WO2014047243A1 - Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation - Google Patents
Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
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- C08F8/00—Chemical modification by after-treatment
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- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
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- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/50—Partial depolymerisation
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
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- C08F2810/00—Chemical modification of a polymer
- C08F2810/10—Chemical modification of a polymer including a reactive processing step which leads, inter alia, to morphological and/or rheological modifications, e.g. visbreaking
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49826—Assembling or joining
Definitions
- the present invention relates to methods of making high molecular weight, functionalized poly(meth)acrylamide polymers. More particularly, the present invention relates to methods in which high molecular weight, functionalized poly(meth)acrylamide polymers are prepared by (trans) amidation of a high molecular weight (meth)acrylamide polymer with at least one amine functional reactant bearing at least one additional functionality other than amine functionality via melt phase reaction, to convert at least a portion of the amide functionality on the polymer to one or more other kinds of amide functionality.
- the poly(meth)acrylamide polymer may be partially hydrolyzed before the reaction, during the reaction in parallel with (trans)amidation, and/or after the
- polymer products are widely used in many areas of industry. For instance, these polymer products are widely used in oil fields for enhanced oil recovery. These products also may be used in other oil field applications, including uses as a flocculant, water thickening for enhanced oil recovery, polymer flooding, water clarification, cement thickening and viscosity stabilization, drag reducing agents, flocculation agents, combinations of these and the like.
- Poly(meth)acrylamide products also are used as coatings and/or are otherwise incorporated into reverse osmosis membranes.
- the products can be incorporated into other industrial and residential primers, paints, varnishes, and other coatings.
- the polymer products can be used as a growing medium additive such as to help prevent water loss from the growing media.
- Polyacrylamide products are also used as superabsorbents in sanitary goods, hygienic goods.
- (meth)acryl with respect to monomers, oligomers, and polymers means methacryl and/or acryl.
- poly(meth)acrylamide polymers refers to polymers obtained by polymerizing methacrylamide and/or acrylamide monomers.
- poly(meth)acrylamide copolymers refers to copolymers obtained by copolymerizing methacrylamide and/or acrylamide monomers with at least one additional copolymerizable reactant such as one or more monomers or oligomers.
- high molecular weight with respect to poly(meth)acrylamide polymer products means that the polymer products have a number average molecular weight that is high enough such that sufficiently high such that the polymer is a solid at 25°C at a pressure of 1 atm at a relative humidity of 10% or less.
- the polymer has a molecular weight of at least 50,000, even at least 100,000 preferably at least 250,000, more preferably at least 500,000, and even more preferably at least 1 ,000,000.
- the number average molecular weight is less than about 50,000,000, preferably less than 35,000,000, more preferably less than 25,000,000.
- Poly(meth)acrylamide polymer products with higher molecular weights generally are more effective at thickening, flocculation, drag reduction, superabsorbency, combinations of these and the like.
- poly(meth)acrylamide polymer products are obtained by polymerizing methacrylamide and/or acrylamide.
- the resultant polymer products have pendant amide functionality.
- poly(meth)acrylamide polymer products include amide functionality and at least one other kind of functionality. Examples of such other functionality include sulfonate, acid, phosphonate, hydroxyl, ether, ester, quarternary amino, epoxy, carboxylic acid, combinations of these and the like.
- Poly(meth)acrylamide polymer products that incorporate not only amide functionality but also one or more other kinds of functionality which may or may not attach to the polymer via an amide group are referred to herein as functionalized or modified poly(meth)acrylamide polymer products.
- Functionalized poly(meth)acrylamide polymer products can be made in different ways. According to a copolymerization approach, functionalized
- poly(meth)acrylamide polymer products are obtained by copolymerizing
- (meth)acrylamide monomers with one or more copolymerizable reactants comprising the desired additional functionalities.
- copolymers with higher molecular weight Due to factors such as the reactivity difference between the different monomers, and chain transfer mechanisms, the molecular weight of the resultant polymer product tends to decrease significantly as the content of the one or more copolymerizable reactants increases.
- functionalized or modified poly(meth)acrylamide polymer products also include polymers in which substantially all of the amide functionality of a poly(meth)acrylamide polymer intermediate is converted into one or more other kinds of functionality, such as carboxylic acid functionality.
- many conventional techniques for converting amide into other functionality are costly, complicated, suffer from low yield, are not easily scalable from lab to commercial production, produce undue amounts of by-products, and/or leave undue amounts of unreacted materials. Amidation reactions have been described in U.S. Pat. Nos. 6,277,768 and 5,498,785.
- the present invention provides processes for making higher molecular weight, functionalized poly(meth)acrylamide polymer products.
