ANIONIC LIPOPHILIC GLYCEROL-BASED POLYMERS FOR ORGANIC
DEPOSITION CONTROL IN PAPERMAKING PROCESSES
Background of the Invention
This invention relates to methods of reducing the deposition of
organic contaminants, such as pitch and stickies, in papermaking processes. The
deposition of organic contaminants on process equipment, screens, and containment
vessels in papermaking can significantly reduce process efficiency and paper
quality. Deposits on machine wires, felts, foils, headbox surfaces, screens, and
instruments can result in costly downtime for cleaning to avoid the problems
associated with poor process control, reduced throughput, and substandard sheet
properties. Such contaminants are generically referred to in the paper industry as
either "pitch" or "stickies". Pitch deposits generally originate from natural resins
present in virgin pulp, including terpene hydrocarbons, rosin/fatty acids or salts
thereof, such as pimaric acid, pinic acid and abietic acid, glyceryl esters of fatty
acid, sterols, etc. Stickies and white pitch generally refer to the hydrophobic
substances used in the manufacture of paper such as sizing agents, coating binders,
and pressure sensitive or contact adhesives. Such substances can form deposits when
reintroduced in recycled fiber systems. Other common organic contaminants that are
chemically similar to stickies and found in recycle applications include wax, which
originates primarily from wax-coated old corrugated containers, and polyisoprene.
Pitch and stickies may also contain entrapped inorganic materials such as talc,
calcium carbonate, or titanium dioxide.
Recycled fiber also refers to secondary fibers which are repulped to
provide the papermaking furnish with raw material for the production of new papers.
The secondary fibers may be either pre-consumer or post-consumer paper material
that is suitable for use in the production of paper products. Sources of secondary
fiber may include old newspaper (ONP), old corrugated containers (OCC), mixed
office waste (MOW), computer printout (CPO), ledger, etc. These once-processed
papers contain various types of adhesives (pressure sensitive, hot melts, etc.), inks,
and coating binders.
Pitch and stickies are hydrophobic in nature and thus unstable as
colloids in aqueous papermaking environments, thereby facilitating their deposition.
The major problems arising from deposition are as follows: (1) reduced throughput
due to plugging of forming fabrics and press felts, (2) sheet holes or paper breaks
due to large deposits breaking loose from the equipment, and (3) reduced sheet
quality due to large particle contaminants incorporated in the final sheet.
One approach used to address pitch and stickies deposition is through
the use of detackifiers. Detackifiers passivate the exposed surfaces of pitch and
sticky particles rendering them non-adhesive and unlikely to deposit. A number of
chemical are known to be effective detackifiers. Effective organic detackifiers
include polyvinyl alcohol, copolymer of vinyl alcohol and vinyl acetate,
polyethylene oxide, polyacrylates, and waterborne globulins. In order for
detackifiers to function well, it must satisfy two crucial functions: 1) it must
selectively and sufficiently attach to the surface of the pitch or sticky surface, and 2)
it must stabilize the resulting sticky/pitch-detackifier complex in water.
The art described in this section is not intended to constitute an
admission that any patent, publication or other information referred to herein is
"Prior Art" with respect to this invention, unless specifically designated as such. In
addition, this section should not be constraed to mean that a search has been made or
that no other pertinent information as defined in 37 CFR § 1.56(a) exists.
Brief Summary of the Invention
At least one embodiment of the invention is directed towards a
method of reducing the deposition of organic contaminants in papermaking
processes. The method comprises adding to pulp or a papermaking system an
effective amount of a composition comprising an anionic lipophilic branched, cyclic
glycerol-based polymer, wherein the composition selectively bonds with the organic
contaminants to form a complex and the complex is stable in papermaking
processes.
The anionic group may be one selected from the list consisting of
phosphates, phosphonates, carboxylates, sulfonates, the like and any combination
thereof. The glycerol-based polymer may be an anionic lipohydrophilic glycerol
based polymer. The glycerol-based polymer may be branched, hyperbranched,
dendritic, cyclic or any combination thereof. The branched, cyclic glycerol-based
polymer may be cross-linked. The anionic branched, cyclic glycerol-based polymer
may comprise a random arrangement of the monomeric units including R indicated
in the following formula:
wherein:
m, n, o, p, q and r are independently 0 to 700;
R and R' are independently -(CH 2) - , wherein each x is independently 0 or
1; and
each R is independently selected from hydrogen, acyl, C1-C50 alkyl and
anionic groups.
Each Ri may be independently selected from hydrogen, C2-Ci alkyl, and -
C(0)CH(OH)CH 3 . Each of m, n, o, p, q and r may be independently selected from
0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25,
26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,
48, 49 and 50. The glycerol-based polymer has a weight-average molecular weight
of about 200 Da to about 500,000 Da.
The method may further comprise adding to the pulp or the
papermaking system at least one component selected from the group consisting of
fixatives, dispersants, and other detackifiers. The organic contaminants may be
pitch, stickies or combination thereof. The composition may be added to a pulp
slurry in a pulper, latency chest, reject refiner chest, disk filter or Decker feed or
accept, Whitewater system, pulp stock storage chest, blend chest, machine chest,
headbox, saveall chest, or any combination thereof in the papermaking process.
