WO2001025214A1 - Procede de production d'imidazolines peu odorantes, imidazolines produites, papier et produits de papier contenant lesdites imidazolines - Google Patents

Procede de production d'imidazolines peu odorantes, imidazolines produites, papier et produits de papier contenant lesdites imidazolines Download PDF

Info

Publication number
WO2001025214A1
WO2001025214A1 PCT/US2000/026961 US0026961W WO0125214A1 WO 2001025214 A1 WO2001025214 A1 WO 2001025214A1 US 0026961 W US0026961 W US 0026961W WO 0125214 A1 WO0125214 A1 WO 0125214A1
Authority
WO
WIPO (PCT)
Prior art keywords
acylating
aldehydic
esterifying agent
ketonic
functional groups
Prior art date
Application number
PCT/US2000/026961
Other languages
English (en)
Inventor
Ferdinand P. Ferraro
Dennis G. Morrell
Lucia Vandekuil
Original Assignee
Hercules Incorporated
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Hercules Incorporated filed Critical Hercules Incorporated
Priority to AU77411/00A priority Critical patent/AU7741100A/en
Publication of WO2001025214A1 publication Critical patent/WO2001025214A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/20—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D233/24—Radicals substituted by nitrogen atoms not forming part of a nitro radical
    • 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
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/07—Nitrogen-containing compounds

