CA2266578C - Polymeric material - Google Patents
Polymeric material Download PDFInfo
- Publication number
- CA2266578C CA2266578C CA002266578A CA2266578A CA2266578C CA 2266578 C CA2266578 C CA 2266578C CA 002266578 A CA002266578 A CA 002266578A CA 2266578 A CA2266578 A CA 2266578A CA 2266578 C CA2266578 C CA 2266578C
- Authority
- CA
- Canada
- Prior art keywords
- group
- compound
- polymeric
- groups
- polymeric compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
Landscapes
- 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)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 bums or recovery of oils.
Description
POLYMERIC MATERIAL
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. In the resin, the group -CH=CH- is photosensitive and, accordingly, the resin can be used in, for example, screen printing where it is found to exhibit high sensitivity.
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.
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 general formula A R' I
R'- B
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. In the resin, the group -CH=CH- is photosensitive and, accordingly, the resin can be used in, for example, screen printing where it is found to exhibit high sensitivity.
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.
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 general formula A R' I
R'- B
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 R' and R 2 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.
Preferably, R' and R2 are independently selected from a hydrogen atom or an optionally substituted, preferably unsubstituted, alkyl group. Preferably, R' and R2 represent the same atom or group. Preferably, R' and R2 represent a hydrogen atom.
Preferably, said solvent is a polar solvent.
Preferably said solvent is an aqueous solvent. More preferably, said solvent consists essentially of water.
Preferably, 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.
It is believed that said molecules of compound I form aggregates or micelles in the solvent, with the C=C bonds aligned with one another so that the molecules effectively align substantially parallel to one another.
Preferably, the molecules align with groups A and B
adjacent to one another.
Preferably, R' and R2 are independently selected from a hydrogen atom or an optionally substituted, preferably unsubstituted, alkyl group. Preferably, R' and R2 represent the same atom or group. Preferably, R' and R2 represent a hydrogen atom.
Preferably, said solvent is a polar solvent.
Preferably said solvent is an aqueous solvent. More preferably, said solvent consists essentially of water.
Preferably, 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.
It is believed that said molecules of compound I form aggregates or micelles in the solvent, with the C=C bonds aligned with one another so that the molecules effectively align substantially parallel to one another.
Preferably, 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 groups C=C in said compound are preferably caused to react in a photochemical reaction. Preferably, the method comprises inducing a photochemical reaction, suitably using ultraviolet light. Preferably, in the method, light of up to 500 nm wavelength is used.
Preferably, 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.
More preferably, 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 heteroatoms 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. Preferably, a or said heteroatom is positioned furthest away from the position of attachment of the heteroaromatic group to the group C=C. For example, where the heteroaromatic group comprises a six-membered ring, the heteroatom is preferably provided at the 4-position relative to the position of the bond of the ring with the group C=C.
Unless otherwise stated, optionally substituted groups described herein, for example groups A and B, 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 haloalkyl groups. Preferably, up to 3, more preferably up to 1 optional substituents may be provided on an optionally substituted group.
Unless otherwise stated, 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.
Preferably, A and B each represent polar atoms or groups. Preferably, A and B each represent optionally-substituted aromatic or heteroaromatic groups wherein the "p" orbital of the aromatic groups are aligned with those of the group C=C. Preferably, A and B represent different atoms or groups.
Preferably, one of groups A and B includes an optional substituent which includes a carbonyl or acetal group with a formyl 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,-4 alkyl group, for example a methyl group, being especially preferred.
The groups C=C in said compound are preferably caused to react in a photochemical reaction. Preferably, the method comprises inducing a photochemical reaction, suitably using ultraviolet light. Preferably, in the method, light of up to 500 nm wavelength is used.
Preferably, 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.
More preferably, 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 heteroatoms 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. Preferably, a or said heteroatom is positioned furthest away from the position of attachment of the heteroaromatic group to the group C=C. For example, where the heteroaromatic group comprises a six-membered ring, the heteroatom is preferably provided at the 4-position relative to the position of the bond of the ring with the group C=C.
Unless otherwise stated, optionally substituted groups described herein, for example groups A and B, 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 haloalkyl groups. Preferably, up to 3, more preferably up to 1 optional substituents may be provided on an optionally substituted group.
Unless otherwise stated, 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.
Preferably, A and B each represent polar atoms or groups. Preferably, A and B each represent optionally-substituted aromatic or heteroaromatic groups wherein the "p" orbital of the aromatic groups are aligned with those of the group C=C. Preferably, A and B represent different atoms or groups.
