Bio-based cyanoacrylate compound

Abstract

The present invention relates to a compound of formula (I) having a biocarbon content of 20% or more TIFF2025518781000073.tif33170(wherein R1 is H or an organic moiety).

Description

Technical Field

[0001] The present invention relates to the field of bio-based cyanoacrylates.

[0002] The present invention also relates to the use of such bio-based cyanoacrylates for preparing adhesive compositions, and to the resulting adhesive compositions.

Background Art

[0003] Cyanoacrylate (CA) is a general name for a family of resistant and fast-acting adhesives based on esters of 2-cyanoacrylic acid. Such compounds have been known for a long time, for example, as described in S. Ebnesajjad Ed., Adhesives Technology Handbook, William Andrew, Norwich, 2008.

[0004] Adhesive compositions based on cyanoacrylate (CA) esters are also well known, for example, as instant adhesives or so-called "super instant adhesives". They are widespread in many application fields and are used by consumers, professional craftsmen, and factory assemblers. They are typically solvent-free 100% reactive materials and are recognized for their ability to form strong adhesive bonds on many different substrates in a few seconds.

[0005] In many industrial and household applications, these compounds are used in one-component or two-component form because they polymerize rapidly when forming a thin film between two substrates in the presence of anions or nucleophilic species. The speed at which the bond is formed and the ease of use contribute to their popularity.

[0006] Efforts are being made to improve those properties (hardness, temperature, humidity, etc.), but the synthetic route of cyanoacrylate itself has remained largely the same industrially since the end of the 1950s. Conventional cyanoacrylates are derived from petrochemical-based chemicals and rely on energy-intensive methods. The use of these materials will contribute to the increase in the greenhouse effect. As the world's oil reserves decrease, the sources of these raw materials are gradually depleting. This is an urgent issue, especially in the carbon neutral goals of many countries by 2050.

[0007] There is a growing desire to reduce the carbon footprint and produce products with less toxicity and more environmental friendliness.

[0008] Biomass-derived raw materials are from renewable sources and have reduced environmental impact. They do not require all the energy-consuming purification steps compared to petroleum products. Since the generation of CO2 is reduced, the contribution to global warming is less.

[0009] However, such sustainable development should not have an adverse effect on the current properties of cyanoacrylate, such as the time until it sets and adhesion properties.

[0010] Therefore, it is necessary to provide an environmentally friendly cyanoacrylate that can solve at least some of the above-mentioned drawbacks.

[0011] More specifically, there is a need for an environmentally friendly cyanoacrylate with a short setting time.

[0012] More specifically, there is a need for an environmentally friendly cyanoacrylate that exhibits at least the same or better properties as conventional petroleum-based cyanoacrylates.

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

Summary of the Invention

[0014] Compound The present invention relates to a compound of formula (I): TIFF2025518781000002.tif33170wherein R1 is H or an organic moiety), and the compound of formula (I) has a biocarbon content of 20% or more.

[0015] The carbon of biomaterials is derived from plant photosynthesis and thus from atmospheric CO2. Therefore, the decomposition of these materials into CO2 (decomposition also means combustion / incineration at the end of their lifespan) does not contribute to warming because the carbon released into the atmosphere does not increase. Thus, the CO2 balance of biomaterials is clearly improved and contributes to reducing the carbon footprint of the resulting products (only the energy for manufacturing should be considered). In contrast, materials of fossil origin that also decompose into CO2 will contribute to an increase in the level of CO2 and thus to global warming.

[0016] Therefore, the components of the present invention have a better carbon footprint than compounds obtained from fossil sources.

[0017] The term "biocarbon" or "bio-based carbon" indicates that the carbon is of renewable or natural origin and is derived from biomaterials, as shown below. Biocarbon content and biomaterial content are expressions that indicate the same value.

[0018] Materials of renewable origin, also called biomaterials, are organic materials in which the carbon is derived from CO2 that has recently been fixed (on a human scale) by photosynthesis from the atmosphere. On Earth, this CO2 is captured or fixed by plants. In the sea, CO2 is captured or fixed by photosynthetic bacteria or plankton. Biomaterials (100% carbon of natural origin) are 10 -12Greater than, typically about 1.2×10 -12 of 14 C / 12 C isotope ratio, while fossil materials have a zero ratio. In fact, the isotope 14 C is formed in the atmosphere and incorporated by photosynthesis on a timescale of up to several decades. 14 The half-life of 14 C is 5730 years. Thus, materials resulting from photosynthesis, i.e., plants, generally and necessarily have a maximum

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

[0020] The first standard describes tests for measuring the 14 C / 12 C ratio of a sample and, by comparing it with the 14 C / 12 C ratio of a reference sample of 100% renewable origin, gives the relative proportion of renewable origin C in the sample. This standard is 14 based on the same concept as

[0021] radiocarbon dating but does not apply the dating equation. The ratio calculated in this way is referred to as "Percent Modern Carbon" (pMC). If the material to be analyzed is a mixture of biogenic (isotope-free) and fossil materials, the pMC value obtained is directly correlated with the amount of biogenic material present in the sample.

