CA1110929A - Microencapsulation with modified aliphatic polyisocyanates - Google Patents
Microencapsulation with modified aliphatic polyisocyanatesInfo
- Publication number
- CA1110929A CA1110929A CA292,306A CA292306A CA1110929A CA 1110929 A CA1110929 A CA 1110929A CA 292306 A CA292306 A CA 292306A CA 1110929 A CA1110929 A CA 1110929A
- Authority
- CA
- Canada
- Prior art keywords
- microcapsules
- water
- chain
- biuret
- reaction
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret groups
-
- 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
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
- C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
- C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
- C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/914—Transfer or decalcomania
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2984—Microcapsule with fluid core [includes liposome]
- Y10T428/2985—Solid-walled microcapsule from synthetic polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2989—Microcapsule with solid core [includes liposome]
Abstract
MICROENCAPSULATION
WITH MODIFIED ALIPHATIC POLYISOCYANATES
Abstract of the Disclosure Microcapsules and a process for the production of these microcapsules the walls of which consist of polycondensates of a film-forming aliphatic polyisocyanate containing at least one biuret group or polyaddition products thereof with a chain-extending agent.
WITH MODIFIED ALIPHATIC POLYISOCYANATES
Abstract of the Disclosure Microcapsules and a process for the production of these microcapsules the walls of which consist of polycondensates of a film-forming aliphatic polyisocyanate containing at least one biuret group or polyaddition products thereof with a chain-extending agent.
Description
T~-le inventlon relates to microcapsules of which the outer s~lell is the reac-tion product of a film-forming modified alipl~atic polyisocyarlate with a chain-extending agent, and to their production.
The microencapsulation of organic and inorganic substances is basically known~ This technique is reported, for example, in "Microencapsulation, Processes and Applications" by J.E.
Vandegaer, Plenum Press9 New York, London (1974). One micro-encapsulation process uses interfacial pGlyaddition, wherein 1Q two components capable of reacting with one another by poly-addition, are mixed in different liquids immiscible with each other, and the polyaddition polymer is formed at the phase interface (cf. US Patents Nos. 3,575,882; 3,577,515 and 3,607,776).
In a practical embodiment initially a stable emulsion is prepared of which the disperse phase consists of the material to be encapsulated and the first component, optionally dissolv-ed or emulsified in an additional solvent, and of which the continuous phase is formed by a liquid immiscible with the disperse phase. Emulsification aids, generally, have to be used for this purpose. The second reaction component soluble in the continuous phase is added to this emulsion. Shells of the polymer formed by polyaddition or polycondensation are then formed around the disperse particles of the material to be encapsulated over a prolonged period (sometimes amounting to several hours). Suitable component pairings for this process are, for example, diisocyanates/diols, diisocyanates/'diamines, dicarboxylic acid chlorides/diamines, disulphonyl chlorides/
diamines or phosgen/diamines.
Le A 17 599 - 1 -9Z'3 ~ ncapsulation processes of this type have some decisive disad~antages. Thus, it is necessary to prepare a stable emul-sion which does not disintegrate, even when the second compon-ent is added. The process cannot be varied to any significant extent bt~cause only few suitable reaction components are avail--,bLe. ~or practical application, only few and very similar polymers can be produced in the manner described. Further-more, the low molecular weight reaction components are sub-stantially non-film forming. Accordingly, only little core material can be encapsulated in a large quantity of shell-forming material~
In order to overcome these disadvan-tages and to utilise film-forming properties, an attempt was made (cf. German Patent No. 2,311,712) to replace the non-film-forming polyisocyanates by their terminal NC0-group-containing reaction products with diols and polyols having molecular weights in the range of from 400 to 10,000 (hereinafter also referred to as "NC0-pre-polymers"). These NC0-prepolymers can be modified in their molecular structure so that they become self-emulsifying and retain their film-forming properties. Although this simplifies making of a stable emulsion, serious disad~antages also arise.
For example, the crosslinking density in the finished shells of the microcapsules decreases. I'he crosslinking density can be increased again by using short-chain low molecular weight NC0 prepolymers, but then the film-forming capacity is consider-ably reduced or disappears altogetherO The film-forming capac-ity disappears totally when the molecular weights of the diols or polyols used for forming the NC0-prepolymers are below 400.
Another disadvantage of the NC0-prepolymers arises out of their content of free monomeric diisocyanates or polyisocyanates ~ - 2 -i9Z~
which call intcrfcre with the polyadclition reaction, as they are hi.ghly rcactivc and difficult to cmulsify. Ihe;r volatil;ty necess:i~ates precauti.ons during their handling. Caysule walls made from NC0-prepolymers llave a d;stinctly iligher permeability, especially, to readily volati.le core materials, such as chloroform, perchloroethylene or buty]. acetate.
The present invention provides microcapsules having walls which comprise a polycondensate of a film-forming aliphatic polyisocyanate contain-ing at least one biuret group or a polyaddition product thereof with a chain-extending agent.
The invention also provides a process for the producti.on of micro-capsules, wherein a film-forming aliphatic polyisocyanate containing biuret groups, or a solution thereof in an i.nert solvent, is dissolved or dispersed in materials to be encapsulated, the resulting solution or dispersion is emulsified in water, a tertiary amine initiating the polycondensation reaction or a basically acting compound or an NC0-reactive chai.n-extending agent is added, the reaction mi.xture obtai.ned is admixed until the microcapsules are formed, and the microcapsules are isolated.
"~ilm-forming aliphatic polyisocyanates containing at least one biuret group" are products which are formed from low molecular weight aliphatic diisocyanates by reactions on the isocyanate groups to form biuret groups. In the polyisocyanates used in accordance with the invention, some - of the isocyanate groups can also be modified by dimerisation or trimerisation or by conversion into carbodiimide groups, and a part is çonverted into biuret groups, for example, by reaction with water, tertiary butanol, formic acid or amines. Aliphatic polyisocyanates modified in this way usually have viscos-ities of from 8,000 to 40,000 centipoises at 25C.
Reactants for these modified polyisocyanates during the ~5 ~
9Z~
microencapsulation ~roccss are low molecular weight cha;n-extending agents, sucll as water, ~llols or polyols, hut especially cun-ines.
The microcclpslllcs according to the invention show adequate crosslink;ng dcnsity and~ therefore, are only slight~y permeahle to easily volatile encapsulated suhstances.
