MXPA99002572A - Polymeric material - Google Patents

Abstract

There is described a method of preparing a first polymeric compound which comprises providing a compound of general formula (I) or a salt thereof where A and B are the same or different and at least one comprises a relatively polar atom or group and R1 and R2 independently comprise relatively non-polar atoms or groups, in a solvent of a type in which ethene itself is generally insoluble and causing the groups C=C in said compound to react with one another to form a polymeric structure. The first polymeric compound may be reacted with a second compound, for example polyvinylalcohol, collagen or the like to produce a colloid or gel which may have applications in the treatment or burns or recovery of oils.

Description

POLYMERIC MATERIAL This invention relates to a polymeric material and particularly, although not exclusively, it relates to a polymeric material which at least is partially formed from a 1,2-substituted ethene compound, for example a substituted styrylpyridinium compound.

UK Patent No. GB 2 030 575 B (Science and Technology Agency) describes a photosensitive resin, which is prepared by reacting a styrylpyridinium salt, which has a formyl or acetal group in the styrylphenyl group with a polyvinyl alcohol or a partially saponified polyvinyl acetate. In the resin, the group -CH = CH- is photosensitive and, therefore, the resin can be used in, for example, stencil printing where it is found to exhibit high sensitivity.

The present invention is based on the discovery of surprising properties of the ethene compounds 1, 2-substituted of the type described, which allow polymeric materials to be prepared, which have several useful properties.

Ref. 029789 According to a first aspect of the present invention there is provided a method of preparing a first polymeric compound, which comprises providing a compound of the general formula R or a salt thereof, where A and B are the same or different and at least one comprises a relatively polar atom or group and R1 and R2 independently comprise relatively non-polar atoms or groups, in a solvent of a type in which ethene itself is generally insoluble and causes the C = C groups in the compound to react with each other to form a polymeric structure.

Preferably, R1 and R2 are independently selected from a hydrogen atom or an alkyl group, preferably unsubstituted, optionally substituted. Preferably, R1 and R2 represent the same atom or group. Preferably, R1 and R2 represent a hydrogen atom.

Preferably, the solvent is a polar solvent. Preferably the solvent is an aqueous solvent. More preferably, the solvent consists essentially of water.

Preferably, the compound of general formula I is provided in the solvent at a concentration to which the compound molecules are added. The aggregation of the compound of the general formula I can be shown or deduced from the results of various analyzes as described below and any one or more such analysis can be used. Preferably, the compound of the general formula I is provided in the solvent at or above a concentration suggested by the relevant vapor pressure measurements as it is an aggregation point of the compound.

It is believed that the molecules of compound I form aggregates or micelles in the solvent, with the C = C bonds aligned with each other, so that the molecules are effectively aligned substantially parallel to each other.

Preferably, the molecules are aligned with groups A and B adjacent to each other.

The compound of the general formula I can be provided in the solvent at a concentration of at least 0.5% by weight, preferably at least 1.0% by weight and, more preferably, at least 1.5% by weight.

The C = C groups in the compound are preferably reacted in a photochemical reaction. Preferably, the method comprises inducing a photochemical reaction, suitably using ultraviolet light. Preferably, light of up to 500 nm wavelength is used in the method.

Preferably A and B are independently selected from alkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aromatics, and optionally substituted heteroaromatics groups. Where group A or B has a cyclic structure, rings of 5 or, more preferably, six members are preferred.

More preferably, A and B are independently selected from optionally substituted aromatic and heteroaromatic groups, with 5 or, more preferably, six members, such groups are especially preferred. Preferred heteroatoms of the heteroaromatic groups include the nitrogen, oxygen and sulfur atoms, of which oxygen and especially nitrogen are preferred. Preferred heteroaromatic groups include only one heteroatom. Preferably, one or the heteroatom is placed further from the position of the heteroaromatic group to the C = C group. For example, where the heteroaromatic group comprises a six-membered ring, the heteroatom is preferably provided at position 4 relative to the position of the ring linkage with the C = C group.

Unless otherwise indicated, the substituted groups optionally described herein, for example groups A and B, may be substituted by halogen atoms, and alkyl, acyl, acetal, hemiacetal, acetalalkyloxy, hemiacetalalkyloxy, nitro, cyano, alkoxy, hydroxy, amine, alkylamino, sulfinyl, alkylsulfinyl, sulfonyl, alkylsulfonyl, sulfonate, amido, alkylamido, alkylcarbonyl, alkoxycarbonyl, halocarbonyl and haloalkyl optionally substituted. Preferably, optional substituents in an optionally substituted group can be provided up to 3, more preferably up to 1.