Definitions

  • This invention relates to methods of producing water soluble or water dispersible imidazolines having low odor levels, and to imidazolines produced by such methods.
  • the invention also relates to paper and paper products containing imidazolines produced by such methods.
  • Paper and paper products such as facial tissue, and similar products are often treated to impart desirable properties thereto, such as improved softness, improved tactile properties and similar attributes.
  • Imidazolines may be added to such products to impart improved properties; however, imidazolines can suffer from odor problems, and thus the use of such imidazolines, while imparting desirable properties to products such as facial tissue, can also impart undesirable odors thereto. However, such odor problems have not been completely understood. Moreover, the source of such problems with the use of imidazolines has not been recognized.
  • U.S. Patent Nos. 5,415,737 and 5,510,000 both to PHAN et al., disclose that conventional quaternary ammonium compounds, such as the well known dialkyl dimethyl ammonium salts (e.g. ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated) tallow dimethyl ammonium chloride etc.) are effective chemical softening agents, but that these quaternary ammonium compounds can be subject to odor problems and can also be difficult to disperse. These patents disclose that the vegetable oil based quaternary ammonium salts also function effectively as chemical softening agents for enhancing the softness of fibrous cellulose materials.
  • dialkyl dimethyl ammonium salts e.g. ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di(hydrogenated) tallow dimethyl ammonium chloride etc.
  • these patents disclose that the vegetable oil
  • Tissue paper made with vegetable oil based quat softeners exhibited good softness and absorbency with improved odor compared to tissue made with animal based quat softeners.
  • good fluidity (low melting points) of the vegetable oil based quat softeners good dispersion with minimum or without diluent usage can be achieved.
  • the manufacture of imidazolinium salts generally involves the reaction of a polyamine with an acyl containing material such as an acid or ester to form an imidazoline and then a quaternizing of the imidazoline.
  • U.S. Patent Nos. 2,355,837, and 2,267,965, to WILSON; and U.S. Patent No. 2,520,102, to TRYON disclose methods of making imidazolines used in making imidazolinium salts. These patents are hereby incorporated by reference as though set forth in full herein.
  • U.S. Patent No. 4,233,451 to PRACHT et al. discloses that, in addition to the imidazoline compound formed in the above-described reaction, primary and secondary amines are also present. During the subsequent quaternization step, these amines cause some of the imidazoline compound to form the imidazoline amine salt rather than the quaternary imidazolinium salt.
  • the imidazoline amine salt when present in an aqueous medium having a near neutral or higher pH, is capable of undergoing ring opening to form free amines which will then react with aldehydic compounds in the composition much the same as free amines which have not been converted to the salt form.
  • the present invention provides methods for making imidazolinium compounds, preferably imidazolinium salts having low levels of odor, and to imidazoline compounds, preferably imidazolinium salts, and compositions produced thereby, as well as the resulting products.
  • the present invention is directed to compounds comprising water soluble or water dispersible imidazoline having low odor.
  • the present invention is directed to compositions comprising water soluble or water dispersible imidazoline compound having, at most, a low content of aldehydic/ketonic compounds and/or aldehydic/ketonic functional groups.
  • the present invention is directed to processes for producing water soluble or water dispersible imidazoline compound comprising reacting polyamine with acylating or esterifying agent, wherein the acylating or esterifying agent has a low content of aldehydic/ketonic compounds and/or aldehydic/ketonic functional groups, and reacting resulting imidazoline compound to form the water soluble or water dispersible imidazoline compound.
  • the compound or composition can contain no or substantially no chemically bound aldehydic/ketonic functional groups, can contain no or substantially no freely associated aldehydic/ketonic compounds, as well as combinations thereof.
  • the compound or composition can contain less than about 1,000 ppm of chemically associated aldehydic/ketonic functional groups and/or freely associated aldehydic/ketonic compounds, based upon 70 wt% active ingredients in a solvent system, more preferably less than about 400 ppm, even more preferably less than about 200 ppm, even more preferably less than about 100 ppm, even more preferably less than about 50 ppm, even more preferably less than about 25 ppm, and even more preferably chemically associated aldehydic/ketonic functional groups and/or freely associated aldehydic/ketonic compounds are not present in detectable amounts, based upon 70 wt% active ingredients in a solvent system.
  • the imidazoline compound can comprise a quaternary imidazoline salt.
  • the quaternary imidazoline salt comprise one or more quaternary imidazoline salts of the following structure:
  • R is a hydrocarbyl group
  • D is a bond, or an organic radical containing from about 1 to about 10 carbon atoms and is composed of elements selected from C, O, N and H, and can contain up to one aldehydic/ketonic functional group; when D is a bond, R 1 is selected from H, -OH, alkyl of from 1-20 carbon atoms; when D is an organic radical R, is aliphatic hydrocarbon group, branch or unbranched, substituted or non- substituted, containing from about 4 to 36 carbon atoms, and containing up to one aldehydic/ketonic functional group; and when D is an organic radical, D and R, can include up to two aldehydic/ketonic functional groups;
  • X is an anion
  • R 2 is any group that enables the imidazoline compound to be water soluble or water dispersible
  • R 3 and R 4 are hydrogen, hydroxy, a short chain alkyl having from 1 to 4 carbon atoms or hydroxy forms of the short chain alkyl.
  • D preferably comprises an amide, ester or alcohol when O and N are present.
  • the imidazoline compound can comprise an alkyloxylated imidazoline compound.
  • the imidazoline compound can comprise an ethoxylated imidazoline compound.
  • the imidazoline compound can comprise a propyloxylated imidazoline compound.
  • the composition can be clear.
  • the imidazoline compound can be formed from an acylating or esterifying agent which is liquid at 25°C.
  • the imidazoline compound can be formed from an acylating or esterifying agent containing up to one aldehydic/ketonic functional group, and more preferably does not contain aldehydic/ketonic functional groups.
  • the acylating or esterifying agent can comprise at least one of saturated fatty acids, mono- unsaturated fatty acids, alkyl esters of saturated fatty acids, alkyl esters of mon-unsaturated fatty acids, and naturally occurring glyceride esters.
  • the acylating or esterifying agent can comprise at least one of lauric acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, myristic acid, pentadecanoic acid, hexadecanoic acid, and palmitic acid.
  • the acylating or esterifying agent can comprise fatty acids mixtures derived from tall oil, soybean or palm oils.
  • the acylating or esterifying agent can comprise at least one of oleic and linoleic fatty acids.
  • the acylating or esterifying agent can comprise at least one of oleic acids from tall oils, olive oils, safflower oil, sunflower oil, soya oil, palm oil, canola oil, and rapeseed oil.
  • the acylating or esterifying agent can have an oleic acid content of at least about 70 wt%., more preferably of at least about 75 wt%, even more preferably of at least about 80 wt%, even more preferably of at least 89 wt%, even more preferably of at least about 92 wt%, and even more preferably of about 100 wt%.
  • the imidazoline compound can be formed from mono-unsaturated acylating or esterifying agent which is preferably unbranched. Also, the imidazoline compound can be formed from a saturated acylating or esterifying agent which is formed from an acylating or esterifying agent which is preferably branched
  • the imidazoline compound can be alkylated using an alkylating agent composing at least one of methyl chlo ⁇ de, ethyl bromide, diethyl sulfate, dimethyl sulfate and hexadecyl chlo ⁇ de
  • the imidazoline compound can be formed using an acylating or esterifying agent at a temperature of less than 165°C, more preferably at a temperature of about 145°C to 155°C, and even more preferably at a temperature of about 145°C to 150°C
  • Aldehydic/ketonic functional groups are present m the acylating or este ⁇ fymg agent, based upon 100% of the acylating or esterifying agent, in amounts of less than about 1,000 ppm, more preferably in amounts of less than about 400 ppm, even more preferably in amounts of less than about 200 ppm, even more preferably in amounts of less than about 100 pp, even more preferably in amounts of less than about 50 ppm, even more preferably m amounts of less than about 25 ppm, and even more preferably in non-detectable amounts
  • the present invention is also directed to products, such as paper products, including the compounds and compositions according to the present invention Still further, the present invention is directed to cellulosic products comprising cellulosic fibers and imidazoline compounds and compositions according to the present invention.
  • a reference to a compound or component includes the compound or component by itself, as well as m combination with other compounds or components, such as mixtures of compounds.
  • the present invention relates to the discovery that water soluble or water dispersible imidazoline compounds, preferably imidazoline salts (also referenced herein as imidazolinium compounds and imidazolinium salts) and compositions having relatively low odor can be prepared Moreover, the present invention relates to the discovery that products, such as paper products, of relatively low odor can be prepared which include the imidazoline compounds of the present invention
  • imidazoline salts also referenced herein as imidazolinium compounds and imidazolinium salts
  • products such as paper products, of relatively low odor
  • Aldehydic/ketonic compounds include the following functional groups:
  • Aldehydic/ketonic compounds include compounds having one or more aldehydic/ketonic functional groups therein.
  • aldehydic/ketonic compounds include components having one or more of -CHO and/or one or more -CC(O)C- functional groups therein.
  • compounds containing amide and or esters groups per se are not aldehydic/ketonic compounds according to the present invention.
  • compounds containing amide and/or ester groups could be considered to be aldehydic/ketonic compounds according to the present invention, if such compounds include one or more -CHO and or one or more -CC(O)C- therein.
