Method of producing polyurethan-polycarbamide microcapsules

专利摘要:
Pressure-resistant polyurethane-polyurea particles with textured internal mass prepared from a liquid phase immiscible with water and containing organic solvents, isocyanate prepolymers and optionally active substances or mixtures of active substances, the liquid phase being dispersed in an aqueous phase at temperatures of from 0 DEG C. to 95 DEG C., wherein the liquid organic phase contains as isocyanate prepolymer a reaction product of a stoichiometric excess of an aliphatic, aromatic, cycloaliphatic, or araliphatic di- or polyisocyanate with a di- or polyol, the reaction product having a mean molecular weight in the range of from about 300 to 10,000, and an alkyl and/or alkoxyalkyl acetate of the formula <IMAGE> in which m is zero, 1 or 2, n is 1 to 4, and R is (C1-C5)alkyl, and the aqueous phase contains a protective colloid and optionally a surface-active agent.
公开号:SU1194259A3
申请号:SU782705013
申请日:1978-12-19
公开日:1985-11-23
发明作者:Хайнрих Рудольф；Френш Хайнц；Альбрехт Конрад
申请人:Хехст Аг (Фирма)；
IPC主号:

专利说明:

.. The invention relates to the field of producing polyurethane microcapsules used as carriers of various substances, for example, black glass, dyes, pharmaceutical finished forms, chemical reagents, plant protection products, etc. The purpose of the invention is to increase the mechanical strength of the microcapsules. Example 1. To obtain an aqueous phase containing 3.75 wt.% Polyvinyl alcohol (PVA), 2 g of PVA prepared by saponification of polyvinyl acetate with a saponification rate of 87.7 + 1.0% viscosity (in based on water solution) 4 + 0.3 cP (Mowioe 4-88), and 2 g of PVA with a degree of saponification of 87.7 + 1.0%, viscosity (per 4% aqueous solution) 18 + 1 , 5 cP (Mowiol 18-28). Dp of the organic phase is mixed with 50 g of dioctyl phthalate, the core used as the material, and 10 g of 2-topoxy ethyl acetate, and 30 g of a 50% solution of prepolymer obtained by reacting 8 mol of toluene diisocyanate are added to the mixture (ratio of isomers 2, 4: 2,6 80:20) with hexanetriolot1, 2,6, butanediol-1,3 and polypropylene glycol mol.m. 1000 in molar amounts of 3: 1: 1. The solvent for the prepolymer mixture is a mixture of 2-ethoxyethyl acetate and xylene in a weight ratio of 2: 3. To the aqueous phase in the reaction flask with a volume of 500 ml, mednoeno is poured with vigorous stirring. At 30 ° C, the organic phase is in a 1: 1 ratio. In this case, a fine distribution of the oil of droplets occurs in the aqueous phase. The size of the resulting droplets strongly depends on the shear stress created by the agitator, and is approximately 1-20 UM. When the required particle size is reached, only a weak stirring of the reaction mass is required. After 30 minutes, the temperature rises to 50 ° C and is held at it for 3 A hours. While the formation of the outer shell of particles occurs instantaneously, the internal structures form much slower. Therefore, it is advisable to mix the valuable half dispersion for several hours at room temperature. After the subsequent dispersion drying of the dispersion, the formed particles are separated. 86 g of a bulk powder with a bulk weight and a weight of after shaking 28.6 and 33.9 g, respectively, per 100 ml, containing 57% by weight of dioctyl phthalate inside the particles, are obtained. Humidity is approximately 0.3-0.8 wt.%, Particle diameter is 120 / c M. Example. 2. The aqueous phase is prepared as in Example 1, however, a solution of 50 g of 7-chloro-bicyclo- (3.2.0) -hepta-2,6-diene-6-yl-dimethylphosphate 15 is added to the organic phase instead of a solution of dioctyl phthalate. ml of methylnaphthalene (technical, which is a mixture of isomers). After rapid drying, 90 g of a free-flowing powder with a bulk weight and weight after shaking 36.5 and 40.5 g, respectively, per 100 m, containing 51% by weight of the core material inside the particles, are obtained. Example 3. Analogously to Example 1, an aqueous phase containing 4.70% by weight of PVA is obtained, using 80 g of water. The organic phase consists of 50 g of 7-chloro-bicyclo- (3,2,0) -hepta-2,6-dien-6-yl-dimethylphosphate in 15 g of ethyl acetate, and also from 40 g of a 50% prepolymer solution - RA isocyanate. Ethyl acetate is used as the solvent for the isocyanate prepolymer. The addition of the organic phase to the aqueous and also the treatment of the reaction mixture take place under the conditions indicated in Example 1. The ratio of the aqueous and organic phases is 1: 0.5. 103 g of loose powder with bulk weight and weight after shaking of 35.0 and 39.3 g, respectively, are obtained, 100 ml containing 45 wt.% Core material inside the particles. Example 4. An aqueous phase containing 4.76 wt.% PVA is prepared analogously to Example 3. The organic phase consists of 40 g of 7-chloro-bicyclo- (3.2.0) hepta-2,6-diene-6. - ethyl dimethyl phosphate in 25 g of ethyl acetate, as well as from 40 g of a 50% aqueous solution of an isocyanate base polymer prepared by reacting 8 mol of toluylene diisocyanate (2.4: 2.6 ratio of 80:20 with 5 mol of hexanetriol -1, 2, 6. As solvent for isocyanate prepolymer
ethyl acetate is used. The organic phase is added to the aqueous phase under the conditions specified in Example 1. The ratio of the aqueous and organic phases is 1: 1. Obtain 189 g of a finely dispersed aqueous dispersion of microcapsules containing 21 wt.%, Core material inside the particles.
Example 5 An aqueous phase containing 2–9 wt.% PVA mixture is prepared analogously to example 1 of 2.5 g of polyvinyl alcohol with a degree of saponification of 87.7 ± I.0% and viscosity of 18 + 1.5 cP, and from 0.5 g of a non-ionic surfactant - polycarbon oil of castor oil.
