WO1997045395A1 - Quaternary ammonium compounds - Google Patents
Quaternary ammonium compounds Download PDFInfo
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- WO1997045395A1 WO1997045395A1 PCT/SE1997/000873 SE9700873W WO9745395A1 WO 1997045395 A1 WO1997045395 A1 WO 1997045395A1 SE 9700873 W SE9700873 W SE 9700873W WO 9745395 A1 WO9745395 A1 WO 9745395A1
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- WO
- WIPO (PCT)
- Prior art keywords
- acid
- quaternary ammonium
- epoxide
- hydroxy
- ammonium compound
- Prior art date
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Classifications
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
- C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C215/40—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton with quaternised nitrogen atoms bound to carbon atoms of the carbon skeleton
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
- C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
- C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
Definitions
- the present invention generlly relates to quaternary ammonium compounds. More specifically, the invention relates to cationic polyurethanes and aqueous dispersions of cationic polyurethanes, their preparation and use in papermaking. The invention further relates to hydroxy-functional quaternary ammonium compounds and compositions thereof, their preparation and use in the production of cationic polyurethanes.
- CPUR cationic polyurethanes
- U.S. Pat. No. 3,971,764 discloses high molecular weight CPUR sizing agents prepared by reacting a diol with a polyisocyanate to form a prepolymer with terminal isocyanate groups which is subsequently reacted with (a) a diol containing a tertiary nitrogen atom which is subsequently converted into the corresponding ammonium compound, or (b) a diol containing a nitrogen atom previously converted into the corresponding ammonium com ⁇ pound; method (a) being preferred.
- the nitrogen atom can be rendered cationic by using an acid or alkylating agent and the patent discloses that hydrogen chloride, hydrochloric acid and dimethyl sulfate are useful for this purpose.
- Such CPUR dispersions generally provide good sizing response using low levels of sizing agent. It has, however, been observed that the CPUR dispersions exhibit stability problems and settling tendencies, in particular in the presence of electrolytes which are commonly added into the size press in order to prevent static electricity being built up during subsequent application, drying or con ⁇ verting processes. The insufficient stability may cause the CPUR particles contained in the dispersions to agglomerate and form deposits, leading to handling and application problems, deteriorated size performance and poorly sized paper.
- CPUR ' s having improved sizing and stability properties can be obtained by using in the polyurethane synthesis a hydroxy-functional quaternary ammonium compound (QUAT), i.e. an organic compound con ⁇ taining one or more hydroxyl groups and a positively charged quaternary nitrogen atom, in which the nitrogen has been quaternized with an epoxide.
- QUAT hydroxy-functional quaternary ammonium compound
- the present invention relates to a method of producing a cationic polyurethane which comprises reacting a dihydroxy compound with a polyisocyanate to form a pre-polymer with terminal isocyanate groups which is then reacted with a hydroxy-functional quaternary ammonium compound containing a quaternary nitrogen that has a substituent derived from an epoxide.
- the invention thus relates to a method of producing cationic polyurethanes, to cationic polyurethanes per se and to their use, as further defined in the claims.
