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WO2016196391A1 - Résines résistantes à l'humidité et à haute efficacité produites à partir de nouveaux agents de réticulation - Google Patents

Résines résistantes à l'humidité et à haute efficacité produites à partir de nouveaux agents de réticulation Download PDF

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Publication number
WO2016196391A1
WO2016196391A1 PCT/US2016/034884 US2016034884W WO2016196391A1 WO 2016196391 A1 WO2016196391 A1 WO 2016196391A1 US 2016034884 W US2016034884 W US 2016034884W WO 2016196391 A1 WO2016196391 A1 WO 2016196391A1
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WIPO (PCT)
Prior art keywords
resin
cross
strengthening resin
linker
polyamine
Prior art date
Application number
PCT/US2016/034884
Other languages
English (en)
Inventor
Clay E. Ringold
Cornel Hagiopol
Dexter C. Johnson
Brian L. Swift
David R. Snead
Original Assignee
Georgia-Pacific Chemicals Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/725,403 external-priority patent/US9982395B2/en
Application filed by Georgia-Pacific Chemicals Llc filed Critical Georgia-Pacific Chemicals Llc
Priority to EP16804179.6A priority Critical patent/EP3303699A4/fr
Priority to BR112017025566-9A priority patent/BR112017025566B1/pt
Priority to JP2018514938A priority patent/JP2018517836A/ja
Priority to KR1020177034622A priority patent/KR102630029B1/ko
Priority to CN201680031342.7A priority patent/CN107683357A/zh
Priority to MX2017015378A priority patent/MX2017015378A/es
Priority to CA2987852A priority patent/CA2987852C/fr
Publication of WO2016196391A1 publication Critical patent/WO2016196391A1/fr
Priority to CONC2017/0012280A priority patent/CO2017012280A2/es

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Classifications

    • 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
    • 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

