CA2255844A1 - Quaternary ammonium compounds - Google Patents
Quaternary ammonium compounds Download PDFInfo
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- CA2255844A1 CA2255844A1 CA002255844A CA2255844A CA2255844A1 CA 2255844 A1 CA2255844 A1 CA 2255844A1 CA 002255844 A CA002255844 A CA 002255844A CA 2255844 A CA2255844 A CA 2255844A CA 2255844 A1 CA2255844 A1 CA 2255844A1
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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
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- 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
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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
- C08G18/08—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
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to cationic polyurethanes and aqueous dispersions of cationic polyurethanes, their preparation and use as sizing agents in the making of paper. The invention further relates to hydroxy-functional quaternary ammonium compounds and compositions thereof, their preparation and use in the production of cationic polyurethanes.
Description
CA 022~844 1998-11-19 ry ~mmonium comDo~ ~nds The present invention generlly relates to quaternary ammonium compounds. More spe~irically the invention relates to cationic polyu,ell,aoes and aqueous dispersions of cationic polyu,t:tllanes their p(~pardlion and use in papermaking. The invention further 5 relates to hydroxy-fun- lional quatemary ammonium compounds and compositions thereof their prepardlion and use in the production of cationic polyuretl ,anes.
It is known in the pape",~a~ing art to use cationic polyurethanes (CPUR) as sizing agents in order to delay or prevent the absGrl,lion and spreading of aqueous solutions in sized paper products. Usually CPUR s in the form of aqueous d;speraions are used in 10 surface sizing in which the sizing agent is applied to the paper surface at the size press.
U.S. Pat. No. 3 971 764 ~isclQses high " c' cu'~r weight CPUR sizing agents prepalêd by reacting a diol with a polyisocyanate to form a prepolymer with terminal isocyanate groups which is s~hsequently reacted with (a) a diol containing a tertiary nitrogen atom which is s~hsequently converted into the con~sponding an,i"on ~rn compound or (b) a 15 diol containing a nil,ugen atom previously converted into the cor,t:sponding ammonium com-pound; method (a) being preferred. In these m~ll,ods the nitrogen atom can be ,endered 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 disperaions generdlly provide good sizing response using low levels of sizing agent. It has however 20 been observed that the CPUR di~per~ions exhibit stability problems and settling tendencies in particular in the pr~sence of electrolytes which are con"~only added into the size press in order to prevent static electricity being built up during s~bsequent ~pp!ica~ion drying or con-verting processes. The insufficient stability may cause the CPUR pa,li-le-~ contained in the dispersions to agglol"erala and form depos~ts leading to handling and ~pplic. lion problems 25 deteriordled size pel fu""allce and poorly sized paper.
According to the present invention it has been found that CPUR s having improvedsizing and stability prupe,lies can be obtained by using in the polyu,t:ll,ane synthesis a hydroxy-fu"ulional qu~ler"ary a""nol,: Im compound (QUAT) i.e. an organic compound con-taining one or more hydroxyl groups and a positively cha,yed quaternary nitrogen atom in 30 which the nitrogen has been quaternized with an epoxide. More specifically 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 quater"ary nitrogen that has a s~ Ihstituent derived from an epoxide. ~he 35 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.
.. . _ _ . .. .. . ... . . .... .
CA 022~844 1998-11-19 The method according to the present invention leads to high mclec~ r weight CPUR s with oulsland;ng prope~lies. Aqueous di;,per~ions of the present CPUR s exhibit improved stability and hereby the pr.,t~'ems ~csociated with prior art sizing dispersions based on CPUR can be reduced or over~ ome. The present CPUR dispt:,~ions 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 econo" .~ benefits.
Dihydroxy compounds, or diols, that can be used as ,I,onG",er~ in order to form the prepolymer, or inlei",edidle product, according to the present invention include aliphatic and aro",alic diols. The term "aliphatic", as used herein, refers to an essenlially hydrocarbon 10 structure apart from deslyl laled hnclional groups, which hydrocarbon structure may be inter-rupted by one or more het~rudlor,~s, e.g. oxygen and nit,ogen, andlor one or more groups containing ht7teroatoms, e.g. carbonyl and acyloxy groups. The term "a,u,nati~:", as used herein, refers to an a~u",alic, essentially hy~ .ca~tJon structure apart from desiy"aled func-tional groups, which hyd,oca,bon structure may be interrupted by one or more he~eru~lor,,s, 15 e.g. oxygen and nitrogen, and/or one or more groups containing ht:terodlunls1 e.g. carbonyl and acyloxy groups. It is generally p~,:fe"ed to use aliphatic diols and pr~erably such diols which have an aliphatic side-chain sl~hstitl~ent which can contain from 1 to 30, suitably at least 5, p,ererdbly at least 10 and most prererdbly from 10 to 22 carbon atoms. The diols may be high n.n's..~ weight polymeric compounds such as polyester, polyether and polybuta-20 diene diols, although it is generally more p,ef~rle:d to use non-polymeric aliphatic dihydroxy compounds which suitably contain from 2 to 20 and preferably from 2 to 10 carbon atoms in the chain connecting the two hydroxyl groups, i.e. in the main chain. Preferred aliphatic main chains include alkylenes and dialkyleneamines containing from 2 to 10 carbon atoms.
Suitably the main chain is substitut~d with an aliphatic side-chain as desc,il,ed above; where 25 the main chain contains a het~,ualol,, which is nitrogen, it is pl~relled that the nit,~gen carries the side-chain. Ex~r,.~'es of suitable aliphatic dihydroxy compounds include ethylene and diethylene glycols, propane and butane diols, and higher mn'~cll~a~ weight compounds such as fatty acid monoesters of triols such as glycerol and trimethylolpropane, e.g. glycerol ll~onoalea(~le and glycerol monobehenate, trimethylolpropane mono~led,dte; oligomeric 30 esterdiols such as diester diols, e.g. those obtained by reacting a dicarboxylic acid, e.g.
adipic acid, with a molar excess of a diol, e.g. ethylene glycots; N-alkyl-diethanolamines, e.g.
N-stearyl-diethanolamine; branched chain dihydroxy alkylenes, e.g. 1,2- and 1,4-dihydroxy-oct~decarles. The higher ",c'e~,la~ weight compounds are generally preferred, especially ~Iycerol monostearate. Examples of aromatic diols that can be used include bisphenol A.
35 Mixtures compri~i"g one or more diots, such as any of those mentioned above, can also be used in the reaction with polyisocyanates.
_ _ CA 022~844 1998-11-19 rolyisocyanates that can be used as ",onG",era to form the prepolymer in this method include aliphatic a~umdlic and mixed aliph~liclarc,",~lic compounds. Among the polyisocyanates it is prefe"~d to use diisocyanates. Where polyisocyanates containing more than two isocyanate groups are used e.g. triisocyanates it is prt:fer,t:d to admix them with diisocyanates. Generally polyisocyanates are known in the art for example as disc~osed in Encyclopedia of PolymerScience and Engineering Vol. 13 Second Ed. 1988 pp. 243-303 which is hereby illcol~Jordled herein by ~ference. Examr'es of suitable diisocyanates include toluene-2 4- and 2 6-diisocyanates diphenyl~"etl,ane~ 4-diisocyanate hexd~nell"~lene diiso-cyanate dicyclohexylmethane44-diisocyanatel cyclohexane-1 4-diisocyanate isophGrune diisocyanate and the like. It is also possible to use blocked isocyanates in known manner.
The reaction of the ",onomeric dihydroxy compound with the polyisocyanate can becarried out in conventional manner for exd""~ e as disclosed in U.S. Pat. No. 3 971 764 which is hereby incorporated herein by r~:fer~nce. As isocyanates are succeptihle to nucleo-philic attack and readily react with water the prepolymer as well as the CPUR are preferdbly pr~part:d in a reaction medium free from water and undesired nu-loeph'e~. Suitably the ,~aclion is carried out in a water-free inert organic solvent e.g. acetone optionally in the presence of a catalyst e.g. diacetoxy-dibutyl-tin. The molar ratio of dihydroxy compound to polyisocyanate can be varied 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 preferdbly about 1:2.
Preferably the hydroxyl- and isocyanate-containing reactants used in the first stage are u"charyed which thus leads to an u"charyed prepolymer.
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 quah",ary a,n",onium compound in order to introduce positive charges into the polyu,t:ti,ane. The second stage can be carried out genercJly as taught in U.S. Pat. No. 3 971 764 except that in the present method there is used a hydroxy-f~ lional QUAT containing a quater"ary nitrogen atom having a substituent derived from an epoxy-f "~tional qualer"i~i"g agent.