The composition may be added to a surface in the papermaking
process selected from a pipe wall, a chest wall, a machine wire, a press roll, a felt, a
foil, an Uhle box, a dryer, or any combination thereof. The anionic branched, cyclic
glycerol-based polymer may be added to a pulp slurry in the papermaking process.
The effective amount of the anionic branched, cyclic glycerol-based polymer may be
from about 5 ppm to about 300 ppm.
Brief Description of the Drawings
A detailed description of the invention is hereafter described with
specific reference being made to the drawings in which:
FIG. 1 is an illustration of an anionic glycerol based polymer used in
the invention.
FIG. 2 is an illustration of a variety of glycerol based structural units
which can be used to form the glycerol based polymer.
FIG. 3 is a graph which demonstrates the effectiveness of the
invention.
Detailed Description of the Invention
The following definitions are provided to determine how terms used
in this application, and in particular how the claims, are to be construed. The
organization of the definitions is for convenience only and is not intended to limit
any of the definitions to any particular category.
"Acyl" as used herein refers to a substituent having the general
formula -C(0)R, wherein R is alkyl, alkenyl, alkynyl, aryl, heteroaryl or
heterocyclyl, any of which may be further substituted
"Alkyl" as used herein refers a linear, branched, or cyclic saturated
hydrocarbon group, such as a methyl group, ethyl group, n-propyl group, isopropyl
group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl
group, n-hexyl group, isohexyl group, cyclopentyl group, cyclohexyl group, and the
like. Alkyl groups may be optionally substituted.
"Branched" means a polymer having branch points that connect
three or more chain segments. The degree of branching may be determined by C
NMR based on a known literature method described in Macromolecules, 1999, 32,
4240. As used herein, a branched polymer includes hyperbranched and dendritic
polymers.
"Cyclic" means a polymer having cyclic or ring structures. The cyclic
structure units can be formed by intramolecular cyclization or any other ways.
"Degree of branching" or DB means the mole fraction of monomer
units at the base of a chain branching away from the main polymer chain relative to
a perfectly branched dendrimer, determined by 13C NMR based on a known
literature method described in Macromolecules, 1999, 32, 4240. Cyclic units or
branched alkyl chains derived from fatty alcohols or fatty acids are not included in
the degree of branching. In a perfect dendrimer the DB is 1 (or 100%).
"Degree of cyclization" or DC means the mole fraction of cyclic
structure units relative to the total monomer units in a polymer. The cyclic structure
units can be formed by intramolecular cyclization of the polyols or any other ways
to incorporate in the polyols. The cyclic structure units comprise basic structure
units (V, VI and VII of FIG. 2) and the analogues thereof. The degree of cyclization
may be determined by 1 C NMR.
"Glycerol-based polymers" refers to any polymers containing
repeating glycerol monomer units such as polyglycerols, polyglycerol derivatives,
and a polymer consisting of glycerol monomer units and at least another monomer
units to other multiple monomers units regardless of the sequence of monomers unit
arrangements, glycerol-based polymers include but are not limited to alkylated,
branched, cyclic polyglycerol esters, as well as those polymers disclosed in US
Patent Applications 13/484,526, 12/720,973, and 12/582,827.
"Hyperbranched" means a polymer, which is highly branched with
three-dimensional tree-like structures or dendritic architecture.
"Lipohydrophilic glycerol-based polymers" means glycerol-based
polymers having lipophilic and hydrophilic functionalities, for example,
lipohydrophilic polyglycerols resulting from lipophilic modification of
polyglycerols (hydrophilic) in which at least a part of and up to all of the lipophilic
character of the polymer results from a lipophilic carbon bearing group engaged to
the polymer, the lipophilic modification being one such as alkylation, and
esterification modifications.
"Multifunctional" means a composition of matter having two or
more functions such as selectively bonding to and forming a complex with a
material and maintaining the stability of that complex in water.
"Papermakingprocess" means a method of making paper products
from pulp comprising forming an aqueous cellulosic papermaking furnish, draining
the furnish to form a sheet and drying the sheet. The steps of forming the
papermaking furnish, draining and drying may be carried out in any conventional
manner generally known to those skilled in the art. The papermaking process may
also include a pulping stage, i.e. making pulp from a lignocellulosic raw material
and bleaching stage, i.e. chemical treatment of the pulp for brightness improvement.
"Substituted" as used herein may mean that any at least one
hydrogen on the designated atom or group is replaced with another group provided
that the designated atom' s normal valence is not exceeded. For example, when the
substituent is oxo (i.e., =0), then two hydrogens on the atom are replaced.
Combinations of substituents and/or variables are permissible provided that the
substitutions do not significantly adversely affect synthesis or use of the compound.
"Surfactant" is a broad term which includes anionic, nonionic,
cationic, and zwitterionic surfactants. Enabling descriptions of surfactants are
stated in Kirk-Othmer, Encyclopedia of Chemical Technology, Third Edition,
volume 8, pages 900-912, and in McCutcheon's Emulsifiers and Detergents, both of
which are incorporated herein by reference.