[0022] The current C-14 standard (oxalic acid II) represents what the current (living plant) C-14 activity was in 1950, which is set as the standard for 100% bio-based activity. The baseline concentration subtracted from the measured activity is also established. The activity of this sample is compared to the activity of oxalic acid II. This gives the pMC or the percentage of current carbon. If a mixture of current carbon and fossil carbon is present in the sample, the resulting pMC (e.g., 85 pMC) indicates that the activity of the current standard was measured at 85%. This sample is reported as 85% bio-based carbon. Due to nuclear tests in the atmosphere in the 1950s and 1960s, C-14 was artificially created in the atmosphere. At one point, this was almost 200% of the natural activity. As time passed, the dilution of fossil fuel CO2 advanced in the atmosphere, and this activity was diluted, and the current C-14 activity in the atmosphere has returned to the same level as the current standard. There is an atmospheric correction factor used to account for these changes in the C-14 activity in the atmosphere. This atmospheric correction factor (REF) was used as follows. Bio-carbon content = pMC / (REF) REF = 1.000 (in 2022). The accuracy of the bio-carbon content percentage is + / - 3% (absolute value).

[0023] The compounds of formula (I) described herein preferably have a bio-carbon content of 25% or more, more preferably 41% or more, even more preferably 50% or more, and more advantageously 55% or more.

[0024] In a preferred embodiment, R1 is H, or a hydrocarbon radical that may contain at least one heteroatom.

[0025] Preferably, R1 is selected from the group consisting of H, alkyl, halogenated alkyl, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, acrylate moiety, oxetane moiety, epoxy moiety, and carboxylic acid ester moiety.

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

[0027] As used herein, the term "alkyl" means a straight-chain or branched hydrocarbon radical, examples of which are methyl, ethyl, and propyl.

[0028] As used herein, the term "alkenyl" means a straight-chain or branched hydrocarbon radical containing at least one double bond. Examples are allyl, propenyl, and butenyl.

[0029] As used herein, the term "alkynyl" means a straight-chain or branched hydrocarbon radical containing at least one triple bond. An example is propargyl.

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

[0031] As used herein, the term "heteroaryl" means a monocyclic or bicyclic aromatic radical containing at least one heteroatom, such as O, S, or N, and preferably containing 4 to 12 carbon atoms. Some examples are furanyl, thiophenyl, pyrrolyl, pyridinyl, indolyl, or imidazolyl.

[0032] As used herein, the term "arylalkyl" or "aralkyl" means an alkyl group substituted with an aryl group, and the arylalkyl preferably contains 7 to 20 carbon atoms. One example is the benzyl group.

[0033] As used herein, the term "alkylaryl" or "alkaryl" means an aryl group substituted with an alkyl group, and the alkylaryl preferably contains 7 to 20 carbon atoms.

[0034] As used herein, the term "cycloalkyl" means a monocyclic or polycyclic saturated system, and preferably contains 3 to 12 carbon atoms. Examples of cycloalkyl groups are cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, or norbornyl.

[0035] As used herein, the term "cycloalkenyl" means a monocyclic or polycyclic unsaturated system, and preferably contains 3 to 12 carbon atoms.

[0036] As used herein, the term "heterocycloalkyl" means a monocyclic or polycyclic saturated system, containing at least one heteroatom such as O, S, or N, and preferably contains 3 to 12 carbon atoms. Examples are the tetrahydrofurfuryl or tetrahydrothiophene groups.

[0037] As used herein, the term "alkoxyalkyl" means radical-alkyl-O-alkyl, where alkyl is as defined above.

[0038] When R1 is an alkyl group, it may 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, n-undecyl.

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

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

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

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

[0043] When R1 is a heteroaryl group, it may be selected from furanyl, methylfuranyl, thiophenyl, pyrrolyl, pyridinyl, indolyl, imidazolyl.

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

[0045] When R1 is a cycloalkyl group, 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, cycloheptenyl.

[0047] When R1 is a heterocycloalkyl group, it may be selected from methyltetrahydrofuryl and tetrahydrofuryl.

[0048] When R1 is an alkoxyalkyl group, it may be selected from 2-methoxymethyl, 2-ethoxymethyl, 2-propoxymethyl, 2-butoxymethyl, 2-isopropoxymethyl, 2-hexyloxymethyl, 2-amyloxymethyl, 2-ethoxypropyl, 2-methoxyethyl, and 2-(1-methoxy)ethyl. Other examples of alkoxyalkyl groups are described in U.S. Patent No. US6977278.