I'he process of the invention has decislve advantages. The reaction of the moclified isocyanates with the reactants is quick enough for continuous operation. Iligh volume/time yields are obtained. The polyisocyanates used in the invention have a good film-forming capacity and yield high crosslinking density. By suitably selecting the reactivity and f~mctionality of the reactants, the degree of crosslinking can be controlled during the wall-forming reaction. By suitably selecting the chemical composition of the reactants, the properties of the memb~anes formed are modified within limits, e.g., improved toughness o~ the shell material and adequate crosslinking without greatly increasing the perme-ability to a given core material can be achieved. Impermeability to a given core material depends in a complex manner on physical and chemical factors; besicles nature and structure of the capsule membranes, other outside factors play an important part.
2n The variabili~y within the classes of substances to be used both in regard to their chemical structure and also in regard to the way in which the reaction is carried out (for example, in regard to the degree of crosslinking), is a remarkable advantage of the invention. Surprising- .
- ly, it is even possible to produce impermeable capsule membranes for halogenated volatile hydrocarbons such as chloroform and perchloroethylene.
The shell polymers are stable to light so that the capsules do not yellow.
By virtue of tlleir substantial involatility, the modified polyisocyanates containing biuret groups are easy to handle and can ~e indefinitely stored providing reactive components are -~e~-~ away.
For carrying out the process according to the invention, which is an encapsulation process by polyreaction at the organ-ic phase interface in a dispersion, the wall-forming polyiso-cyanate can be dissolved or emulsified in the core material either as such or in the form of a solution in an inert solvent or solvent mixture. In a shear gradient which is preferably produced by intensive mixing with small mixers or mixing machines, the organic phase can be dispersed in a phase which is immiscible with it, for example, water, and which contains an isocyanate-reactive polyamine or a catalytically active tertiary amine or similarly active compounds.
The amine can also be added subsequently.
Preferred polyisocyanates containing at least one biuret group are those based on hexamethylene-1,6-diisocyanates, m-xylylene diisocyanate, 4,4'-diisocyanatodicyclohexyl methane and isophorone diisocyanate which contain at least two func-tional isocyanate groups per molecule.
Particularly suitable compounds are polyisocyanates, particularly based on derivatives of hexamethylene-1,6-diiso-cyanate with a biuret structure of which the production is described in German Offenlegungsschrifts Nos. 1,568,017 and 1,931,055.
They form excellent films by reaction wi-th low molecular weight chain-extenders such as, e.g., water, diols or diamines.
Le A 1? 59~
Instead of or ;n addition to the isocyanate groups, carbodiimide, uretdione, uretone imil~e, uretidine dione diimine, oxadiazine trione, 4-imino-oxazolidonone-~2)-, ~-allcylene propiolactone and cyclobutane dione-(1,3)-groups can also be present as reactive groups.
Thus, it is possible to use, for example, polyisocyanatopoly-uretonimines of the type formed by subjecting hexamethylene-1,6-diisocyanate containing biuret groups to carbodiimide formation in the presence of organophosphorus catalysts and by the further reaction of initially formed carbodiimide groups with isocyanate groups to form urethone imine groups.
Furthermore, these isocyanates can be used in admixture with one another and with other aliphatic and aromatic isocyanates.
Depending upon the reaction conditions, the resulting modified polyisocyanate may contain considerable proportions of oxadiazine trione, triisocyanurate and sym. triazine dione imine as structural elements.
Products such as these are also suitable for use as shell-formers.
Organophosphorus catalysts for carbodiimide-forming reactions are described, for example, in United States Patent Nos. 2,663,736;
The microencapsulation of organic and inorganic substances is basically known~ This technique is reported, for example, in "Microencapsulation, Processes and Applications" by J.E.
Vandegaer, Plenum Press9 New York, London (1974). One micro-encapsulation process uses interfacial pGlyaddition, wherein 1Q two components capable of reacting with one another by poly-addition, are mixed in different liquids immiscible with each other, and the polyaddition polymer is formed at the phase interface (cf. US Patents Nos. 3,575,882; 3,577,515 and 3,607,776).
In a practical embodiment initially a stable emulsion is prepared of which the disperse phase consists of the material to be encapsulated and the first component, optionally dissolv-ed or emulsified in an additional solvent, and of which the continuous phase is formed by a liquid immiscible with the disperse phase. Emulsification aids, generally, have to be used for this purpose. The second reaction component soluble in the continuous phase is added to this emulsion. Shells of the polymer formed by polyaddition or polycondensation are then formed around the disperse particles of the material to be encapsulated over a prolonged period (sometimes amounting to several hours). Suitable component pairings for this process are, for example, diisocyanates/diols, diisocyanates/'diamines, dicarboxylic acid chlorides/diamines, disulphonyl chlorides/
diamines or phosgen/diamines.
Le A 17 599 - 1 -9Z'3 ~ ncapsulation processes of this type have some decisive disad~antages. Thus, it is necessary to prepare a stable emul-sion which does not disintegrate, even when the second compon-ent is added. The process cannot be varied to any significant extent bt~cause only few suitable reaction components are avail--,bLe. ~or practical application, only few and very similar polymers can be produced in the manner described. Further-more, the low molecular weight reaction components are sub-stantially non-film forming. Accordingly, only little core material can be encapsulated in a large quantity of shell-forming material~
In order to overcome these disadvan-tages and to utilise film-forming properties, an attempt was made (cf. German Patent No. 2,311,712) to replace the non-film-forming polyisocyanates by their terminal NC0-group-containing reaction products with diols and polyols having molecular weights in the range of from 400 to 10,000 (hereinafter also referred to as "NC0-pre-polymers"). These NC0-prepolymers can be modified in their molecular structure so that they become self-emulsifying and retain their film-forming properties. Although this simplifies making of a stable emulsion, serious disad~antages also arise.
For example, the crosslinking density in the finished shells of the microcapsules decreases. I'he crosslinking density can be increased again by using short-chain low molecular weight NC0 prepolymers, but then the film-forming capacity is consider-ably reduced or disappears altogetherO The film-forming capac-ity disappears totally when the molecular weights of the diols or polyols used for forming the NC0-prepolymers are below 400.
Another disadvantage of the NC0-prepolymers arises out of their content of free monomeric diisocyanates or polyisocyanates ~ - 2 -i9Z~
which call intcrfcre with the polyadclition reaction, as they are hi.ghly rcactivc and difficult to cmulsify. Ihe;r volatil;ty necess:i~ates precauti.ons during their handling. Caysule walls made from NC0-prepolymers llave a d;stinctly iligher permeability, especially, to readily volati.le core materials, such as chloroform, perchloroethylene or buty]. acetate.
The present invention provides microcapsules having walls which comprise a polycondensate of a film-forming aliphatic polyisocyanate contain-ing at least one biuret group or a polyaddition product thereof with a chain-extending agent.
