CA1071232A - Process for the preparation of polyhydroxy methylene ethers and ion exchangers composed of the same - Google Patents
Process for the preparation of polyhydroxy methylene ethers and ion exchangers composed of the sameInfo
- Publication number
- CA1071232A CA1071232A CA260,883A CA260883A CA1071232A CA 1071232 A CA1071232 A CA 1071232A CA 260883 A CA260883 A CA 260883A CA 1071232 A CA1071232 A CA 1071232A
- Authority
- CA
- Canada
- Prior art keywords
- groups
- preparation
- per cent
- polyhydroxy
- ion exchangers
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
- B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
- C08F8/02—Alkylation
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Abstract of the Disclosure This invention relates to a process for the preparation of a poly-hydroxy methylene ether which comprises reacting polyhydioxy methylene with an alkylating agent in an aqueous alkaline medium.
Description
~07~Z3Z
P~OCESS FOR THE PREPARATION OF POLYHYDROXY
METHYLENE ETHERS AND ION EXCHANGERS
COMPOSED OF THE SAME
-The present invention relates to a process for the preparation of polyhydroxy methylene ethers and to ion ex-changers composed of the polyhydroxy methylene ethers prepared in accordance with the process.
Instead of starch and gelatin, cellulose derivatives, for example, have been used for a long time as adhesives and binders or as emulsifiers in the chemical industry. There has been àn increasing demand in recent years for special ion exchangers, in addition to adsorbing materials of the general type, especially in the biochemical industry, for use in chromatographic separating processes, e.g. in order to separate amino acid fractions or protein fractions from mixtures to be treated.
It ls known to use cellulose ethers for this purpose, for example. Generally, cellulose is etherified by reacting lt in an alkaline medium in a non-homogeneous phase with an alkylating agent, for example with halogen fatty acids. If the cellulose ethers are to be used as ion exchangers, the etherification agents used for their preparation carry sub-stituents with lonic groups. In these etherification processes, the primary hydroxyl groups of the anhydro glucose unit are prlmarily attacked, whereas the secondary hydroxyl groups are only secondarily attacked.
These cellulose ethers and the ion exchangers prepared therefrom have the drawback that they are not stable to chemical and enzymatic attack. This property limits their wider use by biochemists, physiologists, and physicians.
It is the ob~ect of the present invention to eliminate this drawback. This is achieved by preparing ethers of ~071Z32 polyhydroxy methylene. The present invention provides a process for the preparation of polyhydroxy methylene ethers, in which polyhydroxy methylene is reacted with alkylating agents in an aqueous-alkaline medium to which an organic solvent may be added, if desired. Further, the present invention relates to ion exchangers composed of etherified polyhydroxy methylene, in which the alkoxy groups have ionic or ionizable groups. The polyhydroxy methylene used as the starting material in the pro-cess of the present invention is a known polymer the preparation of which is described, for example, by H. C. Haas and N. W.
Schuler in "J. Polym. Science", Vol. 31, page 238 (1958).
Surprisingly, it was found that, although polyhydroxy methylene exclusively possesses secondary hydroxyl groups, it may be substituted to form ethers. According to the process of the present invention, the reaction preferably is carried out accordlng to one of the following two methods:
1. The components, i.e. polyhydroxy methylene, isopro-panol, and NaOH solution, are mixed in a kneader and an alkyl-ating agent is added at a temperature between about 50 and 90 C, preferably at about 70C.
P~OCESS FOR THE PREPARATION OF POLYHYDROXY
METHYLENE ETHERS AND ION EXCHANGERS
COMPOSED OF THE SAME
-The present invention relates to a process for the preparation of polyhydroxy methylene ethers and to ion ex-changers composed of the polyhydroxy methylene ethers prepared in accordance with the process.
Instead of starch and gelatin, cellulose derivatives, for example, have been used for a long time as adhesives and binders or as emulsifiers in the chemical industry. There has been àn increasing demand in recent years for special ion exchangers, in addition to adsorbing materials of the general type, especially in the biochemical industry, for use in chromatographic separating processes, e.g. in order to separate amino acid fractions or protein fractions from mixtures to be treated.
