WO2006045916A2 - Preparation of functionalised silanes and silicones by means of enzymatic catalysis - Google Patents
Preparation of functionalised silanes and silicones by means of enzymatic catalysis Download PDFInfo
- Publication number
- WO2006045916A2 WO2006045916A2 PCT/FR2005/002546 FR2005002546W WO2006045916A2 WO 2006045916 A2 WO2006045916 A2 WO 2006045916A2 FR 2005002546 W FR2005002546 W FR 2005002546W WO 2006045916 A2 WO2006045916 A2 WO 2006045916A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- monomer
- oligomer
- copolymer
- polymer
- silane
- Prior art date
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- 229920001296 polysiloxane Polymers 0.000 title claims description 36
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000006555 catalytic reaction Methods 0.000 title description 9
- 230000002255 enzymatic effect Effects 0.000 title description 7
- 150000004756 silanes Chemical class 0.000 title description 4
- 239000004593 Epoxy Substances 0.000 claims abstract description 74
- 239000000178 monomer Substances 0.000 claims abstract description 40
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 38
- 125000005375 organosiloxane group Chemical group 0.000 claims abstract description 37
- 229910000077 silane Inorganic materials 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 36
- 229920001577 copolymer Polymers 0.000 claims abstract description 34
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 15
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 15
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- 150000001875 compounds Chemical class 0.000 claims description 10
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 9
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 8
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- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229920005684 linear copolymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 238000005935 nucleophilic addition reaction Methods 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 101150008001 pl gene Proteins 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000004313 potentiometry Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052990 silicon hydride Inorganic materials 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000007725 thermal activation Methods 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/06—Preparatory processes
- C08G77/08—Preparatory processes characterised by the catalysts used
Definitions
- the field of the invention is that of silicones, namely (poly) organosiloxanes, functionalized in particular by unsaturated carboxylic acid ester groups such as (meth) acrylate functions.
- (meth) acrylates corresponds to the methacrylate or acrylate ester.
- the functionalization of the polyorganosiloxanes by (meth) acrylate groups is a reaction which arouses great interest because it not only gives access to other functionalities by chemical post-treatment, but also makes it possible to obtain polyorganosiloxanes having faster crosslinking than commercially available vinyl organopolysiloxanes.
- (Meth) acrylates are able to react rapidly together, by radical means under actinic and / or thermal activation, according to a polyaddition polymerization mechanism.
- acrylate or methacrylate functional polyorganosiloxanes are generally in the form of polydiorganosiloxane oils and may be formulated alone or in combination with unsaturated monomers or polymers, to be subsequently crosslinked under UV radiation, for example.
- patent application FR-A-2,377,430 describes acrylate silicones obtained by addition of hydroxyalkyl acrylate grafts on silicones with chlorosiloxane functions.
- These acrylate and / or methacrylate functional polyorganosiloxanes thus comprise functional grafts connected to the silicone chain by means of bonds Si-O.
- bonds Si-O bonds
- US-A-5,981,679 discloses polyorganosiloxanes having at both ends (meth) acryloyl groups.
- the starting products used are ⁇ , ⁇ -hydrogenodimethylsiloxy-polyorganosiloxanes, which are reacted by hydrosilylation on one of the double bonds of (meth) acrylate compounds each comprising at least two (meth) acryloyl groups, preferably three.
- this hydrosilylation is carried out in the presence of a metal catalyst, preferably based on platinum.
- the SiH-patterned polyorganosiloxane is preferably an ⁇ , ⁇ -diethoxyhydrogenosiloxy polydimethylsiloxane obtained from an ⁇ , ⁇ -diol polydimethyl siloxane which is condensed with triethoxysilane.
- the problem with this hydrosilylation modified triacrylate (trimethylolpropane type or propyleneoxide triacrylate "ARONIX M-310 ®"), according to US-A-5,981,679 is that it generates 50% of polyorganosiloxanes bearing functionalised grafts acrylates and linked to the silicone chain by stable SiC bonds, but also 50% silicone-bound polyacrylate grafts by an easily hydrolysable Si-OC bridge.
