Bio-based cyanoacrylate compounds

Abstract

The present invention relates to compounds of formula (I) wherein R1 is H or an organic moiety, said compounds of formula (I) having a biochar content equal to or higher than 20%. # imgabs0 #

Description

Field of the Invention The present invention relates to the field of bio-based cyanoacrylates.

[0002] The present invention also relates to the use of the bio-based cyanoacrylate for preparing an adhesive composition, and the obtained adhesive composition. Background Art Cyanoacrylate (CA) is the common name for a family of resistant, fast-acting adhesives based on 2-cyanoacrylates. Such compounds have been known for some time, as described, for example, in S. Ebnesajjad, ed., Adhesives Technology Handbook, William Andrew, Norwich, 2008.

[0004] Adhesive compositions based on cyanoacrylates (CA) are also well known, for example as instant adhesives or so-called "super glues". They are popular in many application areas and are used by consumers, professional craft workers and industrial assemblers. They are generally solvent-free, 100% reactive materials known for their ability to form strong bonds on many different substrates within seconds.

[0005] These compounds are used in one or two component forms in many industrial and domestic applications because they polymerize rapidly when they form a film between two substrates in the presence of anionic or nucleophilic species. The speed and ease of forming a bond contribute to their popularity.

[0006] Although efforts have been made to improve their properties (toughening, temperature, humidity...), the synthetic route of cyanoacrylates themselves has remained largely the same in industry since the late 1950s. Conventional cyanoacrylates are derived from petrochemical-based chemicals and rely on energy-intensive processes. The use of these materials contributes to the intensification of the greenhouse effect. As the world's oil reserves decrease, the sources of these raw materials are gradually being depleted. This is an emergency, especially for the 2050 carbon neutrality goals of many countries.

[0007] There is a growing desire to reduce the carbon footprint and produce less toxic, more environmentally friendly products.

[0008] Raw materials derived from biomass come from renewable sources and have a reduced impact on the environment. They do not require all the energy-intensive refining stages of petroleum products. The production of CO2 is reduced, so that they contribute less to global warming.

[0009] However, such sustainable development should not negatively impact the existing properties of cyanoacrylates, such as, for example, fixation time, adhesive properties, and the like.

[0010] There is therefore a need to provide environmentally friendly cyanoacrylates allowing to resolve at least some of the above-mentioned drawbacks.

[0011] More particularly, there is a need for more environmentally friendly cyanoacrylates that exhibit rapid set times.

[0012] More particularly, there is a need for more environmentally friendly cyanoacrylates that exhibit properties at least similar to or better than conventional petroleum-based cyanoacrylates.

[0013] Furthermore, there is a need for more environmentally friendly cyanoacrylates which can be produced industrially in good yields.

[0014] Description of the invention Compound The present invention relates to compounds of formula (I): Wherein R1 is H or an organic moiety, the compound of formula (I) has a biochar content equal to or higher than 20%.

[0015] The carbon of biomaterials originates from the photosynthesis of plants and therefore from atmospheric CO2. Therefore, the degradation of these materials (degradation also means combustion / incineration at the end of their life) into CO2 does not cause warming, because the carbon emitted to the atmosphere is not increased. Therefore, the CO2 balance of biomaterials is significantly improved and leads to a reduction in the carbon footprint of the obtained products (considering only the energy used for manufacturing). In contrast, materials of fossil origin that also degrade into CO2 will cause an increase in CO2 levels and therefore global warming.

[0016] The components of the invention will therefore have a carbon footprint that is better than that of compounds obtained from fossil sources.

[0017] The term "biocarbon" or "biobased carbon" indicates that the carbon is of renewable or natural origin and is derived from biological material as indicated below. Biocarbon content and biomaterial content are expressions indicating the same value.

[0018] Renewably sourced materials (also called biomaterials) are organic materials in which the carbon is derived from CO2 that has been recently fixed from the atmosphere by photosynthesis (on a human scale). On land, this CO2 is captured or fixed by plants. In the ocean, CO2 is captured or fixed by photosynthesis by bacteria or plankton. 14 C / 12 C isotope ratio greater than 10 -12 , typically about 1.2x10 -12 , while the ratio of fossil materials is zero.14 C is formed in the atmosphere and then integrated through photosynthesis on time scales of up to several decades. 14 The half-life of C is 5730 years. Therefore, materials produced by photosynthesis (i.e., usually plants) must have a maximum 14 C isotope content.

[0019] The biomaterial content or biocarbon content is determined by using the standards ASTM D 6866 (ASTM D 6866-21, Method B) and ASTM D 7026 (ASTM D7026-04). The ASTM D 6866 standard is "Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis", while the ASTM D 7026 standard is "Sampling and Reporting of Results for Determination of Biobased Content of Materials via Carbon Isotope Analysis". The second standard refers to the first standard in its first paragraph.

[0020] The first standard describes a test for measuring the 14 C / 12 C ratio and compared it with the reference sample from 100% renewable sources 14 C / 12 C ratios are compared to give the relative percentage of C from renewable sources in the sample. 14 C dating Same concept, but the dating equation is not used.

[0021] The ratio thus calculated is called "pMC" (percent modern carbon). If the material to be analyzed is a mixture of biological material and fossil material (without radioactive isotopes), the pMC value obtained is directly related to the amount of biological material present in the sample.

[0022] The C-14 modern standard (oxalic acid II) represents the modern (living plant) C-14 activity of 1950, which has been set as a standard for 100% biobased activity. A background level that is subtracted from the measured activity is also established. The activity of the sample is compared with the activity of oxalic acid II. This will give the percentage of pMC or modern carbon. If there is a mixture of modern carbon and fossil carbon in the sample, the resulting pMC (e.g., 85pMC) indicates that we have measured 85% of the modern standard activity. The sample will be reported as 85% biobased carbon. Due to the nuclear tests carried out in the atmosphere in the 1950s and 1960s, C-14 is artificially produced in the atmosphere. It was once close to 200% of the natural activity. Over time, with the dilution of fossil fuel CO2 discharged into the atmosphere, the activity has been diluted so that the C-14 activity in the atmosphere today returns to the same level as the modern standard. Atmospheric correction factors are used to explain these changes in atmospheric C-14 activity. The atmospheric correction factor (REF) is used as follows: Biogenic carbon content = pMC / (REF) Where REF = 1.000 (2022) The accuracy of the % biogenic carbon content is + / - 3% (absolute).

[0023] The biochar content of the compound of formula (I) as defined herein is preferably equal to or higher than 25%, more preferably equal to or higher than 41%, even more preferably equal to or higher than 50% and more advantageously equal to or higher than 55%.

[0024] In a preferred embodiment, R1 is H or a hydrocarbonated group which may contain at least one heteroatom.

[0025] Preferably, R1 is selected from: H, alkyl, haloalkyl, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, acrylate moiety, oxetane moiety, epoxy moiety, carboxylate moiety.

[0026] Alkyl, alkenyl, aryl, alkynyl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl may be substituted, for example, with at least one substituent selected from the group consisting of alkyl, aryl, alkenyl, OH, amine, amide, halogen atom, -CF3, and mixtures thereof.

[0027] The term "alkyl" as used herein means a straight or branched hydrocarbon group. Examples are methyl, ethyl, propyl.

[0028] The term "alkenyl" as used herein denotes a straight or branched hydrocarbon group comprising at least one double bond. Examples are allyl, propenyl, butenyl.

[0029] The term "alkynyl" as used herein denotes a straight or branched chain hydrocarbon group comprising at least one triple bond. An example is propargyl.

[0030] The term "aryl" as used herein means a monocyclic aromatic group or a bicyclic aromatic group, preferably containing 6 to 12 carbon atoms. Phenyl is an example.

[0031] The term "heteroaryl" as used herein means a monocyclic aromatic group or a bicyclic aromatic group containing at least one heteroatom such as, for example, O, S or N, and preferably containing 4 to 12 carbon atoms. Some examples are furanyl, thienyl, pyrrolyl, pyridyl, indolyl or imidazolyl.

[0032] The term "arylalkyl" or "aralkyl" as used herein refers to an alkyl group substituted by an aryl group, the arylalkyl group preferably containing 7 to 20 carbon atoms. An example is benzyl.

[0033] The term "alkylaryl" or "alkaryl" as used herein refers to an aryl group substituted by an alkyl group, the alkylaryl group preferably containing 7 to 20 carbon atoms.

[0034] The term "cycloalkyl" as used herein denotes a monocyclic saturated system or a polycyclic saturated system, preferably containing 3 to 12 carbon atoms. Examples of cycloalkyl are cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or norbornyl.

[0035] The term "cycloalkenyl" as used herein denotes a monocyclic unsaturated system or a polycyclic unsaturated system, preferably containing 3 to 12 carbon atoms.

[0036] The term "heterocycloalkyl" as used herein denotes a monocyclic or polycyclic saturated system comprising at least one heteroatom, such as, for example, O, S or N, preferably comprising 3 to 12 carbon atoms. Examples are tetrahydrofurfuryl or tetrahydrothienyl.

[0037] The term "alkoxyalkyl" as used herein denotes the group -alkyl-O-alkyl, wherein alkyl is as defined above.

[0038] When R1 is an alkyl group, it can be selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 1-methylbutyl, 1-ethylpropyl, neopentyl, n-hexyl, 2-heptyl, 1-methylpentyl, n-heptyl, n-octyl, 2-octyl, 2-ethylhexyl, n-nonyl, n-decyl, and n-undecyl.

[0039] When R1 is an alkylsilane, it may be selected from ethyltrimethylsilane, methyltrimethylsilane or propyltrimethylsilane.

[0040] When R1 is alkenyl, it may be selected from allyl, propenyl, butenyl.

[0041] When R1 is alkynyl, it may be propargyl.

[0042] When R1 is aryl, it may be selected from phenyl, methylphenyl.

[0043] When R1 is heteroaryl, it may be selected from furanyl, methylfuranyl, thienyl, pyrrolyl, pyridyl, indolyl, imidazolyl.

[0044] When R1 is arylalkyl, it may be benzyl.

[0045] When R1 is cycloalkyl, it may be selected from cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, isobornyl, methylbornyl or norbornyl.

[0046] When R1 is a cycloalkenyl group, it may be selected from cyclohexenyl and cycloheptenyl.

[0047] When R1 is heterocycloalkyl, it may be selected from methyltetrahydrofuranyl, tetrahydrofuranyl.

[0048] When R1 is alkoxyalkyl, it can be selected from 2-methoxymethyl, 2-ethoxymethyl, 2-propoxymethyl, 2-butoxymethyl, 2-isopropoxymethyl, 2-hexyloxymethyl, 2-pentyloxymethyl, 2-ethoxypropyl, 2-methoxyethyl and 2-(1-methoxy)ethyl. Other examples of alkoxyalkyl are described in US6977278.

[0049] When R1 is an acrylate moiety, it preferably has the formula: Wherein T is selected from (CH2) z , z is between 1-12, preferably 1-6; branched C2-C12 alkylene; alkynylene; alkenylene; alkylene-O-alkylene; cyclohexylene; biphenylene; -C6H4C(Me)2C6H4-; -C6H4CH2C6H4-; phenylene; -C6H4-alkylene-; and Y is H, Me or CN.

[0050] When R1 is a carboxylate moiety, it preferably has the formula -(CH2) k CO2Y' or -C(=CH2)-CO2Y', wherein k is between 1-18, preferably 1-6, and Y" is a C1-C4 alkyl group.