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.
  • 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 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.
  • a strengthening resin can include a polyamine partially cross-linked with a bridging moiety and having azetidinium ions.
  • the bridging moiety can be derived from a functionally symmetric cross-linker.
  • the functionally symmetric cross-linker can be or include a diisocyanate, a l,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, a dialkyl halide, or any mixture thereof.
  • Strengthening resins e.g., wet strength resins, processes for making the strengthening resins, and processes of treating paper to impart strength using the strengthening resins are provided.
  • an epihalohydrin e.g., epichlorohydrin
  • new strengthening resins e.g., wet strength resins
  • the products and method can provide higher azetidinium ion content, additional degrees of reactive functionalization, maximized molecular weight, and/or good storage stability.
  • the polyamine cross-linking is distinct from the "cationization" process of halohydrin- functionalization and cyclization, a feature that affords substantial flexibility in tailoring the degree of cationic functionality, molecular weight, and/or other resin properties.
  • the functionally-symmetric cross-linkers and the optional mono-functional modifiers used to effect cross-linking and functionalization of the polyamine can be different from the reagent used to impart cationic charge to the resin.
  • the reaction of the polyamine with the functionally symmetric cross-linker can be separate from the reaction of the partially cross- linked polyamine with the epihalohydrin.
  • the functionally-symmetric (or simply "symmetric") cross-linker can be employed in this first step, which may provide substantial control over the cross-linking architecture and properties of the partially cross-linked prepolymer, such as a polyamine or polyamidoamine prepolymer.
  • the step of imparting cationic charge to the resin, the "cationization” process can use any epihalohydrin, e.g., epichlorohydrin to generate the azetidinium ion functionality.
  • the methods for making the strengthening resins can also reduce the amount of epichlorohydrin by-products as compared to the amount generally found in conventional polyamidoamine-epichlorohydrin strengthening resins that are not prepared by this process.
  • the strengthening resins can have substantially reduced levels of l,3-dichloro-2- propanol (1,3-DCP or "DCP") and 3-chloropropane-l,2-diol (3-CPD or "CPD”; also MCPD for monochloropropane diol), which generally accompany epichlorohydrin wet strength resin synthesis.
  • 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 process can further include reacting the polyamine with a deficiency of a mono-functional modifier that includes one secondary amine-reactive moiety. If the polyamine is reacted with a deficiency of the mono-functional modifier, the reaction can occur before, during, or after the polyamine is reacted with the symmetric cross-linker, or at different combinations of these times.
  • the polyamine can have the following structure:
  • PAA polyamidoamine
  • PAE polyamidoamine-epichlorohydrin
  • 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.
  • 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 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
  • PEI polyethyleneimine
  • 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:
  • R 3 is (CH 2 ) q where q is ranging from 0 to 40; and r 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: tNH(G pupil3 ⁇ 4,— NH) ⁇ — CG— (CH 2 ), 3 ⁇ 4 — CO
  • suitable polyamidoamines are generally prepared by reacting a dicarboxylic acid (diacid), or a corresponding dicarboxylic acid halide or diester thereof, with a polyamine such as a polyalkylene polyamine.
  • Suitable polyamines include those polyamines (polyamine prepolymers) disclosed herein that can be used as precursors for the wet strength resins themselves.
  • 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.
  • Suitable polyamines can include JEFF AMINE ® polyetheramines, available from Huntsman.
  • the JEFF AMINE ® polyetheramines contain primary amino groups attached to the terminus of a polyether backbone.
  • the polyether backbone is based propylene oxide (PO), ethylene oxide (EO), or mixed EO/PO.
  • PO propylene oxide
  • EO ethylene oxide
  • mixed EO/PO mixed EO/PO
  • Other JEFFAMINE ® products can contain other backbone segments and can have varied reactivity provided by hindering the primary amine or through secondary amine functionality.
  • 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 symmetric cross-linker to prepolymer molar ratios can be selected to provide more than 0%, but less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 15%, less than 10%, less than 5%, less than 4%, less than 3%, less than 2%, less than 1%, less than 0.75%), or less than 0.5% of the stoichiometric ratio of cross-linker to prepolymer. These values reflect the combined molar amounts when using more than one symmetric cross-linker.
  • 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.
  • 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 symmetric cross-linker can include at least one of: (1) a diisocyanate, a l,3-dialkyldiazetidine-2,4-dione, a dianhydride, a diacyl halide, a dienone, and a dialkyl halide and at least one of: (2) a di-acrylate compound, a bis(acrylamide) compound, a di-epoxide compound, a polyazetidinium compound, N,N'-methylene-bis-methacrylamide, and a poly(alkylene glycol) diglycidyl ether.
  • 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 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 dianhydrides can include, but are not limited to, pyromellitic dianhydride; ethylene glycol bis (trimellitic anhydride); 4,4'-bisphenol A dianhydride, or any mixture thereof.
  • Illustrative diacyl halides can include, but are not limited to, oxalyl chloride, oxalyl bromide, succinyl chloride, benzene- 1,2- dicarbonyl dichloride, benzene- 1,2-dicarbonyl bromide, phthaloyl chloride, 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 polymeric symmetric cross-linkers also can be or can include, for example, copolymers of acrylates, methacrylates, alkenes, dienes, and the like, with other azetidinium- functionalized monomers such as compounds S, T, or U, as shown here.
  • 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 symmetric cross-linker to the polyamine e.g., PAE prepolymer
  • a relatively small fraction of the available secondary amine sites are subject to cross-linking to form the branched or partially cross-linked polyamidoamine prepolymer.
  • the symmetric cross- linker to prepolymer molar ratios can be selected to provide from 0.01% to 5% of the stoichiometric ratio of cross-linker to prepolymer.
  • the symmetric cross-linker to prepolymer molar ratios can provide from 0.1% to 4%, 0.2% to 3.5%, 0.3% to 3%, 0.4% to 2.5%), 0.5%) to 2%), or 0.6%> to 1.5% of the stoichiometric ratio of cross-linker to prepolymer. These values reflect the combined molar amounts when using more than one symmetric cross- linker.
  • the partially cross-linked polyamidoamine prepolymer can be illustrated by the following structure:
  • R bridging moiety has the 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 or include 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- ⁇ , ⁇ , ⁇ -trimethylethanaminium; 3-acrylamido-N,N,N-trimethylpropan-l-aminium; and 1- isopropyl-3-(methacryloyloxy)-l-methylazetidinium chloride.
