KR20150103146A - 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 comprises introducing an anionic glycerol-based polymer into the papermaking process. These anionic polymers prevent the pitch and sticky from depositing and aggregating in the papermaking process.

Description

ANIONIC LIPOPHILIC GLYCEROL-BASED POLYMERS FOR ORGANIC DEPOSITION CONTROL IN PAPER-MAKING PROCESSES FOR CONTROLLING ORGANIC VAPOR IN PAPER PROCESSES [0002]

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

Recycled fibers also represent secondary fibers that are re-pulped to provide raw materials for the production of new paper to the paper stock. The secondary fibers may be pre-consumer or post-consumer paper materials suitable for use in the production of paper products. The source of the secondary fibers may include old newspapers (ONP), old corrugated containers (OCC), mixed office waste (MOW), computerized prints (CPO), books and the like. Such untreated paper contains various types of adhesives (such as pressure-reducing agents, hot melts, etc.), inks, and coating binders.

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

One method used to deal with pitch and sticky deposition is through the use of a detackifier. The viscous removers passivate the exposed surfaces of the pitch and sticky particles to make them non-adhesive and non-deposited. A significant number of chemicals are known to be effective viscous removers. Effective organic viscous removers include polyvinyl alcohol, copolymers of vinyl alcohol and vinyl acetate, polyethylene oxide, polyacrylates and water-soluble globulins. In order for the viscous remover to work well, it has to fulfill two critical functions: 1) it must be selectively and sufficiently attached to the surface of the pitch or sticky surface, and 2) it must be sticky / pitch- .

The techniques described in this paragraph are not intended to be taken as admission that any patent, publication or other information referred to herein is "prior art" in the context of the present invention, unless specifically indicated otherwise. In addition, this paragraph should not be interpreted to imply that no other appropriate information exists or has been investigated as specified in 37 CFR § 1.56 (a).

At least one embodiment of the present invention is directed to a method of reducing the deposition of organic contaminants in a papermaking process. The method comprises adding to the pulp or paper system an effective amount of a composition comprising an anionic lipophilic branched cyclic glycerol-based polymer, wherein the composition selectively binds to organic contaminants to form a complex, .

The anionic group may be selected from the list consisting of phosphates, phosphonates, carboxylates, sulfonates, etc., and any combination thereof. The glycerol-based polymer may be an anionic lipid hydrophilic glycerol-based polymer. The glycerol-based polymer may be branched, hyperbranched, dendritic, annular or any combination thereof. The branched cyclic glycerol-based polymer may be crosslinked. The branched cyclic glycerol-based polymer of the anion may comprise a random arrangement of monomer units comprising R < ₁ >

In this 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, are selected from hydrogen, acyl, C ₁ -C ₅₀ alkyl and anion group.

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 represent 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 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 at least one component selected from the group consisting of fixing agents, dispersants and other viscous removers to the pulp or paper system. The organic contaminants can be pitch, sticky or a combination thereof. The composition can be used in the papermaking process as a pulp maker, a latency chest, a reject refiner chest, a disk filter or a decker feed or receptacle, a whitewater system, A pulp stock storage chest, a blend chest, a machine chest, a headbox, a saveall chest, or any combination thereof. .

The composition may be added to a surface selected from a pipe wall, a chest wall, a machine wire, a press roll, a felt, a foil, a Uhle box, a dryer, or any combination thereof in a papermaking process. Anionic branched, cyclic glycerol-based polymers may be added to the 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.

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

The following definitions are provided to determine the terms used in the present application and particularly how the claims should be interpreted. The construction of a definition is merely for convenience and is not intended to limit any of the definitions to any particular category.

As used herein, " acyl " refers to a substituent having the general formula -C (O) R, wherein R is alkyl, alkenyl, alkynyl, aryl, heteroaryl or heterocyclyl, May be further substituted.

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

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

" Annular " means a polymer having a cyclic or cyclic structure. The cyclic structure unit may be formed by intramolecular cyclization or any other method.