Preferably, one of groups A and B includes an optional substituent which includes a carbonyl or acetal group with a formyl 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,-4 alkyl group, for example a methyl group, being especially preferred.
Pref erably, group A represents a phenyl group substituted, preferably at the 4-position relative to the group C=C, by a formyl group or a group of general formula -O(CHZ)x--CH II
where x is an integer from 1 to 6 and each R3 is independently an alkyl or.phenyl group or together form an alkalene group.
Preferably, group B represents a group of general formula RS
N III
X' R
wherein R' represents a hydrogen_ atom or an alkyl or aralkyl group, RS 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 to line 39 of GB 2 030 575 B, Compounds of general formula I for use according to the present invention may be prepared as described in GB
2 030 575 B.
+'a The invention extends to a novel first polymeric compound preparable by a method according to said first aspect.
According to a second aspect of the present invention, there is provided a novel first polymeric compound having the formula A g ~`~ ~4 1V
~z F~ rt wherein A, B, R' and R'- are as described in any statement herein 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 said first or second aspects in a solvent together with a second polymeric compound and intimately mixing the compounds.
Preferably, 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. Preferably, 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 unsubstituted, polyvinylalcohol, polyvinylacetate, polyalkylene glycols, for example polypropylene glycol, and collagen (and any component thereof).
Preferably, said second polymeric compound is a solid under ambient conditions. Preferably, said intimate mixing is carried out at an elevated temperature. Preferably, 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.
Preferably, water is removed from said 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 said first or second aspects and a second polymeric compound as described in said third aspect.
where x is an integer from 1 to 6 and each R3 is independently an alkyl or.phenyl group or together form an alkalene group.
Preferably, group B represents a group of general formula RS
N III
X' R
wherein R' represents a hydrogen_ atom or an alkyl or aralkyl group, RS 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 to line 39 of GB 2 030 575 B, Compounds of general formula I for use according to the present invention may be prepared as described in GB
2 030 575 B.
+'a The invention extends to a novel first polymeric compound preparable by a method according to said first aspect.
According to a second aspect of the present invention, there is provided a novel first polymeric compound having the formula A g ~`~ ~4 1V
~z F~ rt wherein A, B, R' and R'- are as described in any statement herein 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 said first or second aspects in a solvent together with a second polymeric compound and intimately mixing the compounds.
Preferably, 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. Preferably, 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 unsubstituted, polyvinylalcohol, polyvinylacetate, polyalkylene glycols, for example polypropylene glycol, and collagen (and any component thereof).
Preferably, said second polymeric compound is a solid under ambient conditions. Preferably, said intimate mixing is carried out at an elevated temperature. Preferably, 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.
Preferably, water is removed from said 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 said first or second aspects and a second polymeric compound as described in said third aspect.
Preferably, said 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 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 anti-bacterial 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.
It has been noted that if oil (or the like) is contacted with the reaction mixture of said fifth aspect, up to 50 wt% of oil can be emulsified by the mixture and that the resultant gel holds the oil in a solid matrix.
Accordingly, in a sixth aspect, 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.
According to a seventh aspect, there is provided 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.
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.
Specific embodiments of the invention will now be described, by way of example, with reference to the accompanying figures, wherein:
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;
According to a fifth aspect of the present invention, there is provided 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 anti-bacterial 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.
It has been noted that if oil (or the like) is contacted with the reaction mixture of said fifth aspect, up to 50 wt% of oil can be emulsified by the mixture and that the resultant gel holds the oil in a solid matrix.
Accordingly, in a sixth aspect, 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.
According to a seventh aspect, there is provided 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.
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.
Specific embodiments of the invention will now be described, by way of example, with reference to the accompanying figures, wherein:
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 concentration;
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;
and Figure 7 is a graph showing heats of dilution of SbQ
solutions, at 25 C, as a function of concentration.
P h y s i c o- c h e m i c a 1 s t u d i e s o f 4-( 4-formylphenylethenyl}-1-methvlpyridinium methosulphonate (Sb4) Studies Various physico-chemical studies were undertaken on a sample of purified SbQ in an aqueous solution, as follows:
i. Surface tension measurements - made using a drop profile measurement procedure.
Figure 3 is a graph showing surface tension measurements of SbQ solutions, at 25 C, as a function of concentration;
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;
and Figure 7 is a graph showing heats of dilution of SbQ
solutions, at 25 C, as a function of concentration.
