GB1579320A

GB1579320A - Surface active material

Info

Publication number: GB1579320A
Application number: GB4966675A
Authority: GB
Original assignee: NAT RES DEV; National Research Development Corp of India
Current assignee: NAT RES DEV; National Research Development Corp of India
Priority date: 1975-12-03
Filing date: 1975-12-03
Publication date: 1980-11-19

Description

(54) SURFACE ACTIVE MATERIAL (71) We, NATIONAL RESEARCH DEVELOPMENT CORPORATION, a British Corporation established by Statute, of Kingsgate House, 66--74 Victoria Street, London, S.W.1 do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: This invention relates to a surface active material which finds particular application as a catalyst in increasing the rate of reaction between reactants disposed in separate liquid phases.

It has long been recognised that processes in which reactants are disposed in separate liquid phases are undesirably slow and various proposals have been made for increasing the rate of reaction. For example, dipolar aprotic solvents such as dimethylformamide and dimethyl sulphoxide have been used to dissolve both reactants. This method of increasing the rate of reaction suffers from the disadvantage that it is generally necessary to separate solvent from the reaction product. It has also been proposed that phase transfer catalysts and alternatively crown ether catalysts be employed in a two phase system. In this case however separation of the catalyst from the reaction product may give rise to difficulty.

The use of cationic surfactants represents a further approach to the problem. Such surfactants form micelles which are capable of enhancing the rate of reaction between anions in an aqueous phase and neutral molecules in a less polar phase.

The latter approach suffers however from drawbacks in that reaction must be conducted in dilute aqueous solution and excess surfactant is often difficult to remove from the product on work-up.

A surface active material has now been devised which overcomes the above disadvantages.

According to the present invention, a surface active material comprises a polymeric support material to the polymer backbone of which quaternary ionic species are individually chemically linked by way of aliphatic hydrophobic chains of at least six atoms, the surface active material being substantially insoluble in water or organic solvents.

The polymer is normally of high molecular weight. Synthetic resin polymers such as polystyrene in both microporous and macroreticulai form have proved particularly suitable for catalytic applications and for such applications the surface active material is preferably present in particulate form, for example in the form of beads the mesh size of which conveniently iies in the range 40 to 200. The support material may be appreciably cross-linked to lower its solubility.

It will be appreciated that the support material must have sites to which the hydrophobic chain linking the material to the ionic species can be bound. Aromatic polymers such as polystyrene may be linked to ionic species by way of chains bound to the aromatic nuclei by for example of ester or peptide groups. Active materials comprising such groups may be prepared from polymers containing aminomethylated or chloromethylated aromatic nuclei by reaction thereof with compounds comprising ionic groups and at least six atoms in a chain terminated by an ester group or carboxylate or acyl halide.

The aliphatic hydrophobic chain by way of which the support is linked to the ionic species desirably consists of at least twelve atoms and preferably consists of carbon atoms. The chain is normally unbranched. This latter structure is believed to favour phase boundary conditions at an aqueous interface approximating to those existing at a micellular surface. It is also desirable that support be heavily substituted by chains carrying ionic groups so that the active material is optimally effective and so that micelle-like aggregation is facilitated. In this respect at least 30% and preferably at least 90% of the reactive sites, for example the aromatic nuclei, on the support are substituted The ionic species bound to the support normally possess ion exchange properties.

Cationic species such as the quaternary ionic groups trialkylammonium (-N+R3) and trialkylphosphonium (-P+R3) are of particular interest, especially for the catalysis of reactions which involve anion activation. It will be appreciated that the materials of the present invention also comprise counter ions such as chloride ions which complement the ionic species bound to the support. These materials usually swell when contacted with water.or organic solvents and in aqueous media counter-ion exchange is rapid.

As hereinbefore indicated the present materials find particular application in the catalysis of reactions in which the reactants are separately disposed in distinct liquid phases e.g. in aqueous and organic non polar media. Typically such reactions are nucleophilic substitutions in which an anionic species in an aqueous phase is reacted with a neutral species disposed in a relatively non-polar phase to effect reaction thereof. Examples of interest include the alkylation of oxygen bases, including phenoxides, aromatic and vinylic substitution, nucleophilic substitution on saturated halides and sulphonates by water-soluble anionic nucleophiles and the activation of hydroxide ion and hydroperoxide ion in non-aqueous media. The present method may, for example, find application in the production of 0-benzyl-2-naphthyl ether, in which the aqueous phase contains an alkali metal 2naphthoxide and the relatively non-polar phase comprises benzyl bromide.

