KR102134245B1 - Anionic lipophilic glycerol-based polymers for organic deposition control in paper-making processes - Google Patents

Abstract

The present invention relates to methods and compositions for reducing the deposition of pitch and sticky in a papermaking process. The method involves introducing an anionic glycerol-based polymer into the papermaking process. This anionic polymer prevents pitch and sticky from being deposited and agglomerated in the papermaking process.

Description

Anionic lipophilic glycerol-based polymer for controlling organic deposition in papermaking process {ANIONIC LIPOPHILIC GLYCEROL-BASED POLYMERS FOR ORGANIC DEPOSITION CONTROL IN PAPER-MAKING PROCESSES}

The present invention relates to a method for reducing deposition of organic contaminants such as pitch and sticky in a papermaking process. Deposition of organic contaminants on process equipment, screens and contamination vessels in papermaking can significantly reduce process efficiency and paper quality. Deposition onto machine wires, felts, foils, headbox surfaces, screens, and instruments will costly cause downtime for cleaning to avoid problems associated with poor process control, reduced throughput and poor sheet properties. Can. These contaminants are generally referred to as "pitch" or "sticky" in the paper industry. Pitch deposits are generally derived from natural resins present in natural pulp, including terpene hydrocarbons, rosin/fatty acids or salts thereof, such as pimaric acid, finic acid and abietic acid, glyceryl esters of fatty acids, sterols, and the like. Sticky and white pitch generally represent hydrophobic materials used in paper making, such as sizing agents, coating binders and pressure sensitive or contact adhesives. These materials can form deposits when reintroduced into a recycled fiber system. Other common organic contaminants that are chemically similar to Sticky and found in recycling applications include waxes derived primarily from wax-coated old corrugated containers, and polyisoprene. Pitch and sticky may also contain captured inorganic materials such as talc, calcium carbonate or titanium dioxide.

Recycled fibers also represent secondary fibers that are repulped to provide the paper stock with raw materials for new paper production. The secondary fibers may be pre-consumer or post-consumer paper materials suitable for use in the production of paper products. Sources of secondary fibers may include old newspapers (ONP), old corrugated containers (OCC), mixed office waste paper (MOW), computer printed materials (CPO), ledgers, and the like. These once-treated papers contain various types of adhesives (depressants, hot melts, etc.), inks and coating binders.

Pitch and sticky are virtually hydrophobic and therefore unstable as colloids in aqueous papermaking environments, thus promoting their deposition. The main problems arising from deposition are: (1) reduced throughput due to clogging of the forming fabric and press felt, (2) sheet hole or paper tearing due to large deposits, and falling off the equipment, and (3) final Reduced sheet quality due to large particle contaminants in the sheet.

One method used to address pitch and sticky deposition is through the use of a detackifier. The detackifier passivates the exposed surfaces of the pitch and sticky particles, making them non-adhesive and not deposited. A significant number of chemicals are known to be effective detackifiers. Effective organic viscous agents include polyvinyl alcohol, copolymers of vinyl alcohol and vinyl acetate, polyethylene oxide, polyacrylates and water-soluble globulins. In order for the detackifier to work well, it must satisfy two critical functions: 1) it must be selectively and sufficiently adhered to the surface of the pitch or sticky surface, 2) it is produced in water and sticky/pitch-detackant complex Should stabilize.

The technology described in this paragraph is not intended to be considered as acknowledging that any patent, publication, or other information referred to herein is "prior art" in connection with the present invention, unless specifically indicated otherwise. In addition, this paragraph should not be construed to mean that no other appropriate information exists or that an investigation has been made, as defined in 37 CFR § 1.56(a).

At least one embodiment of the invention relates to a method of reducing deposition of organic contaminants in a papermaking process. The method comprises adding an effective amount of a composition comprising an anionic lipophilic branched glycerol-based polymer to a pulp or paper system, the composition being selectively combined with an organic contaminant to form a composite, the composite being a papermaking process It is stable.

The anionic group can be one selected from the list consisting of phosphate, phosphonate, carboxylate, sulfonate, and the like, and any combinations thereof. The glycerol-based polymer can be an anionic lipid-hydrophilic glycerol based polymer. The glycerol-based polymer can be branched, hyperbranched, dendritic, cyclic, or any combination thereof. Branched cyclic glycerol-based polymers can be crosslinked. The branched cyclic glycerol-based polymer of anions may comprise a random arrangement of monomer units comprising R ₁ represented by the formula:

In the above formula,

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;

Each R ₁ is independently selected from hydrogen, acyl, C ₁ -C ₅₀ alkyl and anionic groups.

