Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/06—Organic solvent

Definitions

• This invention relates to a polymeric material and particularly, although not exclusively, relates to a polymeric material which is at least partially formed from a 1 , 2-substituted ethene compound, for example a substituted styrylpyridinium compound.
• UK Patent No. GB 2 030 575 B (Agency of Science and Technology) describes a photosensitive resin which is prepared by reacting a styryl pyridinium salt which possesses a formyl or acetal group on the styryl phenyl group with a polyvinyl alcohol or a partially saponified polyvinyl acetate.
• the present invention is based on the discovery of surprising properties of 1, 2-substituted ethene compounds of the type described which allow polymeric materials to be prepared which have various useful properties.
• a method of preparing a first polymeric compound which comprises providing a compound of general formula
• R 1 and R 2 are independently selected from a hydrogen atom or an optionally substituted, preferably unsubstituted, alkyl group.
• R 1 and R 2 represent the same atom or group.
• R 1 and R 2 represent a hydrogen atom.
• said solvent is a polar solvent.
• said solvent is an aqueous solvent. More preferably, said solvent consists essentially of water.
• said compound of general formula I is provided in said solvent at a concentration at which molecules of said compound aggregate. Aggregation of said compound of general formula I may be shown or inferred from the results of various analyses as hereinafter described and any one or more of such analyses may be used. Preferably, said compound of general formula I is provided in said solvent at or above a concentration suggested by relevant vapour pressure measurements as being a point of aggregation of the compound.
• the molecules align with groups A and B adjacent to one another.
• Said compound of general formula I may be provided in said solvent at a concentration of at least 0.5 wt%, preferably at least 1.0 wt% and, more preferably, at least 1.5 wt%.
• the method comprises inducing a photochemical reaction, suitably using ultraviolet light.
• light of up to 500 nm wavelength is used.
• a and B are independently selected from optionally-substituted alkyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aromatic and heteroaromatic groups. Where group A or B has a cyclic structure, five or, more preferably, six membered rings are preferred.
• a and B are independently selected from optionally substituted aromatic and heteroaromatic groups, with five or, more preferably, six-membered such groups being especially preferred.
• Preferred heteroato s of said heteroaromatic groups include nitrogen, oxygen and sulphur atoms of which oxygen and especially nitrogen, are preferred.
• Preferred heteroaromatic groups include only one heteroatom.
• optionally substituted groups described herein may be substituted by halogen atoms, and optionally substituted alkyl, acyl, acetal, hemiacetal, acetalalkyloxy, hemiacetalalkyloxy, nitro, cyano, alkoxy, hydroxy, amino, alkylamino, sulphinyl, alkylsulphinyl, sulphonyl, alkylsulphonyl, sulphonate, amido, alkylamido, alkylcarbonyl, alkoxycarbonyl, halocarbonyl and hal ⁇ alkyl groups.
• up to 3 more preferably up to 1 optional substituents may be provided on an optionally substituted group.
• an alkyl group may have up to 10, preferably up to 6, more preferably up to 4 carbon atoms, with methyl and ethyl groups being especially preferred.
• a and B each represent polar atoms or groups.
• a and B represent different atoms or groups.
• one of groups A and B includes an optional substituent which includes a carbonyl or acetal group with a for yl group being especially preferred.
• the other one of groups A and B may include an optional substituent which is an alkyl group, with an optionally substituted, preferably unsubstituted, C M alkyl group, for example a methyl group, being especially preferred.
• x is an integer from 1 to 6 and each R 3 is independently an alkyl or phenyl group or together form an alkalene group.
• group B represents a group of general formula
• R 4 represents a hydrogen atom or an alkyl or aralkyl group
• R 5 represents a hydrogen atom or an alkyl group
• 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 to line 39 of GB 2 030 575 B and said compounds are hereby incorporated into this specification.
• Compounds of general formula I for use according to the present invention may be prepared as described in GB 2 030 575 B and such preparatory methods are also hereby incorporated into this specification.
• the invention extends to a novel first polymeric compound preparable by a method according to said first aspect.
• a method of preparing a formulation comprising providing a first polymeric compound according to said first or second aspects in a solvent together with a second polymeric compound and intimately mixing the compounds .
• said second polymeric compound includes one or more functional groups capable of reacting with said first polymeric compound, preferably in an acid catalysed reaction. Said reaction is preferably a condensation reaction.
• said second polymeric compound includes a functional group selected from an alcohol, carboxylic acid, carboxylic acid derivative, for example an ester, and an amine group.
• Preferred second polymeric compounds include optionally substituted, preferably unsubs t i tu t ed , p o 1 y v i ny 1 a 1 c oho 1 , polyvinylacetate, polyalkylene glycols, for example polypropylene glycol, and collagen (and any component thereof) .
• said second polymeric compound is a solid under ambient conditions.
• said intimate mixing is carried out at an elevated temperature.
• mixing is carried out in the same solvent in which compound I is prepared.
• the mixture may include further polymeric compounds which may be the same type as said second polymeric compounds described above.
• the ratio of the wt% of said first polymeric compound to the wt% of said second polymeric compound (or the sum of the wt% of the second compound and any further compounds) in the mixture is found to influence significantly the properties of the formulation prepared.
• the ratio of the wt% of said first polymeric compound to that of said second polymeric compound may be in the range 0.01 to 100, is preferably in the range 0.05 to 50 and more preferably in the range 0.3 to 20.