P h y s i c o- c h e m i c a 1 s t u d i e s o f 4-( 4-formylphenylethenyl}-1-methvlpyridinium methosulphonate (Sb4) Studies Various physico-chemical studies were undertaken on a sample of purified SbQ in an aqueous solution, as follows:
i. Surface tension measurements - made using a drop profile measurement procedure.
ii. Vapour pressure measurements - made using a Knauer vapour pressure osometer standardised against Analar NaCl solutions.
iii. An analysis of the energy of the structure of the SbQ
molecule, minimised in water - made using a Hyperchem (Trade Mark) molecular modelling package based on MM+
force field calculations iv. Conductivity measurements - made using a Wayne Kerr model B905 automatic measurement bridge.
v. Density measurements - made as described in Eur.
Polym.J., 1987, 23, 711 in order to provide apparent molar volume values.
vi. Light scattering measurements - made using a Sofica photogoniometer model 42000 modified to use a Uniphase 1mW HeNe laser, operating at 543 nm.
vii. Heats of dilution measurements - made using a LKB
Flow Microcalorimeter model 2107-121/127.
Results Referring to Figure 1, the ratio nt/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 analysis using the Hyperchem package predicts a very planar structure. Such a structure for the molecule easily allows for the possibility of stacking of the molecules with the hydrophobic regions one above the other and with the aldehyde and -N-CH3 groups alternating, to produce an aggregate, shown energy minimised in water, for four SbQ molecules, in Figure 2.
Taking the difference between the intercepts in Figure 1 for the two concentration regions as being due to the aggregate, this yields a molar mass for the SbQ
aggregate of about 2800, suggesting that the aggregate stack consists of about eight monomer units, with a critical concentration for the change of 1.25% w/w, or close to 0.04M.
Referring to the surface tension measurements of Figure 3, the pattern seen is the classic one for micellisation of a surfactant with the break occurring at about 0.06M. This evidence therefore suggests that the SbQ
aggregate is in fact a stacked rod-like micelle, with a critical micelle concentration (cmc) value of 0.04 to 0.06M.
The molar conductance values of Figure 4 also show the pattern expected of a micellar forming species, with the change of slope at the cmc occurring at 0.04M.
Referring to Figure 5, 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.
Referring to Figure 6, the sharp increase in scattering which occurs at concentrations approaching 0.04M indicates the appearance of larger particles i.e.
micelles.
Referring to Figure 7, 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.
It should be appreciated from the above that the close correlation between the concentration dependence behaviour of all the experimental measurements is good confirmation of the existence of a monomer-micelle equilibrium in the aqueous solutions of SbQ. This behaviour is utilised in the following examples.
Example 1 Preparation of poly(1,4-di(4-(N-m e t h y 1 p y r i d i n y 1)}- 2 3- d i( 4-( 1-formylphenyl)butylidene(Compound II shown below) An aqueous solution of greater than 1 wto SbQ was exposed to ultraviolet light. This results in a photochemical reaction between the carbon-carbon double bonds of adjacent 4-(4-formylphenylethenyl)-1-methylpyridinium methosulphate molecules (I) in the aggregate, producing a polymer, poly (1,4-di(4-(N-methylpyridinyl))-2,3-di(4-(1-formylphenyl)butylidene (II), as.shown in the reaction scheme below. It should be appreciated that the anions of compounds I and II have been omitted in the interests of clarity.
CHl HO CH, HO CI-I3 'N= ~ / ( N= / f N
\ \ \ \ \ -'.
N' I
> I %w/w Aqueous solution [JV irradiation CH3 fO ~H3 HO ~H3 N N
' Ho &3 HO Cx3 Ho It is believed that polymeric compound II is novel.
Example 2 Preparation of blend using combound II
A typical method for the preparation of a gel is outlined below.
13g of 88% hydrolysed poly(vinyl alcohol) of molecular weight 300,000 was dissolved in 87g of a 2% w/w solution of compound II. The poly(vinyl alcohol) was added slowly with constant stirring to disperse the powder.
Final dissolution was achieved by maintaining the solution at a temperature of 60 C for a period of 6 hours. The resultant poly(vinyl alcohol)/poly(1,4-di(4-(N-methylpyridinyl))-2,3-di(4-(l-formylphenyl)butylidene solution may be cast as a film on PTFE sheet and dried under vacuum. The solid blend is light stable and can be stored in a desiccator until required.
