GB2098601A

GB2098601A - Improvements in or relating to organic compounds

Info

Publication number: GB2098601A
Application number: GB8209278A
Authority: GB
Original assignee: Sandoz Products Ltd
Current assignee: Novartis Pharmaceuticals UK Ltd
Priority date: 1981-04-02
Filing date: 1982-03-30
Publication date: 1982-11-24
Also published as: GB2098601B

Abstract

. Polycationic compounds useful as flocculating agents and demulsifiers may be obtained by the reaction of a diepoxide of formula <IMAGE> in which each of R1 and R2 are selected from C1-5 alkyl and C2-5 hydroxyalkyl radicals Y is selected from C2-6 alkylene radicals, 2-hydroxy-1,3-propylene radicals, and the radicals -CH2CH2NHCONHCH2CH2- and -CH2CH2CH2NHCONHCH2CH2CH2- A<(-)> is an anion and x is an integer of from 0 to 7, with monofunctional and/or bifunctional amines.

Description

SPECIFICATION Improvements in or relating to organic compounds This invention relates to compounds containing multiple cationic nitrogen groups.

It is known from British Patent 1 21 3 745 to prepare bifunctional compounds of formula I in which Z is

each of R1 and R2 are selected from Cr~5 alkyl and C2#5 hydroxyalkyl radicals Y is selected from C2#6 alkylene radicals, 2-hydroxy-1 ,3-propylene radicals, and the radicals -CH2CH2NHCONHCH2CH2- and -CH2CH2CH2NHCONHCH2CH2CH2 A3 is an anion and x is an integer of from 0 to 7, provided that when x is greater than 1 each of the symbols Y need not necessarily have the same significance.

According to the above patent, compounds of formula I are used to crosslink polyamideamines by reaction with secondary amine groups in the polymer chain.

Ourcopending application No. 8011214 discloses the reaction of compounds of formula I in which Z is CH2Cl-CHOH- or CH2Br-CHOH- with mono- and difunctional amines to give linear products useful as flocculating and demulsifying agents.

It has now been found that such products may also be obtained by reaction of mono- and bifunctional amines with compounds of formula I, in which Z is an epoxy group.

The present invention provides a process for the preparation of compounds of formula II

in which Cp has the formula:

in which Rt, R2, Y and x are as defined above; B represents a group of formula III

in which the groups R', which may be the same or different, are selected from hydrogen, C,~20 alkyl, C2#2O alkenyl, C2-6 hydroxyalkyl, aralkyl and groups of formula IV

where each R5 independently is hydrogen or methyl and n is from 2 to 150, preferably 2 to 50, and D is C2-20 alkylene, a group of formula V

in which e is 1 to 5, d and f are independently 2 to 5 and R6 is hydrogen, C,~6 alkyl, C2#6 hydroxyalkyl, or C1#8-haloalkyI, or a group of formula #(CH2)g#P7#(CH2)h# where g and h are independently 0 to 3 and R7 is a 5- to 7-membered ring system which may be saturated or wholly or partially unsaturated and which may contain all carbon atoms or a mixture of carbon, oxygen and/or nitrogen atoms, or B represents a group of formula VI

in which D' together with the two nitrogen atoms represents a ring system comprising one or more 5to 7-membered rings, which may be saturated, unsaturated or aromatic and which may contain further nitrogen atoms, R' and d are as defined above, each p is independently 0 or 1 and q is O or 1;; each Z' independently, is

in which the groups R, which may be the same or different, are selected from hydrogen, C,~20 alkyl, C2#2o alkenyl, C2#e hydroxyalkyl, C3#5 cycloalkyl, phenyl, aralkyl, alkaryl and groups of formula IV above or two groups R, together with the nitrogen atom to which they are attached, form a saturated or unsaturated 5- to 7-membered ring which may contain one or more oxygen or one or more further nitrogen atoms and which may be alkyl substituted in positions not adjacent to the quaternary nitrogen atom or three groups R together with the nitrogen atom to which they are attached form a polycyclic ring system which may contain further oxygen or nitrogen atoms, or represent an aromatic ring system which may contain one or more further nitrogen atoms or a group of formula VIII

in which R' and D are as defined above; k is an integer, preferably from 0 to 10, more preferably from 0 to 5, particularly 0 or 1; with the proviso that when k is 0, each Z' is a group of formula VII or VIII As is an anion; and m is an integer equal to the number of cationic sites in the molecule, characterised in that a compound of formula I in which each Z is

is reacted with one or more amines and/or ammonia.