"Branching" or DB is the compared to the completely branched dendrimers, mean mole fraction of monomer units in the base of the chain is branched off the main polymer chain, and described in the literature [Macromolecules, 1999, 32, 4240 ] Is measured by < ¹³ > C NMR based on the method of the known literature. A cyclic unit derived from a fatty alcohol or a fatty acid or a branched alkyl chain is not included in the branching. In a complete dendrimer, DB is 1 (or 100%).

" Cyclic degree " or DC means the molar fraction of the cyclic structural unit as compared to the total monomer unit in the polymer. The cyclic structure unit may be formed by intramolecular cyclization of the polyol or by any other method for incorporation into the polyol. The annular structural unit comprises basic structural units (V, VI and VII in Fig. 2) and analogues thereof. The circularity can be measured by < ¹³ > C NMR.

A " glycerol-based polymer " refers to any polymer containing repeating glycerol monomer units, such as polyglycerol, polyglycerol derivatives, and glycerol monomer units and at least another monomer unit to another multiple monomer unit Glycerol-based polymers include, but are not limited to, those polymers described in US patent application Ser. Nos. 13 / 484,526, 12 / 720,973, and 12 / 582,827 as well as alkylated, branched cyclic polyglycerol esters.

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

"Lipophilic glycerol-based polymer " means a lipid hydrophilic polyglycerol resulting from the lipophilic modification of a glycerol-based polymer having lipophilic and hydrophilic functionality, for example, polyglycerol (hydrophilic) At least some or all of the lipophilic character is attributed to the lipophilic carbon-containing groups associated with the polymer, and the lipophilic modifications are such as alkylation and esterification modifications.

" Multifunctional " means a composition of two or more functional, eg, materials that selectively bind to and form a complex to maintain the stability of such complexes in water.

By " papermaking process " is meant a process for making a paper product from pulp, including forming an aqueous cellulose paper stock, removing the liquid of the paper stock to form a sheet, and drying the sheet. The steps of papermaking, draining and drying may be performed in any conventional manner generally known to those skilled in the art. The papermaking process may also include a pulping stage, i.e., a stage for making pulp from lignocellulosic raw materials, and a bleaching stage, i.e., chemical treatment of the pulp for brightness enhancement.

" Substituted, " as used herein, may mean that at least one hydrogen of the designated atom or group is replaced with another group, but not exceeding the normal value of the designated atom. For example, when the substituent is oxo (i.e., = O), then two hydrogens on the atom are replaced. A combination of substituents and / or variables is allowed, with the proviso that the substituent does not significantly adversely affect the synthesis or use of the compound.

" Surfactant " is a broad term including anionic, nonionic, cationic and zwitterionic surfactants. A possible explanation of the surface active agent is mentioned in the literature [Kirk- Othmer, Encyclopedia of Chemical Technology , Third Edition, volume 8, pages 900-912] and the method disclosed in [McCutcheon's Emulsifiers and Detergents], both of which are incorporated herein by reference do.

A " viscous remover " is a treatment chemical that reduces or disperses the viscosity of other materials present in the papermaking process, otherwise the materials present in the papermaking process are not dispersed, causing the viscous material to become viscous, The pitches and stickies are less prone to form agglomerates or to be deposited on paper machines or to form spots or holes in the product.

Even if the above definition or the technology referred to elsewhere in this application is not consistent with the meaning (obvious or implied) mentioned in the supply commonly used in the dictionary or incorporated by reference into the present application, It is understood that the claim terms are to be construed in accordance with the definition or description of the present application and do not conform to common definitions, predefined or incorporated definitions as references. In view of the above, if the term can be understood only when interpreted in a dictionary, it is to be understood that such a term is used in Kirk-Othmer Encyclopedia of Chemical Technology , 5th Edition (2005) (Published by Wiley, John & Sons, Inc.). )], This definition will determine how the term should be defined in the claims.

In at least one embodiment of the present invention, the deposition of pitch or sticky in the papermaking process water is controlled by the addition of the novel viscous remover composition to the process water. The composition comprises anionic lipophilic glycerol-based polymers. The polymer comprises a glycerol-based polymer backbone chemically modified with a multi-functional group.