Each R ₁ is independently selected from hydrogen, C ₂ -C ₁₈ alkyl, and -C(O)CH(OH)CH ₃ . m, n, o, p, q and r each independently, 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. Glycerol-based polymers have a weight-average molecular weight of about 200 Da to about 500,000 Da.

The method may further include adding at least one component selected from the group consisting of fixatives, dispersants and other detackifiers to the pulp or paper system. The organic contaminants can be pitch, sticky, or a combination thereof. Compositions include pulp makers, atmospheric chests, reject refiner chests, disk filters or decker feeders or receivers, whitewater systems, pulp in papermaking processes To be added to the pulp slurry in a pulp stock storage chest, blend chest, machine chest, headbox, saveall chest, or any combination thereof. Can.

The composition can be added to a surface selected from a pipe wall, chest wall, machine wire, press roll, felt, foil, Uhle box, dryer, or any combination thereof in the papermaking process. Anionic branched cyclic glycerol-based polymers can be added to the pulp slurry in the papermaking process. An effective amount of anionic branched cyclic glycerol-based polymer can be from about 5 ppm to about 300 ppm.

The detailed description of the drawings is described below in conjunction with the specific reference numbers described in the drawings.
1 is an illustration of an anionic glycerol based polymer used in the present invention.
2 is an illustration of various glycerol based structural units that can be used to form glycerol based polymers.
3 is a graph demonstrating the effectiveness of the present invention.

The following definitions are provided to determine how the terms used in this application and in particular the claims should be interpreted. The definition 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(O)R, wherein R is alkyl, alkenyl, alkynyl, aryl, heteroaryl or heterocyclyl, any of which It may be further substituted.

As used herein, " alkyl " is a linear, branched or cyclic saturated hydrocarbon group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tertiary- Butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, cyclopentyl group, cyclohexyl group and the like. Alkyl groups can be optionally substituted.

"Branched" means a polymer having a branching point connected to a chain of three or more segments. Branching can be measured by ¹³ C NMR based on methods of known literature described in Macromolecules , 1999 , 32, 4240. Branched polymers as used herein include highly branched and resinous polymers.

" Circular " means a polymer having a cyclic or cyclic structure. The cyclic structural unit can be formed by intramolecular cyclization or any other method.

“Branch map ” or DB refers to the molar fraction of monomer units at the base of the chain branched off the main polymer chain, compared to a fully branched dendrimer, as described in Macromolecules , 1999 , 32, 4240. It is measured by ¹³ C NMR based on methods of known literature. Cyclic units or branched alkyl chains derived from fatty alcohols or fatty acids are not included in the branching branch. In a complete dendrimer, DB is 1 (or 100%).

“ Circularity ” or DC refers to the molar fraction of cyclic structural units in the polymer compared to total monomer units. The cyclic structural unit can be formed by intramolecular cyclization of the polyol or any other method for incorporation into the polyol. The annular structural unit includes basic structural units (V, VI and VII in FIG. 2) and analogs thereof. The circularity can be measured by ¹³ C NMR.

" Glycerol-based polymer " is any polymer containing repeating glycerol monomer units such as polyglycerol, polyglycerol derivatives, and glycerol monomer units and at least another monomer unit to other multi-monomer units regardless of the order of the monomer unit arrangement. Composed polymers, glycerol-based polymers include, but are not limited to, alkylated, branched cyclic polyglycerol esters, as well as those described in US patent applications 13/484,526, 12/720,973, and 12/582,827.

" Highly branched " means a highly branched polymer having a three-dimensional tree-like structure or a resinous form.

“Lipophilic glycerol-based polymer ” means a lipophilic polyglycerol resulting from a lipophilic modification of a glycerol-based polymer having lipophilic and hydrophilic functionality, such as polyglycerol (hydrophilic), wherein At least some of all of the lipophilic properties are derived from lipophilic carbon-containing groups that are interlocked with the polymer, and lipophilic modifications are such as alkylation and esterification modifications.

“ Multifunctional ” means the composition of a substance that selectively binds two or more functionalities, such as a substance, to form a complex to maintain the stability of such a complex in water.

“ Paper process ” means a method of making a paper product from pulp, which includes forming an aqueous cellulose paper stock, removing the liquid of the stock to form a sheet and drying the sheet. The steps of papermaking stock formation, drainage and drying can be performed in any conventional manner generally known to those skilled in the art. The papermaking process may also include a pulping stage, that is, a stage for producing pulp from lignocellulosic raw materials, and a bleaching stage, that is, chemical treatment of the pulp for improving brightness.

“ Substituted ” as used herein may mean that any at least one hydrogen on a specified atom or group is replaced by another group, provided that it does not exceed the normal value of the specified atom. For example, if the substituent is oxo (ie =O), then two hydrogens on the atom are replaced. Combinations of substituents and/or variables are permitted provided that the substituents do not significantly affect the synthesis or use of the compound.

