Selective epoxidation of unsaturated (meth)acrylates, new functional (meth)acrylates, and polymers thereof

• Main Authors: ORTAR; AGNES, FORT; YVES, CAUBERE; PAUL
• Format: Patent
• Language: English
• Published: 01.02.1994
• Edition: 5
• Subjects: ACYCLIC OR CARBOCYCLIC COMPOUNDS; ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAININGELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN,SULFUR, SELENIUM OR TELLURIUM; APPARATUS THEREFOR; CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOIDCHEMISTRY; CHEMISTRY; COMPOSITIONS BASED THEREON; GENERAL METHODS OF ORGANIC CHEMISTRY; HETEROCYCLIC COMPOUNDS; MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVINGCARBON-TO-CARBON UNSATURATED BONDS; METALLURGY; ORGANIC CHEMISTRY; ORGANIC MACROMOLECULAR COMPOUNDS; PERFORMING OPERATIONS; PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL; THEIR PREPARATION OR CHEMICAL WORKING-UP; THEIR RELEVANT APPARATUS; TRANSPORTING

An unsaturated (meth)acrylic compound of formula: (I) (X=O, S, NH, NR3 (R3=C1-12-alkyl) or O-(CH2)n (where n=1-16 approximately); R2=C2-20 straight-chain or branched alkyl, monocyclic or polycyclic cycloalkyl or heterocycloalkyl, or alkylaryl hydrocarbon chain, comprising an olefinic double bond in the chain, or at the end of the chain in the case of alkyl or alkylaryl, or an exocyclic or endocyclic olefinic double bond in the case of monocyclic or polycyclic cycloalkyl or heterocycloalkyl; and R1=H or C1-5-alkyl), is reacted at 10 DEG -60 DEG C. with at least one oxidizing compound (hydrogen peroxide) in the presence of at least one catalyst (alkali metal molybdates and tungstates) and in the presence of at least one phase transfer agent and when R2=polycyclic cycloalkyl or hetercycloalkyl, an organic peracid or hydrogen peroxide in the presence of at least one heteropolyacid. To open the epoxide function, the epoxide obtained is reacted with a compound chosen from strong inorganic acids, boron trifluoride etherate complexes, acid salts in the presence of the corresponding acid, halides of trialkylsilanes or trialkoxysilanes, and ketones in the presence of cationic resins. An unsaturated (meth)acrylic compound of formula: (* CHEMICAL STRUCTURE *) (I) (X=O, S, NH, NR3 (R3=C1-12-alkyl) or O-(CH2)n (where n=1-16 approximately); R2=C2-20 straight-chain or branched alkyl, monocyclic or polycyclic cycloalkyl or heterocycloalkyl, or alkylaryl hydrocarbon chain, comprising an olefinic double bond in the chain, or at the end of the chain in the case of alkyl or alkylaryl, or an exocyclic or endocyclic olefinic double bond in the case of monocyclic or polycyclic cycloalkyl or heterocycloalkyl; and R1=H or C1-5-alkyl), is reacted at 10 degrees-60 degrees C. with at least one oxidizing compound (hydrogen peroxide) in the presence of at least one catalyst (alkali metal molybdates and tungstates) and in the presence of at least one phase transfer agent and when R2=polycyclic cycloalkyl or hetercycloalkyl, an organic peracid or hydrogen peroxide in the presence of at least one heteropolyacid. To open the epoxide function, the epoxide obtained is reacted with a compound chosen from strong inorganic acids, boron trifluoride etherate complexes, acid salts in the presence of the corresponding acid, halides of trialkylsilanes or trialkoxysilanes, and ketones in the presence of cationic resins.