In at least one embodiment, the chemical modification of the glycerol-based polymer is carried out with an anionic group and a lipophilic group. The lipophilic group may be an aliphatic and / or aromatic hydrocarbon of 1 to 50 carbon atoms. The anionic groups can be selected from the list consisting of: phosphates, phosphonates, carboxylates, sulfonates, acids and / or analogs thereof including ionic salt forms and any combination thereof. The anionic charge density may be between 1% and 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 Pat. No. 3,580,855. In at least one embodiment, the anionic modification is phosphonization. Representative examples of such phosphonization are described in the literature [ 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 carboxyalkylations are described in US patent applications 2004 / 0018948A1 and 2006 / 0047168A1. In at least one embodiment, the anionic modification is sulfonation. Representative examples of such sulfonations are described in GB patent specification 802325A.

In at least one embodiment, the lipophilic modification of the glycerol-based polymer is accomplished by alkylation, alkoxylation, oxyalkylation, esterification as described in US patent applications 13 / 560,771, 13 / 484,526, 12 / 720,973 and their references Or any combination thereof.

In at least one embodiment, the anionic and lipophilic modifications of the glycerol-based polymer are performed in one step, in two steps, or in a combination thereof.

In at least one embodiment, the lipophilic modification improves the hydrophobic interaction between the pitch / sticky and the anionic glycerol-based polymer. In at least one embodiment, the anionic functionality improves water solubility for dispersing the pitch / sticky. In at least one embodiment, the anionic functionality prevents the sticky in the papermaking process by chelating the 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 deformation synergistically enhances 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, the lipophilic group can interact with, for example, hydrophobic contaminants in the pulp slurry in the papermaking process. Hydrophilic moieties can help disperse lipophilic contaminants in water. The lipophilic group may be introduced via known methods such as alkylation, alkoxylation, esterification or a combination thereof. In at least one embodiment, at least one portion of the glycerol-based polymer has both alkyl and ester functionality. The characteristics of the different polarities from both functionalities can be adjusted to optimally perform pitch and sticky dispersion.

In at least one embodiment, the glycerol-based polymer is a lipid hydrophilic glycerol-based polymer as illustrated in Figure 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; 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 a combination thereof at any one or more of the various locations during the papermaking process. Suitable locations may include pulp mills, atmospheric chests, reject refiner chests, disc filters or decker feeds or receptacles, whitewater systems, pulp stock storage chests (low density (LD), medium roughness (MC) ), Compounding chests, machine chests, headboxes, save olchists, paper machine white water systems, and combinations thereof. The composition may also be added to the pulp slurry in a papermaking process. The composition may also be applied to any equipment surface in contact with the fiber during surface treatment, such as surface, e.g., metal, plastic or ceramic surfaces, such as pipe walls, chest walls, machine wires, press rolls, felts, foils, Lt; / RTI >

The method may comprise contacting the composition with a fiber. The fibers may be cellulosic fibers, such as recycled fibers, dull 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 various paper products or fiber-containing products such as paperboard, news print, printing grade, sanitary or other paper products. These products may include, for example, old corrugated containers (OCC), old newspapers (ONP), mixed office waste (MOW), old magazines and books, or a combination 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 may include bleached or unbleached Kraft, sulfite pulp or other chemical pulp, and gravel (GW) or other mechanical pulp such as thermomechanical pulp (TMP).

Examples of organic hydrophobic contaminants include "sticky" and wood resins, which may include adhesives and the like, glue, hot melt, coatings, coating binders, pressure sensitive binders, synthetic polymers produced from non- Quot; pitch "which may include rosin and resin acid salts. This type of material is typically found in paper-containing products such as news prints, corrugated containers and / or office waste paper. Such hydrophobic contaminants may be present in the presence of the polymer present, such as styrene butadiene rubber, vinyl acrylate polymer, polyisoprene, polybutadiene, natural rubber, ethyl vinyl acetate polymer, polyvinylacetate, ethyl vinyl alcohol polymer, polyvinyl alcohol, styrene acrylate polymer, / RTI > 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 the hydrophobic contaminants present in paper mill stock. For example, the method can reduce, suppress, or eliminate the deposition of hydrophobic contaminants in the papermaking process. The method may also reduce the size of the contaminant particles through dispersion and aggregation inhibition and / or reduce the viscosity of the hydrophobic contaminants as compared to a paperless process in which the composition is not used. For example, the method may be used to provide a composition that is at least about 5% to about 40% (e.g., about 5%, 6%, 7%, 8%, 9%, 10% %, 20%, 25%, 30%, 35% or 40%) of the contaminant particles. In embodiments, the method may further comprise at least about 5% to about 95% (e.g., about 5%, 6%, 7%, 8%, 9%, 10% %, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% It is possible to reduce the deposition of hydrophobic contaminants as much as possible.