~ut~t'e hydroxy-functional QUAT s include compounds obtained by ~t:acti"g a tertiary amine suitably a hydroxyl-containing tertiary amine; with an epoxide e.g. an alkylene oxide such as ethytene oxide and propylene oxide or suitably a halogen-containing epoxide such as epihalohydrin e.g. epichlorohydrin and epibromohydrin pref~r~bly epichlorohydrin; and optionally with an acid. In a preferred embodiment of this invention the hydroxy-functional ~ QUAT is a compound containing one or more hydroxyl groups and a quatemary nitrogen atom having a sllhstihlent denved from a halogen-containing epoxide and having an anion derived from an acid.
..... . .. .. .
CA 022~844 1998-11-19 Suitable QUAT s for use according to the invention can thus be represented by the general formula (I):
R, X (I) wherein R1 and R3 are each i"dependel,lly selecled from aliphatic groups containing 1-10 and pr~rt:r~bly 14 carbon atoms, which may be sl~bstituted with hydroxy, suitable at least one hydroxyl group is present in R1 and/or R~ and pr~:rerably R1 and/or R3 are linear or blanched N a"~anGls, e.g. N-ethanol; R2 is an aliphatic group, suitably alkyl, containing 1-22 and p,~rdbly 14 carbon atoms, p~f~rably methyl, ethyl, propyl or butyl; or alternatively R1 and R2 togetl ,er with N form a linear or branched 5 to 7 membered ring, preferably aliphatic, which may be sl~hstituted with hydroxy and one ortwo carbon atoms may be suhstit~lted with NR5R6 in which R5 and R6 are aliphatic groups, pr~ferably alkyl, containing 14 carbon atoms;
R4 is derived from an epoxide, e.g. an alkylene oxide such as ethylene oxide and propylene oxide, or, suitably, a halogen-containing epoxide, preferably lep.,hl rohydrin; and X is an anion of an acid. In most cases, R" R2, R3 and N of the QUAT are derived from a tertiary amine. Generally, at least one hydroxyl group present in the QUAT is located on the 5llhstjtllent derived from the epoxide as qudle",i~ion of a tertiary amine by means of an epoxide normally leads to ring-opening of the epoxide group and formation of a hydroxyl group. Suitable QUAT's include those desc,ibed in EP 541289 which is i"cor,.,ora~ed herein by reference for all purposes.
The R4 substih~ent can thus be reprt:senled by the general formula (Il) derived from an epoxide of the general formula (Ill):
- R7HC - CH - RB (Il) R7HC - CH - R8 (Ill) \ /
OH O
wherein R7 is hydrogen or an aliphatic group such as alkyl, preferably hydrogen; and RB is hydrogen or an aliphatic or arur"alic group which can contain up to 20 carbon atoms, e.g.
alkyl such as methyl, and which can be suhstih~ted with halogen; R9 suitably being a halogen-containing aromatic or aliphatic group, preferably aliphatic, which may contain from 1 to 12carbon atoms, p~c:ferably the h-'~gen is chlorine and RB is CH2--Cl. In addition, in QUAT s obtained by reacting a tertiary amine with an epoxide of formula (Ill) where R7 = H and RB = H
or alkyl such as methyl, i.e. an alkylene oxide, the R4 substituent of the resulting QUAT of formula (I) may be a linear or branched hydrocarbon chain interrupted by one or more 40 oxygen atoms, i.e. a di- or polyalkyleneoxy group, and containing a hydroxyl group, usually in CA 022~844 1998-11-19 Wo 97/45395 PCT/SE97/00873 a terrninal position, since the quatel"i~dlion reaction may lead to di- or polyaddition of alkylene oxides.
The reaction between the prepolymer and QUAT, i.e. the reaction bel.~een isocyanate groups(s) of the prepolymer and hydroxyl group(s) of the QUAT, leads to chain-5 lengthening of the polyurethane. As will be appreidled, the degree of chain-lenylhening depends on the number of reactive hydroxyl groups present in the QUAT where a mono-hydroxy-functional QUAT will act as a chain-terminator and thus provide less chain-lenythen 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 preferdbly 2 or 3. Mixtures containing more than one QUAT can of course be used. If desired, the QUAT can be used in co,nb ~ation with an additional hydroxy-fu", lional com-pound, such as any of the hydroxylic compounds n,enlioned herein. In many cases, the use of admixtures containing QUAT and additional hydroxylic compound is prtfer,ed, for example where the QUAT exhibits limited solubility in the rea.;tion medium used. Preferred addilional hydroxylic compounds include the diols and hydroxy-h"clional tertiary amines des~,ibed herein. In a prerer,~d embodiment, use is made of a cGr"position 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 adcli~ional hydroxylic compound, when used, can be varied over a broad range depending on, among other things, the isocyanate content in the prepolymer, the desired QUAT content and cationicily of the CPUR and the intended use of the CPUR. Usually, this molar ratio can be from 50:1 to 1:100. The molar ratio of hydroxyl groups to isocyanate groups in the second stage can be varied over a broad range and in most cases the moiar ratio is within the range of from 1:0.5 to 1:2, suitably from 1:0.8 to 1:1.4 and p,ererdbly about 1:1.
The CPUR obtained may have an average "~c'ec~ r weight of at least 1,000, suitably at least 3,500 and preferably at least 4,000. The upper limit of ",clec~ weight is not critical; usually it is about 30,000 and p,t7rer~bly about 15,000. After Co,),F' t~d reaction the reaction mixture containing CPUR can be worked-up and converted into an ~q~leou~
di_pe,sion in conventional manner, for exan~ple as ~isclosed in U.S. Pat. Nos. 3,971,764 and 4,617,341. Examples of useful steps include addition of acid, addition of water, evapor~lion of solvent and the like. In a preferred aspect of the process, an acid is added to acco",; ' h neutralization by converting any tertiary nitrogen atoms present in the CPUR into the co"espondi,lg tertiary nitrogen acid addition salt.
The present invention further re\ates to an aqueous dispersion co"~prisi"g the CPUR, to its use as a sizing agent in the making of paper and similar cell~l'cse based products like board and paper board, wherein the aqueous CPUR dispersion is added to the CA 022~844 1998-11-19 WO 97/4539~ PCT/SE97/00873 papermaking stock or applied to the surface of said products, preferdbly 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, ca'~ ~tcd as dry CPUR on dry cellulose based material 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 specirically, the invention relates to qudler"ary a,nlnooium compounds containing one or more hydroxyl groups and a quale~,ary nitrogen atom having a suhstit~ent derived from a halogen-containing epoxide and having an anion derived from an acid, csr"positions colllpris;"g such QUAT s, their prcpa,dlion and use, as further defined in the claims.
The QUAT according to the invention, which cGntai"s a positively charged nit,ugen attaching four radicals or s~tbstituents, can be l~pr~ser,led by the general formula (I) defined above wherein R4 is derived from a halogen-containing epoxide, pl~rt:l~bly epichlorohydrin.
The QUAT cor,tai"s one or more hydroxyl groups and in most cases not more than 4 hyd-roxyl groups, preferably from 1 to 3 and more p~t7rt:rdbly 2 or 3 hydroxyl groups, which can be located on any of the sl Ibstituents 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. forrnic acid, acetic acid, prop.onic acid",~tl,ane sulfonic acid and p-toluene sulfonic acid, and inorganic acids, e.g.
hydrogen halides and sulfuric acid. In a preferred embodiment, 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 prc:sence 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-fu~,ctional QUAT s can be prepar~d 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-f~",ctional QUAT's containing different N-s~hstituents and counter-ions. Furthermore, after co",, ' ted reaction, the reaction mixture obtained contains essenlially no or very low amounts of oligomeric material and/or undesired by-products whereby the QUAT obtained can be used in the CPUR synthesis without costly pu,iricalion. The QUAT obtained in the method also exhibit good stability. The subject method thus offers subslantial te~;hnical and economic benefits.
Generally, it is common to use water as a solvent in the reaction and/or in the work-up when pr~pari"g qualelllary ammonium compounds. Water, being a polar solvent, CA 022~844 1998-11-19 norrnaliy favours the fo~nalion of charged reaction products like QUAT s and facilitates separalion of the QUAT from the reaction mixture by means of exl,d~tiol1 using water in conjunction with a water-immiscible solvent. However, monomers to be used in CPUR
production should suitably be free from water since isocyanates are susceptihle to 5 nucleophilic attack. It has been exlJerienced that extensively removing water from hydroxy-functional quatemary ammonium salts is cGr", linatec', costly and may lead to decomposition of the QUAT. Therefore, by providing a reaction which is carried out in the substanlial absence of water, there is produced a QUAT e-specia~y useful for subsequent conversion with isocyanates into cationic polyur~thanes.
The tertiary amine used in the present method is an organic compound containing at least one quaternizable tertiary nit~gen atom. Suitably the tertiary amine in an aliphatic amine. The tertiary amine suitably contain from 3 up to 25 carbon atoms, preferably from 4 to 10. Suitable tertiary amines can be represented the general formula (IV):
l 1 (IV) wherein R~, R2, and R3 are as defined above. The tertiary amine suitably contains from 0 to 3 hydroxyl groups and preferdbly 1 or 2 hydroxyl groups.
