CN1230970A - Polymeric material - Google Patents
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- CN1230970A CN1230970A CN97198022.5A CN97198022A CN1230970A CN 1230970 A CN1230970 A CN 1230970A CN 97198022 A CN97198022 A CN 97198022A CN 1230970 A CN1230970 A CN 1230970A
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- 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
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- 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
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- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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Abstract
Here 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 R<1> 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. 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
The present invention relates to polymeric material, the present invention is specifically related at least in part by 1, the polymeric material of the stibazole compound formation that the vinyl compound that 2-replaces for example replaces, and saying so not get rid of the invention still further relates to other aspects.
English Patent No.GB2030575 (Agency of Science and Technology) has described a kind of photosensitive resin, and this photosensitive resin is by stibazole salt that formyl radical or acetal group are arranged on its styryl phenyl and polyvinyl alcohol or partly-hydrolysed polyvinyl acetate reaction are prepared.In this resin-the CH=CH-group is a photosensitive, so this resin can be used for for example silk screen printing, it is found that this resin shows very high susceptibility in this respect.
The present invention is based on that class 1 of once describing, the discovery of the amazing character of the vinyl compound that 2-replaces, this 1, the vinyl compound that 2-replaces can be made with the polymeric material of various useful performances.
According to a first aspect of the invention, the invention provides the method for preparation first polymkeric substance, this method comprises: the compound or its salt shown in the formula I is provided in a kind of solvent,
C=C group in the described compound is reacted mutually to form paradigmatic structure, wherein said solvent is that ethene is insoluble to a kind solvent wherein usually, identical or different and among them at least one of A in the formula and B contains the atom or the group of relative polarity, R
1And R
2Contain nonpolar relatively atom or group independently of each other.
Preferably, R
1And R
2The alkyl (unsubstituted alkyl is preferred) that is selected from hydrogen atom independently of each other or replaces arbitrarily.Preferred R
1And R
2Represent identical atom or group.Preferred R
1And R
2Represent hydrogen atom.
Preferred described solvent is a polar solvent.Preferred described solvent is a water-containing solvent.More preferably described solvent is made up of water basically.
The compound of described formula I preferably is provided with the molecule generation accumulative concentration of described compound in described solvent.The gathering of described generalformula can be shown by the result of various analyses described below or show that described any or multiple analysis all can be adopted.Preferably, under being equal to or higher than the concentration of this compound convergence point of conduct that is recorded by suitable vapor pressure measurement, described solvent formula of I compound provides.
Micella takes place to assemble or form in the molecule that it is believed that described generalformula in described solvent, during the two keys of C=C in same plane each other in being arranged in parallel, make each molecule in same plane, arrange in parallel to each other basically effectively.
Be arranged in parallel preferred its group A and the B of described molecule are contiguous mutually.
Described generalformula can at least 0.5% (weight), preferably at least 1.0% (weight), more preferably the concentration of at least 1.5% (weight) provides in described solution.
Group C=C in the described compound is reacted in photochemical reaction.The inventive method preferably includes suitable employing ultraviolet induction photochemical reaction.Preferably be taken to the light of many 500 nano wave lengths in the method.
Preferred A and B are selected from alkyl, cycloalkyl, cycloalkenyl group, cycloalkynyl radical, aryl and the heteroaryl of any replacement independently of each other.Group A or B are ring texture, are preferably 5-unit ring, more preferably 6-unit ring.
More preferably A and B are selected from the aryl and the heteroaryl of any replacement independently of each other, and the group that wherein has 5-unit ring or 6-unit ring is preferred, especially preferably has the group of 6-unit ring.Preferred heteroatoms in the described heteroaryl comprises nitrogen-atoms, Sauerstoffatom and sulphur atom, and wherein Sauerstoffatom, particularly nitrogen-atoms are preferred.Preferred heteroaryl only comprises a heteroatoms.Heteroatoms is preferably placed at the position that is connected with the C=C group away from heteroaryl.For example, when heteroaryl was 6-unit ring, with respect to the position that this ring links to each other with group C=C, this heteroatoms was preferably placed at the 4-position.