“ Surfactant ” is a broad term including anionic, nonionic, cationic and zwitterionic surfactants. Possible descriptions of surfactants are mentioned in Kirk- Othmer , Encyclopedia of Chemical Technology , Third Edition, volume 8, pages 900-912 and McCutcheon's Emulsifiers and Detergents , both of which are incorporated herein by reference. do.

" Viscous remover " is a treatment chemical that reduces or disperses the viscosity of other substances present in the papermaking process, otherwise it does not disperse, causing the substances present in the papermaking process to become viscous, and the viscous remover is the viscosity of pitch and sticky. When reducing or dispersing them, pitch and sticky become less prone to forming aggregates, depositing onto papermaking equipment, or forming spots or holes in the product.

Even if the above definitions or techniques mentioned elsewhere in this application do not match the meanings (obvious or implied) mentioned in the supply books commonly used in the dictionary or incorporated by reference into this application, this application and in particular It is understood that the claims term should be interpreted according to the definition or description of the present application, and is not to be taken according to common definitions, dictionary definitions or definitions incorporated by reference. In view of the above, if the term is to be understood only when interpreted by a dictionary, such a term is described in Kirk-Othmer Encyclopedia of Chemical Technology , 5th Edition (2005) (Published by Wiley, John & Sons, Inc. )], this definition determines how the term should be defined in the claims.

In at least one embodiment of the invention, the deposition of pitch or sticky in the papermaking process water is controlled by the addition of the new detackifier composition to the process water. The composition comprises an anionic lipophilic glycerol based polymer. The polymer comprises a glycerol-based polymer backbone chemically modified with multi-functional groups.

In at least one embodiment, chemical modification of the glycerol-based polymer is performed with anionic groups and lipophilic groups. The lipophilic group can be an aliphatic and/or aromatic hydrocarbon of 1 to 50 carbon atoms. Anionic groups can be selected from the list consisting of: phosphates, phosphonates, carboxylates, sulfonates, their analogues including acid and/or ionic salt forms and any combinations thereof. The anionic charge density can be from 1% to 99%.

In at least one embodiment, the anionic modification of the glycerol-based polymer is phosphorylation. Representative examples of such phosphorylation are described in US Patent 3,580,855. In at least one embodiment, the anionic modification is phosphonation. Representative examples of such phosphonation are in the journal Science [ Michael Additions to Activated Vinylphosphonates , by Tomasz Janecki et al ., 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 2004/0018948A1 and 2006/0047168A1. 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 of a glycerol-based polymer is alkylated, alkoxylated, oxyalkylated, esterified as described in US patent applications 13/560,771, 13/484,526, 12/720,973 and references therein. Or through any combination of these.

In at least one embodiment, the anionic and lipophilic modification of the glycerol-based polymer is carried out together in one step, separated into two steps or a combination thereof.

In at least one embodiment, the lipophilic modification enhances the hydrophobic interaction between pitch/sticky and anionic glycerol-based polymers. In at least one embodiment, the anionic functionality improves water solubility for dispersing pitch/sticky. In at least one embodiment, the anionic functionality prevents sticky in the papermaking process by chelating cationic ions commonly present in water such as calcium and magnesium to increase the glass transition temperature of the pitch/sticky. In at least one embodiment, a well balanced strain synergistically improves organic deposition control.

In at least one embodiment, the backbone of the anionic lipophilic glycerol-based polymer is a branched cyclic glycerol based polymer as described, for example, in US patent application 2011/0092743A1. Without being bound by theory, lipophilic groups can interact with hydrophobic contaminants, for example, in pulp slurries in papermaking processes. The hydrophilic portion can help disperse the lipophilic contaminants from the water. The lipophilic group can be introduced through 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 functionality. Features of different polarity from both functional groups can be adjusted to optimally perform pitch and sticky dispersion.

In at least one embodiment, the glycerol-based polymer is a lipophilic glycerol-based polymer as illustrated in Figure 1, wherein m, n, o, p, q and r are independently 0-700; R and R'are independently -(CH ₂ ) _x -, where each x is independently 0 or 1; Each R ₁ is independently selected from hydrogen, acyl and alkyl, wherein at least R ₁ is alkyl.