"Detackifiers" means a process chemical that reduces tackiness other
substances present in a papermaking process or which disperses otherwise
undispersed tacky substances present in a papermaking process, when detackifiers
reduce the tackiness of or disperse pitch and stickies, the pitch and stickies have less
tendency to form agglomerates or deposit onto papermaking equipment or create
spots or holes in the product.
In the event that the above definitions or a description stated
elsewhere in this application is inconsistent with a meaning (explicit or implicit)
which is commonly used, in a dictionary, or stated in a source incorporated by
reference into this application, the application and the claim terms in particular are
understood to be construed according to the definition or description in this
application, and not according to the common definition, dictionary definition, or the
definition that was incorporated by reference. In light of the above, in the event that
a term can only be understood if it is construed by a dictionary, if the term is defined
by the Kirk-Othmer Encyclopedia of Chemical Technology, 5th Edition (2005)
(Published by Wiley, John & Sons, Inc.) this definition shall control how the term is
to be defined in the claims.
In at least one embodiment of the invention, deposition of pitch or
stickies in papermaking process water is controlled by the addition of a novel
detackifier composition into the process water. The composition comprises an
anionic lipophilic glycerol based polymer. The polymer comprises a glycerol based
polymer backbone which has undergone chemical modification with multi
functional groups.
In at least one embodiment the chemical modification of glycerolbased
polymers is done with an anionic group and a lipophilic group. The lipophilic
group can be an aliphatic and/or aromatic hydrocarbon of 1 to 50 carbon atoms. The
anionic group can be selected from the list consisting of: phosphates, phosphonates,
carboxylates, sulfonates, the like including acid and/or ionic salt forms and any
combination thereof. The anionic charge density can bel% to 99%.
In at least one embodiment the anionic modification of glycerolbased
polymers is phosphorylation. A representative example of such
phosphorylation is described in US Patent 3,580,855. In at least on embodiment the
anionic modification is phosphonation. A representative example of such
phosphonation is described in the scientific paper: Michael Additions to Activated
Vinylpho sphonates , by Tomasz Janecki et ah, Synthesis, issue 8, pp. 1227-1254
(2009). In at least one embodiment the anionic modification is carboxyalkylation.
Representative examples of such carboxyalkylation are described in US Patent
Applications 2004/00 18948A1 and 2006/0047 168A1. In at least one embodiment
the anionic modification is sulfonation. A representative example of such
sulfonation is described in GB Patent Specification 802325A.
In at least one embodiment the lipophilic modification glycerol-based
polymers is via alkylation, alkoxylation, oxyalkylation, esterification or any
combination thereof, such as described in US Patent Applications 13/560,771,
13/484,526, 12/720,973 and references therein.
In at least one embodiment the anionic and lipophilic modifications
of glycerol-based polymers are done together in one step, separately in two steps or
combination thereof.
In at least one embodiment the lipophilic modification enhances the
hydrophobic interaction between pitch/stickies and the anionic glycerol-based
polymers. In at least one embodiment the anionic functionality enhances the water
solubility for dispersing of the pitch/stickies. In at least one embodiment the anionic
functionality chelates cationic ions commonly existed in water such as calcium and
magnesium to increase the glass transition temperature of the pitch/stickies for
preventing from being sticky in the papermaking processes. In at least one
embodiment the well-balanced modifications synergistically enhance the organic
deposition control.
In at least one embodiment the backbone of anionic lipophilic
glycerol-based polymers is branched, cyclic glycerol based polymer, such as
described in US Patent Application 2011/0092743A1. Without being limited as to
theory the lipophilic groups may interact with hydrophobic contaminants in a
papermaking process, e.g., in a pulp slurry. The hydrophilic portion may aid
dispersing the hydrophilic contaminants in water. The lipophilic groups may be
introduced via known methods such as alkylation, alkoxylation esterification, or
combinations thereof. In at least one embodiment, at least one portion of the
glycerol-based polymer has both alkyl and ester functionalities. The nature of
different polarities from both functionalities may be adjusted to optimally perform in
dispersing pitch and stickies.
In at least one embodiment the glycerol-based polymer is a
lipohydrophilic glycerol-based polymer, as illustrated in FIG. 1, wherein: m, n, o, p,
q and r are independently 0 to 700; R and R' are independently -(CH 2)x- , wherein
each x is independently 0 or 1; and each R is independently selected from
hydrogen, acyl and alkyl, wherein at least Ri is alkyl.
The composition may be added to a papermaking process involving
virgin pulp, recycled pulp or combination thereof at any one or more of various
locations during the papermaking process. Suitable locations may include pulper,
latency chest, reject refiner chest, disk filter or Decker feed or accept, Whitewater
system, pulp stock storage chests (either low density ("LD"), medium consistency
(MC), or high consistency (HQ), blend chest, machine chest, headbox, saveall
chest, paper machine Whitewater system, and combinations thereof. The
composition may be added to a pulp slurry in the papermaking process. The
composition may also be applied to a surface in the papermaking process, such as a
metal, plastic, or ceramic surfaces such as pipe walls, chest walls, machine wires,
press rolls, felts, foils, Uhle boxes, dryers and any equipment surfaces that contact
with fibers during the paper process. The method may include the step of contacting
fibers with the composition. The fibers may be cellulose fibers, such as recycled
fibers, virgin wood cellulose fibers, or combinations thereof.