  • aldehydic/ketonic compounds include compounds having the structure -RCHO or R-CC(O)C-R, wherein R can be any hydrocarbyl group.
  • hydrocarbyl is understood to include “aliphatic,” “cycloaliphatic,” and “aromatic.”
  • the hydrocarbyl groups are understood to include alkyl, alkenyl, alkynyl, cycloalkyl, aryl, arylalkyl, and alkaryl groups.
  • hydrocarbyl is understood to include branched and unbranched compounds, and both non- substituted hydrocarbyl groups, and substituted hydrocarbyl groups, with the latter referring to the hydrocarbon portion bearing additional substituents, besides carbon and hydrogen.
  • aldehydic/ketonic compounds include compounds having a "CHO" group located at the end of a compound and/or a group pendant to a backbone of a compound, as in the case of aldehydes, or in the middle of a compound and/or a group pendant to a backbone of a compound, as in the case of ketones. It is once again noted that amides and esters per se are not included in the definition of aldehydic/ketonic compounds.
  • R when R is an aliphatic group, R can be straight or branched chain, saturated or unsaturated hydrocarbon group, substituted or non-substituted, and can comprise from about 5 to 21 carbon atoms, preferably from about 10 to 21 carbon atoms, more preferably from about 10 to 20 carbon atoms, more preferably from about 16 to 18 carbon atoms, with one preferred value being about 17 carbon atoms.
  • aldehydic/ketonic compounds include, but not limited to, compounds such as aldehydes, ketones and keto-acids.
  • Aldehydic/ketonic compounds also include compounds that are precursors to aldehydic/ketonic compounds, i.e., compounds that form aldehydic/ketonic compounds, such as macrocyclic lactones, and hydroxy-substituted fatty acids which can form from cyclic lactones.
  • the present invention is based upon the discovery that the odor of imidazoline compounds, preferably quaternary imidazoline salts, can be reduced by providing imidazoline compounds having low content of aldehydic/ketonic functional groups, and preferably containing substantially no aldehydic/ketonic functional groups, and even more preferably containing no aldehydic/ketonic functional groups.
  • the present invention is based upon the discovery that the odor of compositions containing imidazoline compounds can be reduced by providing imidazoline compounds having low content of aldehydic/ketonic functional groups, and preferably containing substantially no aldehydic/ketonic functional groups, and even more preferably containing no aldehydic/ketonic functional groups. Still further, the present invention is based upon the discovery that the odor of compositions containing imidazoline compounds can be reduced by having a low content of aldehydic/ketonic functional groups in the compositions, preferably having substantially no aldehydic/ketonic functional groups in the composition, and even more preferably having no aldehydic/ketonic functional groups in the composition.
  • aldehydic/ketonic functional groups can be chemically associated with the imidazoline compounds, such as by comprising a portion of the chemical structure of the imidazoline compounds.
  • these chemically associated aldehydic/ketonic functional groups will be referred to herein as "chemically associated aldehydic/ketonic functional groups”.
  • the aldehydic/ketonic functional groups can be present in a composition containing the imidazoline compounds as aldehydic/ketonic compounds, such as in a mixture of a solvent and the imidazoline compounds.
  • these aldehydic/ketonic compounds will be referred to herein as "freely associated aldehydic/ketonic compounds”.
  • compositions containing imidazoline compounds contain low concentrations of at least one of the chemically bound aldehydic/ketonic functional groups and the freely associated aldehydic/ketonic compounds, preferably low concentrations of both of the chemically bound aldehydic/ketonic functional groups and the freely associated aldehydic/ketonic compounds.
  • compositions containing imidazoline compounds contain substantially none of at least ' one of the chemically bound aldehydic/ketonic functional groups and the freely associated aldehydic/ketonic compounds, and more preferably substantially none of both of the chemically bound aldehydic/ketonic functional groups and the freely associated aldehydic/ketonic compounds.
  • compositions containing imidazoline compounds contain no amounts of at least one of the chemically bound aldehydic/ketonic functional groups and the freely associated aldehydic/ketonic compounds, and most preferably no amounts of either of chemically bound aldehydic/ketonic functional groups and freely associated aldehydic/ketonic compounds.
  • the invention also relates to methods for producing the imidazoline compounds, preferably quaternary imidazoline salts, and compositions thereof.
  • the methods comprise reacting an acylating or esterifying agent with an alkylene or polyalkylene polyamine and quatemizing to form the salt, or ethoxylating or propyloxylating or any other form of alkyloxylating the imidazoline to form the low odor imidazoline compound.
  • the imidazoline compound is not water soluble or water dispersible, and it is necessary to render the compound water soluble or water dispersible, such as by quatemizing or alkyloxylating the imidazoline ring.
  • the acylating or esterifying agents preferably contain no aldehydic/ketonic functional groups, or substantially no aldehydic/ketonic functional groups and can be either unsaturated or mono-unsaturated.
  • the acylating or esterifying agents contain no aldehydic/ketonic functional groups and are mono-unsaturated, such as mono-unsaturated fatty acids including, but not limited to oleic acid.
  • the acylating or esterifying agents should contain no aldehydic/ketonic functional groups and is a branched unsaturated compound, such as a branch unsaturated fatty acid, such as, but not limited to, isostearic acid.
  • R is a hydrocarbyl group, preferably an aliphatic hydrocarbon group, branched or unbranched, substituted or non-substituted, containing from about 4 to 36 carbon atoms, preferably from about 10 to 21 carbon atoms, more preferably about 15 to 19 carbon atoms, with a preferred value of about 17 carbon atoms, and contains up to one aldehydic/ketonic functional group, but preferably contains no aldehydic/ketonic functional groups; preferably R contains only carbon and hydrogen atoms, preferably R is mono-unsaturated, and preferably unbranched. If R is completely saturated, it is preferred that R is branched.
  • D is a bond, or an organic radical containing from about 1 to about 10 carbon atoms and is composed of elements selected from C, O, N and H, and can contain up to one aldehydic/ketonic functional group, but preferably contains no aldehydic/ketonic functional groups, and preferably comprises amides, esters and alcohols when O and N are present;
  • R is selected from H, -OH, alkyl of from 1-20 carbon atoms, preferably alkyl of from 1-10 carbon atoms;
  • D is an organic radical R, is aliphatic hydrocarbon group, branch or unbranched, substituted or non-substituted, containing from about 4 to 36 carbon atoms, preferably from about 10 to 21 carbon atoms, more preferably about 15 to 19 carbon atoms, with a preferred value of about 17 carbon atoms, contains up to one aldehydic/ketonic functional group, but preferably contains no aldehydic/ketonic functional groups, preferably R, contains only carbon
  • X is an anion
  • R 2 is any group that enables the imidazoline compound to be water soluble or water dispersible, and, for example, can include as many as 100 carbon atoms, or more, and is preferably a hydrogen, alkyl, substituted alkyl or aralkyl group containing from about 1 to about 10 carbon atoms, with methyl and ethyl being preferred groups
  • R 3 and R 4 are hydrogen, hydroxy, a short chain alkyl having from 1 to 4 carbon atoms or hydroxy forms of the short chain alkyl.
  • R 2 group is shown as being on the number 3 nitrogen, it may also be present on the number 1 nitrogen.
  • the functional groups in the quaternary imidazoline salts will depend upon the particular starting materials employed to formulate the imidazoline, and in particular, the acylating or esterifying agent employed.
  • imidazoline compounds for exthoxylated and propyloxylated imidazoline compounds, it will be appreciated that the functional groups in the imidazoline compounds, and, in particular, the avoidance of chemically associated aldehydic/ketonic functional groups and freely associated aldehydic/ketonic compounds in the imidazoline compounds and compositions thereof, will depend upon the particular starting materials employed to formulate the imidazoline, and in particular, the acylating or esterifying agent employed. Exemplary descriptions of the processes are therefore provided herein.
  • an imidazoline precursor for a desired imidizolinium compound can be formed by reacting acylating or esterifying agents with alkylene or polyalkylene polyamines having two or three amino groups, one of which is a primary or secondary amino group in the 2 position or a primary amine group.
  • the acylating or esterifying agents should have as low a content of aldehydic/ketonic functional groups as possible, preferably containing substantially no aldehydic/ketonic functional groups, and most preferably containing no aldehydic/ketonic functional groups.
  • Such materials may be unsaturated or mono-unsaturated, branched or unbranched.
  • the higher the content of aldehydic/ketonic functional groups in the quaternary imidazoline salts and its composition the greater will be the odor.
  • the imidazolines of the present invention are preferably prepared from starting materials which will lead to the lowest formation of aldehydic/ketonic functional groups during formation of the imidazoline compounds, such as quaternary imidazoline salts. It is noted that the higher the unsaturation in the acylating or esterifying agent, the lower the oxidation stability, and the higher the odor in the resultant imidazolinium compound of the invention. For example, with respect to fatty acids as acylating or esterifying agents, it is noted that the oxidation rate of a fatty acid having two double bonds as compared to a fatty acid having one double bond will be increased by a factor of about ten.
  • the oxidation rate of a fatty acid having three double bonds as compared to a fatty acid having one double bond will be increased by a factor of about one hundred. Since the oxidation rate is related to the development of peroxide values which is directly related to aldehyde formation, it is readily seen that increasing unsaturation of the acylating or esterifying agent will result in an increase in aldehydic/ketonic functional groups, and consequently an increase in odors of the imidazoline compounds, such as quaternary imidazoline salts, and compositions thereof.
  • the acylating or esterifying agent according to the present invention may comprise any compound, preferably liquid compounds at room temperature, that results in the formation of the above-described R and R, groups in the imidazoline compounds, such as quaternary imidazoline salts.