- the method according to the present invention leads to high molecular weight CPUR ' s with outstanding properties
- Aqueous dispersions of the present CPUR's exhibit improved stability and hereby the problems associated with p ⁇ or art sizing dispersions based on CPUR can be reduced or overcome
- the present CPUR dispersions further provide improved sizing which means that lower levels of sizing agent can be used to give the same sizing effect, thereby leading to cost reduction and economic benefits
- Dihydroxy compounds, or diols, that can be used as monomers in order to form the prepolymer, or intermediate product, according to the present invention include aliphatic and aromatic diols
- aliphatic refers to an essentially hydrocarbon structure apart from designated functional groups, which hydrocarbon structure may be inter ⁇ rupted by one or more heteroatoms, e g oxygen and nitrogen, and/or one or more groups containing heteroatoms, e g carbonyl and acyloxy groups
- aromatic refers to an aromatic, essentially hydrocarbon structure apart from designated func ⁇ tional groups, which hydrocarbon structure may be interrupted by one or more heteroatoms, e g oxygen and nitrogen, and/or one or more groups containing heteroatoms, e g carbonyl and acyloxy groups It is generally preferred to use aliphatic diols and preferably such diols which have an aliphatic side-chain substituent which can contain from 1 to 30 suitably at
- diisocyanates examples include toluene-2,4- and 2,6-d ⁇ socyanates, d ⁇ phenylmethane-4,4'-d ⁇ socyanate, hexamethylene dnso- cyanate, d ⁇ cyclohexylmethane-4,4'-d ⁇ socyanate, cyclohexane-1 ,4-d ⁇ socyanate isophorone dnsocyanate and the like It is also possible to use blocked isocyanates in known manner
- the reaction of the monome ⁇ c dihydroxy compound with the polyisocyanate can be canned out in conventional manner, for example as disclosed in U S Pat No 3,971 ,764, which is hereby incorporated herein by reference
- isocyanates are susceptible to nucleo- philic attack and readily react with water
- the prepolymer as well as the CPUR are preferably prepared in a reaction medium free from water and undesired nucloephiles
- the reaction is earned out in a water-free inert organic solvent, e g acetone, optionally in the presence of a catalyst, e g diacetoxy-dibutyi-tin
- the molar ratio of dihydroxy compound to polyisocyanate can be vaned over a broad range and in most cases the molar ratio is within the range of from 1 1 1 to 1 3, suitably from 1 1 5 to 1 2.5 and preferably about 1 2
- the hydroxyl- and isocyanate-containing reactants used in the first stage are uncharged which thus
- the pre-polymer having terminal isocyanate groups obtained in the first stage of the method is then further reacted in a second stage with a hydroxyl-containing quaternary ammonium compound in order to introduce positive charges into the polyurethane
- the second stage can be carried out generally as taught in U S Pat No 3,971,764 except that in the present method there is used a hydroxy-functional QUAT containing a quaternary nitrogen atom having a substituent derived from an epoxy-functional quater ⁇ izi ⁇ g agent
- Suitable hydroxy-functional QUAT ' s include compounds obtained by reacting a tertiary amine, suitably a hydroxyl-containing tertiary amine, with an epoxide, e g an alkylene oxide such as ethylene oxide and propylene oxide or, suitably, a halogen-containing epoxide such as epihaiohyd ⁇ n, e g epichlorohyd ⁇ n and epibromoh
- R-, and R 3 are each independently selected from aliphatic groups containing 1-10 and preferably 1-4 carbon atoms, which may be substituted with hydroxy, suitable at least one hydroxyl group is present in R ⁇ and/or R 3 and preferably R, and/or R 3 are linear or branched N-alkanols, e.g.
- R 2 is an aliphatic group, suitably alkyl, containing 1-22 and preferably 1-4 carbon atoms, preferably methyl, ethyl, propyl or butyl, or alternatively R ⁇ and R 2 together with N form a linear or branched 5 to 7 membered nng, preferably aliphatic, which may be substituted with hydroxy and one or two carbon atoms may be substituted with NR 5 Re in which R 5 and R ⁇ are aliphatic groups, preferably alkyl, containing 1-4 carbon atoms, R 4 is de ⁇ ved from an epoxide, e.g.
- R ⁇ R 2 , R 3 and N of the QUAT are derived from a tertiary amine
- at least one hydroxyl group present in the QUAT is located on the substituent denved from the epoxide as quaternization of a tertiary amine by means of an epoxide normally leads to ⁇ ng-opening of the epoxide group and formation of a hydroxyl group
- Suitable QUAT ' s include those desc ⁇ bed in EP 541289 which is incorporated herein by reference for all purposes.