Unless otherwise indicated, an alkyl group may have up to 10, preferably up to 6, more preferably up to 4 carbon atoms, with methyl and ethyl groups which are especially preferred.

Preferably, A and B each represent polar atoms or groups. Preferably, A and B each represent optionally substituted aromatic and heteroaromatic groups, wherein the "p" orbital of the aromatic groups is aligned with those of the C = C group. Preferably, A and B represent different atoms or groups.

Preferably, one of the groups A and B includes an optional substituent, which includes a carbonyl or acetal group with a formyl group that is especially preferred. The other of groups A and B may include an optional substituent, which is an alkyl group, with a Cx alkyl group. not preferably substituted, optionally substituted, for example a methyl group, which is especially preferred.

Preferably, group A represents a substituted phenyl group, preferably at the 4-position relative to the C = C group, by a formyl group or a group of the general formula where X is an integer from 1 to 6 and each R3 is independently an alkyl or phenyl group or together they form an alkylene group.

Preferably, group B represents a group of the general formula III wherein R 4 represents a hydrogen atom or an alkyl or aralkyl group, R 5 represents a hydrogen atom or an alkyl group and X represents a strongly acidic ion.

Preferred compounds of general formula I for use according to the present invention include those referred to on page 3, line 8 through line 39 of GB 2 030 575 B and therefore the compounds are incorporated in this specification.

The compounds of the general formula I for use according to the present invention can be prepared as described in the GB 2 030 575 patent and also for this reason such preliminary methods are incorporated in this specification.

The invention extends to a first novel polymeric compound that can be prepared by a method according to the first aspect.

According to a second aspect of the present invention, there is provided a first novel polymeric compound having the formula where A, B, R1 and R2 are as described in any statement here and n is an integer.

According to a third aspect of the present invention, there is provided a method of preparing a formulation comprising providing a first polymeric compound according to the first or second aspects in a solvent together with a second polymeric compound and intimately mixing the compounds.

Preferably, the second polymeric compound includes one or more functional groups capable of reacting with the first polymeric compound, preferably in an acid catalyzed reaction. The reaction is preferably a condensation reaction. Preferably, the second polymeric compound includes a functional group selected from an alcohol, carboxylic acid, carboxylic acid derivative, for example an ester, and an amine group. The second preferred polymeric compounds include polyvinyl alcohol, polyvinyl acetate, polyalkylene glycols, for example polypropylene glycol, and collagen not preferably substituted, optionally substituted (and any component thereof).

Preferably, the second polymeric compound is a solid under ambient conditions. Preferably, the intimate mixing is carried out at an elevated temperature. Preferably, the mixing is carried out in the same solvent, in which the compound I is prepared. The mixture may further include polymeric compounds, which may be of the same type as the second polymeric compounds described above.

The ratio of% by weight of the first polymeric compound to% by weight of the second polymeric compound (or the sum of the% by weight of the second compound and any of the additional compounds) in the mixture is found to significantly influence the properties of the prepared formulation. The ratio of% by weight of the first polymeric compound to that second polymeric compound can be in the range of 0.01 to 100, preferably it is in the range of 0.05 to 50 and more preferably in the range of 0.3 to 20.

Preferably, the water is removed from the formulation to produce a solid material, for example in the form of a film.

According to a fourth aspect of the present invention, there is provided a formulation comprising a first polymeric compound according to the first or second aspects and a second polymeric compound as described in the third aspect.

Preferably, the formulation is provided in a solid form.

According to a fifth aspect of the present invention, there is provided a method of preparing a material, for example a colloid or gel comprising providing a mixture prepared in the third aspect or a mixture according to the fourth aspect in a solvent and causing that the first or second polymeric compounds react with each other.

The reaction can be catalyzed by acid and, therefore, the method can include the step of providing an acid in the mixture. It is found that the concentration of acid used affects the proportion of the colloid / gel production. Preferably, at least 0.05% by weight, more preferably at least 0.05% by weight, is used, more preferably at minus 1% of an acid. Any acid can be used if it is organic or inorganic. Preferred acids include paratoluenesulfonic acid, hydrochloric acid, phosphoric acid, sulfonic acid and naphthalene sulfuric acids.

The concentration of the mixture used affects whether a colloid or gel is formed. Wherein% by weight of a solid formulation of the first and second polymeric compound is less than about 2% by weight, a colloidal viscoelastic solution is formed. On the other hand, a gel can be formed, wherein the concentration is greater than about 2% by weight.

