GB838413A - Modified synthetic condensation polymers and their production - Google Patents
Modified synthetic condensation polymers and their productionInfo
- Publication number
- GB838413A GB838413A GB21896/59A GB2189659A GB838413A GB 838413 A GB838413 A GB 838413A GB 21896/59 A GB21896/59 A GB 21896/59A GB 2189659 A GB2189659 A GB 2189659A GB 838413 A GB838413 A GB 838413A
- Authority
- GB
- United Kingdom
- Prior art keywords
- acid
- polymer
- acids
- unsaturated
- grafted
- 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
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
- D06M14/30—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
- B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
-
- 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
- C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
- C08F291/18—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00 on to irradiated or oxidised macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/04—Physical treatment combined with treatment with chemical compounds or elements
- D06M10/08—Organic compounds
- D06M10/10—Macromolecular compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/20—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin
- D06M14/22—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of natural origin of vegetal origin, e.g. cellulose or derivatives thereof
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M14/00—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials
- D06M14/18—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation
- D06M14/26—Graft polymerisation of monomers containing carbon-to-carbon unsaturated bonds on to fibres, threads, yarns, fabrics, or fibrous goods made from such materials using wave energy or particle radiation on to materials of synthetic origin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2007/00—Flat articles, e.g. films or sheets
- B29L2007/008—Wide strips, e.g. films, webs
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/731—Filamentary material, i.e. comprised of a single element, e.g. filaments, strands, threads, fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
Abstract
Graft polymers, in which the substrate is a synthetic condensation polymer and the grafted structure at least in part contain free carboxyl groups or carboxylate salt groups and are derived from monomers containing reactive non-aromatic carbon-carbon unsaturation, are produced by irradiating the synthetic condensation polymer while it is in intimate contact with a modifier consisting of the corresponding unsaturated acid or an anhydride, half-acid ester or half-acid amide thereof or a derivative thereof that can be subsequently hydrolysed to the acid. The acid grafted structures are preferably in the form of metal salts of the unsaturated carboxylic acids. The modifier which may be dispersed, diffused or coated upon the polymer is preferably kept in an inert atmosphere or is enclosed by polyethylene film or aluminium foil or other material which is impervious to air and water while it is irradiated. Additionally it may be in contact with a compound having protective or antioxidant effect with respect to the polymer or the modifier or both and during the irradiation the temperature is preferably kept between 0 DEG and 75 DEG C., if necessary by cooling. The process is preferably carried out in the presence of calcium tungstate, zinc sulphide, metallic lead or other radiation transfer agents capable of absorbing radiation and re-emitting it in the form of the lower energy. Examples of radiation dosages are given. The unsaturated acid or acid derivative is preferably of relatively low molecular weight, since it is desirable for maximum activation that the double bond is in close proximity to the carboxyl group. Thus ethylenically unsaturated acids with up to 5 carbon atoms are preferred, though acids which have as many as 20 carbons in chain length may be used. Suitable acids are crotonic, furoic, acrylic, maleic, dichlormaleic, fumaric and itaconic acids. The unsaturated acid may contain substituent groups which it may be desirable to attach to the polymer to confer other properties, such as static reduction or moisture repellance. After the unsaturated acid has become attached to the substrate, a metal salt of the acid is formed by subjecting the irradiated composition or article to the action of a solution containing a basic metallic salt. Any positively-charged metal ion from a basic-reacting salt can be attached to the grafted acid. It is merely necessary that the anion of the said metal salt be a somewhat weaker acid than the grafted unsaturated acid. In general the greater this difference in acid strength, the greater is the amount of the metal ion taken up under constant conditions, e.g. irradiation dose, concentration and temperature. It is preferable that the dissociation constant of the anion acid be no greater than about one-thousandth of that for the unsaturated acid, or its first hydrogen in the case of a dibasic acid. Synthetic condensation polymer can be formed by polymerization with elimination of small molecules such as HCl, H2O, NaCl, NH3. Among such polymers may be mentioned polyamides, polyureas, polyurethanes, polyesters, polyethers, polysulphonamides