It ls known to use cellulose ethers for this purpose, for example. Generally, cellulose is etherified by reacting lt in an alkaline medium in a non-homogeneous phase with an alkylating agent, for example with halogen fatty acids. If the cellulose ethers are to be used as ion exchangers, the etherification agents used for their preparation carry sub-stituents with lonic groups. In these etherification processes, the primary hydroxyl groups of the anhydro glucose unit are prlmarily attacked, whereas the secondary hydroxyl groups are only secondarily attacked.
These cellulose ethers and the ion exchangers prepared therefrom have the drawback that they are not stable to chemical and enzymatic attack. This property limits their wider use by biochemists, physiologists, and physicians.
It is the ob~ect of the present invention to eliminate this drawback. This is achieved by preparing ethers of ~071Z32 polyhydroxy methylene. The present invention provides a process for the preparation of polyhydroxy methylene ethers, in which polyhydroxy methylene is reacted with alkylating agents in an aqueous-alkaline medium to which an organic solvent may be added, if desired. Further, the present invention relates to ion exchangers composed of etherified polyhydroxy methylene, in which the alkoxy groups have ionic or ionizable groups. The polyhydroxy methylene used as the starting material in the pro-cess of the present invention is a known polymer the preparation of which is described, for example, by H. C. Haas and N. W.
Schuler in "J. Polym. Science", Vol. 31, page 238 (1958).
Surprisingly, it was found that, although polyhydroxy methylene exclusively possesses secondary hydroxyl groups, it may be substituted to form ethers. According to the process of the present invention, the reaction preferably is carried out accordlng to one of the following two methods:
1. The components, i.e. polyhydroxy methylene, isopro-panol, and NaOH solution, are mixed in a kneader and an alkyl-ating agent is added at a temperature between about 50 and 90 C, preferably at about 70C.
2. Polyhydroxy methylene is dissolved at room tempera-ture ln an about 20 to 50 per cent by weight NaOH solution and the alkylatlng agent is added at a temperature between 20 and 90 C, preferably between about 70 and 90 C.
These reactions may be conducted in an aqueous-alkaline medium in a heterogenous phase, an organic solvent, such as isopropanol, being added as a diluent, if desired; alterna-tively, the reactions may be conducted in a homogeneous phase, whlch is an essential improvement in the art, as compared, for exsmple, with the conditions under which cellulose ethers are prepared, because it enables a more uniform substitution. Poly-hydroxy methylene is insoluble in conventional solvents, ~.
. .,, ~. ~
-such as water, alcohols, esters, acetone, dimethyl formamide, ethers, benzene, toluene, chloroform or dimethyl sulfoxide and swells only slightly in some of them; it is soluble, however, in alkaline solutions, for example in 25 to 50 per cent by weight solutions of NaOH at room temperature. If the temperature is raised as high as approximately 80 C, even a 20 per cent by weight NaOH solution will be sufficient.
If the solutions are diluted or the NaOH concentration is other-wise reduced, part of the polyhydroxy methylene may be re-precipitated during a progressive etherification process according to the second method. If the ether formed is solubte in water, however, the reaction may be continued in a homogeneous phase.
In additlon to one or more groups capable of forming an ether, the alkylatlng agent to be used must have at least one functional ionic or lonlzable group, for exampte a carboxyl group, a sulfo group, a phospho group, a quaternary ammonium group, or a substituted amino group, in order to produce the desired ion exchanging property. Examples of sub-stances whlch may be used for this purpose are:
N ,N-dialkylamino-,B-chloro-alkanes, N ,N-diarylamlno-,13-chloro-alkanes, 2 0 3-chloro-2-hydroxypropyl-trime thyl-ammonium-hydrochloride, 2, 3-epo~ypropyl-trlmethyl-ammonium-hydrochloride, ethylene imine, chloro acetic acid, dlchloro acetic acid, trichloro acetic acid, ~-chloroethane sulfonic acid, inyl sulfonic a~-id, chloroethane phosphonic acid, vinyl phosphonic acid, N ,N-dichloro-ethyl-alkylamine, and N, N-dichloro-ethyl-arylamine .
The products obtained according to the present invention may be water-soluble or preponderantly water-insoluble. These properties may be influenced by a suitable selection of the substituents, the degree of substitution, or by cross-linking with at least bi-functional reactants.
The process according to the present invention has the advantage that the substances produced possess an improved chemical stability and are not easily decomposed. ln particular, they are resistant to enzy-matlc or other biochemlcal decomposing processes. If they possess lonic or ionizable groups, their ion exchanging capacity with ionic or crypto-ionic substances, for example under biochemical or physiological-chemical conditions, is excellent.