[0051] The compound of formula (I) may have one of the following formulae (IA), (IB) or (IC) wherein R1a is an alkyl group, wherein R1b is selected from H, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, oxetane moiety, epoxy moiety, preferably R1b ​​is selected from cycloalkyl, aralkyl, heteroaryl, heterocycloalkyl, alkoxyalkyl; wherein R1c is selected from an acrylate moiety and a carboxylate moiety.

[0052] Examples of compounds of formula (IA) may be ethyl cyanoacrylate, n-propyl cyanoacrylate, n-butyl cyanoacrylate, isobutyl cyanoacrylate, n-heptyl cyanoacrylate, n-octyl cyanoacrylate, n-hexyl cyanoacrylate, n-pentyl cyanoacrylate, nonyl cyanoacrylate, dodecyl cyanoacrylate.

[0053] Preferred compounds of formula (IA) are n-butyl cyanoacrylate, n-pentyl cyanoacrylate.

[0054] A more preferred compound of formula (IA) is n-heptyl cyanoacrylate.

[0055] Examples of compounds of formula (IB) may be: methyl cyanoacrylate, tetrahydrofurfuryl cyanoacrylate, 2-methoxyethyl cyanoacrylate, 2-ethoxyethyl cyanoacrylate, 2-methoxybutyl cyanoacrylate, 2-propoxyethyl cyanoacrylate, propargyl cyanoacrylate, 2-phenylethyl cyanoacrylate, cyclohexenyl cyanoacrylate, trialkylsilylethyl cyanoacrylate, trialkylsilylpropyl cyanoacrylate, trialkylsilylbutyl cyanoacrylate, benzyl cyanoacrylate.

[0056] Examples of compounds of formula (IC) may be: Where Rd is methyl or ethyl

[0057] Preferably, the compound of formula (I) is a compound of formula (IA) or (IB).

[0058] The compound of formula (I) can be selected from methyl cyanoacrylate, ethyl cyanoacrylate, n-propyl cyanoacrylate, n-butyl cyanoacrylate, isobutyl cyanoacrylate, n-heptyl cyanoacrylate, n-octyl cyanoacrylate, n-hexyl cyanoacrylate, n-pentyl cyanoacrylate, nonyl cyanoacrylate, dodecyl cyanoacrylate, tetrahydrofurfuryl cyanoacrylate, 2-ethoxyethyl cyanoacrylate, 2-propoxyethyl cyanoacrylate, 2-methoxyethyl cyanoacrylate, 2-methoxybutyl cyanoacrylate, trialkylsilylethyl cyanoacrylate, trialkylsilylpropyl cyanoacrylate, trialkylsilylbutyl cyanoacrylate, benzyl cyanoacrylate, propargyl cyanoacrylate, 2-phenylethyl cyanoacrylate, and cyclohexenyl cyanoacrylate.

[0059] Preferably, in formula (I), R1 is selected from alkyl and heterocycloalkyl.

[0060] Preferably, in formula (I), R1 is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group, even more preferably a C6 alkyl group.

[0061] Preferably, in formula (I) herein, when R1 is methyl, the biochar content of the compound of formula (I) is higher than or equal to 41%, more preferably higher than or equal to 50%.

[0062] method The present invention also relates to a method for preparing the compound of formula (I): Wherein R1 is H or an organic moiety, the compound of formula (I) has a biochar content equal to or higher than 20%.

[0063] All embodiments and preferred features disclosed above (in the "Compounds" paragraph) for the compounds of formula (I) apply to the process for their preparation and are not reiterated.

[0064] The process for the preparation of a compound of formula (I) as defined herein preferably comprises the step of converting a cyanoacetic acid ester of formula (II) into a compound of formula (I) as defined herein: wherein R1 in formula (II) is as defined herein in formula (I), ie, R1 is H or an organic moiety.

[0065] All embodiments and preferred features disclosed for R1 in the compounds of formula (I) apply here to R1 in the compounds of formula (II) and are not reiterated.

[0066] The compound of formula (II) may have one of the following formulae (II-A), (II-B) or (II-C): wherein R1a is an alkyl group; wherein R1b is selected from H, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, oxetane moiety, epoxy moiety; preferably R1b ​​is selected from cycloalkyl, aralkyl, heteroaryl, heterocycloalkyl, alkoxyalkyl; wherein R1c is selected from an acrylate moiety and a carboxylate moiety.

[0067] Examples of compounds of formula (II-A) may be ethyl cyanoacetate, n-propyl cyanoacetate, n-butyl cyanoacetate, isobutyl cyanoacetate, n-heptyl cyanoacetate, n-octyl cyanoacetate, n-hexyl cyanoacetate, n-pentyl cyanoacetate, nonyl cyanoacetate, dodecyl cyanoacetate. Preferred compounds of formula (II-A) are ethyl cyanoacetate and n-heptyl cyanoacetate.

[0068] Examples of compounds of formula (II-B) may be: methyl cyanoacetate, tetrahydrofurfuryl cyanoacetate, 2-ethoxyethyl cyanoacetate, 2-methoxyethyl cyanoacetate, 2-methoxybutyl cyanoacetate, 2-propoxyethyl cyanoacetate, propargyl cyanoacetate, 2-phenylethyl cyanoacetate, cyclohexenyl cyanoacetate, trialkylsilylethyl cyanoacetate, trialkylsilylpropyl cyanoacetate, trialkylsilylbutyl cyanoacetate, benzyl cyanoacetate.

[0069] Examples of compounds of formula (II-C) can be Where Rd is methyl or ethyl

[0070] Preferably, the compound of formula (II) is a compound of formula (II-A) or (II-B).

[0071] Preferably, in formula (II), R1 is selected from alkyl and heterocycloalkyl.

[0072] Preferably, in formula (II), R1 is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group, even more preferably a C6 alkyl group.

[0073] Preferably, in formula (II) herein, when R1 is methyl, the biochar content of the compound of formula (II) is higher than or equal to 25%, more preferably higher than or equal to 50%.

[0074] The biochar content of the compound of formula (II) is preferably equal to or higher than 25%, more preferably equal to or higher than 45%, and even more preferably equal to or higher than 50%.

[0075] The present invention also relates to compounds of formula (I) as defined herein, readily obtainable by a process comprising the step of converting a cyanoacetic acid ester of formula (II) as defined herein into a compound of formula (I).

[0076] The process for preparing the compounds of formula (I) is preferably selected from process P1 or process P2 as defined below: Wherein R1 is H or an organic moiety, the compound of formula (I) has a biochar content equal to or higher than 20%.

[0077] Method P1 The present invention relates to a process P1 for preparing a compound of formula (I) as defined above, comprising: - Step S1, which comprises subjecting the compound of formula (II) as defined above to a condensation reaction with a formaldehyde derivative: Then - an optional step S2, which comprises washing the product obtained in step S1; - step S3, which comprises depolymerizing the product obtained in step S1 or S2 to provide a compound of formula (I); - an optional step S4 of purifying the compound of formula (I) obtained at the end of step S3.

[0078] Step S1 is usually a Knoevenagel condensation reaction.

[0079] Preferably, step S1 is carried out in the presence of a basic catalyst, which can be selected from: amines, sodium hydroxide, potassium hydroxide, alkali metal alkoxides, and mixtures thereof. The amine catalyst can be piperidine, ethanolamine or diethylamine.

[0080] The content of the basic catalyst may range from 0.01 to 10 mol % based on the compound of formula (II).

[0081] The molar ratio of the compound of formula (II):formaldehyde derivative may range from 1:0.5 to 1:1.5.

[0082] Step S1 may be performed in a solvent, and the solvent may be selected from the group consisting of benzene, toluene, chloroform, trichloroethylene, tetrahydrofuran, water, and mixtures thereof.

[0083] Step S1 is preferably performed at a temperature ranging from 30°C to 150°C, more preferably from 50°C to 100°C.

[0084] The optional step S2 including washing can be carried out using water or an acidic aqueous solution. The acidic aqueous solution can be prepared using an acid selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, and mixtures thereof. The acid concentration in the acidic aqueous solution is preferably in the range of 0.01-5 wt %.

[0085] Washing may be performed at a temperature ranging from 0°C to 100°C.

[0086] The organic phase can be recovered by decantation, and the solvent can be evaporated under reduced pressure.

[0087] Step S3 comprising depolymerizing the product obtained in step S1 or S2 may be performed at a temperature ranging from 100°C to 250°C, preferably from 140°C to 200°C, preferably under reduced pressure.

[0088] Step S3 is preferably carried out in the presence of a depolymerization catalyst such as phosphorus pentoxide, phosphoric acid or polyphosphoric acid.

[0089] The purification step S4 can be distillation, double distillation, crystallization.

[0090] The formaldehyde derivative generally includes paraformaldehyde and a substance that generates formaldehyde in a reaction (formaldehyde precursor). Preferably, the formaldehyde derivative is paraformaldehyde.

[0091] Examples of the substance that generates formaldehyde in the reaction are paraformaldehyde and the like.

[0092] The formaldehyde derivatives may be derived from petroleum-based materials, or may be partially bio-based or even completely bio-based (100% bio-carbon content).

[0093] Bio-based formaldehyde can be produced using biomethanol (Veolia) from conventional partial methanol oxidation (Formaldehyde, Ullmann's Encyclopedia of Industrial Chemistry, Weinheim, Wiley-VCH, 2000).

[0094] As used herein, the term "partially biobased" means that the biogenic carbon content of the material is at least higher than 0%, preferably at least higher than 10%.

[0095] Preferably, method P1 comprises: -Step S1; - step S2, which comprises washing the product obtained in step S1; - step S3, which comprises depolymerizing the product obtained in step S1 or S2 to provide a compound of formula (I); - a step S4 of purifying the compound of formula (I) obtained at the end of step S3.

[0096] The embodiments and preferred embodiments disclosed above for the compound of formula (II) apply to process P1 and are not reiterated.

[0097] Method P2 The present invention relates to a process P2 for preparing a compound of formula (I) as defined above, comprising: - comprising making a compound of formula (II) as defined above With the compound of formula (X): Where E is (CH2X) m , m is between 1 and 20, X is O or s, When n=1, F is selected from the following functional groups: When n=2, F is selected from the following functional groups: When n=3, F is: G is selected from the following functional groups: G and F are chosen independently of each other, and R5 and R6 are independently selected from the functional group H, linear or branched C1-C4 alkyl, C1-C4 haloalkyl, carboxyl-substituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl and heterocycloalkyl, or When n=1, F can be selected from (CH2) v 、(CHR7) v 、(CR7R8) v The R7 group is connected to G, wherein v ranges from 1 to 6, preferably 1 to 4, and more preferably v is 1, R7 and R8 are the same or different C1-C4 alkyl groups, A step of reacting in the presence of a catalytic amount of an ammonium salt or an imine salt (XI); - an optional step of isolating the compound (II) obtained.

[0098] The method is generally disclosed in WO 2015 / 150882.

[0099] The ammonium salt or iminium salt (XI) may be in a homogeneous phase or supported on a solid substrate, preferably in a homogeneous phase.

[0100] The term "ammonium salt" as used herein refers to the product resulting from the reaction of, for example, an acid with a primary amine (eg, methylamine, ethylamine, ethylenediamine, aniline, benzylamine), a secondary amine (eg, piperazine), or a tertiary amine (eg, N,N'-dimethoxymethylpiperazine).

