Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/028—Polyamidoamines
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
  • D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
  • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
  • D21H21/18—Reinforcing agents
  • D21H21/20—Wet strength agents

Definitions

• Embodiments disclosed generally related to strengthening resins. More particularly, such embodiments relate to strengthening resins that can include a polyamine partially cross-linked with a bridging moiety and having azetidinium ions, where the bridging moiety can be derived from a functionally symmetric cross-linker and methods for making and using same.
• Paper is sheet material containing interconnected small, discrete fibers.
• the fibers are usually formed into a sheet on a fine screen from a dilute water suspension or slurry.
• Paper typically is made from cellulose fibers, although occasionally synthetic fibers are used.
• Paper products made from untreated cellulose fibers lose their strength rapidly when they become wet, i.e., they have very little "wet strength".
• Wet strength of ordinary paper is only about 5% of its dry strength.
• the wet strength of paper is defined as the resistance of the paper to rupture or disintegration when it is wetted with water. See U.S. Patent No. 5,585,456. To overcome this disadvantage, various methods of treating paper products have been employed.
• wet strength resins applied to paper are either of the "permanent” type or the "temporary” type, which are defined by how long the paper retains its wet strength after immersion in water. While wet strength retention is a desirable characteristic in packaging materials, it presents a disposal problem because paper products having such characteristics are degradable only under undesirably severe conditions. Some resins impart temporary wet strength and are suitable for sanitary or disposable paper uses; however, these resins often suffer from one or more drawbacks. For example, the wet strength of the resins is generally of a low magnitude (about one-half of the level achievable for permanent-type resins), the resins can be easily attacked by mold and slime, and/or the resins can only be prepared as dilute solutions.
• the second step involves two competing reactions of the pendant chlorohydrin groups: 1) an intramolecular cyclization which generates a cationic azetidinium chloride functionality, in which no increase in molecular weight is observed; and 2) an intermolecular alkylation reaction to cross-link the polymer, which significantly increases its molecular weight.
• the results of both reactions are illustrated in the PAE-epichlorohydrin resin structure D.
• the alkylation of epichlorohydrin, the intra-molecular cyclization and the cross-linking reactions are occurring simultaneously, but at different rates.
• the finished wet strength polymer product contains a small amount of residual pendant chlorohydrin as illustrated in structure D, and a 3 -carbon cross-linked group with 2-hydroxyl functionality, with a fairly large amount of quaternary azetidinium chloride functionality.
• the product also can contain substantial amounts of the epi chlorohydrin hydrolysis products 1,3- DCP, and 3-CPD.
• the relative rates of the three main reactions in this conventional method namely the pendant chlorohydrin formation (ring opening), cyclization to azetidinium ion groups (cationization), and cross-linking (intermolecular alkylation), are approximately 140:4: 1, respectively, when carried out at room temperature. Therefore, the pendant chlorohydrin groups form very quickly from ring opening reaction of the epichlorohydrin epoxide and the secondary amine in the prepolymer.
• This first step is performed at lower temperature (for example, around 25°C to 30°C).
• the chlorohydrin groups relatively slowly cyclize to form cationic azetidinium groups. Even more slowly, cross-linking occurs, for example, by: 1) a tertiary amine, for example, of a chlorohydrin pendent group reacting with moiety secondary amine; and/or 2) intermolecular alkylation of a tertiary amine with a pendant chlorohydrin moiety.
• azetidinium group formation and cross-linking desirably are maximized without gelling the product or providing a product that gels during storage. These conditions, coupled with the desire for high solids to minimize shipping costs, have been limiting aspects of the formation of higher efficiency wet strength resin products.
• the method for making the strengthening resin can include reacting a polyamine, which may be referred to herein as a polyamine prepolymer, with a functionally symmetric cross-linker to produce a partially cross-linked polyamine.
• a polyamine which may be referred to herein as a polyamine prepolymer
• the polyamine can be partially cross-linked with a bridging moiety and the bridging moiety can be derived from the functionally symmetric cross-linker.
• An epihalohydrin can be added to the partially cross-linked polyamine to produce a halohydrin-functionalized polymer.
• the halohydrin-functionalized polymer can be cyclized to form a resin having azetidinium moieties.
• the strengthening resin can be or include the polyamine partially cross-linked with the bridging moiety and have azetidium ions or moieties.
• the polyamine can have the following structure:
• Epichlorohydrin is a difunctional compound having different, hence "asymmetric", chemical functionalities, epoxy and chlorine groups. This asymmetric functionality allows epichlorohydrin to ring open upon reaction with the epoxy group with secondary amines, followed by the pendant chlorohydrin moieties being used for both: 1) intramolecular cyclization to generate a cationic azetidinium functionality; or 2) intermolecular cross-linking the polymer to increase molecular weight.
• Epichlorohydrin resin structure D illustrates the results of both reactions in a polyamidoamine-epichlorohydrin (PAE) resin.