  • 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 second reaction step requires less epichlorohydrin than conventional methods to reach the desired end-point. Further, this second reaction step can be effected under reaction conditions which favor optimized azetidinium group formation over further cross-linking.
  • the asymmetric functionality of epichlorohydrin is useful in this functionalization to allow a relatively facile reaction of the epoxy group with secondary amines to form a pendant chlorohydrin moiety, followed by an intramolecular cyclization of the pendant chlorohydrin to generate a cationic azetidinium functionality. This latter intramolecular cyclization can utilize heating of the halohydrin-functionalized polymer.
  • the second reaction step can be carried out using any epihalohydrin, such as epichlorohydrin, epibromohydrin, and epiiodohydrin, or any combination thereof.
  • epichlorohydrin can be used.
  • epichlorohydrin can be used.
  • any of the epihalohydrins can be used in the process.
  • the formation of the halohydrin-functionalized polymer can be carried out using a range of epichlorohydrin molar ratios. For example, this reaction can be carried out using an excess of epichlorohydrin.
  • the stoichiometric reaction of epichlorohydrin with a secondary amine group requires a 1 : 1 molar ratio of epichlorohydrin with a secondary amine. In an aspect, from about 0.8 mole to about 3 moles of epichlorohydrin per mole of secondary amine can be used.
  • the moles of moles of epichlorohydrin per mole of secondary amine can be about 0.8, about 0.9, about 1.0, about 1.1, about 1.2, about 1.3, about 1.4, about 1.5, or about 1.6.
  • 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.
  • cycloalkyl group as used herein is a general term that refers to a group formed by removing one or more hydrogen atoms (as needed for the particular group) from a cycloalkane. Therefore, an "cycloalkyl group” includes the definition specified by IUPAC of a univalent group formed by formally removing a hydrogen atom from an cycloalkane but also includes, for example, an "cycloalkanediyl 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) when the context requires or allows, as long as the usual rules of chemical valence are applied.
  • Step 1 A glass reactor with 5-neck top was equipped with a glass stirring shaft and Teflon paddle, an equal pressure addition funnel, temperature and pH probe, stainless steel cooling coils, sample valve, and heating mantle. To the reactor was added 1000.00 grams of Polyamidoamine Prepolymer I from Example 1. The stirrer was started and the prepolymer was heated to 40°C. N, N-Methylene-bis-acrylamide, 15.16 grams (Pfaltz & Bauer, Inc), was added slowly while the reaction mixture was heated to 60°C. The reaction mixture then was held at 60°C for about 2 hours, and the viscosity advanced to 4,630 cP (Brookfield-SSA), at which point the viscosity advancement stopped. The reaction was cooled to 25°C.
  • a comparison of wet strength resin performance with standard commercially available wet strength resins is provided in the examples and data tables. Each data table indicates the stock used in the comparisons and the stock freeness (CSF) is reported. The resins were added at the rate shown (lb resin/ton of pulp solids) to a thick stock allowing a 2-minute mixing time. The treated stock was immediately poured into the headbox of the Noble & Wood handsheet machine containing pH pre-adjusted water.
  • composition resins were added at the rate (lb/ton) of pulp solids as indicated with each data table to thick stock (see Tables) allowing a 2-minute mixing time.
  • the treated stock was immediately poured into the headbox of the Noble & Wood handsheet machine containing pH pre-adjusted water (pH of 7.0).
  • the target sheet basis weight is indicated in each Table.
  • Each wet sheet was given two passes through the full load wet press, and then placed on the 105°C drum dryer without the blotter for 1 minute. All sets of handsheets were further cured for 3 minutes at 105°C in a forced air oven.
  • the handsheet samples were continued at a constant humidity (50%) and at a constant temperature (73 °F.) for 24 hours prior to testing.
  • Mw is the weight average molecular weight.
  • DCP @ 25% is the concentration of epichlorohydrin hydrolysis by product 1,3-dichloropropanol (DCP) remaining in the resin at 25% solids.
  • Table 2 illustrates the improvements in wet breaking length of premium grade heavyweight towel when treated with the resins according to this disclosure. Comparisons of the same properties obtained using conventional resins are provided, with data measured at different application rates. Substantial improvements in properties are observed using resins prepared as in this disclosure.
  • Table 3 likewise illustrates the improvements in wet breaking length of recycled heavyweight towel when treated with the resins according to this disclosure at different application rates (5, 10, and 15 lb composition resin per ton of pulp solids). Comparisons of the same properties obtained using conventional resins are provided. In every case, the substantial improvement in performance using the disclosed wet strength resins is illustrated.
  • Embodiments of the present disclosure further relate to any one or more of the following paragraphs:
  • a process for preparing a resin comprising: 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.
  • R is alkyl, hydroxyalkyl, amine, amide, aryl, heteroaryl or cycloalkyl and w is an integer from 1 to about 10,000.
  • a q/p ratio is from about 10 to about 1000;
  • 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.
  • epihalohydrin is selected from epichlorohydrin, epibromohydrin, and epiiodohydrin.
  • [00138] 1 1. The process according to paragraph 10, wherein the mono-functional modifier is selected from a neutral or cationic acrylate compound, a neutral or cationic acrylamide compound, an acrylonitrile compound, a mono-epoxide compound, or a 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 compound, and any combination thereof.
  • 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.
  • a composition comprising a resin, wherein the resin is prepared by a process comprising: 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.
  • 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 a diacrylate, a bis(acrylamide), a di epoxide and polyazetidinium compounds.
  • 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;
  • composition according to paragraph 25, wherein the symmetric cross-linker is selected from 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.
  • epihalohydrin is selected from epichlorohydrin, epibromohydrin, and epiiodohydrin.
  • composition according to paragraph 34 wherein the mono-functional modifier is selected from a neutral or cationic acrylate compound, a neutral or cationic acrylamide compound, an acrylonitrile compound, a mono-epoxide compound, or a combination thereof.
  • the mono-functional modifier is selected from a neutral or cationic acrylate compound, a neutral or cationic acrylamide compound, an acrylonitrile compound, a mono-epoxide compound, or a combination thereof.
  • 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 strengthening paper comprising contacting fibers with 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.
  • 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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  • Organic Chemistry (AREA)
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Abstract