In practice the present material is generally agitated with the multiphase liquid mixture so as to maintain the material at the interface between the phases. After completion of the reaction the catalyst may be separated from the reaction mixture by filtration, centrifugation or distillation of volatile products therefrom.

In addition to catalystic applications the present material is of interest for the extraction of hydrophobic and amphiphilic species from aqueous solutions as a method of water purification and also as a chromatographic material for use in binding hydrophobic molecules in high pressure liquid chromatography, for example.

The invention is illustrated by the following Examples.

EXAMPLE I (a) Preparation of Ji-carboxylundecyltri- methylammonium chloride (I) 11 -carboxylundecylammonium sulphate is prepared by hydrolysis of 2-azacyclotridecanone in 35% H2SO4. To a solution of the salt (40 gm) in methanol (400 ml) and water (5 ml) containing solid K2CO3 (91 gm) there is added methyl iodide (126 gm) and the mixture is refluxed for 2 hours then kept at room temperature overnight. The suspension is filtered, evaporated to dryness and the resulting white solid further dissolved in methanol, then passed through an ion-exchange column (Amberlite 402; chloride form, 250 gms) [Amberlite is a Registered Trade Mark] giving compound I (38 gms m.p. 228-90) on removal of methanol.

Analytically pure material is obtained by Soxhlet extraction with ether.

(b) Preparation of surface active material To the dried sodium salt of I (from 17.76 gms acid) there is added chloromethylated polystyrene (3.46 gms, 2% cross-linked, 200400 mesh, > 95% ring-substituted (hereinafter referred to as OP-CH2 Cl) and the mixture is stirred for 12 hours at 1000 in 300 mls dried dimethylformamide. The resin product is washed with warm NaCl solution, then water, methanol, acetone and dried in vacuo. Analysis shows > 95% reaction to form OP-CH2o2C(CH2)11 NMe3CL (8.3 gms).

EXAMPLE 2 To the para-nitrophenyl ester of I in dimethylformamide (4.5 mls, containing 2.7 mmoles of ester) there is added N-methyl (aminomethyl) polystyrene (0.331 gms, macrorecticular, 9000A pore-size, Amberlite XE-305, 49% ring-substituted (hereinafter referred to as 63)-CH2NHMe)). The mixture is stirred for 24 hours at room temperature and for 6 hours at 1000. The resin product is filtered, washed with Nail, then water, methanol and acetone.

A portion of the resin (0.450 gms) is dried in vacuo at 800, when analysis shows functionalisation of c. 85% of available sites as 63) -CH2N(Me)CO(CH2)11 N+Me3CV EXAMPLE 3 -CH2O2qCH2)11 NMe3CI This material is prepared by treatment of 12) -CH2 C1 with sodium salt of compound I in a similar manner to that described in Example 1.

EXAMPLE 4 -CH2O2C(CH2)5 C8CH2 Vs NMe3 C1 Compound II, 5 -carboxylpentyltrimethylammonium cloride, is prepared from 2azacycloheptanone (caprolactam) in a manner similar to that described in Example 1 for the preparation of compound I. The sodium salt of compound II is reacted with -CH2Cl in a similar manner to that described in Example 1 to produce the required material.

EXAMPLE 5 0P-CH2O2 C(CH2 )s NMe3 Cl This material is prepared from -CH2 Cl and the sodium salt of II in a manner similar to that described in Example 4.

EXAMPLE 6 Phenol alkylation To a solution of sodium 2-naphthoxide (0.050 gms, 0.3 mMoles) in water (1 ml) is added benzyl bromide (0.040 gms, 0.23 mMoles and resin-CH2O2C(CH2)11 NMe3Cl (0.50 gms, 0.12 mMole equivalents). The suspension is stirred for 5 hours at 200 and evaporated to dryness in vacuo. Examination of the residue by n.m.r. after removal of resin by filtration shows 90% 0-benzyl-2-naphthyl ether and 10% 1 -benzyl-2-naphthol. Control experiments in the absence of resin showed 15% 0-benzyl-2 naphthyl ether, 85% 1 -benzyl-2-naphthol. Con trol experiments in which water is replaced by dimethylformamide shows (in the absence of resin) 98% 0-benzyl-2-naphthyl ether.