[0101] The term "iminium salt" as used herein refers to an imine which is produced from the reaction of a primary or secondary amine with an aldehyde or ketone in a neutral or acidic medium, which produces an iminium cation, and contains an anion from the acid.

[0102] The acid used to prepare the ammonium salt and the imine salt may be any acid. Preferably, the acid is selected from acetic acid, trifluoroacetic acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, camphorsulfonic acid, hydrochloric acid, phosphoric acid and mixtures thereof; preferably, the acid is selected from sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and mixtures thereof, and more preferably selected from methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid and mixtures thereof. It is also possible to use mixtures of acids and / or mixtures of amines.

[0103] The ammonium salt and the iminium salt (XI) can be formed in situ during the performance of the process of the invention or can be prepared separately and added independently to the reaction mixture. Preferably, they are prepared in situ.

[0104] Preferably, E is (CH2X) m , m is between 1 and 10, X is O or s, n=1, and F is selected from the following functional groups: G is selected from the following functional groups: G and F are chosen independently of each other, and R5 and R6 are independently selected from the functional group H, linear or branched C1-C4 alkyl, C1-C4 haloalkyl, carboxyl-substituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl and heterocycloalkyl, or When n=1, F can be selected from (CH2) v 、(CHR7) v 、(CR7R8) v The R7 group is connected to G, wherein v ranges from 1-6, preferably 1-4, and more preferably v is 1, and R7 and R8 are the same or different C1-C4 alkyl groups.

[0105] More preferably, E is (CH2X) m , m is between 1 and 3, X (is) 1, and F is: G is: G and F are chosen independently of each other, and R5 and R6 are independently selected from the functional group H, straight or branched C1-C4 alkyl, C1-C4 haloalkyl, carboxyl-substituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl and heterocycloalkyl. Preferably, R5 and R6 are independently selected from the functional group H and straight or branched C1-C4 alkyl.

[0106] Such compounds can be obtained, for example, by reacting formaldehyde gas or a formaldehyde source (e.g. paraformaldehyde or trioxane) or a thioformaldehyde source (e.g. trithiane) with an acid anhydride (such as, for example, acetic anhydride, thioacetic anhydride, dithiocarboxylic anhydride, methanesulfonic anhydride, succinic anhydride, phthalic anhydride or tert-butoxycarboxylic anhydride).

[0107] The formaldehyde source may be bio-based (as disclosed herein above in Process P1 ).

[0108] When X is O (oxygen) and n is 1, the compound is called methylene carboxylate, methylene thiocarboxylate, methylene sulfonate or methylene phosphate, depending on the groups F and G according to the above definition. The preparation of methylene carboxylates is described, for example, in US Pat. No. 3,927,078.

[0109] When X is O (oxygen), and n is 2, depending on the groups F and G defined above, the compound is referred to as carboxylic acid oxy dimethylene ester, thiocarboxylic acid oxy dimethylene ester, sulfonic acid oxy dimethylene ester or phosphooxy dimethylene ester. The preparation of polycarboxylic acid polyoxy methylene esters is described in, for example, US3219630. The preparation of carboxylic acid oxy dimethylene esters is described in, for example, US3927078 and US3931412. The preparation of sulfonic acid oxy dimethylene esters is described in, for example, US4100200.

[0110] The preparation of trioxymethylene carboxylates (X is O and n=3) is described, for example, in US 3931412. The preparation of tri(acyloxymethylene) phosphates is described in International Patent Application WO-A-96 / 40695.

[0111] When X is S (sulfur), and n is 1, the compound is called methylene thioether carboxylate, methylene thioether thiocarboxylate, methylene thioether sulfonate or methylene thioether phosphate, depending on the groups F and G according to the above definition.

[0112] Among the compounds of general formula (X), mention may preferably be made of the compounds listed in the following table: As the compound of formula (X), preferred compounds are methylene diacetate, diacetoxybismethylene ester, methylene dipropionate and dipropionoxybismethylene ester, more preferred are the compounds methylene diacetate and diacetoxybismethylene ester, and still more preferred is methylene diacetate.

[0113] Preferably, the compounds of formula (I) according to the invention are obtained by process P2.

[0114] The compounds of formula (II) as defined herein may be obtained by one of the following processes PA, PB, PC, PD or PE as described below.

[0115] Method PA The preparation method PA of the compound of formula (II) may comprise: - contacting a compound of formula (III) with a compound of formula (IV) in the presence of an acid, more preferably under conditions sufficient to produce a compound of formula (II): wherein R1 is as defined above for formula (I), i.e., is H or an organic moiety, wherein R2=NRR', wherein R and R' are each independently H or alkyl; - optionally isolating the compound of formula (II) therefrom.

[0116] The acid may be any acid catalyst known to those skilled in the art. They may be Lewis acids or Bronsted acids. The acid may be selected from sulfuric acid, p-toluenesulfonic acid, scandium trifluoromethanesulfonate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, hydrochloric acid. Heterogeneous catalysts may also be used, for example: zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay and tungstate zirconium oxide.

[0117] Preferably, the acid is an inorganic acid, even more preferably selected from sulfuric acid, sulfurous acid, sulfonic acid, phosphoric acid, phosphorous acid, phosphonic acid, hydrochloric acid or hydrobromic acid.

[0118] The compound of formula (IV) should be used in excess relative to either or both of the compound of formula (III) and the inorganic acid.

[0119] The compound of formula (IV) may be selected from: -Compound of formula (IV-A): wherein R1a is an alkyl group; -Compound of formula (IV-B): wherein R1b is selected from H, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, oxetane moiety, epoxy moiety; preferably, R1b is selected from cycloalkyl, aralkyl, heteroaryl, heterocycloalkyl, alkoxyalkyl; -Compound of formula (IV-C): wherein R1c is selected from an acrylate moiety and a carboxylate moiety.

[0120] Preferably, in formula (IV), R1 is selected from alkyl and heterocycloalkyl.

[0121] Preferably, in formula (IV), R1 is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group, even more preferably a C6 alkyl group.

[0122] The compound of formula (IV) may be partially bio-based, preferably completely bio-based. In that case, it may be obtained from fermentation, sugar, pyrolysis of oil, organic solution (juice), bio-oil ... The biocarbon content of the compound of formula (IV) is preferably equal to or higher than 20%, more preferably equal to or higher than 50%, even more preferably equal to or higher than 80%, and more advantageously equal to or higher than 99%.

[0123] The compound of formula (IV) is usually commercialized by different companies.

[0124] Examples of at least partially biobased or fully biobased compounds of formula (IV) are bio-derived EtOH supplied by Myhome aromas, bio-derived heptanol supplied by Arkema Oleris, bio-derived ethanol supplied by Pennakem Tetrahydrofurfuryl alcohol (THFA), isobutanol (supplied by Gevo), biomethanol (Veolia), n-butanol supplied by Green biologics, n-propanol supplied by Braskem, 1,10-dodecanediol supplied by Sartomer.

[0125] The compound of formula (IV) can be selected from methanol, ethanol, n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, nonanol, dodecanol, tetrahydrofurfuryl alcohol, ethoxyethanol, propoxyethanol, methoxyethanol, methoxybutanol, trialkylsilylethanol, trialkylsilylpropanol, trialkylsilylbutanol, benzyl alcohol, propargyl alcohol, phenyl-2-ethanol, and cyclohexenylethanol.

[0126] Compounds of formula (III) may be those wherein R=R'=H, or those wherein R=H and R'=alkyl (such as, for example, methyl or ethyl).

[0127] The biochar content of the compound of formula (III) may be equal to or higher than 0%, more preferably equal to or higher than 24%, and even more preferably equal to or higher than 49%.

[0128] In a preferred embodiment, the trace amount of substituted alcohol synthesized in compound (IV) should be (R5 is different from H) is reduced to less than 1%.

[0129] In a preferred embodiment, the compound of formula (III) is not derived from an aspartic acid derivative.

[0130] Method PB The preparation method PB of the compound of formula (II) may comprise: - contacting a compound of formula (V) with a compound of formula (IV) as defined above under conditions sufficient to produce a compound of formula (II): - optionally isolating the compound of formula (II) therefrom.

[0131] This reaction is well known in the art and can be carried out as disclosed in Chem Sci., 2021, 12, 10259-10265 (Wang et al.). It generally corresponds to the esterification of cyanoacetic acid with an alcohol.

[0132] The molar ratio of the compound of formula (IV) to the compound of formula (V) may vary from 1.0-20, preferably from 5.0-10.

[0133] Preferably, the reaction is carried out in the presence of an acid. Esterification acid catalysts are well known to those skilled in the art. They may be Lewis acids or Bronsted acids. The acid may be selected from sulfuric acid, p-toluenesulfonic acid, scandium trifluoromethanesulfonate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, hydrochloric acid. Heterogeneous catalysts may also be used, for example: zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay and tungstate zirconium oxide.

[0134] The reaction may be carried out at a temperature ranging from 25°C to 120°C, preferably from 50°C to 100°C.

[0135] Preferably, process PB for the preparation of the compound of formula (II) comprises a step of optionally isolating the compound of formula (II) from the reaction medium obtained in the first step.

[0136] Method PB preferably comprises: - a step of concentrating the reaction medium under reduced pressure; - a step of adding an organic solvent and an aqueous solution to the obtained residue; then - A step of decanting, recovering the organic phase and evaporating the organic solvent to obtain the compound of formula (II).

[0137] The compound of formula (V) may be petroleum based, or at least partially bio-based or fully bio-based (100% bio-carbon content).

[0138] All descriptions, embodiments and preferred embodiments disclosed above (eg in the paragraphs on process PA) for the compound of formula (IV) apply here to process PB and are not reiterated.

[0139] Compounds of formula (V) are commercially available, for example from Sigma-Aldrich.

[0140] The compound of formula (V) may also be obtained from a process comprising contacting a compound of formula (VI) with potassium cyanide (KCN) or sodium cyanide (NaCN), preferably potassium cyanide, under conditions sufficient to produce the compound of formula (V): wherein X represents a halogen atom, preferably Br or Cl, more preferably Br.

[0141] Potassium cyanide (KCN) or sodium cyanide (NaCN) may optionally be partially bio-based or even completely bio-based. Bio-based potassium cyanide can be obtained in two steps. The first step is the Andrussow oxidation of biomethane (Engie) to obtain hydrogen cyanide HCN (Andrussow L (1935), "The catalytic oxydation of ammonia-methane-mixtures to hydrogen cyanide", Angewandte Chemie, 48 (37): 593-595). Then, the bio-based HCN is reacted with potassium hydroxide (KOH) to form bio-based KCN (Pradyot Patnaik, Handbook of Inorganic Chemicals, McGraw-Hill, 2002, ISBN 0-07-049439-8).

[0142] The PB reaction can generally be carried out as described in Chemistry, a European journal, Vol. 24, No. 71, pp. 18903-18906; or CN2015-10810110 or CN2016-10662675.

[0143] The reaction can be carried out in an alkaline medium in which the pH is above 6, preferably above 7.

[0144] The reaction can be carried out in an alkaline aqueous solution (eg, an aqueous solution of Na2CO3 or NaHCO3).

[0145] The reaction can last from 3 minutes to 24 hours.