• This disclosure provides for formulations and processes for making strengthening resins, e.g., wet strength resins, with increased levels of cationic charge from enhanced azetidinium ion content (greater charge density), additional functionality, optimized or maximized molecular weights, high solids contents, and/or lower concentrations of DCP and CPD.
• the disclosed method separates the resin synthesis into two separate and controllable steps. The first constructs an intermediate molecular weight, cross-linked prepolymer, prepared by reacting the polyamine prepolymer with a functionally-symmetric cross-linker.
• the symmetric cross-linkers of this disclosure utilize the same moiety for reaction with both prepolymer secondary amine groups to effect cross- linking.
• monofunctional groups can be used before, after, or during the cross-linking step to impart additional functionality to a prepolymer without the cross-linking function.
• the second step utilizes epichlorohydrin to impart cationic functionality without it being required for any cross-linking function, by using a reduced amount of epichlorohydrin to maximize azetidinium ion formation on the polymer. This process stands in contrast to conventional practice which is limited by the need to optimize competing azetidinium ion formation and cross- linking mechanisms that occur simultaneously.
• a range of polyamines can be used as a precursor to the wet strength resins disclosed herein.
• the polyamines can be or include primary and/or secondary amine moieties that are linked with at least one spacer.
• the polyamine which may be referred to herein as a polyamine prepolymer, can have the following structure:
• R can be, for example, alkyl, hydroxyalkyl, amine, amide, aryl, heteroaryl or cycloalkyl.
• w can be an integer from 1 to about 10,000, 1 to about 5,000, 1 to about 3,000, 1 to about 1,000, 1 to about 100, or 1 to about 10.
• alkyl in structure P would apply the conventional rules of chemical valence to apply, but would include, for example, an "alkanediyl group” which is formed by formally removing two hydrogen atoms from an alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms).
• alkyl group can be substituted or unsubstituted groups, can be acyclic or cyclic groups, and/or may be linear or branched unless otherwise specified.
• a "hydroxyalkyl” group includes one or more hydroxyl (OH) moieties substituted on the "alkyl” as defined.
• R of structure P can be an alkyl moiety that is linear (straight chain) or branched.
• Moiety R can also be a cycloalkyl, that is, a cyclic hydrocarbon moiety having from 1 to about 25 carbon atoms.
• R can have from 1 to 25, from 1 to 20, from 1 to 15, from 1 to 12, from 1 to 10, from 1 to 8, from 1 to 6, or from 1 to 4 carbon atoms.
• R can have from 2 to 10, 2 to 8, 2 to 6, or 2 to 4 carbon atoms.
• R can be a Ci moiety, a C 2 moiety, a C 3 moiety, a C 4 moiety, a C 5 moiety, a C 6 moiety, a C7 moiety, a C 8 moiety, a C9 moiety, a C 10 moiety, a Cn moiety, a Co moiety, a C 13 moiety, a C 14 moiety, a C 15 moiety, a C 16 moiety, a Cn moiety, a C 18 moiety, a C1 moiety, a C 2 o moiety, a C 21 moiety, a C 22 moiety, a C 23 moiety, a C 24 moiety, a C 25 moiety, a C 26 moiety, a C 27 moiety, a C 28 moiety, a C 29 moiety, a C 30 moiety.
• R also can be a poly-primary amine, such as polyvinyl amine and its copolymers.
• a poly-primary amine that can constitute R in structure P include, but are not limited to the following structures, as well as copolymers with olefins and other unsaturated moieties, where n can be an integer from 1 to about 25:
• n can be an integer from 1 to about 20, 1 to about 15, 1 to about 12, 1 to about 10, or 1 to about 5.
• n can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, or 25.
• Suitable polyamines (polyamine prepolymers) for use in preparing the resins of this disclosure include, but are not limited to, polyalkylene polyamines, such as polyethylenepolyamines including diethylenetriamine (DETA), triethylenetetramine (TETA), aminoethyl piperazine, tetraethylenepentamine, pentaethylenehexamine, N-(2- aminoethyl)piperazine, N,N-bis(2-aminoethyl)-ethylenediamine, diaminoethyl triaminoethylamine, piperazinethyl triethylenetetramine, and the like.
• polyalkylene polyamines such as polyethylenepolyamines including diethylenetriamine (DETA), triethylenetetramine (TETA), aminoethyl piperazine, tetraethylenepentamine, pentaethylenehexamine, N-(2- aminoethyl)piperazine, N,N-bis(2-aminoethyl
• w is a number range corresponding to the polyamine prepolymer Mw mol number from about 2,000 to about 1,000,000.
• the Mw molecular weight of polyamine prepolymer P can also can be from about 5,000 to about 750,000, about 7,500 to about 500,000, about 10,000 to about 200,000, about 20,000 to about 150,000, or about 30,000 to about 100,000.