[0049] When R1 is an acrylate moiety, it preferably has the following formula. TIFF2025518781000003.tif23170(wherein T is selected from (CH2) z and z is a branched C2-C12 alkylene, alkynylene, alkenylene, alkylene-O-alkylene, cyclohexylene, biphenylene, -C6H4C(Me)2C6H4-, -C6H4CH2C6H4-, phenylene, -C6H4-alkylene- consisting of 1 to 12, preferably 1 to 6, Y is H, Me, or CN)

[0050] When R1 is a carboxylic acid ester moiety, R1 preferably has the formula -(CH2) k CO2Y’ or -C(=CH2)-CO2Y’, k consists of 1 to 18, preferably 1 to 6, and Y’’ is a C1-C4 alkyl group.

[0051] The compound of formula (I) may have one of the following formulas (I-A), (I-B), or (I-C). TIFF2025518781000004.tif29170(wherein R1a is alkyl) TIFF2025518781000005.tif33170(wherein, R1b is selected from H, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, oxetane moiety, epoxy moiety, and preferably, R1b is selected from cycloalkyl, aralkyl, heteroaryl, heterocycloalkyl, alkoxyalkyl) TIFF2025518781000006.tif30170(wherein, R1c is selected from acrylate moiety and carboxylate moiety)

[0052] Examples of the compound of formula (I-A) 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 (I-A) are n-butyl cyanoacrylate and n-pentyl cyanoacrylate.

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

[0055] Examples of the compound of formula (I-B) 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 the compound of formula (I-C) can be as follows. TIFF2025518781000007.tif94170 (wherein Rd is methyl or ethyl) TIFF2025518781000008.tif62170

[0057] Preferably, the compound of formula (I) is a compound of formula (I-A) or (I-B).

[0058] The compound of formula (I) may be selected from the group consisting of 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, cyclohexenyl cyanoacrylate.

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

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

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

[0062] Method The present invention also relates to a method for preparing a compound of formula (I): TIFF2025518781000009.tif28170(wherein R1 is H or an organic moiety), and the compound of formula (I) has a bio-carbon content of 20% or more.

[0063] (In the paragraph "Compound") All embodiments and preferred features disclosed for the compound of formula (I) above apply to its preparation method and will not be repeated here.

[0064] The method for preparing the compound of formula (I) described herein preferably comprises the step of converting a cyanoacetate of formula (II) TIFF2025518781000010.tif23170(wherein in formula (II), R1 is as defined in formula (I) herein, i.e., R1 is H or an organic moiety) into the compound of formula (I) described herein.

[0065] All embodiments and preferred features disclosed for R1 in the compound of formula (I) apply herein for R1 in the compound of formula (II) and will not be repeated here.

[0066] The compound of formula (II) may have one of the following formulae (II-A), (II-B), or (II-C). TIFF2025518781000011.tif37170(wherein R1a is alkyl) TIFF2025518781000012.tif23170(wherein R1b is selected from H, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, oxetane moiety, epoxy moiety, and preferably R1b is selected from cycloalkyl, aralkyl, heteroaryl, heterocycloalkyl, alkoxyalkyl) TIFF2025518781000013.tif23170(wherein, R1c is selected from an acrylate moiety and a carboxylate moiety)

[0067] Examples of the compound 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 the compound 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 the compound of formula (II-C) may be as follows. TIFF2025518781000014.tif89170(wherein, Rd is methyl or ethyl) TIFF2025518781000015.tif56170

[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, and even more preferably a C6 alkyl group.

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

[0074] The compound of formula (II) preferably has a biocarbon content of 25% or more, more preferably 45% or more, and even more preferably 50% or more.

[0075] The present invention also relates to a compound of formula (I) herein that is readily obtained by a method comprising the step of converting the cyanoacetate of formula (II) described herein into the compound of formula (I).

[0076] Compound of formula (I) having a biocarbon content of 20% or more: The preparation method of TIFF2025518781000016.tif28170 (wherein R1 is H or an organic moiety) is preferably selected from method P1 or method P2 as described hereinafter.

[0077] Method P1 The present invention relates to the preparation method P1 of the compound of formula (I) described above, and this method is - The compound of formula (II) described above TIFF2025518781000017.tif23170 and a formaldehyde derivative, followed by a condensation reaction in step S1, and then - An optional step S2 including washing the product obtained in step S1, - Step S3 including depolymerizing the product obtained in step S1 or S2 to provide the compound of formula (I), - An optional step S4 of purifying the compound of formula (I) obtained at the end of step S3 is included.

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

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

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

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

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

[0083] Step S1 is preferably carried out at a temperature in the range of 30°C to 150°C, more preferably 50°C to 100°C.

[0084] Optional step S2 includes washing and can be carried out using water or an acidic aqueous solution. The acidic aqueous solution may 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 concentration of the acid is preferably in the range of 0.01 to 5 wt% in the acidic aqueous solution.

[0085] The washing can be carried out at a temperature in the range of 0°C to 100°C.