The invention also provides a process for the producti.on of micro-capsules, wherein a film-forming aliphatic polyisocyanate containing biuret groups, or a solution thereof in an i.nert solvent, is dissolved or dispersed in materials to be encapsulated, the resulting solution or dispersion is emulsified in water, a tertiary amine initiating the polycondensation reaction or a basically acting compound or an NC0-reactive chai.n-extending agent is added, the reaction mi.xture obtai.ned is admixed until the microcapsules are formed, and the microcapsules are isolated.
"~ilm-forming aliphatic polyisocyanates containing at least one biuret group" are products which are formed from low molecular weight aliphatic diisocyanates by reactions on the isocyanate groups to form biuret groups. In the polyisocyanates used in accordance with the invention, some - of the isocyanate groups can also be modified by dimerisation or trimerisation or by conversion into carbodiimide groups, and a part is çonverted into biuret groups, for example, by reaction with water, tertiary butanol, formic acid or amines. Aliphatic polyisocyanates modified in this way usually have viscos-ities of from 8,000 to 40,000 centipoises at 25C.
Reactants for these modified polyisocyanates during the ~5 ~
9Z~
microencapsulation ~roccss are low molecular weight cha;n-extending agents, sucll as water, ~llols or polyols, hut especially cun-ines.
The microcclpslllcs according to the invention show adequate crosslink;ng dcnsity and~ therefore, are only slight~y permeahle to easily volatile encapsulated suhstances.
I'he process of the invention has decislve advantages. The reaction of the moclified isocyanates with the reactants is quick enough for continuous operation. Iligh volume/time yields are obtained. The polyisocyanates used in the invention have a good film-forming capacity and yield high crosslinking density. By suitably selecting the reactivity and f~mctionality of the reactants, the degree of crosslinking can be controlled during the wall-forming reaction. By suitably selecting the chemical composition of the reactants, the properties of the memb~anes formed are modified within limits, e.g., improved toughness o~ the shell material and adequate crosslinking without greatly increasing the perme-ability to a given core material can be achieved. Impermeability to a given core material depends in a complex manner on physical and chemical factors; besicles nature and structure of the capsule membranes, other outside factors play an important part.
2n The variabili~y within the classes of substances to be used both in regard to their chemical structure and also in regard to the way in which the reaction is carried out (for example, in regard to the degree of crosslinking), is a remarkable advantage of the invention. Surprising- .
- ly, it is even possible to produce impermeable capsule membranes for halogenated volatile hydrocarbons such as chloroform and perchloroethylene.
The shell polymers are stable to light so that the capsules do not yellow.
By virtue of tlleir substantial involatility, the modified polyisocyanates containing biuret groups are easy to handle and can ~e indefinitely stored providing reactive components are -~e~-~ away.
For carrying out the process according to the invention, which is an encapsulation process by polyreaction at the organ-ic phase interface in a dispersion, the wall-forming polyiso-cyanate can be dissolved or emulsified in the core material either as such or in the form of a solution in an inert solvent or solvent mixture. In a shear gradient which is preferably produced by intensive mixing with small mixers or mixing machines, the organic phase can be dispersed in a phase which is immiscible with it, for example, water, and which contains an isocyanate-reactive polyamine or a catalytically active tertiary amine or similarly active compounds.
The amine can also be added subsequently.
Preferred polyisocyanates containing at least one biuret group are those based on hexamethylene-1,6-diisocyanates, m-xylylene diisocyanate, 4,4'-diisocyanatodicyclohexyl methane and isophorone diisocyanate which contain at least two func-tional isocyanate groups per molecule.
Particularly suitable compounds are polyisocyanates, particularly based on derivatives of hexamethylene-1,6-diiso-cyanate with a biuret structure of which the production is described in German Offenlegungsschrifts Nos. 1,568,017 and 1,931,055.
They form excellent films by reaction wi-th low molecular weight chain-extenders such as, e.g., water, diols or diamines.
Le A 1? 59~
Instead of or ;n addition to the isocyanate groups, carbodiimide, uretdione, uretone imil~e, uretidine dione diimine, oxadiazine trione, 4-imino-oxazolidonone-~2)-, ~-allcylene propiolactone and cyclobutane dione-(1,3)-groups can also be present as reactive groups.
Thus, it is possible to use, for example, polyisocyanatopoly-uretonimines of the type formed by subjecting hexamethylene-1,6-diisocyanate containing biuret groups to carbodiimide formation in the presence of organophosphorus catalysts and by the further reaction of initially formed carbodiimide groups with isocyanate groups to form urethone imine groups.
Furthermore, these isocyanates can be used in admixture with one another and with other aliphatic and aromatic isocyanates.
Depending upon the reaction conditions, the resulting modified polyisocyanate may contain considerable proportions of oxadiazine trione, triisocyanurate and sym. triazine dione imine as structural elements.
Products such as these are also suitable for use as shell-formers.
Organophosphorus catalysts for carbodiimide-forming reactions are described, for example, in United States Patent Nos. 2,663,736;
2,663,737; 2,663,738 and 2,663,739.
Before they are used for microencapsulation, the polyisocyanates used in accordance with the invention can be additionally modified by `
reac~ion with difunctional and trifunctional chain extenders, for example water, polyfunctional alcohols such as ethane diol, glycerol or trimethylol propane or carboxylic acids such as succinic acid, adipic acid, sebacic acid, in proportions of from 0.01 to 0.5 mole per isocyanate equivalent.
Encapsulation by means of isocyanate-' .~
X
reæ~tive amines a~ ch~in~extenders ls preferred to the u~e of catal~tically active compounds because the oapsule ~hells formed in this way are gen~rally more highly crossllnked and more impermeable than those obt~1ned by catalytically acce:lerating the reaction of isocyanate groups, However, since catalytically active compounds are used in considerably smaller quantities than reactive a~ines (generally in quantities of from 0.1 to 0.5 ~ by wei~ht, based on dispersant), their use also affords a~vantages such as, for e~ample, little un-desirable amine salt in the neutralised capsule slurries after encapsulation.
