent and the lignoSulfonic acid or salt thereof can
`be emulsified and/or dispersed attemperature from about 15°
`C. to about 35° C., about 25°C. to about 55° C., about 65° C.
`to about 85°C., about 80°C. to about 95°C., about 105° C. to
`about 115°C., about 100° C. to about 125°C., or about 135°
`C. to about 155° C.
`The liquid medium can include, but is not limited to, water,
`one or more alcohols, one or more ethers, or any mixture
`thereof. Suitable alcohols can include, but are not limited to,
`methanol, ethanol, propanol, isopropanol, n-butanol, Sec-bu
`tanol, isobutanol, tert-butanol, ethylene glycol, and mixtures
`thereof. Suitable ethers can include, but are not limited to,
`dimethyl ether, diethyl ether, tetrahydrofuran, and mixtures
`thereof.
`In one or more embodiments, the liquid medium can
`include a single liquid medium. In one or more embodiments,
`the liquid medium can be or include two or more different
`liquid media. If the liquid medium includes two different
`liquid media, i.e., a first liquid medium and a second liquid
`medium, the first and second liquid media can be present in
`any amount with respect to one another. For example, the first
`and second liquid media can be present in a weight ratio of
`about 99:1, about 90:10, about 80:20, about 70:30, about
`60:40, about 50:50, about 40:60, about 30:70, about 20:80,
`about 10:90, or about 1:99. In another example, if the liquid
`medium includes a first liquid medium and a second liquid
`medium, the mixture can have a liquid medium that includes
`the first liquid medium in an amount from about 1 wt % to
`about 99 wt % and conversely about 99 wt % to about 1 wt %
`of the second liquid medium, based on the combined weight
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`of the first and second liquid media. In another example, the
`amount of the first liquid medium can be from a low of about
`5 wt %, about 10 wt %, about 15 wt %, about 20 wt %, about
`25 wt % about 30 wt %, about 35 wt %, about 40 wt %, or
`about 45 wt % to a high of about 60 wt %, about 65 wt %,
`about 70 wt %, about 75 wt %, about 80 wt %, about 85 wt %,
`about 90 wt %, or about 95 wt %, based on the combined
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`weight of the first and second liquid media. In another
`example, if three or more liquid media are present, then the
`three or more liquid media can be present in any ratio with
`respect to one another.
`The lignoSulfonic acid and the one or more salts thereof can
`be derived from lignin. Lignin is a polymeric Substance that
`can include Substituted aromatics found in plant and Veg
`etable matter associated with cellulose and other plant con
`stituents. Illustrative plant and vegetable matter can include,
`but is not limited to, Straw, hemp, sisal, cotton Stalk, wheat,
`bamboo, Sabai grass, rice Straw, banana leaves, paper mul
`berry (i.e., bast fiber), abaca leaves, pineapple leaves, esparto
`grass leaves, fibers from the genus Hesperaloe in the family
`Agavaceae jute, Salt water reeds, palm fronds, flax, ground
`nut shells, hardwoods, softwoods, recycled fiberboards such
`as high density fiberboard, medium density fiberboard, low
`density fiberboard, oriented strand board, particleboard, or
`any combination thereof. For example, the plant matter can be
`or include wood, for example hardwoods, Softwoods, or a
`combination thereof. Illustrative types of wood can include,
`but are not limited to, alder, ash, aspen, basswood, beech,
`birch, cedar, cherry, cottonwood, cypress, elm, fir, gum, hack
`berry, hickory, maple, oak, pecan, pine, poplar, redwood,
`Sassafras, spruce, Sycamore, walnut, and willow.
`Suitable lignin material can include, but is not limited to,
`lignin in its native or natural state, i.e., non-modified or unal
`tered lignin, lignoSulfonates, or any combination or mixture
`thereof. Suitable lignosulfonates can include, but are not lim
`ited to, ammonium lignoSulfonate, sodium lignoSulfonate,
`potassium lignoSulfonate, calcium lignoSulfonate, magne
`sium lignoSulfonate, or any combination or mixture thereof.
`The lignosulfonic acid can be used as is and a salt or other
`similar component may be used to modify the acid, or, more
`preferably, the lignoSulfonic acid may be used in its salt form.
`Similar components performing in a manner equivalent to the
`lignoSulfonic acid or its salt can be used as Substitutes there
`fore provided that the desired edge swell, water absorption,
`internal bonding and/or flexural strength properties of the
`composites lignocellulose products are met.
`The one or more hydrophobizing agents can be or include
`one or more waxes, such as petroleum waxes, montan waxes,
`synthetic waxes, and natural waxes, such as Vegetable waxes
`or animal waxes. The hydrophobizing agent can be or include
`alkyl ketene dimers, alkenyl Succinic anhydrides, mineral
`oils, rosins, synthetic esters, sil