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

[0087] Step S3, which includes depolymerization of the product obtained in Step S1 or S2, can be carried out at a temperature in the range of 100°C to 250°C, preferably 140°C to 200°C, and 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 may be distillation, double distillation, or crystallization.

[0090] Formaldehyde derivatives typically include paraformaldehyde and substances that react to produce formaldehyde (precursors of formaldehyde). Preferably, the formaldehyde derivative is paraformaldehyde.

[0091] Examples of substances that react to produce formaldehyde include paraformaldehyde.

[0092] Formaldehyde derivatives can be derived from petroleum-based materials or can be partially bio-based or even completely bio-based (100% bio-carbon content).

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

[0094] As used herein, the term "partially bio-based" means that the bio-carbon content of the material exceeds at least 0%, preferably exceeds at least 10%.

[0095] Preferably, method P1 is - Step S1 and - Step S2, which includes washing the product obtained in Step S1. - To provide a compound of formula (I), step S3 including depolymerizing the product obtained in step S1 or S2, - Step S4 for purifying the compound of formula (I) obtained at the end of step S3, and comprising.

[0096] Embodiments and preferred embodiments regarding the compound of formula (II) disclosed above are applied to method P1 and will not be repeated here.

[0097] Method P2 The present invention relates to method P2 for preparing a compound of formula (I) described above, and this method - In the presence of a catalytic amount of an ammonium salt or an iminium salt (XI), the compound of formula (II) above TIFF2025518781000018.tif23170 and the compound of formula (X) TIFF2025518781000019.tif24170, which is a step including the reaction therebetween, In the above formula, E is (CH2X) m where m is included between 1 and 20, and X is O or S, When n = 1, F is selected from the following functional groups, TIFF2025518781000020.tif28170 When n = 2, F is selected from the following functional groups, TIFF2025518781000021.tif19170 When n = 3, F is as follows, TIFF2025518781000022.tif22170 G is selected from the following functional groups, TIFF2025518781000023.tif27170 G and F are independently selected from each other, R5 and R6 are independently selected from each other from the functional groups H, linear or branched C1-C4 alkyl, C1-C4 halogenated alkyl, carboxy-substituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl, and heterocycloalkyl, or When n = 1, F is (CH2) v , (CHR7) v, (CR7R8) v It may be bonded to G via one R7 group selected from v , where v ranges from 1 to 6, preferably from 1 to 4, and more preferably v is 1, and R7 and R8 are the same or different C1-C4 alkyl groups, and a step, - An optional step for isolating the obtained compound (II).

[0098] This method is typically disclosed in International Publication No. WO2015 / 150882.

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

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

[0101] As used herein, the term "iminium salt" means an imine resulting from the reaction of a primary or secondary amine with an aldehyde or a ketone, which results in an iminium cation in a neutral or acidic medium and contains an anion from an acid.

[0102] The acid used in the preparation of the ammonium salt and the iminium salt can be any acid. Preferably, the acid is selected from the group consisting of 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 the group consisting of sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and mixtures thereof, and more preferably, it is selected from methanesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, and mixtures thereof. It is also possible to use a mixture of acids and / or a mixture of amines.

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

[0104] Preferably, E is (CH2X) m where m is included between 1 and 10, X is O or S, n = 1, and F is selected from the following functional groups TIFF2025518781000024.tif28170G is selected from the following functional groups, TIFF2025518781000025.tif27170G and F are selected independently of each other, R5 and R6 are independently of each other selected from the functional groups H, linear or branched C1-C4 alkyl, C1-C4 halogenated alkyl, carboxy-substituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl, and heterocycloalkyl, or when n = 1, F is (CH2) v , (CHR7) v , (CR7R8) v and can be bonded to G via an R7 group selected therefrom, where v ranges from 1 to 6, preferably from 1 to 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 where m is between 1 and 3, X is 1, and F is as follows: TIFF2025518781000026.tif28170G is as follows: TIFF2025518781000027.tif27170G and F are independently selected from each other R5 and R6 are independently selected from the functional group H, linear or branched C1-C4 alkyl, C1-C4 halogenated alkyl, carboxy-substituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl, and heterocycloalkyl. Preferably, R5 and R6 are independently selected from the functional group H and linear or branched C1-C4 alkyl.

[0106] This kind of compound can be obtained, for example, by the reaction of formaldehyde gas or a formaldehyde source such as paraformaldehyde or trioxane, or a thioformaldehyde source such as trithiane, with an acid anhydride such as acetic anhydride, thioacetic anhydride, dithiocarboxylic anhydride, methanesulfonic anhydride, succinic anhydride, phthalic anhydride, or tert-butoxycarboxylic anhydride.

[0107] The formaldehyde source can be bio-based (as disclosed herein in the above method P1).

[0108] When X is O (oxygen) and n is 1, the compound is referred to as a methylene carboxylic acid ester, methylene thiocarboxylic acid ester, methylene sulfonic acid ester, or methylene phosphoric acid ester according to the groups F and G according to the above definition. The preparation of methylene carboxylic acid esters is described, for example, in U.S. Patent No. US3927078.