[0146] The reaction may be carried out at an overpressure (relative to the ambient atmospheric pressure) in the range of 0.01-1 MPa, preferably at 0.2 MPa.

[0147] The reaction may be carried out at a temperature ranging from 23°C to 100°C.

[0148] The method for preparing the compound of formula (V) preferably comprises isolating the compound of formula (V), which preferably comprises: - an acidification step using an acid such as HCl; - an optional step of evaporating water; - an optional extraction step with an organic solvent, preferably ether; - an optional filtration step to recover the compound of formula (V).

[0149] The compound of formula (VI) may be petroleum based, or partially bio-based or even fully bio-based (100% bio-carbon content).

[0150] Compounds of formula (VI) are commercially available from Sigma-Aldrich, such as, for example, bromoacetic acid.

[0151] The compound of formula (VI) may also be obtained from a process comprising contacting a compound of formula (VII) with a halogenating agent H under conditions sufficient to produce the compound of formula (VI): The reaction can be generally carried out as described in Asian Journal of Chemistry, 30(10), 2310-2316 (2018).

[0152] The halogenating agent H may be selected from PBr3, Br2, Cl2 and PCl5, and mixtures thereof.

[0153] The compound of formula (VII) may be the one commercialized by Sekab (acetic acid, CAS=64-19-7), which is completely bio-based (biocarbon content=100%).

[0154] The compound of formula (VII) may be petroleum based, or at least partially bio-based or fully bio-based (100% bio-carbon content).

[0155] Method PC The preparation method PC of the compound of formula (II) may comprise: - contacting a compound of formula (II') with a compound of formula (IV) as defined above under conditions sufficient to produce a compound of formula (II): wherein R'1 is H or an organic moiety different from R1, and R1 is as defined above; - optionally isolating the compound of formula (II) therefrom.

[0156] The reaction is generally a transesterification reaction well known in the art. It can be carried out, for example, as described in Adhesion (2014), 35(2), 67-68, 79.

[0157] The reaction may be carried out at a temperature ranging from 80°C to 120°C.

[0158] The reaction can be carried out in the presence of a catalyst selected from, for example, titanium isopropoxide, aluminum isopropoxide, tributyltin alkoxide, dibutyltin oxide, and tin acetylacetonate.

[0159] The preparation process PC preferably comprises a step of isolating the compound of formula (II). This step is preferably carried out by distillation, especially distillation under reduced pressure.

[0160] All descriptions, embodiments and preferred embodiments disclosed above (eg in the paragraphs Processes PA and PB) for the compound of formula (IV) apply here to Process PC and are not reiterated.

[0161] The compound of formula (II') may be petroleum-based, or partially bio-based or fully bio-based.

[0162] Compound of formula (II') Wherein R1' is as defined above, may have a biocarbon content equal to or higher than 20%, preferably equal to or higher than 25%, more preferably equal to or higher than 41%, even more preferably equal to or higher than 50%, and even more advantageously equal to or higher than 55%.

[0163] Preferably, R'1 is selected from: H, alkyl, haloalkyl, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, acrylate moiety, oxetane moiety, epoxy moiety, carboxylate moiety.

[0164] Alkyl, alkenyl, aryl, alkynyl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl may be substituted, for example, with at least one substituent selected from the group consisting of alkyl, aryl, alkenyl, OH, amine, amide, halogen atom, -CF3, and mixtures thereof.

[0165] The compound of formula (II') is preferably selected from methyl cyanoacetate, ethyl cyanoacetate, n-propyl cyanoacetate, n-butyl cyanoacetate, isobutyl cyanoacetate, n-heptyl cyanoacetate, n-octyl cyanoacetate, n-hexyl cyanoacetate, n-pentyl cyanoacetate, nonyl cyanoacetate, dodecyl cyanoacetate, tetrahydrofurfuryl cyanoacetate, 2-ethoxyethyl cyanoacetate, 2-methoxyethyl cyanoacetate, 2-methoxybutyl cyanoacetate, 2-propoxyethyl cyanoacetate, propargyl cyanoacetate, 2-phenylethyl cyanoacetate, cyclohexenyl cyanoacetate, trialkylsilylethyl cyanoacetate, trialkylsilylpropyl cyanoacetate, trialkylsilylbutyl cyanoacetate, benzyl cyanoacetate.

[0166] More preferably, the compound of formula (II') is methyl cyanoacetate.

[0167] Method PD The preparation method PD of the compound of formula (II) may comprise: - contacting a compound of formula (VIII) with a compound of formula (IV) under conditions sufficient to produce a compound of formula (II): wherein R1 is as defined above for formula (I), i.e., is H or an organic moiety, wherein R3 is Br, Cl or I; - optionally isolating the compound of formula (II) therefrom.

[0168] Preferably, the reaction is carried out in the presence of an acid. Esterification acid catalysts are well known to those skilled in the art. They may be Lewis acids or Bronsted acids. The acid may be selected from sulfuric acid, p-toluenesulfonic acid, scandium trifluoromethanesulfonate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, hydrochloric acid. Heterogeneous catalysts may also be used, for example: zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay and tungstate zirconium oxide.

[0169] The compound of formula (VIII) may be used in excess relative to either or both of the compound of formula (IV) and the acid.

[0170] The reaction may be carried out at a temperature ranging from 25°C to 120°C, preferably from 50°C to 100°C.

[0171] Preferably, process PD for the preparation of the compound of formula (II) comprises a step of optionally isolating the compound of formula (II) from the reaction medium obtained in the first step.

[0172] Method PD preferably comprises: - a step of concentrating the reaction medium under reduced pressure; - a step of adding an organic solvent and an aqueous solution to the obtained residue; then - A step of decanting, recovering the organic phase, and evaporating the organic solvent to obtain the compound of formula (II).

[0173] The compound of formula (VIII) may be petroleum based, or partially bio-based or fully bio-based (100% bio-carbon content).

[0174] All descriptions, embodiments and preferred embodiments disclosed above (eg in the paragraphs on process PA) for the compound of formula (IV) apply here to process PD and are not reiterated.

[0175] Method PE The preparation method PE of the compound of formula (II) may comprise: - contacting a compound of formula (IX) with a compound of formula (IV) under conditions sufficient to produce a compound of formula (II): wherein R1 is as defined above for formula (I), i.e., is H or an organic moiety, wherein R4 is -OC(=O)-R4, wherein R4 is selected from alkyl or aryl; - optionally isolating the compound of formula (II) therefrom.

[0176] Preferably, the reaction is carried out in the presence of an acid. Esterification acid catalysts are well known to those skilled in the art. They may be Lewis acids or Bronsted acids. The acid may be selected from sulfuric acid, p-toluenesulfonic acid, scandium trifluoromethanesulfonate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, hydrochloric acid. Heterogeneous catalysts may also be used, for example: zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay and tungstate zirconium oxide.

[0177] The compound of formula (IX) should be used in excess relative to either or both of the compound of formula (IV) and the acid.

[0178] The reaction may be carried out at a temperature ranging from 25°C to 120°C, preferably from 50°C to 100°C.

[0179] Preferably, process PE for the preparation of the compound of formula (II) comprises a step of optionally isolating the compound of formula (II) from the reaction medium obtained in the first step.

[0180] Method PE preferably comprises: - a step of concentrating the reaction medium under reduced pressure; - a step of adding an organic solvent and an aqueous solution to the obtained residue; then - A step of decanting, recovering the organic phase, and evaporating the organic solvent to obtain the compound of formula (II).

[0181] The compound of formula (VIII) may be petroleum based, or partially bio-based or fully bio-based (100% bio-carbon content).

[0182] All descriptions, embodiments and preferred embodiments disclosed above (eg in the paragraphs on process PA) for the compound of formula (IV) apply here to process PE and are not reiterated.

[0183] Preferably, the compound of formula (II) is not derived from an aspartic acid derivative.

[0184] In a preferred embodiment, the compound of formula (II) as defined above is obtained by process PB or PC.

[0185] In a preferred embodiment, compounds of formula (II) wherein R1 = methyl are obtained by process PB, which comprises: - contacting a compound of formula (V) with a compound of formula (IV) above wherein R1 = methyl under conditions sufficient to produce a compound of formula (II): - optionally isolating the compound of formula (II) therefrom, in: - the biochar content of the compound of formula (IV) is equal to or higher than 20%, more preferably equal to or higher than 50%, even more preferably equal to or higher than 80%, and more advantageously equal to or higher than 99%; - The compound of formula (V) is petroleum-based, or partially bio-based or fully bio-based.

[0186] In another preferred embodiment, compounds of formula (II) wherein R1 = hexyl or tetrahydrofuranyl are obtained by process PC, which comprises: - contacting a compound of formula (II') with a compound of formula (IV) wherein R1 = hexyl or tetrahydrofuranyl under conditions sufficient to produce a compound of formula (II): wherein R'1 is H or an organic moiety different from R1, - optionally isolating the compound of formula (II) therefrom, in: - the biochar content of the compound of formula (IV) is equal to or higher than 20%, more preferably equal to or higher than 50%, even more preferably equal to or higher than 80%, and more advantageously equal to or higher than 99%; - The compound of formula (II) is petroleum-based, or partially bio-based or fully bio-based.

[0187] use The present invention relates to the use of a compound of formula (I) as described above for the preparation of a composition, preferably an adhesive composition.

[0188] The present invention also relates to a composition, more preferably an adhesive composition, comprising a compound of formula (I) as described above.

[0189] All descriptions, embodiments and preferred embodiments disclosed above (eg in the compounds section) for the compounds of formula (I) apply here to the uses and compositions and are not reiterated.

[0190] The composition may be a 1K or 2K composition.

[0191] Preferably, the binder composition comprising a compound of formula (I) as disclosed above has a biochar content equal to or higher than 20%, even more preferably higher than or equal to 50%.The biochar content is measured as defined above.

[0192] In a preferred embodiment, the composition comprises more than 80 wt. %, even more preferably equal to or more than 85 wt. %, more preferably equal to or more than 90 wt. % of a compound of formula (I) as defined above, based on the total weight of the composition.

[0193] Such compositions comprising cyanoacrylates are well known and may include any ingredients and / or additives well known in the art.

[0194] The composition may comprise an acidity suppressant.

[0195] Acid inhibitors are inhibitors of anionic polymerization. They can be selected from Bronsted acids, Lewis acids, acids provided by acidic ion exchange materials, or photoacids obtained from photoacid generators (also called PAGs), and mixtures thereof; preferably selected from Bronsted acids, Lewis acids, and mixtures thereof. The acid inhibitor is preferably selected from methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic anhydride, hydrofluoric acid, boron trifluoride, boron trifluoride etherate, boron trifluoride dihydrate, sulfur dioxide, sulfur trioxide, tin (IV) chloride, iron (III) chloride, citric acid, trimethylsilyl trifluoromethanesulfonate, and mixtures thereof; more preferably selected from methanesulfonic acid, hydrofluoric acid, boron trifluoride, boron trifluoride etherate, sulfur dioxide, and mixtures thereof.

[0196] The composition may comprise 0 wt% to 0.1 wt%, preferably 0.0001 wt% to 0.05 wt%, more preferably 0.0005 to 0.01 wt% of the acidic inhibitor, based on the total weight of the composition.

[0197] The expressions "free radical stabilizer" and "free radical stabilizing agent" are currently used interchangeably.

[0198] The composition may comprise a free radical stabilizer.

