WO1999028294A1 - Method for making methacrylic thioesters - Google Patents
Method for making methacrylic thioesters Download PDFInfo
- Publication number
- WO1999028294A1 WO1999028294A1 PCT/FR1998/002445 FR9802445W WO9928294A1 WO 1999028294 A1 WO1999028294 A1 WO 1999028294A1 FR 9802445 W FR9802445 W FR 9802445W WO 9928294 A1 WO9928294 A1 WO 9928294A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- methacrylic
- reaction
- methacrylic anhydride
- thioesters
- carried out
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/20—Esters of monothiocarboxylic acids
- C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
Definitions
- the present invention relates to a process for the manufacture of methacrylic thioesters of general formula (I):
- R represents a linear primary alkyl radical containing from 3 to 12 carbon atoms.
- the Depositing Company has developed an alternative route which overcomes all the drawbacks described above.
- the subject of the present invention is in fact a process for the manufacture of a thioester of formula (I) such as defined above, characterized in that methacrylic anhydride is reacted with a mercaptan of formula RSH, R being as defined above.
- the reaction is carried out in the presence of an cation exchange resin in H form as catalyst.
- Resins of interest are those obtained by sulfonating a copolymer of styrene and divinylbenzene.
- reaction according to the invention is generally carried out under a nitrogen atmosphere, at a temperature of 40 to 100 ° C, in particular from 50 to 70 ° C, and preferably in the absence of solvent.
- the molar ratio of methacrylic anhydride to mercaptan RSH is preferably between 0.5 and 2, more particularly between 0.8 and 1.2.
- the methacrylic anhydride is advantageously used by being stabilized by a stabilizer such as bis tert-butyl hydroxytoluene.
- the filtrate stabilized with 5000 ppm of copper dibutyldithiocarbamate, is distilled under reduced pressure to obtain thiobutyl methacrylate with 70% yield and a CPG purity greater than 98%.
Abstract
The invention concerns a method for making methacrylic thioesters of formula (I) in which R represents a primary linear alkyl radical containing 3 to 12 carbon atoms, characterised in that it consists in reacting methacrylic anhydride with a mercaptan of formula RSH, R being as defined above, the reaction being advantageously carried out in the presence of a cationic ion exchanger resin in H+ form as catalyst.
Description
PROCÉDÉ DE FABRICATION DE THIOESTERS MÉTHACRYLIQUES PROCESS FOR THE MANUFACTURE OF METHACRYLIC THIOESTERS
La présente invention porte sur un procédé de fabrication de thioesters méthacryliques de formule générale (I) :The present invention relates to a process for the manufacture of methacrylic thioesters of general formula (I):
H2C O \\ // C—C / \ (I)H2C O \\ // C — C / \ (I)
CHÇ S—RCHÇ S — R
dans laquelle R représente un radical alkyle primaire linéaire comportant de 3 à 12 atomes de carbone.in which R represents a linear primary alkyl radical containing from 3 to 12 carbon atoms.
Jusqu'à maintenant, ces thioesters étaient principalement préparés à partir du mercaptate : RSM (M = K, Na) et du chlorure de méthacryloyle : H-,C=C(CH3) C0C1. Le chlorure de méthacryloyle est cependant un produit délicat à manipuler : il a tendance à former des dimères ; c'est un produit lacrymogène et il nécessite une mise en oeuvre à basse température. C'est pourquoi, du point de vue industriel, il est préférable de faire réagir l'anhydride méthacrylique sur le mercaptan, produisant ainsi, en même temps que le thioester recherché, de l'acide méthacrylique, lequel peut être recyclé à la synthèse de l'anhydride méthacrylique. Dans le brevet américain US-A-5 384 379, est décrite une voie de synthèse à partir d'anhydride méthacrylique et d'un sel de métal alcalin de 1 * alkylthiol correspondant en milieu solvant (tel que le méthyl t-butyl éther) . Cette méthode a été reproduite au laboratoire : des problèmes de décantation ont été rencontrés, assortis d'un rendement moyen, dû essentiellement à une conversion insuffisante des produits de départ.Until now, these thioesters were mainly prepared from mercaptate: RSM (M = K, Na) and methacryloyl chloride: H-, C = C (CH 3 ) C0C1. Methacryloyl chloride is, however, a delicate product to handle: it tends to form dimers; it is a tear gas product and it requires processing at low temperature. This is why, from an industrial point of view, it is preferable to react methacrylic anhydride with mercaptan, thereby producing, at the same time as the desired thioester, methacrylic acid, which can be recycled to the synthesis of methacrylic anhydride. In US patent US Pat. No. 5,384,379, a synthetic route is described starting from methacrylic anhydride and an alkali metal salt of the corresponding alkylthiol in solvent medium (such as methyl t-butyl ether) . This method was reproduced in the laboratory: decantation problems were encountered, accompanied by an average yield, mainly due to insufficient conversion of the starting materials.
