EP0907672A1 - Hydrophobisch modifizierte harzzusammensetzungen und deren verwendungen - Google Patents
Hydrophobisch modifizierte harzzusammensetzungen und deren verwendungenInfo
- Publication number
- EP0907672A1 EP0907672A1 EP98907552A EP98907552A EP0907672A1 EP 0907672 A1 EP0907672 A1 EP 0907672A1 EP 98907552 A EP98907552 A EP 98907552A EP 98907552 A EP98907552 A EP 98907552A EP 0907672 A1 EP0907672 A1 EP 0907672A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- resin composition
- acid
- group
- aminoamide
- amine groups
- Prior art date
- Legal status (The legal status 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 status listed.)
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Classifications
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- 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
- D21H21/16—Sizing or water-repelling 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
- C08G73/0286—Preparatory process from polyamidoamines and epihalohydrins
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- 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
- D21H17/56—Polyamines; Polyimines; Polyester-imides
Definitions
- This invention relates to hydrophobically modified epihalohydrin- aminoamide resins and their uses.
- alkyl ketene dimers styrene-maleic anhydride (SMA) polymers
- SMA styrene-maleic anhydride
- epichlorohydrin-modified bis-stearamides each of these has serious deficiencies in use.
- both the alkyl ketene dimers and the bis-stearamides significantly lower the coefficient of friction of paper when applied to the surface. This adversely affects the performance of the paper in high speed converting operations.
- the bis-stearamides have a negative effect on the tensile properties of the paper.
- SMA solution polymers are foamy, can be supplied only at low solids, and give only limited sizing in some grades.
- SMA polymers are ineffective when applied over paper that does not have internal sizing.
- the materials of the present invention do not cause deterioration of the tensile properties of the paper to which they are applied, nor do they cause a significant reduction in coefficient of friction. They also do not foam excessively and are highly effective sizing agents, even when applied over paper that does not have internal sizing.
- U.S. Patent No. 3,922,243 to Aldrich et al. discloses water-insoluble, water-dispersible thermosetting cationic resins derived by reaction of a water- soluble aminopolyamide, a hydrophobizing compound and an epihalohydrin.
- the aminopolyamide contains secondary amine groups and is prepared using a mole ratio of polyalkylene polyamine to dicarboxylic acid from about 0.9 to about 1.2.
- the amount of hydrophobizing agent is insufficient to react with more than about 50% of the secondary amine groups of the aminopolyamide.
- U.S. Patents 3,923,745, 3,968,317 and 3,992,345 to Dumas disclose water-insoluble, water-dispersible thermosetting cationic resins derived by reaction of a diallylamine polymer, a hydrophobizing compound and epihalohydrin.
- a resin composition comprises the reaction product of epihalohydrin and hydrophobically modified aminoamide obtained by the reaction of: (a) aminoamide containing at least one primary amine group and at least one non-primary amine group selected from the group consisting of secondary and tertiary amine groups, the aminoamide being obtained by reaction of an amine composition comprising polyamine containing at least two primary amine groups and at least one amine group selected from the group consisting of secondary and tertiary amine groups, with dicarboxylic acid or derivatives thereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivative thereof, is greater than about 1.4:1, and,
- hydrophobizing agent having from about 12 to about 40 carbon atoms, wherein the amount of hydrophobizing agent employed is sufficient to react with at least a portion of the primary amine groups, but insufficient to react with more than about 60% of the non-primary amine groups.
- a method for making the resin composition comprises: a) reacting an amine composition comprising polyamine containing at least two primary amine groups and at least one amine group selected from the group consisting of secondary and tertiary amine groups with dicarboxylic acid, or derivatives thereof, wherein the molar ratio of polyamine to dicarboxylic acid or derivative thereof is greater than about 1.4:1, to form aminoamide containing at least one primary amine group and at least one non-primary amine group selected from the group consisting of secondary and tertiary amine groups; b) reacting the aminoamide with hydrophobizing agent having from about 12 to about 40 carbon atoms to form hydrophobically modified aminoamide, wherein the amount of hydrophobizing agent employed is sufficient to react with at least a portion of the primary amine groups, but insufficient to react with more than about 60% of the non-primary amine groups of the aminoamide; and c) reacting the hydrophobically modified aminoamide with epihalohydrin.
- a method for sizing paper comprises adding to the surface of paper sheet an aqueous suspension of the resin composition.
- Another method for sizing paper comprises the steps of (a) providing an aqueous pulp suspension; (b) adding to the aqueous pulp suspension an aqueous suspension of the resin composition; (c) forming the pulp into a sheet; and (d) drying the sheet to obtain sized paper.
- the aminoamides used in preparing the resin compositions are derived by reaction of dicarboxylic acid or derivatives thereof, and polyamine containing at least two primary amine groups and one or more secondary or tertiary amine groups.
- Dicarboxylic acid derivatives suitable for preparing the aminoamides include esters, anhydrides and acid halides.
- Dicarboxylic acids for use in preparing the aminoamides include aliphatic, alicyclic or aromatic dicarboxylic acids, or their derivatives, containing from 2 to about 44 carbon atoms.
- the dicarboxylic acids are selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid, diglycolic acid, C 36 -C 44 dimer acids, alkenyl succinic acids and alkyl succinic acids.
- the dicarboxylic acids are adipic acid and alkenyl succinic acids.
