EP1487844A1 - Verfahren zur herstellung von trihydrocarbylsilylierten carboxylatmonomeren - Google Patents

Verfahren zur herstellung von trihydrocarbylsilylierten carboxylatmonomeren

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Publication number
EP1487844A1
EP1487844A1 EP03742960A EP03742960A EP1487844A1 EP 1487844 A1 EP1487844 A1 EP 1487844A1 EP 03742960 A EP03742960 A EP 03742960A EP 03742960 A EP03742960 A EP 03742960A EP 1487844 A1 EP1487844 A1 EP 1487844A1
Authority
EP
European Patent Office
Prior art keywords
process according
acid
alkyl
substituted
pyridine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP03742960A
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English (en)
French (fr)
Inventor
Mark Plehiers
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Sigma Coatings BV
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Sigma Coatings BV
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Filing date
Publication date
Application filed by Sigma Coatings BV filed Critical Sigma Coatings BV
Priority to EP03742960A priority Critical patent/EP1487844A1/de
Publication of EP1487844A1 publication Critical patent/EP1487844A1/de
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1896—Compounds having one or more Si-O-acyl linkages

Definitions

  • the invention relates to a new method for the preparation of trihydrocarbylsilylated carboxylate monomers
  • Antifouling paints are used to prevent and delay the fouling of underwater structures (e.g. ships' bottom, docks, fishnets, and buoys) by various marine organisms such as shells, seaweed, and aquatic bacteria.
  • underwater structures e.g. ships' bottom, docks, fishnets, and buoys
  • marine organisms such as shells, seaweed, and aquatic bacteria.
  • the surface roughness of the whole ship may be increased to the point of inducing a decrease of velocity of the ship or an increase of fuel consumption.
  • removal of such aquatic organisms from the ship's bottom needs much labour and a long period of working time in a costly dry dock.
  • these organisms adhere and propagate on an underwater structure such as a steel structure, they deteriorate the anticorrosive coating films leading to a reducing of the lifetime of the underwater structure.
  • Underwater structures are therefore coated with antifouling paint employing polymers containing various hydrolysable groups and more specifically organosilyl groups.
  • antifouling paints for example, an antifouling paint of the hydrolysable self-polishing type proposed in WO 84/02915 and JP 63215780 A, which employs a (meth)acrylic ester polymer having triorganosilyl groups in the side chains.
  • Some of the polymers used in the above-described antifouling paints are based on silylated carboxylate monomers.
  • JP 5306290 A discloses a process to obtain a methacrylic functional group- containing organosilicon compound.
  • the process comprises reacting methacrylic acid with a halogenoalkylsilane (e.g. trialkylsilylchloride) in the presence of a tertiary amine compound having a cyclic structure.
  • a halogenoalkylsilane e.g. trialkylsilylchloride
  • This process has disadvantages such as the reduced availability and storage stability of the silyl chloride.
  • the reaction yields as a by-product a hydrogen halide (which provokes the corrosion of the production equipment) or a halide salt (which has to be removed by filtration).
  • JP 10195084 A discloses the reaction of unsaturated carboxylic acids such as acrylic acid or methacrylic acid with a trialkylsilylhydride compound in the presence of a copper catalyst.
  • One of the disadvantages of this method is the risk of hydrogenation of the unsaturated carboxylic anhydride due to a side reaction of the produced H 2 on the carbon-carbon double bond.
  • J.Valade describes in "Compte Rendu de I'Academie des Sciences" n° 246, p. 952-953 (1958) the reaction of hexamethyldisiloxane or hexaethyldisiloxane with acetic anhydride or benzoic anhydride in the presence of zinc chloride whereas maleic anhydride or succinic anhydride do not react with hexamethyldisiloxane or hexaethyldisiloxane in the presence of zinc chloride.
  • an object of the present invention is to provide a novel process capable of readily preparing trihydrocarbylsilylated unsaturated carboxylate monomers in a high yield.
  • Another object of the present invention is to provide a novel process preparing said monomers from easily available starting materials.
  • a further object of the present invention is to provide a novel process offering an improvement vis-a-vis of the disadvantages disclosed above.
  • the present invention is based on the reaction of either linear or cyclic unsaturated carboxylic anhydrides with hexahydrocarbyldisiloxane to synthesise, in the presence of a catalyst, trihydrocarbylsilylated unsaturated carboxylate monomers.
  • the present invention relates to a new process for the preparation of trihydrocarbylsilylated unsaturated carboxylate monomers of either general formula (I)
