Source: https://patents.google.com/patent/US4569844
Timestamp: 2018-02-23 02:47:15
Document Index: 395075099

Matched Legal Cases: ['arts     100', 'arts     10', 'arts     50', 'arts     50', 'arts            0', 'arts            0', 'arts            0', 'arts            0', 'arts     50', 'arts     50', 'art 20', 'art 30', 'arts     30', 'art 30', 'arts     30', 'arts            0', 'arts 20', 'art      40', 'art      50']

US4569844A - Microencapsulation process, microcapsules and use thereof - Google Patents
Microencapsulation process, microcapsules and use thereof
US4569844A
US4569844A US06570436 US57043684A US4569844A US 4569844 A US4569844 A US 4569844A US 06570436 US06570436 US 06570436 US 57043684 A US57043684 A US 57043684A US 4569844 A US4569844 A US 4569844A
US06570436
According to the prior art, it is necessary to use low temperatures of the order of 0° C. (the reaction is normally carried out in an ice bath) in the microencapsulation stage, to add the acid chloride quickly and to control the reaction time within close limits and, at the phase change stage, to effect the change, which terminates polymerisation, as quickly as possible after the polymerisation reaction has proceeded to the desired extent.
The process of the invention is virtually temperature independent and has successfully been carried out over a range of temperatures up to 40° C. While the low temperatures commonly used in the prior art can also be used with the present process, it evidently is most convenient to work at room temperature. Polymerisation proceeds more rapidly at higher temperatures, but because the end point of reaction is generally determined by the non-availability of reactants, there is little advantage in the use of higher temperatures.
0.15 part of adipoyl chloride in 10 parts of cyclohexane were added steadily to the emulsion over a period of 10 seconds. Reaction was continued for 10 minutes at 23.5° C.
The microcapsules formed were allowed to settle and the cyclohexane was decanted off. The capsules were then washed twice with 25 parts of cyclohexane and finally with 25 parts of cyclohexane containing 0.25 parts of lecithin. After a final settling, which took about 3 minutes, all the cyclohexane was decanted. The capsules were taken up in 50 parts of a 15% w/w warm aqueous gelatin solution and rapidly agitated for 2 to 3 minutes. 750 parts of water at approximately 35° C. were then added, while still agitating.
10 parts of cyclohexane containing 0.5 part of diphenylmethane-4,4'-diisocyanate were added steadily over a period of 20 seconds and reaction was continued for 7 minutes at a temperature of 17° C.
After final settling and decanting off of the solvent, the capsules were taken up in 50 parts of a 15% w/w warm aqueous gelatin solution and rapidly agitated for 2 to 3 minutes. 300 parts of water at approximately 35° C. were then added while continuing the agitation.
__________________________________________________________________________                                 ReactionExample                               Time/T°C.No.  Amine Solvent            Surfactant                   Emulsification                           Acid  (mins)                                       Wash    Take                                                     Dilution__________________________________________________________________________ 3   Hb 3 parts      Cyclohex            Span 85 8%                   4 blade 6 min.                           Seb. cl.                                  8/17 2 × 15                                               50 pt.                                                     12:120%   25 parts     100-300μ                           0.15 in 10  cyclohex                                               gelatin                           cyclohex 4   Hb 5 parts      Cyclohex            Span 85 8%                   2 blade 15 min.                           Seb. cl.                                 10/26.5                                       3 × 12.5                                               50 pt.                                                     10:130%   25 parts     10-500μ                           0.15 in 10  cyclohex                                               gelatin                           cyclohex 5   Hb 5 parts      Cyclohex            Span 85 8%                   4 blade 10 min.                           Seb. cl.                                 10/40 1 × 25 1 ×                                               25 pt.                                                     12:120%   25 parts     50-150μ                           0.15 in     cyclohex +                                               gelatin                           cyclohex    0.5%                                       Span 85 6   Hb 5 parts      Cyclohex            Lecithin 1%                   2 blade 15 min.                           Seb. cl.                                 10/26 3 × 12.5                                               50 pt.                                                     2:120%   25 parts     50-150μ                           0.15 in 10  cyclohex                                               gelatin                           cyclohex 7   Hb 5 parts      Cyclohex            Lecithin                   2 blade 15 min.                           Add. cl.                                  4/27 3 × 12.5                                               50 pt.                                                     4:120%   25 parts            0.5%   100-200μ                           0.05 in 10  cyclohex                                               gelatin                           cyclohex 8   Hb 5 parts      Cyclohex            Lecithin                   2 blade 5 min.                           Succ. cl.                                 13/24 3 × 12.5                                               50 pt.                                                     4:120%   25 parts            0.5%   150-300μ                           0.15 in 10  cyclohex                                               gelatin                           cyclohex 9   Hb 5 parts      Cyclohex            Lecithin                   4 blade 15 min.                           