- C 36 -C 44 dimer acids are derived by dimerizing or polymerizing naturally occurring unsaturated fatty acids and are available as EMPOL® dimer acid, from Henkel-Emery, Cincinnati, Ohio.
- Alkenyl succinic acids, or anhydrides are available by reaction of maleic anhydride with straight chain or branched olefins, and have the following general structures I and II
- R' is a straight chain or branched, unsaturated alkyl radical having from about 8 to about 22 carbon atoms, preferably from about 16 to about 22 carbon atoms.
- Alkyl succinic acids or anhydrides may be prepared by hydrogenation of the corresponding alkenyl succinic acid or anhydride.
- anhydrides of formula I are isooctadecenyl succinic anhydride, n-octadecenyl succinic anhydride, n-hexadecenyl succinic anhydride, n-dodecyl succinic anhydride, i-dodecenyl succinic anhydride, n- decenyl succinic anhydride, n-octenyl succinic anhydride, and isobutylene oligomers succinic anhydride.
- the corresponding acids of formula II are derivable from the anhydrides by hydrolysis.
- At least 50 mole % of the amine composition used for reaction with the dicarboxylic acid will be poly-unine containing at least two primary a ine groups and one or more secondary or tertiary amine groups.
- Preferred polyamines are N-alkyl bis(3-aminopropylamine), wherein the N- alkyl group is an alkyl group containing from 1 to about 12 carbon atoms, and polyalkylene polyamines containing two primary amine groups and at least one secondary amine group where the nitrogen atoms are linked together by groups of the formula - H ⁇ -, where n is from 2 to 6.
- Preferred polyalkylene polyamines include polyethylenepolyamines, polypropylenepolyamines and polybutylenepolyamines. Polyethylenepolyamines are more preferred. The most preferred polyethylenepolyamines for use in this invention are diethylenetriamine, triethylenetetramine or tetraethylenepentamine. The most preferred is diethylenetriamine.
- the preferred N-alkyl bis(3-aminopropylamine) is N-methyl bis(3- aminopropylamine).
- the amine composition used for reaction with the dicarboxylic acid may contain other diamines, preferably those having the formulas III, IN and V. H 2 ⁇ -(CH 2 ) X - ⁇ H 2 ,
- x is an integer from 2 to about 10
- y is an integer from 2 to about 100
- b is an integer from 2 to about 100
- a and c which can be the same or different, are integers from 0 to about 5.
- Exemplary diamines of formula III are ethylene diamine, propylene diamine, and hexamethylene diamine.
- Materials corresponding to formulas IV are available as Jeffamine®D-230, D-400, D-2000 and D-4000 from Huntsman Corporation, Houston, Texas.
- Materials corresponding to formula V are available as Jeffamine®ED-600, ED-900 and ED-2001 from Huntsman
- the amine composition is used in substantial molar excess over dicarboxylic acid.
- the aminoamides that result contain substantial quantities of primary amine groups, and are oligomeric, i.e., contain from about 1 to about 6 repeating units.
- the molar ratio of polyamine to dicarboxylic acid is greater than about 1.4 to 1.
- the molar ratios is from about 1.5 to 1 to about 3 to 1, more preferably from about 1.55 to 1 to about 2.5 to 1, and most preferably from about 1.6 to 1 to about 2 to 1.
- Temperatures employed for carrying out the reaction between dicarboxylic acid and amine can vary from about 110°C to about 250°C or higher, at atmospheric pressure.
- reaction time will usually vary from about 1/2 to about 2 hours, although shorter or longer reaction times can be utilized depending on reaction conditions. Reaction times vary inversely with temperature.
- hydrophobizing agents are compounds having from about 12 to about 40 carbon atoms that will react with the primary and secondary amine groups of the aminoamide to form substantially water- insoluble compounds.
- Suitable hydrophobizing agents include, e.g., acids, anhydrides, acid halides, esters and isocyanates.
- the amount of hydrophobizing agent will be that amount sufficient to react with at least a portion of the primary amine groups, but insufficient to react with more than about 60% of the non-primary amine groups of the aminoamide.
- the amount of hydrophobizing agent will be sufficient to react with at least about 20% of the primary amine groups, but insufficient to react with more about 30% of the non-primary amine groups. More preferably the amount of hydrophobizing agent will be sufficient to react with at least 20% of the primary amine groups, but insufficient to react with more than about 10% of the non-primary amine groups.
- hydrophobizing agents are: a) monocarboxylic acids or derivatives thereof, of the formula RCOOH, where the R group is alkyl, alkenyl, aryl, cycloalkyl or cycloalkenyl; b) substituted succinic anhydrides of formula I
- n is an integer of 0 to about 20
- R and R" which may be the same or different, are saturated or unsaturated straight chain or branched alkyl groups having 8 to 24 carbon atoms
- R' is a saturated or unsaturated straight chain or branched alkyl group having from about 5 to about 40 carbon atoms.
- Suitable derivatives of the carboxylic acids RCOOH include esters, anhydrides, acyl halides and isocyanates. With respect to the group of ketene dimers and multimers of formula VI, ketene dimers are preferred.
- the most preferred hydrophobizing agents are substituted succinic anhydrides of formula I.
- the monocarboxylic acids or derivatives thereof, of the formula RCOOH that can be used are rosin acid, myristic acid, palmitic acid, oleic acid and stearic acid.
- Specific examples of the anhydrides of formula I are isooctadecenyl succinic anhydride, n-octadecenyl succinic anhydride, n-hexadecenyl succinic anhydride, n-dodecyl succinic anhydride, i-dodecenyl succinic anhydride, n- decenyl succinic anhydride and n-octenyl succinic anhydride.