The composition may be added to a papermaking process comprising natural pulp, recycled pulp, or combinations thereof at any one or more of a variety of locations during the papermaking process. Suitable locations include pulp maker, atmospheric chest, reject refiner chest, disc filter or decker feed or receiver, whitewater system, pulp stock storage chest (low density ("LD"), medium roughness (MC) or high roughness (HC) ), compound chest, machine chest, headbox, saveall chest, paper machine whitewater system and combinations thereof. The composition can also be added to the pulp slurry in a papermaking process. The composition can also be used in the papermaking process to surface surfaces such as metal, plastic or ceramic surfaces such as pipe walls, chest walls, machine wires, press rolls, felts, foils, rate boxes, dryers and any equipment surfaces that come into contact with fibers during paper processing. Can be applied to.

The method can include contacting the fiber with the composition. The fibers can be cellulosic fibers such as recycled fibers, natural wood cellulose fibers or combinations thereof.

In at least one embodiment, the composition is added to the papermaking process using recycled paper fibers. Recycled fibers can be obtained from a variety of paper products or fiber-containing products such as cardboard, newsprints, printing grades, hygiene products or other paper products. These products may include, for example, old cardboard containers (OCC), old newspapers (ONP), mixed office waste papers (MOW), old magazines and books, or combinations thereof. Paper products of this type typically contain large amounts of hydrophobic contaminants. In embodiments using natural fibers, the method may include the use of pulp derived from softwood, hardwood, or combinations thereof. Natural pulp can include bleached or unbleached kraft, sulfite pulp or other chemical pulp, and wood pulp (GW) or other mechanical pulp such as, for example, thermomechanical pulp (TMP).

Examples of organic hydrophobic contaminants include "sticky" and wood resins, which may include adhesives and analogs, glues, hot melts, coatings, coating binders, pressure sensitive binders, synthetic polymers produced from non-pulped wet steel resins, “Pitch” which may include rosin and resin acid salts, including those known in the art. Materials of this type are typically found in paper containing products such as newsprints, corrugated containers and/or mixed office waste paper. Such hydrophobic contaminants are present polymers such as styrene butadiene rubber, vinyl acrylate polymer, polyisoprene, polybutadiene, natural rubber, ethyl vinyl acetate polymer, polyvinyl acetate, ethylvinyl alcohol polymer, polyvinyl alcohol, styrene acrylate polymer and And/or other synthetic polymers.

The method can control the deposition of hydrophobic contaminants in the papermaking process, for example, onto the components of the papermaking process. For example, the method can control hydrophobic contaminants present in the paper mill stock. For example, the method can reduce, inhibit or eliminate the deposition of hydrophobic contaminants in the papermaking process. The method can also reduce the size of contaminant particles through dispersion and inhibition of aggregation and/or reduce the viscosity of hydrophobic contaminants compared to papermaking processes where the composition is not used. For example, the method comprises at least about 5% to about 40% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15) compared to a papermaking process in which the composition is not used. %, 20%, 25%, 30%, 35% or 40%). In embodiments, the method comprises at least about 5% to about 95% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15) compared to a papermaking process in which the composition is not used. %, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%) It is possible to reduce the deposition of hydrophobic contaminants.

In this method, the composition can be added to the papermaking process in an amount effective to reduce the deposition of hydrophobic contaminants compared to a papermaking process where the composition is not used. For example, the composition may be from about 10 ppm to about 300 ppm, for example from about 50 ppm to about 200 ppm, or from about 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 140 ppm, 150 ppm, It may be added to the pulp slurry in an amount of 160ppm, 170ppm, 180ppm, 190ppm to about 200ppm. The effective amount is at least 5% to about 95% (e.g., about 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 25) compared to a papermaking process in which the composition is not used. %, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% or 95%) Can be reduced. The method may further include adding at least one component selected from the group consisting of fixatives, detackifiers and other dispersants to the papermaking system.

In at least one embodiment, the glycerol-based polymer is any polymer containing repeating glycerol monomer units such as polyglycerol, polyglycerol derivatives, and glycerol monomer units and at least one other monomer unit, regardless of the order of the monomer unit arrangement. It may be a polymer consisting of. Suitably, the other monomers can be polyols or hydrogen active compounds that can react with glycerol or any polyglycerol structure, such as pentaerythritol, glycols, amines, and the like. The polymer can be linear, branched, highly branched, cyclic, resinous, and any combination thereof, and has sub-chain/sub-regions characterized by any combination thereof.

In at least one embodiment, the glycerol-based polymer is branched. In at least one embodiment, the branched structure of the polymer backbone is not present in the lipophilic chain. In at least one embodiment, the branched structure increases the polymer dimension for effective interfacial interaction, leading to exceptional organic deposition control. Branching can be particularly useful as it promotes the increased molecular weight of glycerol-based polymers. Branched polymers include both highly branched and dendritic structures. The branched cyclic glycerol-based polymer can have a branching degree of at least about 0.10, for example about 0.20 to about 0.75 or about 0.30 to about 0.50. For example, branched cyclic glycerol-based polymers are 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 it may have a branching degree of about 0.75.