- the processes use (trans)amidation techniques in the melt phase to react one or more high molecular weight amide functional polymers or copolymers with at least one co-reactive species comprising at least one labile amine moiety and at least one additional functionality other than amine functionality.
- the processes of the present invention thus incorporate one or more additional functionalities onto an already formed or partially formed polymer rather than trying to incorporate all functionality via copolymerization techniques as the polymer is formed from constituent monomers.
- the methods provide an easy way to provide functionalized, high molecular weight poly(meth)acrylamide polymer products.
- transamidation refers to transamidation and/or amidation.
- the amide functionality in the case of transamidation, and/or carboxylic acid functionality (if any) in the case of amidation, on the polymer reacts in the melt phase with the amine functionality on the co -reactive species to convert the amide functionality and or carboxylic acid functionality (if any) into one or more other functionalities.
- the processes accomplish (trans)amidation in the polymer melt phase by reactive extrusion or in equipment capable of high energy mixing of melt phase reactants, such as those commercially available under the trade designations "Haake mixer,” “Haake PolyDrive mixer,” “Haake
- the processes accomplish (trans)amidation at moderate temperatures to help avoid thermal degradation or decomposition.
- the present invention relates to a method of functionalizing an amide functional polymer product, comprising the steps of:
- the polymer or copolymer is a solid at 25°C at a pressure of 1 atm at a relative humidity of 10% or less.
- reactant comprising a labile amine moiety and at least one additional functionality in a manner effective to form a polymer reaction product comprising amide functionality and the at least one additional functionality.
- the present invention relates to a method of functionalizing an amide functional polymer product, comprising the steps of:
- the present invention relates to a method of making an amide functional polymer product having at least one additional functionality, comprising the steps of:
- polymer or copolymer is a solid at 25°C at a pressure of 1 atm at a relative humidity of 10% or less;
- reactant comprising a labile amine moiety and at least one additional functionality under conditions effective to cause a transamidation reaction between the amine moiety and an amide of the polymer.
- Fig. 1 is a C-NMR spectra of an embodiment of a functionalized
- Fig. 2 is a C-NMR spectra of an embodiment of a functionalized polyacrylamide polymer prepared in accordance with the present invention.
- Fig. 3 is a C-NMR spectra of an embodiment of a functionalized
- PAM polyacrylamide polymer
- Fig. 4 is a 13 C-NMR spectra of an embodiment of a functionalized
- PAM polyacrylamide polymer
- Fig. 5 is a 13 C-NMR spectra of an embodiment of a functionalized
- PAM polyacrylamide polymer
- Fig. 1 is a C-NMR spectra of an embodiment of a functionalized
- PAM polyacrylamide polymer
- FIG. 6 schematically illustrates an exemplary transamidation between
- polyacrylamide and a reactant including a co-reactive amine group and a sulfonate group to prpare a sulfonate functionalized polyacrylamide.
- Fig. 7 is a plot of viscosity v. temperature for functionalized functionalized
- Amide functional polymers are polymers and or copolymers that include amide functionality that may be pendant directly from the polymer backbone or may be pendant from side chains that interconnect the amide functionality to the polymer backbone.
- the pendant amide group(s) may be primary, secondary or tertiary.
- the amide group(s) preferably are primary or secondary. More preferably, the amide group(s) are primary.
- Primary, secondary, and tertiary amide functionality may be represented by the following formulae, respectively:
- each R is independently H or a monovalent moiety such as a hydrocarbyl group optionally incorporating one or more heteroatoms such as O, S, N, and or P.
- each R may be a co-member of a ring structure with the other R in some embodiments.
- Exemplary hydrocarbyl moieties are linear, branched, and/or cyclic aliphatic and/or aromatic, preferably aliphatic moieties comprising only C and H atoms. Desirably, such preferred moieties have 1 to 8, preferably 1 to 4, more preferably one carbon atom. Aliphatic moieties are preferred as these react faster in the (trans)amidation reaction(s) with less risk of thermal degradation.
- the amide functional polymer(s) may be linear or nonlinear. Preferred
- the amide functional polymer(s) may be branched and/or crosslinked such as by forming the amide functional polymer from co-reactive reactant(s) that include at least one monomer ingredient that is poly functional with respect to copolymerizable and/or cross- linkable functionality.
- co-reactive reactant(s) that include at least one monomer ingredient that is poly functional with respect to copolymerizable and/or cross- linkable functionality.
- An example of such a polyfunctional ingredient is N,N- methylene bis(meth)acrylamide. See Polym. Commun., 32(11), 322 (1991); J. Polym. Set, Part A: Polym. Chem., 30(10), 2121 (1992).
