WO2000024706A1 - Granules de composes de type azoique - Google Patents
Granules de composes de type azoique Download PDFInfo
- Publication number
- WO2000024706A1 WO2000024706A1 PCT/FR1999/002249 FR9902249W WO0024706A1 WO 2000024706 A1 WO2000024706 A1 WO 2000024706A1 FR 9902249 W FR9902249 W FR 9902249W WO 0024706 A1 WO0024706 A1 WO 0024706A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- azobis
- group
- granules
- powder
- composition according
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/04—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton containing two cyano groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/63—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton
- C07C255/65—Carboxylic acid nitriles containing cyano groups and nitrogen atoms further bound to other hetero atoms, other than oxygen atoms of nitro or nitroso groups, bound to the same carbon skeleton with the nitrogen atoms further bound to nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/02—Systems containing only non-condensed rings with a three-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the subject of the present invention is a composition comprising at least one azo type compound in the form of granules, as well as a process for the preparation of said composition.
- Azo compounds and in particular 2,2'-azobis (isobutyronitrile), are generally sold in the form of a powder, obtained by draining the suspension resulting from the final stage of the synthesis process.
- the particles of this powder have a size of between 3 ⁇ m and 150 ⁇ m, preferably between 10 ⁇ m and 150 ⁇ m.
- This powder makes it possible very quickly to obtain a homogeneous distribution of the chemical compound in the mass of the solvent or of the water. Such a rapid distribution is very desirable, in particular for the use of azo compounds in industrial polymerization installations.
- the azo compounds are in fact either suspended in water or dissolved in organic solvents, such as dichloromethane, methyl ethyl ketone, acetone, chloroform, ethyl acetate, toluene.
- An object of the present invention is to remedy these drawbacks.
- Another object of the present invention is to provide a composition of azo compounds allowing a homogeneous and rapid distribution of these compounds, during their implementation.
- Another object of the present invention is to provide a solid composition of azo compounds which can flow in the manner of a liquid.
- Another object of the present invention is to provide a solid composition of azo compounds not having fine particles or dust, capable of coming into contact with the body of operators, and in particular their respiratory tract. It has now been found that these objects can be achieved in whole or in part by means of the compositions according to the invention.
- inhalable particles is understood to mean particles of size less than 20 ⁇ m, preferably less than 5 ⁇ m, which are liable to appear during any manipulation of the granules as defined below, in particular during their flow, and which, due of their size, can, entrained by air, enter the respiratory tract of operators.
- the content of inhalable particles is measured according to the method explained below.
- the principle of the method consists in dropping a known quantity of granules into a closed measuring chamber, so as to reveal inhalable particles, then in collecting them on a filter by means of a suction device and thus determining the corresponding mass.
- a microporous filter is placed on the filter holder of a filtration device.
- 30 g of granules to be analyzed are poured all at once into the top of the measuring device tube 60 cm high and 4 cm in diameter, ending in a closed cubic chamber 20 cm in edge.
- the filtration device is placed on a lateral face of this chamber.
- the air containing the inhalable particles released during the fall of the granules is aspirated for 60 seconds and the particles are thus collected on the filter.
- the filter is collected and weighed.
- the content of inhalable particles in the granules analyzed, expressed in milligrams, is represented by the difference in filter weight before and after the analysis.
- These 7 funnels are each arranged vertically by means of an appropriate device and aligned on a horizontal work plan in ascending order of their number.
- the principle of the method consists in dropping a known quantity of granules into each funnel in the series starting with the number 1, and in repeating the operation for each funnel in the series, in ascending order of their number.
- the flowability is represented by the number of the last funnel in the series in which the granules flow. The flowability is therefore all the better as the number of the funnel is higher.
- an ability to the flow of 3 corresponds to a non-pourable product.
- a flowability of 4 to 7 indicates a satisfactory behavior in terms of flowability.
- the speed of homogeneous distribution of the granules is evaluated by the following test. 0.5 g of granules are dissolved in 1 I of 50/50% water / acetone mixture with stirring, and the time (in minutes) necessary to obtain the complete disappearance of the granules, observed visually, is measured by the experimenter. As an indication, a homogeneous distribution rate suitable for the use of azo compounds, corresponds to a time of 5 to 15 minutes.