Example 3 Preparation of gel 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.
iii. An analysis of the energy of the structure of the SbQ
molecule, minimised in water - made using a Hyperchem (Trade Mark) molecular modelling package based on MM+
force field calculations iv. Conductivity measurements - made using a Wayne Kerr model B905 automatic measurement bridge.
v. Density measurements - made as described in Eur.
Polym.J., 1987, 23, 711 in order to provide apparent molar volume values.
vi. Light scattering measurements - made using a Sofica photogoniometer model 42000 modified to use a Uniphase 1mW HeNe laser, operating at 543 nm.
vii. Heats of dilution measurements - made using a LKB
Flow Microcalorimeter model 2107-121/127.
Results Referring to Figure 1, the ratio nt/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 analysis using the Hyperchem package predicts a very planar structure. Such a structure for the molecule easily allows for the possibility of stacking of the molecules with the hydrophobic regions one above the other and with the aldehyde and -N-CH3 groups alternating, to produce an aggregate, shown energy minimised in water, for four SbQ molecules, in Figure 2.
Taking the difference between the intercepts in Figure 1 for the two concentration regions as being due to the aggregate, this yields a molar mass for the SbQ
aggregate of about 2800, suggesting that the aggregate stack consists of about eight monomer units, with a critical concentration for the change of 1.25% w/w, or close to 0.04M.
Referring to the surface tension measurements of Figure 3, the pattern seen is the classic one for micellisation of a surfactant with the break occurring at about 0.06M. This evidence therefore suggests that the SbQ
aggregate is in fact a stacked rod-like micelle, with a critical micelle concentration (cmc) value of 0.04 to 0.06M.
The molar conductance values of Figure 4 also show the pattern expected of a micellar forming species, with the change of slope at the cmc occurring at 0.04M.
Referring to Figure 5, 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.
Referring to Figure 6, the sharp increase in scattering which occurs at concentrations approaching 0.04M indicates the appearance of larger particles i.e.
micelles.
Referring to Figure 7, 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.
It should be appreciated from the above that the close correlation between the concentration dependence behaviour of all the experimental measurements is good confirmation of the existence of a monomer-micelle equilibrium in the aqueous solutions of SbQ. This behaviour is utilised in the following examples.
Example 1 Preparation of poly(1,4-di(4-(N-m e t h y 1 p y r i d i n y 1)}- 2 3- d i( 4-( 1-formylphenyl)butylidene(Compound II shown below) An aqueous solution of greater than 1 wto SbQ was exposed to ultraviolet light. This results in a photochemical reaction between the carbon-carbon double bonds of adjacent 4-(4-formylphenylethenyl)-1-methylpyridinium methosulphate molecules (I) in the aggregate, producing a polymer, poly (1,4-di(4-(N-methylpyridinyl))-2,3-di(4-(1-formylphenyl)butylidene (II), as.shown in the reaction scheme below. It should be appreciated that the anions of compounds I and II have been omitted in the interests of clarity.
CHl HO CH, HO CI-I3 'N= ~ / ( N= / f N
\ \ \ \ \ -'.
N' I
> I %w/w Aqueous solution [JV irradiation CH3 fO ~H3 HO ~H3 N N
' Ho &3 HO Cx3 Ho It is believed that polymeric compound II is novel.
Example 2 Preparation of blend using combound II
A typical method for the preparation of a gel is outlined below.
13g of 88% hydrolysed poly(vinyl alcohol) of molecular weight 300,000 was dissolved in 87g of a 2% w/w solution of compound II. The poly(vinyl alcohol) was added slowly with constant stirring to disperse the powder.
Final dissolution was achieved by maintaining the solution at a temperature of 60 C for a period of 6 hours. The resultant poly(vinyl alcohol)/poly(1,4-di(4-(N-methylpyridinyl))-2,3-di(4-(l-formylphenyl)butylidene solution may be cast as a film on PTFE sheet and dried under vacuum. The solid blend is light stable and can be stored in a desiccator until required.
Example 3 Preparation of gel 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.
H H H H H H H
-}-C-H
=CH3 CHi--N
CH +
_'CH3 H+
H H H H H
`--CH3 CH3-N \ / -HO
CH
=CHz 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%. In addition, 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.
Properties of gels prepared following general procedures described herein 1. Gels formed using 2.5 to 13 wt% poly(vinyl alcohol) do not melt or show any visual sign of phase changes on heating to 100 C; at higher temperatures the gel "chars" 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 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.