In at least one embodiment, the composition is added to a
papermaking process using recycled paper fibers. The recycled fibers may be
obtained from a variety of paper products or fiber containing products, such as
paperboard, newsprint, printing grades, sanitary and other paper products. These
products may comprise, for example, old corrugated containers (OCC), old
newsprint (ONP), mixed office waste (MOW), old magazines and books, or
combinations thereof. These types of paper products typically contain large amounts
of hydrophobic contaminants. In embodiments employing virgin fibers, the method
may involve the use of pulp derived from softwood, hardwood or blends thereof.
Virgin pulp can include bleached or unbleached Kraft, sulfite pulp or other chemical
pulps, and groundwood (GW) or other mechanical pulps such as, for example,
thermomechanical pulp (TMP).
Examples of organic hydrophobic contaminants include what is
known in the industry as "stickies" that may include synthetic polymers resulting
from adhesives and the like, glues, hot melts, coatings, coating binders, pressure
sensitive binders, unpulped wet strength resins and "pitch" that may include wood
resins, rosin and resin acid salts. These types of materials are typically found in
paper containing products, such as newsprint, corrugated container, and/or mixed
office waste. These hydrophobic contaminants can have polymers present, such as
styrene butadiene rubber, vinyl acrylate polymers, polyisoprene, polybutadiene,
natural rubber, ethyl vinyl acetate polymers, polyvinyl acetates, ethylvinyl alcohol
polymers, polyvinyl alcohols, styrene acrylate polymers, and/or other synthetic type
polymers.
The method may control hydrophobic contaminants in papermaking
processes, e.g., the deposition of hydrophobic contaminants on components of a
papermaking process. For example, the method may control hydrophobic
contaminants present in paper mill furnish. For example, the method may reduce,
inhibit or eliminate the deposition of hydrophobic contaminants in a papermaking
process. The method may also reduce the size of contaminant particles through
dispersion and suppressing agglomeration, and/or reduce the tackiness of the
hydrophobic contaminants when compared to a papermaking process in which the
composition is not employed. For example, the method may reduce the average size
of contaminant particles by at least about 5% to about 40% (e.g., about 5%, 6%, 7%,
8%, 9%, 10%, 15%, 20%, 25%, 30%, 35% or 40%) when compared to a
papermaking process in which the composition is not employed. In embodiments,
the method may reduce the deposition of hydrophobic contaminants by at least about
5% to about 95% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%,
35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%) when
compared to a papermaking process in which the composition is not employed.
In the method, the composition may be added to a papermaking
process in an amount effective to reduce deposition of hydrophobic contaminants
when compared to a papermaking process in which the composition is not
employed. For example, the composition may be added to pulp slurry in an amount
from about 10 ppm to about 300 ppm, e.g., from about 50 ppm to about 200 ppm, or
about 50ppm, 60ppm, 70ppm, 80ppm, 90ppm, lOOppm, llOppm, 120ppm, 130ppm,
140ppm, 150ppm, 160ppm, 170ppm, 180ppm, 190ppm, to about 200 ppm. The
effective amount may reduce the deposition of hydrophobic contaminants by at least
5% to about 95% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25%, 30%,
35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%) when
compared to a papermaking process in which the composition is not employed. The
method may further include adding to the papermaking system at least one
component selected from the group consisting of fixatives, detackifiers and other
dispersants.
In at least one embodiment the glycerol-based polymer may be any
polymer containing repeating glycerol monomer units such as polyglycerols,
polyglycerol derivatives, and polymers consisting of glycerol monomer units and at
least one other monomer unit, regardless of the sequence of monomers unit
arrangements. Suitably, other monomers may be polyols or hydrogen active
compounds such as pentaerythrital, glycols, amines, etc. capable of reacting with
glycerol or any polyglycerol structures. The polymer may be linear, branched,
hyperbranched, cyclic, dendritic, and any combination thereof and have subchains/
sunregions characterized by any combination thereof.
In at least one embodiment the glycerol-based polymer is branched.
In at least one embodiment the branching structure in the backbone of the polymer,
not in the lipophilic chains. In at least one embodiment the branched structure
increases the polymer dimensions for the effective interfacial interactions to result in
exceptional organic deposit control. Branching may be particularly useful as it
facilitates increased molecular weight of the glycerol-based polymers. Branched
polymers include both hyperbranched and dendritic structures. The branched, cyclic
glycerol-based polymer may have a degree of branching of at least about 0.10, e.g.,
from about 0.20 to about 0.75 or from about 0.30 to about 0.50. For example, a
branched, cyclic glycerol-based polymer may have a degree of branching of about
0.10, about 0.15, about 0.20, about 0.25, about 0.30, about 0.35, about 0.40, about
0.45, about 0.50, about 0.55, about 0.60, about 0.65, about 0.70 or about 0.75.