- the poly(meth)acrylamide polymer may be partially hydrolyzed at the time of the reaction, during the reaction in parallel with (trans)amidation, and/or after the (trans)amidation reaction.
- Hydrolysis converts amide functionality into carboxylic acid functionality or derivatives thereof such as esters and salts.
- partially hydrolyzed poly(meth)acrylamide polymers comprise both amide and carboxylic acid functionality (or derivatives thereof).
- Carboxylic acid functionality (or derivatives thereof) may be desirable in some modes of practice, as this kind of functionality can enhance solubility or dispersibility in aqueous or other polar media. In other embodiments, it may be desirable to limit or avoid providing hydrolyzed embodiments for the reaction.
- the carboxylic acid functionality or derivatives thereof is limited to 0.001 to 30 mole percent, preferably 0.001 to 10 mole percent, more preferably 0.001 to 1 mole percent based on the total moles of amide and carboxylic acid functionality included in the polymer.
- the polymer as provided has substantially no acid functionality or derivatives thereof.
- the amide functional polymer(s) are water soluble. Water soluble means that at least 0.1 gram, preferably at least 0.5 grams, more preferably at least 1.0 grams of the polymer can be dissolved in 100 ml of deionized water at 25°C. This
- the amide functional polymer(s) are water dispersible. Water dispersible means that the polymer remains as a separate solid phase which is dispersed in the liquid water phase at 25°C at equilibrium.
- molecular weight refers to the number average
- a material such as a poly(meth)acrylamide may be present as a population distribution in which the actual molecular weight of individual molecules varies within the population.
- the number average molecular weight provides a statistical way to describe the molecular weight of the population as a weighted average of the actual molecular weights of individual molecules. In other instances, such as for smaller
- the material might be present predominantly in a single molecular form (e.g., acrylamide may be pre
- the actual molecular weight of individual molecules is substantially identical among the population so that the atomic weight and the number average molecular weight of the population are the same.
- the number average molecular weight of acrylamide also is 71.08.
- Molecular weight parameters may be determined using any suitable procedures.
- molecular weight features are determined using size exclusion chromatography.
- “higher molecular weight” means that a material has a number average molecular weight of at least 100,000, preferably at least 250,000, more preferably at least 500,000, and even more preferably at least 1,000,000. In many modes of practice, the number average molecular weight is less than about 50,000,000, preferably less than 35,000,000, more preferably less than 25,000,000.
- amide functional polymers include poly(meth)acrylamide polymer products.
- a poly(meth)acrylamide polymer product is a polymer or copolymer derived from monomer ingredients including
- (meth)acrylamide and optionally one or more copolymerizable ingredients such as one or more free radically co-polymerizable monomers and/or oligomers.
- Free radical polymerization is a method of polymerization by which a polymer forms by the successive addition of free radical building blocks. Free radicals can be formed via a number of different mechanisms usually involving separate initiator molecules. Following its generation, the initiating free radical adds repeating units, thereby growing the polymer chain.
- Free radically polymerized polymer products also are known by a variety of different names, including (meth)acrylic copolymers, vinyl copolymers, acrylic copolymers, free radically polymerized copolymers, and the like.
- (meth)acrylamide refers to methacrylamide and/or acrylamide monomers.
- Exemplary (meth)acrylamide monomers may be represented according to the following formula:
- R l is alkyl (such as methyl) or H.
- Preferred (meth)acrylamide embodiments include acrylamide
- the poly(meth)acrylamide polymer products are obtained by copolymerizing one or more (meth)acrylamide monomers with one or more optional copolymerizable reactants such as one or more free radically co- polymerizable monomers or oligomers. Because the molecular weight of the resultant poly(meth)acrylamide tends to be reduced as the amount of co- polymerizable reactant content is increased, it is desirable to limit or even substantially exclude co-polymerizable reactants from the poly(meth)acrylamide polymers during copolymerization.
- the poly(meth)acrylamide includes no more than from 0 to 10, preferably 0 to 5, more preferably 0 to 2, and even 0 weight percent of co-polymerizable reactants based on the total weight of (meth)acrylamide and co-polymerizable reactants (if any).
- Particularly preferred embodiments of the poly(meth)acrylamide polymer are homopolymers of (meth)acrylamide, more preferably homopolymers of acrylamide, as commercial embodiments of these with higher molecular weights are widely available at low cost from a number of commercial sources.
- any optional co-reactive species are used for copolymerization, these can be selected from a wide variety of one or more free radically co-polymerizable reactants.
- Preferred embodiments are free radically polymerizable monomers that have molecular weights below about 800, preferably below about 500.
- the co- polymerizable reactants may be hydrophilic and or hydrophobic, but preferably are hydrophilic to promote water solubility and/or water dispersibility.