Examples of chain-extending polyamines reactive to isocyan~te groups are hydrazine, hydrazino-2-ethanol, 1,2-ethylene diamine, bis-[3-aminDpropyl)-amine, bis-(2-methyl~mino-ethyl)-methylamine, 1,4-diaminobenzene, 4,4'-diaminodiphenyl methane, 1,4-diaminocyclohexane, 1-aminomethyl-5-amlno-1,3,3-trimethyl cyclohexane 3-amino-1-methylaminopropane, N-hydroxy-ethylethylene diamine, N-methyl-bis-(3-~mlnopropyl)-amine, l-aminoethyl-1,2-ethylene diamine, bis-(N,N'-aminoethyl)-1,2-ethylene diamine, 1,4-di~mino-n-butane, 1,6-diamino-n-hexane and 1,2-ethylene dia~ine-N-ethane ~ulphonic acid (as alkali metal salt), Catalytically active tertiary amines or similarly acting compounds suitable for the production o~ the mlcrocapsules are any compounds of the type known a~ catalysts ~or iso-cyanate reactions.
Examples are triethylamine, N-methyl morpholine, N-ethyl morpholine, N-methyl-N'-dimethylaminoethyl piperazine, N,N,N',N'-tetra~ethyl ethylene diamine, bis-(dimethyl~mino-ethyl)-ether, 1,4-diaz~hicyclo-(2,2,2)-octane, 1,2-dimethyl-imida~ole, 2-methyl imldazole, N~ethyl eth~nolamine;
sila-Amin~s with carbon-s1llcon bonds (for example ~ccording to German Pntent No. l,2~'3,29(1), preferably 2,2,4-trimethyl-2-silamorpholine and mixtures of these catalysts. Slmilarly actin~ compounds ~re those of the type which catalyse trimerisation of the isocyanate groups such as, for example, ~,4,~-tris-(dimethylaminometllyl)-phenol, alkoxides, alkali metal formates, carbonate3 and borohydrides (cf. also Brltish Patent No. ff~7,120 and H. Ulrich "Cycloaddition l~eactions of Heterocumulenes", Academic Press, New York, 19~7).
Organophilic substances immiscible with water or aqueous solutions can be encapsulated in accordance with the invention.
The core materials to be encapsulated must be inert with respect to isocyanate ~roups. The wall-for~ing modi~ied polyisocyanate must b~ miscible therewith or at least readily emulsifiable therein. However, itcan also be added in solution to the core material. In many c~ses, this can al~o be achieved by adding a solution promoter or a solvent mixture boiling below 80C which ca~ be evaporated off during the ~all-forming polyreaction.
Examples of suitable core materials are aliphatic and aromatic hydrocarbons and chlorinated hydrocarbons, colour former --~ solutions for carbonless copying-papers, such as crystal violet ~- 25 lactone and N-~enzoyl leucomethylene blue in aromatic solvents, aliphatic and araliphatLc esters and ethers, perfume oils, pesticides based on thiophosphoric acid esters and i`lamepro~in~ agents based on organic phosphorus and chlorine or bromine compounds~
Le A 17 599 - 8 -gZ9 rO c~lrr~ t th~ ~)ro(~es~ ilcc()rdi~ to the invention, t~ )olyis~cvarlatc i~ ~ti~solve~l or emlllsified in the core ~na~ idL to l~e ~r1cal)sllla~oA or i~ added to the organic ph~se in the form ol` a sollltion miscible therewith a~
described above.
If the polyisocyanate can rea~ily be emulsified in the core materia], the emulsion can be directly used for encapsulation.
In a shear ~radient, which is preferably produced by intensive mixing with small mi~ers or mixing machines, the organic phase is introduced ~nto a liquid pha~e which is immiscible with it, for example water, and which containe an ~ocyanate-reactive diamine or triamine or a catalytically active component. The amine can al~o be added to the aqueous phase immediately a~ter dispersion>
In order to obtain better emulsification and stabilisa~
tion of the dispersion, emulsification aids are preferably added to the aqueous phase. Examples are protective colloids such as polyvinyl alcohol, gelatin, carboxymethyl cellulose and poly~crylates.
EncapsulatioD can be earried out continuously or in batches. The degree of turbulence generated during mi~ing determines the diameters of the microcapsules obtained.
The diameter of the microcapsules ean be from about 5 to about2000 ~m according to the mixing conditions. The ratio by weight of core material to shell material in the finished microcapsules normally is from 60 - 90 to 40 - 10.
_ g _ F:X~PLI I
_ ....
a) ~roduction of the isocyanatc component (biuret polyisocyanate:
_ _ _ 1000 parts hy \~eight of hexametllylene-1,6-diisocyanate (5.952 mole) and 50 parts hy weight of tert.-butyl alcohol (0.676 mole) are mixed at room temperaturc. The molar ratio corresponds to 8.8 moles of di-isocyanate: 1 mole of tert.-butanol. The temperature of the reaction mixture is increased to 160C over a period of about 30 minutes. A
vigorous evolution of carbon dioxide and isobutylene begins at that temperature.
The temperature is slowly increased to 185C over a period of another 30 minutes. After about 3 hours at 185C, the evolution of gas and hence the reaction is over. The reaction product is then freed from monomeric hexamethylene diisocyanate in a thin-layer evaporator under a pressure of 0.2 Torr and at a temperature of 160C. Approximately 284 parts by weight of a viscous biuret polyisocyanate are obtained.
NC0-content: 21.3 % by weight. The product has a viscosity of 10.500 cP at 20C.
b) Encapsulation:
25 ml of trichloroethyl phosphate (TCAP) are mixed with 5 g of ; 20 the biuret polyisocyanate described in la) by means of a laboratory disperser of the Vltra-Turrax* type ~manufactured by Jahnke and Kunkel AG).
300 ml of water containing 1 g of polyvinyl alcohol in solution (Moviol* 50/981 a product of Hoechst AG) are initially introduced and the mixture of TCAP and biuret polyisocyanate is emulsified therein immediately after its _ 10 -* Trade Mark ~, .
preparation by means of u luboratory stirror of the Lenart-I~a~id type ~500 rpm). After about l minute, a solution of`
14 g of ethylene diamine in 50 g of water i~ added to the emulsion. The mixture is then heated to ~0 C and stirred tor 'j appro~i~mately l hour under the same conditions to harden the capsules and is then neutrAlised. The diameter of the capsules produced amounts to between ~00 and l200 ~m.
~XA~IPLE 2
Before they are used for microencapsulation, the polyisocyanates used in accordance with the invention can be additionally modified by `
reac~ion with difunctional and trifunctional chain extenders, for example water, polyfunctional alcohols such as ethane diol, glycerol or trimethylol propane or carboxylic acids such as succinic acid, adipic acid, sebacic acid, in proportions of from 0.01 to 0.5 mole per isocyanate equivalent.