In at least one embodiment the glycerol-based polymer is cyclic, i.e.
has at least one cyclic or ring structure, or has at least one cyclic or ring structured
polymer molecule in the polymer. Such cyclic structures may be formed, for
example, during the polymerization process via intramolecular cyclization reactions.
The rigidity of cyclic structures in the polymer backbone may uniquely extend the
molecular dimensions and increase the hydrodynamic volume, to better act
interfacially for dispersing pitch and stickies. Cyclic glycerol-based polymers may
have a degree of cyclization of about 0.01 to about 0.50. For example, the branched,
cyclic glycerol-based polymer may have a degree of cyclization of at least 0.01, e.g.,
about 0.02 to about 0.19 or about 0.05 to about 0.15. For example, a branched,
cyclic glycerol-based polymer may have a degree of cyclization of about 0.01, about
0.02, about 0.03, about 0.04, about 0.05, about 0.06, about 0.07, about 0.08, about
0.09, about 0.10, about 0.11, about 0.12, about 0.13, about 0.14, about 0.15, about
0.16, about 0.17, about 0.18, or about 0.19.
Suitable branched, cyclic glycerol-based polymers include
compounds as illustrated in FIG. 1. In the these compounds, m, n, o, p, q and r are
independently 0 to 700; R and R' are independently -(CH 2) -, wherein each x is
independently 0 or 1; and each Ri is independently selected from hydrogen, acyl,
alkyl, acid and anionic groups. The anionic groups may be in acid form in acidic
condition, in anionic salt form in neutral or basic condition or any combination
thereof. The anionic group is selected from a list of phosphates -P(0)(OH) 2 or -
(CH2)xOP(0)(OH) 2, phosphonates -(CH 2)xP(0)(OH) 2, carboxylates -
(CH 2) C(0)OH, sulfonates (CH 2) S(0) 2OH and combination thereof, where per H
can be independently substituted by any other groups or atoms, and each x can
independently be any number of integers from 0 to 50. Furthermore, it should be
understood that the compounds illustrated in FIG. 1 are random polymers of the
indicated monomeric units, including Ri groups. For example, in an exemplary
embodiment in which m, n, o, p, q and r are each 1, it is understood that the
monomeric units may be present in any order and not necessarily in the order
illustrated in FIG. 1. In another exemplary embodiment in which m, n, o, p, q and r
are each 2, it is understood that the monomeric units may be present in any order,
where the two "m" units may or may not be adjacent to each other, the two "n" units
may or may not be adjacent to each other, and so on. In another exemplary
embodiment in which one R is H, two Ris are -P(0)(OH) 2 and another two Ris are
dodecanol, it is understood that any of the groups may or may not be on any of the
end groups or non-end groups.
In embodiments of the formula illustrated in FIG. 1, each m, n, o and
p is independently 1-700, and each q and r is independently 0-700. In embodiments
of the formula illustrated in FIG. 1, each m, n, o and q is independently 1-700, and
each p and r is independently 0-700. In embodiments of the formula illustrated in
FIG. 1, each m, n, o, p, q and r is independently selected from 0 to 50, 0 to 40, 0 to
30 or 0 to 25. Suitably, each of m, n, o, p, q and r are independently selected from 0,
1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25,
26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,
48, 49 and 50 (or more).
In embodiments of the formula illustrated in FIG. 1, each Ri is
independently selected from hydrogen, acyl and C1-C50 alkyl. When Ri is alkyl, it
may be, for example, a C1-C50 alkyl, C1-C40 alkyl, C1-C30 alkyl, C1-C24 alkyl, C6-C18
alkyl, C 10-C16 alkyl or C12-C14 alkyl group. For example, each Ri that is alkyl may
independently be a Ci, C2, C3, C4, C5, Ce, C7, C8, C9, Cio, Cn, C12 , C13, C14 , C15, Ci6,
C , Ci8, C19, C20, , C21 , C22 , C23 or C24 alkyl group. The Ri group may be optionally
substituted with other hydrocarbon-based groups, such as branched, cyclic,
saturated, or unsaturated groups.
When i is acyl, it may be, for example, a C1-C15 acyl group. When
Ri is acyl, it may be, for example, -C(0)CH(OH)CH3 (lactate). In embodiments,
lactate or lactic acid may be produced as a co-product during the synthesis of the
branched, cyclic glycerol-based polymer, which may further react with the polymer.
In at least one embodiment, the glycerol-based polymer may
comprise at least two repeating units selected from at least one of the structures
listed in FIG. 2, including but not limited to linear structures I and II, branched
structures III, IV and VIII, cyclic structures V, VI and VII, and any combination
thereof. Any structure in FIG. 2 can be combined with any structure or structures
including itself, in any order. The cyclic linkages of any basic cyclic structures in
FIG. 2 may contain any structure or structures as a part or parts of linkages. In each
of the repeating units depicted in FIG. 2, each Ri is independently selected from
hydrogen, acyl, alkyl and anionic, and each n and n ' is independently 0 to 700.