Except as otherwise noted, for example group A and B can be replaced by halogen atom and the alkyl that replaces arbitrarily, acyl group, acetal radical, hemiacetal group, acetal alkoxyl group, hemiacetal alkoxyl group, nitro, cyano group, alkoxyl group, hydroxyl, amino, alkylamino, sulfurous base (sulphinyl), alkyl sulfurous base, alkylsulfonyl, alkyl sulphonyl, sulfonate group, imino-, alkyl imino, alkyl-carbonyl, alkoxy carbonyl, halo carbonyl and haloalkyl the group of any replacement as herein described.The substituting group arbitrarily that 3 at the most (preferably at the most 1) can be arranged on the substituting group arbitrarily.
Except as otherwise noted, alkyl can have 10 of as many as, preferably have 6 of as many as, more preferably have 4 carbon atoms of as many as, wherein methyl and ethyl are particularly preferred.
Preferred A and B all represent polarity atom or group.Preferred A and B all represent the aryl or the heteroaryl of any replacement, and " p " track of wherein said aryl becomes axial alignment to arrange with the C=C group.Preferred A and different atom and the groups of B representative.
One among preferred A and the B has any substituting group, and described substituting group comprises carbonyl or acetal radical, and wherein formyl radical is particularly preferred.Among A and the B another can have any substituting group for alkyl, wherein (preferably unsubstituted) C that replaces arbitrarily
1-4Alkyl for example methyl is particularly preferred.
Preferred group A representative is replaced the phenyl of (preferably replacing in the 4-position with respect to the C=C group) by the group shown in formyl radical or the general formula II:
X is the integer of 1-6 in the formula, each R
3Constitute the alkane thiazolinyl together for alkyl or phenyl or they independently.
Preferred group B represents the group shown in the general formula III:
R wherein
4Represent hydrogen atom or alkyl or aralkyl, R
5Represent hydrogen atom or alkyl, X represents the strongly-acid ion.
Be used for capable those compounds of mentioning of page 3 8-39 that compound of the present invention is preferably included in GB2030575B shown in the formula I, and described those compounds are incorporated herein this specification sheets.
Being used for compound of the present invention and can also this preparation method being introduced this specification sheets at this shown in formula I by the preparation of the described method of GB2030575B.
The present invention includes first polymkeric substance of the novelty that can prepare according to the method for described first aspect present invention.
According to a second aspect of the invention, the invention provides first polymkeric substance of the novelty shown in the general formula IV:
Wherein A, B, R
1And R
2Meaning as described in other parts of this paper, n is an integer.
According to a third aspect of the invention we, the invention provides the method for preparing prescription, this method is included in to be provided in the solvent according to described first or first polymkeric substance and second polymkeric substance of second aspect, and with these polymkeric substance thorough mixing.
Preferred described second polymkeric substance comprise can with the one or more functional group of described first polymkeric substance (preferably in acid catalyzed reaction) reaction.Described reaction is preferably condensation reaction.Preferred described second polymkeric substance comprises the functional group that is selected from alcohol, carboxylic acid, carboxylic acid derivative such as ester and amido.Preferred second polymkeric substance comprises any replacement (preferably unsubstituted) polyvinyl alcohol, polyvinyl acetate, polyalkylene glycol for example polypropylene glycol and collagen (and any component).
Preferred described second polymkeric substance is solid under envrionment conditions.Preferred described thorough mixing carries out at elevated temperatures.This mixing is preferably carried out in the solvent phase used with preparing chemical compounds I solvent together.The gained mixture can comprise other polymkeric substance, and this polymkeric substance can be same type with the second above-mentioned polymkeric substance.