- the R 4 substituent can thus be represented by the general formula (II) derived from an epoxide of the general formula (III)-
- R 7 is hydrogen or an aliphatic group such as alkyl, preferably hydrogen; and R 8 is hydrogen or an aliphatic or aromatic group which can contain up to 20 carbon atoms, e g alkyl such as methyl, and which can be substituted with halogen; R 8 suitably being a halogen- containing aromatic or aliphatic group, preferably aliphatic, which may contain from 1 to 12 carbon atoms, preferably the halogen is chlo ⁇ ne and R 8 is CH 2 — Cl
- the R 4 substituent of the resulting QUAT of formula (I) may be a linear or branched hydrocarbon chain interrupted by one or more oxygen atoms, i e a di- or
- the reaction between the prepolymer and QUAT i e the reaction between isocyanate groups(s) of the prepolymer and hydroxyl group(s) of the QUAT, leads to chain- lengthening of the polyurethane
- the degree of chain-lengthening depends on the number of reactive hydroxyl groups present in the QUAT where a mono- hydroxy-functional QUAT will act as a chain-term mator and thus provide less chain-lengthen ⁇ ing
- the QUAT used e g.
- the QUAT of formula (I) contains one or more hydroxyl groups and in most cases not more than 4 such groups, suitably from 1 to 3 hydroxyl groups and preferably 2 or 3 Mixtures containing more than one QUAT can of course be used If desired, the QUAT can be used in combination with an additional hydroxy-functional com ⁇ pound, such as any of the hydroxytic compounds mentioned herein In many cases, the use of admixtures containing QUAT and additional hydroxyhc compound is preferred, for example where the QUAT exhibits limited solubility in the reaction medium used Preferred additional hydroxyhc compounds include the diols and hydroxy-functional tertiary amines described herein In a preferred embodiment, use is made of a composition containing QUAT and a hydroxy-functional tertiary amine, suitably the same type of amine used to prepare the QUAT The molar ratio of QUAT to additional hydroxyhc compound, when used, can be va ⁇ ed over a broad range depending on, among other
- the present invention further relates to an aqueous dispersion comprising the CPUR, to its use as a sizing agent in the making of paper and similar cellulose based products like board and paper board, wherein the aqueous CPUR dispersion is added to the papermaking stock or applied to the surface of said products preferably to surface size such products
- the amount of CPUR dispersion added to the stock or applied to the surface of cellulosic products may be from 0 001 to 20% by weight, calculated as dry CPUR on dry cellulose based mate ⁇ al and optional filler, suitably from 0 01 to 2% by weight
- the CPUR dispersions may contain from about 1 to 50% by weight of CPUR, suitably from 5 to 25% by weight
- the CPUR dispersions may of course be diluted with water prior to being used as sizing agents
- the present invention further relates to certain hydroxy-functional QUAT's More specifically, the invention relates to quaternary ammonium compounds containing one or more hydroxyl groups and a quaternary nitrogen atom having a substituent derived from a halogen-containing epoxide and having an anion derived from an acid, compositions comprising such QUAT ' s, their preparation and use, as further defined in the claims
- the QUAT according to the invention which contains a positively charged nitrogen attaching four radicals or substituents, can be represented by the general formula (I) defined above wherein R 4 is derived from a halogen-containing epoxide, preferably epichlorohydnn
- the QUAT contains one or more hydroxyl groups and in most cases not more than 4 hyd ⁇ roxyl groups, preferably from 1 to 3 and more preferably 2 or 3 hydroxyl groups, which can be located on any of the substituents connected to the nitrogen
- the anionic part of the QUAT of formula (I), i e X " is the anion of an acid, prefer- ably a protonic acid such as HX, including organic acids, e g formic acid acetic acid, propionic acid, methane sulfonic acid and p-toluene sulfonic acid, and inorganic acids, e g hydrogen hahdes and sulfu ⁇ c acid
- X is the anion of an organic acid and, in particular, formic acid
- Hydroxy-functional QUAT ' s of this invention can be prepared by reacting a tertiary amine with a halogen-containing epoxide in the presence of an acid