- composition comprising at least one azo compound of formula (I):
- R1, R ⁇ , R3 r R4 ⁇ identical or different, represent:
- alkyl group preferably a C1-C alkyl group, optionally substituted by a hydroxy, alkoxy, carboxy group or by a halogen atom, or
- a cycloalkyl group preferably having from 3 to 6 carbon atoms, optionally substituted by a hydroxy, alkoxy, carboxy group or by a halogen atom, or
- an aryl group such as phenyl or naphthyl, optionally substituted by a hydroxy, alkyl, alkoxy, carboxy group or by a halogen atom, or
- an aralkyl group such as benzyl, phenethyl, optionally substituted by one or more alkyl, alkoxy, hydroxy, carboxy groups, or by one or more halogen atoms; or at least one of the combinations of R ⁇ with R ⁇ , and of R ⁇ with R ⁇ forms, with the carbon atom to which it is (or they are) linked, a cycloalkyl radical; characterized in that it is in the form of granules of size between 200 ⁇ m and 10 mm, preferably between 250 ⁇ m and 5 mm, whose cumulative pore volume is between 0.2 and 2 ml / g, preferably between 0.5 and 1.3 ml / g.
- the compounds of formula (I) are prepared according to methods known per se.
- the term “granules” means solid and cohesive agglomerates of constituent particles, the said particles having a size of between 3 ⁇ m and 1 50 ⁇ m, preferably between 10 ⁇ m and 150 ⁇ m.
- the granules according to the invention are generally of substantially spherical shape, and the size indicated above corresponds to their diameter.
- the granules according to the invention can also have the shape of a cylinder whose length to diameter ratio is between 0.5 and 5, preferably between 1 and 3. In the latter case, the size of the granules indicated corresponds to the length of the cylinder.
- the cumulative pore volume of the granules is measured using a mercury porosimeter according to techniques known per se.
- the composition according to the invention has an excellent ability to dissolve in organic solvents and to suspend in water. It also has a flowability which allows it to be implemented by means of automatic devices for introducing and loading solids into the reactors. At the same time, it has a very significantly improved level of inhalable particles compared to the solid powder formulations already known. Finally, it exhibits satisfactory behavior in terms of absence of caking during storage, and of attrition resistance, in other words of capacity not to regenerate fine particles, during storage and transport.
- R 1 , R 2 is identical to the group comprising the 2 radicals R 3 , R 4 , in other words the compounds symmetrical with respect to the plane perpendicular to the pattern: - N - N-.
- the azo compound of formula (I) is 2,2'-azobis (isobutyronitrile), also called AZDN.
- compositions according to the invention comprise, in addition to the compound of formula (I), a surfactant.
- a surfactant which can be used in the compositions according to the invention, mention may, for example, be made of salts of alkylarylsulfonate type, in particular alkali alkylnaphthalene sulfonates, salts of polycarboxylic acids, polycondensates of ethylene oxide and / or propylene on fatty alcohols or on fatty acids or on fatty amines, substituted phenols (in particular alkylphenols or arylphenols), ester salts of sulfosuccinic acids, polymers of arylsulfonate type, in particular the alkaline polynaphthalene sulfonates obtained by condensation of (alkyl) arylsulfonates with formaldehyde, lignos
- compositions according to the invention taken or not in combination with the previous variant, these comprise a disintegrating agent improving the dispersion of the granules into their constituent particles, after mixing with the processing liquid.
- a disintegrating agent improving the dispersion of the granules into their constituent particles, after mixing with the processing liquid.
- bentonites natural or activated
- starch and its derivatives in particular alkyl starches and carboxyalkyl starches
- celluloses in particular microcrystalline cellulose
- cellulose derivatives in particular carboxyalkylcellulose and methylcellulose
- alginates soluble mineral salts
- crosslinked polyvinylpyrrolidone polyethylene glycols and polypropylene glycols
- polyvinyl alcohol polyvinyl alcohol
- the surfactant and the disintegrating agent can be present in the composition according to the invention at a content of between 0.01% and 5%, preferably between 0.05 and 0.5%.
- the granules of the compositions according to the invention may contain antifoams, densifying agents, sequestering agents, stabilizers, penetration agents, preservatives, adhesives, anti-caking agents, dyes and others.
- compositions according to the invention are preferred, which have:
- the invention also relates to a process for preparing the granules according to the invention. This process successively includes:
- step (i) the percentage of water in the powder corresponds to the weight ratio of water / weight of wet powder.
- step (ii) of the method according to the invention the passage of the moistened powder through the die is carried out for example by a granulating press, in which the powder is pushed against the die by means of rotary blades.