Find the performance of weight percent (wt%) with the prepared prescription of ratio remarkably influenced of the wt% of second polymkeric substance (or total amount of second polymkeric substance and other compounds) of described first polymkeric substance.The ratio of the wt% of the wt% of described first polymkeric substance and described second polymkeric substance can be in the scope of 0.01-100, preferably at 0.05-50, more preferably in the scope at 0.3-20.
Preferably from described prescription, remove and anhydrate to generate solid matter, for example material of film former type.
According to a forth aspect of the invention, the invention provides and comprise according to first or first polymkeric substance of second aspect and according to the prescription of second polymkeric substance of the third aspect.
Preferred described prescription provides with the solid form.
According to a fifth aspect of the invention, the invention provides and prepare for example method of colloid or gel of material, this method is included in to be provided in the solvent by the mixture of described third aspect preparation or the mixture for preparing by described fourth aspect, and first and second polymkeric substance are reacted mutually.
The catalysis of above-mentioned reaction usable acid, therefore, aforesaid method can be included in the step that acid is provided in the mixture.Find that used acid concentration influences the formation speed of colloid/gel.Preferred use at least 0.05% (weight), the more preferably acid of at least 0.1% (weight).Any acid all can be used, and no matter is organic acid or mineral acid.Preferred acid comprises tosic acid, hydrochloric acid, phosphoric acid, sulfuric acid and naphthene sulfonic acid.
Whether the concentration affects colloid or the gel of used mixture form.When the weight percent of the described first and second polymer solids prescriptions is lower than approximately 2% the time, sticking-elasticity colloidal solution forms.On the other hand, when described concentration is higher than approximately 2% the time, can form gel.
By before described first and second polymer reactions, suitably adding other activeconstituentss, described activeconstituents can be mixed in the colloid or gel by the preparation of described the 5th aspect.Preferred activeconstituents comprises antiseptic-germicide, for example the mixture of iodine/iodide, cetyl trimethylammonium bromide and neomycinsulphate.Can prepare the plate-shaped material that contains activeconstituents, because by understanding, be biocompatibility by the preparation of preparation described herein, and described plate-shaped material can be used for burn treatment.
Contact with the reaction mixture of described the 5th aspect if had been noted that oil (or its analogue), the oil of as many as 50% (weight) can be by described emulsifying mixture, and the gel of gained is retained in oil in the solid substrate.Therefore, a sixth aspect of the present invention provides the method for collection and/or separation and/or oil in water emulsion (or its analogue), this method comprise with oil (or its analogue) contact with the reaction mixture of described the 5th aspect so that described oil (or its analogue) is incorporated in a kind of material such as the formed gel.
The present invention also comprises the colloid or the gel that can prepare by the method for the 5th aspect.
According to the 7th aspect, the invention provides a kind of trimerization material of novelty, this polymeric material comprises the reaction product of compound shown in the general formula IV and second polymkeric substance as herein described.
Any feature of any invention that this paper is described herein or any aspect of embodiment can be combined with any feature of any aspect of other any inventions as herein described or embodiment.
Hereinafter will by the mode of embodiment specific embodiments of the present invention be described in conjunction with the accompanying drawings, wherein:
Fig. 1 shows that the aqueous solution of methyl-sulfuric acid 4-(4-formyl radical phenyl vinyl)-1-picoline (SbQ) is at the function of 37 ℃ of its vapor pressure measurement values to concentration.
Fig. 2 represents to estimate the structure of the energy minimum of 4 SbQ molecules in water.
Fig. 3 shows that SbQ solution is at the function of 25 ℃ of its stalagmometry values to concentration.
Fig. 4 shows that SbQ solution is at the function of 25 ℃ of its mole conduction values to concentration.
Fig. 5 shows that SbQ solution is at the function of 25 ℃ of its apparent molecular volumes to concentration.
Fig. 6 shows that SbQ solution is at the function of 25 ℃ of its 90 ° of Rayleigh scatterings to concentration.
Fig. 7 shows that SbQ solution is at the function of 25 ℃ of its heats of dilution to concentration.