[0199] The free radical stabilizer is a free radical polymerization inhibitor. It is preferably selected from hindered phenol compounds or hindered polyphenol compounds; preferably selected from hydroquinone, hydroquinone monomethyl ether, mono-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, p-methoxyphenol, hydroxyanisole, butylated hydroxyanisole, hydroxyanisol butyl ether, 2,6-di-tert-butyl-p-cresol, 2,2′-methylene-bis(6-tert-butyl-4-methylphenol), p-tert-butylcatechol, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, hydroxytoluene butyl ether and mixtures thereof; more preferably selected from hydroquinone monomethyl ether, 2,2′-methylene-bis(6-tert-butyl-4-methylphenol), and mixtures thereof.

[0200] The composition may comprise 0.01-0.7 wt %, preferably 0.01-0.5 wt %, more preferably 0.01-0.4 wt % of the free radical stabilizer, based on the total weight of the composition.

[0201] The expressions "thickener" or "thickening agent" are currently used interchangeably.

[0202] The composition may comprise a thickener.

[0203] Considering that cyanoacrylate-based monomers generally have water-like viscosities at ambient temperature, thickeners are particularly useful for controlling and / or increasing the viscosity of the cyanoacrylate component. Suitable thickeners or thickening agents for the first part of the composition may be selected from those compatible with the main monomers. Examples of such thickeners include poly(meth)acrylates, acylated cellulose polymers (e.g., cellulose acetate), polyvinyl acetate, partially hydrolyzed polyvinyl acetate, polyvinyl pyrrolidone, polyhydroxy acid esters (polyoxylate), polycaprolactone, polycyanoacrylate, vinyl acetate copolymers (e.g., copolymers with vinyl chloride), copolymers of (meth)acrylates with butadiene and styrene, copolymers of vinyl chloride with acrylonitrile, copolymers of ethylene with vinyl acetate, polybutylene terephthalate-co-polyethylene terephthalate, copolymers of lactic acid with caprolactone, and mixtures thereof.

[0204] These thickeners are well known to those skilled in the art and are described in the prior art. Preferably, the thickener is selected from poly(meth)acrylates, polymethyl(meth)acrylates, polyvinylpyrrolidone, polyvinyl acetate, partially hydrolyzed polyvinyl acetate, vinyl acetate copolymers, acylated cellulose polymers, and mixtures thereof. Suitable thickeners for the cyanoacrylate component may be, for example, polymethyl methacrylate (e.g. M 449, Evonik), copolymers of vinyl acetate and vinyl alcohol (e.g. 900, Lanxess), copolymers of vinyl chloride and vinyl acetate (e.g. H 40-60, Wacker), copolymers of ethylene, vinyl acetate and maleic acid esters or maleic acid partial esters (e.g. G, DuPont), and mixtures thereof.

[0205] The composition may comprise 0-10 wt %, preferably 3-8 wt %, more preferably 4-7 wt % of thickener, based on the total weight of the composition.

[0206] The expressions "toughener" or "toughening agent" are currently used interchangeably.

[0207] The composition may comprise a toughening agent.

[0208] The toughening agent may be selected from block copolymers (e.g., polymethyl methacrylate-co-polybutyl acrylate-co-polymethyl methacrylate), elastomeric rubbers, elastomeric polymers, liquid elastomers, polyesters, acrylic rubbers, butadiene / acrylonitrile rubbers, Buna rubbers, polyisobutylene, polyisoprene, natural rubbers, synthetic rubbers (e.g., styrene / butadiene rubber (SBR)), polyurethane polymers, ethylene-vinyl acetate polymers (LEVAMELT 700 and 900), fluorinated rubbers, isoprene-acrylonitrile polymers, chlorosulfonated polyethylene, polyvinyl acetate homopolymers, block copolymers, core-shell rubber particles (e.g., available under the trade name XT100 and XT15 1 are commercially available from Arkema), and mixtures thereof.

[0209] The composition may include 1-20 wt%, preferably 5-12 wt%, of a toughening agent, based on the total weight of the composition.

[0210] The composition may comprise an accelerating agent.

[0211] The expressions "accelerator" or "accelerating agent" are currently used interchangeably.

[0212] The accelerator can be selected from crown ethers (e.g., 15-crown-6 ether, 15-crown-5 ether, 18-crown-6 ether, dibenzo-18-crown-6 ether, and mixtures thereof), cyclodextrins, silylated crown ethers, tetra-tert-butyl calixarene; dimethyl ethers of PEG 400, PEG 500, PEG 600, and PEG 1000; and mixtures thereof; preferably, the accelerator is a crown ether; more preferably, the accelerator is selected from 18-crown-6 ether, dibenzo-18-crown-6 ether, and mixtures thereof; still more preferably, the accelerator is dibenzo-18-crown-6 ether.

[0213] The composition may comprise 0 wt% to 0.8 wt%, preferably 0.05 to 0.5 wt% of the accelerator, based on the total weight of the composition.

[0214] The composition may comprise a viscosity increasing agent.

[0215] The expressions "tackifier" and "tackifying agent" are currently used interchangeably.

[0216] The composition may contain an adhesion promoter for glass, ceramic, porcelain, plastic and / or metal, such as an alkoxysilane compound. Similar to the cyanoacrylate component, an additional component may contain an adhesion promoter for glass, ceramic, porcelain, plastic and / or metal, such as, for example, an alkoxysilane compound, citric acid, lithium tetrafluoroborate, lithium hexafluorophosphate, an aromatic carboxylic acid or anhydride, or an α-substituted acrylic acid (optionally in the form of anhydride). Among the acids and anhydrides, mention may be made of trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 3,3′,4,4′-benzophenonetetracarboxylic dianhydride, itaconic acid, itaconic anhydride and 3-butene-1,2,3-tricarboxylic acid.

[0217] The composition may comprise 0 wt% to 0.1 wt%, preferably 0.06 to 0.08 wt% of the tackifier, based on the total weight of the composition.

[0218] The composition may comprise a thixotropic agent.

[0219] The thixotropic agent may be an organic thixotropic agent or an inorganic thixotropic agent; preferably, the thixotropic agent is selected from hydrogenated castor oil (EFKA RM1900), hydrogenated castor oil modified by reaction with amine, polyamide, silica, and mixtures thereof.

[0220] The silica may be fumed silica; preferably, the silica may be selected from fumed silica, hydrophobic fumed silica, hydrophilic fumed silica and precipitated silica, and mixtures thereof; more preferably, selected from hydrophobic fumed silica. The hydrophobic fumed silica may also serve as a filler. The hydrophobic fumed silica may be obtained under the trade name R202 is commercially available from Evonik.

[0221] The composition may comprise 0-10 wt %, preferably 2.5-8 wt %, more preferably 3-6 wt % of the thixotropic agent, based on the total weight of the composition.

[0222] The composition may comprise a photoinitiator system, i.e. a source of photoinitiators. Photoinitiators promote photopolymerization. The terms "photoinitiator", "photoinitiator system", "photoinitiator system" and "source of photoinitiator" are currently used interchangeably. Suitable photoinitiator systems, which in part comprise free radical photoinitiators, are disclosed in PCT application WO 2017 / 021785A1. The photoinitiator system is in particular an anionic photoinitiator system or a zwitterionic photoinitiator system, i.e. a photoinitiator system suitable for promoting anionic polymerization or zwitterionic polymerization. The expression "anionic photoinitiator system or zwitterionic photoinitiator system" is used interchangeably with "a photoinitiator system suitable for promoting anionic polymerization or zwitterionic polymerization".

[0223] Suitable photoinitiator systems (source of photoinitiators) include metallocene components (also called "synergists"); preferably, the metallocene compound is selected from "sandwich compounds", such as ferrocene compounds, ruthenocenium compounds, bis (cyclopentadienyl) osmium compounds, their derivatives, and mixtures thereof; preferably, the metallocene compound is a ferrocene compound, its derivatives, and mixtures thereof. The ferrocene compound can be: Where R 1 is hydrogen or C 1-4 alkyl, and one or more R 1 Present in one or two rings. Suitable ferrocene compounds are disclosed in US Pat. Nos. 5,824,180 and 6,503,959.

[0224] The suitable photoinitiating system (source of photoinitiator) also comprises an additional photoinitiator.

[0225] The additional photoinitiator may be selected from phenyl substituted acylphosphines, α-diketones, thioxanthones, α-hydroxyketones, benzyl dimethyl ketals, phenyl glyoxylates, camphorquinones, acylgermane compounds, dialkylsilyl glyoxylates, and mixtures thereof. The additional photoinitiator is particularly useful for increasing the polymerization rate of cyanoacrylate-based monomers.

[0226] The acylgermane compound may be one of the following: Where R 2 is methyl or phenyl; Where R 3 is hydrogen or methoxy; and A mixture thereof.

[0227] Suitable additional photoinitiators are commercially available and phenyl-substituted acylphosphines are available under the names 819(BASF) or TPO (BASF) is available commercially; α-hydroxy ketones can be purchased under the name 1 84 / 500 / 2959(BASF) or 1173 (BASF) is commercially available; benzyl dimethyl ketal is available under the name 651 (BASF) is available commercially; phenylglyoxylate is available under the name 754(BASF) or MBF (BASF); camphorquinone is commercially available from Sigma-Aldrich Merck; acylgermane compounds are available under the name Ivocerin TM Commercially available from Ivoclar KGaA & AC Co.; and dialkylsilyl glyoxylate commercially available from Sigma-Aldrich Merck.

[0228] other The invention also relates to the use of at least one raw material R having a biochar content greater than 0% for preparing a compound of formula (I): Wherein R1 is H or an organic moiety, the compound of formula (I) has a biochar content equal to or higher than 20%.

[0229] All descriptions, embodiments and preferred features described above (in the "Compounds" paragraph) for the compounds of formula (I) apply for use herein and are not reiterated.

[0230] The biochar content of the raw material R is preferably equal to or higher than 41%, more preferably equal to or higher than 50%. Even more preferably, the biochar content of the raw material R is equal to or higher than 65%, and more preferably equal to 100%.

[0231] The raw material R may be selected from: acetic acid, ethanol, n-heptanol, isobutanol, n-butanol, 1,10-decanediol, tetrahydrofurfurylethanol, preferably, it is ethanol and n-heptanol, even more preferably n-heptanol.

[0232] The present invention relates to compounds of formula (I) as defined herein, derived from alcohol compounds having a biocarbon content equal to 100%, the alcohol being preferably ethanol or heptanol.

[0233] All descriptions, embodiments and preferred features described above (in the "Compounds" paragraph) for the compounds of formula (I) apply here and are not reiterated.

[0234] The compounds of formula (I) are advantageously derived at least partly from raw materials of renewable origin.

[0235] The compounds of formula (I) advantageously exhibit good adhesive properties, good fixture time.

[0236] The compounds of formula (I) can advantageously be produced industrially in good yields.

[0237] Compounds of formula (I) wherein R1 is C6 alkyl (and / or compositions comprising the same) advantageously additionally exhibit high resistance to hot water (eg at 60°C).

[0238] According to the test method disclosed below in the experimental part, compounds of formula (I) wherein R1 is a C6 alkyl group (and / or compositions comprising the same) advantageously exhibit a strength retention of more than 80% after complete immersion in hot water (at 60°C) for 3-10 days.

[0239] Compounds of formula (I) wherein R1 is C6 alkyl (and / or compositions comprising the same) advantageously exhibit very low blooming according to the test method disclosed hereinafter in the experimental part.