- the direct hydrosilylation of polyacrylates by polyorganosiloxanes with an SiH unit in and / or at the end of the chain may involve, for example, 1,6-hexanedioldiacrylate, trimethylolpropane triacrylate, triethylene glycol diacrylate or neopentylglycol. diacrylate, or else tripropylene glycol-diacrylate and finally bisphenol ethoxylated diacrylate.
- French Patent Application FR-A-2,634,769 describes a thioalkyl acrylate-functional diorganopolysiloxane obtained by reacting a vinyl-containing polyorganosiloxane, for example an ⁇ , ⁇ -dimethylvinylsiloxy linear polydimethylsiloxane, with a mercaptoalkanol which reacts with the vinyl functional groups via thiol groups, so as to produce an ⁇ , ⁇ -thioalkylhydroxylated polydimethylsiloxane.
- This alcohol is able to react with acrylic acid by esterification.
- the Japanese patent application JP-200 098 602 of 7/04/2000 for its part relates in a completely different way the reaction of diethanolamine with acrylic acid to obtain an acrylic aminoester.
- chromium catalysis has the drawback of the toxic nature of chromium itself.
- Another disadvantage of chromium catalysis is related to the fact that the elimination of chromium is very difficult. This results in a residual color of the compounds obtained, which is unacceptable.
- the European patent EP-BO 291 452 describes polyorganosiloxanes carrying at each end of two acrylate or methacrylate functional groups, obtained from a polyorganosiloxane with terminal motifs ⁇ SiH that is reacted with an alkenyl epoxide. The polyorganosiloxane thus epoxidized at its ends is then brought into contact with an aqueous or methanolic base such as NaOH. This polyorganosiloxane is then reacted with a derivative of acrylic or methacrylic acid for introducing an acrylate group.
- These acrylate silicones result from the hydrosilylation of allyl glycidyl ether (AGE) and a vinylcyclohexene epoxide (VCMX) in the presence of a platinum catalyst on an SiH functional polyorganosiloxane.
- the graft polyorganosiloxane thus obtained is reacted with (meth) acrylic acid and or (meth) acrylic acid anhydride.
- the reaction is catalyzed by diazabicyclo (2,2,2) octane.
- This acrylate or methacrylate function grafting via a first epoxy functionalization, intervenes as well on Si-H units located in the chain as on terminal Si-H units.
- one of the essential objectives of the present invention is to provide new perspectives for the use of silanes / epoxy silicones, in particular for those whose ball joint between the epoxy function and the silicone chain is short (number of atoms composing the patella less than 10).
- Another essential objective of the present invention is to propose a novel process for producing a functionalized polyorganosiloxane or silane, in particular by acrylate and / or methacrylate functional groups carried by groups linked to the polysiloxane chain or silane via an Si bond.
- -C which does not have the disadvantages of known methods.
- Another essential objective of the present invention is to provide a new process for producing functionalized silicones or silanes, in particular (meth) acrylate, which makes it possible to obtain good yields without resorting to ecotoxic compounds such as chromium for example and without producing salts.
- the present invention which relates to a new process for preparing a monomer, oligomer, polymer or copolymer of an organosiloxane or functionalized silane (A) comprising the following steps: a) reacting at least one monomer, an oligomer, a polymer or a copolymer of an organosiloxane or a silane (B) bearing at least one reactive group (Y) comprising at least one epoxy function (Ep) with at least one nucleophile carrying at least one function
- the reaction of step a) is carried out at a temperature T1 of between 20 and 100 ° C. and preferably between 30 and 80 ° C.
- polymerization inhibitors examples include hydroquinone and hydroquinone monomethylether (MEHQ). Hydroquinone is particularly preferred.
- the reactive group (Y) comprising at least one epoxy function (Ep) is connected to a silicon atom.
- nucleophiles carrying at least one functional group that are useful according to the invention, mention may be made of those carrying acid functions, acid anhydrides, amides and / or esters.
- the function (Nu) capable of reacting with the epoxy function (Ep) is a -COOH function.
- the function (Nu) capable of reacting with the epoxy function (Ep) is a -COOR function, with R being a linear C 1 -C 12 alkyl, branched C 1 -C 12 or cyclic C 5 -C 10 .