- the reaction can be carried out using water as a solvent although it has been found, in accordance with the present invention, that hydroxy-functional QUAT ' s can be prepared in high yield in a very advantageous manner by reacting these reactants in the substantial absence of water
- the method renders possible production of a wide range of hydroxy-functional QUAT's containing different N-substituents and counter-ions
- the reaction mixture obtained contains essentially no or very low amounts of ohgome ⁇ c material and/or undesired by-products whereby the QUAT obtained can be used in the CPUR synthesis without costly purification
- the QUAT obtained in the method also exhibit good stability
- the subject method thus offers substantial technical and economic benefits Generally, it is common to use water as a solvent in the reaction and/or in the work- up
- R 3 wherein R-i, R 2 , and R 3 are as defined above
- the tertiary amine suitably contains from 0 to 3 hydroxyl groups and preferably 1 or 2 hydroxyl groups
- tertiary amines examples include non-hydroxylic amines such as N-t ⁇ alkyl- amines, monohydroxy amines such as N,N-d ⁇ alkyl alkanolamines, and dihydroxy amines such as N-alkandiol dialkylamines and N-alkyl dialkanolamines Suitable tertiary amines include t ⁇ ethylamine, N,N-d ⁇ methyl stearylamine, N,N-d ⁇ methyl ethanolamme, 1 ,2-propane- d ⁇ ol-3-d ⁇ methylam ⁇ ne, N-methyl diethanolamine, N-ethyl diethanolamine, N-propyl diethanol- amine, N-n- and N-t-butyl diethanolamines, N-stearyl diethanolamine and N-methyl dipropa- nolamine N-alkyl dialkanolamines and N,N-d ⁇ alkyl alkanolamines, such as for example N-
- the epoxide in the present method is an organic compound capable of functioning as a quatemizing agent and contains at least one epoxide, or oxirane, group, and at least one halogen atom
- Suitable halogen-containing epoxides include compounds of the formula (III) defined above, preferably epichlorohyd ⁇ n, which when being reacted with the amine and the acid forms the substituent of formula (II) connected to the nitrogen
- Suitable acids include protonic acids, HX, which forms the anion X " of the QUAT.
- the acid is one that can be supplied as a substantially water-free acid.
- Suitable acid include organic acids such as formic acid, acetic acid, propionic acid, methane sulfonic acid and p-toluene sulfonic acid as well as inorganic acids such as hydrogen chloride, hydrogen bromide and sulfuric acid.
- organic acids such as formic acid, acetic acid, propionic acid, methane sulfonic acid and p-toluene sulfonic acid
- inorganic acids such as hydrogen chloride, hydrogen bromide and sulfuric acid.
- the acid has an important role in the reaction and that higher levels of oligomeric material are usually formed when the reaction between the tertiary nitro ⁇ gen and epoxide takes place in the absence of acid.
- the acid should suitably be present in an amount so that the reaction mixture has a pH of at least 7 and suitably a pH within the range of from 7 to 13.
- the pH of the reaction mixture can be measured in known manner, for example with a pH meter or pH electrode. It is preferred that at least part of the acid is present when bringing the amine into contact with the epoxide.
- the tertiary amine, or part thereof may be present in the form of tertiary amine acid addition salt, e.g.
- the acid is intermittently or continuously fed to the reaction mixture so as to keep the pH within the desired range.
- the pH value is between 7 and 12 and most preferably between 8 and 10.
- the molar ratio of tertiary nitrogen to epoxide usually is at least 0.4:1, suitably at least 0.6:1 , preferably at least 0.8:1.
- the upper limit for the molar ratio tertiary amine to epoxide can be high, for example 15:1 or higher, in many cases 10:1 , usually 5:1 , suitably 1.4:1 and preferably 1.2:1.
- the molar ratio of acid to epoxide can be varied over a broad range depending on, among other thing, the desired pH of the reaction mixture during the reaction.
- the reaction is carried out with the acid and epoxide in approximately equimolar amounts or with a molar excess of the acid. For instance, a molar excess of up to about 30% may be beneficial in terms of product stability.
- the reaction can be carried out neat, i.e., in the absence of a solvent, or in the presence of a solvent.
- the reaction is carried out in the absence of inert organic solvents.