In the present method, the composition may be added to the papermaking process in an amount effective to reduce the deposition of hydrophobic contaminants as compared to a papermaking process where the composition is not used. For example, the composition may comprise from about 10 ppm to about 300 ppm, such as from about 50 ppm to about 200 ppm, or about 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 110 ppm, 120 ppm, 130 ppm, 160 ppm, 170 ppm, 180 ppm, 190 ppm to 200 ppm, based on the total weight of the pulp slurry. An effective amount is at least about 5% to about 95% (e. G., About 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20% Deposition of hydrophobic contaminants as much as 30%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90% . The method may further comprise adding at least one component selected from the group consisting of a fixing agent, a viscous remover, and other dispersants to the papermaking system.

In at least one embodiment, the glycerol-based polymer may be any glycerol monomer unit and at least one other monomer unit, irrespective of the order of any polymer containing repeating glycerol monomer units, such as polyglycerol, polyglycerol derivatives, ≪ / RTI > Suitably, the other monomer may be a polyol or hydrogen active compound capable of reacting with glycerol or any polyglycerol structure, such as pentaerythritol, glycol, amine, and the like. The polymer can be linear, branched, hyperbranched, 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 branch structure of the polymer backbone is not present in the lipophilic chain. In at least one embodiment, the branched structure increases polymer dimensions for effective interfacial interactions leading to exceptional organic deposition control. Branching can be particularly useful because it promotes the increased molecular weight of glycerol-based polymers. The branched polymer comprises both a highly branched structure and a resinous structure. The branched cyclic glycerol-based polymer may have a molecular weight of at least about 0.10, such as from about 0.20 to about 0.75, or from about 0.30 to about 0.50. For example, the branched cyclic glycerol-based polymer may have a weight average molecular weight 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, Or about 0.75 min.

In at least one embodiment, the glycerol-based polymer is cyclic, that is, has at least one cyclic or cyclic structure, or has at least one cyclic or cyclic structured polymer molecule in the polymer. Such cyclic structures can be formed during the polymerization process, for example, through intramolecular cyclization reactions. The stiffness of the annular structure in the polymer backbone uniquely expands the molecular dimensions and increases the hydrodynamic volume to better serve the system area to disperse the pitch and sticky. The cyclic glycerol-based polymer may have a degree of cyclization of from 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, 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 may be present in an amount of from 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 0.14, 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. 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. The anionic groups may be present in acid form at acidic conditions, anionic salt form at neutral or basic conditions, or any combination thereof. Anionic phosphate group -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 may be independently substituted by any other group or atom And each x may independently be an arbitrary number of integers from 0 to 50. In addition, it should be understood that the compounds illustrated in Figure 1 are random polymers of the indicated monomer units comprising the R < _{1 >} group. For example, in an exemplary embodiment where m, n, o, p, q, and r are each 1, it is understood that the monomer units may be in any order and need not necessarily be the order illustrated in FIG. In another exemplary embodiment where m, n, o, p, q and r are each 2, the monomer unit may be such that two "m " units may be close to each other, And may be in any order, such as, but not limited to, and the like. In another exemplary embodiment where one R ₁ is H, two R ₁ are -P (O) (OH) ₂ , and the other two R ₁ are dodecanol, any of the groups may be terminated or Can be present on any of the groups in the non-terminal group.