  • the acylating or esterifying agent can include hydrocarbyl groups as discussed above, and preferably include aliphatic hydrocarbons, branched or unbranched, substituted or non-substituted, containing from about 4 to 36 carbon atoms, preferably from about 10 to 21 carbon atoms, more preferably about 15 to 19 carbon atoms, with a preferred value of about 17 carbon atoms, and containing up to one aldehydic/ketonic functional group, and preferably no aldehydic/ketonic functional groups.
  • acylating or esterifying agents include saturated fatty acids, mono- unsaturated fatty acids, alkyl esters of saturated fatty acids, alkyl esters of mon-unsaturated fatty acids, and naturally occurring glyceride esters.
  • the acylating or esterifying agents are liquid at room temperature.
  • Particularly preferred are lauric, decanoic, undecanoic, dodecanoic, tridecanoic, myristic, pentadecanoic, hexadecanoic, palmitic and the like.
  • Preferred fatty acids are mixtures thereof derived from tall oil, soybean or palm oils.
  • Particularly preferred are oleic or linoleic fatty acids or mixtures thereof.
  • oils such as triglycerides.
  • Preferred acylating or esterifying agents include fatty acids, fatty acid halides, fatty acid anhydrides and/or alkyl fatty esters.
  • Particularly preferred acylating or esterifying agents include mono-unsaturated, non-animal based fatty derivatives, such as oleic acids from tall oils, olive oils, safflower oil, sunflower oil, soya oil, palm oil, canola oil, and rapeseed oil, to synthesize the quaternary ammonium compound.
  • Preferred fatty acids are those that are liquid at room temperature. Additionally, it is expressly contemplated that genetically engineered oils, such as oils from genetically engineered or transgenic plants, could be employed.
  • acylating agents examples include PAMOLYN® 100®, available from Hercules Incorporated, Wilmington, DE; PAMOLYN® 125®, also available from Hercules Incorporated; PAMAK®, also available from Hercules Incorporated; PRIOLENE 6928®, available from Uniqema, Gouda, The Netherlands, and EDENOR® PK1805, EDENOR® TI05 and EDENOR® TI05GA, available from Cognis (Henkel) of Cincinnati, OH and Dusseldorf, Germany.
  • PAMOLYN® 100 is an oleic acid (C18:l, C18H34O2, cis-9-octadecenoic acid), having a minimum oleic content of about 89% (wt wt), typical oleic content of 90-92 % (wt/wt), having a minimum acid number of 196, and a typical acid number of 196, a % saturation of typically 2 % (wt/wt), a % linoleic content of typically 7% (wt/wt), a % unsaponifiable content of 0.5% (wt wt) maximum.
  • PAMOLYN® 100® is a non-animal-derived fatty acid.
  • Exemplary preferred acylating or esterifying agents in accordance with the present invention include acylating or esterifying agents having oleic acid contents of as high as possible, most preferably comprising 100 wt% oleic acid or about 100 wt% oleic acid, and is preferably at least about 70 wt%, more preferably at least about 75 wt%, more preferably at least about 80 wt%, more preferably at least about 89 wt%, more preferably at least about 92%, and a linoleic acid content of less than about 15 wt%, more preferably less than about 10 wt%, more preferably less than about 6 wt%, even more preferably less than about 3 wt%, even more preferably less than about 1 wt%, and most preferably about 0 wt% or 0 wt%.
  • Preferred acylating agents have an iodine number of about 75-160, more preferably about 80-100, and even more preferably about 83-95, a maximum acid number of 204, and a minimum acid number of about 195, a maximum content of unsaponifiable components of about 2 wt%, a maximum content of polyunsaturated acids of about 9 wt%, more preferably less than about 6, more preferably less than about 3, and even more preferably less than about 1, and a maximum content of rosin acids of less than about 5 wt%, more preferably less than about 3 wt%, even more preferably less than about 1, and most preferably 0 or about 0.
  • the acylating or esterifying agents are preferably liquid at room temperature. Therefore, preferred acylating or esterifying agents are mono-unsaturated, preferably unbranched, or if completely saturated, are preferred branched. Most preferably, the acylating or esterifying agent is a mono-unsaturated fatty acid or fatty acid ester, preferably unbranched, such as oleic acid. - l
  • the acylating or esterifying agent is most preferably a branched fatty acid or fatty acid ester, such as isostearic acid.
  • acylating or esterifying agents e.g., fatty acids or esters
  • fatty acids or esters having double bonds are subject to oxidation degradation.
  • Such compounds can be oxidized or degraded or cleaved to form aldehydes.
  • completely saturated acylating or esterifying agents should expected to be useful in the present invention, it is noted that completely saturated compounds that are unbranched, such as unbranched, saturated fatty acids, e.g., stearic acid, are solid or substantially solid compounds. Therefore, it is preferred that when completely saturated acylating or esterifying agents are utilized that these agents be branched compounds, such as branched, saturated fatty acids, e.g., isostearic acid, which are liquid compounds at room temperature.
  • the polyamine material preferably has either two or three amino groups wherein one is a primary or secondary amino group in the 2- position to a primary amine group. These preferably take the following form:
  • X may be, for example, hydrogen, -(-CH 2 -CH 2 ) ⁇ -NH 2 , -(-CH 2 -CH 2 -)-knowingly-OH or -(-CH 2 -CH 2 -) complicat-CH 3 , wherein n is from about 1 to about 6.
  • polyamines include diethylenetriamine, ethylenediamine, hydroxyethyl ethylenediamine, etc.
  • a particularly preferred polyamine material is diethylenetriamine.
  • one particularly preferred form of forming the imidazoline compound is to react the acylating or esterifying agent and the polyalkylene amine by heating in two stages.
  • the acylating or esterifying agent and polyalkylene amine are added together, so that the mole ratio of acylating or esterifying agent to primary amine is at least 1 to 1 , up to 1 to 1.1.
  • acylating or esterifying agent is oleic acid
  • polyalkylene amine is diethylenetriamine
  • 2 moles of oleic acid are preferably added for each mole of diethylenetriamine, so that there will be present one mole of oleic acid present for each mole of primary amine in the diethylenetriamine.
  • temperatures of about 125°C to 165°C with a preferred range of about 145°C to 155°C, more preferably about 145°C to
  • 150°C and with a preferred value of about 145°C, are utilized to react the acylating or esterifying agent with the polyalkylene amine to form a bisamide. Temperatures above 165 °C are not generally not preferred, because the final product can form a precipitate. Moreover, a range of about 145°C to 150°C is preferred because of a lack of formation of a precipitate at this temperature range; whereas, at higher temperatures a precipitate can form in the product. Thus, preferably the water- soluble or water dispersible imidazoline compound according to the present invention does not have visible precipitates.
  • the first heating stage is conducted for a sufficient amount of time so that the percent free fatty acid is below about 5, with the lower the percent free fatty acid the better.
  • the reaction can be conducted for up to 24 hours, or more, more preferably about 6 to 8 hours.
  • temperatures of about 125°C to 260°C are utilized, preferably under a weak vacuum, more preferably less than about 200 mm of mercury, more preferably less than about 100 mm of mercury, more preferably less than about 50 mm of mercury, even more preferably less than about 10 mm of mercury, to form the imidazoline compound.
  • the second heating step is conducted for a sufficient time to obtain at least 70% conversion, more preferably at least 85% conversion, with the desirability being to obtain 100% conversion.
  • the reaction can be conducted for up to 24 hours, or more, more preferably about 6 to 8 hours, such as 7 hours.
  • the percent conversion can be detected using, but not limited to, IR analysis, or NMR analysis, preferably C 13 NMR analysis.
  • R groups are as defined above.
  • the double bond is depicted at position ⁇ 2 . 3 , it should be understood that the double bond could alternatively be located at ⁇ , .2 .
  • the imidazoline compound can be treated with an alkylating agent to form the desired quaternary imidazoline salts.
  • the alkylating agent can be any alkylating agent that is capable of forming the quaternary imidazoline salts from the imidazoline compound, such as methyl chloride, ethyl bromide, diethyl sulfate, dimethyl sulfate and hexadecyl chloride.
  • diethyl sulfate is preferred over dimethyl sulfate as the diethyl sulfate alkylating agent produces imidazoline compounds having lower odor.
  • the imidazoline compound can be treated with an ethoxylating or propyloxylating agent to obtain ethoxylated imidazoline compounds or propyloxylated imidazoline compounds.
  • the alkylating reaction is preferably performed at a temperature of about 23°C to 125°C, more preferably at a temperature of about 40°C to 100°C, and more preferably about 60° to 80°C.
  • the imidazoline compound is preferably diluted with a diluent before the quatemization reaction in order to provide a lower viscosity for quatemization.
  • the diluent is preferably a solvent that provides a water soluble system.
  • Preferred solvents include, but are not limited to, alcohols, such as methanol and ethanol, propylene glycol, and polyethylene glycol.
  • the diluent comprises a non-volatile solvent and/or a substantially low volatilizing solvent, such as polyethylene glycol.
  • a diluent such as polyethylene glycol, such as PEG 400 obtained from Union Carbide, prior to addition of the alkylating agent, such as diethyl sulfate.
  • the amount of alkylating agent used should be equivalent to the amount of the imidazoline treated on a molar basis, and can be lower than the ' amount of imidazoline treated on a molar basis, such as 96 mole % of diethyl sulfate. However, an excess of the alkylating agent can be used to assure maximum quatemization. The amount of excess employed should be sufficient so that the pH of the reaction medium is in the range of from about 5 to about 7.
  • the reaction time generally ranges from about 1 to about 12 hours, and the temperature from about 40°C to 80°C.
  • a base such as KOH or NaOH, may be added during the alkylation to aid quatemization.
  • the imidazoline compound can be ethoxylated or propyloxylated, such as at the number 1 nitrogen when an OH group (hydroxyl) is present, such as an alcohol, to provide water solubility.
  • an OH group hydroxyl
  • the imidazoline compound is not water soluble or water dispersible.
  • Ethoxylation or propyloxylation can be used to obtain water solubility or dispersibility, as with quatemization, by utilizing various techniques, such as by reaction with ethylene oxide or propylene oxide.