• a range of polyamidoamine prepolymers also can be used as a precursor to the wet strength resins according to this disclosure.
• the polyamidoamine prepolymers can be made by the reaction of a polyalkylene polyamine having at least two primary amine groups and at least one secondary amine group with a dicarboxylic acid, in a process to form a long chain polyamide containing the recurring groups as disclosed herein.
• the polyamidoamine prepolymer can have the following structure:
• R 1 is (CH 2 )m where m is 2, 3, 4, or 5;
• R 2 is (CH 2 )n where n is 2, 3, or 4;
• w is 1, 2, or 3;
• p is a number range corresponding to the polyamidoamine prepolymer Mw molecular weight from about 2,000 to about 1,000,000.
• the Mw molecular weight also can be from about 5,000 to about 100,000, about 7,500 to about 80,000, about 10,000 to about 60,000, about 20,000 to about 55,000, or about 30,000 to about 50,000.
• the polyamidoamine prepolymer can have the following structure:
• q can also range from 0 to about 40, 0 to about 35, 0 to about 30, 0 to about 25, 0 to about 20, 0 to about 15, 0 to about 12, 1 to about 40, 1 to about 35, 1 to about 30, 1 to about 25, 1 to about 20, 1 to about 15, 1 to about 12, 1 to about 10, 1 to about 8, or 1 to about 6.
• the polyamidoamine prepolymer can have the following structure: tNH(G pupil3 ⁇ 4,— NH) ⁇ — CG— (CH 2 ), 3 ⁇ 4 — CO
• useful polyamidoamines can be made by reacting suitable polyalkylene polyamines, such as polyethylenepolyamines including ethylenediamine itself, diethylenetriamine (DETA), triethylenetetramine (TETA), aminoethyl piperazine, tetraethylenepentamine, pentaethylenehexamine, N-(2-aminoethyl)piperazine, N,N-bis(2- aminoethyl)-ethylenediamine, diaminoethyl triaminoethylamine, piperazinethyl triethylenetetramine, and the like, with polycarboxylic acids such as succinic, glutaric, 2- methylsuccinic, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, dodecandioic, 2- methylglutaric, 3,3-dimethylglutaric and tricarboxypentanes such as 4-carboxypimelic;
• Adipic acid is readily available and is often used.
• JEFF AMINES ® Low molecular weight JEFF AMINES ® , e.g., JEFFAMINE ® D-230, can be acceptable, as well as higher molecular weight JEFF AMINES ® , e.g., JEFFAMINE ® D-2000.
• the secondary amines of the polyamines can be reacted with the one or more symmetric cross-linkers.
• the reaction of the secondary amines of the polyamine and the symmetric cross-linker can provides a greater degree of control over the cross-linking process, and an intermediate cross-linked prepolymer that has a higher molecular weight than the starting prepolymer.
• the viscosity end-point and thus the molecular weight of the intermediate can be easily pre-determined and controlled, at least in part, by the amount of the symmetric cross-linker employed.
• the cross-linking reaction can proceed to an end-point as the cross- linker is consumed and stop when consumption of the cross-linker is complete. A decreased and measureable amount of secondary amine functionality will remain available for further functionalization.
• the polyamine can be reacted with a deficiency of the symmetric cross-linker, based on the total amount of secondary amines available for cross- linking, to provide a partially cross-linked polyamine.
• the partially cross-linked polyamine has a higher molecular weight than the polyamine, even though it is an intermediate in the process and it retains a portion of the secondary amine groups present in the polyamine.
• the partially cross-linked prepolymer retains a majority of the secondary amine groups present in the polyamine, because less than 50% of the stoichiometry amount of symmetric cross-linker can be used.
• the polyamine can be reacted with the symmetric cross-linker in the presence of water or in the absence of water.
• the polyamine can be reacted with the symmetric cross- linker in an aqueous medium, e.g., water or water containing mixtures.
• the polyamine can be reacted with the symmetric cross-linker in a non-aqueous medium, e.g., a nonaqueous solvent or diluent.
• the polyamine can be reacted with the symmetric cross-linker in the absence of any other liquid medium whether aqueous or nonaqueous.
• the non-aqueous medium e.g., solvent or diluent
• the non-aqueous medium can be non-reactive with the polyamine, the symmetric cross-linker, and/or the partially cross-linked polyamine. If the polyamine is reacted with the symmetric cross-linker in a non-aqueous medium or in the absence of any other liquid medium to produce the polyamine partially cross-linked with a bridging moiety, the polyamine partially cross-linked with a bridging moiety can be maintained free or substantially free of any water or can be mixed with water.
• symmetric cross-linkers can include, but are not limited to, one or more diisocyanates, one or more l,3-dialkyldiazetidine-2,4-diones, one or more dianhydrides, one or more diacyl halides, one or more dienones, one or more dialkyl halides, or any mixture thereof.