[0240] The ranges disclosed in this specification include both their lower and upper limits. For example, the expression "the range is x to y" or "between x and y" includes the upper and lower limits x and y. Example The following ingredients were used in the examples: -Acetic acid, commercialized by Sekab, bio-based acetic acid -Cyanoacetic acid, supplied by Sigma-Aldrich -Bromoacetic acid, supplied by Sigma-Aldrich - Sulfuric acid, hydrochloric acid, supplied by Scharlab -Phosphorus tribromide, supplied by Sigma-Aldrich -Bromine, supplied by Sigma-Aldrich -Sodium carbonate, supplied by Sigma-Aldrich -Sodium thiosulfate, supplied by Sigma-Aldrich -Diethyl ether, toluene, ethyl acetate, supplied by Scharlab -Potassium cyanide, supplied by Sigma-Aldrich - Bio-based ethanol, supplied by Myhome aromas, 99.5% pure - Petroleum-based ethanol, supplied by Ineos -Methylene diacetate, supplied by CMC -Linear dodecylbenzenesulfonic acid, LABSA (CAS 27176-87-0), supplied by Henkel -2-Methylpiperazine, supplied by Sigma-Aldrich -Piperidine, supplied by Sigma-Aldrich -2,2′-methylenebis(4-methyl-6-tert-butylphenol), supplied by TCI - Paraformaldehyde, supplied by Sigma-Aldrich -Piperidine, supplied by Sigma-Aldrich - Bio-based heptanol, supplied by Arkema Oleris, purity >99% -Methyl cyanoacetate, supplied by Hebei -Titanium isopropoxide, supplied by Sigma-Aldrich - p-Toluenesulfonic acid, supplied by Sigma-Aldrich -Phosphorus pentoxide, supplied by Sigma-Addrich -Hydroquinone, supplied by TCI - Bio-based tetrahydrofurfuryl alcohol, supplied by Pennakem -Dibenzo-18-crown-6DBC (18-c-6) from Ferak Berlin GmbH -EFKA RM 1900 from BASF (100% bio-based as analyzed by ASTM D6866) -Butylated hydroxyanisole (BHA), from TCI -Vinnol H40 / 60 from Wacker -Tetrahydrofurfuryl alcohol ( T, Pennakem) -MSA, from Sigma Aldrich -SO2, from carburos metallicos Among those ingredients, n-heptanol (Arkema Oleris), ethanol (Myhome aromas), acetic acid (Sekab), tetrahydrofurfuryl alcohol ( T, Pennakem), EFKA RM 1 900 are bio-materials (100% bio-carbon content).

[0242] The biomaterial content or biocarbon content is determined by using the standards ASTM D 6866 (ASTM D 6866-21, Method B) and ASTM D 7026 (ASTM D7026-04). The ASTM D 6866 standard is "Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis", while the ASTM D 7026 standard is "Sampling and Reporting of Results for Determination of Biobased Content of Materials via Carbon Isotope Analysis". The second standard refers to the first standard in its first paragraph.

[0243] The first standard describes a test for measuring the 14 C / 12 C ratio and compared it with the reference sample from 100% renewable sources 14 C / 12 C ratios are compared to give the relative percentage of C from renewable sources in the sample. 14 C dating Same concept, but the dating equation is not used.

[0244] The ratio thus calculated is called "pMC" (percent modern carbon). If the material to be analyzed is a mixture of biological material and fossil material (without radioactive isotopes), the pMC value obtained is directly related to the amount of biological material present in the sample.

[0245] The C-14 modern standard (oxalic acid II) represents the modern (living plant) C-14 activity of 1950, which has been set as a standard for 100% biobased activity. A background level that is subtracted from the measured activity is also established. The activity of the sample is compared with the activity of oxalic acid II. This will give the percentage of pMC or modern carbon. If there is a mixture of modern carbon and fossil carbon in the sample, the resulting pMC (e.g., 85pMC) indicates that we have measured 85% of the modern standard activity. The sample will be reported as 85% biobased carbon. Due to the nuclear tests carried out in the atmosphere in the 1950s and 1960s, C-14 is artificially produced in the atmosphere. It was once close to 200% of the natural activity. Over time, with the dilution of fossil fuel CO2 discharged into the atmosphere, the activity has been diluted so that the C-14 activity in the atmosphere today returns to the same level as the modern standard. Atmospheric correction factors are used to explain these changes in atmospheric C-14 activity. The atmospheric correction factor (REF) is used as follows: Biogenic carbon content = pMC / (REF), where REF = 1.000 The accuracy of the % biogenic carbon content is + / - 3% (absolute).

[0246] Example 1 : Preparation of ethyl cyanoacrylate (Method P1) Example 1a : Preparation method of bromoacetic acid (corresponding to the compound of formula (VI)) This step was modified from a previously reported procedure (TM Werkhoven et al., Eur. J. Org. Chem. 1999, 2909-2914). A mixture of bio-derived acetic acid (4.0 g, Sekab) and PBr3 (18 g) was mixed at 0°C; then bromine (24.4 g) was added. After the HBr release ceased, the reaction mixture was heated at 75°C for 2.5 hours. The reaction was quenched with water. Diethyl ether and Na2S2O3 solution were added. The aqueous layer was extracted with diethyl ether. The solvent was evaporated to produce 9.11 g (98% yield) of bio-based bromoacetic acid.

[0247] Example 1b : Preparation method of cyanoacetic acid (corresponding to the compound of formula (V)) This step was modified from a previously reported procedure (J. Kremser et al., Chem. Comm. 2017, 53 (96) 12938-12941). The bromoacetic acid (6.99 g) obtained in Example 1a was dissolved in a Na2CO3 solution (pH 11). An aqueous solution of potassium cyanide (3.27 g) was poured into the reaction mixture. The mixture was heated to 80°C for 2 hours and then stirred for another 15 hours at room temperature (23°C). Concentrated HCl (10 mL) was added until pH 1 was reached; the solvent was removed and the solid residue was extracted with diethyl ether. The remaining salts were filtered and washed with additional diethyl ether. The filtrate was evaporated and bio-based cyanoacetic acid (4.28 g; 100% yield) was obtained. This step was repeated several times to obtain higher amounts of bio-based cyanoacetic acid.

[0248] Example 1c : Preparation method of cyanoacetate (corresponding to compound of formula (II)) A mixture of cyanoacetic acid (50.0 g) obtained in Example 1b, biologically derived EtOH (200 ml, Myhome aromas) and concentrated H2SO4 (3.2 ml) was refluxed for 8 hours. The mixture was concentrated under reduced pressure, and EtOAc and water were added to the residue. The organic phase was separated, and the aqueous layer was extracted with EtOAc. The combined organic extracts were dried and concentrated under reduced pressure. Bio-based ethyl cyanoacetate (61.4 g, 92%) was obtained, which was pure enough for the next step.

[0249] Example 1d : Preparation method of cyanoacrylate (corresponding to the compound of formula (I)) 60 parts of paraformaldehyde, 200 parts of toluene and 0.2 parts of piperidine are placed in a four-necked flask equipped with a stirrer, a thermometer, a dehydrator and a dropping funnel. 314 parts of the bio-based ethyl cyanoacetate obtained in Example 1c are added dropwise to the mixture under stirring at 80°C-90°C. After the addition is completed, the mixture is reacted under reflux while removing the water formed by the reaction until all the theoretical amount of water has been distilled off. The reaction mixture is then cooled to room temperature. 300 parts of a 1% aqueous solution of p-toluenesulfonic acid are added to the resulting condensation mixture having a viscosity of 200 centipoise. The mixture is shaken at 70°C and then allowed to stand, at which time it is separated into two layers. The oil layer thereof is taken out.

[0250] The oil layer was distilled under reduced pressure to remove toluene. 3 parts each of phosphorus pentoxide and hydroquinone were added to the condensation product remaining in the kettle. The mixture was subjected to depolymerization by heating at 150° C. to 200° C. under a pressure of 8 to 20 mmHg to obtain 266 parts (83% yield) of crude monomer. The purity of the crude monomer was 96.8%.

[0251] After adding 0.5% of phosphorus pentoxide and 0.5% of hydroquinone to the crude monomer, the resulting mixture was distilled again to obtain 220 parts of bio-based ethyl cyanoacrylate.

[0252] Example 2 : Preparation of ethyl cyanoacrylate (Method P2) Example 2a : Preparation method of cyanoacetate (corresponding to compound of formula (II)) A mixture of cyanoacetic acid (50.0 g, Sigma Aldrich), bio-based EtOH (200 ml, Myhome aromas) and concentrated H2SO4 (3.2 ml) was refluxed for 8 hours. The mixture was concentrated under reduced pressure, and EtOAc and water were added to the residue. The organic phase was separated, and the aqueous layer was extracted with EtOAc. The combined organic extracts were dried and concentrated under reduced pressure. Bio-based ethyl cyanoacetate (61.4 g, 92%) was obtained, which was pure enough for the next step.

[0253] Example 2b : Preparation method of cyanoacrylate (corresponding to the compound of formula (I)) A mixture of bio-based ethyl cyanoacetate (59.2 g) obtained in Example 2a, methylene diacetate (138.2 g), linear alkylbenzenesulfonic acid (20.9 g; LABSA, dodecylbenzenesulfonic acid), 2-methylpiperazine (1.31 g) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (0.30 g) was heated to 125° C. for 2 hours. The desired product, bio-based ethyl cyanoacrylate (52.3 g; 80% yield) was obtained by distillation under reduced pressure.

[0254] Example 3 :Preparation of n-heptyl cyanoacrylate Example 3a : Preparation of n-heptyl cyanoacetate (corresponding to the compound of formula (II)) A mixture of bio-derived n-heptyl alcohol (250 g, Arkema Oleris), methyl cyanoacetate (212 g, commercially available from HEBEI) and titanium isopropoxide (0.61 g) was heated to 120° C. for 3 hours at a residual pressure of 100 mbar. When the methanol stripping was complete, the reaction was stopped and bio-based n-heptyl cyanoacetate (360 g; 92% yield) was obtained by distillation under reduced pressure.

[0255] Example 3b : Preparation of n-heptyl cyanoacrylate (corresponding to the compound of formula (I)) A mixture of bio-based n-heptyl cyanoacetate (300 g) obtained in Example 3a, methylene diacetate (432 g), linear dodecylbenzenesulfonic acid (65.5 g, LABSA), 2-methylpiperazine (4.10 g) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (1.50 g) was heated to 125° C. for 2 hours. The desired product (226 g; 76% yield) was obtained by distillation under reduced pressure. The resulting mixture was distilled again to obtain 1.80 g of bio-based n-heptyl cyanoacrylate.

[0256] Example 4 (Comparative Example) :Preparation of ethyl cyanoacrylate A mixture of cyanoacetic acid (50.0 g; supplied by Sigma-Aldrich, petroleum-based), petroleum-based EtOH (200 ml, Ineos) and concentrated H2SO4 (3.2 ml) was refluxed for 8 hours. The mixture was concentrated under reduced pressure, and ethyl acetate and water were added to the residue. The organic phase was separated, and the aqueous layer was extracted with ethyl acetate. The combined organic extracts were dried and concentrated under reduced pressure. Ethyl cyanoacetate (61.4 g, 92%) was obtained, which was pure enough for the next step.

