WO2002020627A1 - Vinylamine compounds - Google Patents
Vinylamine compounds Download PDFInfo
- Publication number
- WO2002020627A1 WO2002020627A1 PCT/EP2001/010031 EP0110031W WO0220627A1 WO 2002020627 A1 WO2002020627 A1 WO 2002020627A1 EP 0110031 W EP0110031 W EP 0110031W WO 0220627 A1 WO0220627 A1 WO 0220627A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- general formula
- hydrogen
- alkyl
- copolymers
- fuel
- Prior art date
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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
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
Definitions
- the present invention relates to compounds, in particular copolymers, which contain basic vinylamine units.
- the invention further relates to a process for the production of such compounds or copolymers, their use as auxiliaries in mineral oils, mineral oil distillates, fuels and fuels and other areas, concentrates containing them and fuel and fuel compositions.
- Vinylamine polymers can only be obtained indirectly via polymer-analogous reactions, since the base monomer, the vinylamine, cannot be isolated.
- Vinylamine polymers are, for example, by hydrolysis of poly- ⁇ -vinyl amides such as poly- ⁇ -vinyl formamide, poly- ⁇ -vinyl acetamide, poly- ⁇ -vinyl imides such as poly- ⁇ -vinyl succinimide or poly- ⁇ -vinyl phthalimide and by Hofmann's degradation of polyacrylamide Exposure to basic hypochlorite.
- These synthetic routes start from monomers which are difficult to obtain or expensive and have complicated reaction or workup steps. So far, they have only been used in a few special applications, such as flocculants and retention aids.
- Middle distillates such as gas oils, diesel oils or heating oils, which are obtained from petroleum by distillation and from the further processing stages of the refineries, have different proportions of n-paraffins depending on the origin of the crude oil, which can crystallize on cooling , This point is called the cloud point or cloud point (CP).
- CP cloud point
- MD middle distillate
- pour point or pour point Due to the unusual paraffins in the temperature range between cloud point and pour point, the fluidity, especially of fuels, is significantly impaired. The paraffins clog filters and cause an uneven or completely interrupted fuel supply to the engine in the case of fuels. Similar problems occur with heating oils.
- copolymers derived from ethylene and vinyl acetate have been described in many cases, see, for example, DE-A-196 24 861.
- the copolymers described also contain (meth) acrylate basic building blocks which are derived from optionally alkoxylated amino alcohols derived.
- EP-A-0 964 052 relates to the use of nitrogen-containing ethylene copolymers for the production of fuel oils with an improved scanning effect.
- the copolymers also contain structural units which are derived from ethylenically unsaturated compounds which have at least one aromatically or aliphatically bound nitrogen atom.
- alkylamino (meth) acrylates, alkyl (meth) acrylamides, vinylamides, aminoalkyl vinyl ethers, allylamines and heterocycles bearing a vinyl group are listed.
- terpolymers are used which are derived from ethylene, vinyl acetate and 1-vinyl-2-pyrrolidone, N-vinyl-N-methylacetamide or dimethylaminoethyl methacrylate.
- the nitrogen-containing vinyl comonomers sometimes have a complicated structure and are generally not easy and can be prepared from inexpensive raw materials.
- EP-A-0 405 270 relates to a process for improving the flowability of mineral oils and mineral oil distillates by adding a mixture of an ethylene-vinyl acetate copolymer and an ethylene-vinyl acetate-N-
- WO 96/18706 relates to fuel and fuel compositions with a low sulfur content, the flowability of which is increased by the addition of nitrogen-containing compounds.
- amine salts or amides are used which are obtained by reacting hydrocarbon-substituted amines with alkanoic acids.
- the object of the present invention is to provide a process for the preparation of compounds which contain structural elements derived from vinylamine, the introduction of the amine group being said to be inexpensive and inexpensive to introduce.
- copolymers are to be provided which have a number of advantageous properties as auxiliaries in mineral oil, mineral oil distillates, fuels and fuels.
- R, ⁇ , R independently of one another hydrogen, C ⁇ - o-alkyl, C 6 - ⁇ 8 aryl, C _ o-alkaryl, C _ o-aralkyl or polyamine residue
- R 3 hydrogen, C ⁇ _ 2 o-alkyl, C 6 . 18 aryl, C 7 . o-alkaryl, C 7 . 20 aralkyl
- the compounds containing structures of the general formula (I) or (II) can be low molecular weight, oligomeric or polymeric structures. Correspondingly, they can have 1, 2, 3, 4, 5, 6 or more of the structures of the formulas (I) or (II).