The glycerol-based polymer may have a weight-average molecular
weight of about 100 Da to about 1,000,000 Da.
In at least one embodiment the glycerol-based polymer may be
crosslinked. Crosslinked polymers include cross-linkages between one or more
types of polymers which are: linear, branched, hyperbranched, cyclic, dendritic, and
any combination thereof and have sub-chains/sub-regions characterized by any
combination thereof. The glycerol-based polymer may self-crosslink, and/or the
polymer may be crosslinked via addition of a crosslinking agent. Suitable
crosslinking agents typically include at least two reactive groups such as double
bonds, aldehydes, epoxides, halides, and the like. For example, a cross-linking
agent may have at least two double bonds, a double bond and a reactive group, or
two reactive groups. Non-limiting examples of such agents are diisocyanates, N,Nmethylenebis(
meth)acrylamide, polyethyleneglycol di(meth)acrylate,
glycidyl(meth)acrylate, dialdehydes such as glyoxal, di- or tri-epoxy compounds
such as glycerol diglycidyl ether and glycerol triglycidyl ether, dicarboxylic acids
and anhydrides such as adipic acid, maleic acid, phthalic acid, maleic anhydride and
succinic anhydride, phosphorus oxychloride, trimetaphosphates,
dimethoxydimethsilane, tetraalkoxysilanes, 1,2-dichloroethane, 1,2-dibromoethane,
dichloroglycerols 2,4,6-trichloro-s-triazine and epichlorohydrin.
The glycerol-based polymer used for the anionic and lipophilic
modifications may be from a commercially available supplier, or synthesized
according to known methods such as those described in U.S. Patent Nos. 3,637,774,
5,198,532 and 6,765,082 B2, and in U.S. Patent Application Publication Nos.
2008/0306211 and 2011/0092743, or from any combination thereof.
For example, in embodiments, a method of preparing a glycerolbased
polymer for the modifications may include the step of: reacting a reaction
mass comprising at least glycerol monomer in the presence of a strong base catalyst
of a concentration above 2%, in a low reactivity atmospheric environment at a
temperature above 200 °C, which produces a product comprising branched, cyclic
polyols and a co-product comprising lactic acid, lactic salt, and any combination
thereof. Such a method can further comprise the steps of providing a catalyst above
3%. The catalyst may be selected from the group consisting of: NaOH, KOH,
CsOH, a base stronger than NaOH, and any combination thereof. The strong base
catalyst in the particular amount can be used with combining a base weaker than
NaOH. The atmospheric environment may be an atmospheric pressure of less than
760 mm Hg and/or may be a flow of an inert gas selected from the list of N2, C0 2,
He, other inert gases and any combination thereof and the flow is at a rate of 0.2 to
15 mol of inert gas per hour per mol of monomer. The particular atmospheric
environment profile applied can be steady, gradual increase, gradual decrease or any
combination thereof.
The method of preparing the branched, cyclic glycerol-based polymer
may produce glycerol-based polymer products selected from the group consisting of
polyglycerols, polyglycerol derivatives, a polyol having both glycerol monomer
units and non-glycerol monomer units and any combination thereof. The branched,
cyclic glycerol-based polymer products have at least two hydroxyl groups. At least a
portion of the produced polymers may have both at least a 0.1 degree of branching
and at least a 0.01 degree of cyclization. The co-product may be at least 1% by
weight.
The method of preparing the branched, cyclic glycerol-based polymer
may make use of different forms of glycerol including pure, technical, crude, or any
combination thereof. Such methods may further comprise other monomers selected
from the group consisting of polyols such as pentaerythritol and glycols, amines,
other monomers capable of reacting with glycerol or glycerol-based polyol
intermediates and any combination thereof. The monomer(s) and/or catalyst(s) can
be mixed at the very beginning of the reaction, at any time during the reaction and
any combination thereof. The glycerol-based polyol products may be resistant to
biological contamination for at least two years after synthesis. The method may
further comprise the steps of pre-determining the desired molecular weight of the
produced polyglycerol and adjusting the atmospheric environment to match the
environment optimum for producing the desired molecular weight. The method may
further comprise the steps of pre-determining the desired degree of branching and
the desired degree of cyclization of the produced polyglycerol and the desired
amount of co-product, and adjusting the atmospheric environment to match the
environment optimum for producing the desired degree of branching, degree of
cyclization and amount of co-product lactic acid and/or lactate salt.
Anionic, lipophilic glycerol-based polymer may be made from a
lipophilic glycerol-based polymer. The lipohydrophilic glycerol-based polymer may
be produced from glycerol-based polymers, such as those that are commercially
available or those described herein, according to known methods such as alkylation,
esterification and any combinations thereof. For example, such polymers may be
produced from glycerol-based polymers according to known methods such as
alkylation, as described in German Patent Application No. 10307172, in Canadian
Patent No. 2,613,704, in U.S. Patent Nos. 3,637,774, 5,198,532, 6,228,416 and
6,765,082 B2, in U.S. Patent Application Publication Nos. 2008/0306211 and
2011/0220307, in Markova etal. Polymer International, 2003, 52, 1600-1604, and
the like. The glycerol-based polymers may be produced according to known
methods such as esterification of glycerol-based polymers as described in U.S.