[0257] Into a four-necked flask equipped with a stirrer, a thermometer, a dehydrator and a dropping funnel, 60 parts of paraformaldehyde, 200 parts of toluene and 0.2 parts of piperidine were loaded. At 80°C-90°C, 314 parts of ethyl cyanoacetate (obtained above in Example 4) were added dropwise to the mixture under stirring. After the addition was completed, the mixture was reacted under reflux while removing the water formed by the reaction until all theoretical amounts of water had been distilled out. The reaction mixture was then cooled to room temperature. 300 parts of 1% p-toluenesulfonic acid aqueous solution were added to the resulting condensation mixture having a viscosity of 200 centipoise. The mixture was shaken at 70°C and then allowed to stand, at which point it was separated into two layers. Its oil layer was taken out.

[0258] The oil layer was distilled under reduced pressure to remove toluene. 3 parts each of phosphorus pentoxide and hydroquinone were added to the condensation product remaining in the kettle. The mixture was subjected to depolymerization by heating at 150° C. to 200° C. under a pressure of 8 to 20 mmHg to obtain 266 parts (83% yield) of crude monomer. The purity of the crude monomer was 96.8%.

[0259] After adding 0.5% of phosphorus pentoxide and 0.5% of hydroquinone to the crude monomer, the resulting mixture was distilled again to obtain 220 parts of ethyl cyanoacrylate.

[0260] Example 5 :Preparation of Tetrahydrofurfuryl Cyanoacrylate Example 5a : Preparation of tetrahydrofurfuryl cyanoacetate (corresponding to the compound of formula (II)) At a residual pressure of 150 mbar, tetrahydrofurfuryl alcohol of biological origin (306 g, A mixture of 1,2-dihydro-1,4 ...

[0261] Example 5b : Preparation of tetrahydrofurfuryl cyanoacrylate (corresponding to the compound of formula (I)) A mixture of bio-based tetrahydrofurfuryl cyanoacetate (130 g) obtained in Example 5a, methylene diacetate (204 g), linear dodecylbenzenesulfonic acid (30.9 g), 2-methylpiperazine (1.93 g) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (0.65 g) was heated to 125° C. for 2 hours. The desired product (64 g; 46% yield) was obtained by distillation under reduced pressure.

[0262] Example 6 : Preparation of n-heptyl cyanoacrylate (Comparative Example - Petroleum-based) Example 6a : Preparation of n-heptanol from 1-heptyne A heterogeneous mixture of 1-heptyne (300 g; 3.12 mol, petroleum base), NaBH4 (300 g, 7.92 mol) and (tetraphenylporphyrin)rhodium(III) chloride ((TPP)RhCl, 4.0 g, 6 mmol) in THF (21) was stirred for 50 hours at 20-25° C. in dry air. The formation of the oxidation product was monitored by gas chromatography. The reaction afforded an overall yield of 65%. After quenching with water, the pure mixture containing n-heptanol was recovered by distillation (1 mbar, 70° C.; boiler temperature was about 110° C.).

[0263] This synthesis was modified from Aoyama et al., J. Org. Chem., 1987, 52, 2555-2559.

[0264] Example 6b :Preparation of heptyl cyanoacetate Under a residual pressure of 90 mbar, a mixture of the mixture obtained in Example 6a (300 g), methyl cyanoacetate (254.4 g, commercially available from HEBEI) and titanium isopropoxide (0.73 g) was heated to 120° C. for 6 hours. When the methanol stripping was complete, the reaction was stopped and heptyl cyanoacetate (410 g; 87% yield) was obtained by distillation under reduced pressure.

[0265] Example 6c :Preparation of heptyl cyanoacrylate A mixture of heptyl cyanoacetate (360 g), methylene diacetate (518 g), linear dodecylbenzenesulfonic acid (78.5 g, LABSA), 2-methylpiperazine (4.92 g) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (1.80 g) obtained in Example 6c was heated to 125° C. for 2.5 hours. The desired product (257.6 g; 72% yield) was obtained by distillation under reduced pressure. The resulting mixture was distilled again to obtain 210 g of heptyl cyanoacrylate (petroleum base).

[0266] Example 7 : Preparation of Butyl Cyanoacrylate (Comparative Example - Petroleum-based) Example 7a : Preparation of n-butanol from butane (D) Butane (petroleum base, 111.0 g; 1.91 mol) was bubbled into a solution of the complex [V(O)(C1)(PBHA)2](PBHA-=N-phenylbenzohydroxamate) (catalyst, 9.8 mg, 18.8 mmol) in acetonitrile (11) in a closed vessel. 30% H2O2 (300 ml, 2.65 mol) was then added to the above solution and the resulting solution turned yellow. Another 300 ml H2O2 (50 ml x 6 times) was added in portions over a period of 3 hours. The solution was then heated (in an oil bath) to reflux (85°C) for 8 hours. The reaction mixture was cooled to room temperature and extracted with 1 liter of diethyl ether. The extract was concentrated and the pure product was recovered by distillation (20 mbar, 50°C; boiler temperature was about 100°C).

[0267] This synthesis was modified from Si et al., J. Mol. Catal. A. Chem., 2004, 219, 241-249.

[0268] Example 7b :Preparation of Butyl Cyanoacetate Under a residual pressure of 90 mbar, a mixture of the extract obtained in Example 7a (300 g), methyl cyanoacetate (401 g, commercially available from HEBEI) and titanium isopropoxide (1.15 g) was heated to 90° C. for 24 hours. When the methanol stripping was complete, the reaction was stopped and butyl cyanoacetate (432 g; 75% yield) was obtained by distillation under reduced pressure.

[0269] Example 7c :Preparation of butyl cyanoacrylate A mixture of butyl cyanoacetate (360 g) obtained in Example 7b, methylene diacetate (674 g), linear dodecylbenzenesulfonic acid (97.9 g, LABSA), 2-methylpiperazine (6.39 g) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (1.8 mg) was heated to 125° C. for 2.5 hours. The desired product (255 g; 70% yield) was obtained by distillation under reduced pressure. The resulting mixture was distilled again to obtain 210 g of butyl cyanoacrylate (petroleum base).

[0270] Example 8 :Preparation of n-butyl cyanoacrylate Example 8a :Preparation of n-butyl cyanoacetate Under a residual pressure of 90 mbar, a mixture of bio-based n-butanol (obtained from Green biologics) (300 g), methyl cyanoacetate (401 g, commercially available from HEBEI) and titanium isopropoxide (1.15 g) was heated to 90° C. for 24 hours. When the methanol stripping was complete, the reaction was stopped and n-butyl cyanoacetate (439 g; 76% yield) was obtained by distillation under reduced pressure.

[0271] Example 8b :Preparation of n-butyl cyanoacrylate A mixture of n-butyl cyanoacetate (360 g) obtained in Example 8a, methylene diacetate (674 g), linear dodecylbenzenesulfonic acid (97.9 g, LABSA), 2-methylpiperazine (6.39 g) and 2,2′-methylenebis(4-methyl-6-tert-butylphenol) (1.8 mg) was heated to 125° C. for 2.5 hours. The desired product (255 g; 70% yield) was obtained by distillation under reduced pressure. The resulting mixture was distilled again to obtain 210 g of bio-based n-butyl cyanoacrylate.

[0272] Example 9 :result The table below highlights the biochar content analysis and long term instant adhesive properties of selected molecules, particularly during the shelf life (accelerated aging at 82°C for 3 days, simulating the typical time before cyanoacrylate superglue use).

[0273] Method for measuring fixed time FT: The fixing time (FT) is applied at 250 mm 2 The adhesive drop on the surface is able to carry a 3 kg load for a period of 10 seconds at room temperature (23±2°C) at 50% relative humidity (RH). FT is measured on mild steel lap shears (MS). The dimensions of those lap shears are 100x25x1.5 mm and are supplied by Rocholl.

[0274] The fixation time is measured after 3 days of forced aging at 82° C. (3d 82° C.) in uncoated aluminum tubes. In fact, this accelerated aging represents a good method to estimate the reactivity of the cyanoacrylate adhesive during its shelf life (3d 82° C. corresponds to about 9-15 months, depending on formulation and packaging) when it reaches the final consumer.

[0275] The exact reactivity of the bio-based butyl cyanoacrylate monomer and the non-bio-based butyl cyanoacrylate monomer was also evaluated by observing the time required for a standard sample to fully cure in response to an initiator, as performed by many technical experts in the field (method disclosed in WO2015150882).

[0276] For this purpose, the initiator is prepared as a solution of N-oxydiethylenebenzothiazole-2-sulfenamide in a non-nucleophilic solvent. A certain amount of the solution is added to the monomer and mixed thoroughly. Subsequently, a narrow wooden stick of 2 mm diameter is introduced into the mixture and physically moved up and down by hand until the mixture does not flow and the stick is captured in the polymerized adhesive. Since the initiator is neutralized by any acid present in the medium, the time for complete polymerization to occur indicates the reactivity of the monomer. The longer the time necessary to obtain complete polymerization, the slower the reactivity of the monomer.

[0277] *Accuracy is + / -3% (absolute value) **Ratio of expected biobased carbon to total carbon in the molecule nd: Not conducted

[0278] Advantageously, the cyanoacrylate of Example 3 with a biochar content of 65% exhibited shorter fixation times than the petroleum-based counterparts: e.g., 25 s for the bio-based n-heptyl cyanoacrylate of Example 3 vs. 90 s for the petroleum-based heptyl cyanoacrylate of Comparative Example 6. Likewise for the reactivity measurements, 80 s reactivity for the bio-based n-butyl cyanoacrylate of Example 8 vs. 180 s for the petroleum-based butyl cyanoacrylate of Comparative Example 7.

[0279] Example 9 : Preparation of Adhesive Compositions C1 and C2 The following C1 and C2 adhesive compositions were prepared according to the properties and amounts of the ingredients disclosed in Table 1 as follows: The monomers were mixed directly with the free radical stabilizer and the acid stabilizer (except sulfur dioxide) in a high density polyethylene container, the mixture was heated to about 60°C, and then the thickening agent was added under mechanical stirring until completely dissolved (as reported in WO20 1 603851 4). The mixture was cooled to about 40°C and the remaining components (including sulfur dioxide if present) were added.

[0280] Tensile shear strength test data reflects the tensile strength of overlapped lap shear pieces (Grit Blasted Mild Steel (GBMS) standard test pieces) measured in accordance with ASTM D1002 with a 250 mm 2 Contact Area Bond Strength (in MPa) measured after assembly. The bonded lap shears were first clamped and "rested" at room temperature (23°C ± 2°C) for 24 hours before testing after assembly. Testing was performed using an Instron tensile testing machine operating at a crosshead speed of 1.3 mm / min.

[0281] Hot water resistance testing was performed on assembled GBMS lap shear specimens that were fully immersed in hot water (at 60°C) for 3 and 10 days, then left at room temperature for 24 hours and tested to destruction.

[0282] Blooming was qualitatively evaluated by placing a drop of adhesive composition on top of black ABS in a 98% HR / 40° C. oven. The more (self)polymerized vapor was generated around the drop, the more blooming occurred.

[0283] Composition C1 also advantageously exhibits very high resistance to hot water (60° C.) and very low blooming.