Encapsulation by means of isocyanate-' .~
X
reæ~tive amines a~ ch~in~extenders ls preferred to the u~e of catal~tically active compounds because the oapsule ~hells formed in this way are gen~rally more highly crossllnked and more impermeable than those obt~1ned by catalytically acce:lerating the reaction of isocyanate groups, However, since catalytically active compounds are used in considerably smaller quantities than reactive a~ines (generally in quantities of from 0.1 to 0.5 ~ by wei~ht, based on dispersant), their use also affords a~vantages such as, for e~ample, little un-desirable amine salt in the neutralised capsule slurries after encapsulation.
Examples of chain-extending polyamines reactive to isocyan~te groups are hydrazine, hydrazino-2-ethanol, 1,2-ethylene diamine, bis-[3-aminDpropyl)-amine, bis-(2-methyl~mino-ethyl)-methylamine, 1,4-diaminobenzene, 4,4'-diaminodiphenyl methane, 1,4-diaminocyclohexane, 1-aminomethyl-5-amlno-1,3,3-trimethyl cyclohexane 3-amino-1-methylaminopropane, N-hydroxy-ethylethylene diamine, N-methyl-bis-(3-~mlnopropyl)-amine, l-aminoethyl-1,2-ethylene diamine, bis-(N,N'-aminoethyl)-1,2-ethylene diamine, 1,4-di~mino-n-butane, 1,6-diamino-n-hexane and 1,2-ethylene dia~ine-N-ethane ~ulphonic acid (as alkali metal salt), Catalytically active tertiary amines or similarly acting compounds suitable for the production o~ the mlcrocapsules are any compounds of the type known a~ catalysts ~or iso-cyanate reactions.
Examples are triethylamine, N-methyl morpholine, N-ethyl morpholine, N-methyl-N'-dimethylaminoethyl piperazine, N,N,N',N'-tetra~ethyl ethylene diamine, bis-(dimethyl~mino-ethyl)-ether, 1,4-diaz~hicyclo-(2,2,2)-octane, 1,2-dimethyl-imida~ole, 2-methyl imldazole, N~ethyl eth~nolamine;
sila-Amin~s with carbon-s1llcon bonds (for example ~ccording to German Pntent No. l,2~'3,29(1), preferably 2,2,4-trimethyl-2-silamorpholine and mixtures of these catalysts. Slmilarly actin~ compounds ~re those of the type which catalyse trimerisation of the isocyanate groups such as, for example, ~,4,~-tris-(dimethylaminometllyl)-phenol, alkoxides, alkali metal formates, carbonate3 and borohydrides (cf. also Brltish Patent No. ff~7,120 and H. Ulrich "Cycloaddition l~eactions of Heterocumulenes", Academic Press, New York, 19~7).
Organophilic substances immiscible with water or aqueous solutions can be encapsulated in accordance with the invention.
The core materials to be encapsulated must be inert with respect to isocyanate ~roups. The wall-for~ing modi~ied polyisocyanate must b~ miscible therewith or at least readily emulsifiable therein. However, itcan also be added in solution to the core material. In many c~ses, this can al~o be achieved by adding a solution promoter or a solvent mixture boiling below 80C which ca~ be evaporated off during the ~all-forming polyreaction.
Examples of suitable core materials are aliphatic and aromatic hydrocarbons and chlorinated hydrocarbons, colour former --~ solutions for carbonless copying-papers, such as crystal violet ~- 25 lactone and N-~enzoyl leucomethylene blue in aromatic solvents, aliphatic and araliphatLc esters and ethers, perfume oils, pesticides based on thiophosphoric acid esters and i`lamepro~in~ agents based on organic phosphorus and chlorine or bromine compounds~
Le A 17 599 - 8 -gZ9 rO c~lrr~ t th~ ~)ro(~es~ ilcc()rdi~ to the invention, t~ )olyis~cvarlatc i~ ~ti~solve~l or emlllsified in the core ~na~ idL to l~e ~r1cal)sllla~oA or i~ added to the organic ph~se in the form ol` a sollltion miscible therewith a~
described above.
If the polyisocyanate can rea~ily be emulsified in the core materia], the emulsion can be directly used for encapsulation.
In a shear ~radient, which is preferably produced by intensive mixing with small mi~ers or mixing machines, the organic phase is introduced ~nto a liquid pha~e which is immiscible with it, for example water, and which containe an ~ocyanate-reactive diamine or triamine or a catalytically active component. The amine can al~o be added to the aqueous phase immediately a~ter dispersion>
In order to obtain better emulsification and stabilisa~
tion of the dispersion, emulsification aids are preferably added to the aqueous phase. Examples are protective colloids such as polyvinyl alcohol, gelatin, carboxymethyl cellulose and poly~crylates.
EncapsulatioD can be earried out continuously or in batches. The degree of turbulence generated during mi~ing determines the diameters of the microcapsules obtained.
The diameter of the microcapsules ean be from about 5 to about2000 ~m according to the mixing conditions. The ratio by weight of core material to shell material in the finished microcapsules normally is from 60 - 90 to 40 - 10.
_ g _ F:X~PLI I
_ ....
a) ~roduction of the isocyanatc component (biuret polyisocyanate:
_ _ _ 1000 parts hy \~eight of hexametllylene-1,6-diisocyanate (5.952 mole) and 50 parts hy weight of tert.-butyl alcohol (0.676 mole) are mixed at room temperaturc. The molar ratio corresponds to 8.8 moles of di-isocyanate: 1 mole of tert.-butanol. The temperature of the reaction mixture is increased to 160C over a period of about 30 minutes. A
vigorous evolution of carbon dioxide and isobutylene begins at that temperature.
The temperature is slowly increased to 185C over a period of another 30 minutes. After about 3 hours at 185C, the evolution of gas and hence the reaction is over. The reaction product is then freed from monomeric hexamethylene diisocyanate in a thin-layer evaporator under a pressure of 0.2 Torr and at a temperature of 160C. Approximately 284 parts by weight of a viscous biuret polyisocyanate are obtained.
NC0-content: 21.3 % by weight. The product has a viscosity of 10.500 cP at 20C.
b) Encapsulation:
25 ml of trichloroethyl phosphate (TCAP) are mixed with 5 g of ; 20 the biuret polyisocyanate described in la) by means of a laboratory disperser of the Vltra-Turrax* type ~manufactured by Jahnke and Kunkel AG).
300 ml of water containing 1 g of polyvinyl alcohol in solution (Moviol* 50/981 a product of Hoechst AG) are initially introduced and the mixture of TCAP and biuret polyisocyanate is emulsified therein immediately after its _ 10 -* Trade Mark ~, .
preparation by means of u luboratory stirror of the Lenart-I~a~id type ~500 rpm). After about l minute, a solution of`
14 g of ethylene diamine in 50 g of water i~ added to the emulsion. The mixture is then heated to ~0 C and stirred tor 'j appro~i~mately l hour under the same conditions to harden the capsules and is then neutrAlised. The diameter of the capsules produced amounts to between ~00 and l200 ~m.