• symmetric cross-linkers can include, but are not limited to, one or more di- acrylate compounds, one or more a bis(acrylamide) compounds, one or more di-epoxide compounds, one or more polyazetidinium compounds, one or more N,N'-methylene-bis- methacrylamides, one or more poly(alkylene glycol) diglycidyl ethers, or any mixture thereof.
• the diisocyanate can be unblocked or blocked.
• Illustrative unblocked diisocyanates can include, but are not limited to, 4,4'-methylene diphenyl diisocyanate (methylene diphenyl diisocyanate, MDI); toluene-2,4-diisocyanate (toluene diisocyanate, TDI); 1,6-hexane diisocyanate (hexamethylene diisocyanate, HDI); 5-isocyanato-l-(isocyanatomethyl)-l,3,3- trimethyl-cyclohexane (isophorone diisocyanate, IPDI), or any mixture thereof.
• Illustrative blocked diisocyanates can include, but are not limited to, bis-caprolactam blocked 4,4'- methylene diphenyl diisocyanate; 4,4'-methylene diphenyl diisocyanate bis(2-buanone oxime) adduct, bis-(3,5-dimethylpyrazole) blocked 4,4'-methylene diphenyl diisocyanate, or any mixture thereof.
• blocked diisocyanates can include, but are not limited to, the TRIXE E ® BI products available from Baxenden Chemicals such as TRIXE E ® BI 7641, 7642, 7674, 7675, 7950, 7951, 7960, 7961, 7963, and 7982, and the RUCO-Guard products available from Rudolf Group such as RUCO-Guard XCR, XTN, FX 8011, FX 8021, NET, TIE, and WEB.
• Illustrative l,3-dialkyldiazetidine-2,4-diones can include, but are not limited to, 1,3- diazetidine-2,4-dione; l,3-dimethyl-l,3-diazetidine-2,4-dione; l,3-diethyl-l,3-diazetidine-2,4- dione; l,3-Diphenyl-l,3-diazetidine-2,4-dione; or any mixture thereof.
• Illustrative dienones can include, but are not limited to, l,7-octadiene-3,6-dione; bis(2- propen-l-one)-(l,4-benzene), or any mixture thereof.
• Illustrative dialkyl halides can include, but are not limited to, 1,2-dichloroethane; 1,2-dibromoethane; 1,2-diiodoethane; 1,2- dichloropropane; 1,2-dibromopropane; 1,3-dichloropropane; 1,3-dibromopropane; 1,3- diiodopropane; l,4-bis(chloromethyl)benzene; l,4-bis(bromomethyl)benzene, or any mixture thereof.
• symmetric cross-linkers can include, but are not limited to, any one or more of the following: re R 4 is (CH 2 ) t , and where t is 1, 2, or 3;
• x' + y' is from 1 to about 100; and/or , where z is from 1 to about 100; including any combination thereof.
• symmetric cross-linkers can be or include, N,N'-methylene-bis- acrylamide, N,N'-methylene-bis-methacrylamide, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, polyethylene glycol diacrylate, polyazetidinium compounds, and any combination thereof.
• the symmetric cross-linker can be selected from or can include certain polymers or co-polymers that have a type of functional moiety that is reactive with secondary amines, that is, that can function as a symmetric cross-linker according to this disclosure.
• these polymeric symmetric cross-linkers can be polymers or copolymers that include azetidinium functional groups.
• polymeric symmetric cross- linkers can be, for example, copolymers of acrylates, methacrylates, alkenes, dienes, and the like, with azetidinium-functionalized monomers such as l-isopropyl-3-(methacryloyloxy)-l- methylazetidinium chloride Q or l, l-diallyl-3-hydroxyazetidinium chloride R, the structures of which are illustrated.
• the symmetric cross-linker can be selected from or can include a copolymer of an acrylate, a methacrylate, an alkene, or a diene, with an azetidinium- functionalized monomer selected from Q, R, S, T, U, and a combination thereof, where the fraction of azetidinium-functionalized monomer to acrylate, methacrylate, alkene, or diene monomer in the copolymer can be from about 0.1% to about 12%.
• the fraction of azetidinium-functionalized monomer to acrylate, methacrylate, alkene, or diene monomer in the copolymer can be from about 0.2% to about 10%, about 0.2% to about 10%, about 0.5%) to about 8%, about 0.75% to about 6%, or about 1% to about 5%.
• these types of symmetric cross-linker polymers and co-polymers can be found in the following references: Y.Bogaert, E.Goethals and E.Schacht, Makromol. Chem., 182, 2687-2693 (1981); M.Coskun, H.Erten, K.Demirelli and M.Ahmedzade, Polym. Degrad. Stab., 69, 245-249 (2000); and U.S. Patent Number 5,510,004.
• the symmetric cross-linker can be selected from or can include a minimally azetidinium-functionalized polyamidoamine. That is, polyamidoamine can have minimal azetidinium functionalization, which is the reactive moiety in this type of symmetric cross-linker.