- Examples of the co-polymerizable monomers may include one or more alkyl (meth)acrylates, other free radically polymerizable monomers, and the like.
- Suitable alkyl (meth)acrylates may be substituted or unsubstituted and include
- R 1 is described as above, R 2 and R 3 independently are hydrogen or methyl, and R 4 is H or an alkyl group preferably containing one to sixteen carbon atoms and optionally 1 or more hetero atoms such as O, S, P, and/or N.
- the R 4 group can be substituted with one or more, and typically 0 to three, moieties such as hydroxy, halo, phenyl, acid, sulfonate, phosphonate, and alkoxyl, for example.
- the alkyl (meth)acrylate typically is an ester of acrylic or methacrylic acid.
- R 1 is hydrogen or methyl
- R 2 and R 3 are hydrogen
- R 3 is an alkyl group having one to eight carbon atoms.
- R ⁇ R 2 and R 3 are hydrogen and R 4 is an alkyl group having one to four carbon atoms.
- alkyl (meth)acrylates include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl
- (meth)acrylate isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, decyl (meth)acrylate, isodecyl
- (meth)acrylate hydroxypropyl (meth)acrylate, hydroxyisopropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxyisobutyl (meth)acrylate, tetrahychof1 ⁇ 2furyl (meth)acrylate, ethylene urea ethyl (meth)acrylate, 2-sulfoethylene (meth)acrylate, nonyl (meth)acrylate, combinations of these and the like.
- free radically polymerizable monomers include styrene, substituted styrene such as methyl styrene, halostyrene, isoprene, diallylphthalate, divinylbenzene, conjugated butadiene, alpha-methylstyrene, vinyl toluene, vinyl naphthalene, N-vinyl-2-pyrrolidone, (meth)acrylaniide, (meth)acrylonitrile, acrylamide, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate, isobutoxymethyl (meth)acrylamide, N-substituted (meth)acrylamide, urea ethyl (meth)acrylamide, vinylsulfonic acid, vinylbenzenesulfonic acid, a- (meth)acrylamidomethyl-propanesulfonic acid, vinyl phosphonic acid and / or its ester and mixtures thereof.
- styrene substitute
- the amide functional polymer is further functionalized by converting at least a portion of the pendant amide functionality into one or more additional kinds of functionality. This functionalization occurs in the melt phase. Without wishing to be bound by theory, it is believed that the functionalization occurs via
- Transamidation is accomplished by reacting at least one high molecular weight amide functional polymer with one or more reactant(s) (hereinafter also referred to as the functionalizing reactant) comprising labile amine functionality and at least one other functionality in the melt phase.
- the labile amine functionality is reactive with the amide functionality in a manner effective to cause at least one other functionality to become pendant from the amide functional polymer.
- Fig. 6 schematically illustrates an exemplary transamidation reaction between polyacrylamide homopolymer 10 and a reactant 14 including a primary amine group 16 and a sulfonate group 18, wherein M may be selected from H or a cation such as Li, K, Na, quaternary ammonium, and combinations of these.
- the reaction product 20 is a poly(meth)acrylamide polymer in which a portion 22 of the product 20 incorporates pendant sulfonate functionality.
- the reaction reacts amine functionality with the amide functionality to cause the residue of the reactant 14 to be coupled to the polymer backbone of product 20.
- Fig. 1 shows the partial 13C-NMR of the reaction product of PAM and 2 -amino ethanesulfonic acid sodium salt in the presence of water as a plasticizer.
- this allows an embodiment of homopolymer 12 to be used that has a higher molecular weight as compared to a conventional reaction in which sulfonate is incorporated into product 20 only via copolymerization.
- the reaction scheme provides a way to provide high molecular weight poly(meth)acrylamide polymers that are functionalized with amide functionality and at least one other kind of functionality.
- functionality may be incorporated into the
- poly(meth)acrylamide polymer using both copolymerization and transamidation techniques.
- a poly(meth)acrylamide polymer may be provided that is the copolymerized product of acrylamide and acrylic acid, wherein the acrylic acid content is limited so that the poly(meth)acrylamide polymer has a higher molecular weight as defined herein.
- This initial polymer has acid functionality from the (meth)acrylic acid in addition to the amide functionality.
- a transamidation scheme at least a portion of the amide groups can be reacted with a reactant including a labile amine group and an additional functionality such as sulfonate or the like.
- the resultant transamidation product would then include amide, acid and sulfonate functionality. It can be appreciated, therefore, that the transamidation strategy of the present invention is an easy way to provide functionalized, high molecular weight poly(meth)acrylamide polymers.