It will be understood that where a formula such as that of Cp above contains one or more cationic groups, it will be accompanied by a number of anions As equal to the number of cationic groups present. For the sake of simplicity, these anions will not be represented in the formulae.

When any symbol appears more than once in a formula, it may have the same or different significances unless stated otherwise. All groups capable of bearing substituents are unsubstituted unless otherwise stated.

The "coupling agent" I, as described in British Patent 1 213 745, is obtained by the reaction of a specific excess of epihalohydrin, preferably epichlorohydrin, with a monofunctional secondary amine for example dimethylamine or a bifunctional tertiary amine, for example tetramethyl ethylenediamine, or mixtures of these. In order to make the coupling agent with epoxy end groups, the free base form of the amine should be used.

By the term "monofunctional amine" is to be understood an amine having a single amino functional group, irrespective of whether this group is primary, secondary or tertiary; the terms "bifunctional", "polyfunctional" etc. are to be understood similarly as referring to the number of non quaternised amino groups present in the molecule which are capable of reacting with epoxy groups.

The coupling agent, having two reactive end groups, may then be reacted further with monofunctional or polyfunctional amines. Reaction with monofunctional tertiary amines will result in the formation of one quaternary ammonium group for each molecule of amine reacted, and these quaternary end groups will then be incapable of reacting further. Monofunctional tertiary amines may therefore be regarded as terminating groups, having the function of terminating the reaction sequence. Similarly, ammonia or monofunctional primary or secondary amines will give rise to cationic amine salt groups. On the other hand reaction with bifunctional amines may be controlled by varying the molar ratio of the reactants in such a way that either free coupling agent end groups or free amino groups are left at the ends of the molecule, and these groups are capable of further reaction.A bifunctional amine may thus give rise to a bridging group B capable of extending the size of the molecule, or it may also terminate the reaction sequence by giving an end group Z' of formula VIII, having free amino groups.

An amine is described herein as "bifunctional" if it has two reactive amino groups which readily react with coupling agent, even if it may in addition have one or more less reactive nitrogen atoms which will not react as readily. Thus for example diethylene triamine, H2N-C2H4-NH-C2H4-NH2, may be regarded as a bifunctional amine, although under more vigorous conditions it may act as a polyfunctional amine.

Reaction with tertiary amine groups requires the presence of a proton source. This may be provided by the tertiary amine being at least partially in acid addition salf form.

A preferred class of monofunctional amines are monofunctional tertiary amines of formula (P)3N in which all groups Pare other than hydrogen, preferably C,~20 alkyl or C2#6 hydroxyalkyl. A further preferred class are primary, secondary or tertiary amines having at least one C6#16 alkyl group.

Preferred tertiary amines are those in which either all three R groups are C2#4 hydroxyalkyl (particularly hydroxyethyl, or one R group is C8~,8 alkyl (preferably C10#14) and the remaining two R groups are C1#4 alkyl (preferably methyl) or C2#4 hydroxyalkyl (preferably hydroxyethyl).

Preferred primary and secondary amines are those in which the R groups which are other than hydrogen are C1#20 alkyl, C2#6 hydroxyalkyl, or benzyl. Particularly preferred primary and secondary amines are those having at least one C6#16 alkyl group, for example coconut or hardened tallow fatty acid amines.

Preferred groups B are of formula Ill in which each R' is independently hydrogen or methyl and D is D" where D" is C2--12 alkylene, preferably #2H4-, -(-cH2-)6- or -(#H2-)12-, or a group of formula V in which e is 1, d and f are independently 2 or 3 and R6 is hydrogen; or B is a group of formula Vl in which D' forms with the nitrogens a piperazine ring, each p=1, R' is H, d is 2 and q=0 or 1.