Examples of useful tertiary amines include non-hydroxylic amines such as N-trialkyl-amines, monohydroxy amines such as N,N-dialkyl alkanola"""es, and dihydroxy amines 25 such as N ~":an 'icl dialkylamines and N-alkyl dialkanolamines. Suitable tertiary amines include triethylamine, N,N-dimethyl stearylamine, N,N-dimethyl ethanolamine, 1,2-propane-diol-3-dimethylamine, N-methyl ciietl,anola"line, N-ethyl diethanolamine, N-propyl diethanol-amine, N-n- and N-t-butyl diethanola"~..,es, N-stearyl diell,anola"line and N-methyl dipropa-nolamine. N-alkyl dialkanola~ es and N,N-dialkyl alkanolamines, such as for example N-30 alkyl u'i~:',anola~lines and N,N-dialkyl elhanolan,ines, in which the alkyl groups contain 1 to 4 carbon atoms are preferred, in particular N-methyl diethanolar";"e and N,N-dimethyl ethanol-amine.
The epoxide in the present method is an organic compound capable of functioning as a qu~er"i~i"g agent and con~a."s at least one epoxide, or oxirane, group, and at least 35 one halogen atom. Monoepoxy- and monohalogen-f~"ctional compounds are preferred.
Suit~'e halogen-containing epoxides include compounds of the formula (Ill) defined above, preferably erich'~rohydrin, which when being reacted with the amine and the acid forms the sllhstituent of formula (Il) connected to the nitrogen.
... ..
CA 022~844 1998-11-19 Suitable acids include protonic acids, HX, which forms the anion X of the QUAT.
P~fe,ably the acid is one that can be supplied as a substantially water-free acid. Examples of 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 brur,,;de and sulfuric acid. In a preferred embodiment of the invention, use is made of organic acids and, in particular, formic acid.
It has been found that the acid has an illlpolldnt role in the reaction and that higher levels of In' ~o.,leric ",aterial are usually formed when the reaction between the tertiary nitro-gen and epoxide takes place in the ab5ence of acid. When carrying out the reaction, 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.
Hereby the tertiary amine, or part thereof, may be present in the form of tertiary amine acid addition salt, e.g. R,R2R3N H X, wherein R~, R2, R3, and X are as defined above. In a prefer-red er"bodi."ent of the invention, the acid is i"te""illently or continuously fed to the reaction mixture so as to keep the pH within the desired range. Preferably, the pH value is between 7 and 12 and most prt:ferdbly between 8 and 10.
In the method, the molar ratio of tertiary r. ~.ogen 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 examr'e 15:1 or higher, in many cases 10:1, usually 5:1, suitably 1.4:1 and prefe~ably 1.2:1. In the method, the molar ratio of acid to epoxide can be varied over a broad range dependi"g on, among other thing, the desired pH of the reaction mixture during the reaction. Suitably the reaction is carried out with the acid and epoxide in approxi",al~,ly e~uimolar amounts or with a molar excess of the acid. For instance, a molar excess of up to about 30% may be bener,cial 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. In a preferred aspect of the invention the reaction is carried out in the absence of inert organic solvents. Where solvents are used, it is preferred to use inert organic polar solvents. Suitable solvents include dimethyl~u",~a",ide, py~l.l;d~ne, hexa-methylene phospho,l~iam ~e and the like. It is further possible to use protic solvents such as alcohols, e.g. methanol, ethanol, isopropanol and the like. However, in cases where the QUAT is to be used in the production of CPUR s, protic solvents are prt:ferdbly removed from the QUAT prior to use since protic solvents readily react with isocyanates. Ther~fore, 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.
CA 0225~844 1998-11-19 The present method should be carried out in the subslantial absence of water.
Hereby is meant that the amount of water present during 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 pr~rt "ed aspect of the invention, no 5 water at all is present. The reaction can be run at a te",pe,dlure below 50~C, suitably below 35~C and preferably below 25~C. The lower limit is not crucial and the reaction can be carried out at a temperature above -80~C, suitably above -25~C and pr~rcbly above 0~C. It may be advant~geous to cool the reaction mixture during the reaction, especially when adl"b~i"g the reactants.
In another aspect of this invention there is provided a method of producing a hydroxy-fLI"~tional quater"ary a"""on.;~m compound useful in the CPUR production which co",yrises r~a~illg a tertiary amine with an epoxide in the presence of an acid and in the suL.-~ldr,lial 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 fu.,-,lior,i.,g as a quater-nizing agent containing at least one epoxide, or oxirane, group, pref~,dbly having the general forrnula (Ill) above. The reaction is carried out in the suL~la"lial 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 cor"t~. ,ed weight of water and organic solvent.
After c,o,rFl~t~d reaction, the pH of the reaction mixture can be ad3usted to 4-9 for the purpose of improving the stability of the QUAT, suitably to pH 5-8 and preferably to pH 6-7. This may be acco".F' shed by means of any acid that is essentially water-free, e.g. any of those mentioned above. The solvent used in the reaction, if any, can be removed from the reaction mixture by evaporation, suitably at reduced pressure. The product forrned can be used directly, for example in the production of CPUR's, without purification. If desired, 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-f~."ulional QUATs in high yields with low or no formation of ~1.3~n,eric and polymeric material.
Fu,ll,er",o,e, where epichlorohydrin is used as a quater"i~i"g agent to produce the QUAT, low levels of unreacted epichlorohydrin and u,ldesi,ed by-products such as 1-chloro-2,3-propane diol (CPD) and 1,3-dichloro-2-prupanol (DCP) are usually obtained. Generally, the conversion of ep..,'-'cruhydrin to CPD is less than 5% and normally less than 3%, based on the weight of ep.~h'~rohydrin used in the reaction, and the conversion of ~ep ehloruhydrin to 35 DCP is less than 1% and normally less than 0.1% by weight. Accor.li,lyly, one of the advantages of using the QUAT s of this invention in CPUR production is that CPUR s and .... .. .... .. . .
CA 022~844 1998-11-19 di~per~ions thereof can be provided with very low co,l~ent~ of unreacted halogen-containing epoxide, e.g. epich'orùhydrin, and undesired by-products derived from the halogen-functional epoxide, e.g. CPD and DCP. In the CPUR's and CPUR .li~per~ions according to the invention, the amount of halogen-containing epoxide such as epichlorohydrin present can be 5 less than 10 ppm, suitably less than 5 and preferably less than 1 ppm, c~c~ ted as haiogen-cor,lai.,i"g epoxide and based on CPUR solids, and the amount of halogenaled by-products can be less than 1% by weight and suitably less than 0.5 % by weight, calculated as total amount of halogehdtud by-products and based on CPUR solids. Notably, when using epichlorohydrin, the CPD content can be less than 0.1% by weight, suitably less than 0.05%
10 by weight and prer~,ably less than 10 ppm~ based on CPUR solids, and the DCP content can be less than 0.5% by weight, suitably less than 0.1% by weight and pr~ferably less than 10 ppm, based on CPUR solids.
The invention further relates to a c~",uosition cor"pri~i"g the present hydroxy-func-tional quatemary ammonium compound, as further defined in the claims. The cG",position is 15 subs~a"lially free from water, as defined above. In addition to the QUAT, the co",position can for example contain unreacted starting "~aleric.ls such as any of those used in the ,e:action, e.g. any ",dteridl used in excess, and minor amounts of reaction-typical by-products. The co" ,position may also contain additional compounds admixed with the cGmposition.
Examples of such additional compounds include acids and tertiary amines, e.g. any of those 20 defined herein. In a prt:rer,ed embodiment, the QUAT is present in the cor"position in a pre-dominant amount, based on weight, i.e., the weight ratio of QUAT to each of the other co",ponenLs present in the COI"pOSitiOI~ is higher than 1. In another pref~"ed embodiment, a hydroxy-functional tertiary amine and/or its acid addition salt is present in the composilion in a predo"~inanl amount, based on weight, preferably the tertiary amine. Such co",posilions 25 are particularly useful in the pr~para~ion of CPUR. The tertiary amines and acids for fol",alion of the acid addition salt may be any of those defined herein and suitably the same type of compounds used as ~e:a~;tants in the method of the invention.
The invention is further illustrated in the follo~.i"g E~cd~r'~s which, ho.~_ver, are not i"lended to limit same. Parts and percentages relate to parts by weight and percent by 30 weight, ,especli~/ely, unless otherwise stated.