- Labile with respect to the amine group of the functionalizmg reactant means that the amine group includes at least one hydrogen on the amino nitrogen.
- the amine groups may be primary (two hydrogens) and/or secondary (one hydrogen).
- Secondary amines are preferred. If secondary amines are used, it is often desirable if the non-hydrogen substituent of the nitrogen is a hydrocarbyl moiety of 8 or less carbon atoms, preferably 1-4 carbon atoms, more preferably 1 to 2 carbon atoms, as such embodiments of secondary amine groups tend to react faster under transamidation conditions than amine groups including larger substituents.
- cyclic amines such as morpholine, pyrrolidine, piperidine.
- the reactant includes at least one other functionality to be incorporated into the poly(meth)acrylamide polymer.
- a wide variety of other functional group(s) may be used. Examples include sulfonate, sulfonic acid, phosphonate, phosphonic acid, hydroxyl, ether, ester, quarternary amino, epoxy, carboxylic acid, pyrrolidone, metal salts of an acid (ionomer), combinations of these and the like. If more than one kind of additional functionality is used, the functionality may be included on the same or on different reactants. For example, reactants comprising labile amine as well as sulfonate and carboxylic acid functionality may be used such as those described in U.S. Pat. No. 4,680,339.
- reactants containing at least one labile amine group and at least one additional functionality may be used. Examples include one or more of the amine/acid/sulfonate functional reactants described in U.S. Pat. No. 4.680,339, 4,921,903, and 5,075,390, and the like.
- the functionalizing reactant is an amine and sulfonate functional compound of the formula
- each R is as defined above with the proviso that at least one R is hydrogen, and R is a divalent linking group containing 1 to 12, preferably 1 to 8, more preferably 1 to 4 carbon atoms.
- R 5 optionally may include 1 or more hetoratoms.
- R 3 is a hydrocarbyl moiety containing 2 to 3 carbon atoms.
- M may be selected from H or a cation such as Li, K, Na, quaternary ammonium, and combinations of these. Smaller reactants are preferred as these tend to react faster with the poly(meth)acrylamide polymer.
- the two reactants can be thoroughly mixed to allow the desired functionalization reaction to occur with the ingredients in intimate contact.
- the reactants can be combined before and/or during melt phase reaction, whether or not a melt actually exists at the time of combination.
- poly(meth)acrylamide polymer with a molecular weight of 5 to 6 million was reacted with 15 mol% of this amine with a plasticizing amount of water at 125°C to 160°C for 10 to 20 minutes produced a transamidated product whose 13C-NM spectra is shown in Fig. 3 ;
- Suitable amines include polyetherarnines such as those
- JEFFAMINE ® available under the trade designation JEFFAMINE ® .
- Jeffamine polyetherarnines of any series may be used such as the M series. These can be used to impart toughness, flexibility, and other desired characteristics. Such amines have low toxicity and resist discoloration. These also promote compatibility with water or other polar plasticizers.
- Melt phase processing means that the reaction occurs under conditions such that the amide functional polymer is in a molten state at or above the glass transition temperature (Tg) of the amide functional polymer. With melt phase processing, the amide functional polymer returns to the solid state at lower temperatures. Melt phase processing is differentiated from solution-based processing in that melt phase processing does not substantially rely on a solvent to achieve a fluid phase. Melt phase processing is therefore more easily scaled up from lab to commercial scales in terms of solvent demand.
- plasticizers e.g., liquid plasticizers and/or solid plasticizers that dissolve in the polymer and/or in the presence of other plasticizer(s), can be included -to reduce the Tg and to facilitate mixing action during the reaction.
- the plasticizer is used in amounts to facilitate plasticizing and is generally present in too small an amount to solubilize the amide functional polymer into a solution phase.
- water is an example of a liquid that can be used as a plasticizer in an amount too small to solubilize many poly(meth)acrylamide polymers. If present in a sufficient quantity, water can function as a solvent to create a poly(meth)acrylamide polymer solution.
- due to the higher molecular weight of the plasticizer is used in amounts to facilitate plasticizing and is generally present in too small an amount to solubilize the amide functional polymer into a solution phase.
- water is an example of a liquid that can be used as a plasticizer in an amount too small to solubilize many poly(meth)acrylamide polymers. If present in a sufficient quantity, water can function as a solvent to create a poly(meth)acrylamide polymer solution.
- due to the higher molecular weight of the plasticizer is an example of a liquid that can be used as a plastic
- the resultant solutions are typically very dilute in order to cause the poly(meth)acrylamide polymer to be in solution.
- a poly(meth)acrylamide polymer may decompose below the melting temperature of the polymer.
- a poly(meth)acrylamide polymer embodiment may have a melting temperature of 245°C, but unduly decompose at 210°C or higher.