EXAMPLE 7 Nucleophilic displacement To a mixture of l-bromooctane (0.7 mls, 0.8 gms) and aqueous sodium cyanide (2 mls of saturated solution) there is added resin 0)-CH2O2C(CH2)" NMe3Cr (0.20 gms, 0.5 mMole, 12 mole to based on halide). The mix ture is stirred for 10 hours at 1000, after which time the upper layer is essentially pure 1 cyanooctane. In the absence of resin no reaction occurs in this period.

EXAMPLE 8 When the procedure of Example 7 is repeated except that the resin -CH202C(CH2)11 NMe3Cl~ is replaced by -CH2O2C(CH2)11 NMe3 C1-, reaction is complete in 3 hours.

EXAMPLE 9 Adsorption ofsolutes from aqueous solution A solution of methyl orange (25 mls, 1.02 x 10-3 is stirred with resin P CH2O2C(CH2)11 NMe3 Cl (9.1 mgs, 22,up). Analysis of the ultra violet spectrum shows the concentration of methyl orange to be reduced to 4.9 x 10)-5 M.

From this and similar experiments a binding constant of > 104 M-l for resinldye interaction is obtained.

WHAT WE CLAIM IS: 1. A surface active material which comprises a polymeric support material to the polymer backbones of which quaternary ionic species are individually chemically linked by way of aliphatic hydrophobic chains of at least six atoms;the surface active material being substan tially insoluble in water or organic solvents.

2. A surface active material according to claim 1, in which the support material is a high molecular weight cross-linked polymer.

3. A surface active material according to any preceding claim, in which the support material is a synthetic resin.

4. A surface active material according to claim 3, in which the support material is poly styrene.

5. A surface active material according to any preceding claim, in which the chain is of at least twelve atoms.

6. A surface active material according to any preceding claim, in which the chain consists of carbon atoms.

7. A surface active material according to any preceding claim, in which the chain is linked to the polymer backbone by way of an ester group or a peptide group.

8. A surface active material according to any preceding claim, in which the chain is unbranched.

9. A surface active material according to any preceding claim, in which the chain is linked to the polymer backbone by way of an aromatic nucleus.

10. A surface active material according to any preceding claim, in which the ionic species are - trialkylammonium or trialkylphosphonium groups.

11. A surface active material as described in any one of Examples 1 to 5.

12. A process for the production of a surface active material according to claim 1, in which a polymer comprising chloromethylated aromatic nuclei is reacted with a compound comprising an ionic group linked to a carboxylate group by at least six atoms in an aliphatic hydrophobic chain.

13. A process for the production of a surface active material according to claim 1, in which a polymer comprising aminomethylated aromatic nuclei is reacted with a compound comprising an ionic group linked to an ester group by at least six atoms in an aliphatic hydrophobic chain.

14. A process for the production of a surface active material according to claim 1, in which a polymer comprising aminomethylated aromatic nuclei is reacted with a compound comprising an ionic group linked to an acyl halide group by at least six atoms in an aliphatic hydrophobic chain.

15. A process for the production of a surface active material substantially as described in any one of the Examples 1 to 5.

16. A surface active material when prepared by a process according to any of claims 12 to 15.

17. A chemical process in which the reaction mixture comprises distinct liquid phases in which the reactants are respectively disposed, the process being catalysed by the presence in the reaction mixture of a surface active material according to any of claims 1 to 11.

18. A process according to claim 17, which proceeds by nucleophilic substitution by an ionic species disposed in an aqueous phase of a neutral species disposed in a relatively non-polar phase.

19. A process according to claim 18 for the production of 0-benzyl-2-naphthyl ether in which the aqueous phase contains an alkali metal 2-naphthoxide and the relatively non-pola phase comprises benzyl bromide.

20. A water purification process in which a hydrophobic or amphiphilic species is extracted from an aqueous solution thereof by treatment of the solution with a surface active material according to any of claims 1 to 11.