- nucleophile carrying at least one functional group (Nu) from the group consisting of: acrylic acid, methacrylic acid, (meth) acrylic anhydride, benzoic acid diacids such as terephthalic acid or adipic acid, fatty acids such as lauric acid, stearic acid or palmitic acid, uronic acids such as glucuronic acid or galacturonic acid, amino acids such as aspartic acid and mixtures thereof.
- nucleophile from the group consisting of acrylic acid, methacrylic acid and mixtures thereof.
- the enzyme used according to the invention is a lipase of class EC 3.1.1.3 or EC 3.1.1.13 and preferably a lipase of the genera Alcaligenes, Pseudomenas Rhizopus Burkholderia or Aspergillus.
- the genus Alcaligenes spp, of the family Alcaligenacae includes several species, such as for example: Alcaligenes aestus, Alcaligenes aquamarinus, Alcaligenes Alcaligenes eufrophus, Alcaligenes faecalis, Alcaligenes denitrificans, Alcaligenes eutrophus, Alcaligenes faecalis, Alcaligenes laius, Alcaligenes pacificus, Alcaligenes paradoxus, Alcaligenes piechaudii, Alcaligenes ruhlandii, Alcaligenes venustus, Alcaligenes xylosoxidans.
- the lipases of the invention can be obtained for example from culture of the genera Alcaligenes, Pseudomonas, Rhizopus Burkholderia, Candida or Aspergillus.
- the culture conditions may vary depending on the type of strains used. It is recommended to choose these conditions in order to produce lipases in the most advantageous way possible.
- the culture temperature is generally between 5 and 80 ° C.
- the culture period is generally between 1 and 10 days.
- the recovery of lipases can be carried out in various ways well known to those skilled in the art. It is for example possible to separate the bacteria and the culture medium, in particular by centrifugation or filtration, and then carry out a purification of the lipases.
- the purification of lipases can be carried out by precipitation, lyophilization, ion exchange chromatography, immunoaffinity using specific mono- or polyclonal antibodies, and / or dialysis.
- the lipases can also be recovered by destroying the bacteria, for example by sonication and recovery of the ground material, or by enzymatic lysis of the cell walls.
- the lipases of the invention can be purified, for example to the genus Alcaligenes from strains 1 Alcaligenes spp by addition of salts, using for example ammonium sulphate, passage through an ion exchange chromatography and then gel filtration.
- lipases for example: the lipase PL of the strain of Alcaligenes sp (supplied by the company Meito Sangyo), the lipase
- the lipase F-AP 15 of the Rhizopus oryzae strain supplied by the company by Amano-Enzyme Inc.
- the CE lipase Choesterol Esterase
- the strain Pseudomonas sp supplied by the company Amano-Enzyme Inc
- Burkholderia cepacia strain AH lipase supplied by Amano-Enzyme Inc.
- Aspergillus niger lipase AS supplied by Amano-Enzyme Inc.
- the EC 3.1.1.3 or EC 3.1.1.13 classes are particularly preferred, for example the PL lipase of the strain of Alcaligenes sp (supplied by the company Meito Sangyo), the lipase PL in its form.
- PLC lipase supplied by the company Meito Sangyo
- PLAG lipase supplied by the company Meito Sangyo
- IM TL lipase of the strain Pseudomonas stutzeri supplied by the company Meito Sangyo
- the lipase QLM of the strain Alcaligenes sp the lipase QLM of the strain Alcaligenes sp.
- lipase F-AP 15 of the strain Rhizopus oryzae supplied by the company Amano-Enzyme Inc-Enzyme Inc.
- lipase CE Choesterol Esterase
- Pseudomonas sp supplied by Amano-Enzyme Inc.
- Burkholderia cepacia strain AH lipase supplied by Amano-Enzyme Inc.
- Aspergillus niger lipase AS supplied by Amano-Enzyme Inc.
- 3.1.1.13 used according to the invention make it possible to obtain a degree of conversion ( ⁇ -i) of opening of the epoxy functions (Ep) of the compound (B) of greater than or equal to 10%, preferably greater than 30% and even more more preferably greater than 40%.