- the compounds having the structures of the formula (I) preferably have a total of 4 to 100,000 carbon atoms, particularly preferably 10 to 10,000 carbon atoms, in particular 10 to 1000 carbon atoms, provided that they are low-molecular or oligomeric compounds.
- the compounds are particularly preferably polymers which contain vinylamine basic units of the general formula (I) in the main chain.
- the polymers contain 1 or 2, 3, 4, 5, 6 or more of the basic building blocks of the general formula (I).
- the compounds are preferably polymers which contain one or more vinylamine basic units of the general formula (I) in the main chain and are obtained by reductive amination of polymers which contain one or more vinyl ester basic units of the general formula (II) in the main chain.
- the polymers to be aminated are particularly preferred which contain C - C 1 -olefin basic building blocks and vinyl esters of C 1 2 monocarboxylic acids as basic building blocks.
- copolymers to be aminated are ethylene-vinyl acetate copolymers.
- R and R are, independently of one another, preferably hydrogen or C ⁇ _ ⁇ 2 alkyl, particularly preferably hydrogen or C ⁇ alkyl, especially hydrogen.
- Ammonia is particularly preferably used as the compound of the general formula (III).
- R 3 is preferably hydrogen or -CC 2 alkyl, particularly preferably -C-alkyl, in particular methyl. These are, in particular, vinyl acetate building blocks.
- Particularly preferred compounds which have the structures of the general formula (I) or (II) are polymers with a molecular weight (number average) of 100 to 10,000,000, particularly preferably 500 to 100,000.
- the reductive amination according to the invention can be carried out analogously to known processes for the reductive amination of e.g. Aldehydes, ketones or esters and
- Alcohols are carried out. It is preferably carried out using suitable catalysts. Suitable catalysts are known and described for example in the older, not prepublished DE-A-199 10 960.
- Catalysts customary for reductive amination are, for example, those based on Ni, Co, Cu, Fe, Pd, Pt, Ru, Rh, Al, Si, Ti, Zr, Nb, Mg, Zn or a combination thereof.
- Typical reaction conditions are temperatures from 50 to 300 ° C and pressures up to about 600 bar.
- a preferred catalyst contains as a catalytically active mass before the reduction with hydrogen
- a particularly preferred catalyst has the composition 51% by weight NiO, 17% by weight CuO, 30.5% by weight ZrO 2 and 1.5% by weight MoO 3 .
- the catalyst is preferably composed only of catalytically active composition and, if appropriate, a shaping aid such as graphite or stearic acid.
- the catalyst can be used in any suitable form, for example as tablets, balls, rings, extrudates.
- the catalytically active composition may optionally also contain one or more elements or their inorganic or organic compounds selected from Groups IA to IVA and IB to VIIB and VIII of the Periodic Table of the Elements.
- catalysts which, after the last heat treatment and before the reduction with hydrogen, contain less than 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight, very particularly less than 1% by weight.
- % Cobalt calculated as CoO.
- the catalytically active composition very particularly preferably does not contain any catalytically active amounts of cobalt or its compounds.
- the catalysts can be prepared by various processes, for example by peptizing powdery mixtures of the hydroxides, carbonates, oxides and / or other salts of the components with water and then extruding and tempering the mass obtained in this way. In general, however, known precipitation methods are used to prepare the catalysts.
- the individual components can be precipitated individually or together as mixed precipitation.
- the precipitation products are generally dried at 80 to 200 ° C., preferably at 100 to 150 ° C. and then calcined at 300 to 800 ° C., preferably 400 to 600 ° C., in particular 450 to 500 ° C.
- the amines of the general formula (III) can be used in stoichiometric amounts, based on the ester groups to be reacted. However, an excess of the amines is preferably used, for example a more than 5-molar excess. Ammonia in particular is generally used in a 5 to 250 times, preferably 10 to 100 times, in particular 25 to 80 times, molar excess.
- the process according to the invention can be carried out batchwise or continuously, the catalyst preferably being arranged as a fixed bed in the reactor is.
- the reaction can be carried out in the liquid phase or in the gas phase.