A further active ingredient can be incorporated into the colloid or gel prepared as described in the fifth aspect, suitably by addition of the active ingredient prior to the reaction of the first and second polymeric compounds. Preferred active ingredients include the antibacterial agents, for example a mixture of iodine / iodide, cetyltrimethylammonium bromide and neomycin sulfate. The sheet materials can be prepared by incorporating active ingredients and since it is understood that the preparations prepared as described herein are biocompatible, the sheet materials can be used in the treatment of combustions.

It has been observed that if the oil (or the like) is contacted with the reaction mixture of the fifth aspect, up to 50% by weight of oil can be emulsified by the mixture and that the resulting gel keeps the oil in a solid matrix. . Accordingly, in a sixth aspect, the invention provides a method of collection and / or isolation and / or emulsification of oil (or the like), which comprises contacting oil (or the like) with a reaction mixture in accordance to the fifth aspect, so that oil (or the like) becomes incorporated into a material, for example a gel, which is formed.

The invention extends to a colloid or gel that can be prepared by the method of the fifth aspect.

According to a seventh aspect, a third novel polymeric material is provided, which comprises the reaction product of a compound of the general formula IV with a second polymeric material as described herein.

Any feature of any aspect of any invention or example described herein may be combined with any feature of any aspect of any other invention or example described herein.

The specific embodiments of the invention will now be described, by way of example, with reference to the appended figures, wherein: Figure 1 is a graph showing the vapor pressure measurements in aqueous methosulfonate solutions of 4- (4-formylphenylethenyl) -1-methylpyridinium (SbQ) at 37 ° C as a function of concentration; Figure 2 is a representation of the minimized predicted energy structure of four molecules of SbQ in water, - Figure 3 is a graph showing the surface tension measurements of the SbQ solutions, at 25 ° C, as a function of the concentration; Figure 4 is a graph showing the molar conductance values of the SbQ solutions, at 25 ° C, as a function of the concentration; Figure 5 is a graph showing the values of the apparent molar volume of SbQ, at 25 ° C, as a function of concentration; Figure 6 is a graph of the Rayleigh scattering at 90 ° C of the SbQ solutions, at 25 ° C, as a function of the concentration; Figure 7 is a graph showing the heats of dilution of the SbQ solutions, at 25 ° C, as a function of concentration.

Physico-chemical studies with methosulfonate and 4- (4-formylphenylethenyl) -1-methylpyridinium (sbO).

Studies Several physicochemical studies were attempted on a sample of purified SbQ in an aqueous solution, as follows: i. Surface tension measurements - made using a procedure to measure the voltage drop profile. ii. Steam pressure measurements - made using a vapor pressure osmometer standardized by solutions of Analar NaCl. iii. An analysis of the structure energy of the SbQ molecule, minimized in water - made using a Hyperchem molecular modeling package (Trade Mark) based on the calculations of the MM + force field. iv. Conductivity measurements - made using an automatic measurement bridge model B905 Wayne Kerr. v. Measurements of density - made as described in Eur. Polym. J., 1987, 23, 711 to provide apparent molar volume values. saw. Light scattering measurements - made using a Sofica model 42000 photonometer modified to use a HeNe lmW Unifase laser, operating at 543 nm. vii. Measurements of the heats of dilution - made using an LKB Flow Microcalorimeter model 2107-121 / 127.

Results In relation to Figure 1, the ratio? T / C represents the difference in temperature between the reference test of the solvent and the test of the solution at a concentration C in g / kg. The graph shows two linear regions, both with good correlation coefficients of 0.996 and 0.998 respectively, which intersect at a concentration value of 1.25% weight / weight. The intersection of the low range of solution concentrations is used in the usual way to produce a value for the average molar mass number for the SbQ of 341, close to the expected value of 335. The difference in slope at the higher concentrations suggests that, above the concentration of 1.25% weight / weight, there has been a certain form of aggregation of SbQ molecules.The analysis using the Hyperchem package predicts a very flat structure. Such a structure for the molecule easily takes into account the possibility of superposition of the molecules with the hydrophobic regions on top of each other and with the alternative aldehyde and -N-CH3 groups, to produce an aggregate, sample energy minimized in water, for four SbQ molecules, in Figure 2.

