CA1122616A - Polyalkylene polyamine ether derivatives of polyoxyalkylene compounds - Google Patents
Polyalkylene polyamine ether derivatives of polyoxyalkylene compoundsInfo
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- CA1122616A CA1122616A CA319,247A CA319247A CA1122616A CA 1122616 A CA1122616 A CA 1122616A CA 319247 A CA319247 A CA 319247A CA 1122616 A CA1122616 A CA 1122616A
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Abstract
POLYALKYLENE POLYAMINE ETHER
DERIVATIVES OF POLYOXYALKYLENE COMPOUNDS
ABSTRACT OF THE DISCLOSURE:
Polyamines are prepared by first reacting a poly-oxyalkylene polyol having one to eight active hydrogen sites with an epihalohydrin. The resulting polyether is, then, reacted with an amine to replace the chlorine atoms with amine functions. The polyamines hereof are useful as intermediates for preparing cationic polyelectrolytes, such as drainage aids and the like.
DERIVATIVES OF POLYOXYALKYLENE COMPOUNDS
ABSTRACT OF THE DISCLOSURE:
Polyamines are prepared by first reacting a poly-oxyalkylene polyol having one to eight active hydrogen sites with an epihalohydrin. The resulting polyether is, then, reacted with an amine to replace the chlorine atoms with amine functions. The polyamines hereof are useful as intermediates for preparing cationic polyelectrolytes, such as drainage aids and the like.
Description
ll;~Z~
BACKGROUND OF THE INVENTION
1. Field of the Invention _ _ The present invention pertains to polyamine compounds.
More particularly, the present invention pertains to polyamine ether compounds and m~thods of preparation therefor. Even more particularly, the present invention concerns polyamines derived from polyoxyalkylene polyols and methods of preparation thereof.
BACKGROUND OF THE INVENTION
1. Field of the Invention _ _ The present invention pertains to polyamine compounds.
More particularly, the present invention pertains to polyamine ether compounds and m~thods of preparation therefor. Even more particularly, the present invention concerns polyamines derived from polyoxyalkylene polyols and methods of preparation thereof.
2. Background of the Invention ...._ The fundamental reaction of an amine and a halogen-containing polyether is, of course, well documented. The resulting polyether amine products enjoy a wide range of utility including, utility as intermediates for the preparation of paper pro~uct-related items, such as drainage aids, wet and dry strength additives and the like.
These amine containing ethers are, also, useful as cross-linking agents for synthetic resins such as ureas and urethanes.
Of course, the full gamut of utility is well documented.
It is to be appreciated that fundamental is the reaction of the amine and the halogen-containing polyether.
Heretofore, the art has only recorded such a reaction.
An alternate class of compounds known in the art are the polyoxyalkylene polyamines. Ordinarily, such compounds are prepared by the direct amination of a polyoxyalkylene glycol. Such compounds, of course, are, also, of wide-ranging utility.
Another method comprises reacting the hydroxyl groups of the glycol with acrylonitrile to produce cyanoethyl ethers and hydrogenation of the nitrile groups to give amino groups.
However~ these methods provide only one amine function per 11;~2616 terminal hydroxyl group and do not pro~ide polyamines, as contemplated by the present invention.
The art is constantly striving to define new and economically attractive polyamine ethers and their attendant resultants. The present invention, as will subsequently be detailed, provides new polyamine ethers. Furthermore, these new polyamines incorporate therewithin the polyoxyalkylene moieties as well as moieties derived from an epihalohydrin.
STATEMENT OF RELEVANT ART
To the best of applicant's knowledge the most closely related art is found in:
U.S. Patent Nos. 3,607,792 2,537,726 2,601,597 2,898,349 2,174,762 SUMMARY OF THE INVENTION
In accordance with the present invention polyamine ethers are prepared by reacting an amine with a polyether derived from the reaction of a polyol having one to eight active hydrogen sites and is halogenated epoxide.
The amine may be either a monoamine or a polyamine.
Also, the amine may be primary, secondary or tertiary.
The polyol used herein is preferably a polyoxy-alkylene polyol having from one to eight hydroxyl groups.
The halogenated epoxide is, preferably, an epihalohydrin.
The products hereof are prepared by reacting the polyol and the epihalohydrin in the presence of a suitable catalyst for about 0.5 to five hours at a temperature ranging from about 30C to about 100C. Thereafter, the amine is reacted with the halohydrin ether at a temperature ranging l~ZZ616 from about 100C to about 150C for about one to five hours at a ratio of at least about two moles of amine per chlorine equivalent.