The physical-chemical research research of methyl-sulfuric acid 4-(4-formoxyl phenyl vinyl)-1-picoline (SbQ)
The aqueous sample of following SbQ to purifying is carried out various physical-chemical researchs:
ⅰ. stalagmometry-employing drop profile mensuration carries out.
ⅱ. vapor pressure measurement-employing is with the Knauer vapour pressure of Analar NaCl solution calibration Meter carries out.
ⅲ. the energy spectrometer of the SbQ molecular structure of energy minimum-employing is based on MM in water+Hyperchem (trade mark) molecular simulation that calculate in the field of force is arranged instrument and is carried out.
ⅳ. conductivity measurement-automatic measuring bridge of employing B905 type Wayne Kerr carries out.
ⅴ. density measure-by European polymer magazine (Eur.Polym.J.), 1987,23, 711 described carrying out provide the Apparent Molar Volumes value.
ⅵ. light scattering measurement-employing is through improved use Uniphase 1mW HeNe laser 42000 type Sofica light goniometers carry out at 543nm.
ⅶ. 2107-121/127 type LKB streaming microcalorimeter (Flow is measured-adopted to the heat of dilution Microcalorimeter) carry out. The result
About Fig. 1, ratios delta t/C represents between reference solvent and the solution when concentration C (g/kg) Temperature gap. This curve has shown 2 ranges of linearity, and both all have good coefficient correlation, Be respectively 0.996 and 0.998, intersect the concentration place at 1.25%w/w. With common mode profit With the intercept (intercept) in the low scope of solution concentration, the average molar mass that obtains SbQ is 341, this is worth close to desired value 335. Difference prompting concentration at the slope at higher concentration place exists When 1.25%w/w was above, the gathering of some form had taken place in the SbQ molecule.
The analyses and prediction of adopting Hyperchem to arrange instrument go out the extremely structure on plane. This of molecule Kind of structure is easy to make with the molecule of hydrophobic region stack each other, simultaneously aldehyde radical and-N-CH3The group alternative arrangement, to be created in the water aggregation that shows the energy minimum, as shown in Figure 24 Individual SbQ molecule.
The difference of the intercept in two concentration districts among Fig. 1 as the result that aggregation produces, is drawn SbQ The molal weight of aggregation is about 2800, points out described aggregation by about 8 monomeric unit groups Become, the critical concentration that this variation takes place is 1.25% or close to 0.04M.
About stalagmometry value shown in Figure 3, the figure of seeing is that surfactant forms The typical graphics of micella is undergone mutation at about 0.06M. Therefore, this evidence prompting SbQ assembles Thing in fact is stack rod-shaped micelle together, and its critical micelle concentration (cmc) value is 0.04-0.06M.
The mole conductance of Fig. 4 has also shown the figure that is formed the material expection by micella, described Slope variation during cmc occurs in 0.04M.
About Fig. 5, the violent variation of slope of seeing at 0.04M means that the SbQ molecule exists This takes comparatively closely knit form to exist more than concentration, this and SbQ molecular aggregates form micella time institute Expect that contingent phenomenon is very alike.
About Fig. 6, the suddenly increase of scattering takes place when concentration trend 0.04M, this point shows Bigger molecule (that is, micella) occurs.
About Fig. 7, heat of dilution measured value also demonstrates the suddenly variation of slope at the 0.035M place, Great variety has taken place in this state that shows again solute in solution, become glue from monomer Bundle.
Should be realized that from above very being correlated with between the concentration dependent behavior of all test measurements is to have SbQ monomer-fabulous proof of micella equilibrated in the aqueous solution.In following examples, utilized the behavior.Embodiment 1
Poly-(1,4-two (N-picolyl))-2, the 3-two (preparation of 4-(1-formyl radical phenyl) divinyl (compound ii hereinafter)
With the SbQ aqueous solution more than the uviolizing 1wt%.This irradiation causes between the C=C key in adjoining methyl-sulfuric acid 4-in aggregation (4-formyl radical phenyl vinyl)-1-picoline molecule (I) photochemical reaction taking place; produce polymkeric substance-poly-(1; 4-two (N-picolyl))-2; (4-(1-formyl radical phenyl) divinyl (II) is shown in following reaction scheme for 3-two.Should find out for brevity, omit the negatively charged ion of chemical compounds I and II.