and copolymers of such materials. Of particular interest are the linear polyamides which are prepared from polymerizable monoamino-carboxylic acids or their amide-forming derivatives, or from suitable diamines and suitable dicarboxylic acids or amide-forming derivatives of these compounds, especially polyamides having at least one aliphatic -HCR- group in each repeating unit of the polymer molecule, -R- being -O-, hydrogen, halogen or other monovalent atom or radical. The production of such polyamides is illustrated in Specification 461,236 and U.S.A. Specifications 2,071,250 and 2,130,948. The modifiers may be incorporated in a polymer before shaping or they may be applied to the shaped articles, e.g. as solutions or in suitable cases as pure compounds, for example by spraying, calendering, immersion, padding or exposure to vapour condensations. In suitable cases a solution of the melt may be applied to the surface of the shaped article and the solvents flashed-off before the irradiations. If desired, excess liquid may be removed before irradiation by squeezing. A particular advantage possessed by textile articles and films and other shaped articles comprising the graft copolymers of the invention, especially those in which the substrate is a polyamide, lies in their increased resistance to melting. Other advantages include increased resistance to flash heat, higher zero strength temperature and a high unexpected degree of elasticity and deformability at high temperatures, for example about 185 DEG C.; thus a polyamide fabric, after being treated, may be given a three-dimensional shape at high temperatures (e.g. by forming or embossing) without fusing of the individual filaments and without deleterious effect on the fabric hand, which shape is retained on cooling. When reheated above about 185 DEG C., the fabric returns substantially to its original shape. Treated yarns may be elongated (drawn) at temperatures of 185 DEG C. or above, whereby they acquire new tensile properties. Alternatively, if a treated polyamide fibre is left free to retract when heated to temperatures of 185 DEG C. or above, shrinkages of 50% or more are observed. This property permits textured effects to be obtained when treated and untreated yarns are combined in the same fabric, or when the unsaturated acid or the metal ions are applied in a pattern (i.e. non-uniformly), or indeed when portions of the shaped substrate are shielded from the irradiation. It has also been found that the elastic modulus (at 25 DEG C.) of a polyamide treated in accordance with this invention is substantially increased, especially when the polyamide is held under tension during irradiation. Specifications 543,466, 758,735 and 798,340 also are referred to.ALSO:Graft polymers, in which the substrate is a synthetic condensation polymer and the grafted structure at least in part contain free carboxyl groups or carboxylate salt groups and are derived from monomers containing reactive non-aromatic carbon-carbon unsaturation, are produced by irradiating the synthetic condensation polymer while it is in intimate contact with a modifier consisting of the corresponding unsaturated acid or an anhydride, half-acid ester or half-acid amide thereof or a derivative thereof that can be subsequently hydrolysed to the acid. The acid grafted structures are preferably in the form of metal salts of the unsaturated carboxylic acids. The modifier, which may be dispersed, diffused or coated upon the polymer is preferably kept in an inert atmosphere or is enclosed by polyethylene film or aluminium foil or other material which is impervious to air and water while it is irradiated. Additionally it may be in contact with a compound having protective or antioxidant effect with respect to the polymer or the modifier or both and during the irradiation the temperature is preferably kept between 0 DEG and 75 DEG C., if necessary by cooling. The process is preferably carried out in the presence of calcium tungstate, zinc sulphide, metallic lead or other radiation transfer agents capable of absorbing radiation and re-emitting it in the form of the lower energy. Examples of radiation dosages are given. The unsaturated acid or acid derivative is preferably of relatively low molecular weight, since it is desirable for maximum activation that the double bond is in close proximity to the carboxyl group. Thus ethylenically-unsaturated acids with up to 5 carbon atoms are preferred, though acids with as many as 20 carbons in chain length may be used. Suitable acids are crotonic, furoic, acrylic, maleic, dichlormaleic, fumaric and itaconic acids. The unsaturated acid may contain substituent groups which it may be desirable to attach to the polymer to confer other properties, such as static reduction or moisture repellance. After the unsaturated acid has become attached to the substrate, a metal salt of the acid is formed by subjecting the irradiated composition or article to the action of a solution containing a basic metallic salt. Any positively-charged metal ion from a basic-reacting salt can be attached to the grafted acid. It is merely necessary that the anion of the said metal salt be a somewhat weaker acid than the grafted unsaturated acid. In general the greater