Taking the difference between the intersections in Figure 1 for the two concentration regions as is appropriate for the aggregate, this yields a molar mass for the SbQ aggregate of approximately 2800, which suggests that the aggregate number consists of approximately 8 units of monomer, with a critical concentration for the change of 1.25% weight / weight, or about 0.04M.

In relation to the measurements of the surface tension of Figure 3, the pattern seen is the classic one for the micellization of a surfactant with the rupture occurring at approximately 0.06M. This evidence therefore suggests that the SbQ aggregate is actually a micelle similar to a superimposed rod, with a critical micelle concentration value (eme) of 0.04 to 0.06M.

The molar conductance values of Figure 4 also show the expected pattern of a species of micelle formation, with the change of inclination to the eme that occurs at 0.04M.

In relation to Figure 5, the pronounced change of inclination seen at 0.04M means that the SbQ molecule adopts a more compact form greater than this concentration, exactly as it can be expected to happen when the aggregation forms a micelle.

In relation to Figure 6, the pronounced increase in dispersion, which occurs at concentrations close to 0.04M, indicates the appearance of larger particles, ie micelles.

In relation to Figure 7, the measurements of the heats of dilution also show a pronounced change of inclination, in this case to 0.035M, but in addition there has been an indication of a greater change in the solution state of the solute, from the monomer up to the micelle.

It should be noted from the above that the close correlation between the concentration dependence behavior of all the test measurements is a good confirmation of the existence of a monomer-micelle equilibrium in the aqueous solutions of SbQ. This behavior is used in the following examples.

Example 1 Preparation dej. poly (1,4-di (4- (N-tnenylpyridinyl) i-2,3-di (4- (1-formylphenyl) butylidene (Compound II shown below) An aqueous solution of greater than 1% by weight of SbQ is exposed to ultraviolet light. This results in a photochemical reaction between the carbon-carbon double bonds of the adjacent 4- (4-formyl-phenylethenyl) -1-methylpyridinium methosulfate molecules (I) in the aggregate, which produces a polymer, poly (1,4- di (4- (N-methylpyridinyl)) -2, 3-di (4- (1-formylphenylDbutilidene (II), as shown in the reaction scheme below.) It should be noted that the anions of compounds I and II have been omitted in the benefits of clarity.

UV 25 It is believed that the polymeric compound II is new.

Example 2 Preparation of the mixture using compound II A typical method for the preparation of a gel is summarized below. 13 g of 88% hydrolyzed polyvinyl alcohol of 300,000 molecular weight are dissolved in 87 g of a 2% w / w solution of compound II. The polyvinyl alcohol is added slowly with constant stirring to disperse the powder. The final solution is achieved by maintaining the solution at a temperature of 60 ° C for a period of 6 hours. The resulting polyvinyl alcohol / 1,4-di (4- (N-methylpyridinyl)) -2, 3-di (4- (1-formylphenyl) butylidene alcohol can be poured as a film onto a PTFE sheet and It is dried under vacuum.The solid mixture is unstable and can be stored in a desiccator until required.

Example _ Preparation of the gel The film described in Example 2 can be redissolved in water together with an acid, for example paratoluensulfuric acid. This causes a condensation reaction of aldol catalyzed by acid according to the scheme below.

+ The concentration of the film used affects the properties of the resulting gel. For example, rigid gels are formed at concentrations greater than 2.5% by weight. In addition, the gelation time is dependent on the concentration of the acid used. 0.1% by weight of acid gives a gelation time of 16 hours, while 1% by weight of acid gives a gelation time of 10 minutes.

Properties of sels prepared following the general procedures described here. 1. The gels formed using polyvinyl alcohol at 2.5 up 13% by weight do not melt or show any visual signal of phase changes with heating up to 100 CC; at higher temperatures the gel "carbonizes" but does not burn. 2. The gels are rigid and optically clear. 3. The time required for gelation can be controlled by varying the concentration of the acid used to catalyze the gelation reaction. The variable gelation time allows the melting of different forms of gel merely by pouring the reaction mixture in a mold. There is no significant volume decrease of the material in gel formation.

Gels are insoluble in all common organic solvents, although some gels increase their volume slightly. Gels are also insoluble in aqueous solutions.

Rigid gels can be produced using a mixture of 50% by weight collagen and 50% polyvinyl alcohol by weight instead of only polyvinyl alcohol, described in Examples 2 and 3. The gels produced show resistance to organic solvents and increase of limited volume in water.

After addition of the acid to catalyze the gelation reaction in Example 3, up to 50% by weight of oil can be emulsified by the reaction mixture. The resulting gel which forms, keeps the oil in a solid matrix.