- a plasticizer may be included to lower the Tg and melting temperature of the resultant admixture to a temperature at which undue decomposition is avoided.
- mixing 100 parts by weight of the polymer with 50 parts by weight of water may reduce the melting temperature to 125°C or lower, thereby allowing melt phase processing below the
- a solution of a higher molecular weight polymer may need to be as dilute as 10 weight percent or less, or even 5 weight percent or less, of the polymer based on the total weight of the polymer and the water to provide a single phase solution.
- water and poly(meth)acrylamide polymer are combined in more concentrated mixtures, the water plasticizes the polymer but is not present in a sufficient quantity to provide a single phase solution.
- the melt phase poly(meth)acrylamide polymer is plasticized by water when the weight ratio of the polymer to the water is in the range from 1000:1 to 1:3, preferably 50:1 to 1:1.
- melt phase processing is thus contrasted to solution phase processing in which the amide functional polymer is dissolved in a sufficient quantity of a suitable solvent to achieve a single phase, liquid state.
- solution phase processing is substantially more difficult to scale up.
- solutions must be very dilute to dissolve the polymer and avoid very high viscosities that would limit the rate of heat and mass transfer of reactants. This means that a substantial amount of solvent is needed to form the dilute solutions. Additionally, a substantial amount of effort is needed to remove so much solvent if the functionalized polymer product is subsequently to be recovered from the solvent.
- Solution phase processes for higher molecular weight poly(meth)acrylamide polymers are not as practical and are much more expensive overall than melt phase processing.
- the melt phase reaction may occur at a wide range of temperatures in which the poly(meth)acrylamide polymer(s) are in a melt phase. If the temperature is too low, though, the reaction may proceed at a slower rate than might be desired to achieve throughput goals. On the other hand, if the temperature is too high, the risk of thermal degradation of the amide functional polymer and/or the
- the melt phase reaction desirable occurs at a temperature in the range from 0 to 200°C, desirably 80 to 180°C, or even 100 to 1 0°C.
- the melt phase reaction mixture is a relatively viscous admixture.
- the amide functional polymer and the functionalizing reactant desirably are mixed in equipment capable of handling such viscous mixtures.
- Exemplary equipment suitable for melt phase mixing of viscous admixtures include single and twin rotor extruders, Haake mixers, Banbury mixers, two roll mills, and the like. Such mixing may cause some chain degradation of amide functional polymer and/or functionalized amide functional polymer to occur. If this happens, the
- functionalized amide functional polymer product may have a lower number average molecular weight than the starting amide functional polymer reactant. Less chain degradation has been observed using extruders for mixing.
- chain degradation may be observed as a reduction in viscosity of the melt phase admixture.
- a polyacrylamide homopolymer with a number average molecular weight of 20 million is observed to have an initial viscosity of 97 centipoise at 80°F and at a pressure of 400 psi.
- This polymer reactant is modified to have sulfonate functionality in accordance with the present invention by reacting the polymer with a sulfonate functional amine. The reaction occurs in the melt phase while mixing with a high shear mixer capable of handling the relatively viscous admixture.
- reactant may vary over a wide range. Selecting appropriate relative amounts of the reactants will depend on factors such as the amount of amide functionality to be converted to the additional functionality, the molecular weight of the
- the poly(meth)acrylamide polymer is reacted with a sufficient amount of functionalizing reactant such that the molar ratio of labile amine functionality on the functionalizing reactant(s) to amide functionality on the poly(meth)acrylamide polymer is in the range from 0.01 :1000 to 3:1, preferably 0.01 : 1000 to 1:1, more preferably from 1 : 1000 to 1 : 1, or even more preferably
- melt phase reaction occurs in a protected
- the reactants may be mixed in the melt phase for a time period selected over a wide range.
- the melt phase admixture is mixed for a time period in the range from 3 seconds to 72 hours, desirably from about 1 minute to 24 hours, more desirably from 1 minute to about 60 minutes.
- the reaction may substantially proceed to completion during melt phase mixing.
- the reactants may continue to react subsequently after mixing has stopped and the melt phase is cooling down.
- the reactants may continue to react in the solid phase.
- reaction admixture optionally may include one or more additional ingredients.
- one or more transamidation catalysts may be incorporated into the admixture in catalytically effective amounts.
- the admixture may include at least one
- plasticizer At least one plasticizer may be used in order to reduce the effective thermal, glass transition temperature of the polymer. Glass transition temperature (Tg) may be measured using differential scanning calorimetry (DSC) techniques. Examples of plasticizers include water, one or more polyethers, combinations of these, and the like. Water is a preferred plasticizer.