- solvents include dimethylformamide, pyrrolidone, hexa- methylene phosphortriamide and the like.
- protic solvents such as alcohols, e.g. methanol, ethanol, isopropanol and the like.
- protic solvents are preferably removed from the QUAT prior to use since protic solvents readily react with isocyanates. Therefore, if used, the solvent preferably is a non-protic solvent. Appropriate amounts of solvent to be used can easily be determined by the skilled person through routine experimentation.
- the present method should be earned out in the substantial absence of water Hereby is meant that the amount of water present dunng the reaction and work-up should be low, for example below 15% by weight, suitably below 5% by weight and preferably below 3% by weight, based on the weight of reactants. In a most preferred aspect of the invention, no water at all is present.
- the reaction can be run at a temperature below 50°C, suitably below 35°C and preferably below 25"C.
- the lower limit is not crucial and the reaction can be earned out at a temperature above -80 ⁇ C, suitably above -25°C and preferably above 0"C. It may be advantageous to cool the reaction mixture dunng the reaction, especially when admixing the reactants.
- a method of producing a hydroxy-functional quaternary ammonium compound useful in the CPUR production which comp ⁇ ses reacting a tertiary amine with an epoxide in the presence of an acid and in the substantial absence of water and organic solvents.
- the tertiary amine and the acid can be as defined above and the epoxide is an organic compound capable of functioning as a quater- nizmg agent containing at least one epoxide, or oxirane, group, preferably having the general formula (III) above.
- the reaction is earned out in the substantial absence of water and organic solvents and hereby is meant that the amount of water and organic solvents, e.g. any of those defined above, should be low, for example in amounts defined above with respect to water but in this aspect meaning to the combined weight of water and organic solvent.
- the pH of the reaction mixture can be adjusted to 4-9 for the purpose of improving the stability of the QUAT, suitably to pH 5-8 and preferably to pH 6- 7.
- the solvent used in the reaction if any, can be removed from the reaction mixture by evaporation, suitably at reduced pressure.
- the product formed can be used directly, for example in the production of CPUR's, without pu ⁇ fication.
- the ammonium salt obtained may of course be subjected to any conventional purifiction step, e.g. extraction and crystallization in known manner.
- the present method shows high selectivity and thus produces hydroxy-functional QUAT ' s in high yields with low or no formation of oligome ⁇ c and polymeric material. Furthermore, where epichlorohydrin is used as a quaternrzmg agent to produce the QUAT, low levels of unreacted epichlorohydnn and undesired by-products such as 1-chloro-2,3- propane diol (CPD) and 1 ,3-dichloro-2-propa ⁇ ol (DCP) are usually obtained.
- CPD 1-chloro-2,3- propane diol
- DCP 1 ,3-dichloro-2-propa ⁇ ol
- the conversion of epichlorohydrin to CPD is less than 5% and normally less than 3%, based on the weight of epichlorohydrin used in the reaction, and the conversion of epichlorohyd ⁇ n to DCP is less than 1% and normally less than 0.1% by weight
- one of the advantages of using the QUAT ' s of this invention in CPUR production is that CPUR's and dispersions thereof can be provided with very low contents of unreacted halogen-containing epoxide, e g epichlorohydrin, and undesired by-products derived from the halogen-functional epoxide, e g CPD and DCP
- the amount of halogen-containing epoxide such as epichlorohydrin present can be less than 10 ppm, suitably less than 5 and preferably less than 1 ppm, calculated as halogen- containing epoxide and based
- the invention further relates to a composition comp ⁇ sing the present hydroxy-func ⁇ tional quaternary ammonium compound, as further defined in the claims