- Example 1 AZDN granules
- AZDN powder 100 kg of AZDN powder, obtained after spinning at the end of the final stage of the synthesis process, of average size 50 ⁇ m and at 15% humidity, are loaded into a coulter mixer of the Lôdige type (manufactured by the company of the same name). 30 liters of water are sprayed using a nozzle, so as to obtain a powder with 35% humidity.
- This powder is granulated by passage through a granulating press of the type
- Frewitt (marketed by the company of the same name).
- the powder is pushed by means of rotary blades against a die constituted by a grid of thickness 1 mm and provided with perforations of 2 mm in diameter.
- the temperature of the AZDN powder remains at all points below 30 ° C.
- the granules are then dried at a temperature of 35 ° C.
- the granules obtained are substantially spherical and have an average size of 2 mm and a cumulative pore volume equal to 1.2 ml / g.
- Their content of inhalable particles is less than 10 mg, their flowability is 5.
- Their homogeneous distribution speed is 11 minutes.
- Example 1 is repeated by spraying, onto the AZDN powder, 15 liters of water in which 100 g of a C 13 fatty alcohol _C-
- Example 2 is repeated by adding 100 g of a polyethylene glycol with a mass of 4,000 g (disintegrating agent) to the spray water in addition to the surfactant.
- the granules obtained have the same characteristics, except for their homogeneous distribution speed which is 10 minutes.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Medicinal Preparation (AREA)
- Glanulating (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerization Catalysts (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP99943023A EP1123273A1 (fr) | 1998-10-23 | 1999-09-22 | Granules de composes de type azoique |
IL14227499A IL142274A0 (en) | 1998-10-23 | 1999-09-22 | Azo-type compound granules |
AU56313/99A AU5631399A (en) | 1998-10-23 | 1999-09-22 | Azo-type compound granules |
CA002347161A CA2347161A1 (fr) | 1998-10-23 | 1999-09-22 | Granules de composes de type azoique |
KR1020017004950A KR20010080260A (ko) | 1998-10-23 | 1999-09-22 | 아조형 화합물의 과립 |
JP2000578278A JP2002528431A (ja) | 1998-10-23 | 1999-09-22 | アゾ型化合物の顆粒 |
MXPA01004068A MXPA01004068A (es) | 1998-10-23 | 1999-09-22 | Granulos de compuestos tipo azo.. |
US09/837,064 US20020016490A1 (en) | 1998-10-23 | 2001-04-18 | Granules of azo-type compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR98/13325 | 1998-10-23 | ||
FR9813325A FR2784987B1 (fr) | 1998-10-23 | 1998-10-23 | Granules de composes de type azoique |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/837,064 Continuation US20020016490A1 (en) | 1998-10-23 | 2001-04-18 | Granules of azo-type compounds |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000024706A1 true WO2000024706A1 (fr) | 2000-05-04 |
Family
ID=9531926
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1999/002249 WO2000024706A1 (fr) | 1998-10-23 | 1999-09-22 | Granules de composes de type azoique |
Country Status (12)
Country | Link |
---|---|
US (1) | US20020016490A1 (fr) |
EP (1) | EP1123273A1 (fr) |
JP (1) | JP2002528431A (fr) |
KR (1) | KR20010080260A (fr) |
CN (1) | CN1328541A (fr) |
AU (1) | AU5631399A (fr) |
CA (1) | CA2347161A1 (fr) |
FR (1) | FR2784987B1 (fr) |
ID (1) | ID30072A (fr) |
IL (1) | IL142274A0 (fr) |
MX (1) | MXPA01004068A (fr) |
WO (1) | WO2000024706A1 (fr) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2826652A1 (fr) * | 2001-06-28 | 2003-01-03 | Atofina | Procede de preparation de composes type azoique. |
FR3140287A1 (fr) | 2022-10-03 | 2024-04-05 | Arkema France | Procede de granulation de composes azoiques et granules obtenus |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7899900B1 (en) * | 2002-08-22 | 2011-03-01 | Ricoh Company, Ltd. | Method and system for monitoring network connected devices with multiple protocols |