- the reaction is usually carried out at temperatures from 50 to 300 ° C., preferably 80 to 250 ° C., particularly preferably 80 to 230 ° C., in particular 100 to 220 ° C.
- reaction is carried out at a pressure of 1 to 400 bar, preferably 10 to 250 bar, in particular 20 to 200 bar.
- the hydrogen is generally fed in the reaction in an amount of 5 to 400 NI, preferably 50 to 250 NI per mole of ester component to be reacted.
- the reaction can be carried out without an additional solvent.
- a solvent which is inert under the reaction conditions for example in tetrahydrofuran, dioxane, N-methylpyrrolidone, mihagol, ethylene glycol dimethyl ether or cyclohexane and hexane or generally aliphatic or aromatic solvents.
- the invention also relates to the copolymers produced by the process according to the invention, particularly preferably a copolymer containing polymerized vinylamine basic units of the general formula (I)
- R 1 , R 2 independently of one another hydrogen, ⁇ o-alkyl, C 6 - ⁇ 8 aryl, C 7 . 20 alkaryl, C 7 . 2 o-aralkyl or polyamine radical,
- R 5 as R or - OC (O) -R 6 ,
- R 6 is hydrogen, C 20 alkyl, C 6 8 aryl, C 7 . 20 alkaryl, C 7 - 2 o-aralkyl, which may be optionally substituted by
- D R9 independently of one another hydrogen or C ⁇ -alkyl.
- R 1 and R 2 have the preferred meaning given above.
- R 6 has the preferred meaning given above for R 3 .
- R 4 are preferably hydrogen or methyl, in particular methyl.
- R 5 preferably has the meaning R 6 or -OC (O) -R 6 . If the radical R 5 is the radical R 6 , then R 6 preferably has the meaning hydrogen, Ci- ⁇ -alkyl, phenyl or C 7 - ⁇ o-alkaryl, R 6 is particularly preferably hydrogen, methyl, ethyl or phenyl.
- the copolymer particularly preferably contains basic units of the general formula (IVa) -CH 2 -CR 4 (-OC (O) -R 6 ) - (IVa)
- R 5 is hydrogen, C ⁇ o-alkyl, C 6-18 aryl.
- copolymers have both the basic building blocks of the general formulas (I), (IVa) and (IVb).
- Such copolymers can also contain up to 20% by weight, based on the total copolymer, of further basic units, particularly preferably they are composed essentially or only from the basic units of the general formulas (I), (IVa) and (IVb). It is particularly preferred to use ethylene-vinyl acetate-vinylamine terpolymers.
- the copolymers or terpolymers preferably have a molecular weight (number average) of 100 to 10,000,000, particularly preferably 500 to 100,000.
- copolymers according to the invention can be prepared by any suitable method.
- the copolymers are particularly preferably prepared by radical copolymerization of vinyl esters of the general formula (V)
- H 2 C CH (OC (O) -R 3 ) (V)
- R 3 hydrogen, C 6 _ ⁇ 8 aryl, C 7 . 2 o-alkaryl, C. 2 o-aralkyl,
- H 2 C CR 4 R 5 (VI) with the meaning given for R and R 5 and optionally further vinylic comonomers to form a copolymer and subsequent reductive amination by the above process.
- the ethylene-vinyl acetate copolymers are produced, for example, by radical polymerization using the high-pressure mass process, optionally in stirred autoclaves, tubular reactors or segmented tubular reactors. Such processes are described, for example, in DE-A-197 54 039, DE-A-197 19 689 and M. Russisch, Petroleum and Coal-Natural Gas-Petrochemicals combined with Fuel Chemistry, 42 (4) 1989.
- copolymers according to the invention can be used in a large number of applications. Preference is given to use as auxiliaries in mineral oils, mineral oil distillates and fuels, in chromatography, as an ion exchanger, in dispersions, as an emulsifier, in paper production (Wochenbl. Textilfabr.
- the copolymers are suitable for optimizing retention and drainage as well as for fixing anionic substances in papermaking (retention, drainage, flocculation and fixing agents). In addition, the polymers achieve an improvement in dry and wet paper strength (see also Klibl. Textilfabr. (1999), 127 (8), 511-518). (2) The copolymers are suitable for dye (substance) removal from waste water from paper manufacture (according to US Pat. No. 5,476,594).
- the polymers are suitable as water-soluble or water-swellable, cationic polyelectrolyte for aqueous adhesive dispersions for the production of multi-layer paper or paper materials (according to DE 198 29 757).