A further preferred class of groups B are those of formula Ill in which three groups R' are hydrogen and one group R' is C8~20 alkyl, preferably C11#15 alkyl, and D is D" as defined above.

Compounds II containing such bridging groups B are obtained by reaction of an excess of coupling agent I with the corresponding bifunctional amine.

According to the invention, by careful control of the reagents and their mole ratios at each step, as well as control of reaction conditions such as temperature and pH, a high degree of control over the structures of the products may be obtained.

Preferably, in the coupling agent of formula I, R, and R2 are methyl and, independently, x is O or 1 preferably 1 and Y is 2-hydroxy-1 ,3-propylene.

It will be appreciated that the compounds of formula II all contain multiple cationic sites and will therefore be associated with as many equivalents of anions as there are cationic sites. The nature of the anion is generally unimportant, and will for example normally be that derived from the epihalohydrin used to make the coupling agent, particularly Ciao. The anions may however be exchanged by conventional methods, and it may be desirable for some purposes to insert a specific anion at one or more sites.

If a polyvalent anion is present, for example SO?40, the symbol As is to be understood as referring to one equivalent of anion, for example 1/2 Soy4@.

It will be appreciated that the cationic groupings in the molecule may be amine salt groups or quaternary ammonium groups. By treatment with base amine salt groups will lose Hs and revert to secondary amine groups -NH- or tertiary amine groups -N P'- where R' is other than H. This will of course affect the acid-base properties and the water solubility of the product molecule, and will provide sites for further reaction with coupling agent if desired.

The properties of compounds of formula II will in general depend upon their chain length, the spacing of cationic groups along the chain, and the nature of the side groups which are present. For example while the compounds will normally be water-soluble, it is possible by incorporating a relatively high number of lipophilic groups to produce water-insoluble products.

Mixtures of compounds of formula II may be obtained by the use of mixtures of reagents at one or more steps of the reaction sequence, after the initial preparation of the coupling agent I.

The compounds of formula II are useful for example as flocculating agents and demulsifiers for the breaking of oil-in-water or water-in-oil emulsions.

The conditions employed for preparation of any adduct will depend both on the desired end products and the nature of the starting materials for each step of the particular reaction sequence planned. In the case of the more reactive amines, the reaction usually is exothermic even when the coupling agent is in aqueous solution, and one reagent will be added slowly to the other at a starting temperature such that the reaction exotherm will commence. The rate of addition of reagent is then used to control the reaction temperature in the manner usual in such cases with application of external cooling if necessary.Starting temperatures are usually between 0 to 1 000C, preferably 20~60 C, whilst the reaction tempeature upper limit is dictated by the boiling point of the amine or the solvent employed and the nature of the product desired. In some cases, the addition of water to the reaction mass or one or both of the reagents may be required, in others the coupling agent may itself have been prepared in aqueous solution and require no further water addition. Conversely, the preparation of certain materials may require their production by reaction in the absence of water. When it is desired to carry out reaction in the presence of only small quantities of water, it may be advantageous to use an epoxy-ended coupling agent prepared using the minimum amount of water.Alternatively organic solvents of suitable polarity may also be employed where required. Reaction will normally be carried out under mild acid conditions, or at least in the presence of a protonic solvent.

Amines of low water solubility or reactivity will usually require rather different reaction conditions and may require careful control of reaction pH. A polar solvent is usually employed to ensure that the reaction mixture is homogeneous, the two reactants normally but not necessarily being mixed together in the solvent at ambient temperature and then brought to reaction temperature. In such cases, the reaction temperatures will be higher than those employed for the more reactive amines, and a reaction exotherm is not usually detected. The nature of the solvent taken is a matter of choice dictated by the nature of the reactants used, the temperature of reaction and the final product properties required.

Clearly the boiling point of the solvent must be equal to or greater than the maximum temperature of reaction. Such reaction temperatures generally lie in the range 60-1 000C. Suitable solvents include the lower alcohols, particularly methanol, ethanol, n-propanol and isopropanol. The solvent may then be distilled off from the reaction mass before proceeding, or allowed to remain for subsequent steps or - even remain as a component of the final product formulation should it be so desired.