  • each R independently represents an alkyl, a substituted alkyl, an aryl or a substituted aryl group
  • R 1 , R 2 each independently represents a hydrogen atom or an alkyl or substituted alkyl group, an aryl or a substituted aryl group
  • R 3 represents a hydrogen atom, an alkyl or substituted alkyl group, an aryl or a substituted aryl group or -COOR 6 wherein R 6 represents an alkyl, a substituted alkyl, an aryl or a substituted aryl group
  • R 4 , R 5 each independently represents a hydrogen atom or an alkyl or substituted alkyl group, an aryl or substituted aryl group
  • R is as already defined above either with an unsaturated carboxylic anhydride of formula (IV),
  • R 1 , R 2 , R 3 are as already defined above
  • R 4 , R 5 are as already defined above.
  • the catalyst used in the present invention consists of a mixture of a strong acid and a nucleophilic base.
  • alkyl relates to saturated hydrocarbon radicals having straight, branched, cyclic or polycyclic moieties or combinations thereof and contains 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 6 carbon atoms, yet more preferably 1 to 4 carbon atoms.
  • Said radical may be a substituted alkyl group, i.e. optionally substituted with one or more substituents independently selected from alkyl, aryl, alkoxy, halogen, hydroxy or amino radicals.
  • alkyl radicals may be independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2- methylbutyl, 2, 3-d i methyl butyl, lauryl, pentyl, iso-amyl, n-amyl, n-hexyl, cyclohexyl, 3-methylpentyl, n-octyl, t-octyl, n-dodecyl and the like.
  • R, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a linear, branched, or cyclic or polycyclic alkyl, substituted alkyl, aryl or substituted aryl group, saturated or unsaturated, containing from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 carbon atoms, yet more preferably R is 4 carbon atoms.
  • R is chosen from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-methyl butyl, 2,3-dimethylbutyl, lauryl, pentyl, n- amyl, iso-amyl, n-hexyl, cyclohexyl, 3-methylpentyl, n-octyl, t-octyl, n-dodecyl, phenyl or substituted phenyl, and the like.
  • R is chosen from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec- butyl, t-butyl, 2,3-dimethylbutyl, n-amyl, n-hexyl, n-octyl, t-octyl, n-dodecyl, lauryl, phenyl or substituted phenyl wherein the substituents may be linear or branched alkyl, aryl, halogene, alkoxy, phenoxy or nitro. Yet in a more preferred embodiment R is n-butyl, or isopropyl.
  • R 1 , R 2 , R 3 , R 4 and R 5 each independently represent hydrogen atom or a methyl group.
  • aryl as used herein, relates to an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes any monocyclic, bicyclic or polycyclic carbon ring of up to 7 members in each ring, wherein at least one ring is aromatic.
  • Said radical may be a substituted aryl group ie optionally substituted with one or more substituents independently selected from alkyl, alkoxy, halogen, hydroxy or amino radicals.
  • aryl includes phenyl, p-methylphenyl, stearyl, phenethyl, (2-methyl)-phenethyl, 4-methoxyphenyl, 4-(tert-butoxy)phenyl, 3-methyl-4-methoxyphenyl, 4- fluorophenyl, 4-chlorophenyl, 3-nitrophenyl, 3-aminophenyl, 3- acetamidophenyl, 4-acetamidophenyl, 2-methyl-3-acetamidophenyl, 2-methyl- 3-aminophenyl, 3-methyl-4-aminophenyl, 2-amino-3-methyIphenyl, 2,4- dimethyl-3-aminophenyl, 4-hydroxyphenyl, 3-methyl-4-hydroxyphenyl, 1- naphthyl, 2-naphthyl, 3-amino-1-naphthyl, 2-methyl-3-amino-1-naphthyl, 6- amino-2-na
  • the trihydrocarbylsilylated unsaturated carboxylates of general formula (I) and the unsaturated carboxylic compound (IV) can be of either cis (maleic) or trans (fumaric) configuration.
  • the trihydrocarbylsilylated unsaturated carboxylates obtained by the process of the invention are trihydrocarbylsilyl acrylates or trihydrocarbylsilyl methacrylates.
  • the present invention relates to a new process for the synthesis of trihydrocarbylsilylated unsaturated carboxylates according either to the general scheme 1 :
  • Unsaturated carboxylic anhydride represented by the above formula (IV) or (V) is mixed with hexahydrocarbyldisiloxane of formula (III) with or without solvent.
  • solvents which can be used in the process according to the invention, include hexane, cyclohexane, toluene, xylene, pentane, heptane, benzene, mesitylene, ethylbenzene, octane, decane, decahydronaphthalene, diethylether, diisopropyl ether, diisobutyl ether, THF, Dioxane, dichloromethane or mixtures thereof.
  • an inert solvent is used, more preferably, a hydrocarbon inert solvent such as hexane, cyclohexane, toluene or xylene.
  • the reaction may be conducted with an added polymerisation inhibitor.
  • a radical polymerisation inhibitor is used.
  • a suitable polymerisation inhibitor is o-methoxyphenol.
  • the reaction progress may be monitored by any suitable analytical method.