4. The gels are insoluble in all common organic solvents, although some gels swell slightly. The gels are also insoluble in aqueous solutions.
5. 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.
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.
7. 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.
8. At concentration less than 2 wt% visco-elastic solutions are produced, wherein viscosity is enhanced ten-fold when compared with the unreacted mixture.
This behaviour has a potential for use in tertiary oil recovery, wherein the reacting mixture can be pumped into fissures in an oil well and as the reaction proceeds, the visco-elastic properties of the cross-linked polymer solution increase thus holding the fissures open.
All the gels of Examples 1 to 3 and as described above may be rapidly destroyed by the process of periodate splitting of the poly(vinyl alcohol) chain. The solution produced has low viscosity and is easily washed away with water. In the case of the emulsified oil gel mentioned in 6 above, periodate splitting results in gel destruction so that the oil can be recovered.
-}-C-H
=CH3 CHi--N
CH +
_'CH3 H+
H H H H H
`--CH3 CH3-N \ / -HO
CH
=CHz 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%. In addition, 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.
Properties of gels prepared following general procedures described herein 1. Gels formed using 2.5 to 13 wt% poly(vinyl alcohol) do not melt or show any visual sign of phase changes on heating to 100 C; at higher temperatures the gel "chars" 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 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.
4. The gels are insoluble in all common organic solvents, although some gels swell slightly. The gels are also insoluble in aqueous solutions.
5. 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.
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.
7. 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.
8. At concentration less than 2 wt% visco-elastic solutions are produced, wherein viscosity is enhanced ten-fold when compared with the unreacted mixture.
This behaviour has a potential for use in tertiary oil recovery, wherein the reacting mixture can be pumped into fissures in an oil well and as the reaction proceeds, the visco-elastic properties of the cross-linked polymer solution increase thus holding the fissures open.
All the gels of Examples 1 to 3 and as described above may be rapidly destroyed by the process of periodate splitting of the poly(vinyl alcohol) chain. The solution produced has low viscosity and is easily washed away with water. In the case of the emulsified oil gel mentioned in 6 above, periodate splitting results in gel destruction so that the oil can be recovered.
All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive.
Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
The invention is not restricted to the details of the foregoing embodiment(s) . The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
Each feature disclosed in this specification (including any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series of equivalent or similar features.
The invention is not restricted to the details of the foregoing embodiment(s) . The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
Claims (31)
1. A polymeric compound having a repeat unit of the formula wherein A is an optionally-substituted aromatic group, B is an optionally-substituted heteroaromatic group and at least one of A or B comprises a relatively polar atom or group and R1 and R2 independently comprise relatively non-polar atoms or groups.
2. A compound according to claim 1, wherein B includes a nitrogen heteroatom.
3. A compound according to claim 1 or claim 2, wherein one of groups A and B comprises a carbonyl or acetal group.
4. A compound according to claim 3, wherein said one of groups A and B comprises a formyl group.
5. A compound according to claim 3 or claim 4, wherein the other one of groups A and B comprises an alkyl group as a substituent.
6. A compound according to claim 5, wherein said alkyl group is an optionally-substituted C1-4 alkyl group.
7. A compound according to claim 5 or claim 6, wherein said alkyl group is a methyl group.
8. A compound according to any one of claims 1 to 7, wherein group A represents a phenyl group substituted by a formyl group or a group of general formula where x is an integer from 1 to 6 and each R3 is independently an alkyl or phenyl group or together form an alkalene group.
9. A compound according to any one of claims 1 to 8, wherein group B represents a group of general formula wherein R4 represents a hydrogen atom or an alkyl or aralkyl group, R5 represents a hydrogen atom or an alkyl group and X represents a ion that is a strong acid.
10. A compound according to any one of claims 1 to 9, wherein R1 and R2 are independently selected from a hydrogen atom or an optionally-substituted alkyl group.
11. A compound according to any one of claims 1 to 10, wherein R1 and R2 are independently selected from a hydrogen atom or an unsubstituted alkyl group.
12. A compound according to any one of claims 1 to 11, wherein R1 and R2 represent the same atom or group.
13. A compound according to any one of claims 1 to 12, wherein R1 and R2 represent a hydrogen atom.
14. A compound according to claim 1, wherein:
A represents B represents and R1 and R2 each represent hydrogen atoms.
A represents B represents and R1 and R2 each represent hydrogen atoms.