1, each of m, n, o, and p is independently 1-700, and each q and r is independently 0-700. In the embodiment of the structural formulas illustrated in Figure 1, each of m, n, o and q is independently 1-700, and each p and r independently is 0-700. In the embodiment of the structural formulas illustrated in FIG. 1, each of 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 is independently 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, , 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 an embodiment of the structural formulas illustrated in FIG. 1, each R ₁ is independently selected from hydrogen, acyl, and C ₁ -C ₅₀ alkyl. When R ₁ is alkyl, which 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 - C ₁₆ alkyl or C ₁₂ -C ₁₄ alkyl can be a. For example, alkyl of each R ₁ 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 groups. The R ₁ group may be optionally substituted with other hydrocarbon-based groups such as branched, cyclic, saturated or unsaturated groups.

When R < _{1 >} is acyl, it may, for example, be a C1-C15 acyl group. When the R ₁ is acyl, which may be, for example, -C (O) CH (OH ) CH 3 ( lactate). In embodiments, the lactate or lactic acid may be produced as a by-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 Figure 2, including, but not limited to, linear structures I and II, branched structures III and IV And VIII, cyclic structures V, VI and VII, and any combination thereof. Any of the structures of FIG. 2 may be combined with any structure or structure including itself in any order. The cyclic linkage of any of the basic cyclic structures of Figure 2 may 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 an anion, wherein each n and n 'is independently 0 to 700.

The glycerol-based polymer may have a weight-average molecular weight of from about 100 Da to about 1,000,000 Da.

In at least one embodiment, the glycerol-based polymer may be crosslinked. The cross-linked polymer is a cross-linking between one or more types of polymers having a sub-chain / sub-region characterized by any combination of linear, branched, highly branched, cyclic, . The glycerol-based polymer may be self-crosslinking and / or the polymer may 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 may have at least two double bonds, a double bond and a reactive group, or two reactive groups. Nonlimiting examples of such agents include, but are not limited to, diisocyanates, N, N-methylenebis (meth) acrylamide, polyethylene glycol dimethacrylate, glycidyl (meth) acrylate, dialdehyde such as glyoxal, - 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 , Dimethoxydimethylsilane, 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 may come from commercially available suppliers or may be derived from polymers such as those described in U.S. Patent Nos. 3,637,774, 5,198,532 and 6,765,082 B2 and U.S. Patent Application Publication Nos. 2008/0306211 and 2011/0092743 Or may be any combination thereof. ≪ RTI ID = 0.0 >

For example, in embodiments, a method of making a glycerol-based polymer for modification comprises reacting a reaction mass comprising at least glycerol monomer in the presence of a strong base catalyst at a concentration of greater than 2% , Comprising the step of producing a product comprising a branched cyclic polyol and a byproduct comprising lactic acid, a lactate salt, and any combination thereof. This method may further comprise providing more than 3% of the catalyst. The catalyst may be selected from the group consisting of NaOH, KOH, CsOH, a base stronger than NaOH, and any combination thereof. Certain amounts of strong base catalysts can be used in combination with weaker bases than NaOH. The atmospheric environment can be atmospheric pressure 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 combination thereof, and the flow rate is the time per mole of monomer 0.2 to 15 mol of an inert gas. The particular atmosphere profile applied may be normal, gradual increase, gradual decrease, or any combination thereof.

A method of making a branched cyclic glycerol-based polymer comprises reacting a glycerol-based polymer product selected from the group consisting of polyglycerols, polyglycerol derivatives, polyols having both a glycerol monomer unit and a non-glycerol monomer unit, and any combination thereof Can be generated. The branched cyclic glycerol-based polymer product has at least two hydroxyl groups. At least a portion of the resulting polymer may have at least 0.1 minute map and at least 0.01 roundness. The byproduct may be at least 1% by weight.

The process for preparing the branched cyclic glycerol-based polymer may use various forms of glycerol, including pure glycerol, technical glycerol, crude glycerol, or any combination thereof. Such methods may additionally comprise a polyol such as pentaerythritol and other monomers selected from the group consisting of glycols, amines, glycerol or other monomers capable of reacting with glycerol-based polyol intermediates and any combination thereof. The monomer (s) and / or catalyst (s) can be mixed very early in the reaction, at any time during the reaction, and any combination thereof. The glycerol-based polyol product may be resistant to biological contaminants for at least two years after synthesis. The method may further comprise 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 present methods include the steps of pre-determining the desired fraction of the polyglycerol produced, the desired degree of cyclization and the desired amount of by-product, and the desired degree of cyclization and the desired degree of cyclization and by-product lactic acid and / or lactate salt And adjusting the atmospheric environment to match the optimal environment for generating the quantity.