Believe that this polymkeric substance II is novel.Embodiment 2
Adopt compound ii to prepare blend
Description the preparation gel typical method.
With 13 grams, molecular weight is that the polyvinyl alcohol of 300000 88% hydrolysis is dissolved in 87 and digests in the solution of 2%w/w of compound II.Described polyvinyl alcohol is slowly added to disperse described powder under lasting the stirring.Reach 6 hours solution is dissolved fully by solution being maintained 60 ℃.Can be with polyvinyl alcohol/poly-(1,4-two (N-picolyl))-2 of gained, (4-(1-formyl radical phenyl) butadiene solution is being cast into film on the PTFE sheet material He under the dry vacuum to 3-two.The solid blend of gained is that light is stable, and can preserve until use in moisture eliminator.Embodiment 3
The preparation of gel
Can with embodiment 2 described films and acid for example tosic acid be dissolved in the water again together.This step causes the aldolisation shown in the acid catalyzed following reaction scheme.
The performance of the concentration affects gained gel of used film.For example in concentration during greater than 2.5% (weight), rigid gel forms.In addition, gelation time also depends on the concentration of used acid.It is 16 hours that the acid of 0.1wt% causes gelation time, and it is 10 minutes that the acid of 1wt% then causes gelation time.
Press the performance of the gel of this paper general step preparation
1. the formed gel of polyvinyl alcohol that adopts 2.5-13wt% not fusion or demonstrate any visible phase transformation sign when being heated to 100 ℃; Under higher temperature, this gel zoom is deceived but is not burnt.
2. this gel is an inflexible, and is optically transparent.
3. the required time of concentration may command pectisation that is used for the acid of catalysis gelling reaction by change.Rely on this transformable gelation time, only need just can carry out the casting of different shapes gel by reaction mixture is injected mould.When gel formation, material therefor does not significantly shrink.
4. this gel is insoluble in all common organic solvents, though some gel swelling slightly.This gel also is insoluble in the aqueous solution.
5. adopt the collagen of 50wt% and 50% polyvinyl alcohol to replace among the embodiment 2 and 3 the only polyvinyl alcohol of usefulness, can produce the inflexible gel.The gel that is produced shows organic solvent-resistant, and the swelling in water is also limited.
6. add acid with after the catalysis gelling reaction in embodiment 3, the oil of as many as 50wt% can be by reaction mixture emulsification.The gel of gained is retained in oil in the solid substrate.
7. adopt the solvent mixture of the polypropylene glycol 400 that contains as many as 50wt% can prepare gel.The swelling behavior of gained gel in water decided by the amount of polypropylene glycol in solvent.
8. when concentration was lower than 2wt%, sticking-elastic sols formed, and compared with unreacted mixture, and the viscosity of this sticking-elastic sols has improved 10 times.This behavior has the potential purposes in the oil recovery in the tertiary period, wherein reaction mixture can be pumped in the oil well crack, and along with the carrying out of reaction, the sticking-elasticity of cross-linked polymer solution increases, and blocks the opening in crack thus.
By the periodate cleavage method of polyvinyl alcohol chain, gel and the above-described gel of embodiment 1-3 can be destroyed apace.The solution that is produced has lower viscosity, and is easy to be rinsed out by water.Above 6. mention under the situation of emulsive oleogel, periodate cleavage causes gel to destroy, and makes described oil can obtain reclaiming.
Reader's attention should point to this specification sheets simultaneously or submit before this relevant and with this application to disclosed all paper spares of the public and file, it is for referencial use that the content in this paper spare and the file is incorporated herein this paper.