- Other optional ingredients include one or more antioxidants, UV stabilizers, processing aids, color concentrates, surfactants, lubricating agents, catalysts, neutralizing agents, fungicides, bactericides, other biocides, antistatic agents, dissolution aids, fillers, reinforcing fibers, and the like
- the functionalized amide functional polymer product may be any suitable functionalized amide functional polymer product.
- recovery may be accomplished using techniques such as filtration, distillation, drying, centrifugation, decanting, chromatography, combinations of these and the like.
- the resultant functionalized amide functional polymer product often will be a polymer comprising amide functionality and one or more additional kinds of functionality obtained via transamidation of a portion of the amide functionality of the original amide functional polymer reactant.
- an exemplary functionalized amide functional polymer product may be a polymer comprising repeating units of the formulae:
- R, and R 1 independently is as defined above;
- F A is a moiety that comprises at least one functionality selected from sulfonate, sulfonate, sulfonic acid, acid, phosphonate, phosphonic acid, hydroxyl, ether, ester, quarternary amino, epoxy, carboxylic acid, polyethylene glycol, polypropylene glycol, combinations of these and the like, and b and n are selected so that the ratio of b to n is 0.01:1000 to 3:1, preferably 0.01:1000 to 1:1, more preferably from 1 : 1000 to 1 : 1 , or even more preferably from 1 :200 to 1 :5 and such that the polymer has a higher molecular weight in the ranges recited herein.
- the modified polymers optionally may be partially hydrolyzed to promote compatibility with the water, such as a polymer having repeating units with the following structures
- a functionalized amide functional polymer product comprises repeating units of the formulae:
- R is a divalent hydrocarbyl moiety of 2 to 5, preferably 2 carbon atoms.
- the functionalized amide functional polymer products have many uses.
- the functionalized poly(meth)acrylamide polymer products can be used as coatings on or otherwise incorporated into reverse osmosis membranes.
- the products can be incorporated into other industrial and residential primers, paints, varnishes, and other coatings.
- the polymer products can be used for growing medium additive.
- the polymer products also are useful for a wide range of oil field applications, including uses as a flocculant, water thickening for enhanced oil recovery, polymer flooding, water clarification, cement thickening and viscosity stabilization, drag reducing agents, combinations of these and the like.
- a Haake mixer with an approximately 50-mL mixing chamber is used.
- the rotation rate is set at 100 rpm and the heater is set at 125 °C or 150 °C.
- the mixing time is set for 10 to 20 minutes.
- a mixture of high molecular weight PAM, an amine, and a plasticizer e.g., water
- the Haake mixer system is then turned off and is allowed to cool to ambient temperature.
- the resulting material is collected and may be analyzed by 13 C-NMR.
- PAM Mw 5,000,000-6,000,000, 17.77 g, 250 mmol of CONH 2 group
- a solution of 2-aminoetanesulfonic acid sodium salt (37.5 mmol, prepared by mixing 2-aminoethanesulfonic acid 4.7 g, 37.5 mmol, sodium hydroxide 1.5 g, 37.5 mmol, and water 17.77 g) at ambient temperature.
- PAM (Mw 5,000,000 - 6,000,000, 12.5 g, 175.8 mmol of CONH 2 group) was mixed with l-(3-aminopropyl)pyrrolidin-2-one (3.75 g, 26.4 mmol) and water (12.5 g). The resulting mixture was added to the Haake mixer and was processed at 150 C to 160 °C for 10 min at 100 rpm. After cooling, the resulting material was collected (14.1 g). Analysis of the material by C- MR showed a new amide group from transamidation of PAM with l-(3-aminopropyl)pyrrolidin-2-one ( Figure 2).
- PAM Mw 5,000,000-6,000,000, 17.77 g, 250 mmol of CONH 2 group
- morpholine 6.54 g, 75 mmol
- water 17.77 g
- the resulting mixture was added to the Haake mixer and was processed at 125 C to 160 °C for 14 min at 100 rpm. After cooling, the resulting material was collected. Analysis of the material by 13 C-NMR showed a new amide group from transamidation of PAM with the morpholine ( Figure 3).
- PAM Mw 18,000,000, 17.77 g, 250 mmol of COMH 2 group
- 2-aminoetanesulfonic acid sodium salt 37.5 mmol, prepared by mixing 2-aminoethanesulfonic acid 4.7 g, 37.5 mmol, sodium hydroxide 1.5 g, 37.5 mmol, and water 17.77 g
- the resulting mixture was added to the Haake mixer and was processed at 125 C to 160 °C for 20 min at 100 rpm. After cooling, the resulting material was collected (20.1 g). Analysis of the material by 13 C-NMR showed a new amide group from transamidation of PAM with the 2-aminoethanesulfonic acid sodium salt ( Figure 4).