  • the imidazoline compound such as the imidazolinium salt as formed above, has outstanding paper conditioning properties, including tissue softening, tissue debonding and antistatic properties, while additionally having a low content of chemically bound aldehydic/ketonic functional groups and or freely associated aldehydic/ketonic compounds.
  • a preferred imidazolinium salt contains R, and R groups having 17-18 carbon atoms such as the following wherein the R, and R groups are tall oil cuts:
  • C 0jeic is an aliphatic hydrocarbon chain derived from tall oil fatty acid.
  • Other quaternary imidazolinium salts having desirable properties can be formed by substituting different groups for oleic in the acylating or esterifying agent, different alkylene or polyalkylene polyamine for diethylenetriamine, and a different alkyl, substituted alkyl or aralkyl for the ethyl group present, as well as a different anion, in the alkylating agent.
  • the above-discussed two stage heating method utilizing about a 1 to 1 mole ratio of acylating or esterifying agent to primary amine is a preferred method for forming the imidazoline compound.
  • other methods of forming the imidazoline compounds of the present invention can be used.
  • the imidazoline precursor for the desired imidazolinium compound may be formed by reacting acylating or esterifying agents with the polyalkylene polyamines at a temperature of about 100°C to 250°C for a period of from about 3 to 24 hours, at a molar ratio of acylating or esterifying agent to primary amine and hydroxyl groups ranging from about 0.33:1 to about 1.5:1, preferably from about 1 :1 to about 1.5:1, and under reflux or at atmospheric pressure or slightly greater.
  • the reaction mixture may subsequently be subjected to a vacuum of from about 0.4 mm to 10 mm of mercury for a period of from about 1 to about 8 hours.
  • the resulting mixture contains, in addition to the desired - 18 - imidazoline, some of the original acylating or esterifying agent, some of the original polyamine, some of the noncyclized intermediate amide products and other mixed reaction products.
  • the amount of acylating or esterifying agent used is not sufficient to form an amide or ester with at least two of the amine or hydroxyl groups present in the polyamine (the molar ratio of acyl groups to primary amine or hydroxyl groups being from about 0.33 to about 1.2), the imidazoline formed will only have a long chain group of the type desired positioned at the 2- position rather than at both the 1- and 2- positions of the imidazoline ring. The mono-substituted material then has to be reacted further with an acylating or esterifying agent.
  • the reaction temperature is generally the same as the generalized reaction given above while the molar ratio of acylating agent or esterifying agent to mono substituted imidazoline ranges from about 1:1 to about 1.5:1 and the reaction time ranges from about 1 to about 24 hours.
  • a vacuum of from about 0.4 to about 10 mm of mercury is drawn.
  • the primary amine present in the imidazoline formed above is then converted to an amide to attach the second long chain R group in the following manner:
  • R j is an aliphatic or cycloaliphatic hydrocarbon group containing from about 10 to about 22 carbon atoms.
  • D may be another radical, or completely absent, depending on the choice and concentration of polyamine and acylating or esterifying agent. See, for example, U.S. Patent No. 2,267,965 to WILSON, where a hydroxy group is attached to the 1 position of the imidazoline ring, and U.S. Patent No. 2,355,837 to WILSON, for other polyamines, which patents are hereby incorporated by reference herein for such disclosures.
  • the amount of acylating or esterifying agent used contains a number of acylating groups sufficient to form an amide or ester with at least two of the amine or hydroxyl groups (ratio of acyl to primary amine or hydroxyl groups is from about 0.67 to about 1.5:1, preferably 1 :1 to about 1.1:1)
  • the long chain group in the 1 position would be present as a result of the initial imidazoline forming reaction.
  • the chemically associated aldehydic/ketonic functional groups and/or freely associated aldehydic/ketonic compounds in the imidazoline compounds and compositions thereof are preferably present in amounts, based upon 70 wt% active ingredients in a solvent system, such as water, propylene glycol, ethylene glycol, of less than about 1 ,000 ppm, more preferably less than about 900 ppm, even more preferably less than about 800 ppm, even more preferably less than about 700 ppm, even more preferably less than about 600 ppm, even more preferably less than about 500 ppm, even more preferably less than about 400 ppm, even more preferably less than about 300 ppm, even more preferably less than about 250 ppm, even more preferably less than about 200 ppm, even more preferably less than about 150 ppm, even more preferably less than about 100 ppm, even more preferably less than about 75 ppm, even more preferably less than about 60 ppm, even more preferably less than about 50
  • the chemically associated aldehydic/ketonic functional groups are present in amounts equal to or less than indicated above
  • the freely associated aldehydic/ketonic compounds in the imidazoline salts and compositions thereof are present in amounts equal to or less than indicated above
  • the combination of the chemically associated aldehydic/ketonic functional groups and the freely associated aldehydic/ketonic compounds in the imidazoline compounds and compositions thereof are present in amounts equal to or less than indicated above
  • concentrations of chemically associated aldehydic/ketomc functional groups and/or freely associated aldehydic/ketonic compounds in the imidazoline compounds and compositions thereof are those that are present when the imidazoline compounds are produced, and can also be applied to mate ⁇ als at ageing and/or further treatment, such as oxidization
  • aldehydic ketomc functional groups in the acylating or este ⁇ fying agents are also preferably present, based upon 100% of the acylating or este ⁇ fying agent, in amounts of less than about 1,000 ppm, more preferably less than about 900 ppm, even more preferably less than about 800 ppm, even more preferably less than about 700 ppm, even more preferably less than about 600 ppm, even more preferably less than about 500 ppm, even more preferably less than about 400 ppm, even more preferably less than about 300 ppm, even more preferably less than about 250 ppm, even more preferably less than about 200 ppm, even more preferably less than about 150 ppm, even more preferably less than about 100 ppm, even more preferably less than about 75 ppm, even more preferably less than about 60 ppm, even more preferably less than about 50 ppm, even more preferably less than about 25 ppm, and even more preferably less than about 20 ppm, and are
  • the aldehydic/ketomc functional groups will p ⁇ ma ⁇ ly be composed of aldehydes in the acylating or este ⁇ fying agents, especially when the acylatmg or este ⁇ fying agents comp ⁇ se fatty acids or fatty acid esters
  • aldehydes will include heptanal, 2-heptenal, octanal, 2-octenal, nonanal, 2-nonenal, decanal, 2-decenal, 2,4-decdienal and 2-undecenal.
  • the parameters employed are as follows:
  • the GC injector is a GUSTEL CIS-3 in split mode; the GC injector temperature is 300°C; the GC employed is an HP 6890; the column GC is a 30m DB-1 x 250 ⁇ m X 0.25 ⁇ m; temperature of 70°-4°/minute - 320°C-20 minutes.
  • the MSD model is an HP 5472, set to total ion mode.
  • the odor of the imidazoline product can be determined by overlaying a GC by a so-called aromagram (obtained with a trained human nose). Mass spectroscopy together with such an aromagram can be employed for identifying odor-causing compounds.
  • the odor components can be isolated by vacuum steam distillation, such as counter current vacuum steam distillation, or by continuous extraction with pentane/dichloromethane (bp 30cc°C), and concentrated using a Widmer column. Identification of odor components can be made by GC-MSD and GC-sniff out using people with so-called trained nose.
  • compositions The present invention is also directed to papermaking compositions and compositions for treating paper, comprising imidazolium compounds, preferably imidazolium salts, preferably 1,2 substituted quaternary imidazolinium salts, having low odor, such compositions containing low or no amounts of aldehydic/ketonic compounds and/or aldehydic/ketonic functional groups.
  • imidazolium compounds preferably imidazolium salts, preferably 1,2 substituted quaternary imidazolinium salts, having low odor, such compositions containing low or no amounts of aldehydic/ketonic compounds and/or aldehydic/ketonic functional groups.
  • the desired imidazolinium compound can be prepared using the processes previously described, or another process which will yield the imidazolinium compound and will not have more than the above indicated levels of the aldehydic/ketonic compounds and/or aldehydic/ketonic functional groups.
  • compositions of the present invention are preferably liquid, or aqueous solutions and may contain any desired level of the imidazolinium compound. Because many imidazolinium compounds are liquid at room temperature, they can be employed "neat"; i.e., without dilution or the addition of other materials, or without dilution and containing additives.
  • Aqueous compositions are preferably in emulsion form and preferably contain from about 1 to about 15 w% of the salt and most preferably from about 2 to about 8 wt%.
  • the optimum amount employed can be determined based on the foregoing guidelines for the aqueous compositions.
  • compositions of the present invention may also contain other conventional components or papermaking and paper treating agents.
  • Such other agents may be described as fixatives, solvents, co-solvents, hydrotropes, anti-oxidants, stabilizers, pH adjusters, buffers, biodegradable antimicrobials, builders, fillers, enzymes, peroxides, thickeners, fluorescent brighteners, absorbency agents, surfactants, polymers, dispersants, synthetic organic detergents, silicones, clay, kaolin, humectants, starches, sugars, inorganic salts, and antifoamers.
  • fixatives solvents, co-solvents, hydrotropes, anti-oxidants, stabilizers, pH adjusters, buffers, biodegradable antimicrobials, builders, fillers, enzymes, peroxides, thickeners, fluorescent brighteners, absorbency agents, surfactants, polymers, dispersants, synthetic organic detergents, silicones, clay, kaolin, humectants, starches,
  • compositions according to the invention may be in aqueous or non-aqueous, preferably liquid form and may be prepared by adding the imidazoline compound with our without conventional additives, with or without heating, then, optionally, adding them to water.
  • the agents can be heated to form a liquid oily phase. They can be added with mixing to heated or unheated water to form liquid emulsions.
  • anti-oxidants such as BHT (butylhydroxy toluene) are employed to retard the formation of oxidation/degradation products of the acylating/esterifying agents and the imidazolinium compounds having the substituents defined above.