• the cross-linking function is effected by the azetidinium moieties, which can react with secondary amines of the polyamidoamine prepolymer.
• Polyamidoamines that are suitable for preparing minimally azetidinium-functionalized polyamidoamines are the same general structures and formulas that can be used for the preparation of the resin itself, such as structures X, Y, and Z illustrated herein.
• An example of a minimally azetidinium-functionalized polyamidoamine suitable for use as a symmetric cross- linker is illustrated in the following structure:
• the q/p ratio is from about 10 to about 1000, and the structure includes at least two azetidinium moieties that function to cross-link, and that qualify a structure such as X as a functionally symmetric cross-linker.
• the q/p ratio indicates, there is a small fraction of azetidinium moieties as compared to acid and amine residues.
• the polyamidoamine X also can have the structure where the q/p ratio is from about 12 to about 500, about 14 to about 400, about 16 to about 300, about 18 to about 200, or about 20 to about 100.
• One type of minimally azetidinium-functionalized polyamidoamine is provided in, for example, U.S. Patent No. 6,277,242.
• the partially cross-linked polyamidoamine prepolymer can be illustrated by the following structure:
• the secondary amine groups of the polyamines also can be reacted with one or more mono-functional compounds to impart any desired chemical functionality to the prepolymer.
• the mono-functional compounds have a reactive group able to react with secondary or primary amine and a non-reactive part which can be cationic (to increase the cationic charge density), hydrophilic or hydrophobic (to adjust the interaction with non-ionic segments of the cellulose fibers).
• the polyamine can be reacted with a deficiency of a mono-functional modifier that can include one secondary amine-reactive moiety either before, during, or after, the step of reacting the polyamine with a deficiency of the symmetric cross-linker.
• the reaction with a stoichiometric deficiency of a mono-functional modifier can also be carried using any combination of reaction or addition before, during, or after, reaction with the symmetric cross-linker.
• the mono-functional modifier can be selected from or can include a neutral or cationic acrylate compound, a neutral or cationic acrylamide compound, an acrylonitrile compound, a mono-epoxide compound, or any combination thereof.
• the mono-functional modifier can be selected from or can include an alkyl acrylate, acrylamide, an alkyl acrylamide, a dialkyl acrylamide, acrylonitrile, a 2-alkyl oxirane, a 2-(allyloxyalkyl)oxirane, a hydroxyalkyl acrylate, an Q-(acryloyloxy)-alkyltrimethylammonium compound, an Q-(acrylamido)-alkyltrimethylammonium compound, and any combination thereof. Examples of mono-functional modifiers are illustrated below.
• the mono-functional modifier can be reacted with the polyamine in an amount from a low of about 0.0001 moles, about 0.0005 moles, about 0.001 moles, about 0.005 moles, or about 0.01 moles to a high of about 0.05 moles, about 0.07 moles, about 0.1 moles, about 0.15 moles, or about 0.2 moles per mole of secondary amine groups.
• the mono-functional modifier can be reacted with the secondary amine groups of the polyamine in an amount of about 0.0001 moles to about 0.1 moles per mole of the secondary amine groups.
• the amount of the symmetric cross-linker and epihalohydrin can be sufficient to produce a strengthening resin that can have substantially no secondary amine groups.
• This result can be effected by using the molar amounts and ratios disclosed herein, but resin compositions prepared by this disclosure can include substantially no secondary amine groups even when molar amounts and ratios outside those recited are used.
• substantially no secondary amine groups it is intended to mean that less than 10% of the original secondary amines in the starting PAE resin prior to the cross-linking, functionalization, and cationization reactions remain.
• the following resin composition structure Z illustrates the results of the cyclization step to form the quaternary nitrogen (“cationization") based on the chlorohydrin-functionalized polymer Y shown supra, which has been subjected to conditions sufficient to intramolecularly cyclize the pendant chlorohydrin to impart azetidinium functionality.
• the resin composition is generated by subjecting the halohydrin-functionalized polymer to cyclization conditions sufficient to convert the halohydrin groups to form azetidinium ions. At least a portion of the halohydrin groups can be cyclized to form azetidinium ions or moieties. In one example, at least 90% of the halohydrin groups can be cyclized to form azetidinium ions.
• the resulting strengthening resin can have a charge density that is enhanced over that of conventional resins.
• the strengthening resin can have a charge density of about 2 to about 4 mEq/g of solids.
• the strengthening resin can have a charge density from about 2.25 to about 3.5 mEq/g of solids, about 2.3 to about 3.35 mEq/g of solids, about 2.4 to about 3.2 mEq/g of solids, or about 2.5 to about 3.0 mEq/g of solids.
• the Mw molecular weight also can be from about 0.6 x 10 6 to about 1.6 x 10 6 , about 0.7 x 10 6 to about 1.5 x 10 6 , about 0.8 x 10 6 to about 1.3 x 10 6 , or about 0.9 x 10 6 to about 1.1 x 10 6 .