Patent No. 2,023,388, U.S. Patent Application Publication No. 2006/0286052 and
the like. The esterification may be carried out with or without a catalyst such as
acid(s) or base(s).
Anionic, lipophilic glycerol-based polymers may be made from
crosslinked polymers. The crosslinked glycerol-based polymers may be produced in
a continuous process under a low reactivity atmospheric environment according to a
method described in US Patent Application No. 13/484,526, filed on May 31, 2012.
The method may comprise the steps of: a) reacting a reaction mass comprising at
least glycerol monomer in the presence of a strong base catalyst of a concentration
of above 2% at a temperature above 200 degrees C which produces a first product
comprising polyols which are both branched and cyclic, and a co-product
comprising lactic acid, lactic salt, and any combination thereof, b) esterifying the
first product in presence of an acid catalyst of a concentration above 5% at a
temperature above 115 degrees C to produce a second product, c) alkylating the
second product at a temperature above 115 degrees C to form a third product, and d)
crosslinking the third product at a temperature above 115 degrees C to form an end
product. The resulting polymer may further react with the acid catalyst to form the
desired anionic polymer.
EXAMPLES
The foregoing may be better understood by reference to the following
examples, which is presented for purposes of illustration and is not intended to limit
the scope of the invention.
Example 1: Synthesis of Polyglycerols
100 Units (or using different amounts) of glycerol were added to a
reaction vessel followed by 3.0 to 4.0% of active NaOH relative to the reaction
mixture. This mixture was agitated and then gradually heated up to 240° C under a
particular low reactivity atmospheric environment of nitrogen flow rate of 0.2 to 4
mol of nitrogen gas per hour per mol of monomer. This temperature was sustained
for at least three hours to achieve the desired polyglycerol compositions, while being
agitated under a particular low reactivity atmospheric environment. An in-process
polyglycerol sample was drawn before next step for the molecular
weight/composition analysis/performance test. For the performance test, the
polyglycerol was dissolved in water as 50% product. The analysis of polyglycerols
(PG) is summarized in Table 1.
Table 1: Composition of polyglycerols
Example 2 : Synthesis of Anionic, Lipophilic Polyglycerol (ALPG)
To a reaction vessel with 100 units of polyglycerol (PG2) was added
polyphosphoric acid (116.2% by wt. relative to polylgycerol). The mixture was
gradually heated to 130° C under nitrogen atmosphere while agitating whenever
stirrable, and kept at this condition for hours to achieve the desired phosphorylation.
After cooling down 1-hexanol (31.9% by wt. relative to polyglycerol) was added.
The mixture was gradually heated to 150° C under nitrogen atmosphere while
stirring, and kept at this condition for hours to result in the final composition. The
ALPG was dissolved in water as 60% product.
Example 3 : Performance Test
For the organic deposition control experiment, file fold label
(TopStick 4282) is used as adhesives, and baffle test method is used to evaluate the
effectiveness of chemistry by deposition mass comparing to that of a blank test.
The topstick label (12.4 cm x 21.0 cm) is placed on a plain copy
paper, and the paper with the adhesives is cut or torn into 2.5 cm square pieces and
put in a disintegrator vessel. Plain copy paper without adhesives is also cut or torn
in 2.5 cm square pieces and added to the disintegrator vessel to make up 18.75 g of
paper material in total. To the disintegrator vessel, hot water is added to a total
weight of 1875 g of the suspension, and the suspension is mechanically disintegrated
for 30 minutes to result in pulp of 1% consistency. The pulp is transferred to the
baffle testing vessel, and diluted with 1875 g of hot water, followed by mixing to
form the pulp in 0.5% consistency for the test. The baffle testing vessel is heated on
a hot plant and controlled at 50° C while mixing at 425 rpm. After 60 minutes at
this temperature, the baffles (plastic strips) are removed, rinsed with cooled water
and finally air dried. The weight increase of strips is the deposition mass of the
blank test, which is without addition of any chemicals.
For evaluation of chemistry, a chemical sample or product is added
before heated to the testing temperature 50° C in the baffle test, and the deposition
control effectiveness is calculated by the deposition mass difference from the blank
divided by the deposition mass of the blank.
FIG. 3 graphically conveys the effectiveness of the invention (ALPG)
as a superior detackifier of organic contaminants comparing to non-modified
glycerol based polymer PG1 and a Nalco current product 64231 (a copolymer of
vinyl alcohol and vinyl acetate).
While this invention may be embodied in many different forms, there
described in detail herein specific preferred embodiments of the invention. The
present disclosure is an exemplification of the principles of the invention and is not
intended to limit the invention to the particular embodiments illustrated. All patents,
patent applications, scientific papers, and any other referenced materials mentioned
herein are incorporated by reference in their entirety. Furthermore, the invention
encompasses any possible combination of some or all of the various embodiments
described herein and/or incorporated herein. In addition the invention encompasses
any possible combination that also specifically excludes any one or more of the
various embodiments described herein and/or incorporated herein.