The products hereof, generally, correspond to the formula:
IRl CIH2Z OH
R~(CH2CH)n ( OCH2CH )m OCH2 2 ~X
wherein:
R is the residue of a hydroxyl compound having 1 to 8 hydroxyl groups:
Rl is H2, CH3 or C2H5;
Z is the residue of an amine selected from the group consisting of -NR2' in ~hich R'` is hydrogen or a 1 to 8 carbon alkyl group, an alkylene diamine or a polyalkylene polyamine;
n is a number ranging from about 1 to about 100;
m is a number ranging from about 1 to about 30;
X is an integer ranging from 1 to 8, and wherein at least one R" is a 1 to 8 carbon alkyl group when Z is NR3'.
For a more complete understanding of the present invention reference is made to the following detailed descrip-tion and accompanying examples.
DESCRIPTION OF TH~ PREFERRED EMBODIMENT
In accordance with the present invention there is provided polyamine ethers represented by the formula:
~ OCH2 H )n ( OcH2cH-t-ocH2cHcH2z?x wherein:
R is the residue of a hydroxyl containing compound having 1 to 8 hydroxyl groups;
Rl is either H, CH3 or C2H5;
Z is the residue of an amine selected from the group consisting of -NR2' in which R" is hydrogen or a Cl to llZZ616 C8 alkyl group, alkylene diamine or polyalkylenepolyamine;
n is a number ranging from about 1 to about 100;
m is a number ranging from about 1 to about 30;
X is an integer ranging from 1 to 8, and when Z is -NR3' at least one R" is a 1 to 8 carbon alkyl group.
The ethers hereof are prepared by reacting (1) a polyol wlth a halogenated epoxide and thereafter (2) reacting the product of a (1) with an amine. More specifically, the present ethers are prepared from (1) a polyol having from one to eight hydroxyl groups and an epihalohydrin to form an ether and (2) reacting the ether with an amine to replace the available halogen atom.
Suitable polyols contemplated for use herein are polyoxyalkylated derivatives of hydroxyl compounds having from one to eight hydroxyl groups. Suitable hydroxyl compounds include, for example, alkanols, such as methanol, ethanol, - propanol, butanol and so forth, as well as mixtures thereof.
Representative polyhydroxy compounds include ethylene glycol, propylene glycol, butylene glycol, glycerol, diglycerol, triglycerol, higher polyglycerols, pentaerythritols, di-and tri-methylolpropane, di- and tri-methyloebutane, sucrose, erythritol, sorbitol, mannitol, dextrose and so forth as well as mixtures thereof.
Suitable alkylene oxides are ethylene oxide, propylene oxide, butylene oxides, as well as mixtures thereof.
The adducts are prepared by the reaction of the selected hydroxyl compound and the alkylene oxide under suit-able oxyalkylation conditions.
In addition to the above enumerated hydroxyl compounds it is to be understood that other polyhydroxy compounds can be used herein. Such polyhydroxyl compounds, which are used to form oxyalkylated derivative thereof are, for example, ~. . .
l~LZZ616 aminohydroxy compounds, cyclic alcoholic compounds, such as 1, 4- dihydroxy cyclohexane; aromatic compounds, such as dimethylolbenzene, phenol, hydroquinone, resorcinol and the like, as well as mixtures thereof.
In practicing the present invention the preferred polyol comprises a propylene oxide adduct of propylene glycol.
The halogenated epoxides utilized herein, are epihalohydrins corresponding to the formula:
CH ~ CH2 - CH2X
wherein X is halogen. In practicing the present invention, the preferred epihalohydrin is epichlorohydrin.
According to the first step of the process used herein, the polyol and the epihalohydrin are reacted together to form the adduct thereof. Generally, the reaction is carried out at a temperature ranging from at 30C to about 100C and, preferably, from about 50C to about 80C. The reaction is usually carried out for a period ranging from about 0.5 to five hours, and, preferably, one to three hours.
The reaction is carried out in the presence of a catalyst. Suitable catalysts include those enumerated in U.S. Patent No. 3,496,120. Exemplifying such as catalysts are the Friedel-Crafts type, such as AlC13, BF3, ZnC12, FeC13 etherates; acid catalysts, such as HF, H2SO4, H3PO4 and the like. The preferred catalyst is borontrifluoride which is conventionally deployed in the form of an etherate. Generally, about 0.1 to five parts of catalyst, per hundred parts, by weight, of polyol are used.