15. A method of preparing a polymeric compound which comprises providing a compound of general formula in an aqueous solvent and causing the group C=C in said compound to react with one another to form said polymeric compound, wherein A and B are the same or different, are selected from optionally-substituted aromatic and heteroaromatic groups and at least one comprises a relatively polar atom or group, R1 and R2 independently comprise relatively non-polar atoms or groups.
16. A method according to claim 15, wherein A, B, R1 and R2 are as described in any one of claims 1 to 14.
17. A method according to claim 15 or 16, wherein said compound of general formula I is provided in said solvent at a concentration at which molecules of said compound aggregate.
18. A method according to any one of claims 15 to 17, wherein the groups C=C in said compound are caused to react in a photochemical reaction.
19. A method of preparing a formulation comprising providing a first polymeric compound according to any one of claims 1 to 14 or a first polymeric compound prepared in a method according to any one of claims 15 to 18 in a solvent together with a second polymeric compound and intimately mixing the compounds.
20. A method according to claim 19, wherein said second polymeric compound includes one or more functional groups capable of reacting with said first polymeric compound.
21. A method according to claim 19 or claim 20, wherein said second polymeric compound includes a functional group selected from an alcohol, carboxylic acid, carboxylic acid derivative and an amine group.
22. A method according to any one of claims 19 to 21, wherein said second polymeric compound is selected from optionally-substituted polyvinylalcohol, polyvinylacetate, polyalkylene glycols and collagen.
23. A method according to any one of claims 19 to 22, wherein said second polymeric compound is polyvinylalcohol.
24. A formulation comprising a first polymeric compound according to any one of claims 1 to 13 or a first polymeric compound prepared in a method according to any one of claims 15 to 18 and a second polymeric compound as described in any one of claims 19 to 23.
25. A method of preparing a material, the method comprising providing a formulation as described in claim 24 in a solvent and causing the first and second compounds to react with one another.
26. A method according to claim 25, wherein an acid is provided.
27. A method according to claim 25 or claim 26, wherein said material prepared is a colloid or gel.
28. A method according to claim 27, wherein an active ingredient is incorporated into said colloid or gel.
29. A method according to claim 28, wherein said active ingredient is incorporated into said colloid or gel by addition of said active ingredient prior to reaction of said first and second polymeric compounds.
30. A method according to claim 28, wherein said active ingredient is an anti-bacterial agent.
31. The material prepared by the method according to any one of claims 25 to 30.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9619419.6 | 1996-09-18 | ||
| GBGB9619419.6A GB9619419D0 (en) | 1996-09-18 | 1996-09-18 | Polymeric material |
| PCT/GB1997/002529 WO1998012239A1 (en) | 1996-09-18 | 1997-09-16 | Polymeric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2266578A1 CA2266578A1 (en) | 1998-03-26 |
| CA2266578C true CA2266578C (en) | 2008-12-23 |
Family
ID=10800073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002266578A Expired - Fee Related CA2266578C (en) | 1996-09-18 | 1997-09-16 | Polymeric material |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0935622A1 (en) |
| JP (2) | JP4159609B2 (en) |
| CN (1) | CN1217967C (en) |
| AU (1) | AU734288C (en) |
| BR (1) | BR9712059A (en) |
| CA (1) | CA2266578C (en) |
| GB (2) | GB9619419D0 (en) |
| NO (1) | NO991276L (en) |
| NZ (1) | NZ335075A (en) |
| RU (1) | RU2249603C2 (en) |
| WO (1) | WO1998012239A1 (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0106195D0 (en) * | 2001-03-14 | 2001-05-02 | Corpro Systems Ltd | Apparatus and method |