The institute of disclosed all features of this specification sheets (comprising appended any claim, summary and accompanying drawing) and/or disclosed any method can the arbitrary combination mode make up in steps, unless at least some of these features and/or step are to repel mutually.
The disclosed various features of this specification sheets (comprising appended any claim, summary and accompanying drawing) can be played a same function, be equal to or the alternative features displacement of similar purpose, unless expressly stated otherwise.Therefore, except as otherwise noted, various features disclosed herein only be a series of total be equal to or similar characteristics in an example.
The present invention is not limited to the detailed description of previous embodiments part.The present invention includes the disclosed any new feature of this specification sheets and any new combination of these features, or any new combination of disclosed any novel method and these methods.
Claims (16)
1. the method for preparing first polymkeric substance, this method comprises: the compound or its salt shown in the formula I is provided in a kind of solvent,
Identical or different and among them at least one of A in the formula and B contains the atom or the group of relative polarity, R
1And R
2Contain nonpolar relatively atom or group independently of each other, described solvent is that ethene is insoluble to a kind of solvent wherein usually; And the C=C group in the described compound is reacted mutually to form paradigmatic structure.
2. R wherein in accordance with the method for claim 1,
1And R
2The alkyl that is selected from hydrogen atom independently of each other or replaces arbitrarily.
3. according to claim 1 or 2 described methods, wherein said solvent is a polar solvent.
4. according to the described method of aforementioned arbitrary claim, the compound shown in the wherein said formula I is causing in described solvent under the described compound generation accumulative concentration and is providing.
5. according to the described method of aforementioned arbitrary claim, the C=C group in the described compound is reacted in photochemical reaction.
6. according to the described method of aforementioned arbitrary claim, wherein A and B are selected from alkyl, cycloalkyl, cycloalkenyl group, cycloalkynyl radical, aryl and the heteroaryl of any replacement independently of each other.
7. according to the described method of aforementioned arbitrary claim, wherein A and B represent any substituted aryl or heteroaryl independently of each other.
8. first polymkeric substance that has the novelty of following general formula:
Wherein A and B are identical or different, and in them at least one comprises the atom or the group of relative polarity, R
1And R
2Comprise nonpolar relatively atom or group independently of each other, n is an integer.
9. first polymkeric substance and second polymkeric substance that provides in the solvent by the method preparation of each described method or claim 8 among the claim 1-7 is provided for the preparation method of a prescription, this method, and makes these polymkeric substance thorough mixing.
10. method according to claim 9, wherein said second polymkeric substance comprise can with the one or more functional group of described first polymer reaction.
11. according to the method for claim 9 or 10, wherein said second polymkeric substance is selected from polyvinyl alcohol, polyvinyl acetate, polyalkylene glycol and the collagen (and any component) of any replacement.
12. a prescription comprises according to first polymkeric substance of the described method preparation of each described method or claim 8 among the claim 1-7 and second polymkeric substance for preparing according to each described method among the claim 9-11.
Provide in the solvent according to the mixture of any described and preparation among the claim 9-11 or according to the prescription of claim 12 13. the preparation method of a material, this method are included in, and first and second polymkeric substance are reacted mutually.
14. in accordance with the method for claim 13, wherein used acid.
15. the method for collection and/or separation and/or oil in water emulsion or its analogue, this method comprise oil or its analogue are contacted with reaction mixture according to claim 13 or 14, so that described oil or its analogue are incorporated in the formed material.
16. can be according to the material of method preparation any among the claim 13-15.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9619419.6 | 1996-09-18 | ||
| GBGB9619419.6A GB9619419D0 (en) | 1996-09-18 | 1996-09-18 | Polymeric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1230970A true CN1230970A (en) | 1999-10-06 |
| CN1217967C CN1217967C (en) | 2005-09-07 |
Family
ID=10800073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97198022.5A Expired - Fee Related CN1217967C (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) |
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| 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 |
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| 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
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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 |
| 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 |
| CA2266578C (en) | 2008-12-23 |
| 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 |
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