The so-produced adduct is, then, reacted with an amine to define the present products. As noted, hereinabove, the amine may be a mono- or polyamine of either primary, secondary or tertiary functionality. Representative of the ~ ,.~
~ -6-6it;
amines which can be used herein are, preferably, alkyl and alkylene amines which are optimally, saturated compounds containing no double bonds. Also, N-alkyl polyamines, N, N -dialkyl polyamines, etc. can be used herein, but are not preferred. Other types of amines which may be used herein are found in U.S. Patent Nos. 2,644,670 and 3,152,188.
In practicing the present invention the preferred amine reactants are primary amines. Thus, monoalkyl amines, alkylenepolyamines, polyalkylenepolyamines, cyclic amines and the like can be used herein. Representative monoalkyl amines include methylamine, ethyl amine, propylamine, i-propyl-amine, n-propylamine,-n-butylamine, i-butylamine, t-butylamine and so forth. Representative alkylene polyamines include ethylenediamine, propylenediamine, butylenediamine, and so forth. Suitable polyalkylenepolyamines include triaminobutane, diethylene triamine, dipropylenetriamine, triethylenetetra2mine, and so forth. Suitable cyclic amines are represented by piperazine and the like. As noted above, if desired, secondary or tertiary amines can be used if quaternary ammonium salts are the desired end products.
In practicing the present invention, the preferred aminè is ethylenediamine.
In reacting the amine with the adduct, generally, in excess of three moles of amine per available halogen atom in the adduct is employed. Less than three moles of amine per available halogen atom can be used herein, if desired, by adoption of the method identified in copending. Patent Application Serial No. 319,246, entitled Process for Preparing PolyaIkylene Polyamine Polyethers~, and filed on evendate herewi~h.
The reaction normally proceeds at a temperature ranging from about 100C to about 150C, for a period ranging . ..
112Z61~i from about 0.5 hours to about twenty-four hours, depending on the nature of the amine reactant. Preferably, the reaction is carried out at a temperature ranging from about 115C to about 150C for a period ranging from about one to ten hours.
The products produced hereby are useful as inter-mediates for the preparation of retention aids, dry and wet strength paper additives, flocculants for ore beneficiation, and waste treatment. In addition the compounds hereof are useful as intermediates for the production of cationic and amphoteric surfactants; polyquaternary ammonium salts for ion exchange resins; water thickeners and drainage aids. Also, these compounds may be used as active-hydrogen compounds and as cross-linking agents used in the preparation of epoxy and urethane resins.
For a more complete understanding of the present invention reference is made to the following examples il-lustrating the principles of the present invention. In the examples, which are to be construed as illustrative, and not limitative of the invention, all parts are by weight absent contrary indications.
EXAMPLE
A. ADDUCT PREPARATION
Into a two-liter flask equipped with a stirrer, reflux condenser, addition funnel and a thermometer was added four hundred and thirty-five parts of a polyol comprising an oxypropylated propyleneglycol having a hydroxyl number of 258 and two and seven-tenths parts of boron trifluoride etherate, as a catalyst.
The polyol and catalyst were heated in the flask to 60C. One thousand three hundred and eighty-six parts of epichlorohydrin was then added to the flask, with stirring over a one hundred and sixty-five minute period, while main-ll;~Z~:16 taining the temperature between 58C to 68C. Since thereaction was exothermic a cooling bath was deployed to maintain the denoted temperature range in the flask. Also, during the last half of the eplchlorohydrin addltion, three additional one part additions of catalyst were made to sustain the reac-tion. After the addition was completed agitation was maintained for one and one-half hours to ensure complete reaction. There-after, the vessel was vacuum stripped at 120C at 4 torr and one hundred and twenty-one parts of strippings were recovered.
A yield of one thousand seven hundred and seven parts of a clear, brown viscous liquid was attained. Gas chromatographicanalysis of the strippings indicated eithty-three parts of epichlorohydrin. Thus, one thousand three hundred and three parts of epichlorohydrin were consumed. Hence, the adduct was an approximate fourteen mole adduct.
B. POLYAMINE SYNTHESIS
To a one liter reaction flask equipped with agitation means, reflux condenser, thermometer, addition funnel and heating means was charged six hundred parts of ethylene diamine.
The diamlne was heated to reflux (117C) and, then, two hundred and flfty parts of the product of A was then added thereto over an eighty minute period. The temperature in the v~ssel was controlled by refluxing at a final temperature of 127C.
After the addition was completed, excess ethylene-diamine was vacuum stripped off up to a temperature of 14BC
at three mls. of pressure thereby yielding three hundred and seventy-eight parts of polyether. Based upon the amount of ethylene diamine in the strippings, it was calculated that 2.3 moles of amine had reacted per available chlorine present in the adduct. The resulting polyamine product was a viscous fluid.