| US7281579B2 (en) * | 2001-12-07 | 2007-10-16 | Aqueolic Canada Ltd. | Method for terminating or reducing water flow in a subterranean formation |
| NO315937B1 (en) * | 2001-12-10 | 2003-11-17 | Asbjoern Nes | Silage of grass balls without wrapping in plastic |
| GB0207376D0 (en) * | 2002-03-28 | 2002-05-08 | Advanced Gel Technology Ltd | Recovering materials |
| US7651981B2 (en) | 2002-03-28 | 2010-01-26 | Advanced Gel Technology Limited | Recovering materials |
| GB0212528D0 (en) * | 2002-05-31 | 2002-07-10 | Advanced Gel Technology Ltd | Dispersion |
| GB0225761D0 (en) * | 2002-11-05 | 2002-12-11 | Univ Bradford | Polymeric materials |
| GB0306333D0 (en) | 2003-03-20 | 2003-04-23 | Advanced Gel Technology Ltd | Restricting fluid passage and novel materials therefor |
| GB0312781D0 (en) | 2003-06-04 | 2003-07-09 | Ythan Environmental Services L | Method |
| GB0323065D0 (en) * | 2003-10-02 | 2003-11-05 | Advanced Gel Technology Ltd | Fracturing of subterranean formations |
| GB0323064D0 (en) * | 2003-10-02 | 2003-11-05 | Advanced Gel Technology Ltd | Cleaning contaminated materials |
| GB0323067D0 (en) * | 2003-10-02 | 2003-11-05 | Advanced Gel Technology Ltd | Viscous fluids |
| AU2004284273B2 (en) * | 2003-10-02 | 2010-08-26 | Oilflow Solutions Holdings Limited | Method for reducing the viscosity of viscous fluids |
| GB2408330B (en) * | 2003-11-22 | 2008-12-03 | Advanced Gel Technology Ltd | Polymeric materials comprising pH indicators for use in wound dressings |
| GB0408145D0 (en) * | 2004-04-13 | 2004-05-19 | Aubin Ltd | Crude oil mobility |
| GB0410961D0 (en) | 2004-05-17 | 2004-06-16 | Caltec Ltd | A separation system for handling and boosting the production of heavy oil |
| GB0609778D0 (en) * | 2006-05-17 | 2006-06-28 | Agt Sciences Ltd | Delivery means |
| GB0711635D0 (en) | 2007-06-15 | 2007-07-25 | Proflux Systems Llp | Hydrocarbons |
| US7832478B2 (en) | 2007-11-07 | 2010-11-16 | Schlumberger Technology Corporation | Methods for manipulation of air flow into aquifers |
| GB0918051D0 (en) | 2009-10-15 | 2009-12-02 | Oilflow Solutions Holdings Ltd | Hydrocarbons |
| GB201113229D0 (en) | 2011-08-01 | 2011-09-14 | Oilflow Solutions Holdings Ltd | Recovery of oil |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3658771A (en) * | 1969-01-14 | 1972-04-25 | Dow Chemical Co | Preparing ammonium polyacrylates |
| US4039542A (en) * | 1974-05-06 | 1977-08-02 | American Cyanamid Company | Unsaturated pyrimidine |
| US4272620A (en) * | 1978-08-09 | 1981-06-09 | Agency Of Industrial Science And Technology | Polyvinyl alcohol-styrylpyridinium photosensitive resins and method for manufacture thereof |
| US4709767A (en) * | 1986-01-06 | 1987-12-01 | American Colloid Company | Production process for manufacturing low molecular weight water soluble acrylic polymers as drilling fluid additives |
| JPS62262457A (en) * | 1986-05-09 | 1987-11-14 | Nippon Oil & Fats Co Ltd | High-molecular lb film electric element |
| CA2014538A1 (en) * | 1989-04-15 | 1990-10-15 | Yoshitaka Okude | Aqueous resin composition |
| US5258473A (en) * | 1989-11-20 | 1993-11-02 | Basf Aktiengesellschaft | Preparation of finely divided, water-soluble polymers |
| JP2723200B2 (en) * | 1992-09-07 | 1998-03-09 | 均 笠井 | Manufacturing method of organic microcrystal for nonlinear optics |
-
1996
- 1996-09-18 GB GBGB9619419.6A patent/GB9619419D0/en active Pending
-
1997
- 1997-09-16 RU RU99107383/04A patent/RU2249603C2/en not_active IP Right Cessation
- 1997-09-16 CN CN97198022.5A patent/CN1217967C/en not_active Expired - Fee Related
- 1997-09-16 EP EP97919164A patent/EP0935622A1/en not_active Withdrawn
- 1997-09-16 NZ NZ335075A patent/NZ335075A/en unknown
- 1997-09-16 JP JP51439898A patent/JP4159609B2/en not_active Expired - Fee Related
- 1997-09-16 WO PCT/GB1997/002529 patent/WO1998012239A1/en active Application Filing
- 1997-09-16 CA CA002266578A patent/CA2266578C/en not_active Expired - Fee Related
- 1997-09-16 BR BR9712059-6A patent/BR9712059A/en not_active IP Right Cessation