FR2880347B1 (fr) * | 2005-01-05 | 2008-11-14 | Arkema Sa | Procede de recristallisation et/ou purification de composes type azoique |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2713576A (en) * | 1949-07-22 | 1955-07-19 | Rohm & Haas | Preparation of azo compounds |
JPS55151544A (en) * | 1979-05-12 | 1980-11-26 | Wako Pure Chem Ind Ltd | Fine particle of organic azonitrile and its production |
EP0249039A2 (fr) * | 1986-05-13 | 1987-12-16 | Wako Pure Chemical Industries Ltd | Procédé de granulation de sels d'azobisamidine |
EP0639331A2 (fr) * | 1993-08-20 | 1995-02-22 | Sumitomo Chemical Company, Limited | Formulation de fumigation |
-
1998
- 1998-10-23 FR FR9813325A patent/FR2784987B1/fr not_active Expired - Fee Related
-
1999
- 1999-09-22 AU AU56313/99A patent/AU5631399A/en not_active Abandoned
- 1999-09-22 MX MXPA01004068A patent/MXPA01004068A/es unknown
- 1999-09-22 IL IL14227499A patent/IL142274A0/xx unknown
- 1999-09-22 ID IDW20010898A patent/ID30072A/id unknown
- 1999-09-22 CA CA002347161A patent/CA2347161A1/fr not_active Abandoned
- 1999-09-22 EP EP99943023A patent/EP1123273A1/fr not_active Withdrawn
- 1999-09-22 KR KR1020017004950A patent/KR20010080260A/ko not_active Application Discontinuation
- 1999-09-22 CN CN99811741A patent/CN1328541A/zh active Pending
- 1999-09-22 JP JP2000578278A patent/JP2002528431A/ja active Pending
- 1999-09-22 WO PCT/FR1999/002249 patent/WO2000024706A1/fr not_active Application Discontinuation
-
2001
- 2001-04-18 US US09/837,064 patent/US20020016490A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2713576A (en) * | 1949-07-22 | 1955-07-19 | Rohm & Haas | Preparation of azo compounds |
JPS55151544A (en) * | 1979-05-12 | 1980-11-26 | Wako Pure Chem Ind Ltd | Fine particle of organic azonitrile and its production |
EP0249039A2 (fr) * | 1986-05-13 | 1987-12-16 | Wako Pure Chemical Industries Ltd | Procédé de granulation de sels d'azobisamidine |
EP0639331A2 (fr) * | 1993-08-20 | 1995-02-22 | Sumitomo Chemical Company, Limited | Formulation de fumigation |
Non-Patent Citations (3)
Title |
---|
CHEMICAL ABSTRACTS, vol. 94, no. 14, 6 April 1981, Columbus, Ohio, US; abstract no. 104131, WAKO PURE CHEMICAL INDUSTRIES, LTD., JAPAN: "Milling of organic azo nitriles" XP002109091 * |
CHEMICAL ABSTRACTS, vol. 98, no. 26, 27 June 1983, Columbus, Ohio, US; abstract no. 216466, KHRISTOFOROV, A. I. ET AL: "Wet forming of blowing agent concentrates" XP002109130 * |
IZV. VYSSH. UCHEBN. ZAVED., KHIM. KHIM. TEKHNOL. (1983), 26(3), 352-5, XP002109129 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2826652A1 (fr) * | 2001-06-28 | 2003-01-03 | Atofina | Procede de preparation de composes type azoique. |
WO2003002521A2 (fr) * | 2001-06-28 | 2003-01-09 | Atofina | Procede de preparation de composes type azoique |
WO2003002521A3 (fr) * | 2001-06-28 | 2004-04-15 | Atofina | Procede de preparation de composes type azoique |
FR3140287A1 (fr) | 2022-10-03 | 2024-04-05 | Arkema France | Procede de granulation de composes azoiques et granules obtenus |
WO2024074779A1 (fr) | 2022-10-03 | 2024-04-11 | Arkema France | Procede de granulation de composes azoiques et granules obtenus |
Also Published As
Publication number | Publication date |
---|---|
EP1123273A1 (fr) | 2001-08-16 |
KR20010080260A (ko) | 2001-08-22 |
CA2347161A1 (fr) | 2000-05-04 |
AU5631399A (en) | 2000-05-15 |
US20020016490A1 (en) | 2002-02-07 |
MXPA01004068A (es) | 2003-03-10 |
ID30072A (id) | 2001-11-01 |
CN1328541A (zh) | 2001-12-26 |
JP2002528431A (ja) | 2002-09-03 |
FR2784987A1 (fr) | 2000-04-28 |
FR2784987B1 (fr) | 2001-01-12 |
IL142274A0 (en) | 2002-03-10 |
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