- the R and R" groups are alkyl or alkenyl groups having at least 6 carbon atoms, cycloalkyl groups having at least 6 carbon atoms, aryl having at least 6 carbon atoms, aralkyl having at least 8 carbon atoms, alkaryl having at least 10 carbon atoms, and mixtures thereof.
- ketene dimer is selected from the group consisting of (a) octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl, ⁇ -naphthyl, and cyclohexyl ketene dimers, and (b) ketene dimers prepared from organic acids selected from the group consisting of montanic acid, naphthenic acid , 9, 10-decylenic acid, 9, 10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, eleostearic acid, naturally occurring mixtures of fatty acids found in coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rape oil, beef tallow, lard, whale
- Suitable ketene dimers are disclosed in U.S. Patent No. 4,279,794, in United Kingdom Patent Nos. 903,416; 1,373,788 and 1,533,434, and in European Patent Application Publication No. 0666368 A3.
- Ketene dimers are commercially available, as Aquapel® and Precis® sizing agents from Hercules Incorporated, Wilmington, Delaware. Preferred are Aquapel®364 and Precis 787® sizing agents.
- Ketene multimers for use in the process of this invention have the formula VI where n is an integer of at least 1, R and R", which may be the same or different, are saturated or unsaturated straight chain or branched alkyl groups having 8 to 24 carbon atoms, preferably 14 or 16 carbon atoms; and R' is a saturated or unsaturated straight chain or branched alkyl group having from about 5 to about 40 carbon atoms, preferably 5 to about 20 carbon atoms.
- Ketene multimers are described in: European Patent Application
- the reaction of aminoamide and hydrophobizing agent can be carried out neat or in solvent. It is carried out under relatively mild conditions such that essentially the only reaction taking place is the reaction of the hydrophobizing agent with the primary and secondary (if present) amine, whereby the amines are converted into amides, ureas, ⁇ -ketoamides, imidazolines, or ⁇ -amidoacids, depending on the specific hydrophobizing agent and reaction conditions utilized.
- the a-minoamide and hydrophobizing agent are reacted under atmospheric or higher pressure at a reaction temperature of from about 0°C to about 250°C to produce a reaction product that is essentially water-insoluble.
- hydrophobizing agent is a substituted succinic anhydride of formula I
- it is particularly convenient to carry out the reaction in the absence of solvent, and it has been found that the relatively mild temperature conditions of 100°-150°C are suitable. Reaction of substituted succinic anhydrides with primary amine may lead to the formation of cyclic imide under sufficiently high temperatures.
- the reaction of epihalohydrin, preferably epichlorohydrin, with the water-insoluble reaction product of aminoamide and hydrophobizing agent yields a cationic, hydrophobically modified resin.
- the reaction with epihalohydrin occurs at the amine groups of the hydrophobically modified aminoamide.
- tertiary amines react with epihalohydrin by initial opening, then reclosure of the epoxide ring with expulsion of the halide ion, to form a glycidyl (2,3-epoxypropyl) ammonium salt; secondary amines react with epihalohydrin to form tertiary aminohalohydrins, which cyclize to form reactive 3-hydroxy-azetidinium salts; and primary amine groups react to form a halohydroxypropyl-substituted secondary amine, which can then react with a second mole of epihalohydrin as described above for secondary amines.
- the reaction with epihalohydrin may be carried out in aqueous medium or in solvent.
- suitable solvents include: alcohols, e.g., methanol, ethanol, propanol, isopropanol and butanol; benzene; toluene, and the like. Mixtures of two or more solvents can be used if desired. It is to be understood that the solvent employed is non-reactive with the reactants or the reaction product under the reaction conditions.
- the reaction with epihalohydrin is carried out at a temperature of from about 0°C to about 100°C, preferably from about 20°C to about 40°C, for a period of time of from about 1/2 hour to about 3 hours (time varies inversely with temperature).
- the amount of epihalohydrin used will be that amount sufficient to react with at least 40%, preferably at least 70%, and most preferably at least 90% of the amine groups present in the hydrophobically modified aminoamide.
- the epihalohydrin-reacted composition may be crosslinked by further heating at a temperature of from about 40°C to about 90°C.
- the solids level of the hydrophobized aminoamide is preferably from about 5% to about 50%. If the reaction with epihalohydrin is carried out in aqueous medium, the hydrophobized aminoamide may be provided to the reaction as an aqueous dispersion. When the reaction of hydrophobizing agent with aminoamide is carried out molten, such dispersions are readily prepared by adding water to the molten reaction product under agitation. Further dispersion may be accomplished by homogenization.
- reaction with epihalohydrin is to be carried out in solvent
- the neat hydrophobized aminoamide can be dissolved in the appropriate solvent prior to the reaction with epihalohydrin.
- the product solution may be used for the epihalohydrin reaction directly. Water may be added to the reaction mixture before, during, or after addition of the epihalohydrin.
- the reaction product which is a thermosettable cationic resin
- the pH of the dispersion may be adjusted to pH of from about 2.5 to about 8 to provide for optimum stability of the dispersion. In this way stable dispersions having a solids content of from about 5% to about 50% can be prepared.
- aqueous dispersions of the product can be prepared by the following procedure.