La Société déposante a développé une voie alternative qui permet de s ' affranchir de tous les inconvénients décrits ci-dessus.The Depositing Company has developed an alternative route which overcomes all the drawbacks described above.
La présente invention a en effet pour objet un procédé de fabrication d'un thioester de formule (I) telle
que définie ci-dessus, caractérisé par le fait que l'on fait réagir de l'anhydride méthacrylique avec un mercaptan de formule RSH, R étant tel que défini ci-dessus.The subject of the present invention is in fact a process for the manufacture of a thioester of formula (I) such as defined above, characterized in that methacrylic anhydride is reacted with a mercaptan of formula RSH, R being as defined above.
Conformément à un mode de réalisation préféré, on conduit la réaction en présence d'une résine echangeuse d'ions cationique sous forme H comme catalyseur.According to a preferred embodiment, the reaction is carried out in the presence of an cation exchange resin in H form as catalyst.
La résine cationique est alors avantageusement utilisée à raison de 2 à 15% en poids par rapport à la charge totale. Des résines intéressantes sont celles obtenues en sulfonant un copolymère de styrène et de divinylbenzène.The cationic resin is then advantageously used at a rate of 2 to 15% by weight relative to the total charge. Resins of interest are those obtained by sulfonating a copolymer of styrene and divinylbenzene.
Par ailleurs, la réaction selon l'invention est généralement conduite sous atmosphère d'azote, à une température de 40 à 100 °C, en particulier de 50 à 70°C, et, de préférence, en l'absence de solvant.Furthermore, the reaction according to the invention is generally carried out under a nitrogen atmosphere, at a temperature of 40 to 100 ° C, in particular from 50 to 70 ° C, and preferably in the absence of solvent.
Le rapport molaire de l'anhydride méthacrylique au mercaptan RSH est, de préférence, compris entre 0,5 et 2, plus particulièrement entre 0,8 et 1,2.The molar ratio of methacrylic anhydride to mercaptan RSH is preferably between 0.5 and 2, more particularly between 0.8 and 1.2.
L'anhydride méthacrylique est avantageusement mis en oeuvre en étant stabilisé par un stabilisant tel que le bis tertiobutyl hydroxytoluène.The methacrylic anhydride is advantageously used by being stabilized by a stabilizer such as bis tert-butyl hydroxytoluene.
L'Exemple suivant illustre la présente invention sans toutefois en limiter la portée.The following example illustrates the present invention without however limiting its scope.
EXEMPLEEXAMPLE
Dans un réacteur de 250 ml équipé d'un réfrigérant, d'une ampoule à addition, d'un barbotage à azote et d'une allonge pour prélèvement, on introduit 50,1 g (1 équivalent) d'anhydride méthacrylique stabilisé par 5000 ppm de bis tertiobutyl hydroxytoluène, avec 3,4 g d'une résine cationique sous forme H+ commercialisée sous la marque "AMBERLYST 15".50.1 g (1 equivalent) of methacrylic anhydride stabilized by 5000 are introduced into a 250 ml reactor equipped with a condenser, an addition funnel, a nitrogen sparge and an extension tube for sampling. ppm of bis tert-butyl hydroxytoluene, with 3.4 g of a cationic resin in H + form sold under the brand "AMBERLYST 15".
On ajoute goutte à goutte, sous agitation et barbotage d'azote à 60 °C (température obtenue à l'aide d'un bain d'eau chauffé), 32,2 g de n-butanethiol (1,1 équivalent).
Après 3 heures de réaction, tout l'anhydride méthacrylique a disparu. Le mélange réactionnel est refroidi, puis filtré pour récupérer les résines.32.2 g of n-butanethiol (1.1 equivalent) are added dropwise, with stirring and bubbling with nitrogen at 60 ° C. (temperature obtained using a heated water bath). After 3 hours of reaction, all the methacrylic anhydride has disappeared. The reaction mixture is cooled, then filtered to recover the resins.
Le filtrat, stabilisé avec 5000 ppm de dibutyldithiocarbamate de cuivre, est distillé sous pression réduite pour obtenir le méthacrylate de thiobutyle avec 70% de rendement et une pureté CPG supérieure à 98%.
The filtrate, stabilized with 5000 ppm of copper dibutyldithiocarbamate, is distilled under reduced pressure to obtain thiobutyl methacrylate with 70% yield and a CPG purity greater than 98%.