F~mple 1 In acco,dance with the present invention, (3-chloro-2-hydroxypropyl)-bis(2-hydroxyethyl)-methylammonium fu""idle was prepared as follows:
3~ To cooled 11.9 9 (0.1 moles) of N-methyl diethanGlal"i"e, 98% concenl,a~ed formic acid was added with stirring to produce a pH of betNeen 9 and 10, as measured by means of CA 022~844 1998-11-19 WO 97/4539~ PCT/SE97/00873 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 20~C 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 5 as shown by 13C-NMR and GPC and the fo"~,dlion of by-products was low. Essentially no oligomeric and polymenc ~"dlerial was formed. The product so obtained was stabie for more than three months at room te",terd~ure FY~mple 2 The procedure of Example 1 was followed except that the amine used was N N-dimethylethanolamine and that the amine and e~c ~h ~ruhydrin were used in equimolar amounts. The desired product (3-chloro-2-hydroxypropyl)-(2-hydroxyethyl)-dimethyl-a,nr"or Im for",id~e was obtained in high yield. Only minor amounts of impurities were forrned and there were essentially no for",alion of ol.goi"eric and polymeric material.
FY~rnDle 3 (Comparison) The procedure of Example 1 was followed except that no acid was used in the method. An exoll,er~"ic reaction between N-methyl diethanolamine and ep.~hl~r~,hydrin took place which was very difficult to control and phase sepa,dlion was observed i"dicdti"g formation of oligomeric/polymeric material. After two days the reaction mixture had been cGrrl,~ ~t~y converted to a solid mass and no monomeric compounds could be detected.
F~rnple 4 A cationic polyurethane accordi, ,9 to the invention was prepared as follows:
To a solution of 18.3 g of glycerol monosteardle and 18.3 9 of toluene diisocyanate in 50 g of water-free acetone at a l~",~erdlure of 40~C was added 17 mg of dibutyl tin-di-cet~te in acetone. The solution was refluxed for 1 hour under vigorous stirring. A sample of the solution was taken away for dete""i ,~tion of residual NCO-groups and showed a residue of 14%. A mixture of 5.1 9 of N-methyl diethanolar":ne (N-MDEA) and 2.2 9 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 mixture was diluted with 250 ml of water.
Acetone was evaporated under reduced pressure at 60-70~C to afford a clear residue in the form of a clisper~ion containing approximately 15-17% of CPUR at pH 4. The contents of epichlorohydrin CPD and DCP were all below the detection limit of the gas chromatographic CA 022~844 1998-11-19 Wo 97/45395 12 PCT/S~:97/00873 method used; the ep~ch orohydrin content was below 1 ppm the CPD and DCP contents were both below 10 ppm.
FY~mple 5 A cationic poly~ ane according to the invention was prepared as in Example 4 except that the molar ratio of N-MDEA to QUAT was 4:1.
FY~rnple 6 A cationic polyu~ll,ane accordi.,g to the invention was prepared as in Example 4except that the molar ratio of N-MDEA to QUAT was 3:1 which thus corresponded to about 25% qudL~,.,i~ation of the nit,ogen atoms.
FY~mr~le 7 (Con"~arison) In this test a CPUR was prepared by reacting HCI with a polyurethane containing tertiary amine groups.
Glycerol monostearate was reacted with toluene diisocyanate as in Example 2 and then the pre-polymer with temminal NCO-groups was reacted with solely N-methyl diethanol-amine. The u"charyed polyurethane was rendered cationic by addition of 1 M HCI which converted tertiary nitrogen atoms into the corresponding acid addition salt. Work-up was made as in Example 4 which yielded a dispersion containing about 15-16% of CPUR at pH 4.
Example 8 (Cor"pa,ison) 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 quaLen~i~ation of about 25% of the nitrogen atoms and then 1 M HCI was added forneut,dli~ation. The work-up was carried out as in Example 4 which resulted in a dispe,aion containing about 15% of CPUR at pH 4.
FY~mple 9 Stability of the cationic polyurethane di~peraions of Exdlrr s 4-8 was evaluated by adding a saturated aqueous solution of sodium sulfate to 100 ml of aclueous di~peraion containing 0.5% by weight of cationic polyurethane. The mixtures were stirred at 20~C and then inspected visually. Table I shows the results.
CA 022~844 1998-11-19 Table I
Na2SO4(aq.) Appearance of Cationic Polyurethane D;sper~ion aWed (ml) FY 4 Fx. 5 F~t. 6 F~. 7 Fx. 8 o Clear Clear Clear Clear Clear 1.0 Clear Clear Clear Precip Clear 2.0 Clear Clear Clear Precip S-Turb 3 0 Clear Clear Clear Precip S-Turb 4 0 - - S-Turb - V-Turb 5.0 - - S-Turb - Precip 10 wherein S-Turb = slightly turbid V-Turb = very turbid Precip = precipitation - = not analyzed As is evident from Table 1, the dispersions of cationic polyurethane of Ex~ !e s 4-6 15 according to the invention were consi~erdbly more stable than the polyurethane dispersion used for comparison purposes.
FY~rnple 10 Sizing efficiency of the CPUR dispersions accor.li"g to Examples 4-7 was evaluated 20 by means of the Cobb Test, using German DIN s~anda,.l 53/32, which is conventional in the art. The Cobb-values col,espond to paper absoi~tion of water, expressed in g/m2 of water take-up after contact for 1 minute. The values measured on the sized paper sheets are set forth in Table ll, where dosage (%) refers to dry cationic polyurethane on dry sheet.
Table ll Sizing agent Cobb-value obtai,)ed using Polyurethane Sizing Disper~ion dosage (%) Fx. 4 F~ 5 FY 6 F~. 7 0.075 80 80 74 0.10 40 36 36 74 0.15 22 21 23 29 0.20 - - - 22 As can be seen from Table ll, the sizing agents of Examr'~s 4 to 6 according to the invention showed markedly improved sizing eflciency over the sizing agent of Example 7 used for compa,ison.
It is known in the pape",~a~ing art to use cationic polyurethanes (CPUR) as sizing agents in order to delay or prevent the absGrl,lion and spreading of aqueous solutions in sized paper products. Usually CPUR s in the form of aqueous d;speraions are used in 10 surface sizing in which the sizing agent is applied to the paper surface at the size press.
U.S. Pat. No. 3 971 764 ~isclQses high " c' cu'~r weight CPUR sizing agents prepalêd by reacting a diol with a polyisocyanate to form a prepolymer with terminal isocyanate groups which is s~hsequently reacted with (a) a diol containing a tertiary nitrogen atom which is s~hsequently converted into the con~sponding an,i"on ~rn compound or (b) a 15 diol containing a nil,ugen atom previously converted into the cor,t:sponding ammonium com-pound; method (a) being preferred. In these m~ll,ods the nitrogen atom can be ,endered 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 disperaions generdlly provide good sizing response using low levels of sizing agent. It has however 20 been observed that the CPUR di~per~ions exhibit stability problems and settling tendencies in particular in the pr~sence of electrolytes which are con"~only added into the size press in order to prevent static electricity being built up during s~bsequent ~pp!ica~ion drying or con-verting processes. The insufficient stability may cause the CPUR pa,li-le-~ contained in the dispersions to agglol"erala and form depos~ts leading to handling and ~pplic. lion problems 25 deteriordled size pel fu""allce and poorly sized paper.
According to the present invention it has been found that CPUR s having improvedsizing and stability prupe,lies can be obtained by using in the polyu,t:ll,ane synthesis a hydroxy-fu"ulional qu~ler"ary a""nol,: Im compound (QUAT) i.e. an organic compound con-taining one or more hydroxyl groups and a positively cha,yed quaternary nitrogen atom in 30 which the nitrogen has been quaternized with an epoxide. More specifically 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 quater"ary nitrogen that has a s~ Ihstituent derived from an epoxide. ~he 35 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.
.. . _ _ . .. .. . ... . . .... .
CA 022~844 1998-11-19 The method according to the present invention leads to high mclec~ r weight CPUR s with oulsland;ng prope~lies. Aqueous di;,per~ions of the present CPUR s exhibit improved stability and hereby the pr.,t~'ems ~csociated with prior art sizing dispersions based on CPUR can be reduced or over~ ome. The present CPUR dispt:,~ions 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 econo" .~ benefits.