~XA~IPLE 2
3 g of the biuret polyisocyanate described in la) are 1~ dissolved in 2~ g of the thiophosphoric acid triester marketed by ~ayer AG under the nameVolaton (85 ~ solution in n-butanol).
The solution is emulsified in 300 ml of water containing l g of polyvinyl alcohol (moviol 50/98, a product of lloechst AG).
A Kotthofr mi~ing siren of the MSl-CAAllG type is used Ior ~mulsification (l minute at ~500 rpm). About 40 seconds after the organic phase has been added, a solution of 3 g of hydrazine hydrate in 67 g of water is added to the resulting emulsion and, after emulsification for 1 minute, the mixing siren is replaced by a laboratory xtirrer o~ the Lenart-napid type (500 rpm).
To harden the microcapsules formed, the resulting capsule dispersion is allowed to after-react for about l hour at ~0 ~C under the same stirring conditions. The batch is then neutralised with semi-concentrated acetic add . The diameter of the microcapsules amounts to between 20 and 30 pm.
5 g of the biuret polyisocyanate described in la) are dissolved in 25 g of phthalic acid di-n-butyl ester. The solution is emulsified in 300 ml Or water containing l.5 g * T~ade ~ark - 11 -~L$~gZ9 ot`,~iovioI i()/~)~, A l~ottho:rf mixing siren is used ~or emulsi~ication (I minute at 8900 rpm).
During the emulsirication process, a solution o~ 27 g of l-aminoethvl-1,2..ethylene diamine (diethylene triamine) in 5 43 Æ of water is added to the batch. .F`or a~ter-reaction, the resultin~ capsule dispersion is stirred for about 1 hour at (~()C with a laboratory stirrer of the l.enart-llapid type (50n rpm~.
The microcapsules formed hnve a diameter in the range oi from 1 to 20 ~m.
The capsule dispersion is neutralised or freed from excess amine by centrifuging with a laboratory centri~uge (for about 10 to 20 mlnutes at 2000 rpm) and decanting off ; t he aqueous phase.
- ~5 ~XA~IPLE 4 1 g of crystal violet lactone (colouring component in carbonless copying-papers) is dissolved in 25 g o~ solvent naphtha ~ (a mixture Or aromatic hydrocarbons produced by ~Y Ar~l).
;~ ~ g of the biuret polyisocyanate described in la) are added to and mixed with this solution by means oi ~ laboratory disperser of the Ultra-Turrax type (~anufactured by Jahnke and Kunkel AG).
300 ml of.water containing 1.5 g of Moviol 50/98 are initially introduced and the mixture of core material and wall-forming biuret polyisocyanate is emulsifi.ed therein immediately after its preparation. Emulsification is carried out in the same WAy as described in Example 3.
During th~ emulsification process, a solution of 56 g of pentaethylene hexamine in 64 ~ Or water is added to the batch ~: Le A 17 ~9~ - 12 -,~
( 9Zg aI)o~I~ 40 seconds after ad(~ition of the organlc phase.
,~fter rIlnning for about l minute, the mlxin~ siren used tor ~mulsi~ication i~ replaced by a laboratory stirrer of the I,~n~rt-I~api~l type (5~I) rpm) and the microcapsule (lisI)eIsion i~ stirre(I for l hour at (,0 C, The microcapsules fotme~ ave (tiameters in the range of from 4 to 30 ~m.
EXI~IPII~ ~
a) I'roduct;ion of the isocyanate component (urethanised billret polyisocyanate).
~ollowing the procedure described in la), a b~uret pol isocyanate with the following data is prepared by increasing the proportion of hexamethylene~ diisocyanate to a reactant ~atio of ll mo]es of hexnmethvlene~ diisocyanate to l mole O I' t.(?l't .-~utyl alcohoa:
vi~cosit~ at ~0C 2800cT~, NC()-content: 23.3 ~ by weight.
Corresponding to an avera~e molecular weight of the reaction product of approximately o70, this per "mole"
biuret polyisocyanate may be modified by chain extension with 0,~5 mole of ~lycerol. This reaction product has the following data:
viscosit;y at ~0C; 8300 cP, N00-content: 21.2 ~ by weight.
b ? Encapsu~ation:
For encapsulation, 300 ml of ~ater containing l g of Moviol 50/98 in solution are initi~lly introduced as the outer - 25 phase. 25 ~of per-chloroethylene and 5 g of the polyisocyanate described in Example 5a) are mixed by means of a laboratory dis-perser of the Ultra-Turrax type, in the same way as described in Example 4, and similarly further proce~oed with the dif~erence that12 g of hydrazine hydrate in 5~ g of water are added as amine during emulsificatlon of the outer phase.
Le A~~ 2~ - 13 -g2~
Af`ter l hour'~ aft,er-reactlon at (0(~ (laborator~
stirrer, I,enart-l~apid ty~e t~o~,ating at 500 rpm), microcaps~
~itll diameter~ in the range ol t`rom 5 to 35~m are obtained.
, ~ of the biuret pol~i~o(vanate described in l~'xampl~
l~) nre r~issolved in 2~ Ir of pht,llalic acid di-n-butyl e~ter, The sollltion is emulsified in ,0~) ml of water containing 1, r~ g of ~loviol 50/9~. A l~otthof f mixing siren is used for e~lllsification ( l minute at 990() rpm).
At the be~inning of the en~ulsification process, a solution Of .5 6 Of ~-methyl-N'-dimethylaminoethyl piperazine in 70 ~ of water i~ added to the aqueous ph~se.
After about 1 minute, the mixing siren is replaced by a laborator~ stirrer o~ the Lenart-l~apid type by which the hatch is stirred for l hour at 500 rpm with an increase in temperature to (~0 C. The resulting microc~psules have diameters in the range of from 4 to 1~ ~m.
Le A 17 599 - 14 -
The solution is emulsified in 300 ml of water containing l g of polyvinyl alcohol (moviol 50/98, a product of lloechst AG).
A Kotthofr mi~ing siren of the MSl-CAAllG type is used Ior ~mulsification (l minute at ~500 rpm). About 40 seconds after the organic phase has been added, a solution of 3 g of hydrazine hydrate in 67 g of water is added to the resulting emulsion and, after emulsification for 1 minute, the mixing siren is replaced by a laboratory xtirrer o~ the Lenart-napid type (500 rpm).