[0109] When X is O (oxygen) and n is 2, the compound is, according to the above definition and depending on groups F and G, called oxybis(methylene)carboxylate, oxybis(methylene)thiocarboxylate, oxybis(methylene)sulfonate, or oxybis(methylene)phosphate. The preparation of polyoxymethylene polycarboxylates is described, for example, in U.S. Patent No. US3219630. The preparation of oxybis(methylene)carboxylates is described, for example, in U.S. Patent Nos. US3927078 and US3931412. The preparation of oxybis(methylene)sulfonates is described, for example, in U.S. Patent No. US4100200.

[0110] The preparation of trioxymethylene carboxylate (X is O, n = 3) is described, for example, in U.S. Patent No. US3931412. The preparation of tris(acyloxymethylene)phosphates is described in International Patent Application No. WO-A-96 / 40695.

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

[0112] Among the compounds of general formula (X), those listed in the following table may be preferably mentioned. TIFF2025518781000028.tif160170

[0113] As compounds of formula (X), preferred compounds are methylene diacetate, oxybis(methylene) diacetate, methylene dipropionate, and oxybis(methylene) dipropionate, more preferred compounds are methylene diacetate and oxybis(methylene) diacetate, and even more preferred compound is methylene diacetate.

[0114] Preferably, the compound of formula (I) of the present invention is obtained from method P2.

[0115] The compound of formula (II) described herein may be obtained by one of the following methods P-A, P-B, P-C, P-D, or P-E, as described below.

[0116] Method P-A The preparation method P-A of the compound of formula (II) is - contacting a compound of formula (III) and a compound of formula (IV) in the presence of an acid, more preferably under conditions sufficient to produce the compound of formula (II), and TIFF2025518781000029.tif23170(wherein R1 is as defined above with respect to formula (I), i.e., H or an organic moiety) (wherein R2 = NRR', and each of R and R' is, independently of one another, H or an alkyl group) - optionally, separating the compound of formula (II) therefrom.

[0117] The acid can be any acid catalyst known to those skilled in the art. They can be either a Lewis acid or a Bronsted acid. The acid may be selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, scandium triflate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, and hydrochloric acid. Also, heterogeneous catalysts such as zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay, and zirconia tungstate may be used.

[0118] Preferably, the acid is a mineral acid, and even more preferably, it is selected from the group consisting of sulfuric acid, sulfurous acid, sulfonic acid, phosphoric acid, phosphorous acid, phosphonic acid, hydrochloric acid, or hydrobromic acid.

[0119] The compound of formula (IV) should be used in an amount greater than either or both of the compound of formula (III) and the mineral acid.

[0120] The compound of formula (IV) is - a compound of formula (IV-A): TIFF2025518781000030.tif8170(wherein R1a is alkyl) - a compound of formula (IV-B): TIFF2025518781000031.tif8170(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) - a compound of formula (IV-C): TIFF2025518781000032.tif9170(wherein R1c is selected from acrylate moiety and carboxylate moiety) and may be selected from

[0121] Preferably, in formula (IV), R1 is selected from an alkyl group and a heterocycloalkyl.

[0122] 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.

[0123] The compound of formula (IV) can be partially bio-based and preferably can be completely bio-based. In that case, it may be obtained from fermentation, sugars, pyrolysis of oils, organic solutions (juices), bio-oils, etc.

[0124] The compound of formula (IV) preferably has a bio-carbon content of 20% or more, more preferably 50% or more, even more preferably 80% or more, and more advantageously 99% or more.

[0125] The compounds of formula (IV) are typically commercially available from different companies.

[0126] Examples of at least partially bio-based or fully bio-based compounds of formula (IV) are Biosource EtOH from Myhome aromas, Biosource heptanol from Arkema Oleris, Viridisol® T Tetrahydrofurfuryl Alcohol (THFA) from Pennakem, isobutanol (from Gevo), biomethanol (Veolia), n-butanol from Green biologics, n-propanol from Braskem, 1,10 dodecanediol from Sartomer.

[0127] The compounds of formula (IV) may be selected from the group consisting of methanol, ethanol, n-propanol, n-butanol, isobutanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, nonanol, dodecanol, tetrahydrofurfrole, ethoxyethanol, propoxyethanol, methoxyethanol, methoxybutanol, trialkylsilylethanol, trialkylsilylpropanol, trialkylsilylbutanol, benzyl alcohol, propargyl alcohol, phenyl-2-ethanol, cyclohexenylethanol.

[0128] The compounds of formula (III) can be compounds where R = R’ = H, or compounds where R = H and R’ has an alkyl such as methyl or ethyl for example.

[0129] The compounds of formula (III) can have a biocarbon content of 0% or more, more preferably 24% or more, even more preferably 49% or more.