22. A catalytic process substantially as de scribed in any one of Examples 6, 7 or 8.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims

**WARNING** start of CLMS field may overlap end of DESC **.

shows 90% 0-benzyl-2-naphthyl ether and 10% 1 -benzyl-2-naphthol. Control experiments in the absence of resin showed 15% 0-benzyl-2 naphthyl ether, 85% 1 -benzyl-2-naphthol. Con trol experiments in which water is replaced by dimethylformamide shows (in the absence of resin) 98% 0-benzyl-2-naphthyl ether.

EXAMPLE 7 Nucleophilic displacement To a mixture of l-bromooctane (0.7 mls, 0.8 gms) and aqueous sodium cyanide (2 mls of saturated solution) there is added resin 0)-CH2O2C(CH2)" NMe3Cr (0.20 gms, 0.5 mMole, 12 mole to based on halide). The mix ture is stirred for 10 hours at 1000, after which time the upper layer is essentially pure 1 cyanooctane. In the absence of resin no reaction occurs in this period.

EXAMPLE 8 When the procedure of Example 7 is repeated except that the resin -CH202C(CH2)11 NMe3Cl~ is replaced by -CH2O2C(CH2)11 NMe3 C1-, reaction is complete in 3 hours.

EXAMPLE 9 Adsorption ofsolutes from aqueous solution A solution of methyl orange (25 mls, 1.02 x 10-3 is stirred with resin P CH2O2C(CH2)11 NMe3 Cl (9.1 mgs, 22,up). Analysis of the ultra violet spectrum shows the concentration of methyl orange to be reduced to 4.9 x 10)-5 M.

From this and similar experiments a binding constant of > 104 M-l for resinldye interaction is obtained.

WHAT WE CLAIM IS:

1. A surface active material which comprises a polymeric support material to the polymer backbones of which quaternary ionic species are individually chemically linked by way of aliphatic hydrophobic chains of at least six atoms;the surface active material being substan tially insoluble in water or organic solvents.

2. A surface active material according to claim 1, in which the support material is a high molecular weight cross-linked polymer.

3. A surface active material according to any preceding claim, in which the support material is a synthetic resin.

4. A surface active material according to claim 3, in which the support material is poly styrene.

5. A surface active material according to any preceding claim, in which the chain is of at least twelve atoms.

6. A surface active material according to any preceding claim, in which the chain consists of carbon atoms.

7. A surface active material according to any preceding claim, in which the chain is linked to the polymer backbone by way of an ester group or a peptide group.

8. A surface active material according to any preceding claim, in which the chain is unbranched.

9. A surface active material according to any preceding claim, in which the chain is linked to the polymer backbone by way of an aromatic nucleus.

10. A surface active material according to any preceding claim, in which the ionic species are - trialkylammonium or trialkylphosphonium groups.

11. A surface active material as described in any one of Examples 1 to 5.

12. A process for the production of a surface active material according to claim 1, in which a polymer comprising chloromethylated aromatic nuclei is reacted with a compound comprising an ionic group linked to a carboxylate group by at least six atoms in an aliphatic hydrophobic chain.

13. A process for the production of a surface active material according to claim 1, in which a polymer comprising aminomethylated aromatic nuclei is reacted with a compound comprising an ionic group linked to an ester group by at least six atoms in an aliphatic hydrophobic chain.

14. A process for the production of a surface active material according to claim 1, in which a polymer comprising aminomethylated aromatic nuclei is reacted with a compound comprising an ionic group linked to an acyl halide group by at least six atoms in an aliphatic hydrophobic chain.

15. A process for the production of a surface active material substantially as described in any one of the Examples 1 to 5.

16. A surface active material when prepared by a process according to any of claims 12 to 15.

17. A chemical process in which the reaction mixture comprises distinct liquid phases in which the reactants are respectively disposed, the process being catalysed by the presence in the reaction mixture of a surface active material according to any of claims 1 to 11.

18. A process according to claim 17, which proceeds by nucleophilic substitution by an ionic species disposed in an aqueous phase of a neutral species disposed in a relatively non-polar phase.

19. A process according to claim 18 for the production of 0-benzyl-2-naphthyl ether in which the aqueous phase contains an alkali metal 2-naphthoxide and the relatively non-pola phase comprises benzyl bromide.

20. A water purification process in which a hydrophobic or amphiphilic species is extracted from an aqueous solution thereof by treatment of the solution with a surface active material according to any of claims 1 to 11.

22. A catalytic process substantially as de scribed in any one of Examples 6, 7 or 8.