  • BHT butylhydroxy toluene
  • Various optional ingredients can be added according to methods known in the art.
  • compositions of the present invention may be employed in any manner that additives used in the paper industry are employed. They are preferably used in the wet end of conventional papermaking operations, although the compositions can be applied to paper that has already been formed. Generally, the composition employed for treatment of the web is provided at a level that is sufficient to impart a perceptible degree of softness/debonding to the web. Treatment of the wet web with the composition can be accomplished by various means, for instance the treatment step can comprise spraying compositions prepared as above on the web or adding the composition to the furnish at the wet end.
  • compositions of the present invention when compositions of the present invention are added to the thick stock of a tissue making furnish the agents are generally present at levels of from about 0.025 wt% to about 0.75 wt% based on the dry weight of the fiber used to form the web, preferably from about 0.1 wt% to about 0.5 wt% based on the dry weight of the fiber used to form the web. These concentration levels achieve superior softening/debonding results.
  • Paper and paper products containing imidazoline compounds of the invention having low odor include soft tissue products such as facial tissue, bath towels, diapers, sanitary napkins, non- woven gowns, and similar products and the invention has particular utility in such products.
  • soft tissue products such as facial tissue, bath towels, diapers, sanitary napkins, non- woven gowns, and similar products and the invention has particular utility in such products.
  • Other uses contemplated for the invention include antistatic agents, textile softeners, corrosion inhibitors, flotation agents, asphalt and petroleum additives, lubricants, laundry detergents, wetting agents, cosmetics and personal care products.
  • antistatic agents such as facial tissue, bath towels, diapers, sanitary napkins, non- woven gowns, and similar products and the invention has particular utility in such products.
  • textile softeners such as facial tissue, bath towels, diapers, sanitary napkins, non- woven gowns, and similar products and the invention has particular utility in such products.
  • Other uses contemplated for the invention include antistatic agents, textile soften
  • the reactor used was a 10 gallon stainless steel agitated reactor which has a condenser and receiver for water removal, a vacuum system, an oil- filled jacket for heating the reactor, inert gas inlets, etc.
  • Pamolyn®100 Hercules Incorporated (14.5 kg, 51.43 g-moles) is added.
  • Diethylenetriamine (2.65 kg; 25.73 g mole) (Aldrich Chemical Company, Milwaukee) is added over 50 minutes. The rate of addition is controlled to obtain a temperature profile from ambient temperature to ⁇ 120°C ⁇ 10°C at the end of the addition time.
  • the salt of diethylenetriamine and oleic acid is converted to the bisamide by heating the mixture to 145°C ⁇ 10°C. Water is removed from the reactor through the condenser. The free fatty acid is determined for the product by using a modified Acid Number method. The conversion to the bisamide is acceptable when the percent free fatty acid number is below 5. Total time at 145°C was 7 hours Conversion to the Imidazoline:
  • the bisamide mixture is heated to 184°C ⁇ 10°C under vacuum. At ⁇ 50 mm of Hg the reaction mixture is heated for seven hours to obtain the imidazoline.
  • the imidazoline conversion is determined by infrared analysis.
  • Example 2 was essentially identical to Example 1 except that the imidazoline reaction was done at 182°C for 5 hours.
  • Example 3
  • Example 3 was essentially identical to Example 1 except that the imidazoline reaction was done at 172°C for 5.75 hours and then heated to 182°C for 5.75 hours.
  • Example 4 was essentially identical to example 1 except the time for forming the bisamide was 8 hours.
  • Example 5 was essentially identical to Example 1 except that the Pamolyn ®100 was replaced with Pamolyn ®125 and the diethylenetriamine source was Dow chemical company.
  • Example 5 13C NMR analysis of Example 5 product, indicated total imidazoline of 70.90 wt%, total bisamide of 2.50 wt% and total polyethylene glycol of 16.90 wt%.
  • Example 6 was essentially identical to Example 1 except that the Pamolyn ®100 was replaced with Pamolyn ®125 (Hercules Incorporated).
  • the free fatty acid is titrated with an alcoholic KOH titrant.
  • the acid is calculated as oleic acid.
  • Phenolphthalein or a combination pH electrode is used to determine the end point.
  • the imidazoline content is determined by infrared analysis.
  • the spectrophotometer used is Nicolet Magna 560 or equivalent.
  • PH is measured as a 5 wt% in water with a pH meter.
  • Viscosity is measured at 25°C and the viscosity in centipoises determined with a Brookfield viscometer using an appropriate spindle and speed setting. (Brookfield Engineering Laboratories Stoughton MA)
  • a pulp slurry was prepared with 70 wt% softwood and 30 wt% hardwood in 23 to 27°C, distilled water to 2.5 wt% consistency. A portion of this pulp slurry was diluted with distilled water so as to make a 30 pound per 3000 sq. ft. handsheet. The pH of this pulp slurry was adjusted to 7.5. Next, the imidazoline composition was added to the pulp slurry at the desired level and the pulp slurry stirred for five minutes. This pulp slurry mixture was added to the head box of a Noble and Wood Handsheet Machine. The pulp slurry mixture was diluted with distilled water and mixed in the head box.
  • the pulp slurry mixture was allowed to drained onto a 100 mesh screen where a wet web was formed on it.
  • the wet web was dried on a drum dryer for 50 to 55 seconds at 230°F to 3 to 5 wt% moisture content.
  • a handsheet generated by the above method was tested for reduced dry tensile strengths listed in Table 2, and reduced burst strength or Mullen values listed in Table 2, and compared against a known additive for this application, Varisoft 3690, commercially available from Witco Corporation.
  • Tensile strength was determined on a Thwing Albert type tester using TAPPI T494 "Tensile Breaking Properties of Paper And Paperboard (Using Constant Rate Of Elongation Apparatus)' ' ' as a guide.
  • Burst strength or Mullen Value was determined on a Mullen type tester using TAPPI T 403 "Bursting Strength Of Paper” as a guide.
  • Pamolyn 100 obtained from Hercules Incorporated, Wilmington, Delaware (acid number : 199.03 mg KOH g; 930.1 g) was charged to a flask and was sparged with nitrogen (20 ml min), and was heated to 64°C.
  • Diethylenetriamine obtained from Aldrich Chemical Company, Milwaukee,
  • Wisconsin was charged at 170.2 g to the flask by a self-equalizing addition funnel and added to the flask over a 17 minute period with a nitrogen sparge (20 ml/min).
  • the temperature ranges from an initial temperature of 64°C to a maximum temperature of 122°C.
  • the mixture was then held at 120°C for 30 minutes with a nitrogen sparge (20 ml min).
  • the mixture was then heated to 165°C over a 1.7-hour period with nitrogen sparging (20 ml/min). After reacting at 165°C for 5 hours with nitrogen sparging, the reaction mixture contained 6.85% free fatty acid (as oleic).
  • the mixture contained 3.80% free fatty acid (as oleic).
  • a vacuum was gradually applied at 165°C, and after one hour the vacuum was 98 mm of Hg, reaction temperature at 165°C and nitrogen flow at 300 ml/min. After 1.42 hours, the vacuum was 20 mm Hg, reaction temperature at 164°C and nitrogen flow at 790 ml/min. After 10.8 hours under vacuum, the % ring closure was 89.2% by C13 NMR.
  • the reaction was cooled to room temperature and 55.1 g of polyethylene glycol 400 MW, was mixed with 200 g of the imidazoline.
  • the free oleic acid was 5.99%.
  • the reaction was then held overnight (an additional 15 hours) at 145°C to finish the diamide cook. After this hold period, the free oleic acid was 2.47%.
  • Vacuum was gradually stepped down to 50 mm Hg with nitrogen sparging at 20 ml/min as the reaction was heated to 165°C.
  • the % imidazoline ring closure was 85.9 by C13 NMR. 285.6 g of the imidazoline and 78.6 g of polyethylene glycol 400 MW was charged to a flask. The reaction was then set at 55°C under a nitrogen blanket.
  • a self-equalizing addition funnel was purged with nitrogen and 67.8 g diethyl sulfate was added to the funnel.
  • the diethyl sulfate was added at a rate so that the reaction temperature did not exceed 67°C.
  • the total addition time was 1 hour.
  • the diethyl sulfate addition was postcooked at 62°C for 4 hours. At this point, the free amine content was 4.58% (0.0747 meq/g).
  • the reaction was cooled to 30°C.
  • the color of the quaternary compound had a Gardner
  • Example 16 was essentially identical to Example 14 utilizing dimethyl sulfate instead of diethyl sulfate. A panel of five people identified the compound made with the dimethyl sulfate as having an offensive odor, and was worst smelling than the compound made with the diethyl sulfate.
  • Example 2 These examples are essentially identical to Example 1 with temperature, pressure and raw material being varied as indicated in Table 3. It is noted that Pamolyn 100 and Pamolyn 125 were obtained from Hercules Incorporated;
  • Priolene 6928 was obtained from Uniqema; Acme Hardesty, Oleic Acid was obtained from Acme
  • Example 27 the diethyl sulfate was added prior to addition of the PEG 400, which acts as a solvent. This reversal of order was tried in an attempt to reduce potential effect of water in PEG
  • the product was a very thick, material that appeared like latex paint when it was transferred from the reactor. Within 3 days the opacity of the product disappeared and a normally amber liquid formed.
  • Example 28 triple pressed stearic acid was used, and the PEG 400 charge was increased by a factor of three to obtain a fluid product at 60°C. At room temperature, the resulting product is solid. Therefore, while products according to the present invention are preferably liquid at room temperature, e.g., 25°C, the products can also be solid. Examples 29 and 30 are not representative. Example 29 was restarted 3 times due to weather conditions, and Example 30 was terminated when a target free fatty acid limit of less than 5.0 could not be achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des compositions et leurs procédés de production. Ces compositions comprennent un composé d'imidazoline peu odorant dispersible ou soluble dans l'eau, et un faible contenu de composés aldéhydiques/cétoniques, et/ou des groupes fonctionnels aldéhydiques/cétoniques.
PCT/US2000/026961 1999-10-01 2000-09-28 Procede de production d'imidazolines peu odorantes, imidazolines produites, papier et produits de papier contenant lesdites imidazolines WO2001025214A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU77411/00A AU7741100A (en) 1999-10-01 2000-09-28 Method of producing low-odor imidazolines, imidazolines produced thereby and paper and paper products containing the same