_g_ 6~
The product was, then, cooled at 120C and diluted with three hundred and fifteen parts of water to provide a 54.6% solution of amine hydrochloride useful for preparing a drainage aid for paper pulp.
EXAMPLE II
This example illustrates the utility of the poly-aminepolyethers hereof.
One hundred parts of the hydrochloride solution finally obtained in Example I was further diluted with ninety-seven parts of water and neutralized with twenty-three parts of a 50~ NaQA solution. The resulting solution was, thus, calculated to be a 20% polyamine solution. This polyamine solution was then charged to a reaction vessel equipped with agitation means and heating means.
To the polyamine solution was added, with stirring and at 100C, one hundred fifty-five and one-half parts of a 20% solution of a bischlorohydrin ether of a polyol to-provide a paper pulp drainage aid. The polyol was the same as that described in the above referred to copending application, a yield of three hundred seventy-four and one-half parts of drainage aid product was obtained. This product had a number 4 Ford cup vi~cosity of 39 seconds and a calculated nitrogen content of 2.2~. The product evidenced superior drainage aid properties when tested according to Canadian Freeness procedures.
The polyol reactant used herein was a 400 molecular weight polyoxyethylene glycol having an epichlorohydrin cap thereon.
EXAMPLE III
A. ADDUCT PREPARATION
Using apparatus equipped as in Example I, one thousand sixty-nine parts of a polyoxypropylene glycol having a hydroxyl number of 105 and four parts of boron trifluoride \ - --10 llZZ616 etherate was added to the flask. The flask was heated to 60C. Thereafter, nlne hundred and twenty-five parts of epichlorohydrin was added thereto in a one hundred and seventy minute period. The addition was conducted at a temperature ranging from 62C to 70C, at the 70% addition point and at the end of the addition additional two parts and one part, respectively, of the catalyst was added to the vessel.
After the addition was completed, the contents in the vessel were stirred for an additional one hour at 72C
to ensure complete reaction. Thereafter, the volatiles were vacuum stripped up to a temperature of 130C at 4 torr. One hundred and ninety-four parts of volatiles were recovered, after correction and analysis for epichlorohydrin in the volatiles it was determined that 7.9 moles of epichlorohydrin had reacted with the polyol.
B. POLYAMINE PREPARATION
To a two-liter reaction flask equipped with agitator means, reflux condenser, thermometer, addition funnel and heating means was added nine hundred and sixty parts (16 molesj of ethylenediamine. The diamine was heated to reflux (117C).
Thereafter~ five hundred and seventeen parts (4Cl equivalents) of the adduct of step A hereof was added thereto over a two hundred and ten minute period. During this time the temperature was raised to 124C and controlled thereat by reflux.
After the addition was completed, excess ethylene-diamine was stripped by vacuum stripping up to 140C at 4 torr. Seven hundred and ninety-nine parts of ethylenediamine were, thus, recovered thereby indicating that 2.7 moles thereof had reacted. The final yield in the vessel was, thus, six hundred and seventy-eight parts of product.
The entire batch of product was then diluted with four hundred and fifty-two parts of water to provide a 60%
~lZ;261~;
amine hydrochloride solution.
Having, thus, described the invention what is claimed is:
.~ ..
These amine containing ethers are, also, useful as cross-linking agents for synthetic resins such as ureas and urethanes.
Of course, the full gamut of utility is well documented.
It is to be appreciated that fundamental is the reaction of the amine and the halogen-containing polyether.
Heretofore, the art has only recorded such a reaction.
An alternate class of compounds known in the art are the polyoxyalkylene polyamines. Ordinarily, such compounds are prepared by the direct amination of a polyoxyalkylene glycol. Such compounds, of course, are, also, of wide-ranging utility.
Another method comprises reacting the hydroxyl groups of the glycol with acrylonitrile to produce cyanoethyl ethers and hydrogenation of the nitrile groups to give amino groups.
However~ these methods provide only one amine function per 11;~2616 terminal hydroxyl group and do not pro~ide polyamines, as contemplated by the present invention.
The art is constantly striving to define new and economically attractive polyamine ethers and their attendant resultants. The present invention, as will subsequently be detailed, provides new polyamine ethers. Furthermore, these new polyamines incorporate therewithin the polyoxyalkylene moieties as well as moieties derived from an epihalohydrin.