- the composition is substantially free from water, as defined above
- the composition can for example contain unreacted starting mate ⁇ als such as any of those used in the reaction, e g any material used in excess, and minor amounts of reaction-typical by-products
- the composition may also contain additional compounds admixed with the composition Examples of such additional compounds include acids and tertiary amines, e g any of those defined herein
- the QUAT is present in the composition in a pre ⁇ dominant amount, based on weight, i e , the weight ratio of QUAT to each of the other components present in the composition is higher than 1
- a hydroxy-functional tertiary amine and/or its acid addition salt is present in the composition in a predominant amount, based on weight, preferably the tertiary amine
- Such compositions are particularly
- (3-chloro-2-hydroxypropyl)-b ⁇ s(2- hydroxyethyO-methylammonium formiate was prepared as follows To cooled 11 9 g (0 1 moles) of N-methyl diethanolamine, 98% concentrated formic acid was added with stirring to produce a pH of between 9 and 10, as measured by means of a pH electrode To this mixture was added 7 4 g (0 08 moles) of epichlorohydrin, and the reaction mixture was cooled so as to keep the temperature at ⁇ OX, and additional formic acid was continuously added to keep the pH between 9 and 10 After stirring for 10 hours pH was adjusted to 6 5 by addition of formic acid The desired product was formed in high yield, as shown by 13 C-NMR and GPC, and the formation of by-products was low Essentially no ohgome ⁇ c and polyme ⁇ c material was formed The product so obtained was stable for more than three months at room temterature
- Example 2 The procedure of Example 1 was followed except that the amine used was N,N- dimethylethanolamme and that the amine and epichlorohyd ⁇ n were used in equimolar amounts
- Example 1 The procedure of Example 1 was followed except that no acid was used in the method An exothermic reaction between N-methyl diethanolamine and epichlorohydrin took place which was very difficult to control and phase separation was observed, indicating formation of oligome ⁇ c/polyme ⁇ c mate ⁇ al After two days the reaction mixture had been completely converted to a solid mass and no mo ⁇ ome ⁇ c compounds could be detected
- a cationic polyurethane according to the invention was prepared as follows To a solution of 18 3 g of glycerol monostearate and 18 3 g of toluene dnsocyanate in 50 g of water-free acetone at a temperature of 40 ⁇ C was added 17 mg of dibutyl tin- diacetate in acetone The solution was refluxed for 1 hour under vigorous stir ⁇ ng A sample of the solution was taken away for determination of residual NCO-groups and showed a residue of 14% A mixture of 5 1 g of N-methyl diethanolamine (N-MDEA) and 2 2 g of QUAT according to Example 1 , where the mixture had a molar ratio N-MDEA to QUAT of 5 1 , was added to the solution at 50 ⁇ C followed by addition of further 50 ml of acetone The mixture was refluxed for 1 hour and then 40 ml of 1 M HCI was added for neutralization and formation of tertiary amine acid addition salt and then the
- Example 5 A cationic polyurethane according to the invention was prepared as in Example 4 except that the molar ratio of N-MDEA to QUAT was 4 1
- a cationic polyurethane according to the invention was prepared as in Example 4 except that the molar ratio of N-MDEA to QUAT was 3:1 which thus corresponded to about 25% quaternization of the nitrogen atoms.
- a CPUR was prepared by reacting HCI with a polyurethane containing tertiary amine groups.
- Example 7 The procedure of Example 7 was followed up to the reaction with N-methyl diethanolamine. The polyurethane so formed was reacted with dimethyl sulfate to effect quaternization of about 25% of the nitrogen atoms and then 1 M HCI was added for neutralization The work-up was carried out as in Example 4 which resulted in a dispersion containing about 15% of CPUR at pH 4.