[0284] Example 10: Testing of Bio-based Compositions Example 10.1 : Counting beta decays using a Geiger counter with a screen wall The first method to detect the amount of binder was inspired by the oldest C14 dating technique as reported in "WS Broecker, in Treatise on Geochemistry, 2007" or "ARTIFICIAL PRODUCTION OF 14C FROM NUCLEAR WEAPON TESTS AND ITS UPTAKE BY MAN", ProQuest 11018029, December 1974. C14 decays were counted by beta emitting particles using a Geiger counter with a screened wall.

[0285] The formulation of Example C1 according to Example 9 (60% biobased content) was prepared using 200 ppm ferrocene (sigma Aldrich) and 750 ppm Ivocerin (sigma aldrich) for the purpose of (measuring) the curethrough volume. The comparative formulation containing C3 had a similar formulation except that the petroleum-based heptyl cyanoacrylate of Comparative Example 6 was included.

[0286] A Ranger EXP Geiger counter with very low sensitivity in the beta radiation section was used.

[0287] Place two mild steel (rocholl) lap shears approximately 15 mm apart from each other with a 250 mm 2 Overlapping, and with a 15 mmmm thick steel spacer, a well was created. The blank CPM (counts per minute) was recorded over a period of approximately 30 minutes. One measurement was performed for each sample over a period of 30 minutes.

[0288] In the first part, the amount of C1 composition added to the wells (1 g, 2 g, and 4 g) was weighed and illuminated using a 405 nm LED (20 mW / cm 2 ) is light cured during 60 seconds, creating a strong bond.

[0289] Unknown amounts of C1 and comparative C3 adhesives were then inserted into the wells. Using linear regression of the calibration curves, approximately 2.8 g of the bio-based adhesive was detected in the wells, while the comparative C3 composition (derived from petroleum) was not detected.

[0290] Example 10.2 :Liquid Extraction / Liquid Scintillation Counting (LSC) Use an even more sensitive scintillation method. Perform liquid scintillation counting (LSC) as used in ASTM D6866-12 guidelines. The method described in the following literature is easily used: "Charles Doll, Andrew Plymale, Christopher Thompson, Matthew O'Hara and Mariefel V. Olarte, 2021, Determination of Biogenic Content by 14C Measurement using Liquid Scintillation Counter (LSC), Richland, WA: Pacific Northwest National Laboratory". Toluene (≥99.5%, petroleum / fossil based) is used as the extraction medium. Use a Hidex 600SL LSC.

[0291] Composition C1 and comparative composition C3 were used.

[0292] Two mild steel (rocholl) lap shears were used. An accurate amount of C1 (0 (blank), 30 mg, 50 mg, 70 mg) was weighed and placed on top of the first lap shear and then tightly bonded for 24 hours. The adhesive was then broken in a similar peel test to open the lap shears to expose the adhesive. Toluene was used to extract the adhesive in the solvent and LSC was performed directly.

[0293] Then use the unknown quantity C1 and compare C3 between the lap shears.

[0294] Using linear regression of the calibration curve, approximately 62 mg of bio-based adhesive was detected between the bonded lap shear pieces, while no signal was detected for C3.

[0295] Example 10.3 :Solid combustion / acceleration mass spectrometry (AMS) Finally, the most sensitive C14 detection method was used. Accelerated mass spectrometry (AMS) was performed as used in ASTM D6866-12 guidelines and methods (directly inspired by (https: / / www,radiocarbon.com / accelerator-mass-spectrometry,htm; Introduction to Radiocarbon Determination by the Accelerator Mass Spectrometry Method)).

[0296] Two mild steel (rocholl) lap shears were used. An accurate amount of C1 (0 (blank), 10 mg, 20 mg, 30 mg) was weighed on top of the first lap shear and then tightly bonded for 24 hours. The assembly was easily burned at 900°C-1000°C to form CO2, which was then graphitized and analyzed in AMS. 14 C content.

[0297] Unknown amounts of C1 and C3 were then used between the lap shears. Using linear regression of the calibration curve, approximately 62 mg of bio-based adhesive was detected between the bonded lap shears, while no signal was detected for C3.

[0298] An important aspect of sustainable bonding is to use reliable industrial bonding methods, especially to ensure that the parts to be bonded are adequately dispensed with adhesive. Current solutions include simple gravimetric measurements (weighing before and after the bonded assembly), but this solution is cumbersome because not all bonded parts can be placed on a precision laboratory balance (typical dosage of cyanoacrylate adhesives is 5-15 mg). Other popular solutions present on the market, especially to solve daily quality checks, are (detection of) the presence of dyes / uv traces in cyanoacrylate adhesives. This solution is still not 100% quantitative (more qualitative) and is only valid for transparent assemblies (e.g. transparent pin bonding).

[0299] As demonstrated above, the inventive composition can more easily detect sustainable bonding when it comprises the compound of formula (I) as defined in the present invention.

Claims

1. Compound of formula (I): Wherein R1 is H or an organic moiety, the compound of formula (I) has a biochar content equal to or higher than 20%.

2. The compound according to claim 1, having a biochar content equal to or higher than 25%.

3. The compound according to claim 1, having a biocarbon content equal to or higher than 41%, more preferably equal to or higher than 50%, and more preferably equal to or higher than 55%.

4. The compound according to any one of claims 1 to 3, wherein R1 is selected from: H, alkyl, haloalkyl, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, acrylate moiety, oxetane moiety, epoxy moiety, carboxylate moiety.

5. The compound according to any one of claims 1 to 4, characterized in that It has one of the following formulae (IA), (IB) or (IC): wherein R1a is an alkyl group, wherein R1b is selected from H, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, oxetane moiety, epoxy moiety, preferably, R1b is selected from cycloalkyl, aralkyl, heteroaryl, heterocycloalkyl, alkoxyalkyl; wherein R1c is selected from an acrylate moiety and a carboxylate moiety; The compound of formula (I) preferably has formula (IA) or (IB).

6. The compound according to any one of claims 1 to 4, wherein R1 is selected from alkyl and heterocycloalkyl.

7. The compound according to any one of claims 1-4 or 6, wherein R1 is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group.

8. A compound according to any one of claims 1-4 or 6, wherein R1 is a C6 alkyl group.

9. The compound according to claim 1, characterized in that They are n-butyl cyanoacrylate and n-heptyl cyanoacrylate.

10. A process for the preparation of a compound of formula (I) as defined in any one of claims 1 to 9.

11. The method according to claim 10, comprising the step of converting a cyanoacetic acid ester of formula (II) into a compound of formula (I): wherein R1 is as defined in any one of claims 1-9.

12. The method according to any one of claims 10 or 11, comprising: - Step S1, which comprises subjecting the compound of formula (II) to a condensation reaction with a formaldehyde derivative: Then - an optional step S2, which comprises washing the product obtained in step S1; - step S3, which comprises depolymerizing the product obtained in step S1 or S2 to provide a compound of formula (I); - an optional step S4 of purifying said compound of formula (I) obtained at the end of step S3.

13. The method according to any one of claims 10 or 11, comprising: - comprising making a compound of formula (II) With the compound of formula (X): Where E is (CH2X) m , m is between 1 and 20, X is O or S, when n=1, F is selected from the following functional groups: When n=2, F is selected from the following functional groups: When n=3, F is: G is selected from the following functional groups: G and F are chosen independently of each other, and R5 and R6 are independently selected from the functional group H, linear or branched C1-C4 alkyl, C1-C4 haloalkyl, carboxyl-substituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl and heterocycloalkyl, or When n=1, F can be selected from (CH2) v 、(CHR7) v 、(CR7R8) v The R7 group is connected to G, wherein v ranges from 1 to 6, preferably 1 to 4, and more preferably v is 1, R7 and R8 are the same or different C1-C4 alkyl groups, A step of reacting in the presence of a catalytic amount of an ammonium salt or an imine salt (XI); - an optional step of isolating the compound (II) obtained.

14. The method according to any one of claims 11 to 13, wherein the compound of formula (II) is obtained by one of the following methods PA, PB, PC, PD or PE: ■The preparation method PA of the compound of formula (II) comprises: - contacting a compound of formula (III) with a compound of formula (IV) in the presence of an acid, more preferably under conditions sufficient to produce a compound of formula (II): wherein R1 is as defined in any one of claims 1 to 9, wherein R2=NRR', wherein R and R' are each independently H or alkyl; - optionally isolating the compound of formula (II) therefrom; ■The preparation method PB of the compound of formula (II) comprises: - contacting a compound of formula (V) with a compound of formula (IV) under conditions sufficient to produce a compound of formula (II): wherein R1 is as defined in any one of claims 1 to 9, - optionally isolating the compound of formula (II) therefrom; ■The preparation method PC of the compound of formula (II) comprises: - contacting a compound of formula (II') with a compound of formula (IV) under conditions sufficient to produce a compound of formula (II): wherein R'1 is H or an organic moiety different from R1, and R1 is as defined in any one of claims 1 to 9; - optionally isolating the compound of formula (II) therefrom; ■The preparation method PD of the compound of formula (II) comprises: - contacting a compound of formula (VIII) with a compound of formula (IV) under conditions sufficient to produce a compound of formula (II): wherein R1 is as defined above for formula (I), wherein R3 is Br, Cl or I; - optionally isolating the compound of formula (II) therefrom; ■The preparation method PE of the compound of formula (II) comprises: - contacting a compound of formula (IX) with a compound of formula (IV) under conditions sufficient to produce a compound of formula (II): wherein R1 is as defined above for formula (I), wherein R4 is -OC(=O)-R4, wherein R4 is selected from alkyl or aryl; - optionally isolating the compound of formula (II) therefrom.

15. The method according to any one of claims 13 or 14, wherein the compound of formula (IV) is a compound wherein R1 is selected from alkyl and heterocycloalkyl, preferably R1 is C1-C20 alkyl, more preferably C1-C10 alkyl, even more preferably C6 alkyl.

16. The method of any one of claims 14-15, wherein the compound of formula (V) is obtained from a process comprising contacting a compound of formula (VI) with potassium cyanide (KCN) or sodium cyanide (NaCN) under conditions sufficient to produce the compound of formula (V): wherein X represents a halogen atom, preferably Br or Cl, more preferably Br, and wherein the compound of formula (VI) is preferably obtained from a process comprising contacting a compound of formula (VII) with a halogenating agent H under conditions sufficient to produce a compound of formula (VI):

17. The method of claim 16, wherein: - the compound of formula (V) is petroleum-based, or partially bio-based or fully bio-based (100% biocarbon content), and / or - the compound of formula (VI) is petroleum-based, or partially bio-based or even completely bio-based (100% biocarbon content), and / or - The compound of formula (VII) is petroleum-based, or partially bio-based or fully bio-based (100% biocarbon content).

18. A composition, preferably an adhesive composition, comprising a compound of formula (I) as defined in any one of claims 1 to 9, wherein the content of the compound of formula (I) is preferably higher than 80% by weight, more preferably equal to or higher than 85% by weight, even more preferably equal to or higher than 90% by weight, based on the total weight of the composition.

19. A composition according to claim 18, having a biochar content equal to or higher than 20%, even more preferably higher than or equal to 50%.

20. Use of at least one raw material R having a biochar content greater than 0% for preparing a compound of formula (I): Wherein R1 is H or an organic moiety, the compound of formula (I) has a biochar content equal to or higher than 20%.

21. Use according to claim 20, wherein the biochar content of the raw material R is equal to or higher than 41%, preferably equal to or higher than 50%, more preferably equal to or higher than 65% and even more preferably equal to 100%.

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