- the proportion of the enzyme catalyzing the nucleophilic opening of epoxy function (s) is between 0.5 and 10% by weight and preferably between 2 and 5%. by weight relative to the weight of the compound of formula (B).
- the following test may be carried out: a) the reaction is carried out in a reactor of 100 m L 1 optionally in the presence of a solvent such as methyl isobutyl ketone or methyl ethyl ketone, at least a monomer, an oligomer, a polymer or a copolymer of an organosiloxane or a silane (B) carrying at least one reactive group (Y) comprising at least one epoxy functional group (Ep) with the nucleophile carrying from minus a function (Nu) capable of reacting with the epoxy function (Ep) in the presence of the enzyme to be tested while keeping the temperature of the reaction medium T1 constant between 20 and 100 ° C.
- a solvent such as methyl isobutyl ketone or methyl ethyl ketone
- the degree of conversion (O 1 ) of opening of the epoxy functional groups is measured, for example, by integration of the signal Rmn of the proton -CH- of the epoxy ring :
- ( ⁇ -i) [(% signal area at t 0 -% signal area after a reaction time ( ⁇ t)) /% signal area at t 0 ] x 100 and c) the transformation rate must be greater than 10%, preferably greater than 20% and even more preferably greater than 40%.
- the lipases used according to the method of the invention have an amino acid sequence having a percentage of homology greater than or equal to 80%, in particular 90%, preferably 95, more preferably 100% with the acid sequence.
- amines of the lipase PL of the strain of Alcaligenes sp the protein having an activity in the opening reaction of an epoxy function by a nucleophile.
- the lipases used according to the invention may originate from nucleotide sequences having a homology percentage greater than or equal to 80%, in particular 90%, preferably 95, more preferably 100%, with the nucleotide sequence of the lipase PL gene of the strain.
- Alcaligenes sp the lipase obtained having an activity in the opening reaction by a nucleophile of an epoxy function carried by a silane, an organosiloxane or a polyorganosiloxane.
- homology refers to the perfect similarity or identity between the compared amino acids but also to the non-perfect resemblance that is termed similarity.
- the amino acid sequences may differ from the reference sequence by substitution, deletion and / or insertion of one or more amino acids, preferably a reduced number of amino acids, in particular by substitution of natural amino acids. by non-natural amino acids or pseudo-amino acids, at positions such that these modifications do not significantly affect the biological activity of the protein. Homology is generally determined using sequence analysis software (eg, Sequence Analysis Software Package of the Genetics Computer Group, University of Wisconsin Biotechnology Center, 1710 University Avenue, Madison, WI 53705, or BLAST software of the National Center. for Biotechnology Information, US National Library of Medicine, 8600 Rockville Pike Bethesda, MD 20894).
- sequence analysis software eg, Sequence Analysis Software Package of the Genetics Computer Group, University of Wisconsin Biotechnology Center, 1710 University Avenue, Madison, WI 53705, or BLAST software of the National Center. for Biotechnology Information, US National
- the amino acid sequences of natural, synthetic, chimeric and / or recombinant synthetic lipases may be of the same length as the reference sequences. It is understood that according to the invention the lipases of class EC 3.1.1.3 can originate from the bacteria of the genera Alcaligenes, Pseudomonas, Rhizopus, Burkholderia or Aspergillus. However, for example in the context of industrial process for manufacturing these lipases, it is possible that these are produced by host cells or by chemical processes.
- the lipase may be immobilized on a suitable solid or non-immobilized support.
- the solid support may be chosen from the group consisting of: diethylaminoethylcellulose
- DEAE-cellulose diethylaminoethylsepharose
- DAO-Sepharose diethylaminoethylsepharose
- diatom silica
- alumina alginate beads
- alginate beads polypropylene ceramic particles and mixtures thereof.
- the isolated lipase can be used directly in the reaction medium or in organic solvents.
- the organic solvent may be an aliphatic, cyclic or aromatic hydrocarbon compound and / or ketone.
- the organic solvent is preferably selected from the group comprising: methyl ethyl ketone and methyl isobutyl ketone.
- the enzymatic catalysis reaction of step a) is preferably carried out at a temperature of between 20 and 100 ° C. and preferably between 30 and 80 ° C.