[0130] In a preferred embodiment, the substituted alcohol in compound (IV) It is necessary to reduce the synthetic trace of TIFF2025518781000033.tif27170 (R5 is different from H) to less than 1%.

[0131] In a preferred embodiment, the compound of formula (III) is not derived from an aspartic acid derivative.

[0132] Method P-B The preparation method P-B of the compound of formula (II) is - contacting the compound of formula (V) with the compound of formula (IV) as described above under conditions sufficient to produce the compound of formula (II), TIFF2025518781000034.tif23170 - optionally separating the compound of formula (II) therefrom and comprising.

[0133] 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.). This typically corresponds to the esterification of cyanoacetic acid and an alcohol.

[0134] The molar ratio of the compound of formula (IV) to the compound of formula (V) can vary from 1.0 to 20, preferably from 5.0 to 10.

[0135] Preferably, this reaction is carried out in the presence of an acid. Esterification acid catalysts are well-known to those skilled in the art. They can be either Lewis acids or Bronsted acids. The acid may be selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, scandium triflate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, hydrochloric acid. Also, heterogeneous catalysts such as zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay, and zirconia tungstate may be used.

[0136] This reaction can be carried out at a temperature in the range of 25°C to 120°C, preferably 50°C to 100°C.

[0137] Preferably, the preparation method P-B of the compound of formula (II) includes a step of optionally separating the compound of formula (II) from the reaction medium obtained in the first step.

[0138] The method P-B preferably - a step of concentrating the reaction medium under reduced pressure, and - a step of adding an organic solvent and an aqueous solution to the obtained residue, and then - a step of performing decantation, recovery of the organic phase, and evaporation of the organic solvent to obtain the compound of formula (II). and includes.

[0139] The compound of formula (V) can be petroleum-based or can be at least partially bio-based or completely bio-based (100% bio-carbon content).

[0140] All the descriptions, embodiments, and preferred embodiments disclosed above for the compound of formula (IV) (for example, in the paragraph of method P-A) apply to method P-B herein and will not be repeated.

[0141] The compound of formula (V) may be, for example, commercially available from Sigma-Aldrich.

[0142] The compound of formula (V) can also be a compound of formula (VI) under conditions sufficient to produce the compound of formula (V): TIFF2025518781000035.tif27170 (wherein X represents a halogen atom, preferably Br or Cl, more preferably Br) It may be obtained from a method including contacting with potassium cyanide (KCN) or sodium cyanide (NaCN) (preferably potassium cyanide).

[0143] Potassium cyanide (KCN) or sodium cyanide (NaCN) can optionally be partially or even completely bio-based. Bio-based potassium cyanide can be obtained from 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.

[0144] The P-B reaction can typically be carried out as described in Chemistry, a European journal, vol 24, issue 71, p. 18903-18906 or Chinese Patent No. CN2015-10810110 or Chinese Patent No. CN2016-10662675.

[0145] This reaction can be carried out in a basic medium having a pH greater than 6, preferably greater than 7.

[0146] This reaction can be carried out in an aqueous basic solution, for example, an aqueous solution of Na2CO3 or NaHCO3.

[0147] This reaction can last from 3 minutes to 24 hours.

[0148] This reaction can be carried out at an overpressure (relative to the ambient atmosphere) in the range of 0.01 - 1 MPa, preferably 0.2 MPa.

[0149] This reaction can be carried out at a temperature in the range of 23°C to 100°C.

[0150] The method for preparing the compound of formula (V) preferably includes the isolation of the compound of formula (V), preferably - an acidification step using an acid, for example, HCl, and - an optional step of evaporating water, and - an optional extraction step using an organic solvent, preferably ether, and - an optional filtration step of recovering the compound of formula (V). It includes.

[0151] The compound of formula (VI) can be petroleum-based, or can even be partially bio-based or completely bio-based (bio-carbon content 100%).

[0152] The compound of formula (VI) may be, for example, one commercially available from Sigma-Aldrich such as bromoacetic acid.

[0153] The compound of formula (VI) can also be obtained from a method including contacting the compound of formula (VII): TIFF2025518781000036.tif22170 with a halogenating agent H under conditions sufficient to produce the compound of formula (VI).

[0154] This reaction can typically be carried out as described in Asian Journal of Chemistry, 30(10), 2310 - 2316 (2018).

[0155] The halogenating agent H may be selected from PBr3, Br2, Cl2, and PCl5, and mixtures thereof.

[0156] The compound of formula (VII) may be one commercially available from Sekab (acetic acid, CAS = 64 - 19 - 7), which is completely bio-based (bio-carbon content = 100%).

[0157] The compound of formula (VII) can be petroleum-based or can be at least partially or fully bio-based (100% bio-carbon content).