Thus, the polyhydroxy methylene ethers according to the present inventlon may be widely used, for example as ion exchangers in blochem-lstry, medicine, and physiological chemistry.
In the following examples, the percentages are by weight and the letters "MS" state the degree of molar substitution.
Example 1 50 g of polyhydroxy methylene (1.67 moles, calculated on the polymer base unit) were mixed for 30 minutes in a kneader with 250 ml of 87 per cent isopropanol and 66.8 g of a 50 per cent by weight aqueous NaOH solution (0.84 mole) at a temperature of 25 C . Etherification was effected by drop-wise adding 168 g of a 50 per cent by weight aqueous solution of 3-chloro-2-hydroxypropyl-trimethyl ammonium hydrochloride (0.45 mole), followed by one hour's heatin~ to 70 C. The reaction - 1071Z3Z K-24l4 mixture was then diluted with methanol and neutralized, with phenol-phthalein serving as the indicator, by adding glacial acetic acid. The white powder obtained after filtration was washed with aqueous metha-nol and dried at 60C. It contained 0.4 per cent by weight oE nitrogen, which corresponds to an MS of about 0 .01.
Example 2 15 g of polyhydroxy methylene (0.5 mole)wereadded to 120 g of a 24 per cent aqueous NaOH solution (0.7 mole) in a three-necked flask of 500 ml capacity, heated to 70C and stirred for 45 minutes at this temperaturè. Etherlfication was effected by drop-wise adding 188 g of a 50 per cent by weight aqueous solution of 3-chloro-2-hydroxypropyl-trimethyl-ammonium hydrochloride to the viscous, yellowish solution over a period of 10 minutes. The solution lost some of its viscosity and part of the substance precipitated. The reaction mixture was poured into 500 ml of water, filtered, washed with water, lsopropyl alcohol and ace-tone, drled at 60 C, and finally ground . The resulting white powder contalned 1.8 per cent by weight of N, which corresponds to an MS of 0.05.
Example 3 10 g of polyhydroxy methylene (0.33 mole)weredissolved in 75 g of a 40 per cent aqueous NaOH solution (0. 75 mole) and stirred for 45 minutes at 70C. Etherification was effected by adding 65 g of glycidyl-trimethyl-ammonium chloride (0.43 mole), followed by heating and 45 minutes' stirring at 70C. The reaction mixture was poured into 500 ml of water, filtered, washed neutral with water, dried at 60C, and then ground. After dialysis in an aqueous suspension against water, followed by freeze-drying, a water-insoluble powder was obtained which contained 1 . 0 per cent by weight of N corresponding to an MS of 0. 02 .
` - 1071232 Example 4 The procedure described in Example 3 was repeated, except that 100 g of the sodium salt of 2-chloroethane-sulfonic acid (0.6 mole) were used as the etherification agent. The water-insoluble powder ob-tained contained 3 . O per cent by weight of S correspondlng to a degree of substitution of O . 03 .
ExamDle 5 The procedure described in Ex. 3 was repeated, except that 58 g of 2-chloroethyl-dlethyl-amine (0.43 mole) were used as the etheri-flcation agent. The water-insoluble powder obtained contained 4.3 per cent by weight of N correspondlng to a degree of substitution of 0.13 .
ExamPle 6 15 g of polyhydroxy methylene (O.S mole) were dissolved ln a sodlum hydroxlde solutlon containing 44 g of NaOH (1.1 moles) in 200 g of water, and the vlscous mass was then heated for 45 mlnutes to 80 to 90 C. Etherlficatlon was effected by drop-wlse adding S9 g of an 80 per cent by welght aqueous monochloro acetlc acid solutlon (0.5 mole), followed by one hour's heatlng to 80 to 90C. After cooling the mixture and neutralizlng lt wlth glaclal acetlc acid, uslng phens~lphthaleln as the lndlcator, the mass was dlluted to 500 ml by adding water and pour-ed lnto about 4 llters of methanol, whereupon the reactlon product pre-clpltated. After flltratlon, a whlte powder was obtalned whlch was freed from chlorldes by washlng lt three tlmes wlth pure methanol. The mass was drled at 60C and pulverlzed ln a mortar. Yleld: 17.6 g. The water-soluble substance contalned 8.85 per cent by welght of Na, whlch corresponds to a degree of substltutlon of 0.175.