- copolymers are suitable for modifying cleaned or chemically pretreated metal surfaces, which are then particularly suitable for electrocoating (in accordance with EP 0 672 467).
- copolymers are suitable as dye transfer inhibitors for detergents (according to DE 441 3 720).
- the copolymers are suitable as a starting substance for the preparation of polymers containing carbamate units. These polymers are suitable as retention aids, drainage aids and flocculants and as a fixing agent in the production of paper, as a protective colloid for the production of aqueous alkyldiketene dispersions and as
- Dispersant for the production of aqueous filler slurries (according to WO 98/35999).
- copolymers are suitable for equipping and producing viscose products with cationic polymers (according to WO 99/36604).
- the copolymers are suitable as water-soluble amine-based polymer components in multilayer membranes for separating acid gases from gaseous mixtures (according to DE 196 00 954).
- the copolymers are suitable for the production of aqueous and organic dispersions, emulsions or solutions of amine-based polymers.
- the amine-based polymers, dispersions, emulsions or solutions are particularly suitable for coating and hydrophobicizing surfaces (lacquered surfaces, Packing coating, impregnation of building materials, chipboard, stone, metal, textiles, plastics, leather, wood, paper), for equipping various materials (stone, metal, textiles, plastics, leather, wood, paper), as a process chemical in the textile industry, as an additive in Printing inks and varnishes, as well as mold release agents.
- the copolymers are suitable as an effective corrosion inhibitor in coolant mixtures.
- copolymers are particularly preferably used as flow improvers, wax-anti-settling additives, lubricity improvers, frictional wear reducers, corrosion inhibitors and / or internal combustion engine inlet system cleaners in mineral oils, mineral oil distillates and fuels.
- the copolymers according to the invention are preferably used in fuel and fuel compositions, in particular in middle distillates such as diesel fuels and light heating oils. They can be used together with other common additives.
- the copolymers according to the invention can be incorporated directly into the mineral oils, mineral oil distillates and fuels, in particular a middle distillate, but preferably as 20 to 70% by weight solutions.
- Hydrocarbon solvents are preferably used as solvents. Suitable solvents are described for example in DE-A-196 24 861 and DE-A-43 41 528.
- the copolymers of the invention can be dissolved in a large amount in a hydrocarbon solvent.
- the solutions preferably contain 5 to 80% by weight, preferably 20 to 70% by weight, in particular 40 to 60% by weight, of one or more copolymers according to the invention, alone or together with other auxiliaries, for. B. according to the aforementioned fields of application.
- the invention also relates to such concentrates or mixtures.
- the concentrates can be used, for example, for the production of fuel and fuel compositions, see DE-A-196 24 861.
- the invention also relates to fuel and fuel compositions which contain 5 to 5000 ppm by weight, preferably 10 to 500 ppm by weight, of the copolymer, based on the total weight of the composition, alone or together with other auxiliaries.
- the suspension obtained was filtered and the filter cake was washed with deionized water until the electrical conductivity of the filtrate was about 20 mS. Then 1.5% MoO 3 was stirred in as an aqueous solution of ammonium heptamolybdate.
- the filter cake was then dried at a temperature of 150 ° C. in a drying cabinet or in a spray dryer.
- the hydroxide / carbonate mixture obtained in this way was then heated at a temperature of 500 ° C. over a period of 4 h.
- the catalyst thus obtained had the following composition:
- an ethylene-vinyl acetate copolymer was made which was composed of 70.3% by weight of ethylene and 29.7% by weight of vinyl acetate.
- the melt viscosity at 120 ° C was 65 mm 2 / s.
- the preparation was carried out as described in DE-A-197 54 039.
- 75 g of this copolymer was mixed with 75 g of cyclohexane as a solvent and mixed with 850 g of liquid ammonia in an autoclave. Then they were heated at 200 bar hydrogen pressure in the presence of 50 g of the catalyst described above at 200 ° C for 16 h. The mixture was then cooled, let down, and the contents of the autoclave were removed. After filtering off the catalyst and separating off the cyclohexane, 80 g of a liquid, colorless product were obtained.
- the content of ethylene, vinyl acetate and vinylamine was determined by NMR spectroscopy.
- the terpolymer contained 75.6% by weight of ethylene, 14.7% by weight of vinyl acetate and 9.7% by weight of vinylamine polymerized.