In at least one embodiment, the glycerol-based polymer is cyclic, ie, at least one cyclic or cyclic structure, or has at least one cyclic or cyclic structured polymer molecule in the polymer. Such a cyclic structure can be formed during the polymerization process, for example, through an intramolecular cyclic reaction. The stiffness of the annular structure in the polymer backbone uniquely expands the molecular dimensions and increases the hydrodynamic volume, acting better interfacially to disperse pitch and sticky. The cyclic glycerol-based polymer can have a degree of cyclization of about 0.01 to about 0.50. For example, a branched cyclic glycerol-based polymer can have a degree of cyclization of at least 0.01, for example from about 0.02 to about 0.19 or from about 0.05 to about 0.15. For example, the branched cyclic glycerol-based polymer is 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 these compounds, 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; Each R ₁ is independently selected from hydrogen, acyl, alkyl, acid and anionic groups. Anionic groups can be present in acidic form in acidic conditions, anionic salt form in neutral or basic conditions, or any combination thereof. Anionic groups phosphate -P(O)(OH) ₂ or -(CH2) _x OP(O)(OH) ₂ , phosphonate -(CH ₂ ) _x P(O)(OH) ₂ , carboxylate- (CH ₂ ) _x C(O)OH, sulfonate (CH ₂ ) _x S(O) ₂ OH and combinations thereof, wherein H can be independently substituted by any other group or atom Each x can be any number from 0 to 50 independently. Moreover, it should be understood that the compound illustrated in FIG. 1 is a random polymer of indicated monomer units comprising R ₁ groups. For example, it is understood that in an exemplary embodiment where m, n, o, p, q and r are each 1, the monomer units may be present in any order and need not necessarily be the order illustrated in FIG. 1. In another exemplary embodiment where m, n, o, p, q and r are each 2, the monomer units may or may not have two “m” units close to each other, and two “n” units close to each other. It is understood that it may or may not exist, and so forth, in any order. In another exemplary embodiment, wherein one R ₁ is H, two R ₁ is -P(O)(OH) ₂ , and another two R ₁ is dodecanol, any group of groups is an end group or It is understood that it may or may not be present on any of the non-terminal groups.

In the embodiment of the exemplary structural formula of Figure 1, each m, n, o and p is independently 1-700, and each q and r is independently 0-700. In the embodiment of the structural formula illustrated in Figure 1, each m, n, o and q is independently 1-700, and each p and r is independently 0-700. In the embodiment of the structural formula illustrated in Figure 1, each m, n, o, p, q and r are 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 is independently 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 structural formula illustrated in Figure 1, each R ₁ is independently selected from hydrogen, acyl and C ₁ -C ₅₀ alkyl. When R ₁ is alkyl, it is, for example, C ₁ -C ₅₀ alkyl, C ₁ -C ₄₀ alkyl, C ₁ -C ₃₀ alkyl, C ₁ -C ₂₄ alkyl, C ₆ -C ₁₈ alkyl, C _10- It may be a C ₁₆ alkyl or C ₁₂ -C ₁₄ alkyl group. For example, each R _{1 that} is alkyl is independently C ₁ , C ₂ , C ₃ , C ₄ , C ₅ , C ₆ , C ₇ , C ₈ , C ₉ , C ₁₀ , C ₁₁ , C ₁₂ , C ₁₃ , C ₁₄ , C ₁₅ , C ₁₆ , C ₁₇ , C ₁₈ , C ₁₉ , C ₂₀ , C ₂₁ , C ₂₂ , C ₂₃ or C ₂₄ alkyl group. The R ₁ group can be optionally substituted with other hydrocarbon-based groups such as branched, cyclic, saturated or unsaturated groups.

When R ₁ is acyl, it may be, for example, a C1-C15 acyl group. When R ₁ is acyl, it may be, for example, -C(O)CH(OH)CH ₃ (lactate). In embodiments, lactate or lactic acid may be produced as a by-product during synthesis of branched cyclic glycerol-based polymers, which may further react with the polymer.

In at least one embodiment, the glycerol-based polymer can include at least two repeat units selected from at least one of the structures recorded in FIG. 2, which include, but are not limited to, linear structures I and II, branched structures III, IV And VIII, cyclic structures V, VI and VII, and any combinations thereof. Any structure in FIG. 2 can be combined with any structure or a structure including itself in any order. The cyclic linkage of any basic cyclic structure of FIG. 2 can contain any structure or structures as part or portions of the linkage. In each of the repeating units shown in Figure 2, each R ₁ is independently selected from hydrogen, acyl, alkyl and anion, and each n and n'is independently 0-700.