[0158] Process P-C The process P-C for preparing the compound of formula (II) comprises - contacting a compound of formula (II’) with a compound of formula (IV) as described above under conditions sufficient to produce the compound of formula (II), TIFF2025518781000037.tif24170(wherein R’1 is H or an organic moiety different from R1 and R1 is as defined above) - optionally, separating the compound of formula (II) therefrom and

[0159] This reaction is typically a transesterification reaction well-known in the art. It can be carried out as described, for example, in Zhanjie Zazhishe (2014), 35(2), 67 - 68, 79.

[0160] This reaction can be carried out at a temperature in the range of 80 °C to 120 °C.

[0161] This reaction can be carried out in the presence of a catalyst selected from the group consisting of titanium isopropoxide, aluminum isopropoxide, tributyltin alkoxide, dibutyltin oxide, tin acetylacetonate.

[0162] The process P-C preferably includes a step of separating the compound of formula (II). This is preferably carried out by distillation, especially under reduced pressure.

[0163] All the descriptions, embodiments, and preferred embodiments disclosed above with respect to the compound of formula (IV) (for example, in the paragraphs of processes P-A and P-B) apply to process P-C herein and will not be repeated.

[0164] The compound of formula (II’) can be petroleum-based or can be partially or fully bio-based.

[0165] The compound of formula (II’) TIFF2025518781000038.tif24170 (wherein R1’ is as defined above) can have a biocarbon content of 20% or more, preferably 25% or more, more preferably 41% or more, even more preferably 50% or more, and even more advantageously 55% or more.

[0166] Preferably, R’1 is selected from the group consisting of H, alkyl, halogenated alkyl, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, acrylate moiety, oxetane moiety, epoxy moiety, carboxylic acid ester moiety.

[0167] Alkyl, alkenyl, aryl, alkynyl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl may be substituted by at least one substituent selected from the group consisting of, for example, alkyl, aryl, alkenyl, OH, amine, amide, halogen atom, -CF3, and mixtures thereof.

[0168] 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.

[0169] More preferably, the compound of formula (II’) is methyl cyanoacetate.

[0170] Method P-D The preparation method P-D 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), TIFF2025518781000039.tif22170(wherein R1 is as defined above with respect to formula (I), i.e., H or an organic moiety) (wherein R3 is Br, Cl or I) - optionally, separating the compound of formula (II) therefrom and

[0171] Preferably, this reaction is carried out in the presence of an acid. Esterification acid catalysts are well-known to those skilled in the art. They can be either Lewis acids or Bronsted acids. The acid may be selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, scandium triflate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, and hydrochloric acid. Also, heterogeneous catalysts such as zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay, and zirconia tungstate may be used.

[0172] The compound of formula (VIII) may be used in an amount greater than either or both of the compound of formula (IV) and the acid.

[0173] This reaction can be carried out at a temperature in the range of 25 °C to 120 °C, preferably 50 °C to 100 °C.

[0174] Preferably, the method P-D for preparing the compound of formula (II) includes the step of optionally separating the compound of formula (II) from the reaction medium obtained in the first step.

[0175] Method P-D preferably - a step of concentrating the reaction medium under reduced pressure, and - a step of adding an organic solvent and an aqueous solution to the obtained residue, and then - a step of performing decantation, recovering the organic phase, and evaporating the organic solvent to obtain the compound of formula (II) and includes.

[0176] The compound of formula (VIII) can be petroleum-based, or can be partially bio-based or completely bio-based (100% bio-carbon content).

[0177] All the descriptions, embodiments, and preferred embodiments disclosed above regarding the compound of formula (IV) (for example, in the paragraph of method P-A) are applicable to method P-D herein and will not be repeated.

[0178] Process P-E The preparation process P-E 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), TIFF2025518781000040.tif23170(wherein R1 is as defined above with respect to formula (I), i.e., H or an organic moiety) (wherein R4 is -O-C(=O)-R4 and R4 is selected from alkyl or aryl) - optionally separating the compound of formula (II) therefrom and may include.

[0179] Preferably, this reaction is carried out in the presence of an acid. Esterification acid catalysts are well known to those skilled in the art. They can be either Lewis acids or Bronsted acids. The acid may be selected from the group consisting of sulfuric acid, p-toluenesulfonic acid, scandium triflate, methanesulfonic acid, dodecylbenzenesulfonic acid, boron trifluoride, phosphoric acid, perchloric acid, hydrochloric acid. Also, heterogeneous catalysts such as zirconium tetrasulfate, Amberlyst 46, acid-modified montmorillonite (K10) clay, and zirconia tungstate may be used.

[0180] The compound of formula (IX) should be used in an amount greater than either or both of the compound of formula (IV) and the acid.

[0181] This reaction can be carried out at a temperature in the range of 25 °C to 120 °C, preferably 50 °C to 100 °C.

[0182] Preferably, the preparation process P-E of the compound of formula (II) includes the step of optionally separating the compound of formula (II) from the reaction medium obtained in the first step.