Anionic lipophilic glycerol-based polymers may be prepared from lipophilic glycerol-based polymers. The lipophilic glycerol-based polymers may 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 No. 10307172, Canadian Patent No. 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, and the like. 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. Esterification may be carried out in the presence or absence of a catalyst, such as acid (s) or base (s).

Anionic lipophilic glycerol-based polymers may be prepared from cross-linked polymers. The crosslinked glycerol-based polymer may be produced in a continuous process under a low reactive atmospheric environment in accordance with the process described in U.S. Patent Application No. 13 / 484,526, filed May 31, Comprising the steps of: a) reacting a reactant comprising at least glycerol monomer in the presence of a strong base catalyst at a concentration of greater than 2% at a temperature of greater than 200 degrees Celsius, comprising the step of reacting a first product comprising a polyol that is both branched and cyclic , And a by-product comprising lactic acid, a lactate salt, and any combination thereof; b) esterifying the first product at a temperature above 115 degrees Celsius in the presence of an acid catalyst in excess of 5% to produce a second product c) alkylating the second product at a temperature above 115 degrees Celsius to form a third product And d) crosslinking the third product at a temperature of greater than 115 degrees Celsius to form the final product. The resulting polymer may be further reacted with an acid catalyst to form the desired anionic polymer.

Example

The foregoing can 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) of glycerol were added to the reaction vessel and 3.0 to 4.0% of active NaOH was added as compared to the reaction mixture. This mixture was stirred and then gradually heated to 240 占 폚 in a specific low reactive atmospheric environment at a nitrogen flow rate of nitrogen gas of 0.2 to 4 moles per mole of monomer per hour. This temperature was maintained for at least 3 hours while stirring under a particular low reactive atmospheric environment to achieve the desired polyglycerol composition. Manufacturing process Polyglycerol samples were taken prior to 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 Lactic acid weight 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)

Polyphosphoric acid (116.2 wt.% Relative to polyglycerol) was added to a reaction vessel having 100 units of polyglycerol (PG2). The mixture was gradually heated to 130 DEG C under a nitrogen atmosphere with stirring whenever possible, and maintained under these conditions for several hours to achieve the desired phosphorylation. After cooling, 1-hexanol (31.9 wt.% Relative to polyglycerol) was added. The mixture was viscously heated to 150 < 0 > C under nitrogen atmosphere with stirring and held under these conditions for several hours to produce the final composition. ALPG was dissolved in water as 60% product.

Example 3: Performance evaluation

For organic deposition control experiments, a file fold label (TopStick 4282) was used as an adhesive and the effectiveness of the chemical by deposition mass was evaluated by comparing it with 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 shredder container. The adhesive-free flat copy paper was also cut into 2.5 cm square pieces and placed in a shredder container to form a total of 18.75 grams of paper material. Hot water was added to the grinder vessel to make a total weight of 1875 g, and the suspension was mechanically pulverized for 30 minutes to produce 1% rough pulp. The pulp was transferred to a baffle evaluation vessel, diluted with 1875 g of hot water, and mixed to form a 0.5% roughness pulp for evaluation. The baffle evaluation vessel was heated on a hot plant and adjusted to 50 DEG C while 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 gain of the strip is the deposition mass of the blank evaluation without any chemicals added.

For chemical evaluation, a chemical sample or product was added followed by heating to an evaluation temperature of 50 DEG 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.

Figure 3 graphically illustrates the efficacy of the present invention (ALPG) as an excellent viscous remover for organic contaminants as compared to the non-modified glycerol-based polymer PG1 and Nalco current product 64231 (a copolymer of vinyl alcohol and vinyl acetate).

While the invention may be embodied in many different forms, certain particularly preferred embodiments of the invention have been described in detail herein. The present disclosure is illustrative of the principles of the present invention and is not intended to limit the invention to the specific embodiments illustrated. All patents, patent publications, scientific papers, and any other references mentioned herein are incorporated by reference in their entirety. The present invention also encompasses any possible combinations of some or all of the various embodiments described herein and / or incorporated herein. The present invention also encompasses any possible combination of any one or more of the various embodiments described herein and / or incorporated herein.