- test oils had the following characteristics. Table l:
- the polymers according to the invention were introduced into the test oils and the cold filter plugging point (CFPP value) was determined in accordance with EN116.
- the cloud point (CP) was also determined in accordance with ISO 3015.
- the CFPP is listed in Table 2 below.
- the lubricating effect of the ethylene-vinyl acetate-vinylamine Te ⁇ olymer (II) described was determined in test oil 5 according to DIN ISO 121546-1 (HFRR measurement). The results in Table 3 are given as wear scar diameters (WS 1.4). A low wear scar shows a good lubricating effect.
- a commercially available lubricity improver product Kerokorr® LA 99 (K) was used.
- paraffin sedimentation (wax anti-settling) in test oil 3 was determined by an ARAL method, see Table 4. 500 ml of the diesel fuel were stored at -13 ° C for 16 hours. The ethylene-vinyl acetate copolymer (C) described and the inventive vinyl acetate-vinylamine copolymer (T) were tested as additives. The quality of the influencing of paraffin sedimentation (wax anti-settling) is carried out by visual assessment:
- Substances are effective as wax-antisettling additives, which lead to the results case (A) and case (B) in the experiment.
- the lower 20% determine the cloud point (CP) and the CFPP.
- Table 4 shows that the ethylene-vinyl acetate copolymer used for the production of the ethylene-vinyl acetate-vinylamine Te ⁇ olymer has no effect on the paraffin sedimentation. Adding the ethylene-vinyl acetate-vinylamine Te ⁇ olymer to the ethylene-vinyl acetate copolymer has a positive influence on the paraffin sedimentation.
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-2003-7003309A KR20030029927A (en) | 2000-09-07 | 2001-08-30 | Vinylamine compounds |
CA002421439A CA2421439A1 (en) | 2000-09-07 | 2001-08-30 | Vinylamine compounds |
JP2002525246A JP2004508436A (en) | 2000-09-07 | 2001-08-30 | Vinylamine compound |
AU2001285917A AU2001285917A1 (en) | 2000-09-07 | 2001-08-30 | Vinylamine compounds |
EP01965237A EP1373330A1 (en) | 2000-09-07 | 2001-08-30 | Vinylamine compounds |
NO20031040A NO20031040L (en) | 2000-09-07 | 2003-03-06 | Vinyl amine compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10044164.5 | 2000-09-07 | ||
DE10044164A DE10044164A1 (en) | 2000-09-07 | 2000-09-07 | Vinyl amine compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2002020627A1 true WO2002020627A1 (en) | 2002-03-14 |
Family
ID=7655349
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2001/010031 WO2002020627A1 (en) | 2000-09-07 | 2001-08-30 | Vinylamine compounds |
Country Status (9)
Country | Link |
---|---|
US (1) | US20030177690A1 (en) |
EP (1) | EP1373330A1 (en) |
JP (1) | JP2004508436A (en) |
KR (1) | KR20030029927A (en) |
AU (1) | AU2001285917A1 (en) |
CA (1) | CA2421439A1 (en) |
DE (1) | DE10044164A1 (en) |
NO (1) | NO20031040L (en) |
WO (1) | WO2002020627A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005000977A2 (en) * | 2003-06-17 | 2005-01-06 | The Board Of Trustees Of The University Of Illinois | Polyelectrolyte ink |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10138631A1 (en) * | 2001-08-13 | 2003-02-27 | Basf Ag | Process for the production of coated paper with high whiteness |
DE10225944A1 (en) * | 2002-06-11 | 2004-01-08 | Basf Ag | Process for binding particulate, water-absorbent, acid group-containing polymers to a carrier material |
US20040226620A1 (en) * | 2002-09-26 | 2004-11-18 | Daniel Therriault | Microcapillary networks |
US7956102B2 (en) * | 2007-04-09 | 2011-06-07 | The Board Of Trustees Of The University Of Illinois | Sol-gel inks |
US7922939B2 (en) * | 2008-10-03 | 2011-04-12 | The Board Of Trustees Of The University Of Illinois | Metal nanoparticle inks |