STATEMENT OF RELEVANT ART
To the best of applicant's knowledge the most closely related art is found in:
U.S. Patent Nos. 3,607,792 2,537,726 2,601,597 2,898,349 2,174,762 SUMMARY OF THE INVENTION
In accordance with the present invention polyamine ethers are prepared by reacting an amine with a polyether derived from the reaction of a polyol having one to eight active hydrogen sites and is halogenated epoxide.
The amine may be either a monoamine or a polyamine.
Also, the amine may be primary, secondary or tertiary.
The polyol used herein is preferably a polyoxy-alkylene polyol having from one to eight hydroxyl groups.
The halogenated epoxide is, preferably, an epihalohydrin.
The products hereof are prepared by reacting the polyol and the epihalohydrin in the presence of a suitable catalyst for about 0.5 to five hours at a temperature ranging from about 30C to about 100C. Thereafter, the amine is reacted with the halohydrin ether at a temperature ranging l~ZZ616 from about 100C to about 150C for about one to five hours at a ratio of at least about two moles of amine per chlorine equivalent.
The products hereof, generally, correspond to the formula:
IRl CIH2Z OH
R~(CH2CH)n ( OCH2CH )m OCH2 2 ~X
wherein:
R is the residue of a hydroxyl compound having 1 to 8 hydroxyl groups:
Rl is H2, CH3 or C2H5;
Z is the residue of an amine selected from the group consisting of -NR2' in ~hich R'` is hydrogen or a 1 to 8 carbon alkyl group, an alkylene diamine or a polyalkylene polyamine;
n is a number ranging from about 1 to about 100;
m is a number ranging from about 1 to about 30;
X is an integer ranging from 1 to 8, and wherein at least one R" is a 1 to 8 carbon alkyl group when Z is NR3'.
For a more complete understanding of the present invention reference is made to the following detailed descrip-tion and accompanying examples.
DESCRIPTION OF TH~ PREFERRED EMBODIMENT
In accordance with the present invention there is provided polyamine ethers represented by the formula:
~ OCH2 H )n ( OcH2cH-t-ocH2cHcH2z?x wherein:
R is the residue of a hydroxyl containing compound having 1 to 8 hydroxyl groups;
Rl is either H, CH3 or C2H5;
Z is the residue of an amine selected from the group consisting of -NR2' in which R" is hydrogen or a Cl to llZZ616 C8 alkyl group, alkylene diamine or polyalkylenepolyamine;
n is a number ranging from about 1 to about 100;
m is a number ranging from about 1 to about 30;
X is an integer ranging from 1 to 8, and when Z is -NR3' at least one R" is a 1 to 8 carbon alkyl group.
The ethers hereof are prepared by reacting (1) a polyol wlth a halogenated epoxide and thereafter (2) reacting the product of a (1) with an amine. More specifically, the present ethers are prepared from (1) a polyol having from one to eight hydroxyl groups and an epihalohydrin to form an ether and (2) reacting the ether with an amine to replace the available halogen atom.
Suitable polyols contemplated for use herein are polyoxyalkylated derivatives of hydroxyl compounds having from one to eight hydroxyl groups. Suitable hydroxyl compounds include, for example, alkanols, such as methanol, ethanol, - propanol, butanol and so forth, as well as mixtures thereof.
Representative polyhydroxy compounds include ethylene glycol, propylene glycol, butylene glycol, glycerol, diglycerol, triglycerol, higher polyglycerols, pentaerythritols, di-and tri-methylolpropane, di- and tri-methyloebutane, sucrose, erythritol, sorbitol, mannitol, dextrose and so forth as well as mixtures thereof.
Suitable alkylene oxides are ethylene oxide, propylene oxide, butylene oxides, as well as mixtures thereof.
The adducts are prepared by the reaction of the selected hydroxyl compound and the alkylene oxide under suit-able oxyalkylation conditions.
In addition to the above enumerated hydroxyl compounds it is to be understood that other polyhydroxy compounds can be used herein. Such polyhydroxyl compounds, which are used to form oxyalkylated derivative thereof are, for example, ~. . .
l~LZZ616 aminohydroxy compounds, cyclic alcoholic compounds, such as 1, 4- dihydroxy cyclohexane; aromatic compounds, such as dimethylolbenzene, phenol, hydroquinone, resorcinol and the like, as well as mixtures thereof.
In practicing the present invention the preferred polyol comprises a propylene oxide adduct of propylene glycol.
The halogenated epoxides utilized herein, are epihalohydrins corresponding to the formula:
CH ~ CH2 - CH2X
wherein X is halogen. In practicing the present invention, the preferred epihalohydrin is epichlorohydrin.