The above description is intended to be illustrative and not exhaustive. This description will suggest many variations and alternatives to those skilled in the art. The compositions and methods described herein may comprise, consist of, or consist essentially of the recorded elements or steps. The term " comprising " as used herein means "including but not limited to. The term "consisting essentially" as used herein is intended to encompass a composition or method comprising any of the elements or steps described and any other element or step that does not materially affect the novel and essential characteristics of the composition or method . For example, a composition essentially composed of the 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 encompassed by the claims.

It is understood that all ranges and parameters recited herein are intended to encompass any sub-ranges and sub-ranges encompassed therein and all numbers between end-points. For example, the ranges "1 to 10" mentioned may include any subranges between minimum value 1 and maximum value 10 (and including 1 and 10) and all subranges: a minimum value of 1 or greater 1 to 6.1) and all subranges ending with a maximum value of 10 or less (e.g., 2.3 to 9.4, 3 to 8, 4 to 7) and finally within each of the numbers 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10.

All numerical values are presumed to be varied by the term "about" herein, whether or not precisely stated. The term "about" generally refers to a range of numbers that one of ordinary skill in the art would consider equivalent to the stated value (i.e., having the same function or result). In many instances, the term " about "may include an approximated number for the nearest significant number. Weight percent, percent by weight, wt%, wt%, and so on are synonymous and represent the concentration of the material divided by the weight of the composition and multiplied by 100. All percentages and ratios are by weight unless otherwise stated.

The singular forms as used in this specification and the appended claims include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to a composition containing a "compound" includes a mixture of two or more compounds. The word "or" as used in this specification and the appended claims is generally used herein to mean "including and / or" unless explicitly indicated to the contrary.

We have completed the description of preferred and alternative embodiments of the present invention. Those skilled in the art will recognize other equivalents to the specific embodiments described herein, and equivalents thereof are intended to be encompassed by the claims appended hereto.

Claims (16)

A method of reducing organic contaminant deposition in a papermaking process, including adding an effective amount of a composition comprising an anionic lipophilic branched cyclic glycerol-based polymer to a pulp or paper system, To form a composite and the composite is stable in the papermaking process. The method of claim 1, wherein the anionic group is selected from the list consisting of phosphates, phosphonates, carboxylates, sulfonates, and the like and any combination 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, annular, or any combination thereof. The method of claim 1, wherein the branched cyclic glycerol-based polymer is crosslinked. 6. The method of claim 1, wherein the anionic branched cyclic glycerol-based polymer is a random polymer of monomer units comprising R < ₁ >

In this 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 an anionic group. 7. The method of claim 6, wherein each R ₁ is independently selected from hydrogen, C ₂ -C ₁₈ alkyl, and -C (O) CH (OH) CH ₃ . 7. The compound of claim 6 wherein m, n, o, p, q and r are independently 0,1,2,3,4,5,6,7,8,9,10,11,12,13,14, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50. The process of claim 1, wherein the weight average molecular weight of the glycerol-based polymer is from about 200 Da to about 500,000 Da. The method of claim 1, further comprising adding at least one component selected from the group consisting of fixatives, dispersants, and other detackifiers to the pulp or paper system. The method of claim 1, wherein the organic contaminants are sticky. The method of claim 1, wherein the organic contaminants are pitch, sticky, or a combination thereof. The method of claim 1, wherein the composition is selected from the group consisting of a pulper, a latency chest, a reject refiner chest, a disk filter or a decker feed, It can be used for accept, whitewater system, pulp stock storage chest, blend chest, machine chest, headbox, saveall chest, chest), or any combination thereof. The method of claim 1 wherein the composition is selected from the group consisting of a pipe wall, a chest wall, a machine wire, a press roll, a felt, a foil, a Uhle box, a dryer, ) Or any combination thereof. The method of claim 1, wherein the anionic branched cyclic glycerol-based polymer is added to the pulp slurry in a papermaking process. 6. The method of claim 1 wherein the effective amount of anionic branched cyclic glycerol-based polymer is from about 5 ppm to about 300 ppm.

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