• water is removed from said formulation to produce a solid material, for example in the form of a film.
• a formulation comprising a first polymeric compound according to said first or second aspects and a second polymeric compound as described in said third aspect.
• said formulation is provided in a solid form.
• a method of preparing a material for example a colloid or a gel comprising providing a mixture prepared in said third aspect or a mixture according to said fourth aspect in a solvent and causing the first and second polymeric compounds to react with one another.
• the reaction may be acid catalysed and, accordingly, the method may include the step of providing an acid in the mixture. It is found that the concentration of acid used affects the rate of colloid/gel production. Preferably, at least 0.05 wt%, more preferably at least 0.1% of an acid is used. Any acid may be used whether organic or inorganic. Preferred acids include paratoluene sulphonic acid, hydrochloric acid, phosphoric acid, sulphonic acid and napthalene sulphuric acids.
• the concentration of the mixture used affects whether a colloid or gel forms. Where the wt% of a said solid formulation of said first and second polymeric compound is less than about 2 wt%, a visco-elastic colloidal solution is formed. On the other hand, where the concentration is greater than about 2 wt%, a gel may be formed.
• a further active ingredient may be incorporated into the colloid or gel prepared as described in said fifth aspect, suitably by addition of said active ingredient prior to the reaction of the first and second polymeric compounds.
• Preferred active ingredients include antibacterial agents, for example an iodine/iodide mixture, cetyl trimethyl ammonium bromide and neomycin sulphate.
• Sheet materials may be prepared incorporating active ingredients and since it is understood that preparations prepared as described herein are biocompatible, the sheet materials may be used in burns treatment.
• the invention provides a method of collecting and/or isolating and/or emulsifying oil (or the like) which comprises contacting oil (or the like) with a reaction mixture according to said fifth aspect so that said oil (or the like) becomes incorporated into a material, for example a gel which is formed.
• the invention extends to a colloid or gel preparable by the method of the fifth aspect.
• a novel third polymeric material which comprises the reaction product of a compound of general formula IV with a second polymeric material as described herein.
• Figure 1 is a graph showing vapour pressure measurements on aqueous solutions of 4- (4- formylphenylethenyl) -1-methylpyridinium methosulphonate (SbQ) at 37°C as a function of concentration;
• Figure 2 is a representation of the predicted energy minimised structure of four SbQ molecules in water;
• Figure 3 is a graph showing surface tension measurements of SbQ solutions, at 25°C, as a function of concen ration
• Figure 4 is a graph showing molar conductance values of SbQ solutions, at 25°C, as a function of concentration
• Figure 5 is a graph showing apparent molar volume values of SbQ, at 25°C, as a function of concentration
• Figure 6 is a graph showing Rayleigh scattering at 90° of SbQ solutions, at 25°C, as a function of concentration
• Figure 7 is a graph showing heats of dilution of SbQ solutions, at 25°C, as a function of concentration.
• the ratio ⁇ t/C represents the difference in temperature between the solvent reference probe and the solution probe at a concentration C in g/kg.
• the plot shows two linear regions, both with good correlation coefficients of 0.996 and 0.998 respectively, intersecting at a concentration value of 1.25% w/w.
• the intercept of the low range of solution concentrations was utilised in the usual manner to -yield a value for the number average molar mass for SbQ of 341, close to the expected value of 335.
• the difference of slope at the higher concentrations suggests that, above the concentration of 1.25% w/w, some form of aggregation of SbQ molecules has occurred.
• the molar conductance values of Figure 4 also show the pattern expected of a icellar forming species, with the change of slope at the cmc occurring at 0.04M.
• the sharp change of slope seen at 0.04M means that the SbQ molecule adopts a more compact form above this concentration, exactly what might be expected to happen when aggregating to form a micelle.
• the heats of dilution measurements also show a sharp change of slope, in this case at 0.035M, yet again indicating a major change in the solution state of the solute, from monomer to micelle has occurred.
• Example 2 The film described in Example 2 may be re-dissolved in water together with an acid, for example paratoluene sulphuric acid. This causes an acid catalysed aldol condensation reaction according to the scheme below.
• an acid for example paratoluene sulphuric acid. This causes an acid catalysed aldol condensation reaction according to the scheme below.
• the concentration of film used affects the properties of the resultant gel. For example, rigid gels are formed at concentrations greater than 2.5 wt%.
• the gelling time is dependent on the concentration of acid used. 0.1 wt% acid gives a gelling time of 16 hours, whereas 1 wt% acid gives a gelling time of 10 minutes.
• the gels are rigid and optically clear.
• the time required for gelation can be controlled by varying the concentration of acid used to catalyse the gelling reaction.
• the variable gel time permits the casting of different shapes of gel merely by pouring the reaction mixture into a mould. There is no significant shrinkage of the material on gel formation.
• the gels are insoluble in all common organic solvents, although some gels swell slightly. The gels are also insoluble in aqueous solutions.
• Rigid gels can be produced using a mixture of 50 wt% collagen and 50 wt% poly(vinyl alcohol) instead of only poly(vinyl alcohol) described in Examples 2 and 3.
• the gels produced show resistance to organic solvents and limited swelling in water.
• Example 6 After addition of the acid to catalyse the gelling reaction in Example 3, up to 50 wt% oil may be emulsified by the reaction mixture. The resultant gel which is formed holds the oil in a solid matrix.
• Gels can be produced using solvent mixtures containing up to 50 wt% polypropylene glycol 400.
• the swelling behaviour of the resultant gels in water is controlled by the amount of polypropylene glycol in the solvent.