this difference in acid strength, the greater is the amount of the metal ion taken up under constant conditions, e.g. irradiation dose, concentration and temperature. It is preferable that the dissociation constant of the anion acid be no greater than about one thousandth of that for the unsaturated acid, or its first hydrogen in the case of a dibasic acid. Synthetic condensation polymer can be formed by polymerization with elimination of small molecules such as HCl, H2O, NaCl, NH3. Among such polymers may be mentioned polyamides, polyureas, polyurethanes, polyesters, polyethers, polysulphonamides and copolymers of such materials. Of particular p interest are the linear polyamides which are prepared from polymerizable monoamino-carboxylic acids or their amide-forming derivatives, or from suitable diamines and suitable dicarboxylic acids or amide-forming derivatives of these compounds, especially polyamides having at least one aliphatic -HCR- group in each repeating unit of the polymer molecule, -R- being -O-, hydrogen, halogen or other monovalent atom or radical. The production of such polyamides is illustrated in Specification 461,236 and U.S.A. Specifications 2,071,250 and 2,130,948. The modifiers may be incorporated in a polymer before shaping or they may be applied to the shaped articles, e.g. as solutions or in suitable cases as pure compounds, for example by spraying, calendering, immersion, padding or exposure to vapour condensations. In suitable c
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US49975455A | 1955-04-06 | 1955-04-06 | |
US50379055A | 1955-04-25 | 1955-04-25 | |
US56997656A | 1956-03-01 | 1956-03-01 | |
US57306256A | 1956-03-16 | 1956-03-16 | |
US57306156A | 1956-03-16 | 1956-03-16 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB838413A true GB838413A (en) | 1960-06-22 |
Family
ID=27541789
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB21896/59A Expired GB838413A (en) | 1955-04-06 | 1956-04-06 | Modified synthetic condensation polymers and their production |
GB10659/56A Expired GB834557A (en) | 1955-04-06 | 1956-04-06 | Process for modifying fibres or films from natural or regenerated natural polymers |
GB10657/56A Expired GB838412A (en) | 1955-04-06 | 1956-04-06 | Process for modifying synthetic condensation polymers |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB10659/56A Expired GB834557A (en) | 1955-04-06 | 1956-04-06 | Process for modifying fibres or films from natural or regenerated natural polymers |
GB10657/56A Expired GB838412A (en) | 1955-04-06 | 1956-04-06 | Process for modifying synthetic condensation polymers |
Country Status (8)
Country | Link |
---|---|
BE (1) | BE546815A (en) |
CA (2) | CA947699A (en) |
CH (1) | CH380372A (en) |
DE (1) | DE1420639A1 (en) |
FR (1) | FR1149298A (en) |
GB (3) | GB838413A (en) |
IT (1) | IT566909A (en) |
NL (5) | NL113533C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1303559A1 (en) * | 2000-07-14 | 2003-04-23 | Mimotopes Pty Ltd | Activated modular grafted polymeric surfaces |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3284156A (en) * | 1961-09-28 | 1966-11-08 | Du Pont | Synthetic polyamide textile material having a polyorganosiloxane grafted thereto |
US4277242A (en) | 1977-02-07 | 1981-07-07 | Australian Atomic Energy Commision | Ionizing radiation treatment of wool textiles with resin for shrink resistance |
EP0532624B1 (en) * | 1990-06-05 | 1995-07-26 | E.I. Du Pont De Nemours And Company | Bonded fibrous articles |
WO2005028741A1 (en) * | 2003-09-18 | 2005-03-31 | Surface Innovations Limited | Fibrous products and methods of making and using them |
-
0
- IT IT566909D patent/IT566909A/it unknown
- NL NL113532D patent/NL113532C/xx active
- NL NL206079D patent/NL206079A/xx unknown
- NL NL206078D patent/NL206078A/xx unknown
- BE BE546815D patent/BE546815A/xx unknown
- NL NL113531D patent/NL113531C/xx active
-
1956
- 1956-04-04 CA CA704,830A patent/CA947699A/en not_active Expired
- 1956-04-05 CA CA704936A patent/CA920536A/en not_active Expired
- 1956-04-06 NL NL206080A patent/NL113533C/xx active
- 1956-04-06 FR FR1149298D patent/FR1149298A/en not_active Expired
- 1956-04-06 GB GB21896/59A patent/GB838413A/en not_active Expired
- 1956-04-06 GB GB10659/56A patent/GB834557A/en not_active Expired
- 1956-04-06 GB GB10657/56A patent/GB838412A/en not_active Expired
- 1956-04-06 CH CH3182256A patent/CH380372A/en unknown
- 1956-04-06 DE DE19561420639 patent/DE1420639A1/en active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1303559A1 (en) * | 2000-07-14 | 2003-04-23 | Mimotopes Pty Ltd | Activated modular grafted polymeric surfaces |
EP1303559A4 (en) * | 2000-07-14 | 2004-06-30 | Mimotopes Pty Ltd | Activated modular grafted polymeric surfaces |
Also Published As
Publication number | Publication date |
---|---|
NL113532C (en) | 1900-01-01 |
NL113531C (en) | 1900-01-01 |
NL113533C (en) | 1967-02-15 |
NL206078A (en) | 1900-01-01 |
CA947699A (en) | 1974-05-21 |
GB834557A (en) | 1960-05-11 |
DE1420639A1 (en) | 1968-10-31 |
IT566909A (en) | 1900-01-01 |
BE546815A (en) | 1900-01-01 |
FR1149298A (en) | 1957-12-23 |
CA920536A (en) | 1973-02-06 |
GB838412A (en) | 1960-06-22 |
CH380372A (en) | 1964-07-31 |
NL206079A (en) | 1900-01-01 |
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