- a person skilled in the art is perfectly able to easily determine the optimal duration conditions for a given substrate. This can be done by carrying out regular samples of the reaction medium on which the conversion rate is evaluated.
- immobilized enzymes lies essentially in the possibility of recovering them without difficulty from the medium in which they have been implemented and in which the enzyme itself develops its activities for which it is conventionally used, to purify them in as needed and to put them to work in another environment.
- the silicone (B) bearing at least one reactive group (Y) comprising at least one epoxy functional group (Ep) useful according to the invention is a monomer, an oligomer, a polymer or an essentially linear copolymer bearing units of formulas:
- radicals R 2 are identical or different from each other and each represents an alkyl, an aryl or an arylalkyl; preferably linear or branched C 1 -C 10 alkyl or phenyl;
- the radical (Y) is a reactive group comprising at least one epoxy function (Ep); • a and b are chosen so that:
- 0 ⁇ a + b preferably 0 ⁇ a + b ⁇ 500, and even more preferably 10 ⁇ a + b ⁇ 200 and even more preferably 50 ⁇ a + b ⁇ 150;
- organosiloxane (B) it is preferably linear and of formula (V):
- radicals R 1 are identical or different from each other and each represents an alkyl, an aryl, an arylalkyl or the radical (Y); preferably a C 1 -C 0 linear or branched or phenyl;
- radicals R 2 are identical or different from each other and each represents an alkyl, an aryl or an arylalkyl; preferably linear or branched C 1 -C 10 alkyl or phenyl;
- the radical R 3 represents an alkyl, an aryl, an arylalkyl or the radical (Y); preferably linear or branched C 1 -C 10 alkyl or phenyl;
- the radical (Y) is a reactive group comprising at least one epoxy function (Ep); • a and b are chosen so that:
- B can be equal to 0 and in this case at least one of the radicals R 1 or R 2 represents the radical (Y).
- radicals R 3 since they are different from the radical (Y), independently respond to the same definition as that given above for R 2 and R 1 .
- the reactive groups (Y) comprising at least one epoxy function (Ep) are preferably in the chain and optionally on at least one of the terminal Si of the formula (V).
- silane (B) carrying an epoxy functional group As an example of a silane (B) carrying an epoxy functional group, mention may be made of 3-glycidoxypropylt ⁇ methoxysilane (GLYMO), 3,4-epoxycyclohexylethyltrimethoxysilane and those described in the book “Chemistry and Technology of Silicones", Walter NoII, published by Académie. Press Inc, 1968, at page 173.
- GLYMO 3-glycidoxypropylt ⁇ methoxysilane
- 3,4-epoxycyclohexylethyltrimethoxysilane those described in the book "Chemistry and Technology of Silicones", Walter NoII, published by Académie. Press Inc, 1968, at page 173.
- the reactive group (Y) comprising at least one epoxy function (Ep) is selected from the group consisting of the following radicals (1) to (10):
- the radical (Y) is the following unit (11):
- the polyorganosiloxanes (B) may be oils with a dynamic viscosity at 25 ° C. of the order of 10 to 10,000 mPa.s, generally of the order of 50 to 5,000 mPa.s, and even more preferably of 100 to 600 mPa.s, or gums having a molecular mass of the order of 1x10 6 g.
- the dynamic viscosity at 25 ° C. of all the silicones considered in the present disclosure can be measured using a BROOKFIELD viscometer, according to the AFNOR NFT 76 102 standard of February 1972.
- the polyorganosiloxanes B used contain from 1 to 10 epoxyfunctional groups per macromolecular chain. For an epoxyfunctional group this corresponds to epoxide levels ranging from 20 to 2000 meq. molar / 100 g of polyorganosiloxane.
- the polyorganosiloxanes B may be dynamic viscosity oils at 25 0 C 1 of the order of 10 to 10 OOO mPa.s at 25 ° C, generally of the order of 20 to 5000 mPa.s at 25 ° C and , more more preferably, from 20 to 600 mPa.s at 25 ° C, or gums having a molecular weight of about 1,000,000.