Example 7 The procedure described in Example 3 was repeated, except that 84 g of dichloro-acetic acid (0.66 mole) wereused as the etherification agent. The resulting water-insoluble powder contained 1.5 per cent by weight of Na.
Example 8 The procedure described in Example 3 was repeated, except that 35 g of trichloro acetic acid (0.22 mole)wereused as the etherification agent. A water-insoluble powder was obtained which contained 3 .1 per cent by weight of Na.
It wlll be obvious to those skilled in the art that many modifica-tions may be made within the scope of the present invention without de-parting from the spirit thereof, and the invention includes all such modlf ications .
These reactions may be conducted in an aqueous-alkaline medium in a heterogenous phase, an organic solvent, such as isopropanol, being added as a diluent, if desired; alterna-tively, the reactions may be conducted in a homogeneous phase, whlch is an essential improvement in the art, as compared, for exsmple, with the conditions under which cellulose ethers are prepared, because it enables a more uniform substitution. Poly-hydroxy methylene is insoluble in conventional solvents, ~.
. .,, ~. ~
-such as water, alcohols, esters, acetone, dimethyl formamide, ethers, benzene, toluene, chloroform or dimethyl sulfoxide and swells only slightly in some of them; it is soluble, however, in alkaline solutions, for example in 25 to 50 per cent by weight solutions of NaOH at room temperature. If the temperature is raised as high as approximately 80 C, even a 20 per cent by weight NaOH solution will be sufficient.
If the solutions are diluted or the NaOH concentration is other-wise reduced, part of the polyhydroxy methylene may be re-precipitated during a progressive etherification process according to the second method. If the ether formed is solubte in water, however, the reaction may be continued in a homogeneous phase.
In additlon to one or more groups capable of forming an ether, the alkylatlng agent to be used must have at least one functional ionic or lonlzable group, for exampte a carboxyl group, a sulfo group, a phospho group, a quaternary ammonium group, or a substituted amino group, in order to produce the desired ion exchanging property. Examples of sub-stances whlch may be used for this purpose are:
N ,N-dialkylamino-,B-chloro-alkanes, N ,N-diarylamlno-,13-chloro-alkanes, 2 0 3-chloro-2-hydroxypropyl-trime thyl-ammonium-hydrochloride, 2, 3-epo~ypropyl-trlmethyl-ammonium-hydrochloride, ethylene imine, chloro acetic acid, dlchloro acetic acid, trichloro acetic acid, ~-chloroethane sulfonic acid, inyl sulfonic a~-id, chloroethane phosphonic acid, vinyl phosphonic acid, N ,N-dichloro-ethyl-alkylamine, and N, N-dichloro-ethyl-arylamine .
The products obtained according to the present invention may be water-soluble or preponderantly water-insoluble. These properties may be influenced by a suitable selection of the substituents, the degree of substitution, or by cross-linking with at least bi-functional reactants.
The process according to the present invention has the advantage that the substances produced possess an improved chemical stability and are not easily decomposed. ln particular, they are resistant to enzy-matlc or other biochemlcal decomposing processes. If they possess lonic or ionizable groups, their ion exchanging capacity with ionic or crypto-ionic substances, for example under biochemical or physiological-chemical conditions, is excellent.
Thus, the polyhydroxy methylene ethers according to the present inventlon may be widely used, for example as ion exchangers in blochem-lstry, medicine, and physiological chemistry.
In the following examples, the percentages are by weight and the letters "MS" state the degree of molar substitution.
Example 1 50 g of polyhydroxy methylene (1.67 moles, calculated on the polymer base unit) were mixed for 30 minutes in a kneader with 250 ml of 87 per cent isopropanol and 66.8 g of a 50 per cent by weight aqueous NaOH solution (0.84 mole) at a temperature of 25 C . Etherification was effected by drop-wise adding 168 g of a 50 per cent by weight aqueous solution of 3-chloro-2-hydroxypropyl-trimethyl ammonium hydrochloride (0.45 mole), followed by one hour's heatin~ to 70 C. The reaction - 1071Z3Z K-24l4 mixture was then diluted with methanol and neutralized, with phenol-phthalein serving as the indicator, by adding glacial acetic acid. The white powder obtained after filtration was washed with aqueous metha-nol and dried at 60C. It contained 0.4 per cent by weight oE nitrogen, which corresponds to an MS of about 0 .01.
Example 2 15 g of polyhydroxy methylene (0.5 mole)wereadded to 120 g of a 24 per cent aqueous NaOH solution (0.7 mole) in a three-necked flask of 500 ml capacity, heated to 70C and stirred for 45 minutes at this temperaturè. Etherlfication was effected by drop-wise adding 188 g of a 50 per cent by weight aqueous solution of 3-chloro-2-hydroxypropyl-trimethyl-ammonium hydrochloride to the viscous, yellowish solution over a period of 10 minutes. The solution lost some of its viscosity and part of the substance precipitated. The reaction mixture was poured into 500 ml of water, filtered, washed with water, lsopropyl alcohol and ace-tone, drled at 60 C, and finally ground . The resulting white powder contalned 1.8 per cent by weight of N, which corresponds to an MS of 0.05.
Example 3 10 g of polyhydroxy methylene (0.33 mole)weredissolved in 75 g of a 40 per cent aqueous NaOH solution (0. 75 mole) and stirred for 45 minutes at 70C. Etherification was effected by adding 65 g of glycidyl-trimethyl-ammonium chloride (0.43 mole), followed by heating and 45 minutes' stirring at 70C. The reaction mixture was poured into 500 ml of water, filtered, washed neutral with water, dried at 60C, and then ground. After dialysis in an aqueous suspension against water, followed by freeze-drying, a water-insoluble powder was obtained which contained 1 . 0 per cent by weight of N corresponding to an MS of 0. 02 .
` - 1071232 Example 4 The procedure described in Example 3 was repeated, except that 100 g of the sodium salt of 2-chloroethane-sulfonic acid (0.6 mole) were used as the etherification agent. The water-insoluble powder ob-tained contained 3 . O per cent by weight of S correspondlng to a degree of substitution of O . 03 .
ExamDle 5 The procedure described in Ex. 3 was repeated, except that 58 g of 2-chloroethyl-dlethyl-amine (0.43 mole) were used as the etheri-flcation agent. The water-insoluble powder obtained contained 4.3 per cent by weight of N correspondlng to a degree of substitution of 0.13 .
ExamPle 6 15 g of polyhydroxy methylene (O.S mole) were dissolved ln a sodlum hydroxlde solutlon containing 44 g of NaOH (1.1 moles) in 200 g of water, and the vlscous mass was then heated for 45 mlnutes to 80 to 90 C. Etherlficatlon was effected by drop-wlse adding S9 g of an 80 per cent by welght aqueous monochloro acetlc acid solutlon (0.5 mole), followed by one hour's heatlng to 80 to 90C. After cooling the mixture and neutralizlng lt wlth glaclal acetlc acid, uslng phens~lphthaleln as the lndlcator, the mass was dlluted to 500 ml by adding water and pour-ed lnto about 4 llters of methanol, whereupon the reactlon product pre-clpltated. After flltratlon, a whlte powder was obtalned whlch was freed from chlorldes by washlng lt three tlmes wlth pure methanol. The mass was drled at 60C and pulverlzed ln a mortar. Yleld: 17.6 g. The water-soluble substance contalned 8.85 per cent by welght of Na, whlch corresponds to a degree of substltutlon of 0.175.
Example 7 The procedure described in Example 3 was repeated, except that 84 g of dichloro-acetic acid (0.66 mole) wereused as the etherification agent. The resulting water-insoluble powder contained 1.5 per cent by weight of Na.
Example 8 The procedure described in Example 3 was repeated, except that 35 g of trichloro acetic acid (0.22 mole)wereused as the etherification agent. A water-insoluble powder was obtained which contained 3 .1 per cent by weight of Na.
It wlll be obvious to those skilled in the art that many modifica-tions may be made within the scope of the present invention without de-parting from the spirit thereof, and the invention includes all such modlf ications .
Claims (2)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An ion exchanger composed of etherified polyhydroxy methylene in which the alkoxy groups carry ionic or ionizable substituents.
2. An ion exchanger according to claim 1, in which the ionic or ionizable substituents are carboxyl groups, sulfo groups, phospho groups, quaternary ammonium groups, or sub-stituted amino groups.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2540688A DE2540688C3 (en) | 1975-09-12 | 1975-09-12 | Process for the production of ethers of polyhydroxymethylene which can be used as ion exchangers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1071232A true CA1071232A (en) | 1980-02-05 |
Family
ID=5956300
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA260,883A Expired CA1071232A (en) | 1975-09-12 | 1976-09-10 | Process for the preparation of polyhydroxy methylene ethers and ion exchangers composed of the same |
Country Status (18)
| Country | Link |
|---|---|
| JP (1) | JPS5233979A (en) |
| AT (1) | AT355312B (en) |
| AU (1) | AU504619B2 (en) |
| BE (1) | BE846006A (en) |
| CA (1) | CA1071232A (en) |
| CH (1) | CH599253A5 (en) |
| DE (1) | DE2540688C3 (en) |
| DK (1) | DK410276A (en) |
| ES (1) | ES451448A1 (en) |
| FI (1) | FI61495C (en) |
| FR (1) | FR2323713A1 (en) |
| GB (1) | GB1489865A (en) |
| IE (1) | IE43427B1 (en) |
| IT (1) | IT1066290B (en) |
| LU (1) | LU75773A1 (en) |
| NL (1) | NL7610013A (en) |
| NO (1) | NO145976C (en) |
| SE (1) | SE7610018L (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2818086C2 (en) * | 1978-04-25 | 1984-11-29 | Sumitomo Chemical Co., Ltd., Osaka | Carrier material for immobilizing enzymes and process for their production |
-
1975
- 1975-09-12 DE DE2540688A patent/DE2540688C3/en not_active Expired
-
1976
- 1976-09-08 AU AU17543/76A patent/AU504619B2/en not_active Expired
- 1976-09-09 FI FI762591A patent/FI61495C/en not_active IP Right Cessation
- 1976-09-09 CH CH1145876A patent/CH599253A5/xx not_active IP Right Cessation
- 1976-09-09 BE BE170480A patent/BE846006A/en not_active IP Right Cessation
- 1976-09-09 NO NO763099A patent/NO145976C/en unknown
- 1976-09-09 IE IE2018/76A patent/IE43427B1/en unknown
- 1976-09-09 NL NL7610013A patent/NL7610013A/en not_active Application Discontinuation
- 1976-09-10 ES ES451448A patent/ES451448A1/en not_active Expired
- 1976-09-10 LU LU75773A patent/LU75773A1/xx unknown
- 1976-09-10 FR FR7627251A patent/FR2323713A1/en active Granted
- 1976-09-10 AT AT673076A patent/AT355312B/en not_active IP Right Cessation
- 1976-09-10 DK DK410276A patent/DK410276A/en not_active Application Discontinuation
- 1976-09-10 IT IT51214/76A patent/IT1066290B/en active
- 1976-09-10 SE SE7610018A patent/SE7610018L/en not_active Application Discontinuation
- 1976-09-10 CA CA260,883A patent/CA1071232A/en not_active Expired
- 1976-09-10 GB GB37627/76A patent/GB1489865A/en not_active Expired
- 1976-09-13 JP JP51109727A patent/JPS5233979A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| NO763099L (en) | 1977-03-15 |
| IE43427B1 (en) | 1981-02-25 |
| NO145976B (en) | 1982-03-29 |
| FI61495B (en) | 1982-04-30 |
| NO145976C (en) | 1982-07-07 |
| FR2323713B1 (en) | 1981-05-29 |
| JPS5233979A (en) | 1977-03-15 |
| FR2323713A1 (en) | 1977-04-08 |
| GB1489865A (en) | 1977-10-26 |
| ATA673076A (en) | 1979-07-15 |
| ES451448A1 (en) | 1978-05-01 |
| AU504619B2 (en) | 1979-10-18 |
| LU75773A1 (en) | 1978-05-12 |
| FI762591A (en) | 1977-03-13 |
| IT1066290B (en) | 1985-03-04 |
| DE2540688A1 (en) | 1977-03-17 |
| DE2540688B2 (en) | 1979-03-08 |
| IE43427L (en) | 1977-03-12 |
| CH599253A5 (en) | 1978-05-31 |
| BE846006A (en) | 1977-03-09 |
| AT355312B (en) | 1980-02-25 |
| AU1754376A (en) | 1978-03-16 |
| DK410276A (en) | 1977-03-13 |
| DE2540688C3 (en) | 1979-10-31 |
| NL7610013A (en) | 1977-03-15 |
| SE7610018L (en) | 1977-03-13 |
| FI61495C (en) | 1982-08-10 |
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