The progress of any reaction step may be monitored by following the disappearance of amine or coupling agent functional groups, or the formation of ions where this occurs during the reaction. The amount of unreacted material, as determined using conventional analytical procedures, may then be compared with the theoretical quantity expected when reaction of that stage is complete.

The following Examples, in which all parts are by weight and temperature are in degrees Centigrade, illustrate the invention:~ Example 1 a) Coupling agent with epoxy end groups To 50 parts (1 mole) of tetramethylethylene diamine are added dropwise 50 parts of water with cooling. To this mixture is added 79.8 parts (2 moles) of epichlorohydrin at such a rate that the exotherm is maintained between 35 40 with external cooling. After approximately 25% of the total addition of epichlorohydrin, the reaction mass clouds and becomes viscous. A further 80 parts of water are added to clear and dilute the reaction mass. Dropwise addition of epichlorohydrin is continued, taking a total of 2-3 hours. The reaction mass is then heated at 400 for 2 hours and 600 for 2 hours.

b) Termination of epoxy-ended coupling agent with primary amine To the coupling agent prepared as described in a) (1 mole) is added, slowly at 350, 181.9 parts (2 moles) of a fatty alkyl primary amine having the formula RfNH2 where Rf is a mixture of 70% C13 alkyl and 30% C15 alkyl groups. The temperature is maintained between 35 to 400 during addition, cooling as necessary, then increased gradually over 2 hours to 650. The reaction is terminated after heating at 650 for a further 2 hours.

Example 2 Termination of epoxy-ended coupling agent with tertiary amine To the coupling agent prepared as described in 1 a) above (1 mole) is added slowly, at 350, 235.2 parts (2 moles) of a 35% aqueous solution of trimethylamine hydrochloride. The temperature is maintained between 35 to 400 with cooling or heating as necessary for a further 2 hours.

Example 3 Termination with ammonia 58.2 Parts of the product from 1 a) are stirred at 500 and 10.2 parts (2 moles) of 33.5% aqueous ammonia is added over 1 hr. The mixture is stirred for a further hour at 500, then at 700 overnight.

Example 4 Termination with a long-chain fattv amine To 48.2 parts (2 moles) of a N,N-dimethyl long-chain alkylamine the alkyl group of which has the composition: C13 70%, C15 30% is added 10 parts (2 moles) of 36.5% aqueous hydrochloric acid, slowly and with efficient cooling. This mixture is then added over 2 hr to 58.2 parts (1 mole) of the product of Example 1 a), stirring at SOO.The reaction is continued for a further hour, then the temperature is raised over 2 hr to 850 and held there for 10 hr. after which the product is cooled.

Example 5 Bridging of epoxy-ended coupling agent with bifunctional amine To the coupling agent prepared as described in 1 a) above (2 moles) is added slowly, at 350, 60 parts (1 mole) of ethylene diamine. After addition the mixture is warmed to 650 over 2 hours and maintained at this temperature for a further 2 hours.

Example 6 Termination of bridged product with tertiary amine To the product of Example 5 is added slowly, at 350, 371 parts (2 moles) of triethanolamine hydrochloride in the form of a 40% aqueous solution. The mixture is warmed to 85--950 and held at this temperature for 4 hours.

The products of Examples 1 to 6 could be used in a concentration range of 500-5000 ppm to break oil-in-water emulsions such as waste rolling oils.

Claims

1. A process for the preparation of compounds of formula II

in which Cp has the formula:

in which each of R1 and R2 are selected from C1#5 alkyl and C2#5 hydroxyalkyl radicals Y is selected from C2#6 alkylene radicals, 2-hydroxy-1 3-propylene radicals, and the radicals -CH2CH2NHCONHCH2CH2- and -CH2CH2CH2NHCONHCH2CH2CH2- As is an anion and x is an integer of from 0 to 7, provided that when x is greater than 1 each of the symbols Y need not necessarily have the same significance;; B represents a group of formula Ill