Dihydroxy compounds, or diols, that can be used as ,I,onG",er~ in order to form the prepolymer, or inlei",edidle product, according to the present invention include aliphatic and aro",alic diols. The term "aliphatic", as used herein, refers to an essenlially hydrocarbon 10 structure apart from deslyl laled hnclional groups, which hydrocarbon structure may be inter-rupted by one or more het~rudlor,~s, e.g. oxygen and nit,ogen, andlor one or more groups containing ht7teroatoms, e.g. carbonyl and acyloxy groups. The term "a,u,nati~:", as used herein, refers to an a~u",alic, essentially hy~ .ca~tJon structure apart from desiy"aled func-tional groups, which hyd,oca,bon structure may be interrupted by one or more he~eru~lor,,s, 15 e.g. oxygen and nitrogen, and/or one or more groups containing ht:terodlunls1 e.g. carbonyl and acyloxy groups. It is generally p~,:fe"ed to use aliphatic diols and pr~erably such diols which have an aliphatic side-chain sl~hstitl~ent which can contain from 1 to 30, suitably at least 5, p,ererdbly at least 10 and most prererdbly from 10 to 22 carbon atoms. The diols may be high n.n's..~ weight polymeric compounds such as polyester, polyether and polybuta-20 diene diols, although it is generally more p,ef~rle:d to use non-polymeric aliphatic dihydroxy compounds which suitably contain from 2 to 20 and preferably from 2 to 10 carbon atoms in the chain connecting the two hydroxyl groups, i.e. in the main chain. Preferred aliphatic main chains include alkylenes and dialkyleneamines containing from 2 to 10 carbon atoms.
Suitably the main chain is substitut~d with an aliphatic side-chain as desc,il,ed above; where 25 the main chain contains a het~,ualol,, which is nitrogen, it is pl~relled that the nit,~gen carries the side-chain. Ex~r,.~'es of suitable aliphatic dihydroxy compounds include ethylene and diethylene glycols, propane and butane diols, and higher mn'~cll~a~ weight compounds such as fatty acid monoesters of triols such as glycerol and trimethylolpropane, e.g. glycerol ll~onoalea(~le and glycerol monobehenate, trimethylolpropane mono~led,dte; oligomeric 30 esterdiols such as diester diols, e.g. those obtained by reacting a dicarboxylic acid, e.g.
adipic acid, with a molar excess of a diol, e.g. ethylene glycots; N-alkyl-diethanolamines, e.g.
N-stearyl-diethanolamine; branched chain dihydroxy alkylenes, e.g. 1,2- and 1,4-dihydroxy-oct~decarles. The higher ",c'e~,la~ weight compounds are generally preferred, especially ~Iycerol monostearate. Examples of aromatic diols that can be used include bisphenol A.
35 Mixtures compri~i"g one or more diots, such as any of those mentioned above, can also be used in the reaction with polyisocyanates.
_ _ CA 022~844 1998-11-19 rolyisocyanates that can be used as ",onG",era to form the prepolymer in this method include aliphatic a~umdlic and mixed aliph~liclarc,",~lic compounds. Among the polyisocyanates it is prefe"~d to use diisocyanates. Where polyisocyanates containing more than two isocyanate groups are used e.g. triisocyanates it is prt:fer,t:d to admix them with diisocyanates. Generally polyisocyanates are known in the art for example as disc~osed in Encyclopedia of PolymerScience and Engineering Vol. 13 Second Ed. 1988 pp. 243-303 which is hereby illcol~Jordled herein by ~ference. Examr'es of suitable diisocyanates include toluene-2 4- and 2 6-diisocyanates diphenyl~"etl,ane~ 4-diisocyanate hexd~nell"~lene diiso-cyanate dicyclohexylmethane44-diisocyanatel cyclohexane-1 4-diisocyanate isophGrune diisocyanate and the like. It is also possible to use blocked isocyanates in known manner.
The reaction of the ",onomeric dihydroxy compound with the polyisocyanate can becarried out in conventional manner for exd""~ e as disclosed in U.S. Pat. No. 3 971 764 which is hereby incorporated herein by r~:fer~nce. As isocyanates are succeptihle to nucleo-philic attack and readily react with water the prepolymer as well as the CPUR are preferdbly pr~part:d in a reaction medium free from water and undesired nu-loeph'e~. Suitably the ,~aclion is carried out in a water-free inert organic solvent e.g. acetone optionally in the presence of a catalyst e.g. diacetoxy-dibutyl-tin. The molar ratio of dihydroxy compound to polyisocyanate can be varied 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 preferdbly about 1:2.
Preferably the hydroxyl- and isocyanate-containing reactants used in the first stage are u"charyed which thus leads to an u"charyed prepolymer.
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 quah",ary a,n",onium compound in order to introduce positive charges into the polyu,t:ti,ane. The second stage can be carried out genercJly as taught in U.S. Pat. No. 3 971 764 except that in the present method there is used a hydroxy-f~ lional QUAT containing a quater"ary nitrogen atom having a substituent derived from an epoxy-f "~tional qualer"i~i"g agent.
~ut~t'e hydroxy-functional QUAT s include compounds obtained by ~t:acti"g a tertiary amine suitably a hydroxyl-containing tertiary amine; with an epoxide e.g. an alkylene oxide such as ethytene oxide and propylene oxide or suitably a halogen-containing epoxide such as epihalohydrin e.g. epichlorohydrin and epibromohydrin pref~r~bly epichlorohydrin; and optionally with an acid. In a preferred embodiment of this invention the hydroxy-functional ~ QUAT is a compound containing one or more hydroxyl groups and a quatemary nitrogen atom having a sllhstihlent denved from a halogen-containing epoxide and having an anion derived from an acid.
..... . .. .. .
CA 022~844 1998-11-19 Suitable QUAT s for use according to the invention can thus be represented by the general formula (I):
R, X (I) wherein R1 and R3 are each i"dependel,lly selecled from aliphatic groups containing 1-10 and pr~rt:r~bly 14 carbon atoms, which may be sl~bstituted with hydroxy, suitable at least one hydroxyl group is present in R1 and/or R~ and pr~:rerably R1 and/or R3 are linear or blanched N a"~anGls, e.g. N-ethanol; R2 is an aliphatic group, suitably alkyl, containing 1-22 and p,~rdbly 14 carbon atoms, p~f~rably methyl, ethyl, propyl or butyl; or alternatively R1 and R2 togetl ,er with N form a linear or branched 5 to 7 membered ring, preferably aliphatic, which may be sl~hstituted with hydroxy and one ortwo carbon atoms may be suhstit~lted with NR5R6 in which R5 and R6 are aliphatic groups, pr~ferably alkyl, containing 14 carbon atoms;
R4 is derived from an epoxide, e.g. an alkylene oxide such as ethylene oxide and propylene oxide, or, suitably, a halogen-containing epoxide, preferably lep.,hl rohydrin; and X is an anion of an acid. In most cases, R" R2, R3 and N of the QUAT are derived from a tertiary amine. Generally, at least one hydroxyl group present in the QUAT is located on the 5llhstjtllent derived from the epoxide as qudle",i~ion of a tertiary amine by means of an epoxide normally leads to ring-opening of the epoxide group and formation of a hydroxyl group. Suitable QUAT's include those desc,ibed in EP 541289 which is i"cor,.,ora~ed herein by reference for all purposes.
The R4 substih~ent can thus be reprt:senled by the general formula (Il) derived from an epoxide of the general formula (Ill):
- R7HC - CH - RB (Il) R7HC - CH - R8 (Ill) \ /
OH O
wherein R7 is hydrogen or an aliphatic group such as alkyl, preferably hydrogen; and RB is hydrogen or an aliphatic or arur"alic group which can contain up to 20 carbon atoms, e.g.
alkyl such as methyl, and which can be suhstih~ted with halogen; R9 suitably being a halogen-containing aromatic or aliphatic group, preferably aliphatic, which may contain from 1 to 12carbon atoms, p~c:ferably the h-'~gen is chlorine and RB is CH2--Cl. In addition, in QUAT s obtained by reacting a tertiary amine with an epoxide of formula (Ill) where R7 = H and RB = H
or alkyl such as methyl, i.e. an alkylene oxide, the R4 substituent of the resulting QUAT of formula (I) may be a linear or branched hydrocarbon chain interrupted by one or more 40 oxygen atoms, i.e. a di- or polyalkyleneoxy group, and containing a hydroxyl group, usually in CA 022~844 1998-11-19 Wo 97/45395 PCT/SE97/00873 a terrninal position, since the quatel"i~dlion reaction may lead to di- or polyaddition of alkylene oxides.
The reaction between the prepolymer and QUAT, i.e. the reaction bel.~een isocyanate groups(s) of the prepolymer and hydroxyl group(s) of the QUAT, leads to chain-5 lengthening of the polyurethane. As will be appreidled, the degree of chain-lenylhening depends on the number of reactive hydroxyl groups present in the QUAT where a mono-hydroxy-functional QUAT will act as a chain-terminator and thus provide less chain-lenythen 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 preferdbly 2 or 3. Mixtures containing more than one QUAT can of course be used. If desired, the QUAT can be used in co,nb ~ation with an additional hydroxy-fu", lional com-pound, such as any of the hydroxylic compounds n,enlioned herein. In many cases, the use of admixtures containing QUAT and additional hydroxylic compound is prtfer,ed, for example where the QUAT exhibits limited solubility in the rea.;tion medium used. Preferred addilional hydroxylic compounds include the diols and hydroxy-h"clional tertiary amines des~,ibed herein. In a prerer,~d embodiment, use is made of a cGr"position 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 adcli~ional hydroxylic compound, when used, can be varied over a broad range depending on, among other things, the isocyanate content in the prepolymer, the desired QUAT content and cationicily of the CPUR and the intended use of the CPUR. Usually, this molar ratio can be from 50:1 to 1:100. The molar ratio of hydroxyl groups to isocyanate groups in the second stage can be varied over a broad range and in most cases the moiar ratio is within the range of from 1:0.5 to 1:2, suitably from 1:0.8 to 1:1.4 and p,ererdbly about 1:1.