According to the first step of the process used herein, the polyol and the epihalohydrin are reacted together to form the adduct thereof. Generally, the reaction is carried out at a temperature ranging from at 30C to about 100C and, preferably, from about 50C to about 80C. The reaction is usually carried out for a period ranging from about 0.5 to five hours, and, preferably, one to three hours.
The reaction is carried out in the presence of a catalyst. Suitable catalysts include those enumerated in U.S. Patent No. 3,496,120. Exemplifying such as catalysts are the Friedel-Crafts type, such as AlC13, BF3, ZnC12, FeC13 etherates; acid catalysts, such as HF, H2SO4, H3PO4 and the like. The preferred catalyst is borontrifluoride which is conventionally deployed in the form of an etherate. Generally, about 0.1 to five parts of catalyst, per hundred parts, by weight, of polyol are used.
The so-produced adduct is, then, reacted with an amine to define the present products. As noted, hereinabove, the amine may be a mono- or polyamine of either primary, secondary or tertiary functionality. Representative of the ~ ,.~
~ -6-6it;
amines which can be used herein are, preferably, alkyl and alkylene amines which are optimally, saturated compounds containing no double bonds. Also, N-alkyl polyamines, N, N -dialkyl polyamines, etc. can be used herein, but are not preferred. Other types of amines which may be used herein are found in U.S. Patent Nos. 2,644,670 and 3,152,188.
In practicing the present invention the preferred amine reactants are primary amines. Thus, monoalkyl amines, alkylenepolyamines, polyalkylenepolyamines, cyclic amines and the like can be used herein. Representative monoalkyl amines include methylamine, ethyl amine, propylamine, i-propyl-amine, n-propylamine,-n-butylamine, i-butylamine, t-butylamine and so forth. Representative alkylene polyamines include ethylenediamine, propylenediamine, butylenediamine, and so forth. Suitable polyalkylenepolyamines include triaminobutane, diethylene triamine, dipropylenetriamine, triethylenetetra2mine, and so forth. Suitable cyclic amines are represented by piperazine and the like. As noted above, if desired, secondary or tertiary amines can be used if quaternary ammonium salts are the desired end products.
In practicing the present invention, the preferred aminè is ethylenediamine.
In reacting the amine with the adduct, generally, in excess of three moles of amine per available halogen atom in the adduct is employed. Less than three moles of amine per available halogen atom can be used herein, if desired, by adoption of the method identified in copending. Patent Application Serial No. 319,246, entitled Process for Preparing PolyaIkylene Polyamine Polyethers~, and filed on evendate herewi~h.
The reaction normally proceeds at a temperature ranging from about 100C to about 150C, for a period ranging . ..
112Z61~i from about 0.5 hours to about twenty-four hours, depending on the nature of the amine reactant. Preferably, the reaction is carried out at a temperature ranging from about 115C to about 150C for a period ranging from about one to ten hours.
The products produced hereby are useful as inter-mediates for the preparation of retention aids, dry and wet strength paper additives, flocculants for ore beneficiation, and waste treatment. In addition the compounds hereof are useful as intermediates for the production of cationic and amphoteric surfactants; polyquaternary ammonium salts for ion exchange resins; water thickeners and drainage aids. Also, these compounds may be used as active-hydrogen compounds and as cross-linking agents used in the preparation of epoxy and urethane resins.
For a more complete understanding of the present invention reference is made to the following examples il-lustrating the principles of the present invention. In the examples, which are to be construed as illustrative, and not limitative of the invention, all parts are by weight absent contrary indications.
EXAMPLE
A. ADDUCT PREPARATION
Into a two-liter flask equipped with a stirrer, reflux condenser, addition funnel and a thermometer was added four hundred and thirty-five parts of a polyol comprising an oxypropylated propyleneglycol having a hydroxyl number of 258 and two and seven-tenths parts of boron trifluoride etherate, as a catalyst.
The polyol and catalyst were heated in the flask to 60C. One thousand three hundred and eighty-six parts of epichlorohydrin was then added to the flask, with stirring over a one hundred and sixty-five minute period, while main-ll;~Z~:16 taining the temperature between 58C to 68C. Since thereaction was exothermic a cooling bath was deployed to maintain the denoted temperature range in the flask. Also, during the last half of the eplchlorohydrin addltion, three additional one part additions of catalyst were made to sustain the reac-tion. After the addition was completed agitation was maintained for one and one-half hours to ensure complete reaction. There-after, the vessel was vacuum stripped at 120C at 4 torr and one hundred and twenty-one parts of strippings were recovered.