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
• Polymerisation Methods In General (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

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• 1996
  • 1996-09-18 GB GBGB9619419.6A patent/GB9619419D0/en active Pending
• 1997
  • 1997-09-16 BR BR9712059-6A patent/BR9712059A/pt not_active IP Right Cessation
  • 1997-09-16 NZ NZ335075A patent/NZ335075A/xx unknown
  • 1997-09-16 EP EP97919164A patent/EP0935622A1/en not_active Withdrawn
  • 1997-09-16 RU RU99107383/04A patent/RU2249603C2/ru not_active IP Right Cessation
  • 1997-09-16 AU AU43097/97A patent/AU734288C/en not_active Ceased
  • 1997-09-16 CA CA002266578A patent/CA2266578C/en not_active Expired - Fee Related
  • 1997-09-16 JP JP51439898A patent/JP4159609B2/ja not_active Expired - Fee Related
  • 1997-09-16 WO PCT/GB1997/002529 patent/WO1998012239A1/en not_active Ceased
  • 1997-09-16 CN CN97198022.5A patent/CN1217967C/zh not_active Expired - Fee Related
  • 1997-09-18 GB GB9719759A patent/GB2317895B/en not_active Expired - Fee Related
• 1999
  • 1999-03-16 NO NO19991276A patent/NO991276L/no not_active Application Discontinuation
• 2008
  • 2008-02-20 JP JP2008038750A patent/JP2008174756A/ja active Pending

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