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US15701699P 1999-10-01 1999-10-01
US60/157,016 1999-10-01
US52802700A 2000-03-17 2000-03-17
US09/528,027 2000-03-17

Publications (1)

Publication Number Publication Date
WO2001025214A1 true WO2001025214A1 (fr) 2001-04-12

Family

ID=26853755

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2000/026961 WO2001025214A1 (fr) 1999-10-01 2000-09-28 Procede de production d'imidazolines peu odorantes, imidazolines produites, papier et produits de papier contenant lesdites imidazolines

Country Status (2)

Country Link
AU (1) AU7741100A (fr)
WO (1) WO2001025214A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674365B2 (en) 2004-10-07 2010-03-09 Rohm And Haas Company Formulations useful as asphaltene dispersants in petroleum products
WO2014120798A1 (fr) 2013-01-29 2014-08-07 Continental Structural Plastics, Inc. Composition de préforme de moulage de fibres et procédé de formation de préforme
CN104557714A (zh) * 2014-12-15 2015-04-29 山东师范大学 一种氨基修饰的nit类氮氧自由基的合成方法
CN106832165A (zh) * 2016-12-23 2017-06-13 广昌达新材料技术服务（深圳）股份有限公司 一种用作缓蚀剂主剂的水溶性咪唑啉季铵盐及其制备方法和应用
US10907473B2 (en) 2017-11-14 2021-02-02 Chevron U.S.A., Inc. Low volume in-line filtration methods for analyzing hydrocarbon-containing fluid to evaluate asphaltene content and behavior during production operations
WO2024073492A1 (fr) 2022-09-28 2024-04-04 Championx Llc Composition d'inhibiteur d'asphaltène à libération prolongée