A yield of one thousand seven hundred and seven parts of a clear, brown viscous liquid was attained. Gas chromatographicanalysis of the strippings indicated eithty-three parts of epichlorohydrin. Thus, one thousand three hundred and three parts of epichlorohydrin were consumed. Hence, the adduct was an approximate fourteen mole adduct.
B. POLYAMINE SYNTHESIS
To a one liter reaction flask equipped with agitation means, reflux condenser, thermometer, addition funnel and heating means was charged six hundred parts of ethylene diamine.
The diamlne was heated to reflux (117C) and, then, two hundred and flfty parts of the product of A was then added thereto over an eighty minute period. The temperature in the v~ssel was controlled by refluxing at a final temperature of 127C.
After the addition was completed, excess ethylene-diamine was vacuum stripped off up to a temperature of 14BC
at three mls. of pressure thereby yielding three hundred and seventy-eight parts of polyether. Based upon the amount of ethylene diamine in the strippings, it was calculated that 2.3 moles of amine had reacted per available chlorine present in the adduct. The resulting polyamine product was a viscous fluid.
_g_ 6~
The product was, then, cooled at 120C and diluted with three hundred and fifteen parts of water to provide a 54.6% solution of amine hydrochloride useful for preparing a drainage aid for paper pulp.
EXAMPLE II
This example illustrates the utility of the poly-aminepolyethers hereof.
One hundred parts of the hydrochloride solution finally obtained in Example I was further diluted with ninety-seven parts of water and neutralized with twenty-three parts of a 50~ NaQA solution. The resulting solution was, thus, calculated to be a 20% polyamine solution. This polyamine solution was then charged to a reaction vessel equipped with agitation means and heating means.
To the polyamine solution was added, with stirring and at 100C, one hundred fifty-five and one-half parts of a 20% solution of a bischlorohydrin ether of a polyol to-provide a paper pulp drainage aid. The polyol was the same as that described in the above referred to copending application, a yield of three hundred seventy-four and one-half parts of drainage aid product was obtained. This product had a number 4 Ford cup vi~cosity of 39 seconds and a calculated nitrogen content of 2.2~. The product evidenced superior drainage aid properties when tested according to Canadian Freeness procedures.
The polyol reactant used herein was a 400 molecular weight polyoxyethylene glycol having an epichlorohydrin cap thereon.
EXAMPLE III
A. ADDUCT PREPARATION
Using apparatus equipped as in Example I, one thousand sixty-nine parts of a polyoxypropylene glycol having a hydroxyl number of 105 and four parts of boron trifluoride \ - --10 llZZ616 etherate was added to the flask. The flask was heated to 60C. Thereafter, nlne hundred and twenty-five parts of epichlorohydrin was added thereto in a one hundred and seventy minute period. The addition was conducted at a temperature ranging from 62C to 70C, at the 70% addition point and at the end of the addition additional two parts and one part, respectively, of the catalyst was added to the vessel.
After the addition was completed, the contents in the vessel were stirred for an additional one hour at 72C
to ensure complete reaction. Thereafter, the volatiles were vacuum stripped up to a temperature of 130C at 4 torr. One hundred and ninety-four parts of volatiles were recovered, after correction and analysis for epichlorohydrin in the volatiles it was determined that 7.9 moles of epichlorohydrin had reacted with the polyol.
B. POLYAMINE PREPARATION
To a two-liter reaction flask equipped with agitator means, reflux condenser, thermometer, addition funnel and heating means was added nine hundred and sixty parts (16 molesj of ethylenediamine. The diamine was heated to reflux (117C).
Thereafter~ five hundred and seventeen parts (4Cl equivalents) of the adduct of step A hereof was added thereto over a two hundred and ten minute period. During this time the temperature was raised to 124C and controlled thereat by reflux.
After the addition was completed, excess ethylene-diamine was stripped by vacuum stripping up to 140C at 4 torr. Seven hundred and ninety-nine parts of ethylenediamine were, thus, recovered thereby indicating that 2.7 moles thereof had reacted. The final yield in the vessel was, thus, six hundred and seventy-eight parts of product.
The entire batch of product was then diluted with four hundred and fifty-two parts of water to provide a 60%
~lZ;261~;
amine hydrochloride solution.
Having, thus, described the invention what is claimed is:
.~ ..