The above disclosure is intended to be illustrative and not exhaustive.
This description will suggest many variations and alternatives to one of ordinary
skill in this art. The compositions and methods disclosed herein may comprise,
consist of, or consist essentially of the listed components, or steps. As used herein
the term "comprising" means "including, but not limited to". As used herein the
term "consisting essentially of refers to a composition or method that includes the
disclosed components or steps, and any other components or steps that do not
materially affect the novel and basic characteristics of the compositions or methods.
For example, compositions that consist essentially of listed ingredients do not
contain additional ingredients that would affect the properties of those compositions.
Those familiar with the art may recognize other equivalents to the specific
embodiments described herein which equivalents are also intended to be
encompassed by the claims.
All ranges and parameters disclosed herein are understood to
encompass any and all subranges subsumed therein, and every number between the
endpoints. For example, a stated range of " 1 to 10" should be considered to include
any and all subranges between (and inclusive of) the minimum value of 1 and the
maximum value of 10; that is, all subranges beginning with a minimum value of 1 or
more, (e.g. 1 to 6.1), and ending with a maximum value of 10 or less, (e.g. 2.3 to
9.4, 3 to 8, 4 to 7), and finally to each number 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10
contained within the range.
All numeric values are herein assumed to be modified by the term
"about," whether or not explicitly indicated. The term "about" generally refers to a
range of numbers that one of skill in the art would consider equivalent to the recited
value (i.e., having the same function or result). In many instances, the term "about"
may include numbers that are rounded to the nearest significant figure. Weight
percent, percent by weight, %by weight, wt %, and the like are synonyms that refer
to the concentration of a substance as the weight of that substance divided by the
weight of the composition and multiplied by 100. All percentages and ratios are by
weight unless otherwise stated.
As used in this specification and the appended claims, the singular
forms "a," "an," and "the" include plural referents unless the content clearly dictates
otherwise. Thus, for example, reference to a composition containing "a compound"
includes a mixture of two or more compounds. As used in this specification and the
appended claims, the term "or" is generally employed in its sense including "and/or"
unless the content clearly dictates otherwise.
This completes the description of the preferred and alternate
embodiments of the invention. Those skilled in the art may recognize other
equivalents to the specific embodiment described herein which equivalents are
intended to be encompassed by the claims attached hereto.

Claims
1. A method of reducing the deposition of organic contaminants in
papermaking processes, comprising adding to pulp or a papermaking system an
effective amount of a composition comprising an anionic lipophilic branched, cyclic
glycerol-based polymer, wherein the composition selectively bonds with the organic
contaminants to form a complex and the complex is stable in papermaking
processes.
2. The method of claim 1, wherein the anionic group is one selected from the
list consisting of phosphates, phosphonates, carboxylates, sulfonates, the like and
any combination thereof.
3. The method of claim 1, wherein the glycerol-based polymer is an anionic
lipohydrophilic glycerol based polymer.
4. The method of claim 1, wherein the glycerol-based polymer is branched,
hyperbranched, dendritic, cyclic or any combination thereof.
5. The method of claim 1, wherein the branched, cyclic glycerol-based polymer
is cross-linked.
6. The method of claim 1, wherein the anionic branched, cyclic glycerol-based
polymer is a random polymer of the monomeric units including R indicated in the
following formula:
wherein:
m, n, o, p, q and r are independently 0 to 700;
R and R' are independently -(CH 2) - , wherein each x is independently 0 or
1; and
each R is independently selected from hydrogen, acyl, C1-C50 alkyl and
anionic groups.
7. The method of claim 6, wherein each Ri is independently selected from
hydrogen, C2-Ci8 alkyl, and-C (0 )CH(OH)CH3.
8. The method of claim 6, wherein m, n, 0 , p, q and r are independently selected
from 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23,
24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45,
46, 47, 48, 49 and 50.
9. The method of claim 1, wherein the glycerol-based polymer has a weightaverage
molecular weight of about 200 Da to about 500,000 Da.
10. The method of claim 1, further comprising adding to the pulp or the
papermaking system at least one component selected from the group consisting of
fixatives, dispersants, and other detackifiers.
11. The method of claim 1, wherein the organic contaminants are stickies.
12. The method of claim 1, wherein the organic contaminants are pitch, stickies
or combination thereof.
13. The method of claim 1, wherein the composition is added to a pulp slurry in
a pulper, latency chest, reject refiner chest, disk filter or Decker feed or accept,
Whitewater system, pulp stock storage chest, blend chest, machine chest, headbox,
saveall chest, or any combination thereof in the papermaking process.
14. The method of claim 1, wherein the composition is added to a surface in the
papermaking process selected from a pipe wall, a chest wall, a machine wire, a press
roll, a felt, a foil, an Uhle box, a dryer, or any combination thereof.
15. The method of claim 1, wherein the anionic branched, cyclic glycerol-based
polymer is added to a pulp slurry in the papermaking process.
16. The method of claim 1, wherein the effective amount of the anionic
branched, cyclic glycerol-based polymer is from about 5 ppm to about 300 ppm.