- the solution of the reaction product is dispersed in water with vigorous agitation such as, for example, by homogenization at pressures of from about 1,000 to 5,000 p.s.i., to provide an aqueous emulsion that is essentially stable. Subsequently, the organic solvent is removed by distillation, either under atmospheric pressure or under vacuum, to provide a stable aqueous dispersion of the reaction product.
- the resin compositions of this invention may be used in the manufacture of paper and other fibrous substrates.
- they are used in the manufacture of surface treated paper, particularly surface sized paper by application to the surface of the paper after sheet formation, generally at a size press.
- They may also be incorporated into a pulp slurry at the wet end of a paper machine to provide sizing or other properties such as, for example, improved pitch dispersion, deposit control, sheet bulk, sheet softness, and size promotion.
- the amount of resin employed for the sizing of paper will usually be from about 0.05% to about 2% based on the weight of the dry pulp fibers.
- the resins After incorporation of the resin compositions of this invention into the paper, either by incorporation into the pulp slurry or by addition to the surface, the resins are cured to a thermoset state by application of heat. Generally the heating will take place during drying of the paper sheet at temperatures of from about 85°C to about 125°C for periods of from about 5 seconds to about 60 seconds. In actual practice, the conventional drum drying of the treated paper sheet will provide for sufficient curing of the resin.
- This invention is illustrated by the following examples, which are exemplary only and not intended to be limiting. All percentages, parts, etc., are by weight, based on the weight of the dry pulp, unless otherwise indicated.
- Example 1 This example illustrates the preparation of an aminoamide from adipic acid and diethylenetriamine and its reaction with the hydrophobizing agent hexadecenylsuccinic anhydride.
- Adipic acid 131.5 g (0.9 moles) was added to diethylenetriamine, 154.8 g (1.5 moles) in a stirred reaction vessel. The mixture was brought to 170°C and held for 3 hours while the water of condensation was removed by distillation. The molten aminoamide was then cooled to 120°C . Using the assumption that all of the carboxyl groups reacted with primary amine, it is calculated that the product contained 1.5 equivalents of secondary amine and 1.2 equivalents of primary amine in 254 g.
- ASA 100 predominately hexadecenylsuccinic anhydride
- the product after cooling had an acid number of 25 mg KOH/g and an amine number of 4.05 meq/g (equating to an amine equivalent weight of 247).
- Example 2 This example describes the preparation of a crosslinked hydrophobically modified cationic resin composition by reaction of epichlorohydrin with the hydrophobically modified aminoamide prepared in Example 1.
- Example 1 The aminoamide of Example 1 (98.5 g, 0.40 equivalents of amine) was crushed and dispersed in 281 g of water. Epichlorohydrin (43.2 g, 0.47 moles) was then slowly added to the dispersion while the temperature was maintained at below about 40°C. The resulting reaction mixture was then stirred for 30 minutes at 40°C and then crosslinked by heating at 85°C for 2 hours. The crosslinked resin was homogenized hot using a laboratory homogemzer, and then cooled to room temperature. The product contained 19.1% total solids, had pH 5.02 and particle size of 0.50 microns. It contained 0.70% 1,3- dichloropropan-2-ol, 0.19% 2,3-chloropropanediol, and less than 0.01% residual epichlorohydrin.
- This example describes the preparation of a crosslinked, hydrophobically modified cationic resin composition by reaction of epichlorohydrin with the hydrophobically modified aminoamide prepared in Example 1 in an organic solvent.
- the hydrophobically modified aminoamide of Example 1 (97.6 g, 0.39 equivalents of amine) was crushed and dissolved in a mixture of toluene (440 g) and ethanol (496 g).
- Deionized water (468 g) was added to the solution of aminoamide to form a dispersion.
- Epichlorohydrin (43.4 g, 0.47 moles) was then slowly added to the dispersion while the temperature was maintained at below about 40°C.
- the resulting reaction mixture was then stirred for 2 hours at 40°C and then crosslinked by heating to reflux at 75°C for 2 hours.
- the crosslinked resin was cooled to 20°C, further diluted with water (1180 g), blended and homogenized using a laboratory homogenizer. The solvent was removed by distillation.
- the product contained 10.8% total solids, had pH 6.6 and particle size 0.047 microns. It contained 0.48% l,3-dichloropropan-2-ol, 0.12% 2,3-chloropropanediol, and less than 0.01% residual epichlorohydrin.
- This example illustrates preparation of an aminoamide from adipic acid and diemylenetriamine modified by reaction with the hydrophobizing agent hexadecenylsuccinic anhydride.
- Adipic acid (65.77 g, 0.45 moles) was added to diethylenetriamine (77.35 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to 170°C and held at this temperature for 3 hours while the water of condensation was removed by distillation. The molten product was cooled to 123°C, and then there was added 97.8 g (0.3 moles) of hexadecenylsuccinic anhydride (Accosize®18, from Cytek Industries, West Patterson, New Jersey), The resulting mixture was held at 125°C for 1 hour, at 146°C for 1 hour, and then quenched by addition of water.
- the product aminoamide had an amine number of 4.51 meq/g (amine equivalent weight, 222) and acid number of 38.
- the molecular weight determined by SEC was 756 number average and 1468 weight average.
- the product was diluted with enough water to produce a dispersion with 23.3% solids as measured in a 150°C oven.
- the dispersion had a pH of 10.2.
- Example 5 A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Example 4.
- the dispersed hydrophobically modified aminoamide (125.4 g, 29.2 g solids, 0.13 amine equivalents) was blended with 65.1 g of water.