US8187500B2 (en) * | 2008-10-17 | 2012-05-29 | The Board Of Trustees Of The University Of Illinois | Biphasic inks |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2118713A (en) * | 1934-08-07 | 1938-05-24 | Ig Farbenindustrie Ag | Manufacture of nitrogen containing derivatives of polymerized vinyl esters of halogen fatty acids |
FR975461A (en) * | 1948-01-28 | 1951-03-06 | Du Pont | Polymerized products and their preparation process |
FR2329679A1 (en) * | 1975-10-30 | 1977-05-27 | Monsanto Co | CATALYTIC AMINATION PROCESS OF POLYMERIC POLYOLS AND NEW PRODUCTS THUS OBTAINED |
EP0546570A1 (en) * | 1991-12-12 | 1993-06-16 | Kuraray Co., Ltd. | Vinyl alcohol copolymer having terminal amino group |
WO1995017440A1 (en) * | 1993-12-20 | 1995-06-29 | Monsanto Company | Controlled functional density polyamines and method for preparation thereof |
EP0693509A1 (en) * | 1994-07-22 | 1996-01-24 | Basf Aktiengesellschaft | Reaction products of polyolefins and vinyl esters and use thereof as lubricating oil and fuel additives |
-
2000
- 2000-09-07 DE DE10044164A patent/DE10044164A1/en not_active Withdrawn
-
2001
- 2001-08-30 WO PCT/EP2001/010031 patent/WO2002020627A1/en not_active Application Discontinuation
- 2001-08-30 KR KR10-2003-7003309A patent/KR20030029927A/en not_active Application Discontinuation
- 2001-08-30 CA CA002421439A patent/CA2421439A1/en not_active Abandoned
- 2001-08-30 AU AU2001285917A patent/AU2001285917A1/en not_active Abandoned
- 2001-08-30 JP JP2002525246A patent/JP2004508436A/en not_active Withdrawn
- 2001-08-30 EP EP01965237A patent/EP1373330A1/en not_active Withdrawn
- 2001-08-30 US US10/363,659 patent/US20030177690A1/en not_active Abandoned
-
2003
- 2003-03-06 NO NO20031040A patent/NO20031040L/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2118713A (en) * | 1934-08-07 | 1938-05-24 | Ig Farbenindustrie Ag | Manufacture of nitrogen containing derivatives of polymerized vinyl esters of halogen fatty acids |
FR975461A (en) * | 1948-01-28 | 1951-03-06 | Du Pont | Polymerized products and their preparation process |
FR2329679A1 (en) * | 1975-10-30 | 1977-05-27 | Monsanto Co | CATALYTIC AMINATION PROCESS OF POLYMERIC POLYOLS AND NEW PRODUCTS THUS OBTAINED |
EP0546570A1 (en) * | 1991-12-12 | 1993-06-16 | Kuraray Co., Ltd. | Vinyl alcohol copolymer having terminal amino group |
WO1995017440A1 (en) * | 1993-12-20 | 1995-06-29 | Monsanto Company | Controlled functional density polyamines and method for preparation thereof |
EP0693509A1 (en) * | 1994-07-22 | 1996-01-24 | Basf Aktiengesellschaft | Reaction products of polyolefins and vinyl esters and use thereof as lubricating oil and fuel additives |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2005000977A2 (en) * | 2003-06-17 | 2005-01-06 | The Board Of Trustees Of The University Of Illinois | Polyelectrolyte ink |
WO2005000977A3 (en) * | 2003-06-17 | 2005-03-31 | Univ Illinois | Polyelectrolyte ink |
GB2418918A (en) * | 2003-06-17 | 2006-04-12 | Univ Illinois | Polyelectrolyte ink |
US7141617B2 (en) | 2003-06-17 | 2006-11-28 | The Board Of Trustees Of The University Of Illinois | Directed assembly of three-dimensional structures with micron-scale features |
GB2418918B (en) * | 2003-06-17 | 2008-07-09 | Univ Illinois | Directed assembly of three-dimensional structures with micron-scale features |
Also Published As
Publication number | Publication date |
---|---|
DE10044164A1 (en) | 2002-03-21 |
NO20031040L (en) | 2003-05-06 |
US20030177690A1 (en) | 2003-09-25 |
CA2421439A1 (en) | 2003-03-06 |
AU2001285917A1 (en) | 2002-03-22 |
KR20030029927A (en) | 2003-04-16 |
EP1373330A1 (en) | 2004-01-02 |
NO20031040D0 (en) | 2003-03-06 |
JP2004508436A (en) | 2004-03-18 |
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