The CPUR obtained may have an average "~c'ec~ r weight of at least 1,000, suitably at least 3,500 and preferably at least 4,000. The upper limit of ",clec~ weight is not critical; usually it is about 30,000 and p,t7rer~bly about 15,000. After Co,),F' t~d reaction the reaction mixture containing CPUR can be worked-up and converted into an ~q~leou~
di_pe,sion in conventional manner, for exan~ple as ~isclosed in U.S. Pat. Nos. 3,971,764 and 4,617,341. Examples of useful steps include addition of acid, addition of water, evapor~lion of solvent and the like. In a preferred aspect of the process, an acid is added to acco",; ' h neutralization by converting any tertiary nitrogen atoms present in the CPUR into the co"espondi,lg tertiary nitrogen acid addition salt.
The present invention further re\ates to an aqueous dispersion co"~prisi"g the CPUR, to its use as a sizing agent in the making of paper and similar cell~l'cse based products like board and paper board, wherein the aqueous CPUR dispersion is added to the CA 022~844 1998-11-19 WO 97/4539~ PCT/SE97/00873 papermaking stock or applied to the surface of said products, preferdbly 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, ca'~ ~tcd as dry CPUR on dry cellulose based material 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 specirically, the invention relates to qudler"ary a,nlnooium compounds containing one or more hydroxyl groups and a quale~,ary nitrogen atom having a suhstit~ent derived from a halogen-containing epoxide and having an anion derived from an acid, csr"positions colllpris;"g such QUAT s, their prcpa,dlion and use, as further defined in the claims.
The QUAT according to the invention, which cGntai"s a positively charged nit,ugen attaching four radicals or s~tbstituents, can be l~pr~ser,led by the general formula (I) defined above wherein R4 is derived from a halogen-containing epoxide, pl~rt:l~bly epichlorohydrin.
The QUAT cor,tai"s one or more hydroxyl groups and in most cases not more than 4 hyd-roxyl groups, preferably from 1 to 3 and more p~t7rt:rdbly 2 or 3 hydroxyl groups, which can be located on any of the sl Ibstituents 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. forrnic acid, acetic acid, prop.onic acid",~tl,ane sulfonic acid and p-toluene sulfonic acid, and inorganic acids, e.g.
hydrogen halides and sulfuric acid. In a preferred embodiment, 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 prc:sence 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-fu~,ctional QUAT s can be prepar~d 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-f~",ctional QUAT's containing different N-s~hstituents and counter-ions. Furthermore, after co",, ' ted reaction, the reaction mixture obtained contains essenlially no or very low amounts of oligomeric material and/or undesired by-products whereby the QUAT obtained can be used in the CPUR synthesis without costly pu,iricalion. The QUAT obtained in the method also exhibit good stability. The subject method thus offers subslantial te~;hnical and economic benefits.
Generally, it is common to use water as a solvent in the reaction and/or in the work-up when pr~pari"g qualelllary ammonium compounds. Water, being a polar solvent, CA 022~844 1998-11-19 norrnaliy favours the fo~nalion of charged reaction products like QUAT s and facilitates separalion of the QUAT from the reaction mixture by means of exl,d~tiol1 using water in conjunction with a water-immiscible solvent. However, monomers to be used in CPUR
production should suitably be free from water since isocyanates are susceptihle to 5 nucleophilic attack. It has been exlJerienced that extensively removing water from hydroxy-functional quatemary ammonium salts is cGr", linatec', costly and may lead to decomposition of the QUAT. Therefore, by providing a reaction which is carried out in the substanlial absence of water, there is produced a QUAT e-specia~y useful for subsequent conversion with isocyanates into cationic polyur~thanes.
The tertiary amine used in the present method is an organic compound containing at least one quaternizable tertiary nit~gen atom. Suitably the tertiary amine in an aliphatic amine. The tertiary amine suitably contain from 3 up to 25 carbon atoms, preferably from 4 to 10. Suitable tertiary amines can be represented the general formula (IV):
l 1 (IV) wherein R~, R2, and R3 are as defined above. The tertiary amine suitably contains from 0 to 3 hydroxyl groups and preferdbly 1 or 2 hydroxyl groups.
Examples of useful tertiary amines include non-hydroxylic amines such as N-trialkyl-amines, monohydroxy amines such as N,N-dialkyl alkanola"""es, and dihydroxy amines 25 such as N ~":an 'icl dialkylamines and N-alkyl dialkanolamines. Suitable tertiary amines include triethylamine, N,N-dimethyl stearylamine, N,N-dimethyl ethanolamine, 1,2-propane-diol-3-dimethylamine, N-methyl ciietl,anola"line, N-ethyl diethanolamine, N-propyl diethanol-amine, N-n- and N-t-butyl diethanola"~..,es, N-stearyl diell,anola"line and N-methyl dipropa-nolamine. N-alkyl dialkanola~ es and N,N-dialkyl alkanolamines, such as for example N-30 alkyl u'i~:',anola~lines and N,N-dialkyl elhanolan,ines, in which the alkyl groups contain 1 to 4 carbon atoms are preferred, in particular N-methyl diethanolar";"e and N,N-dimethyl ethanol-amine.
The epoxide in the present method is an organic compound capable of functioning as a qu~er"i~i"g agent and con~a."s at least one epoxide, or oxirane, group, and at least 35 one halogen atom. Monoepoxy- and monohalogen-f~"ctional compounds are preferred.
Suit~'e halogen-containing epoxides include compounds of the formula (Ill) defined above, preferably erich'~rohydrin, which when being reacted with the amine and the acid forms the sllhstituent of formula (Il) connected to the nitrogen.
... ..
CA 022~844 1998-11-19 Suitable acids include protonic acids, HX, which forms the anion X of the QUAT.
P~fe,ably the acid is one that can be supplied as a substantially water-free acid. Examples of 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 brur,,;de and sulfuric acid. In a preferred embodiment of the invention, use is made of organic acids and, in particular, formic acid.
It has been found that the acid has an illlpolldnt role in the reaction and that higher levels of In' ~o.,leric ",aterial are usually formed when the reaction between the tertiary nitro-gen and epoxide takes place in the ab5ence of acid. When carrying out the reaction, 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.
Hereby the tertiary amine, or part thereof, may be present in the form of tertiary amine acid addition salt, e.g. R,R2R3N H X, wherein R~, R2, R3, and X are as defined above. In a prefer-red er"bodi."ent of the invention, the acid is i"te""illently or continuously fed to the reaction mixture so as to keep the pH within the desired range. Preferably, the pH value is between 7 and 12 and most prt:ferdbly between 8 and 10.
In the method, the molar ratio of tertiary r. ~.ogen 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 examr'e 15:1 or higher, in many cases 10:1, usually 5:1, suitably 1.4:1 and prefe~ably 1.2:1. In the method, the molar ratio of acid to epoxide can be varied over a broad range dependi"g on, among other thing, the desired pH of the reaction mixture during the reaction. Suitably the reaction is carried out with the acid and epoxide in approxi",al~,ly e~uimolar amounts or with a molar excess of the acid. For instance, a molar excess of up to about 30% may be bener,cial 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. In a preferred aspect of the invention the reaction is carried out in the absence of inert organic solvents. Where solvents are used, it is preferred to use inert organic polar solvents. Suitable solvents include dimethyl~u",~a",ide, py~l.l;d~ne, hexa-methylene phospho,l~iam ~e and the like. It is further possible to use protic solvents such as alcohols, e.g. methanol, ethanol, isopropanol and the like. However, in cases where the QUAT is to be used in the production of CPUR s, protic solvents are prt:ferdbly removed from the QUAT prior to use since protic solvents readily react with isocyanates. Ther~fore, 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.
CA 0225~844 1998-11-19 The present method should be carried out in the subslantial absence of water.
Hereby is meant that the amount of water present during 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 pr~rt "ed aspect of the invention, no 5 water at all is present. The reaction can be run at a te",pe,dlure below 50~C, suitably below 35~C and preferably below 25~C. The lower limit is not crucial and the reaction can be carried out at a temperature above -80~C, suitably above -25~C and pr~rcbly above 0~C. It may be advant~geous to cool the reaction mixture during the reaction, especially when adl"b~i"g the reactants.