• cross-linking occurs, for example, by: 1) a tertiary amine, for example, of a chlorohydrin pendent group reacting with an azetidinium moiety; and/or 2) intermolecular alkylation of a tertiary amine with a pendant chlorohydrin moiety.
• a tertiary amine for example, of a chlorohydrin pendent group reacting with an azetidinium moiety
• intermolecular alkylation of a tertiary amine with a pendant chlorohydrin moiety there are substantially no remaining secondary amine groups.
• Cross-linking results in an increase in molecular weight, which is manifested in the increase in resin viscosity.
• the manufacturing process can be carried out under high temperature and high concentration conditions, where the reaction rates between intramolecular cyclization and cross-linking become competitive.
• the cross-linking reaction rate becomes fast enough that the desired viscosity end-point (molecular weight) is achieved at the expense of azetidinium ion group formation. If the reaction was allowed to continue beyond the desired viscosity end-point in order to generate higher levels of azetidinium groups, the reaction mixture would likely gel and form a solid mass.
• wet strength resin properties with standard commercially available wet strength resins is provided in the Examples and Tables.
• the wet strength resin properties of the resin prepared according to this disclosure were examined and compared to standard commercially available wet strength resin products, including the AMRES® series (Georgia- Pacific) of resins and the KYME E® (Ashland) resins. Both properties of the resins themselves and the performance of the resins for imparting wet strength are compared in the following tables.
• a strengthening resin for enhancing the wet strength of paper can include reacting a polyamine with a symmetric cross-linker to produce a partially cross-linked polyamine.
• An epihalohydrin can be added to the partially cross-linked polyamine to produce a halohydrin- functionalized polymer.
• the halohydrin-functionalized polymer can be cyclized to form the resin having azetidinium moieties.
• a further aspect of this disclosure provides a resin for enhancing the strength, e.g., wet strength, of paper, where the resin includes a polyamidoamine polymer that is crosslinked with a bridging moiety derived from the functionally symmetric cross-linker and has azetidinium ions.
• a method for preparing the resin or resin composition can include reacting a polyamidoamine (PAA) prepolymer having secondary amine groups with a deficiency of a symmetric cross-linker having secondary amine-reactive moieties to provide a partially cross- linked polyamidoamine prepolymer that retains a portion, e.g., a majority, of the secondary amine groups present in the polyamidoamine prepolymer.
• the polyamidoamine prepolymer can be reacted with a deficiency of a mono-functional modifier that can include one secondary amine-reactive moiety before, during, or after reaction with the symmetric cross- linker.
• the partially cross-linked polyamidoamine prepolymer can be reacted with an epihalohydrin to provide a halohydrin-functionalized polymer.
• a resin composition can be formed by subjecting the halohydrin-functionalized polymer to conditions sufficient to cyclize at least a portion of the halohydrin groups to form azetidinium ions.
• any paper strengthened with the strengthening resin is also an aspect of this disclosure and provided for herein.
• a process for treating paper to impart wet strength can include treating fibers used to make the paper with dry resin solids, where the resin is any resin in the present disclosure.
• the process can include treating fibers used to make a paper with from about 0.05% to about 2 % by weight dry resin solids based on the dry weight of the fibers of a cationic thermosetting resin or resin composition, in which the resin or resin composition is made in accordance with this disclosure.
• the process for treating paper to impart wet strength can include treating fibers used to make a paper with from about 0.01% to about 2 % by weight dry resin solids based on the dry weight of the fibers of a cationic thermosetting resin composition.
• the process can employ from about 0.05% to about 1.8 % by weight, about 0.075% to about 1.6 % by weight, or about 0.1% to about 1.5 % by weight dry resin solids based on the dry weight of the fibers.
• the fibers can be pulp fibers.
• each resin composition property disclosed herein is explained in detail independent of other properties, it is intended that any resin composition property can occur with any other resin property or properties in the disclosed resins.
• the disclosure of the properties herein encompasses a composition that can have at least one, at least two, at least three, at least four, or at least five of the following properties: a) a charge density of about 1.0 to about 4.0 mEq/g of solids; b) a ratio of azetidinium ions to amide residues in the resin is from about 0.5 to about 0.9.
• compositions and methods are described in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of or “consist of the various components or steps.
• any carbon-containing group for which the number of carbon atoms is not specified can have, according to proper chemical practice, 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, or 30 carbon atoms, or any range or combination of ranges between these values.
• any carbon-containing group can have from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20 carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, or from 1 to 5 carbon atoms, and the like.
• other identifiers or qualifying terms may be utilized to indicate the presence or absence of a particular substituent, a particular regiochemistry and/or stereochemistry, or the presence of absence of a branched underlying structure or backbone.