The gels can be produced using solvent mixtures containing up to 50% by weight polypropylene glycol 400.

The behavior of the volume increase of the resulting gels in water is controlled by the amount of polypropylene glycol in the solvent.

At a concentration of less than 2% by weight, viscoelastic solutions are produced, wherein the viscosity is increased 10-fold when compared to the unreacted mixture. This behavior has a potential for use in the recovery of tertiary oil, where the reaction mixture can be pumped into cracks in an oil well and since the reaction continues, they increase the viscoelastic properties of the crosslinked polymer solution, so both open fissures are maintained.

All gels of Examples 1 to 3 and as described above can be rapidly destroyed by the process of dissociation of periodate from the polyvinyl alcohol chain. The solution produced has low viscosity and is easily washed constantly with water. In the case of the emulsified oil gel mentioned in 6 above, the dissociation of periodate results in the destruction of the gel, so that the oil can be recovered.

The reader's attention is directed to all the papers and documents, which are currently presented with or prior to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all papers and documents. Documents are incorporated here by reference.

All the features described in this specification (including any of the claims, summary and accompanying drawings), and / or all steps of any method or process so described, may be combined in any combination, except combinations where at least a part of the characteristics and / or steps are exclusive reciprocally.

Each feature described in this specification (including any of the claims, summary and attached drawings), may be replaced by alternative features that serve the same or similar equivalent purpose, unless expressly stated otherwise. Therefore, unless expressly stated otherwise, each characteristic described is a unique example of a generic series of equivalent and similar features.

The invention is not restricted to the details of the modality (s) mentioned above. The invention extends to any new, or any new combination, of the features described in this specification (including any of the claims, summary, appended drawings), or any new, or any new combination, of the steps of any method or process so described.

It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Having described the invention as above, the content of the following is claimed as property.

Claims (16)

1. A method of preparing a first polymeric compound, characterized in that it comprises providing a compound of the general formula or a salt thereof, where A and B are the same or different and at least one comprises a relatively polar atom or group and R1 and R2 independently comprise relatively non-polar atoms or groups, in a solvent of a type in which ethene itself is generally insoluble and causes the C = C groups in the compound to react with each other to form a polymeric structure.

2. A method according to claim 1, characterized in that R1 and R2 are independently selected from a hydrogen atom or an optionally substituted alkyl group.

3. A method according to claim 1 or claim 2, characterized in that the solvent is a polar solvent.

4. A method according to any preceding claim, characterized in that the compound of the general formula I is provided in the solvent at a concentration to which the molecules of the compound are added.

5. A method according to any preceding claim, characterized in that the C = C groups in the compound are reacted in a photochemical reaction.

6. A method of conformance to any preceding claim, characterized in that A and B are independently selected from alkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aromatics and heteroaromatics optionally substituted.

7. A method according to any preceding claim, characterized in that A and B each independently represent optionally substituted aromatic or heteroaromatic groups.

8. A first new polymeric compound that has the formula characterized in that A and B are the same or different and at least one comprises a relatively polar atom or group, R1 and R2 independently comprise relatively non-polar atoms or groups and n is an integer.

9. A method of preparing a formulation, characterized in that it comprises providing a first polymeric compound prepared in a method according to any of claims 1 to 7 or according to claim 8 in a solvent together with a second polymeric compound and intimately mixing the compounds

10. A method according to claim 9, characterized in that the second polymeric compound includes one or more functional groups capable of reacting with the first polymeric compound.

11. A method according to claim 9 or claim 10, characterized in that the second polymeric compound is selected from polyvinyl alcohol, polyvinyl acetate, polyalkylene glycols and optionally substituted collagen (and any component thereof).

12. A formulation, characterized in that it comprises a first polymeric compound prepared in a process according to any of claims 1 to 7 or as described in claim 8 and a second compound as described in any of claims 9 to 11.

13. A method of preparing a material, characterized in that the method comprises providing a mixture prepared as described in any of claims 9 to 11 or a formulation according to claim 12 in a solvent and causing the first and second compounds to react between yes.

14. A method according to claim 13, characterized in that an acid is provided.

15. A method of collection and / or isolation and / or emulsification of oil (or the like), characterized in that it comprises contacting the oil (or the like) with a reaction mixture according to claim 13 or claim 14, so that the oil (or similar) becomes incorporated into a material which is formed.

16. A material, characterized in that it can be prepared by a method according to any of claims 13 to 15.