  • the solvent is at least 10 wt% of the total reaction mix at the start of the reaction, more preferably, at least 20 wt%, most preferably, at least 30 wt%.
  • the reaction may also be without solvent and accordingly suitable ranges of solvent are 0-99 wt% of the total reaction mix, more preferably, 20- 80 wt%, most preferably 30-70 wt%.
  • unsaturated carboxylic anhydrides which can be used in the process according to the invention include acrylic anhydride, methacrylic anhydride, crotonic anhydride, angelic anhydride, tiglic anhydride, maleic anhydride, citraconic anhydride (methylmaleic anhydride).
  • trihydrocarbylsilylated unsaturated carboxylate monomers prepared by the process of the invention using (meth)acrylic anhydride examples include trimethylsilyl (meth)acrylate, triethylsilyl (meth)acrylate, tri-n-propylsilyl (meth)acrylate, triisopropylsilyl (meth)acrylate, tri-n-butylsilyl (meth)acrylate, triisobutylsilyl (meth)acrylate, tri-s-butylsilyl (meth)acrylate, tri-n-amylsilyl (meth)acrylate, tri-n-hexylsilyl (meth)acrylate, tri-n-octylsilyl (meth)acrylate, tri- n-dodecylsilyl (meth)acrylate, triphenylsilyl (meth)acrylate, tri-p- methylphenylsilyl (meth)acrylate
  • ethyldimethylsilyl methacrylate ethyldimethylsilyl methacrylate
  • n-butyldimethylsilyl methacrylate bis(trimethylsilyl) itaconate
  • t-butyl dimethylsilyl (meth)acrylate diisopropyl-n-butylsilyl (meth)acrylate
  • n-octyldi-n-butylsilyl (meth)acrylate diisopropylstearylsilyl (meth)acrylate, dicyclohexylphenylsilyl (meth)acrylate, t- butyldiphenylsilyl (meth)acrylate
  • phenyldimethylsilyl (meth)acrylate n- hexyldimethylsilyl (meth)acrylate
  • tert-octyldimethylsilyl (meth)acrylate phenethyldi
  • trihydrocarbylsilylated unsaturated carboxylate monomers prepared by the process of the invention using maleic anhydride include bis triisopropylsilyl maleate, bis tri-n-butylsilyl maleate, bis t-butyldiphenylsilyl maleate, bis t-butyldiphenylsilyl maleate or the corresponding fumarate isomers.
  • the reaction is conducted in the presence of a catalyst comprising of, more preferably consisting of, a mixture of a strong acid and a nucleophilic base.
  • a catalyst comprising of, more preferably consisting of, a mixture of a strong acid and a nucleophilic base.
  • strong acid we mean an acid having a pKa value preferably less than 5, more preferably less than 2, and most preferably less than -5.
  • the "strong acid” is stronger than acetic acid, more preferably stronger than chloroacetic acid, most preferably, stronger than trichloroacetic acid.
  • nucleophilic base we mean a base having an available electron pair for donation.
  • 'nucleophilic base we mean an organic Lewis base having an electron pair available for interacting in a reversible manner with the acylation agent, more preferably the base is a nitrogen containing molecule which is more basic than triethylamine, more preferably this amine is a heteroaromatic amine, more preferably an heteroaromatic mono or polyamine substituted or not with one or more amino groups, more preferably an heteroaromatic mono or polyamine substituted or not with one or more amino groups in which at least one of the nitrogen electron pairs is conjugated with the aromatic ring in such a manner that it brings an increase in negative charge on another amino function of the molecule.
  • a preferred strong acid is trifluoromethanesulphonic acid.
  • nucleophilic bases that can be used, one can cite pyridine, 2- (dimethylamino)pyridine, 4-(dimethylamino)pyridine, 4- piperidino pyridine, 4-(4-methylpiperidino)pyridine, 4-pyrrolidinopyridine, 4- morpholinopyridine, imidazole, 1-methylimidazole, 2-methylimidazole, 4- methylimidazole, polymer- bound dimethylaminopyridine (examples of which may be found in US 4997944 incorporated herein by reference), 1- methylbenzimidazole, 2-methylbenzimidazole, benzimidazole and, in addition, N-methyl imidazole(NMI), N,N-dimethylamino pyridine(DMAP), hexamethylphosphoric triamide(HMPA), 4,4 dimethyl imidazole, N-methyl-2- pyridone(NMP), pyridine N-oxide, triphenylphosphine oxide, pyr
  • Preferred nucleophilic bases include 2- (dimethylamino)pyridine, 4- (dimethylamino)pyridine, 4-(4-methylpiperidino)pyridine, 4-pyrrolidinopyridine, imidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, polymer- bound dimethylaminopyridine, 1-methylbenzimidazole, 2-methylbenzimidazole, benzimidazole.
  • a more preferred nucleophilic base is 4-(dimethylamino) pyridine or derivatives thereof.
  • the catalyst is present at a level of 0.2-40 mol % (mol/mol siloxane), more preferably 1-24 mol %, most preferably 2-10 mol % in the reaction medium at the start of the reaction.
  • mol/mol siloxane mol/mol siloxane
  • the catalyst level relative to moles of siloxane in the starting reaction medium will increase during the reaction, whereas in a continuous process the catalyst level will remain relatively constant throughout the process except towards the end of any such process when it may rise relative to the level of siloxane as feed reactants are no longer added to the process.