- cyclic polyorganosiloxanes B these consist of units which may be, for example, of the dialkylsiloxy or alkylarylsiloxy type. These cyclic polyorganosiloxanes have a viscosity of the order of 1 to 5,000 mPa.s at 25 ° C.
- the epoxy functional organosiloxanes or polyorganosiloxanes B may be prepared by hydrosilylation reaction between Si-H units and epoxyfunctional compounds such as, for example, 4-vinylcyclohexeneoxide or allylglycidylether. Obtaining such organosiloxanes or epoxy functionalized silanes is perfectly within the reach of a person skilled in the art of silicone chemistry.
- the subject of the invention is a composition comprising the mixture of:
- - optionally at least one solvent, preferably a solvent selected from the group consisting of: methyl isobutyl ketone, methyl ethyl ketone and mixtures thereof; and
- a polymerization inhibitor preferably hydroquinone.
- the subject of the invention is the use of the monomer, oligomer, polymer, organosiloxane copolymer or functionalized silane (A) obtained by the process as defined above as a main or secondary constituent in useful compositions. for cosmetics, pharmacy, personal care, home care and the preparation of paper non-stick coatings.
- A functionalized silane
- the silicone substrates used are oils functionalized with allyl glycidyl ether.
- the intended reaction is nucleophilic addition to the epoxy function by enzymatically catalyzed acrylic acid.
- the expected structures for the functionalized polyorganosiloxane (A) are therefore as follows:
- the reaction is monitored by 1 H NMR.
- the sample is first filtered through a 0.2 ⁇ m microfilter and then dissolved in CDCl 3 . Spectrum acquisition is performed on a 300 MHz Br ⁇ cker device at room temperature.
- the conversion rate (TT) is calculated from the peak integrals of the epoxy CH at about 3.1 ppm (which decreases during the reaction) and the CH 2 at silicon alpha at 0.41 ppm (which remains constant during the reaction). the reaction).
- the final product is characterized by 1 H NMR after evaporation of the excess of acrylic acid.
- the flask is heated to 70 ° C .; 1600 g of a silicone oil of structure MD 110 D 5 M (1.002 equivalent of SiH) are cast at a rate of 8.2 g / min.
- conversion rate of the SiH functions 100%).
- the medium is treated with black 2S for 2h at 80 ° C., followed by filtration and distillation without column and under vacuum (1 mm Hg, 3h at 130 ° C.).
- This silicone oil has reactive functions (here epoxy) connected to the siloxane chain by a -CH 2 -CH 2 -CH 2 -O- patella. It follows that the length of this patella is therefore much lower than a polyoxyethylene ball (Poe) and therefore has reactive groups a priori difficult to access for enzymatic catalysis because of an adverse steric environment.
- Re epoxy polyoxyethylene ball
- the screening type tests are carried out in a carousel accepting 12 test tubes.
- the reaction volume is about 11 ml, the temperature is regulated to the desired value.
- the stirring is done by magnetic bar. Operating conditions:
- Enzyme to be tested 0.25 g
- Duration from 4 to 6 days; temperature 60 ° C;
- Methyl isobutyl ketone 3.5 ml.
- Epoxy silicones (MD 5 D 110 epoxy M): 7 g.
- reaction medium is stirred at 700 rpm for 7 days and samples are taken regularly and analyzed by 1 H NMR. After reaction, the medium is filtered in order to separate the solid catalyst from the liquid reagents and is then subjected to a rotavapor distillation twice. at 70 0 C at 7 mb at 110 rpm to remove excess acrylic acid. '
- lipase QLM lipase QLM
- lipase TL IM lipase TL IM
- Example 3 In test No. 3, the conditions of Example 3 are reproduced, but 9.2 g of an organosiloxane monomer (B) of formula MD epoxy M (ie 0.028 epoxy equivalent) are introduced in place of the ® silicone oil Di inhabitcxy 5 10 M. the molar ratios are identical, the missing volume being replaced with methyl isobutyl ketone (MIBK).
- MIBK methyl isobutyl ketone
- the enzyme used is PL lipase.
- This test (referenced G-4) was conducted in parallel with a standard test with lipase PL (referenced H-4). The results are shown in Table III below.