In another aspect of this invention there is provided a method of producing a hydroxy-fLI"~tional quater"ary a"""on.;~m compound useful in the CPUR production which co",yrises r~a~illg a tertiary amine with an epoxide in the presence of an acid and in the suL.-~ldr,lial 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 fu.,-,lior,i.,g as a quater-nizing agent containing at least one epoxide, or oxirane, group, pref~,dbly having the general forrnula (Ill) above. The reaction is carried out in the suL~la"lial 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 cor"t~. ,ed weight of water and organic solvent.
After c,o,rFl~t~d reaction, the pH of the reaction mixture can be ad3usted to 4-9 for the purpose of improving the stability of the QUAT, suitably to pH 5-8 and preferably to pH 6-7. This may be acco".F' shed by means of any acid that is essentially water-free, e.g. any of those mentioned above. The solvent used in the reaction, if any, can be removed from the reaction mixture by evaporation, suitably at reduced pressure. The product forrned can be used directly, for example in the production of CPUR's, without purification. If desired, 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-f~."ulional QUATs in high yields with low or no formation of ~1.3~n,eric and polymeric material.
Fu,ll,er",o,e, where epichlorohydrin is used as a quater"i~i"g agent to produce the QUAT, low levels of unreacted epichlorohydrin and u,ldesi,ed by-products such as 1-chloro-2,3-propane diol (CPD) and 1,3-dichloro-2-prupanol (DCP) are usually obtained. Generally, the conversion of ep..,'-'cruhydrin to CPD is less than 5% and normally less than 3%, based on the weight of ep.~h'~rohydrin used in the reaction, and the conversion of ~ep ehloruhydrin to 35 DCP is less than 1% and normally less than 0.1% by weight. Accor.li,lyly, one of the advantages of using the QUAT s of this invention in CPUR production is that CPUR s and .... .. .... .. . .
CA 022~844 1998-11-19 di~per~ions thereof can be provided with very low co,l~ent~ of unreacted halogen-containing epoxide, e.g. epich'orùhydrin, and undesired by-products derived from the halogen-functional epoxide, e.g. CPD and DCP. In the CPUR's and CPUR .li~per~ions according to the invention, the amount of halogen-containing epoxide such as epichlorohydrin present can be 5 less than 10 ppm, suitably less than 5 and preferably less than 1 ppm, c~c~ ted as haiogen-cor,lai.,i"g epoxide and based on CPUR solids, and the amount of halogenaled by-products can be less than 1% by weight and suitably less than 0.5 % by weight, calculated as total amount of halogehdtud by-products and based on CPUR solids. Notably, when using epichlorohydrin, the CPD content can be less than 0.1% by weight, suitably less than 0.05%
10 by weight and prer~,ably less than 10 ppm~ based on CPUR solids, and the DCP content can be less than 0.5% by weight, suitably less than 0.1% by weight and pr~ferably less than 10 ppm, based on CPUR solids.
The invention further relates to a c~",uosition cor"pri~i"g the present hydroxy-func-tional quatemary ammonium compound, as further defined in the claims. The cG",position is 15 subs~a"lially free from water, as defined above. In addition to the QUAT, the co",position can for example contain unreacted starting "~aleric.ls such as any of those used in the ,e:action, e.g. any ",dteridl used in excess, and minor amounts of reaction-typical by-products. The co" ,position may also contain additional compounds admixed with the cGmposition.
Examples of such additional compounds include acids and tertiary amines, e.g. any of those 20 defined herein. In a prt:rer,ed embodiment, the QUAT is present in the cor"position in a pre-dominant amount, based on weight, i.e., the weight ratio of QUAT to each of the other co",ponenLs present in the COI"pOSitiOI~ is higher than 1. In another pref~"ed embodiment, a hydroxy-functional tertiary amine and/or its acid addition salt is present in the composilion in a predo"~inanl amount, based on weight, preferably the tertiary amine. Such co",posilions 25 are particularly useful in the pr~para~ion of CPUR. The tertiary amines and acids for fol",alion of the acid addition salt may be any of those defined herein and suitably the same type of compounds used as ~e:a~;tants in the method of the invention.
The invention is further illustrated in the follo~.i"g E~cd~r'~s which, ho.~_ver, are not i"lended to limit same. Parts and percentages relate to parts by weight and percent by 30 weight, ,especli~/ely, unless otherwise stated.
F~mple 1 In acco,dance with the present invention, (3-chloro-2-hydroxypropyl)-bis(2-hydroxyethyl)-methylammonium fu""idle was prepared as follows:
3~ To cooled 11.9 9 (0.1 moles) of N-methyl diethanGlal"i"e, 98% concenl,a~ed formic acid was added with stirring to produce a pH of betNeen 9 and 10, as measured by means of CA 022~844 1998-11-19 WO 97/4539~ PCT/SE97/00873 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 20~C 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 5 as shown by 13C-NMR and GPC and the fo"~,dlion of by-products was low. Essentially no oligomeric and polymenc ~"dlerial was formed. The product so obtained was stabie for more than three months at room te",terd~ure FY~mple 2 The procedure of Example 1 was followed except that the amine used was N N-dimethylethanolamine and that the amine and e~c ~h ~ruhydrin were used in equimolar amounts. The desired product (3-chloro-2-hydroxypropyl)-(2-hydroxyethyl)-dimethyl-a,nr"or Im for",id~e was obtained in high yield. Only minor amounts of impurities were forrned and there were essentially no for",alion of ol.goi"eric and polymeric material.
FY~rnDle 3 (Comparison) The procedure of Example 1 was followed except that no acid was used in the method. An exoll,er~"ic reaction between N-methyl diethanolamine and ep.~hl~r~,hydrin took place which was very difficult to control and phase sepa,dlion was observed i"dicdti"g formation of oligomeric/polymeric material. After two days the reaction mixture had been cGrrl,~ ~t~y converted to a solid mass and no monomeric compounds could be detected.
F~rnple 4 A cationic polyurethane accordi, ,9 to the invention was prepared as follows:
To a solution of 18.3 g of glycerol monosteardle and 18.3 9 of toluene diisocyanate in 50 g of water-free acetone at a l~",~erdlure of 40~C was added 17 mg of dibutyl tin-di-cet~te in acetone. The solution was refluxed for 1 hour under vigorous stirring. A sample of the solution was taken away for dete""i ,~tion of residual NCO-groups and showed a residue of 14%. A mixture of 5.1 9 of N-methyl diethanolar":ne (N-MDEA) and 2.2 9 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 mixture was diluted with 250 ml of water.
Acetone was evaporated under reduced pressure at 60-70~C to afford a clear residue in the form of a clisper~ion containing approximately 15-17% of CPUR at pH 4. The contents of epichlorohydrin CPD and DCP were all below the detection limit of the gas chromatographic CA 022~844 1998-11-19 Wo 97/45395 12 PCT/S~:97/00873 method used; the ep~ch orohydrin content was below 1 ppm the CPD and DCP contents were both below 10 ppm.
FY~mple 5 A cationic poly~ ane according to the invention was prepared as in Example 4 except that the molar ratio of N-MDEA to QUAT was 4:1.
FY~rnple 6 A cationic polyu~ll,ane accordi.,g to the invention was prepared as in Example 4except that the molar ratio of N-MDEA to QUAT was 3:1 which thus corresponded to about 25% qudL~,.,i~ation of the nit,ogen atoms.
FY~mr~le 7 (Con"~arison) In this test a CPUR was prepared by reacting HCI with a polyurethane containing tertiary amine groups.
Glycerol monostearate was reacted with toluene diisocyanate as in Example 2 and then the pre-polymer with temminal NCO-groups was reacted with solely N-methyl diethanol-amine. The u"charyed polyurethane was rendered cationic by addition of 1 M HCI which converted tertiary nitrogen atoms into the corresponding acid addition salt. Work-up was made as in Example 4 which yielded a dispersion containing about 15-16% of CPUR at pH 4.
Example 8 (Cor"pa,ison) 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 quaLen~i~ation of about 25% of the nitrogen atoms and then 1 M HCI was added forneut,dli~ation. The work-up was carried out as in Example 4 which resulted in a dispe,aion containing about 15% of CPUR at pH 4.
FY~mple 9 Stability of the cationic polyurethane di~peraions of Exdlrr s 4-8 was evaluated by adding a saturated aqueous solution of sodium sulfate to 100 ml of aclueous di~peraion containing 0.5% by weight of cationic polyurethane. The mixtures were stirred at 20~C and then inspected visually. Table I shows the results.