Claims (14)
1. A polyamine corresponding to the formula:
wherein:
R is the residue of a hydroxyl compound having 1 to 8 hydroxyl groups:
R1 is H, CH3 or C2H5;
Z is the residue of an amine selected from the group consisting of -NR? in which R" is hydrogen or C1 to C8 alkyl group, an alkylene diamine or a poly alkylene polyamine;
n is a number ranging from about 1 to about 100;
m is a number ranging from about 1 to about 30;
X is an integer ranging from 1 to 8, and wherein at least one R" is a C1 to C8 alkyl group when Z is NR3".
wherein:
R is the residue of a hydroxyl compound having 1 to 8 hydroxyl groups:
R1 is H, CH3 or C2H5;
Z is the residue of an amine selected from the group consisting of -NR? in which R" is hydrogen or C1 to C8 alkyl group, an alkylene diamine or a poly alkylene polyamine;
n is a number ranging from about 1 to about 100;
m is a number ranging from about 1 to about 30;
X is an integer ranging from 1 to 8, and wherein at least one R" is a C1 to C8 alkyl group when Z is NR3".
2. The polyamine of claim 1 wherein:
R is the residue of propylene glycol and R1 is CH3.
R is the residue of propylene glycol and R1 is CH3.
3. The polyamine of claim 1 wherein Z is the residue of ethylenediamine.
4. The polyamine of claim 1 wherein:
R is the residue of propylene glycol, R1 is CH3 and Z is the residue of ethylene diamine.
R is the residue of propylene glycol, R1 is CH3 and Z is the residue of ethylene diamine.
5. The polyamine of claim 1 wherein:
the polyamine comprises the reaction product of (a) an ether, prepared by reacting a polyol having from 1 to 8 hydroxyl groups and an epihalohydrin and (b) an amine.
the polyamine comprises the reaction product of (a) an ether, prepared by reacting a polyol having from 1 to 8 hydroxyl groups and an epihalohydrin and (b) an amine.
6. The polyamine of claim 5 wherein:
the polyol comprises a polyoxyalkylated derivative of a hydroxyl compound having from 1 to 8 hydroxyl groups.
the polyol comprises a polyoxyalkylated derivative of a hydroxyl compound having from 1 to 8 hydroxyl groups.
7. The polyamine of claim 6 wherein:
the polyol is oxyalkylated with either ethylene oxide, propylene oxide, a butylene oxide or mixtures thereof.
the polyol is oxyalkylated with either ethylene oxide, propylene oxide, a butylene oxide or mixtures thereof.
8. The polyamine of claim 5 wherein:
the epihalohydrin is epichlorohydrin.
the epihalohydrin is epichlorohydrin.
9. The polyamine of claim 5 wherein:
the amine is a primary amine selected from the group consisting of monoalkylamines, alkylenepolyamines, poly-alkylenepolyamines and cyclic amines.
the amine is a primary amine selected from the group consisting of monoalkylamines, alkylenepolyamines, poly-alkylenepolyamines and cyclic amines.
10. The polyamine of claim 9 wherein:
the amine is ethylene diamine.
the amine is ethylene diamine.
11. The polyamine of claim 5 wherein:
the reaction is carried out at a temperature ranging from about 100°C to about 150°C for about 0.5 to about twenty-four hours.
the reaction is carried out at a temperature ranging from about 100°C to about 150°C for about 0.5 to about twenty-four hours.
12. The polyamine of claim 5 wherein:
the amine is present in an amount of at least two moles thereof per available halogen atom in the ether.
the amine is present in an amount of at least two moles thereof per available halogen atom in the ether.
13. The polyamine of claim 12 wherein:
at least three moles of amine per available halogen atom is employed.
at least three moles of amine per available halogen atom is employed.
14. The polyamine of claim 5 wherein:
(a) the polyether comprises the reaction product of epichlorohydrin and a propylene oxide adduct of propylene glycol, and (b) the amine is ethylenediamine.
(a) the polyether comprises the reaction product of epichlorohydrin and a propylene oxide adduct of propylene glycol, and (b) the amine is ethylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA319,247A CA1122616A (en) | 1979-01-08 | 1979-01-08 | Polyalkylene polyamine ether derivatives of polyoxyalkylene compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA319,247A CA1122616A (en) | 1979-01-08 | 1979-01-08 | Polyalkylene polyamine ether derivatives of polyoxyalkylene compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1122616A true CA1122616A (en) | 1982-04-27 |
Family
ID=4113259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA319,247A Expired CA1122616A (en) | 1979-01-08 | 1979-01-08 | Polyalkylene polyamine ether derivatives of polyoxyalkylene compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1122616A (en) |
-
1979
- 1979-01-08 CA CA319,247A patent/CA1122616A/en not_active Expired
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