The organic phase consists of. 30 g of endosulfan, 6,758.9510.1 O-hexachloro, 5 5 5as 9a tetrahydro-6; 9- мет metha 54.3 benzo-dioxâtippin 3-oxide in 30 g of methylnaphthalene (a technical product, a mixture of isomers), as well as from 45 g of the prepolymer solution obtained by reacting 8 washings of toluene diisocyanate (
1 hour of isomers 2.4: 2.6 80; 20 / s
one .
, 1,1-trimetypolpropane ,. butanediolOM, 3
mol.m. 000, taken in molar quantities 3; 1; 1. A mixture of 2-ethoxy ethyl acetate and xylene in a weight ratio of 2: 1 is used as a solution.
The addition of the organic phase to the aqueous occurs under the conditions given in Example 1,
The preparation of 208 g of finely dispersed water dispersion of microcapsules containing 13 wt.% Of core material inside the particles.
Example 6, The aqueous phase containing 4.76 May,% PVA is prepared similarly to Prz Chmer 3. The organic phase consists of 64 g of dinosebaca 2 sec, α-butyl-4,6 Dinitrophenyl acetate in 10 g of 2-ethoxy ethyl acetate, and also of 40 g of prepolymer solution. specified in example K As a solvent for the isocyanate prepolymer, a mixture of 2-ethoxyethyl acetate and xylene in a weight ratio of 2; 3 is used. Adding the organic phase to the aqueous, and also treating the reaction mixture under the conditions given in example I, and organic phases lJl, 3
This gives 05 g of a bulk powder with a bulk weight and a weight after shaking 41.6 and 51.4 g, respectively, per 100 ml containing particles
54 wt.% Material core.
Example 7 An aqueous phase containing 4.76% by weight of PVA is prepared analogously to example 1 of 4.5 g of polyvinyl alcohol with a viscosity of 4+
+0.5 cP and 4.5 g of polyvinyl alcohol with a viscosity of 18 + 1.5 cP in 200 g of water. The organic phase consists of 125 g of pyrazophos and 2 g of zpichlorohydrin in 50 g of xylene, and also of 85 g
A 50% solution of the prepolymer mixture specified in Example 1, a mixture of prepolymers and a mixture of 2-ethoxyethyl acetate and xylene in a weight ratio of 2 are also used; 3 The addition of the orgalgic phase to the aqueous occurs under the conditions S specified in example i . The ratio of zodia and organic phases; 0,, 5, after the reaction hours
50 ° C, as well as a cooldown time of 10-12 hours at room temperature, the particles are dried by spray drying.
1 230 g of free-flowing powder are obtained.
bulk weight and weight after shaking 36 and 42.5 g, respectively, per 100 ml 5 containing 47 wt.% pyrazophos inside the particles.
Plrazofos 2 (0, 0 dII ethylthiono (} jus fopil) -5-methyl 6-carbztoxypyrazolo- - 1, 5a-n1-fish scale.
Example 8 An aqueous phase containing 4.3 wt.% Of a mixture of air defense with ryi-rm arabes is prepared as in Example 1 of 3 g of gum arabic, 1.5 g of polyvinyl alcohol with viscosity. -18 + 1.5 cp and 100 g of water. The organic phase consists of 125 g of triazofos and
2 g of zpychlorohydrin in 30 g of 2 ™ ethoxy 1-1-ethyl acetate, and also from 50 g of a 50% solution of the prepolymer mixture specified in Example 1, which is also dissolved in a mixture of 2-ethoxyethyl acetate
and xylene in a weight ratio of 2: 3. The addition of the organic phase to the aqueous occurs in the CONDITIONS OF THE EXAMPLE indicated in example i, with the same reaction time. The ratio of aqueous and organic phases is 1: 2,
Get g fine water dispersion of microcapsules containing less than 400 wt.% Triazofos. Rou 1 get a water phase from 5 g Mowiol, 3 g Nowiol 18-88 and 80 g water. The organic phase consists of 50 g of heptenophos in 15 g of ethyl acetate and 40 g of isocyanate solution propylene polymer of Example 1.
Ethyl glycol acetate is used as a solvent for the iso-cyanate prepolymer. The addition of the organic phase to the water occurs at 50 s as indicated in Example 1. The reaction mixture is processed in the same manner as in Example 1. The ratio of the aqueous and organic phases is 1: 0.5. 103 g. Of bulk powder with a bulk weight or weight during shaving are obtained, 35.0 or 39.3 g, respectively, per 100 mp, which contains 45% by weight of heptenophos.
Example 10. Similar to irimer 1 of 5.5 g of (R) Mowiol 4-88, i 0.5 g of a non-ionic surfactant, castor oil polyglycolic ether with 40 AEO units and 100 g of water forms an aqueous phase containing 5 , 7 wt.% PVA and surfactant.
The organic phase consists of 30 g of indosulfan in 30 g of methylnaphthapine (technical mixture of isomers) and 45 g of a 50% prepolymer solution, which is obtained by converting 10 mol of toluene diisocyanate (the ratio of isolates is 5: 1: 1. The solvent from 5 of ethyl acetate and acid in a weight ratio of 2: 1.
The addition of the organic phase to the aqueous phase is carried out at 10 ° C with constant 10 JANH weak cooling. Ratio
Lata in 15 g of butyl acetate and 40 g of a 50% solution of isocyanate prepolymer, which is obtained by transformation
12 mol of toluene diisocyanate (isomer ratio: 2.4: 2.6: 80:20) with 5 mol of hexanetriol-I, 2.6. Ethyl acetate is used as the solvent for the isocyanate prepolymer. Add-
The organic phase is produced at 60 C. The ratio of the aqueous and organic phases is 1: 1.1.
Get I83 g of a finely dispersed aqueous dispersion of microcapsules, in which the proportion included in the capsule
dioctyl phatalate is 21.8 wt.%; Table B shows the content of components in the organic phase. $ 11942596 Triazofos - 0,0-diethyl- (1-phenyl measures 2,4: 2,6 80:20) with I, 1,1-trimethyl1, 2,4-triazole 3-yl-tonionophosphate. olpropane, butanediol-, 3 and polySample 9. Similarly, the example is propylene glycol mol.m. 1000 in the aqueous, organic and organic 1: 1 phases. 211 g of a finely dispersed aqueous dispersion of microcapsules is obtained, in which the proportion of endosulfan introduced into the capsule is 14% by weight. Example 11. Analogously to Example 1 of 7 g of (R) Mowiol 4-88 and 1 g of (R) Mowiol 18-88, 80 g of water forms an aqueous phase containing 9.0% by weight of PVA. The organic phase consists of 40 g dioctylft