Tereph cl.                                 15/23.5                                       2 × 12.5                                               50 pt.                                                     4:120%   25 parts            0.5%   100-300μ                           .075 in 10  cyclohex                                               gelatin                           cyclohex10   Hb 5 parts      Cyclohex            Lactadan LR                   4 blade 8 min.                           Succ. cl.                                  4/23 1 × 25                                               50 pt.                                                     20:120%   25 parts            0.2%   50-100μ          cyclohex                                               gelatin                                       1 × 25                                       cyclohex +                                       0.5%                                       Lecithin11   Hb 5 parts      Cyclohex            Span 85 4%                   4 blade 5 min.                           Succ. Anh.                                 15/18 2 × 25                                               50 pt.                                                     6:120%   25 parts     50-150μ                           0.125 in 5  cyclohex                                               gelatin                           cyclohex +                           5 Chl.12   Hb whole      Cyclohex            Span 85 4%                   2 blade 15 min.                           Seb. cl.                                 15/28 4 × 12.5                                               50 pt.                                                     4:1egg (3:1)      25 parts     50-150μ                           0.15 in 10  cyclohex                                               gelatin5 part 20%                 cyclohex13   whole egg      Cyclohex            Lecithin 2%                   2 blade 5 min.                           Seb. cl.                                 12/23.5                                       2 × 25                                               50 pt.                                                     20:15 part 30%      25 parts     30-100μ                           0.15 in 10  cyclohex                                               gelatin                           cyclohex    1 × 25                                       cyclohex +                                       0.5%                                       Lecithin14   whole egg      cyclohex            Lecithin 2%                   2 blade 6 min.                           Succ. cl                                  8/23.5                                       2 × 25                                               50 pt.                                                     4:15 part 30%      25 parts     30-100μ                           0.15 in 10  cyclohex                                               gelatin                           cyclohex    1 × 25                                       cyclohex +                                       0.5%                                       Lecithin15   Hb 5 part      cyclohex            Lecithin                   4 blade 15 min.                           Succ. cl.                                 15/23.5                                       Cyclohex decanted to leave20%   25 parts            0.5    50-150μ                           0.25 in 10  25 parts; poured in to 250                           cyclohex    parts 20% aqueous NaCl16   Hb 5 part      40/60 pet.            Span. 85 4%                   4 blade 2 min.                           Succ. Cl.                                  5/19 1 × 25                                               50 pt.                                                     6:120%   ether        50-150μ                           0.1 in 10   pet. ether +                                               gelatin      25 parts             Pet. ether  2%                                       span17   Full cream      n-decane            Span 85 4%                   4 blade 2 min.                           Succ. cl.                                  3/19 2 × 25                                               50 pt.                                                     6:1condensed      25 part      50-150μ                           0.1 in 10   decane +milk 5 part                decane      2%66%                                    span__________________________________________________________________________ Hb = bovine haemoglobin Cyclohex = cyclohexane Seb. cl. = Sebacoyl Chloride Add Cl. = Adipoyl chloride Succ. Cl. = Succinoyl chloride Tereph. Cl. = Terephthaloyl Chloride Succ. Anh. = Succinic Anhydride Chl. = Chloroform
1. A method for making microcapsules containing an aqueous solution of a hydrophilic protein having a plurality of free amine groups, which method comprises forming an emulsion of said aqueous solution as the disperse phase in a liquid hydrocarbon which is a non-solvent for the protein and which is substantially non-polar or which has a polarity less than that of a 4:1 w/w mixture of cyclohexane and chloroform as the continuous phase, and adding to the resulting emulsion a solution of a compound selected from the group consisting of di- and poly-basic carboxylic acids, and anhydrides and chlorides of such acids, capable of reacting with amine groups to form a polymer, whereby an interfacial condensation polymerization reaction occurs between the protein and said compound to form microcapsules with a wall consisting substantially completely of cross-linked protein, the ratio of the continuous phase to said disperse phase being less than 12:1 to as little as 6:1 and said interfacial polymerization reaction occurring in at most 15 minutes at a temperature from room temperature up to 40° C.