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2267965A (en) * 1939-07-18 1941-12-30 Carbide & Carbon Chem Corp Hydroxyalkyl glyoxalidines
US2520102A (en) * 1946-09-03 1950-08-22 Commercial Solvents Corp Condensation products of diamines and fatty acids
US4233451A (en) * 1976-05-20 1980-11-11 The Procter & Gamble Company Process for making imidazolinium salts
US4770815A (en) * 1986-10-24 1988-09-13 The Procter & Gamble Company Detergent plus softener with imidazoline ingredient
EP0294886A2 (fr) * 1987-06-10 1988-12-14 The Procter & Gamble Company Produits pour traiter le linge
US5415737A (en) * 1994-09-20 1995-05-16 The Procter & Gamble Company Paper products containing a biodegradable vegetable oil based chemical softening composition
US5510000A (en) * 1994-09-20 1996-04-23 The Procter & Gamble Company Paper products containing a vegetable oil based chemical softening composition
WO1997004166A1 (fr) * 1995-07-21 1997-02-06 Kimberly-Clark Worldwide, Inc. Procede de crepage de bandes de papier mousseline contenant un adoucissant, grace a l'emploi d'une poche de crepage fermee
WO1998017750A1 (fr) * 1996-10-21 1998-04-30 The Procter & Gamble Company Composition concentree d'assouplissant de textile

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2267965A (en) * 1939-07-18 1941-12-30 Carbide & Carbon Chem Corp Hydroxyalkyl glyoxalidines
US2520102A (en) * 1946-09-03 1950-08-22 Commercial Solvents Corp Condensation products of diamines and fatty acids
US4233451A (en) * 1976-05-20 1980-11-11 The Procter & Gamble Company Process for making imidazolinium salts
US4770815A (en) * 1986-10-24 1988-09-13 The Procter & Gamble Company Detergent plus softener with imidazoline ingredient
EP0294886A2 (fr) * 1987-06-10 1988-12-14 The Procter & Gamble Company Produits pour traiter le linge
US5415737A (en) * 1994-09-20 1995-05-16 The Procter & Gamble Company Paper products containing a biodegradable vegetable oil based chemical softening composition
US5510000A (en) * 1994-09-20 1996-04-23 The Procter & Gamble Company Paper products containing a vegetable oil based chemical softening composition
WO1997004166A1 (fr) * 1995-07-21 1997-02-06 Kimberly-Clark Worldwide, Inc. Procede de crepage de bandes de papier mousseline contenant un adoucissant, grace a l'emploi d'une poche de crepage fermee
WO1998017750A1 (fr) * 1996-10-21 1998-04-30 The Procter & Gamble Company Composition concentree d'assouplissant de textile

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7674365B2 (en) 2004-10-07 2010-03-09 Rohm And Haas Company Formulations useful as asphaltene dispersants in petroleum products
WO2014120798A1 (fr) 2013-01-29 2014-08-07 Continental Structural Plastics, Inc. Composition de préforme de moulage de fibres et procédé de formation de préforme
CN105073366A (zh) * 2013-01-29 2015-11-18 康廷南拓结构塑料有限公司 纤维模塑预制件合成物及用于预制件形成的方法
EP2950988A4 (fr) * 2013-01-29 2017-02-22 Continental Structural Plastics, Inc. Composition de préforme de moulage de fibres et procédé de formation de préforme
CN107234744A (zh) * 2013-01-29 2017-10-10 赛史品威奥（唐山）结构复合材料有限公司 纤维模塑预制件合成物及用于预制件形成的方法
US10286574B2 (en) 2013-01-29 2019-05-14 Continental Structural Plastics, Inc. Fiber molding preform composition and process for preform formation
CN107234744B (zh) * 2013-01-29 2019-06-11 赛史品威奥（唐山）结构复合材料有限公司 纤维模塑预制件合成物及用于预制件形成的方法
CN104557714A (zh) * 2014-12-15 2015-04-29 山东师范大学 一种氨基修饰的nit类氮氧自由基的合成方法
CN106832165A (zh) * 2016-12-23 2017-06-13 广昌达新材料技术服务（深圳）股份有限公司 一种用作缓蚀剂主剂的水溶性咪唑啉季铵盐及其制备方法和应用
US10907473B2 (en) 2017-11-14 2021-02-02 Chevron U.S.A., Inc. Low volume in-line filtration methods for analyzing hydrocarbon-containing fluid to evaluate asphaltene content and behavior during production operations
WO2024073492A1 (fr) 2022-09-28 2024-04-04 Championx Llc Composition d'inhibiteur d'asphaltène à libération prolongée

Also Published As

Publication number Publication date
AU7741100A (en) 2001-05-10

Similar Documents

Publication Publication Date Title
US5753079A (en) Obtaining enhanced paper production using cationic compositions containing diol and/or diol alkoxylate
EP0633963B1 (fr) Papier absorbant doux contenant un compose adoucissant d'amine-ester quaternise biodegradable et une resine a resistance temporaire a l'humidite
EP0635081B1 (fr) Papier absorbant doux contenant un compose adoucissant d'amine-ester quaternise biodegradable et une resine de resistance permanente a l'humidite
AU2015330180B2 (en) Fabric softener active composition
US20070265469A1 (en) Fatty Acid Esters of Alkanolamines and Their Use as Softening Agents
EP1169515B1 (fr) Composition d'appret
US5643498A (en) Quaternary cationic surfactants having multiple hydrophobic and hydrophilic groups
CA2341007A1 (fr) Derives amphoteres de polyamines aliphatiques ayant reagi avec des acides gras, des esters ou des triclycerides
WO2001085109A1 (fr) Nouveaux composes quaternaires, compositions les contenant et utilisations desdits composes
JP2015505585A (ja) 繊維柔軟仕上げ剤活性組成物
CN102388181B (zh) 用于纸张施胶的产品
AU2013381757B2 (en) Fabric softener compositions
WO2001025214A1 (fr) Procede de production d'imidazolines peu odorantes, imidazolines produites, papier et produits de papier contenant lesdites imidazolines
EP2083050A1 (fr) Compositions pour construction de route
JP3870687B2 (ja) 古紙再生用添加剤および再生紙の製造方法
WO2000021918A1 (fr) Composes de polyester polyquaternaires, compositions les renfermant et leur utilisation
US5824635A (en) Cationic compositions containing hydroxyester
US5182033A (en) Polyamide salts
JP2840377B2 (ja) ケテンダイマー系サイズ剤および該サイズ剤を用いてなる紙サイジング方法
JP2017066569A (ja) 液体柔軟剤組成物
JPS6410640B2 (fr)
CN117126064A (zh) 用于制备酯基季铵盐的方法
SU1016408A1 (ru) Способ получени антистатика дл синтетических волокон
JP2007270397A (ja) 紙用柔軟剤
JPH07189175A (ja) 紙用サイズ剤及びサイジング方法

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CR CU CZ DE DK DM DZ EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP