EP0000565B1 - Wässrige Copolymerisatlösungen, Verfahren zu deren Herstellung und deren Verwendung als Hüllenbildner für die Herstellung von Microkapseln durch Komplexkoazervation - Google Patents
Wässrige Copolymerisatlösungen, Verfahren zu deren Herstellung und deren Verwendung als Hüllenbildner für die Herstellung von Microkapseln durch Komplexkoazervation Download PDFInfo
- Publication number
- EP0000565B1 EP0000565B1 EP78100470A EP78100470A EP0000565B1 EP 0000565 B1 EP0000565 B1 EP 0000565B1 EP 78100470 A EP78100470 A EP 78100470A EP 78100470 A EP78100470 A EP 78100470A EP 0000565 B1 EP0000565 B1 EP 0000565B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- copolymer
- solution
- copolymers
- maleic acid
- aqueous
- 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
- 229920001577 copolymer Polymers 0.000 title claims description 56
- 238000000034 method Methods 0.000 title claims description 11
- 239000007864 aqueous solution Substances 0.000 title claims description 10
- 238000005354 coacervation Methods 0.000 title claims description 8
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000003094 microcapsule Substances 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title description 4
- 239000000463 material Substances 0.000 title 1
- 239000000243 solution Substances 0.000 claims description 62
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 19
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 16
- 239000011976 maleic acid Substances 0.000 claims description 16
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003999 initiator Substances 0.000 claims description 9
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003839 salts Chemical group 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 108010010803 Gelatin Proteins 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005538 encapsulation Methods 0.000 description 4
- 238000012673 precipitation polymerization Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000001427 coherent effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical group 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 150000002168 ethanoic acid esters Chemical class 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 description 1
- -1 aliphatic alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 150000002976 peresters Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/10—Complex coacervation, i.e. interaction of oppositely charged particles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions 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; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
- C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Definitions
- the invention relates to aqueous copolymer solutions, processes for their preparation and their use as shell formers for the production of microcapsules by complex coacervation.
- the aqueous polymer solutions according to the invention are those whose polymer content is 5 to 30% by weight and consists of a mixture of (A) a copolymer with an intrinsic viscosity [ 'I] of 0.05 to 1 (dl / g) to its statistically distributed structural units 65 to 90 mol% consist of residues of acrylamide and 10 to 35 mol% of residues of maleic acid or maleic anhydride and (B) a corresponding hydrolyzed copolymer with an intrinsic viscosity [q] of 0.05 to 1.5 (dl / g) whose statistically distributed structural units accordingly consist of residues of acrylamide, acrylic acid and maleic acid, the maleic acid residues being at least partially in salt form, and which is characterized in that the weight ratio of the copolymers (A) and (B) is 1
- the copolymers (A) can be obtained by radical copolymerization of 65-90 mol% acrylamide and 10-35 mol% maleic anhydride or maleic acid.
- the copolymerization of acrylamide and maleic anhydride is advantageously carried out as a precipitation polymerization in organic solvents which are inert to anhydride groups.
- organic solvents which are inert to anhydride groups.
- Particularly cheap solvents are acetone and acetic acid esters of alcohols with 1-3 carbon atoms because of their good solvent power for the monomers and not least because of their low volatility.
- the polymerization can be initiated with the usual free-radical initiators such as aliphatic azo compounds or organic per-compounds such as peroxides or peresters.
- the polymerization temperature is determined by the decomposition properties of the initiator and, when using azoisobutyronitrile in batches, is 50 ° -80 ° C. In this process, the copolymers are obtained as finely divided powders and can easily be filtered off and freed of residual monomers by washing.
- copolymerization of acrylamide and maleic acid to give copolymers (A) can be carried out both as precipitation polymerization in organic solvents and also as solution polymerization in water.
- the precipitation copolymers can be dissolved in solvent or, after drying, in water to 5-30% by weight solutions.
- the anhydride groups of the acrylamide-maleic anhydride copolymers pass into maleic acid groups.
- the organic solvent is then separated off by decanting and / or distillation.
- aqueous solutions of the copolymers (A) is the solution copolymerization of acrylamide and maleic acid in water.
- the maleic acid can either be prepared by dissolving the appropriate amount of the andydride in water before the polymerization or used as such.
- Suitable initiators are water-soluble per compounds such as persulfates or hydrogen peroxide, optionally in combination with a reducing agent and / or heavy metal salt. Azo compounds with sufficient water solubility are also suitable initiators. Azoisobutyronitrile is sufficiently soluble in water, especially at elevated temperatures, and is particularly preferred because it does not affect the salt content of the solutions.
- the solution polymerization can be carried out batchwise with presentation of the entire batch or according to a semi-batch feed process with metering in of the monomers.
- the preferred method of solution polymerization is that the aqueous solution of the monomers, which contains the initiator in dissolved or finely suspended form, is added at about 80 ° -120 ° C. with the exclusion of oxygen to a stirred charge of oxygen-free water in about 1-10 hours.
- the azoisobutyronitrile can also be added dropwise as a solution in an organic solvent in synchronism with the monomer solution, it being possible for the solvent to be distilled off continuously. After the monomer addition has ended, the mixture is stirred for 15-120 minutes and the solution is then cooled to room temperature.
- copolymers (A) obtained by solution polymerization still contain small amounts of residual monomers, but these generally have no adverse effect on the application properties of the solutions.
- copolymers (A) prepared in aqueous solution already contain small amounts of acrylic acid and maleic acid salt units formed by hydrolysis during the polymerization.
- Copolymers (A) according to the invention are obtained by copolymerization of 65-90 mol% of acrylamide and 10-35 mol% of maleic acid or maleic anhydride. Copolymers (A) of 70-85 mol% of acrylamide and 15-30 mol% of maleic acid or maleic anhydride are preferably used.
- the copolymers (A) contain the structural units made of acrylamide and Maleic anhydride in statistical distribution and in proportions that correspond to the compositions of the monomer mixtures.
- the free radical initiators are added in amounts of 0.1-10% by weight, preferably 0.3-3.0% by weight, based on monomers. In precipitation polymerizations, the polymer yields are generally 75-95%.
- the copolymers (A) have intrinsic viscosity [ 1 /] of 0.05-l ', 0 [dl / g], preferably 0.08 to 0.4 [dl / g] (determined in 0.9% aqueous sodium chloride solution) .
- the solutions of the copolymers (B)) can be obtained by heating the aqueous solutions of the copolymers (A) at temperatures of 60 ° -150 ° C., preferably 80-130 ° C. for a long time, optionally under pressure in an autoclave. Hydrolysis under reflux conditions at normal pressure is particularly preferred. Partial hydrolysis of acrylamide units occurs during heating. The resulting ammonia neutralizes some of the maleic acid building blocks and thereby causes an increase in the pH of the solution. As a result of the hydrolysis, the acrylamide-maleic acid copolymer converts into a copolymer which consists of acrylamide-acrylic acid and maleic acid units and in which the maleic acid units are at least partially in salt form.
- Solutions of copolymers (B) according to the invention are obtained by heating solutions of the copolymers (A) according to the invention to 60 ° -150 ° C., preferably 80 ° -130 ° C. and particularly preferably to about 100 ° C. (reflux under normal pressure) until the pH of the solutions has risen to 3.8 to 4.9, preferably 4.0 to 4.6.
- the intrinsic viscosity of the copolymers (B) determined in 0.9% aqueous sodium chloride solution, is 0.05 to 1.5 [dl / g], preferably 0.08 to 1.0 [dl / g ].
- the solutions of the copolymers (A) and the solutions of the copolymers (B) also form coacervates on their own with gelatin, if necessary after adjusting the pH with ammonia or alkali metal hydroxide solution or with acetic acid.
- these coacervates do not form a shell or a closed shell and / or are very sticky.
- aqueous solutions of the copolymers (A) and (B) according to the weight ratio of the dissolved copolymers (A): (B) as 1: 2 to 20: 1, surprisingly polymer solutions are obtained which, together with gelatin, provide coacervates which form uniform, closed shells and are therefore particularly suitable for the production of microcapsules.
- the optimal mixing ratio is mainly influenced by the composition of the copolymer (A) and by the pH of the solution of the copolymer (B), which is a measure of the degree of hydrolysis, and must be determined experimentally for each pair of copolymers.
- solutions of copolymers (A) can also be mixed with solutions of copolymers (B) which have been obtained from copolymers (A ') with a different composition by hydrolysis (for example copolymer (A) with 70 mol% acrylamide and 30 mol% % Of maleic acid units, and copolymer solution (B) from copolymer (A ') with 80 mol% of acrylamide and 20 mol% of maleic acid units).
- changing the pH of the polymer solution by adding ammonia or alkali hydroxide or acetic acid can have a favorable effect on the coacervation behavior.
- microencapsulation by complex coacervation is known in principle. It is based on dispersing the encapsulating substance in finely divided form in an aqueous solution suitable for coacervate formation, and then triggering the coacervation. This is done by diluting, changing the pH or cooling or by a combination of these measures, depending on the system used.
- the aqueous polymer solutions of the invention form complex coacervates with gelatin by dilution and / or cooling. They can be mixed, for example, in 10-15% by weight aqueous solution with a 10-15% by weight gelatin solution and coacervated by dilution and cooling. It is astonishing that such highly concentrated solutions can be used. It is also surprising that the coacervates obtained, which are a separate soft gel phase, already contain 20-30 % by weight of solids. This high solids content makes it very easy to dry the coacervates into powders. Since the coacervates form extremely coherent shells or coatings, they are particularly suitable for the production of microcapsules. During coacervation, the separate gel phase forms as a coherent layer on small, liquid or solid separate particles dispersed in the solution and envelops these particles.
- the combination of polymer solutions according to the invention and gelatin can be used to microencapsulate a large number of liquid or solid dispersible or water-insoluble or sparingly water-insoluble or water-resistant substances.
- Examples include: organic solvents, paraffin oils, perfume oils, silicone defoamers, Phosphoric acid esters, liquid crystals and color pigments, as well as pharmaceuticals and pesticides.
- Example 1 a) and 1 b) are mixed in the ratios given in the table.
- the mixtures are puffed according to the method given in Example 1 c).
- the encapsulation behavior is said to be "good” if the oil droplets are surrounded by a closed, regularly shaped and uniformly thick shell.
- a “medium” is a closed, irregularly shaped and unevenly thick shell.
- a “bad” encapsulation behavior occurs if the casing is not closed and coherent, the capsules stick very strongly or no casing is formed at all.
- Example 2 The mixed solutions are tested according to the method described in Example 1 c). The encapsulation behavior is assessed according to Example 2.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing Of Micro-Capsules (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paper (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19772734577 DE2734577A1 (de) | 1977-07-30 | 1977-07-30 | Polymerloesungen |
DE2734577 | 1977-07-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0000565A1 EP0000565A1 (de) | 1979-02-07 |
EP0000565B1 true EP0000565B1 (de) | 1981-04-29 |
Family
ID=6015335
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78100470A Expired EP0000565B1 (de) | 1977-07-30 | 1978-07-21 | Wässrige Copolymerisatlösungen, Verfahren zu deren Herstellung und deren Verwendung als Hüllenbildner für die Herstellung von Microkapseln durch Komplexkoazervation |
Country Status (6)
Country | Link |
---|---|
US (1) | US4181639A (it) |
EP (1) | EP0000565B1 (it) |
JP (1) | JPS5426843A (it) |
DE (2) | DE2734577A1 (it) |
DK (1) | DK335578A (it) |
IT (1) | IT1106614B (it) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3016170A1 (de) | 1980-04-26 | 1981-10-29 | Bayer Ag, 5090 Leverkusen | Mikrokapseln mit definierter oeffnungstemperatur, verfahren zu deren herstellung sowie deren verwendung |
USRE33749E (en) * | 1987-07-20 | 1991-11-19 | Dow Corning Corporation | Storage stable heat curable organosiloxane compositions containing microencapsulated platinum-containing catalysts |
US4784879A (en) * | 1987-07-20 | 1988-11-15 | Dow Corning Corporation | Method for preparing a microencapsulated compound of a platinum group metal |
US5268419A (en) * | 1988-01-28 | 1993-12-07 | Rohm And Haas Company | Fast curing binder for cellulose |
US5314943A (en) * | 1990-11-30 | 1994-05-24 | Rohm And Haax Company | Low viscosity high strength acid binder |
DE69321765T3 (de) * | 1992-06-04 | 2006-08-24 | Arjo Wiggins Ltd., Basingstoke | Druckempfindliches Aufzeichnungsmaterial |
GB9522233D0 (en) * | 1995-10-31 | 1996-01-03 | Wiggins Teape Group The Limite | Pressure-sensitive copying paper |
DE19634393A1 (de) * | 1996-08-26 | 1998-03-05 | Bayer Ag | Verfahren zur Herstellung vernetzter Polymerisate |
DE19840583A1 (de) | 1998-09-05 | 2000-03-09 | Bayer Ag | Mikrokapsel-Formulierungen |
US6653256B1 (en) | 1999-08-24 | 2003-11-25 | Bayer Aktiengesellschaft | Microcapsule formulations |
US7919331B2 (en) * | 2006-12-21 | 2011-04-05 | Silver Lake Research Corporation | Chromatographic test strips for one or more analytes |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1900865A1 (de) * | 1969-01-09 | 1970-08-27 | Bayer Ag | Verfahren zur Herstellung von Mikrokapseln |
US3635915A (en) * | 1969-11-28 | 1972-01-18 | Deering Milliken Res Corp | Copolymers of maleic acid and acrylic acid |
DE2010117C3 (de) * | 1970-03-04 | 1979-06-07 | Bayer Ag, 5090 Leverkusen | Verfahren zur Herstellung von thermoreversiblen Koazervaten |
DE2060571A1 (de) * | 1970-12-09 | 1972-06-15 | Bayer Ag | Verfahren zur Herstellung von thermoreversiblen Koazervaten |
DE2217696C3 (de) * | 1972-04-13 | 1979-06-28 | Basf Ag, 6700 Ludwigshafen | Verteilungsstabile Dispersionen von Mikrokapseln |
-
1977
- 1977-07-30 DE DE19772734577 patent/DE2734577A1/de not_active Withdrawn
-
1978
- 1978-07-21 EP EP78100470A patent/EP0000565B1/de not_active Expired
- 1978-07-21 DE DE7878100470T patent/DE2860645D1/de not_active Expired
- 1978-07-25 US US05/927,895 patent/US4181639A/en not_active Expired - Lifetime
- 1978-07-28 JP JP9165278A patent/JPS5426843A/ja active Granted
- 1978-07-28 DK DK335578A patent/DK335578A/da unknown
- 1978-07-28 IT IT50520/78A patent/IT1106614B/it active
Also Published As
Publication number | Publication date |
---|---|
DK335578A (da) | 1979-01-31 |
IT1106614B (it) | 1985-11-11 |
IT7850520A0 (it) | 1978-07-28 |
EP0000565A1 (de) | 1979-02-07 |
DE2860645D1 (en) | 1981-08-06 |
US4181639A (en) | 1980-01-01 |
JPS627948B2 (it) | 1987-02-19 |
JPS5426843A (en) | 1979-02-28 |
DE2734577A1 (de) | 1979-02-08 |
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