- PAM (MW 18,000,000, 17.77 g, 250 mmol of CONH 2 group) was mixed with a solution of 2-aminoetanesulfonic acid sodium salt in water (75 mmol, prepared by mixing 2-aminoethanesulfonic acid 9.4 g, 75 mmol and sodium hydroxide 3.0 g, 75 mmol in water 17.77 g) at ambient temperature. The resulting mixture was added to the Haake mixer and was processed at 125 C to 160 °C for 14 min at 100 rpm. After cooling, the resulting material was collected. Analysis of the material by C-NMR showed a new amide group from transamidation of PAM with the 2- aminoethanesulfonic acid sodium salt (Figure 5).
- the instrument is a coquette, coaxial, cylindrical high pressure and temperature rheometer with maximum pressure rating of 1000 psi.
- the polymers solution was kept under a pressure of approximately 400 psi (applied by high pressure nitrogen source) during the experiments to keep water from boiling.
- Chain degradation might be one of the causes contributing to the reduction in viscosity.
- the figure also shows viscosity measurements for a PAM with a molecular weight of 5,000,000 Da.
- the viscosity of the modified polymer in Example 5 is higher than the unmodified PAM polymer with a molecular weight of 5,000,000 Da.
- the molecular weight of the modified polymer in Example 5 is higher than 5,000,000 Da and the post-modification process disclosed herein is capable of producing functionalized high molecular weight poly (meth) acrylamides.
Abstract
Description
Claims
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RU2015114542A RU2015114542A (en) | 2012-09-19 | 2013-09-19 | OBTAINING FUNCTIONALIZED FIELDS (MET) OF ACRYLAMIDE POLYMERS OF HIGH MOLECULAR MASS BY THE REAMIDATION METHOD |
BR112015005866A BR112015005866A2 (en) | 2012-09-19 | 2013-09-19 | method for functionalizing an amide-functional polymeric product and method for preparing an amide-functional polymeric product |
CN201380048938.4A CN105164169A (en) | 2012-09-19 | 2013-09-19 | Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation |
EP13771023.2A EP2897986A1 (en) | 2012-09-19 | 2013-09-19 | Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation |
MX2015003534A MX2015003534A (en) | 2012-09-19 | 2013-09-19 | Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation. |
US14/427,803 US20150252149A1 (en) | 2012-09-19 | 2013-09-19 | Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation |
CA2881701A CA2881701A1 (en) | 2012-09-19 | 2013-09-19 | Preparation of high molecular weight, functionalized poly(meth)acrylamide polymers by transamidation |
AU2013318071A AU2013318071B2 (en) | 2012-09-19 | 2013-09-19 | Preparation of high molecular weight, functionalized poly(meth) acrylamide polymers by transamidation |
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EP3078720A1 (en) | 2015-04-10 | 2016-10-12 | Snf Sas | Method for diverting a subterranean formation |
CN109734831A (en) * | 2018-12-28 | 2019-05-10 | 广东工业大学 | A kind of polyacrylamide polymer and preparation method thereof |
FR3088068A1 (en) | 2018-11-06 | 2020-05-08 | S.N.F. Sa | AUTO INVERSIBLE POLYMERIC REVERSE EMULSION |
FR3088071A1 (en) | 2018-11-06 | 2020-05-08 | S.N.F. Sa | ASSISTED OIL RECOVERY PROCESS BY INJECTION OF AN AQUEOUS POLYMERIC COMPOSITION |
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CN109575896B (en) * | 2017-09-28 | 2020-11-10 | 中国石油化工股份有限公司 | Polyether organic base/surfactant composite oil displacement system and application thereof |
KR102307978B1 (en) * | 2018-12-20 | 2021-09-30 | 삼성에스디아이 주식회사 | Separator for rechargeable lithium battery and rechargeable lithium battery including the same |
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- 2013-09-19 AU AU2013318071A patent/AU2013318071B2/en not_active Expired - Fee Related
- 2013-09-19 US US14/427,803 patent/US20150252149A1/en not_active Abandoned
- 2013-09-19 BR BR112015005866A patent/BR112015005866A2/en not_active IP Right Cessation
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- 2013-09-19 AR ARP130103373A patent/AR092632A1/en unknown
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CN105164169A (en) | 2015-12-16 |
EP2897986A1 (en) | 2015-07-29 |
MX2015003534A (en) | 2015-07-14 |
US20150252149A1 (en) | 2015-09-10 |
AU2013318071B2 (en) | 2016-12-15 |
RU2015114542A (en) | 2016-11-10 |
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