- Table III Reactor Testing RPAS 100 ml: grafting kinetics in comparison to an epoxy monomer compound and the polyorganosiloxane M MD MD 5 D 110 epoxy M.
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Abstract
Description
Claims
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Application Number | Priority Date | Filing Date | Title |
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FR0411251A FR2877007B1 (en) | 2004-10-22 | 2004-10-22 | PREPARATION OF SILICONES AND SILANES FUNCTIONALIZED VIA AN ENZYMATIC CATALYSIS |
FR0411251 | 2004-10-22 |
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WO2006045916A2 true WO2006045916A2 (en) | 2006-05-04 |
WO2006045916A3 WO2006045916A3 (en) | 2006-06-22 |
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FR (1) | FR2877007B1 (en) |
WO (1) | WO2006045916A2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011028214A1 (en) * | 2009-09-02 | 2011-03-10 | Momentive Performance Materials Inc. | Silicone modified fatty acids, method of preparation and usage thereof |
Citations (4)
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EP0676414B1 (en) * | 1994-03-11 | 1999-10-20 | Studiengesellschaft Kohle mbH | Lipases immobilized in sol-gel processed hydrophobic materials |
US6194596B1 (en) * | 1999-03-09 | 2001-02-27 | Goldschmidt Ag | Polysiloxanes containing carbonate groups and modified with linear polyesters and their use as additives in coatings |
US6288129B1 (en) * | 1998-11-03 | 2001-09-11 | Th. Goldschmidt Ag | Process for preparing acrylic esters and/or methacrylic esters of hydroxy-functional siloxanes and/or polyoxyalkylene-modified siloxanes and their use |
US6617411B1 (en) * | 2000-09-18 | 2003-09-09 | Basf Aktiengesellschaft | Polycondensation of organic silicon compounds |
-
2004
- 2004-10-22 FR FR0411251A patent/FR2877007B1/en not_active Expired - Fee Related
-
2005
- 2005-10-14 WO PCT/FR2005/002546 patent/WO2006045916A2/en not_active Application Discontinuation
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0676414B1 (en) * | 1994-03-11 | 1999-10-20 | Studiengesellschaft Kohle mbH | Lipases immobilized in sol-gel processed hydrophobic materials |
US6288129B1 (en) * | 1998-11-03 | 2001-09-11 | Th. Goldschmidt Ag | Process for preparing acrylic esters and/or methacrylic esters of hydroxy-functional siloxanes and/or polyoxyalkylene-modified siloxanes and their use |
US6194596B1 (en) * | 1999-03-09 | 2001-02-27 | Goldschmidt Ag | Polysiloxanes containing carbonate groups and modified with linear polyesters and their use as additives in coatings |
US6617411B1 (en) * | 2000-09-18 | 2003-09-09 | Basf Aktiengesellschaft | Polycondensation of organic silicon compounds |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011028214A1 (en) * | 2009-09-02 | 2011-03-10 | Momentive Performance Materials Inc. | Silicone modified fatty acids, method of preparation and usage thereof |
EP2620464A1 (en) * | 2009-09-02 | 2013-07-31 | Momentive Performance Materials Inc. | Silicone modified fatty acids, method of preparation and usage thereof |
KR101444168B1 (en) * | 2009-09-02 | 2014-09-26 | 모멘티브 퍼포먼스 머티리얼즈 인크. | Silicone modified fatty acids, method of preparation and usage thereof |
US8846843B2 (en) | 2009-09-02 | 2014-09-30 | Momentive Performance Materials Inc. | Silicone modified fatty acids, method of preparation and usage thereof |
US8975357B2 (en) | 2009-09-02 | 2015-03-10 | Natura Inovacao E Tecnologia De Produtos Ltda. | Silicone modified fatty acids, method of preparation and usage thereof |
JP2016153390A (en) * | 2009-09-02 | 2016-08-25 | モメンティブ パフォーマンス マテリアルズ インコーポレイテッド | Silicone modified fatty acids, method of preparation and usage thereof |
Also Published As
Publication number | Publication date |
---|---|
WO2006045916A3 (en) | 2006-06-22 |
FR2877007A1 (en) | 2006-04-28 |
FR2877007B1 (en) | 2006-12-08 |
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