CA 022~844 1998-11-19 Table I
Na2SO4(aq.) Appearance of Cationic Polyurethane D;sper~ion aWed (ml) FY 4 Fx. 5 F~t. 6 F~. 7 Fx. 8 o Clear Clear Clear Clear Clear 1.0 Clear Clear Clear Precip Clear 2.0 Clear Clear Clear Precip S-Turb 3 0 Clear Clear Clear Precip S-Turb 4 0 - - S-Turb - V-Turb 5.0 - - S-Turb - Precip 10 wherein S-Turb = slightly turbid V-Turb = very turbid Precip = precipitation - = not analyzed As is evident from Table 1, the dispersions of cationic polyurethane of Ex~ !e s 4-6 15 according to the invention were consi~erdbly more stable than the polyurethane dispersion used for comparison purposes.
FY~rnple 10 Sizing efficiency of the CPUR dispersions accor.li"g to Examples 4-7 was evaluated 20 by means of the Cobb Test, using German DIN s~anda,.l 53/32, which is conventional in the art. The Cobb-values col,espond to paper absoi~tion of water, expressed in g/m2 of water take-up after contact for 1 minute. The values measured on the sized paper sheets are set forth in Table ll, where dosage (%) refers to dry cationic polyurethane on dry sheet.
Table ll Sizing agent Cobb-value obtai,)ed using Polyurethane Sizing Disper~ion dosage (%) Fx. 4 F~ 5 FY 6 F~. 7 0.075 80 80 74 0.10 40 36 36 74 0.15 22 21 23 29 0.20 - - - 22 As can be seen from Table ll, the sizing agents of Examr'~s 4 to 6 according to the invention showed markedly improved sizing eflciency over the sizing agent of Example 7 used for compa,ison.
Claims (25)
1. A method of producing a cationic polyurethane, characterised in that it comprises (a) reacting a dihydroxy compound with a polyisocyanate to form a pre-polymer having terminal isocyanate groups;
(b) reacting the pre-polymer with a hydroxy-functional quaternary ammonium compound containing a quaternary nitrogen having a substituent derived from a halogen-containing epoxide.
(b) reacting the pre-polymer with a hydroxy-functional quaternary ammonium compound containing a quaternary nitrogen having a substituent derived from a halogen-containing epoxide.
2. A method according to claim 1, characterised in that the hydroxy-functional quaternary ammonium compound contains a quaternary nitrogen having a substituent derived from epichlorohydrin.
3. A method according to claim 1 or 2, characterised in that the quaternary ammonium compound contains from 1 to 3 hydroxyl groups and a quaternary nitrogenhaving a substituent derived from epichlorohydrin and has an anion derived from an acid.
4. A method according to claim 1, 2 or 3, characterised in that the quaternary ammonium compound has general formula (I):
wherein R1 and R3 independently are selected from aliphatic groups containing 1-4 carbon atoms which may be substituted with hydroxy, at least one hydroxyl group being present in R1 and/or R3; R2 is an alkyl group containing 1-4 carbon atoms; R4 is derived from epichlorohydrin and X is an anion of an acid.
wherein R1 and R3 independently are selected from aliphatic groups containing 1-4 carbon atoms which may be substituted with hydroxy, at least one hydroxyl group being present in R1 and/or R3; R2 is an alkyl group containing 1-4 carbon atoms; R4 is derived from epichlorohydrin and X is an anion of an acid.
5. A method according to claim 1, 2, 3 or 4, characterised in that the quaternary ammonium compound has an anion of an organic acid.
6. A method according to any of the preceding claims, characterised in that the dihydroxy compound comprises an aliphatic compound substituted with an aliphatic side-chain containing at least 5 carbon atoms.
7. A method according to any of the preceding claims, characterised in that the dihydroxy compound comprises an aliphatic compound containing from 2 to 10 carbon atoms in a main chain connecting the two hydroxyl groups, the main chain being substituted with an aliphatic side-chain containing at least 10 carbon atoms.
8. A method according to any of the preceding claims, characterised in that the polyisocyanate comprises toluene diisocyanate.
9. A method according to any of the preceding claims, characterised in that the cationic polyurethane formed has a molecular weight of at least 3500.
10. A cationic polyurethane obtainable by a method according to any of claims 1 to 9.
11. An aqueous dispersion comprising a cationic polyurethane according to claim 10.
12. An aqueous dispersion according to claim 11, characterised in that the content of epichlorohydrin is less than 10 ppm, based on cationic polyurethane solids.
13. An aqueous dispersion according to claim 11 or 12, characterised in that the content of 1-chloro-2,3-propane diol (CPD) is less than 0.05% by weight, based on cationic polyurethane solids, and the content of 1,3-dichloro-2-propanol (DCP) is less than 0.1% by weight, based on cationic polyurethane solids.
14. Use of an aqueous dispersion comprising a cationic polyurethane according toclaim 11, 12 or 13 as a sizing agent for cellulose based products.
15. A hydroxy-functional quaternary ammonium compound containing one or more hydroxyl groups and a quaternary nitrogen having a substituent derived from a halogen-containing epoxide and having an anion derived from an acid, with the proviso that the anion is not chloride.
16. A quaternary ammonium compound according to claim 15 having the general formula (I):
wherein R1 and R3 independently are selected from aliphatic groups containing 1-4 carbon atoms which may be substituted with hydroxy, at least one hydroxyl group being present in R1 and/or R3; R2 is an alkyl group containing 1-4 carbon atoms; R4 is derived from epichlorohydrin and X is an anion of an acid.
wherein R1 and R3 independently are selected from aliphatic groups containing 1-4 carbon atoms which may be substituted with hydroxy, at least one hydroxyl group being present in R1 and/or R3; R2 is an alkyl group containing 1-4 carbon atoms; R4 is derived from epichlorohydrin and X is an anion of an acid.
17. A quaternary ammonium compound according to claim 15 or 16 having an anion of an organic acid.
18. A substantially water-free composition comprising a quaternary ammonium compound according to any of claims 15 to 17 and a hydroxyl-containing tertiary amine and/or an acid addition salt thereof.
19. A composition according to claim 18, characterised in that the hydroxyl-containing tertiary amine and/or acid addition salt thereof is present in a predominant amount, based on weight.
20. A method of producing a hydroxy-functional quaternary ammonium compound by reacting a tertiary amine with a halogen-containing epoxide in the presence of an acid and in the substantial absence of water.
21. A method according to claim 20, characterised in that the tertiary amine being reacted with the epoxide and the acid is N-alkyl diethanolamine or N,N-dialkyl ethanolamine in which the alkyl groups contains from 1 to 4 carbon atoms.
22. A method according to claim 20 or 21, characterised in that that the acid is formic acid, acetic acid, propionic acid, methane sulfonic acid, p-toluene sulfonic acid, hydrogen chloride, hydrogen bromide or sulfuric acid.
23. A method according to any of claims 20 to 22, characterised in that that the epoxide is epichlorohydrin.
24. A method according to any of claims 20 to 23, characterised in that at least part of the acid is present when bringing the amine into contact with the epoxide and that additional acid is intermittently or continuously fed to the reaction mixture during the reaction.
25. Use of a hydroxy-functional quaternary ammonium compound according to any of claims 15 to 17 or a composition comprising a hydroxy-functional quaternary ammonium compound according to claim 18 or 19 for the production of a cationic polyurethane.
Applications Claiming Priority (5)
| 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 | |
| US60/19200 | 1996-06-06 | ||
| PCT/SE1997/000873 WO1997045395A1 (en) | 1996-05-28 | 1997-05-27 | Quaternary ammonium compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2255844A1 true CA2255844A1 (en) | 1997-12-04 |
Family
ID=26662639
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002255844A Abandoned CA2255844A1 (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) |
Families Citing this family (4)
| 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 |
| BRPI0806170B1 (en) * | 2007-10-22 | 2019-02-26 | Bridgestone Corporation | FUNCTIONALIZED POLYMER, METHOD FOR PREPARING A FUNCTIONALIZED POLYMER, AND COMPOSITION UNDERSTANDING A FUNCTIONALIZED POLYMER |
| 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 |
| WO2019036508A1 (en) | 2017-08-15 | 2019-02-21 | Hbi Branded Apparel Enterprises, Llc | Functionalized fibrous material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2400490C2 (en) * | 1974-01-05 | 1982-06-03 | Akzo Gmbh, 5600 Wuppertal | Cationic polyurethanes and processes for their manufacture |
| ES2143096T3 (en) * | 1991-11-01 | 2000-05-01 | Witco Corp | COMPOSITIONS OF CATIONIC POLYURETHANE, QUATERNARY AMMONIUM SALTS AND PROCEDURES FOR ITS PREPARATION. |
-
1997
- 1997-05-27 JP JP9542192A patent/JPH11511792A/en active Pending
- 1997-05-27 CA CA002255844A patent/CA2255844A1/en not_active Abandoned
- 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 WO PCT/SE1997/000873 patent/WO1997045395A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11511792A (en) | 1999-10-12 |
| EP0904261A1 (en) | 1999-03-31 |
| AU2987297A (en) | 1998-01-05 |
| WO1997045395A1 (en) | 1997-12-04 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| FZDE | Discontinued |