- Epichlorohydrin (11.1 g,
- the product of the second part had 15.1% solids, pH 5.4, particle size 0.15 microns and contained 0.16% l,3-dichloropropan-2- ol, 0.07% 2,3-chloropropanediol and less than 0.01% residual epichlorohydrin.
- Potassium sorbate (0.1%) was added to both portions as a biocide.
- This example demonstrates the surface sizing efficiency of products of Examples 2 and 3 of this invention compared to conventional commercial sizing agents.
- Waterleaf paper was prepared on a trial paper machine at a basis weight of 64.9 kg /1,000 m 2 from a 50:50 blend of bleached kraft hardwood and softwood pulps.
- the paper was prepared at a papermaking pH of 8.0 and contained 0.5% alum (based on dry pulp). The paper was unfilled and was not surface treated.
- the paper was treated with an aqueous dispersion of resin using a laboratory size press operating at room temperature.
- the resin level required in the aqueous dispersion to achieve the desired sizing agent level in the paper was determined by first determming the amount of absorbed water picked up when the paper was treated with water only in the size press. The level of the resin in the dispersion was then adjusted accordingly to give the desired level of addition to the paper.
- the paper was drum dried at 104°C immediately following treatment. Sizing was measured after storing the paper for 1 week, using the
- Hercules Size Tester Hercules Incorporated., Wilmington, DE
- Hercules Incorporated. At 80% reflectance with an ink containing 1% formic acid and a green dye.
- the commercial sizing agents used for comparison were Scripset®740 styrene maleic anhydride copolymer from Monsanto Corp., St. Louis, MO and Hercon®70 alkylketene dimer based sizing agent from Hercules Incorporated, Wilmington, DE).
- Alkylketene dimers are known to impart slip related problems to paper when applied to the surface of the sheet in sufficient quantities.
- Example 7 This example illustrates preparation of an aminoamide from adipic acid and diethylenetriamine modified by reaction with hexadecenylsuccinic anhydride hydrophobizing agent.
- Adipic acid (66.0 g, 0.45 moles) was added to ⁇ ethylenetriamine (77.4 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to 170°C and held at this temperature for 3 hours while the water of condensation was removed by distillation.
- the molten product was cooled to 122°C, and then there was added 97.8 g (0.3 moles) of hexadecenylsuccmic anhydride (ASA 100). The resulting mixture was held at 123°C for 2 hours and then quenched with water.
- the product aminoamide had an amine number of 4.44 meq/g (amine equivalent weight, 225) and acid number of 44.
- the product was diluted with enough water to produce a dispersion with a measured solids of 20.6%.
- the dispersion had a pH of 10.6.
- Example 8 A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Example 7.
- the dispersed hydrophobically modified aminoamide 142.0 g, 29.4 g solids, 0.13 amine equivalents
- the dispersed hydrophobically modified aminoamide 142.0 g, 29.4 g solids, 0.13 amine equivalents
- Epichlorohydrin (11.1 g, 0.12 moles) was slowly added while keeping the temperature below 40°C.
- the resulting reaction mixture was stirred for 30 minutes at 40°C and then crosslinked by heating at 65°C for 2 hours.
- the hot product was homogenized using a laboratory homogenizer.
- the product had 20.2% solids, pH 6.2 and particle size 0.074 microns. It contained 0.17% l,3-dichloropropan-2-ol, 0.06% 2,3-chloropropanediol and less than 0.02% residual epichlorohydrin.
- This example illustrates the reduced tendency to foam of the crosslinked hydrophobically modified cationic resin composition of Example 8 compared to common commercial surface sizing agents.
- the modified laboratory foam cell consisted of a pump and air introduction device to allow air percolation through a starch solution containing the crosslinked hydrophobically modified cationic resin composition. Time for the foam to reach a designated height in a graduated cylinder was recorded.
- the test solution 700 g
- the commercial sizing agents used for comparison are Scripset®720 and Scripset 740 styrene maleic anhydride copolymers from Monsanto Corp., St. Louis, MO.
- the results, presented in Table 2 are the time for the foam to reach a volume of 1800 ml. Higher values indicate a lower foaming tendency.
- Example 10 This example illustrates preparation of an aminoamide from adipic acid and diethylenetriamine modified by reaction with hexadecenylsuccinic anhydride hydrophobizing agent.
- Adipic acid 54.80 g, 0.375 moles
- diethylenetriamine 77.35 g, 0.75 moles
- the mixture was brought to 170°C and held at this temperature for 3 hours while the water of condensation was removed by distillation.
- the molten product was cooled to 125°C, and then there was added 91.28 g (0.28 moles) of hexadecenylsuccinic anhydride (ASA 100).
- ASA 100 hexadecenylsuccinic anhydride
- the resulting mixture was held at 125°C for 1 hour, at 140°C for 1 hour, and then quenched by addition of water.
- the product had an amine number of 5.60 meq/g (amine equivalent weight, 178) and acid number of 42 (acid equivalent weight, 1,336). It was diluted with enough water to produce a dispersion with 23.4% solids.
- the dispersion had a pH of 10.4.
- a crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Example 10.
- the dispersed hydrophobically modified aminoamide (123.3 g, 28.9 g solids, 0.16 amine equivalents) was blended with 65.4 g of water.
- Epichlorohydrin (11.1 g, 0.12 moles) was slowly added while keeping the temperature below 40°C.