L'invention concerne des résines de renforcement et leurs procédés de fabrication et d'utilisation. La résine de renforcement peut comporter une polyamine partiellement réticulée avec une fraction de pontage et possédant des ions azétidinium. La fraction de pontage peut être issue d'un agent de réticulation fonctionnellement symétrique. L'agent de réticulation fonctionnellement symétrique peut comprendre un diisocyanate, un 1,3-dialkyldiazétidine-2,4-dione, un dianhydride, un halogénure de diacyle, un diénone, un halogénure de dialkyle, ou un mélange quelconque de ceux-ci.
PCT/US2016/034884 2015-05-29 2016-05-27 Résines résistantes à l'humidité et à haute efficacité produites à partir de nouveaux agents de réticulation WO2016196391A1 (fr)

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EP16804179.6A EP3303699A4 (fr) 2015-05-29 2016-05-27 Résines résistantes à l'humidité et à haute efficacité produites à partir de nouveaux agents de réticulation
BR112017025566-9A BR112017025566B1 (pt) 2015-05-29 2016-05-27 Resina de fortalecimento
JP2018514938A JP2018517836A (ja) 2015-05-29 2016-05-27 新しい架橋剤からの高効率湿潤紙力増強樹脂
KR1020177034622A KR102630029B1 (ko) 2015-05-29 2016-05-27 신규한 가교제로부터 고효율 습윤 강도 수지
CN201680031342.7A CN107683357A (zh) 2015-05-29 2016-05-27 源自新型交联剂的高效湿强度树脂
MX2017015378A MX2017015378A (es) 2015-05-29 2016-05-27 Resinas de resistencia a la humedad de alta eficiencia de nuevos reticuladores.
CA2987852A CA2987852C (fr) 2015-05-29 2016-05-27 Resines resistantes a l'humidite et a haute efficacite produites a partir de nouveaux agents de reticulation
CONC2017/0012280A CO2017012280A2 (es) 2015-05-29 2017-11-29 Resinas de resistencia a la humedad de alta eficiencia de nuevos reticuladores

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