- 1997-09-16 AU AU43097/97A patent/AU734288C/en not_active Ceased
- 1997-09-18 GB GB9719759A patent/GB2317895B/en not_active Expired - Fee Related
-
1999
- 1999-03-16 NO NO19991276A patent/NO991276L/en not_active Application Discontinuation
-
2008
- 2008-02-20 JP JP2008038750A patent/JP2008174756A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| GB9719759D0 (en) | 1997-11-19 |
| GB9619419D0 (en) | 1996-10-30 |
| CA2266578A1 (en) | 1998-03-26 |
| AU4309797A (en) | 1998-04-14 |
| GB2317895A (en) | 1998-04-08 |
| BR9712059A (en) | 2000-01-18 |
| EP0935622A1 (en) | 1999-08-18 |
| NZ335075A (en) | 2001-03-30 |
| CN1230970A (en) | 1999-10-06 |
| RU2249603C2 (en) | 2005-04-10 |
| CN1217967C (en) | 2005-09-07 |
| NO991276L (en) | 1999-05-12 |
| AU734288C (en) | 2003-03-27 |
| GB2317895B (en) | 2001-04-11 |
| AU734288B2 (en) | 2001-06-07 |
| WO1998012239A1 (en) | 1998-03-26 |
| JP2008174756A (en) | 2008-07-31 |
| NO991276D0 (en) | 1999-03-16 |
| JP2001500558A (en) | 2001-01-16 |
| JP4159609B2 (en) | 2008-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2266578C (en) | Polymeric material | |
| Alexandridis | Structural polymorphism of poly (ethylene oxide)− poly (propylene oxide) block copolymers in nonaqueous polar solvents | |
| Pindzola et al. | Cross-linked normal hexagonal and bicontinuous cubic assemblies via polymerizable gemini amphiphiles | |
| JP4934797B2 (en) | Ionic organic compounds | |
| Liu et al. | Thermoresponsive micelles from well‐defined block copolymers synthesized via reversible addition–fragmentation chain transfer polymerization | |
| Lee et al. | Controlled self-assembly of asymmetric dumbbell-shaped rod amphiphiles: Transition from toroids to planar nets | |
| An et al. | One-step microwave preparation of well-defined and functionalized polymeric nanoparticles | |
| Zou et al. | Supramolecular hydrogels via light-responsive homoternary cross-links | |
| US6660802B2 (en) | Polymeric material | |
| Allain et al. | Sol-gel transition of hydrolyzed polyacrylamide+ chromium (III): rheological behavior versus crosslink concentration | |
| Osada | Hydrothermal contraction–dilation of polymer networks by reversible complexation with a complementary macromolecule | |
| Du et al. | Linear alternating associative polymer with ultrahigh molecular weight: facile preparation by self-assembly assisted dimerization of anthracene and rheology in aqueous solution | |
| Ren et al. | pH-dependent morphology and photoresponse of azopyridine-terminated poly (N-isopropylacrylamide) nanoparticles in water | |
| Choi et al. | A new class of conjugated ionic polyacetylenes. 3. Cyclopolymerization of alkyldipropargyl (4-sulfobutyl) ammonium betaines by transition metal catalysts | |
| Yoshida | Ionic gelators: oligomeric and polymeric electrolytes as novel gel forming materials | |
| CN103073659B (en) | Water-soluble organic silicon macromolecular photoinitiator and preparation method thereof | |
| Rao et al. | Ordering in Poly (allylamine hydrochloride) Gels | |
| Shedge et al. | Hydrophobically modified poly (acrylic acid) using 3‐pentadecylcyclohexylamine: synthesis and rheology | |
| MXPA99002572A (en) | Polymeric material | |
| JPH04112863A (en) | Amino acid derivative and gelling agent | |
| Seiffert et al. | Amine‐Functionalized Polyacrylamide for Labeling and Crosslinking Purposes | |
| Cleij et al. | Nonionic water-soluble polysilynes. Synthesis and properties of a novel class of functionalized materials | |
| Zhao et al. | The thermodynamics of long-tail surfactant aggregation driven by water addition in ethanol | |
| Hachisako et al. | Recognition of molecular planarity of cationic dyes by anionic, crystalline bilayer aggregates. Evidence using metachromatic and solvatochromic properties | |
| Deen et al. | New piperazine‐based polymerizable monoquaternary cationic surfactants: Synthesis, polymerization, and swelling characteristics of gels |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |
Effective date: 20140916 |