- the resulting reaction mixture was stirred for 30 minutes at 40°C and then crosslinked by heating at 65°C for 2 hours, after which it was quenched and diluted by adding enough water to bring the mixture to about 15% solids.
- the product had 15.7% solids, pH 6.0 and particle size 0.070 microns and contained 0.23% l,3-dichloropropan-2-ol, 0.16% 2,3-chloropropanediol and less than 0.01% residual epichlorohydrin.
- This example illustrates another preparation of aminoamide from adipic acid and diethylenetriamine followed by reaction with hexadecenylsuccinic anhydride.
- Adipic acid 54.80 g, 0.375 moles was added to diethylenetriamine (77.38 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to 170°C and held at this temperature for 3 hours while the water of condensation was removed by distillation. The molten product was cooled to 125°C, and then there was added 146.7 g (0.45 moles) of hexadecenylsuccinic anhydride
- ASA 100 ASA 100
- the resulting mixture was held at 125°C for 1 hour, at 140°C for 1 hour, and then quenched by addition of water.
- the product had an amine number of 3.69 meq/g (amine equivalent weight, 271) and acid number of 57.5 (acid equivalent weight, 975).
- the product was diluted with enough water to produce a dispersion with 23.3% solids.
- the dispersion had a pH of 10.1.
- a crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Example 12.
- the dispersed hydrophobically modified aminoamide (152.0 g, 35.4 g solids, 0.13 amine equivalents) was blended with 69.3 g of water.
- Epichlorohydrin (11.1 g, 0.12 moles) was slowly added while keeping the temperature below 40°C.
- the resulting reaction mixture was stirred for 30 minutes at 40°C and then crosslinked by heating at 65°C for 2 hours, after which it was quenched and diluted by adding enough water to bring the mixture to about 15% solids.
- the product had 15.3% solids, pH 5.8 and particle size 2.18 microns and contained 0.084% l,3-dichloropropan-2-ol, 0.075% 2,3-chloropropanediol and less than 0.01% residual epichlorohydrin.
- This example illustrates another preparation of aminoamide from adipic acid and diethylenetriamine hydrophobically modified by reaction with hexadecenylsuccinic anhydride.
- Adipic acid (58.40 g, 0.40 moles) was added to diethylenetriamine (68.78 g, 0.66 moles) in a stirred reaction vessel. The mixture was brought to
- a crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Example 14.
- the dispersed hydrophobically modified aminoamide (178.65g, 43.0 g solids, 0.10 amine equivalents) was blended with 80.75 g of water.
- Epichlorohydrin (7.4 g,
- Comparative Example A This is a comparative example illustrating preparation of an aminoamide from adipic acid and diethylenetriamine hydrophobically modified with hexadecenylsuccinic anhydride using polyamine to dicarboxylic acid ratios described in U.S. Patent No. 3,922,243, but using water as a dispersing medium.
- Adipic acid (109.61 g, 0.75 moles) was added to diethylenetriamine (77.38 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to
- ASA 100 hexadecenylsuccinic anhydride
- the product had an amine number of 3.26 meq/g (amine equivalent weight, 307) and acid number of 33 (acid equivalent weight, 1696).
- the product had a measured solids of 22.1% and a pH of 8.11.
- a crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Comparative Example B.
- the dispersed aminoamide (155.52g, 34.37 g solids, 0.11 amine equivalents) was blended with 60.73 g of water.
- Epichlorohydrin 11.10 g, 0.12 moles was slowly added while keeping the temperature below 40°C.
- the resulting reaction mixture was stirred for 30 minutes at 40°C and then crosslinked by heating at 65°C for 2 hours, after which it was quenched and diluted by adding enough water to bring the mixture to about 15% solids.
- Co parative Example D This is a comparative example illustrating preparation of aminoamide from adipic acid and diethylenetriamine hydrophobically modified by reaction with hexadecenylsuccinic anhydride using polyamine to dicarboxylic acid ratios as described in U.S. Patent No. 3,922,243. The milder reaction conditions of this patent were applied.
- Adipic acid (73.07 g, 0.50 moles) was added to diethylenetriamine (51.59 g, 0.50 moles) in a stirred reaction vessel. The mixture was brought to 160°C and held at this temperature until 1/3 of the theoretical water of condensation was removed by distillation. The molten product was cooled to
- ASA 100 hexadecenylsuccmic anhydride
- the resulting mixture was held at 125°C for 1 hour and 140°C for 1 hour and then quenched by addition of water to give a nominal 25% solids.
- the product had an amine number of 1.53 meq/g (amine equivalent weight, 652) and acid number of 76 (acid equivalent weight, 740).
- the product had a measured solids of 24.0% and a pH of 5.7.
- Comparative Example E A crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Comparative
- Example D The dispersed hydrophobically modified aminoamide (197.71g, 47.41 g solids, 0.07 amine equivalents) was blended with 84.34 g of water. Epichlorohydrin (11.10 g, 0.12 moles) was slowly added while keeping the temperature below 40°C. The resulting reaction mixture was stirred for 30 minutes at 40°C and then crosslinked by heating at 65°C for 2 hours, after which it was quenched and diluted by adding enough water to bring the mixture to about 15% solids.
- Epichlorohydrin 11.10 g, 0.12 moles
- Comparative Example F This is a comparative example illustrating preparation of aminoamide from adipic acid and diethylenetriamine hydrophobically modified by reaction with hexadecenylsuccmic anhydride using polyamine to dicarboxylic acid ratios as described in U.S. Patent No. 3,922,243, but higher than those used in the previous comparative examples. The milder reaction conditions of the patent were applied.