- Example 9 Stability of the cationic polyurethane dispersions of Examples 4-8 was evaluated by adding a saturated aqueous solution of sodium sulfate to 100 ml of aqueous dispersion containing 0.5% by weight of cationic polyurethane The mixtures were stirred at 20 ⁇ C and then inspected visually. Table I shows the results. Table 1
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU29872/97A AU2987297A (en) | 1996-05-28 | 1997-05-27 | Quaternary ammonium compounds |
CA002255844A CA2255844A1 (en) | 1996-05-28 | 1997-05-27 | Quaternary ammonium compounds |
EP97924459A EP0904261A1 (en) | 1996-05-28 | 1997-05-27 | Quaternary ammonium compounds |
JP9542192A JPH11511792A (en) | 1996-05-28 | 1997-05-27 | Quaternary ammonium compounds |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE9602041-7 | 1996-05-28 | ||
SE9602041A SE9602041D0 (en) | 1996-05-28 | 1996-05-28 | Quaternary ammonium compounds |
US1920096P | 1996-06-06 | 1996-06-06 | |
US60/019,200 | 1996-06-06 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997045395A1 true WO1997045395A1 (en) | 1997-12-04 |
Family
ID=26662639
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/SE1997/000873 WO1997045395A1 (en) | 1996-05-28 | 1997-05-27 | Quaternary ammonium compounds |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0904261A1 (en) |
JP (1) | JPH11511792A (en) |
AU (1) | AU2987297A (en) |
CA (1) | CA2255844A1 (en) |
WO (1) | WO1997045395A1 (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6524978B1 (en) | 1998-12-18 | 2003-02-25 | The Dow Chemical Company | Aqueous polyurethane dispersions useful for preparing polymers with improved moisture resistance properties |
WO2012084846A2 (en) | 2010-12-22 | 2012-06-28 | Bayer Materialscience Ag | Process for the production of sized and/or wet-strength papers, paperboards and cardboards |
US10640918B2 (en) | 2017-08-15 | 2020-05-05 | Hbi Branded Apparel Enterprises, Llc | Functionalized fibrous material |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BRPI0806170B1 (en) * | 2007-10-22 | 2019-02-26 | Bridgestone Corporation | FUNCTIONALIZED POLYMER, METHOD FOR PREPARING A FUNCTIONALIZED POLYMER, AND COMPOSITION UNDERSTANDING A FUNCTIONALIZED POLYMER |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1491091A (en) * | 1974-01-05 | 1977-11-09 | Akzo Nv | Cationic polyurethanes |
EP0541289A1 (en) * | 1991-11-01 | 1993-05-12 | Witco Corporation | Methods for the preparation of cationic polyurethane compositions and quaternary ammonium salts |
-
1997
- 1997-05-27 EP EP97924459A patent/EP0904261A1/en not_active Ceased
- 1997-05-27 AU AU29872/97A patent/AU2987297A/en not_active Abandoned
- 1997-05-27 CA CA002255844A patent/CA2255844A1/en not_active Abandoned
- 1997-05-27 JP JP9542192A patent/JPH11511792A/en active Pending
- 1997-05-27 WO PCT/SE1997/000873 patent/WO1997045395A1/en not_active Application Discontinuation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1491091A (en) * | 1974-01-05 | 1977-11-09 | Akzo Nv | Cationic polyurethanes |
EP0541289A1 (en) * | 1991-11-01 | 1993-05-12 | Witco Corporation | Methods for the preparation of cationic polyurethane compositions and quaternary ammonium salts |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6524978B1 (en) | 1998-12-18 | 2003-02-25 | The Dow Chemical Company | Aqueous polyurethane dispersions useful for preparing polymers with improved moisture resistance properties |
US6864312B2 (en) | 1998-12-18 | 2005-03-08 | Dow Global Technologies, Inc. | Aqueous polyurethane dispersions useful for preparing polymers with improved moisture resistance properties |
WO2012084846A2 (en) | 2010-12-22 | 2012-06-28 | Bayer Materialscience Ag | Process for the production of sized and/or wet-strength papers, paperboards and cardboards |
US8647471B2 (en) | 2010-12-22 | 2014-02-11 | Bayer Materialscience Llc | Process for the production of sized and/or wet-strength papers, paperboards and cardboards |
US10640918B2 (en) | 2017-08-15 | 2020-05-05 | Hbi Branded Apparel Enterprises, Llc | Functionalized fibrous material |
Also Published As
Publication number | Publication date |
---|---|
JPH11511792A (en) | 1999-10-12 |
AU2987297A (en) | 1998-01-05 |
EP0904261A1 (en) | 1999-03-31 |
CA2255844A1 (en) | 1997-12-04 |
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