Claims
REVENDICATIONS
1 - Procédé de fabrication de thioesters méthacryliques de formule (I) :1 - Process for the manufacture of methacrylic thioesters of formula (I):
dans laquelle R représente un radical alkyle primaire linéaire comportant de 3 à 12 atomes de carbone, caractérisé par le fait que l'on fait réagir de l'anhydride méthacrylique avec un mercaptan de formule RSH, R étant tel que défini ci-dessus. 2 - Procédé selon la revendication 1, caractérisé par le fait que l'on conduit la réaction en présence d'une résine echangeuse d'ions cationique sous forme H comme catalyseur.in which R represents a linear primary alkyl radical containing from 3 to 12 carbon atoms, characterized in that methacrylic anhydride is reacted with a mercaptan of formula RSH, R being as defined above. 2 - Process according to claim 1, characterized in that the reaction is carried out in the presence of a cationic ion exchange resin in H form as a catalyst.
3 - Procédé selon la revendication 2 , caractérisé par le fait que l'on choisit la résine cationique parmi celles obtenues en sulfonant un copolymère de styrène et de divinylbenzène.3 - Process according to claim 2, characterized in that the cationic resin is chosen from those obtained by sulfonating a copolymer of styrene and divinylbenzene.
4 - Procédé selon l'une des revendications 2 et 3 , caractérisé par le fait que l'on utilise la résine cationique à raison de 2 à 15% en poids par rapport à la charge totale.4 - Method according to one of claims 2 and 3, characterized in that the cationic resin is used in an amount of 2 to 15% by weight relative to the total charge.
5 - Procédé selon l'une des revendications 1 à 4, caractérisé par le fait que l'on conduit la réaction sous atmosphère d'azote à une température de 40 à 100 °C, en particulier de 50 à 70°C.5 - Method according to one of claims 1 to 4, characterized in that the reaction is carried out under a nitrogen atmosphere at a temperature of 40 to 100 ° C, in particular from 50 to 70 ° C.
6 - Procédé selon l'une des revendications 1 à 5, caractérisé par le fait que le rapport molaire de l'anhydride méthacrylique au mercaptan RSH est compris entre 0,5 et 2, en particulier entre 0,8 et 1,2. 7 - Procédé selon l'une des revendications 1 à 6, caractérisé par le fait que l'on conduit la réaction en 1 • absence de solvant.
8 - Procédé selon l'une des revendications 1 à 7, caractérisé par le fait que l'anhydride méthacrylique est mis en oeuvre en étant stabilisé par un stabilisant tel que le bis tertiobutyl hydroxytoluène.
6 - Method according to one of claims 1 to 5, characterized in that the molar ratio of methacrylic anhydride to mercaptan RSH is between 0.5 and 2, in particular between 0.8 and 1.2. 7 - Method according to one of claims 1 to 6, characterized in that the reaction is carried out in 1 • absence of solvent. 8 - Method according to one of claims 1 to 7, characterized in that the methacrylic anhydride is used while being stabilized by a stabilizer such as bis tert-butyl hydroxytoluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU12432/99A AU1243299A (en) | 1997-11-27 | 1998-11-17 | Method for making methacrylic thioesters |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR97/14936 | 1997-11-27 | ||
| FR9714936A FR2771410B1 (en) | 1997-11-27 | 1997-11-27 | PROCESS FOR THE MANUFACTURE OF METHACRYLIC THIOESTERS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1999028294A1 true WO1999028294A1 (en) | 1999-06-10 |
Family
ID=9513881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/FR1998/002445 WO1999028294A1 (en) | 1997-11-27 | 1998-11-17 | Method for making methacrylic thioesters |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU1243299A (en) |
| FR (1) | FR2771410B1 (en) |
| WO (1) | WO1999028294A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2269523A1 (en) * | 1974-05-01 | 1975-11-28 | Pennwalt Corp | |
| US5424472A (en) * | 1992-10-10 | 1995-06-13 | Roehm Gmbh Chemische Fabrik Patentabteilung | Method of manufacturing a (meth)acryloylthio compound |
-
1997
- 1997-11-27 FR FR9714936A patent/FR2771410B1/en not_active Expired - Fee Related
-
1998
- 1998-11-17 WO PCT/FR1998/002445 patent/WO1999028294A1/en active Application Filing
- 1998-11-17 AU AU12432/99A patent/AU1243299A/en not_active Abandoned
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2269523A1 (en) * | 1974-05-01 | 1975-11-28 | Pennwalt Corp | |
| US5424472A (en) * | 1992-10-10 | 1995-06-13 | Roehm Gmbh Chemische Fabrik Patentabteilung | Method of manufacturing a (meth)acryloylthio compound |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1243299A (en) | 1999-06-16 |
| FR2771410B1 (en) | 2000-01-14 |
| FR2771410A1 (en) | 1999-05-28 |
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