• substituted when used to describe a group, for example, when referring to a substituted analog of a particular group, is intended to describe any non-hydrogen moiety that formally replaces a hydrogen in that group, and is intended to be non-limiting. However, applicants reserve the right to proviso out any group, for example, to limit the scope of any claim to account for a prior disclosure of which Applicants may be unaware.
• a group or group may also be referred to herein as “unsubstituted” or by equivalent terms such as "non-substituted,” which refers to the original group in which a non-hydrogen moiety does not replace a hydrogen within that group.
• “Substituted” is intended to be non-limiting and include inorganic substituents or organic substituents as specified and as understood by one of ordinary skill in the art.
• An alkyl group can be substituted or unsubstituted groups, can be acyclic or cyclic groups, and/or may be linear or branched unless otherwise specified.
• the two hydrogen atoms can be formally removed from the same ring carbon, from two different ring carbons, or from one ring carbon and one carbon atom that is not a ring carbon.
• an aromatic compound is compound containing a cyclically conjugated hydrocarbon that follows the Hiickel (4n+2) rule and containing (4n+2) pi-electrons, where n is an integer from 1 to about 5. Therefore, aromatic compounds and hence "aryl groups" may be monocyclic or polycyclic unless otherwise specified.
• hydroxyalkyl refers to a group formed by formally removing one or more hydrogen atoms (as needed for the particular group) from the alkyl portion of a hydroxy-substituted alkane.
• the hydroxy-substituted alkane can include one or more hydroxy substituents.
• a "hydroxyalkyl” group includes, for example, a hydroxy-substituted “alkanediyl” group which is formed by formally removing two hydrogen atoms from a "hydroxyalkyl” alkane (either two hydrogen atoms from one carbon atom or one hydrogen atom from two different carbon atoms) when the context requires or allows, as long as the usual rules of chemical valence are applied.
• the alkyl group can be substituted or unsubstituted groups, can be acyclic or cyclic groups, and/or may be linear or branched unless otherwise specified.
• the azetidinium ratio is the ratio of the polymer segments containing azetidinium ion to the total number of polymer segments.
• a single polymer segment is defined by a condensation moiety derived from one diacid molecule (for example, adipic acid) and one triamine molecule (for example, diethylenetriamine or DETA), illustrated below.
• the polycationic resin is preferentially adsorbed at the surface of the test cell and its oscillating displacement piston, and as a diffuse cloud of counter-ions is sheared off the cationic colloids by the liquid flow in the test cell, a so-called streaming current is induced. Electrodes in the test cell wall measure this streaming current.
• the PAE resins are titrated with PVSK until the PAE resin reaches the point of zero charge, and the original resin charge is calculated from the titrant consumption.
• the streaming current is used to calculate the milliequivalents of cationic charge per gram solid resin (meq+/gram) as follows: ⁇ . PVSK(mL) * PVSK(N) meq +
• a glass reactor with a 5-neck top was equipped with a stainless steel stirring shaft, a reflux condenser, temperature probe, and a hot oil bath.
• DETA diethylenetriamine
• the stirrer was turned on and 730 grams of adipic acid was added slowly to the reactor over 45 minutes with stirring.
• the reaction temperature increased from 25°C to 145°C during adipic acid addition.
• the reactor was immersed in a hot oil bath heated to 160°C. At 150°C the reaction mixture began to reflux.
• the reflux condenser was reconfigured for distillation, and distillate was collected in a separate receiver. The reaction mixture was sampled at 30 minute intervals.
• Step 2 To the reactor configured as described in Step 1 was added 366.04 grams of intermediate (partially cross-linked) prepolymer from Step 1 above. The reaction temperature was adjusted to 25°C and 120.13 grams of water was added. The viscosity of the reaction mixture was 837 cP. To the intermediate partially cross-linked prepolymer was added 77.89 grams of epichlorohydrin at 25°C over 90 minutes. 428.19 Grams of water was added to the reaction mixture. The reaction was held at 25°C for 18 hours while sampling periodically for 13 C MR analysis.
• Step 2 The reaction temperature of the intermediate prepolymer mixture from Step 1 was adjusted to 25°C, and 80.10 grams of water was added. To the reactor was added 118.79 grams of epichlorohydrin over 75 minutes. The reaction was allowed to warm to 30°C over 45 minutes, and 431.35 grams of water was added. The reaction was warmed to 45°C over 45 minutes and after 2 hours was heated to 50°C. After about 3.5 hours the viscosity of the reaction was about 320 cP (Gardner-Holdt bubble tube), and then a mixture of formic acid and sulfuric acid was added to adjust the pH to 3.00. The reaction mixture was cooled to 25°C and water was added to adjust the solids to 25.0%. The viscosity of the resultant wet strength resin was 219 cP.
• a fraction of the azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%; and any combination thereof.
• the symmetric cross-linker is selected from ⁇ , ⁇ '-methylene-bis-acrylamide, N,N'-methylene-bis-methacrylamide, poly(ethylene glycol) diglycidyl ether, poly(propylene glycol) diglycidyl ether, polyethylene glycol diacrylate, polyazetidinium compounds and any combination thereof.