US06570436 1978-12-19 1984-01-16 Microencapsulation process, microcapsules and use thereof Expired - Fee Related US4569844A (en)
GB7849034 1978-12-19
GB49034/78 1978-12-19
GB7936873 1979-10-24
US10339479 Continuation 1979-12-13
US4569844A true US4569844A (en) 1986-02-11
ID=26270013
US06570436 Expired - Fee Related US4569844A (en) 1978-12-19 1984-01-16 Microencapsulation process, microcapsules and use thereof
US (1) US4569844A (en)
CA (1) CA1148800A (en)
ES (1) ES8100100A1 (en)
FR (1) FR2444497B1 (en)
CN104365517A (en) * 2014-11-27 2015-02-25 浙江海洋学院 Device for determining deepwater spawning site
JPS51128485A (en) * 1976-04-19 1976-11-09 Tanabe Seiyaku Co Ltd A process for preparing stable insolubilized urease
Chang et al., Canadian Journal of Physiology and Pharmacology, 44, 115 128, (1966). *
Chang et al., Canadian Journal of Physiology and Pharmacology, 44, 115-128, (1966).
Chemical and Engineering News, 12, 16 & 17, (1974), [TP1 I 418].
Chemical and Engineering News, 12, 16 & 17, (1974), TP1 I 418 . *
Feedstuffs, 45, 35, (Apr. 16, 1973), [SF 95.A1 F4].
Feedstuffs, 45, 35, (Apr. 16, 1973), SF 95.A1 F4 . *
Jones et al., Chap. 6 of "Microencapsulation", J. R. Nixon, Marcel Dekker Inc., New York, (1976), [RS 201.C3.I57 1974].
Jones et al., Chap. 6 of Microencapsulation , J. R. Nixon, Marcel Dekker Inc., New York, (1976), RS 201.C3.I57 1974 . *
Jones et al., Nature, 247, 233 235, (Jan. 25, 1974), Q IN2 . *
Jones et al., Nature, 247, 233-235, (Jan. 25, 1974), [Q IN2].
Mackinney, SPE Transactions, p. 71, (Jan. 1963). *
Meyers et al., The American Fish Farmer, Jul. 1971, pp. 15, 16, 18 & 20. *
Meyers, Feedstuffs, 43,27 (Jul. 10, 1971), [SF95.A1 F4].
Meyers, Feedstuffs, 43,27 (Jul. 10, 1971), SF95.A1 F4 . *
Watanabe et al., Chap. 2 of "Microencapsulation", J. R. Nixon, Marcel Dekker, Inc., New York, (1976), [RS 201.C3.I57 1974].
Watanabe et al., Chap. 2 of Microencapsulation , J. R. Nixon, Marcel Dekker, Inc., New York, (1976), RS 201.C3.I57 1974 . *
CA1148800A1 (en) grant
ES8100100A1 (en) 1981-01-16 application
CA1148800A (en) 1983-06-28 grant
ES487510D0 (en) grant
ES487510A0 (en) 1980-11-01 application
FR2444497B1 (en) 1984-09-07 grant
FR2444497A1 (en) 1980-07-18 application
Guzey et al. 2006 Formation, stability and properties of multilayer emulsions for application in the food industry
Dickinson 2008 Interfacial structure and stability of food emulsions as affected by protein–polysaccharide interactions
Raikos 2010 Effect of heat treatment on milk protein functionality at emulsion interfaces. A review
Dalgleish 2006 Food emulsions—their structures and structure-forming properties