  • the molar ratio of strong acid to nucleophilic base in the catalyst is in the range 1 :10 to 10:1 , more preferably, 1 :5 to 5:1 , most preferably 1 :2 to 2:1. Especially preferred is a range between 3:2 to 2:3, more especially preferred is a ratio of approximately 1 :1.
  • the reaction is preferably carried out at a temperature between 30°C and 130°C, more preferably between 40°C and 120°C, and most preferably between 50°C and 100°C, for example at 60°C or 90°C.
  • the reaction takes place in less than 24 hours, more preferably, less than 20 hours, more preferably less than 12 hours.
  • the polymerisation inhibitor is present in the range 0.001-10% wt/wt of the total reaction mix, more preferably 0.001-5% wt/wt and most preferably 0.01-2% wt/wt.
  • the molar ratio of siloxane:anhydride is between 1 :100 and 50:1 , more preferably between 10:1 and 1 :10, most preferably, between 2:1 and 1 :2.
  • the molar ratio of siloxane:anhydride is approximately 1 :1.
  • the reaction may be carried out at any convenient pressure, for instance atmospheric pressure.
  • the advantage of this invention is that the process uses reactants, which can be easily handled.
  • Hexahydrocarbyl disiloxanes may be considered as easily accessible since they are formed as a by-product during acidic deprotection of silyl protected reactive functional groups such as e.g. alcohols, amines or carboxylic acids (as described in "Protective Groups in Organic Synthesis” T.W.Greene and P.G.M.Wuts J.Wiley & Sons, 1999).
  • Another advantage lies in the simplicity and safety of the procedure (no byproducts, hence no trapping of corrosive gaseous matter).
  • the present invention is a substantial improvement over the existing methods. Moreover, due to the possibility of using numerous hexahydrocarbyldisiloxanes as reactants leading to the production of a wide range of trihydrocarbylsilylated unsaturated carboxylate monomers, the process of the present invention is a substantial improvement over the existing methods.
  • the trihydrocarbylsilylated unsaturated carboxylate monomers obtained by the process of the invention can be polymerised with various other monomers such as vinyl monomers including acrylic esters, methacrylic esters, styrene, vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate), vinyltoluene, alpha-methylstyrene, crotonic esters, and itaconic esters.
  • vinyl monomers including acrylic esters, methacrylic esters, styrene, vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate), vinyltoluene, alpha-methylstyrene, crotonic esters, and itaconic esters.
  • the polymers and copolymers of said monomers are useful in coating or paint composition. More preferably they are used in antifouling coating or paint compositions.
  • the antifouling coating compositions prepared using the monomers obtained by the process of the invention are tin-free coatings and provide an alternative to the present self-polishing coating technology based on hydrolysable tributyltin polymers (the use of which is due to be banned in antifouling paints by 2003).
  • the trihydrocarbylsilylated unsaturated carboxylate monomers provided by the process of the invention compared to organotin monomers are less toxic, less polar, more hydrophobic and more stable.
  • Example 1 (according to the invention) 285 mg of 4-(dimethylamino)pyridine and 352 mg of trifluoromethanesulfonic acid were successively added, at room temperature, to a mixture of 3.8g of hexamethyldisiloxane and 3.6g of methacrylic anhydride. The solution heated at 60°C for 16h to furnish trimethylsilyl methacrylate.
  • Trimethysilyl methacrylate 13 C NMR : 167.7, 137.6, 127.1 , 18.2, -0.257 ; 29 Si NMR : 24.3; IR (film): 2963, 1703, 1335, 1256, 1178, 874, 854 crr ⁇ 1 .
  • Triisopropylsilyl methacrylate 13 C NMR: 167.7, 138.0, 126.2, 18.8, 18.1 , 2.4;
  • Comparative example 1 (according to J.Valade in Compte Rendu de I'Academie des Sciences n° 246, p. 952-953 (1958)) 8.4 g of zinc chloride were added, at room temperature, to a mixture of 5 g of hexamethyldisiloxane and 6.25 g of methacrylic anhydride. The solution was heated at 110°C. After 16h no transformation was observed.
  • Comparative example 4 (catalyst is strong acid and weak nucleophilic base) 185 mg of pyridine and 352 mg of trifluoromethanesulfonic acid was added, at room temperature, to a mixture of 3.8 g of hexamethyldisiloxane and 3.6 g of methacrylic anhydride. The solution was heated at 60°C. After 16h no transformation was observed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP03742960A 2002-02-26 2003-02-26 Verfahren zur herstellung von trihydrocarbylsilylierten carboxylatmonomeren Withdrawn EP1487844A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP03742960A EP1487844A1 (de) 2002-02-26 2003-02-26 Verfahren zur herstellung von trihydrocarbylsilylierten carboxylatmonomeren