- Adipic acid (81.84 g, 0.56 moles) was added to diethylenetriamine (77.38 g, 0.75 moles) in a stirred reaction vessel. The mixture was brought to 170°C and held for 3 hours while the water of condensation was removed by distillation. The molten product was cooled to 129°C, and then there was added 122.25 g (0.375 moles) of hexadecenylsuccinic anhydride (ASA 100). The resulting mixture was held at 125°C for 1 hour and 140°C for 1 hour and then quenched by addition of water to give a nominal 25% solids. The product had an amine number of 2.78 meq/g (amine equivalent weight, 360) and acid number of 49 (acid equivalent weight, 1156). The product had a measured solids of 25.2% and a pH of 9.0.
- ASA 100 hexadecenylsuccinic anhydride
- a crosslinked hydrophobically modified cationic resin composition was prepared from the hydrophobically modified aminoamide of Comparative
- Example F The dispersed hydrophobically modified aminoamide (138.46g, 34.88 g solids, 0.10 amine equivalents) was blended with 80.34 g of water. Epichlorohydrin (11.10 g, 0.12 moles) was slowly added while keeping the temperature below 40°C. The resulting reaction mixture was stirred for 30 minutes at 40°C and then crosslinked by heating at 65°C for 2 hours, after which it was quenched and diluted by adding enough water to bring the mixture to about 15% solids. The product had 14.2% solids, pH 5.4, and particle size 0.30 microns. It contained 0.04 % l,3-dichloropropan-2-ol, 0.15 % 2,3-chloropropanediol and less than 0.01 % residual epichlorohydrin.
- Example 16 This example demonstrates the sizing efficiency of resins of this invention compared to materials described in U.S. Patent No. 3,922,243.
- Waterleaf paper was prepared on a trial paper machine.
- the paper was prepared at a basis weight of 64.9 kg /1,000 m 2 from a 50:50 blend of bleached kraft hardwood and softwood pulps.
- the paper was prepared at a papermaking pH of 8.0 and contained 0.5% alum and 12% Albacar 5970TM precipitated calcium carbonate (Speciality Minerals Inc., Bethlehem, Pa.).
- the paper was not surface treated. All additive amounts are on a dry basis based on the dry weight of pulp.
- the paper was treated with an 8% solution of an GPC D-150 oxidized starch (from Grain Processing Company, Muscatine, IA), also containing the resin of this invention in dispersed form, using a laboratory size press operating at
- the level of resin needed in the starch solution was determined by first determining the amount of adsorbed starch solution when the paper was treated with starch solution only in the size press. The level of resin in the starch solution was then adjusted accordingly to give the desired level of addition to the paper (0.25 %).
- the sizing solutions were prepared both with (at a level of 0.2% based on paper) and without optical brightener (Phorwite P, Mobay Corp., Pittsburgh, PA). Optical brightening agents are commonly used in the size press to increase the brightness of paper. The paper was drum dried at
- Sizing results are shown in Table 3. Sizing was measured on the paper after storage for 2 weeks, using the Hercules Size Tester (Hercules, Inc., Wilmington, DE) at 80% reflectance with an ink containing 1% formic acid and a green dye. A duplicate of Example 2 was used as the control. The molar ratios of polyamine to dicarboxylic acid and hydrophobizing agent to polyamine used to prepare the hydrophobically modified aminoamide are shown for comparison.
- Example 17 This example demonstrates the sizing efficiency of the products of this invention compared to materials described in U.S. Patent No. 3,922,243.
- a waterleaf paper was prepared on a trial papermachine. The paper was prepared at a basis weight of 64.9 kg /1,000 m 2 from a 50:50 blend of bleached kraft hardwood and softwood pulps. The paper was prepared at a papermaking pH of 8.0 and contained 0.5% alum. The paper was not filled and not surface treated. All additive amounts are on a dry basis based on the dry weight of pulp.
- the paper was treated with an aqueous dispersion of the resin using a laboratory size press operating at room temperature.
- the paper was drum dryed immediately following treatment at 104° C.
- the level of sizing agent needed in the aqueous dispersion was determined by first determining the amount of absorbed water picked up when the paper was treated with water only in the size press. The level of resin in the dispersion was then adjusted accordingly to give the desired level of addition to the paper (0.2%).
- Sizing results are shown below in Table 4. Sizing was measured after storing the paper for 1 week, using the Hercules Size Tester at 80% reflectance with an ink containing 1% formic acid and a green dye. A duplicate of Example 2 was used as the control. The molar ratios of polyamine to dicarboxylic acid and hydrophobizing agent to polyamine used to prepare the hydrophobically modified aminoamide are shown for comparison.
- Example 11 2.00 0.4 no-/
- Comparative Example J This example describes preparation of a crosslinked cationic resin composition from the bis-stearamide of Comparative Example H.
- Paper was prepared on a trial papermachine with sizing agents added both internally and to the surface of the sheet at the size press.
- the paper was prepared at a basis weight of 64.9 kg /1,000 m 2 from a 75:25 blend of bleached kraft hardwood and softwood pulps refined to 425 CSF.
- the paper was prepared at a papermaking pH of 8.0, contained 0.25% alum (based on pulp), was filled with Albacar 5970 precipitated calcium carbonate at 10%, and was surface treated with a size press solution containing 4% Stayco M oxidized starch and 0.05% sodium chloride at 55°C.