权利要求:
Claims (1)
[1]
METHOD FOR PRODUCING POLYURETHANE POLICAR B AMIDIC MICROCapsules by dispersing at 10-60 ° С the organic phase, which includes a water-immiscible organic liquid as the core material, a prepolymer based on toluene diisocyanate and polyol and an organic solvent, in the aqueous phase containing 2.9-9.0 wt.% polyvinyl alcohol or a mixture of it with polyglycol ether of castor oil or gum arabic in a ratio of 1: 0.1-2 with a ratio of organic and aqueous phases 1: 1-2: 1 until microcapsules with a diameter of 120 μm are formed and mixing in the region temperatures from 50 ° C to room temperature with simultaneous exposure at 50 ° C for 35 hours and at room temperature for 5-12 hours, characterized in that, in order to increase the mechanical strength of the microcapsules, the reaction product is 8-12 mol of toluene diisocyanate with 5 mol , hexanetriol —1,2,6— or a mixture of the latter, or 1,1,1 — three— S of methylpropane with butanediol-1,3 and polypropylene glycol mol.m. 1000 in a molar ratio of 3-5: 1: 1 and 6.5-19.5 wt.% 2-ethoxyethyl acetate or 33-43 wt.% Ethyl acetate are additionally introduced into the organic phase.
© ζ ©

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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DE2757017A|DE2757017C3|1977-12-21|1977-12-21|Process for the production of pressure-resistant polyurethane-polyurea capsules with a structured inner mass|

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