Glycerol-based polymers can 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 can be crosslinked. Crosslinked polymers are linear, branched, highly branched, cyclic, resinous, and any combination thereof, and cross-linking between one or more types of polymers having sub-chain/sub-regions characterized by any combination thereof. It includes. The glycerol-based polymer can be self-crosslinking and/or the polymer can be crosslinked through the 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, the crosslinking agent can have at least two double bonds, double bonds and reactive groups, or two reactive groups. Non-limiting examples of such agents are diisocyanate, N,N-methylenebis(meth)acrylamide, polyethylene glycol dimeth)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, trimetaphosphate , Dimethoxydimethsilane, tetraalkoxysilane, 1,2-dichloroethane, 1,2-dibromoethane, dichloroglycerol 2,4,6-trichloro-s-triazine and epichlorohydrin.

Glycerol-based polymers used for anionic and lipophilic modifications can come from commercially available suppliers or are described in U.S. Pat.Nos. 3,637,774, 5,198,532 and 6,765,082 B2 and U.S. Patent Application Publication Nos. 2008/0306211 and 2011/0092743 It can be synthesized according to known methods, such as, or any combination thereof.

For example, in an embodiment, a method of preparing a glycerol-based polymer for modification reacts a reaction mass comprising at least glycerol monomer in the presence of a strong base catalyst at a concentration greater than 2% in a low reactive atmosphere environment at temperatures above 200°C. As a preliminary step, a product comprising a branched cyclic polyol and a by-product comprising lactic acid, lactic salt, and any combination thereof may be included. The method may further include providing more than 3% catalyst. The catalyst can be selected from the group consisting of NaOH, KOH, CsOH, a base stronger than NaOH, and any combinations thereof. A certain amount of strong base catalyst can be used in combination with a weaker base than NaOH. The atmospheric environment can be an atmospheric pressure of less than 760 mm Hg and/or can be a flow of inert gas selected from the list of N ₂ , CO ₂ , He, other inert gases and any combinations thereof, the flow rate being the time per mole of monomer It is an inert gas of 0.2 to 15 mol of sugar. The specific atmospheric environment profile applied can be normal, gradual increase, gradual decrease, or any combination thereof.

The method of making a branched cyclic glycerol-based polymer is a glycerol-based polymer product selected from the group consisting of polyglycerols, polyglycerol derivatives, polyols having both glycerol monomer units and non-glycerol monomer units, and any combinations thereof. You can create The branched cyclic glycerol-based polymer product has at least two hydroxyl groups. At least a portion of the resulting polymer can have both at least 0.1 branching degree and at least 0.01 cyclization degree. The by-product may be at least 1% by weight.

Methods of making branched cyclic glycerol-based polymers can use various forms of glycerol, including pure glycerol, technical glycerol, crude glycerol, or any combination thereof. Such methods may further include other monomers selected from the group consisting of polyols such as pentaerythritol and other monomers capable of reacting with glycol, amine, glycerol or glycerol-based polyol intermediates and any combinations thereof. The monomer(s) and/or catalyst(s) can be mixed at the very beginning of the reaction, any time during the reaction and any combination thereof. The glycerol-based polyol product may be resistant to biological contaminants for at least 2 years after synthesis. The method may further include pre-determining the desired molecular weight of the resulting polyglycerol and adjusting the atmospheric environment to match the optimal environment to produce the desired molecular weight. The method comprises pre-determining the desired branching degree and the desired degree of cyclization and the desired amount of by-products of the resulting polyglycerol, and the desired degree of branching, the desired degree of cyclization and byproducts of the lactic acid and/or lactate salt. The method may further include adjusting the atmospheric environment to conform to the optimal environment for generating the amount.

Anionic lipophilic glycerol-based polymers can be prepared from lipophilic glycerol-based polymers. Lipophilic glycerol-based polymers can be produced from glycerol-based polymers such as those commercially available or those described herein, according to known methods such as alkylation, esterification, and any combination thereof. For example, such polymers are described in German Patent Application Nos. 10307172, Canadian Patent Nos. 2,613,704, U.S. Patent Nos. 3,637,774, 5,198,532, 6,228,416 and 6,765,082 B2, U.S. Patent Application Publication Nos. 2008/0306211 and 2011/0220307, Markova et al. Polymer International , 2003 , 52, 1600-1604] and the like can be produced from glycerol-based polymers according to known methods such as alkylation. Glycerol-based polymers can be produced according to known methods such as esterification of glycerol-based polymers as described in US Pat. No. 2,023,388, US Patent Application Publication No. 2006/0286052 and the like. Esterification can be carried out with or without a catalyst such as acid(s) or base(s).