in which the groups R', which may be the same or different, are selected from hydrogen, C1#20 alkyl, C2#20 alkenyl, C2#6 hydroxyalkyl, aralkyl and groups of formula IV

where each Rs independently is hydrogen or methyl and n is from 2 to 150, and D is C2#20 alkylene, a group of formula V

in which e is 1 to 5, d and f are independently 2 to 5 and R6 is hydrogen, C1#6 alkyl, C2#6 hydroxyalkyl, or C,~6 haloalkyl, or a group of formula~(CH2)g~R7~(CH2)h~ where g and h are independently 0 to 3 and R7 is a 5- to 7-membered ring system which may be saturated or wholly or partially unsaturated and which may contain all carbon atoms or a mixture of carbon, oxygen and/or nitrogen atoms, or B represents a group of formula Vl

in which D' together with the two nitrogen atoms represents a ring system comprising one or more 5to 7-membered rings, which may be saturated, unsaturated or aromatic and which may contain further nitrogen atoms, R' and d are as defined above, each p is independently 0 or 1 and q is O or 1; each Z'independently, is

in which the groups R, which may be the same or different, are selected from hydrogen, C1#20 alkyl, C2#20 alkenyl, C2#6 hydroxyalkyl, C3#8 cycloalkyl, phenyl, aralkyl, alkaryl and groups of formula IV above or two groups R, together with the nitrogen atom to which they are attached, form a saturated or unsaturated 5 to 7-membered ring which may contain one or more oxygen or one or more further nitrogen atoms and which may be alkyl substituted in positions not adjacent to the quaternary nitrogen atom or three groups R together with the nitrogen atom to which they are attached form a polycyclic ring system which may contain further oxygen or nitrogen atoms, or represent an aromatic ring system which may contain one or more further nitrogen atoms or a group of formula VIII

in which R' and D are as defined above; k is an integer, preferably from 0 to 10, more preferably from 0 to 5, particularly 0 or 1; with the proviso that when k is 0, each Z' is a group of formula VII or VIII As is an anion; and m is an integer equal to the number of cationic sites in the molecule, characterised in that a compound of formula I

in which R1, R2, Y, x and As are as defined above and each Z is

is reacted with one or more amines and/or ammonia.

2. A process as claimed in Claim 1 in which the compound of formula I is reacted with a monofunctional tertiary amine (P)3N in which either all three R groups are C2#4 hydroxyalkyl or one R group is C8#18 alkyl and the remaining two R groups are C1#4 hydroxyalkyl.

3. A process as claimed in Claim 2 in which in the amine (R)3 either all three R groups are hydroxyethyl or one R group is C10#14 alkyl and the remaining two R groups are selected from methyl and hydroxyethyl.

4. A process as claimed in Claim 1 in which the compound of formula I is reacted with a monofunctional primary or secondary amine (P)3N in which one or two groups R are hydrogen and the remaining groups R are selected from C1#20 alkyl, C2#6 hydroxyalkyl and benzyl.

5. A process as claimed in Claim 4 in which the amine (R)3N contains at least one C8~18 alkyl group.

6. A process as claimed in Claim 1 in which an excess of compound of formula I is reacted with a bifunctional amine.

7. A process as claimed in Claim 6 in which the bifunctional amine is of formula (P')2N-D"-N(P')2 in which either each R' is independently hydrogen or methyl or one group R' is C8#20 alkyl and the other three are hydrogen and D" is C2#12 alkylene or a group of formula -(-C H 2-)d-N H-(-CH 2#)f in which d and f, independently, are 2 or 3.

8. A process as claimed in Claim 6 in which the bifunctional amine is of formula

where q is O or 1.

9. A process as claimed in any one of Claims 6 to 8 in which the product of reacting an excess of compound of formula I with the bifunctional amine is further reacted with a monofunctional amine.

10. A process as claimed in Claim 9 in which the monofunctional amine is as defined in any one of Claims 2 to 5.

11. A process as claimed in any one of the preceding claims in which, in the compound of formula I, Rr and R2 are methyl, x is O or 1 and Y is 2-hydroxy-1 ,3-propylene.

1 2. A process for the preparation of a compound of formula II as described in any one of the examples.