• R is alkyl, hydroxyalkyl, amine, amide, aryl, heteroaryl or cycloalkyl and w is an integer from 1 to about 10,000.
• composition according to paragraph 25, wherein the polyamine has molecular weight of about 2,000 to about 1,000,000.
• composition according to paragraph 25, wherein the symmetric cross-linker is selected from:
• R is (CH 2 ) t , wherein t is 1, 2, or 3;
• x is from 1 to about 100;
• z is from 1 to about 100;
• fraction of azetidinium-functionalized monomer to the acrylate monomer, the methacrylate monomer, the alkene monomer, or the diene monomer in the copolymer is from about 0.1% to about 12%; and any combination thereof.
• epihalohydrin is selected from epichlorohydrin, epibromohydrin, and epiiodohydrin.
• composition according to paragraph 34 wherein the mono-functional modifier is selected from an alkyl acrylate, acrylamide, an alkyl acrylamide, a dialkyl acrylamide, acrylonitrile, a 2-alkyl oxirane, a 2-(allyloxyalkyl)oxirane, a hydroxyalkyl acrylate, an co- (acryloyloxy)-alkyltrimethylammonium compound, an Q-(acrylamido)-alkyltrimethylammonium compound, and any combination thereof.
• the mono-functional modifier is selected from an alkyl acrylate, acrylamide, an alkyl acrylamide, a dialkyl acrylamide, acrylonitrile, a 2-alkyl oxirane, a 2-(allyloxyalkyl)oxirane, a hydroxyalkyl acrylate, an co- (acryloyloxy)-alkyltrimethylammonium compound, an Q-(acrylamido)-alkyltrimethylammonium
• the mono-functional modifier comprises at least one of: methyl acrylate, alkyl acrylate, acrylamide, N-methylacrylamide, N,N- dimethylacrylamide, acrylonitrile, 2-methyloxirane; 2-ethyloxirane, 2-propyloxirane, 2- (allyloxymethyl)oxirane, 2-hydroxyethyl acrylate, 2-(2-hydroxyethoxy)ethyl acrylate, 2- (acryloyloxy)-N,N,N-trimethylethanaminium, 3-(acryloyloxy)-N,N,N-trimethylpropan-l- aminium; 2-acrylamido-N,N,N-trimethylethanaminium, 3-acrylamido-N,N,N-trimethylpropan-l- aminium, and l -isopropyl-3-(methacryloyloxy)-l-methylazetidinium chloride.
• composition according to paragraph 25, wherein the ratio of azetidinium ions to secondary amine moieties in the resin is from about 0.4 to about 1.0.
• composition according to paragraph 40 wherein the acid is acetic acid, formic acid, hydrochloric acid, phosphoric acid, sulfuric acid, organic or mineral acid or a combination thereof.
• [00170] 42 The composition according to paragraph 40, wherein the pH of the resin is adjusted to about pH 2.0 to about pH 4.5.
• [00171] 43 The composition according to paragraph 25, wherein the solids content of the resin is adjusted from about 10% to about 50%.
• a process of treating paper to impart wet strength comprising treating pulp fibers used to make a paper with a resin composition made by: a) reacting a polyamine with a symmetric cross-linker to produce a partially cross-linked polyamine; b) adding a epihalohydrin to the partially cross-linked polyamine to produce a halohydrin-functionalized polymer; and c) cyclizing the halohydrin-functionalized polymer to form the resin having azetidinium moieties.
• a strengthening resin comprising a polyamine partially cross-linked with a bridging moiety and having azetidinium ions, wherein the bridging moiety is derived from a functionally symmetric cross-linker comprising a diisocyanate, a l,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or any mixture thereof.
• a method for making a strengthening resin comprising: reacting a polyamine and a functionally symmetric cross-linker to produce a partially cross-linked polyamine, wherein the functionally symmetric cross-linker comprises a diisocyanate, a 1,3 -dialkyl diazetidine-2,4-di one, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or any mixture thereof; and reacting the partially cross-linked polyamine with an epihalohydrin to produce a strengthening resin having azetidinium ions.
• the functionally symmetric cross-linker further comprises a diacrylate compound, a bis(acrylamide) compound, a diepoxide compound, a polyazetidinium compound, ⁇ , ⁇ '- methylene-bis-methacrylamide, a poly(alkylene glycol) diglycidyl ether, or any mixture thereof.
• [00193] 65 The strengthening resin or method according to any one of paragraphs 48 to 60, wherein the strengthening resin has a charge density of 2.25 mEq/g of solids to 3.5 mEq/g of solids, an azetidinium equivalent weight of 2,000 to 3,500, a weight average molecular weight of 900,000 to 1,700,000, and contains less than 10,000 ppm of l,3-dichloro-2-propanol.

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