To harden the microcapsules formed, the resulting capsule dispersion is allowed to after-react for about l hour at ~0 ~C under the same stirring conditions. The batch is then neutralised with semi-concentrated acetic add . The diameter of the microcapsules amounts to between 20 and 30 pm.
5 g of the biuret polyisocyanate described in la) are dissolved in 25 g of phthalic acid di-n-butyl ester. The solution is emulsified in 300 ml Or water containing l.5 g * T~ade ~ark - 11 -~L$~gZ9 ot`,~iovioI i()/~)~, A l~ottho:rf mixing siren is used ~or emulsi~ication (I minute at 8900 rpm).
During the emulsirication process, a solution o~ 27 g of l-aminoethvl-1,2..ethylene diamine (diethylene triamine) in 5 43 Æ of water is added to the batch. .F`or a~ter-reaction, the resultin~ capsule dispersion is stirred for about 1 hour at (~()C with a laboratory stirrer of the l.enart-llapid type (50n rpm~.
The microcapsules formed hnve a diameter in the range oi from 1 to 20 ~m.
The capsule dispersion is neutralised or freed from excess amine by centrifuging with a laboratory centri~uge (for about 10 to 20 mlnutes at 2000 rpm) and decanting off ; t he aqueous phase.
- ~5 ~XA~IPLE 4 1 g of crystal violet lactone (colouring component in carbonless copying-papers) is dissolved in 25 g o~ solvent naphtha ~ (a mixture Or aromatic hydrocarbons produced by ~Y Ar~l).
;~ ~ g of the biuret polyisocyanate described in la) are added to and mixed with this solution by means oi ~ laboratory disperser of the Ultra-Turrax type (~anufactured by Jahnke and Kunkel AG).
300 ml of.water containing 1.5 g of Moviol 50/98 are initially introduced and the mixture of core material and wall-forming biuret polyisocyanate is emulsifi.ed therein immediately after its preparation. Emulsification is carried out in the same WAy as described in Example 3.
During th~ emulsification process, a solution of 56 g of pentaethylene hexamine in 64 ~ Or water is added to the batch ~: Le A 17 ~9~ - 12 -,~
( 9Zg aI)o~I~ 40 seconds after ad(~ition of the organlc phase.
,~fter rIlnning for about l minute, the mlxin~ siren used tor ~mulsi~ication i~ replaced by a laboratory stirrer of the I,~n~rt-I~api~l type (5~I) rpm) and the microcapsule (lisI)eIsion i~ stirre(I for l hour at (,0 C, The microcapsules fotme~ ave (tiameters in the range of from 4 to 30 ~m.
EXI~IPII~ ~
a) I'roduct;ion of the isocyanate component (urethanised billret polyisocyanate).
~ollowing the procedure described in la), a b~uret pol isocyanate with the following data is prepared by increasing the proportion of hexamethylene~ diisocyanate to a reactant ~atio of ll mo]es of hexnmethvlene~ diisocyanate to l mole O I' t.(?l't .-~utyl alcohoa:
vi~cosit~ at ~0C 2800cT~, NC()-content: 23.3 ~ by weight.
Corresponding to an avera~e molecular weight of the reaction product of approximately o70, this per "mole"
biuret polyisocyanate may be modified by chain extension with 0,~5 mole of ~lycerol. This reaction product has the following data:
viscosit;y at ~0C; 8300 cP, N00-content: 21.2 ~ by weight.
b ? Encapsu~ation:
For encapsulation, 300 ml of ~ater containing l g of Moviol 50/98 in solution are initi~lly introduced as the outer - 25 phase. 25 ~of per-chloroethylene and 5 g of the polyisocyanate described in Example 5a) are mixed by means of a laboratory dis-perser of the Ultra-Turrax type, in the same way as described in Example 4, and similarly further proce~oed with the dif~erence that12 g of hydrazine hydrate in 5~ g of water are added as amine during emulsificatlon of the outer phase.
Le A~~ 2~ - 13 -g2~
Af`ter l hour'~ aft,er-reactlon at (0(~ (laborator~
stirrer, I,enart-l~apid ty~e t~o~,ating at 500 rpm), microcaps~
~itll diameter~ in the range ol t`rom 5 to 35~m are obtained.
, ~ of the biuret pol~i~o(vanate described in l~'xampl~
l~) nre r~issolved in 2~ Ir of pht,llalic acid di-n-butyl e~ter, The sollltion is emulsified in ,0~) ml of water containing 1, r~ g of ~loviol 50/9~. A l~otthof f mixing siren is used for e~lllsification ( l minute at 990() rpm).
At the be~inning of the en~ulsification process, a solution Of .5 6 Of ~-methyl-N'-dimethylaminoethyl piperazine in 70 ~ of water i~ added to the aqueous ph~se.
After about 1 minute, the mixing siren is replaced by a laborator~ stirrer o~ the Lenart-l~apid type by which the hatch is stirred for l hour at 500 rpm with an increase in temperature to (~0 C. The resulting microc~psules have diameters in the range of from 4 to 1~ ~m.
Le A 17 599 - 14 -
Claims (8)
- THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. Microcapsules having walls which comprise a polycondensate of a film-forming aliphatic polyisocyanate containing at least one biuret group or a polyaddition product thereof with a chain-extending agent. - 2. Microcapsules as claimed in claim 1, wherein the polyisocyanate is a biuret group-containing reaction product of hexamethylene-1,6-diisocyanate with water, tertiary butanol, formic acid or an amine.
- 3. Microcapsules as claimed in claim 1, wherein the chain-extending agent is water, a diol or polyol or a polyamine.
- 4. Microcapsules as claimed in claim 1, wherein polycondensation is produced by a tertiary amine or a basically acting compound.
- 5. A process for the production of microcapsules, wherein a film-forming aliphatic polyisocyanate containing biuret groups, or a solution thereof in an inert solvent, is dissolved or dispersed in materials to be encapsulated, the resulting solution or dispersion is emulsified in water, a tertiary amine initiating the polycondensation reaction or a basically acting compound or an NCO-reactive chain-extending agent is added, the reaction mixture obtained is admixed until the microcapsules are formed, and the microcapsules are isolated.
- 6. A process as claimed in claim 5, wherein the polyisocyanate contain-ing biuret groups is a reaction product of hexamethylene-1,6-diisocyanate with water, tertiary butanol, formic acid or an amine.
- 7. A process as claimed in claim 5, wherein the chain-extending agent is water, a diol or polyol or a polyamine.