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP02075760A EP1340763A1 (de) 2002-02-26 2002-02-26 Herstellungsverfahren für Trikohlenwasserstoffsilylierte ungesättigte Carboxylatmonomere
EP02075760 2002-02-26
EP03742960A EP1487844A1 (de) 2002-02-26 2003-02-26 Verfahren zur herstellung von trihydrocarbylsilylierten carboxylatmonomeren
PCT/EP2003/001990 WO2003072585A1 (en) 2002-02-26 2003-02-26 Process for the preparation of trihydrocarbylsilylated carboxylate monomers

Publications (1)

Publication Number Publication Date
EP1487844A1 true EP1487844A1 (de) 2004-12-22

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Family Applications (2)

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EP02075760A Withdrawn EP1340763A1 (de) 2002-02-26 2002-02-26 Herstellungsverfahren für Trikohlenwasserstoffsilylierte ungesättigte Carboxylatmonomere
EP03742960A Withdrawn EP1487844A1 (de) 2002-02-26 2003-02-26 Verfahren zur herstellung von trihydrocarbylsilylierten carboxylatmonomeren

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP02075760A Withdrawn EP1340763A1 (de) 2002-02-26 2002-02-26 Herstellungsverfahren für Trikohlenwasserstoffsilylierte ungesättigte Carboxylatmonomere

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EP (2) EP1340763A1 (de)
JP (1) JP2005518450A (de)
KR (1) KR20040095227A (de)
AU (1) AU2003210366A1 (de)
WO (1) WO2003072585A1 (de)

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Publication number Priority date Publication date Assignee Title
US3403169A (en) * 1963-08-23 1968-09-24 Koppers Co Inc Addition of organometallic compounds to activated olefins
JP3841907B2 (ja) * 1997-01-31 2006-11-08 日東化成株式会社 重合性トリオルガノシリル不飽和カルボキシレートの製造法

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* Cited by examiner, † Cited by third party
Title
See references of WO03072585A1 *

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JP2005518450A (ja) 2005-06-23
AU2003210366A1 (en) 2003-09-09
WO2003072585A1 (en) 2003-09-04
KR20040095227A (ko) 2004-11-12
EP1340763A1 (de) 2003-09-03

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