Anionic lipophilic glycerol-based polymers can be prepared from crosslinked polymers. Cross-linked glycerol-based polymers can be produced in a continuous process under a low reactive atmospheric environment according to the method described in US Patent Application No. 13/484,526 filed May 31, 2012. This method comprises the steps of a) reacting a reactant comprising at least a glycerol monomer in the presence of a strong base catalyst at a concentration greater than 2% at a temperature above 200 degrees Celsius, the first product comprising both branched and cyclic polyols , And producing a by-product comprising lactic acid, a lactic salt and any combinations thereof; b) esterifying the first product at a temperature above 115 degrees Celsius in the presence of an acid catalyst at a concentration greater than 5% to produce a second product, c) alkylating the second product at a temperature above 115 degrees Celsius and the third product And d) crosslinking the third product at a temperature above 115 degrees Celsius to form the final product. The resulting polymer can further react with an acid catalyst to form the desired anionic polymer.

Example

The above may be better understood with reference to the following examples, which are presented for purposes of illustration and are not intended to limit the scope of the invention.

Example 1: Synthesis of polyglycerol

100 units (or different amounts of glycerol) were added to the reaction vessel followed by 3.0 to 4.0% active NaOH compared to the reaction mixture. This mixture was stirred and then gradually heated to 240° C. under a specific low reactive atmospheric environment at a nitrogen flow rate of 0.2 to 4 moles of nitrogen gas per hour per mole per monomer. This temperature was maintained for at least 3 hours while stirring under a certain low reactive atmospheric environment to achieve the desired polyglycerol composition. Manufacturing process Polyglycerol samples were taken before the next step for molecular weight/composition analysis/performance evaluation. For performance evaluation, polyglycerol was dissolved in water as a 50% product. The analysis of polyglycerol (PG) is summarized in Table 1.

Table 1: Composition of polyglycerol

Polyglycerol MW DB Weight of lactic acid compared to PG Remark PG1 9,300 0.34 15% Used for performance evaluation PG2 320 0.24 9% Used in the synthesis of ALPG

Example 2: Synthesis of anionic lipophilic polyglycerol (ALPG)

To the reaction vessel with 100 units of polyglycerol (PG2), polyphosphoric acid (116.2 wt% compared to polyglycerol) was added. The mixture was gradually heated to 130° C. under a nitrogen atmosphere with stirring whenever it was possible to stir and maintained under these conditions for several hours to achieve the desired phosphorylation. After cooling, 1-hexanol (31.9% by weight compared to polyglycerol) was added. The mixture was heated adhesively to 150° C. under a nitrogen atmosphere while stirring, and kept under these conditions for several hours to produce a final composition. ALPG was dissolved in water as a 60% product.

Example 3: Performance evaluation

For the organic deposition control experiment, a file fold label (TopStick 4282) was used as the adhesive, and the effectiveness of the chemicals by the deposition mass was evaluated by comparing with that of the blank evaluation using a baffle evaluation method.

The top stick label (12.4 cm x 21.0 cm) was placed on a flat copy paper, and the copy paper with adhesive was cut into 2.5 cm square pieces and placed in a grinder container. The flat, adhesive-free copy paper was also cut into 2.5 cm square pieces and placed in a crusher container to make up a total of 18.75 g of paper material. Hot water was added to the grinder container to a suspension of 1875 g in total weight, and the suspension was mechanically crushed for 30 minutes to produce 1% roughness of pulp. The pulp was transferred to a baffle evaluation container, diluted with 1875 g of hot water, and then mixed to form a pulp of 0.5% roughness for evaluation. The baffle evaluation vessel was adjusted to 50° C. while heating on a hot plant and mixing at 425 rpm. After 60 minutes at this temperature, the baffle (plastic strip) was removed, rinsed with cold water and finally air dried. The weight increase of the strip is a blank evaluation deposition mass without any chemicals added.

For chemical evaluation, the chemical sample or product was added and then heated to an evaluation temperature of 50° C. in the baffle evaluation, and the deposition control effectiveness was calculated by the deposition mass difference from the blank divided by the deposition mass of the blank.

FIG. 3 graphically illustrates the effectiveness of the present invention (ALPG) as an excellent detackifier for organic contaminants compared to non-modified glycerol based polymers PG1 and Nalco current products 64231 (copolymers of vinyl alcohol and vinyl acetate).

Although many different forms of the invention can be included, specific preferred embodiments of the invention have been described herein in detail. This description is an illustration of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated. All patents, patent publications, scientific journals, and any other referenced material mentioned herein are incorporated by reference in their entirety. In addition, the present invention encompasses any possible combination of some or all of the various embodiments described herein and/or incorporated herein. In addition, the present invention encompasses any possible combination that also specifically excludes any one or more of the various embodiments described and/or incorporated herein.