- 8. A process as claimed in claim 5, wherein the catalytically active compound is a tertiary amine or a basically acting compound.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DEP2655048.1 | 1976-12-04 | ||
DE19762655048 DE2655048A1 (en) | 1976-12-04 | 1976-12-04 | MICRO ENCAPSULATION WITH MODIFIED ALIPHATIC POLYISOCYANATES |
Publications (1)
Publication Number | Publication Date |
---|---|
CA1110929A true CA1110929A (en) | 1981-10-20 |
Family
ID=5994694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA292,306A Expired CA1110929A (en) | 1976-12-04 | 1977-12-02 | Microencapsulation with modified aliphatic polyisocyanates |
Country Status (14)
Country | Link |
---|---|
US (1) | US4193889A (en) |
JP (1) | JPS5855811B2 (en) |
BE (1) | BE861423A (en) |
BR (1) | BR7708035A (en) |
CA (1) | CA1110929A (en) |
CH (1) | CH631356A5 (en) |
DE (1) | DE2655048A1 (en) |
DK (1) | DK538177A (en) |
FR (1) | FR2372656A1 (en) |
GB (1) | GB1581255A (en) |
IL (1) | IL53500A (en) |
IT (1) | IT1092165B (en) |
NL (1) | NL7713313A (en) |
SE (1) | SE7713639L (en) |
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DE3421865A1 (en) * | 1984-06-13 | 1985-12-19 | Bayer Ag, 5090 Leverkusen | CONTINUOUS PRODUCTION OF MICROCAPSLE DISPERSIONS |
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JP4824158B2 (en) * | 2000-10-06 | 2011-11-30 | 日本エンバイロケミカルズ株式会社 | Paint composition |
ES2318025T3 (en) * | 2001-05-25 | 2009-05-01 | The Usa, Represented By The Administrator Of National Aeronautics And Space Administration | SUPPLY AGENT OF FLAME, SYSTEM AND USES. |
JP5443675B2 (en) * | 2006-08-16 | 2014-03-19 | 三菱製紙株式会社 | Thermal storage material microcapsule |
PL2395843T3 (en) * | 2009-02-13 | 2018-01-31 | Monsanto Technology Llc | Encapsulation of herbicides to reduce crop injury |
UY33563A (en) | 2010-08-18 | 2012-03-30 | Monsanto Technology Llc | EARLY APPLICATION OF ACETAMIDS ENCAPSULATED TO REDUCE DAMAGE TO CROPS |
UA121966C2 (en) | 2014-01-27 | 2020-08-25 | Монсанто Текнолоджі Елелсі | Aqueous herbicidal concentrates |
JP6883514B2 (en) | 2014-11-07 | 2021-06-09 | ジボダン エス エー | Capsule composition |
EP3215265B1 (en) | 2014-11-07 | 2019-06-19 | Basf Se | Process for preparing microcapsules having a polyurea shell and a lipophilic core material |
WO2018231913A1 (en) | 2017-06-13 | 2018-12-20 | Monsanto Technology Llc | Microencapsulated herbicides |
EP3917319A4 (en) | 2019-01-30 | 2022-11-23 | Monsanto Technology LLC | Microencapsulated acetamide herbicides |
FR3092502A1 (en) | 2019-02-12 | 2020-08-14 | Européenne D'application Des Cristaux Liquides | Formulation of microcapsules with reinforced aminoplast membrane |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS42446B1 (en) * | 1963-10-21 | 1967-01-13 | ||
JPS4928255B1 (en) * | 1969-04-30 | 1974-07-25 | ||
ES390653A1 (en) * | 1970-04-28 | 1974-03-16 | Fuji Photo Film Co Ltd | Process for the production of oily liquid-containing microcapsules and the microcapsules produced thereby |
DE2308015B2 (en) * | 1973-02-17 | 1980-07-31 | Bayer Ag, 5090 Leverkusen | Process for the production of polyisocyanates with a biuret structure |
DE2311712B2 (en) * | 1973-03-09 | 1978-08-10 | Bayer Ag, 5090 Leverkusen | Process for the production of microcapsules |
DE2557407A1 (en) * | 1975-12-19 | 1977-06-30 | Bayer Ag | Polyurethane-polyurea microcapsule prodn. - by reacting polyisocyanate (prepolymer) soln. with polyamines and removing the solvent |
DE2617747C2 (en) * | 1976-04-23 | 1982-07-01 | Bayer Ag, 5090 Leverkusen | Reaction carbonless papers |
-
1976
- 1976-12-04 DE DE19762655048 patent/DE2655048A1/en active Granted
-
1977
- 1977-11-29 US US05/855,743 patent/US4193889A/en not_active Expired - Lifetime
- 1977-12-01 NL NL7713313A patent/NL7713313A/en not_active Application Discontinuation
- 1977-12-01 SE SE7713639A patent/SE7713639L/en unknown
- 1977-12-01 IL IL53500A patent/IL53500A/en unknown
- 1977-12-02 DK DK538177A patent/DK538177A/en unknown
- 1977-12-02 BE BE183102A patent/BE861423A/en not_active IP Right Cessation
- 1977-12-02 CA CA292,306A patent/CA1110929A/en not_active Expired
- 1977-12-02 JP JP52144073A patent/JPS5855811B2/en not_active Expired
- 1977-12-02 FR FR7736405A patent/FR2372656A1/en active Granted
- 1977-12-02 IT IT52038/77A patent/IT1092165B/en active
- 1977-12-02 BR BR7708035A patent/BR7708035A/en unknown
- 1977-12-02 GB GB50305/77A patent/GB1581255A/en not_active Expired
- 1977-12-05 CH CH1484677A patent/CH631356A5/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
---|---|
JPS5855811B2 (en) | 1983-12-12 |
DE2655048C2 (en) | 1990-05-17 |
FR2372656A1 (en) | 1978-06-30 |
FR2372656B1 (en) | 1983-09-02 |
CH631356A5 (en) | 1982-08-13 |
US4193889B1 (en) | 1991-10-15 |
GB1581255A (en) | 1980-12-10 |
US4193889A (en) | 1980-03-18 |
IT1092165B (en) | 1985-07-06 |
IL53500A0 (en) | 1978-03-10 |
JPS5370985A (en) | 1978-06-23 |
BE861423A (en) | 1978-06-02 |
BR7708035A (en) | 1978-08-15 |
NL7713313A (en) | 1978-06-06 |
DE2655048A1 (en) | 1978-06-08 |
DK538177A (en) | 1978-06-05 |
SE7713639L (en) | 1978-06-05 |
IL53500A (en) | 1980-11-30 |
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