- the solids level of resin and sodium chloride needed to apply the desired amount of material was determined by first determining the amount of absorbed starch solution picked up when the paper was treated with starch solution only in the size press. The level of resin and sodium chloride in the starch solution was then adjusted accordingly to give the desired level of addition to the paper.
- the paper was dried to give 4-6% moisture at the reel.
- Sizing agent was applied either internally or in the size press solution.
- the base sheet had at least 0.05% of Hercon®70 alkylketene dimer sizing agent in all sheets to aid in size press operation.
- Sizing and coefficient-of-friction (COF) results are shown in Table 5. All results were measured after storing the paper for 1 week. Sizing was measured using the Hercules Size Tester
- Example 3 0.025 surface 41 0.575
- Hercon 70 is in all sheets at 0.05% unless otherwise indicated.
- Example 19 This example illustrates the preparation of an aminoamide from adipic acid and diethylenetriamine hydrophobically modified by reaction with stearic acid.
- Adipic acid 65.7 g (0.45 moles) was added to diethylenetriamine, 77.4 g
- Example 20 This example describes the preparation of a crosslinked hydrophobically modified cationic resin composition by reaction of epichlorohydrin with the hydrophobically modified aminoamide prepared in Example 19.
- the dispersed hydrophobically modified aminoamide of Example 19 (674.4 g, 147. 7 g solids, 0.8 equivalents of amine) was blended with 308.7 g of water.
- Epichlorohydrin (61.1 g, 0.66 moles) was then slowly added to the dispersion while the temperature was maintained at below about 40°C.
- the resulting reaction mixture was then stirred for 30 minutes at 40°C and then crosslinked by heating at 65°C for 2 hours, after which it was quenched and diluted by adding enough water to bring the mixture to about 10.5% solids.
- the product contained 10.7% total solids, had pH 5.91, and particle size of zl.00 microns. It contained 0.076% l,3-dichloropropan-2-ol, 0.04% 2,3- chloropropanediol, and less than 0.01% residual epichlorohydrin.
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US81209297A | 1997-03-04 | 1997-03-04 | |
US812092 | 1997-03-04 | ||
PCT/US1998/003358 WO1998039376A1 (en) | 1997-03-04 | 1998-02-20 | Hydrophobically modified resin compositions and uses thereof |
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EP0907672A1 true EP0907672A1 (de) | 1999-04-14 |
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EP98907552A Withdrawn EP0907672A1 (de) | 1997-03-04 | 1998-02-20 | Hydrophobisch modifizierte harzzusammensetzungen und deren verwendungen |
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EP (1) | EP0907672A1 (de) |
AU (1) | AU726005B2 (de) |
CA (1) | CA2261954A1 (de) |
TW (1) | TW495538B (de) |
WO (1) | WO1998039376A1 (de) |
ZA (1) | ZA981848B (de) |
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US6702923B1 (en) | 1999-11-19 | 2004-03-09 | Akzo Nobel Nv | Wet strength agent and method for production thereof |
US20020096281A1 (en) | 1999-11-19 | 2002-07-25 | Hans Wallenius | Wet-strong tissue paper |
RU2223972C1 (ru) * | 1999-11-19 | 2004-02-20 | Акцо Нобель Н.В. | Агент для повышения влагопрочности и способ его получения |
US6673205B2 (en) | 2001-05-10 | 2004-01-06 | Fort James Corporation | Use of hydrophobically modified polyaminamides with polyethylene glycol esters in paper products |
SE522783C2 (sv) * | 2001-05-18 | 2004-03-09 | Sca Hygiene Prod Ab | Våtstarkt tissuepapper |
CA2461629C (en) | 2003-03-24 | 2012-05-08 | Nof Corporation | Paper additive composition and method for producing paper using the same |
US7041197B2 (en) | 2003-04-15 | 2006-05-09 | Fort James Corporation | Wet strength and softness enhancement of paper products |
US8651285B2 (en) † | 2009-08-19 | 2014-02-18 | Johns Manville | Performance polymeric fiber webs |
US8871055B2 (en) * | 2011-03-31 | 2014-10-28 | Solenis Technologies, L.P. | Sizing compositions |
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US3922243A (en) * | 1973-08-31 | 1975-11-25 | Hercules Inc | Ketene dimer modified water-dispersible thermosettable cationic resins |
US4478682A (en) * | 1981-07-02 | 1984-10-23 | Hercules Incorporated | Sizing method and sizing composition for use therein |
DE4200715A1 (de) * | 1992-01-14 | 1993-07-15 | Bayer Ag | Vinylpolymerisat-dispersionen |
-
1998
- 1998-02-20 AU AU63326/98A patent/AU726005B2/en not_active Ceased
- 1998-02-20 WO PCT/US1998/003358 patent/WO1998039376A1/en not_active Application Discontinuation
- 1998-02-20 CA CA002261954A patent/CA2261954A1/en not_active Abandoned
- 1998-02-20 EP EP98907552A patent/EP0907672A1/de not_active Withdrawn
- 1998-03-04 ZA ZA981848A patent/ZA981848B/xx unknown
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ZA981848B (en) | 1998-09-04 |
AU6332698A (en) | 1998-09-22 |
AU726005B2 (en) | 2000-10-26 |
CA2261954A1 (en) | 1998-09-11 |
WO1998039376A1 (en) | 1998-09-11 |
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