The above description is intended to be illustrative and not exhaustive. This description will present many variations and alternatives to the skilled person. The compositions and methods described herein can include, consist of, or consist essentially of recorded elements or steps. The term "comprising" as used herein means "including but not limited to." As used herein, the term “consisting essentially of” refers to a composition or method comprising the elements or steps described and any other elements or steps that do not materially affect the novel and basic characteristics of the composition or method. Shows. For example, a composition consisting essentially of recorded ingredients does not contain additional ingredients that will affect the properties of these compositions. Those skilled in the art will recognize other equivalents to the specific embodiments described herein, and such equivalents are also intended to be covered by the claims.

It is understood that all ranges and variables described herein encompass any subranges and all subranges subsumed therein, and all numbers between endpoints. For example, the stated range "1 to 10" means any subrange and all subranges between a minimum value of 1 and a maximum value of 10 (including 1 and 10): i.e., 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 all sub-ranges finally included within the range 1, 2, It should be considered to include 3, 4, 5, 6, 7, 8, 9, and 10.

All numerical values are assumed to be changed by the term “about” herein, whether or not they have been explicitly specified. The term “about” generally refers to a range of numbers that a person skilled in the art can regard as equivalent to the stated value (ie, having the same function or result). In many cases, the term “about” can include a rounded number for the nearest significant digit. Weight percent, percent by weight, weight percent, wt percent, and the like are synonymous and refer to the concentration of a substance divided by the weight of the 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 form includes a plurality of indications, unless expressly indicated otherwise. Thus, for example, reference to a composition containing “a compound” includes a mixture of two or more compounds. The term “or” as used in this specification and the appended claims is generally used in its sense including “and/or” unless expressly indicated otherwise.

This application concludes the description of preferred and alternative embodiments of the invention. Those skilled in the art will recognize other equivalents to the specific embodiments described herein, and these equivalents are intended to be covered by the claims appended hereto.

Claims (16)

A method of reducing deposition of organic contaminants in a papermaking process, comprising adding an effective amount of a composition comprising an anionic lipophilic branched glycerol-based polymer to a pulp or paper system, wherein the composition is Combined to form a composite and the composite is a stable method in the papermaking process. The method of claim 1, wherein the glycerol-based polymer is modified by an anionic group selected from the list consisting of phosphate, phosphonate, carboxylate, sulfonate and any combinations thereof. The method of claim 1, wherein the glycerol-based polymer is an anionic lipohydrophilic glycerol based polymer. The method of claim 1, wherein the glycerol-based polymer is branched, hyperbranched, dendritic, or any combination thereof. The method of claim 1, wherein the branched cyclic glycerol-based polymer is crosslinked. The method according to claim 1, wherein the anionic branched cyclic glycerol-based polymer is a random polymer of monomer units comprising R ₁ shown in the following structural formula:

In the above formula,
m, n, o, p, q and r are independently integers from 1 to 700;
R and R'are independently -(CH ₂ ) _x -, wherein each x is independently 0 or 1;
Each R ₁ is independently selected from hydrogen, acyl, C ₁ -C ₅₀ alkyl and anionic groups, provided that at least one R ₁ is an anionic group. 7. The method of claim 6, wherein each R ₁ is independently selected from hydrogen, C ₂ -C ₁₈ alkyl, -C(O)CH(OH)CH ₃ and anionic group, provided that at least one R ₁ is anionic Caused method. According to claim 6, m, n, o, p, q and r are independently 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, Method selected from 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50. The method of claim 1, wherein the glycerol-based polymer has a weight average molecular weight of 200 Da to 500,000 Da. The method of claim 1, further comprising adding to the pulp or paper system at least one component selected from the group consisting of fixatives, dispersants and detackifiers. The method of claim 1, wherein the organic contaminants are sticky. The method of claim 1, wherein the organic contaminants are pitch, sticky or combinations thereof. The composition of claim 1, wherein the composition is used in a papermaking process to produce a pulp, latency chest, reject refiner chest, disk filter or decker feed or Acceptance, whitewater system, pulp stock storage chest, blend chest, machine chest, headbox, saveall chest chest), or any combination thereof, to the pulp slurry. The composition according to claim 1, wherein the composition is used in a papermaking process in a pipe wall, a chest wall, a machine wire, a press roll, a felt, a foil, a Uhle box, and a dryer. ) Or any combination thereof. The method of claim 1, wherein an anionic branched cyclic glycerol-based polymer is added to the pulp slurry in a papermaking process. The method of claim 1 wherein the effective amount of anionic branched cyclic glycerol-based polymer is 5 ppm to 300 ppm.

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