[0183] Process P-E preferably comprises - concentrating the reaction medium under reduced pressure, - adding an organic solvent and an aqueous solution to the resulting residue, and then - a step of performing decantation, recovery of the organic phase, and evaporation of the organic solvent to obtain the compound of formula (II), and including.

[0184] The compound of formula (VIII) can be petroleum-based or can be partially bio-based or completely bio-based (100% bio-carbon content).

[0185] All the descriptions, embodiments, and preferred embodiments disclosed above for the compound of formula (IV) (for example, in the paragraph of method P-A) are applicable to method P-E herein and will not be repeated.

[0186] Preferably, the compound of formula (II) is not derived from an aspartic acid derivative.

[0187] In a preferred embodiment, the compound of formula (II) as described above is obtained from method P-B or P-C.

[0188] In a preferred embodiment, the compound of formula (II) where R1 = methyl is obtained by method P-B, and this method - contacting the compound of formula (V) with the compound of formula (IV) where R1 = methyl under conditions sufficient to produce the compound of formula (II), and TIFF2025518781000041.tif23170 - optionally separating the compound of formula (II) therefrom, and including, - the compound of formula (IV) has a bio-carbon content of 20% or more, more preferably 50% or more, even more preferably 80% or more, and more advantageously 99% or more, - the compound of formula (V) is petroleum-based or is partially bio-based or completely bio-based.

[0189] In another preferred embodiment, the compound of formula (II) where R1 = hexyl or tetrahydro is obtained by method P-C, and this method - contacting a compound of formula (II’) with a compound of formula (IV) wherein R1 is hexyl or tetrahydro under conditions sufficient to produce a compound of formula (II), TIFF2025518781000042.tif24170(wherein R’1 is H or an organic moiety different from R1) - optionally, separating the compound of formula (II) therefrom comprising - the compound of formula (IV) has a biocarbon content of 20% or more, more preferably 50% or more, even more preferably 80% or more, and more advantageously 99% or more, - the compound of formula (II) is petroleum-based or partially or fully bio-based.

[0190] Use The present invention relates to the use of a compound of formula (I) as described above for preparing a composition, preferably an adhesive composition.

[0191] The present invention also relates to a composition, more preferably an adhesive composition, comprising a compound of formula (I) as described above.

[0192] All descriptions, embodiments, and preferred embodiments disclosed above with respect to the compound of formula (I) (for example, in the compound paragraph) apply herein to the use and composition and will not be repeated.

[0193] The composition may be a 1K or 2K composition.

[0194] Preferably, the adhesive composition comprising a compound of formula (I) as disclosed above has a biocarbon content of 20% or more, even more preferably 50% or more. The biocarbon content is measured as described above.

[0195] In a preferred embodiment, the composition comprises more than 80% by weight, even more preferably 85% by weight or more, and still more preferably 90% by weight or more of the compound of formula (I) as described above, based on the total weight of the composition.

[0196] This type of composition containing cyanoacrylate is well-known and can contain any components and / or additives well-known in this field.

[0197] The composition may contain an acid inhibitor.

[0198] The acid inhibitors are inhibitors of anionic polymerization. They may be selected from the group consisting of Bronsted acids, Lewis acids, acids provided by acidic ion exchange materials, or photoacids obtained from photoacid generators (also known as PAGs), and mixtures thereof, and are preferably those from Bronsted acids, Lewis acids, and mixtures thereof. The acid inhibitors are preferably selected from the group consisting of methanesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic anhydride, hydrofluoric acid, boron trifluoride, boron trifluoride etherate complex, boron trifluoride dihydrate, sulfur dioxide, sulfur trioxide, tin(IV) chloride, iron(III) chloride, citric acid, trimethylsilyl triflate, and mixtures thereof, and more preferably those from methanesulfonic acid, hydrofluoric acid, boron trifluoride, boron trifluoride etherate complex, sulfur dioxide, and mixtures thereof.

[0199] The composition may contain from 0 to 0.1% by weight, preferably from 0.0001 to 0.05% by weight, and more preferably from 0.0005 to 0.01% by weight of an acid inhibitor, based on the total weight of the composition.

[0200] The expressions "radical stabilizer" and "radical stabilizing agent" are currently used synonymously.

[0201] The composition may contain a radical stabilizer.

[0202] The radical stabilizer is a free radical polymerization inhibitor. This is preferably selected from the group consisting of hindered phenol or polyphenol compounds, and is preferably from hydroquinone, hydroquinone monomethyl ether, monotertiary butyl hydroquinone, 2,5 - ditertiary butyl hydroquinone, p - methoxyphenol, hydroxyanisole, butylated hydroxyanisole, hydroxyanisole 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, and more preferably from hydroquinone monomethyl ether, 2,2'-methylene - bis-(6 - tert - butyl - 4 - methylphenol), and mixtures thereof.

[0203] The composition may contain 0.01 to 0.7% by weight, preferably 0.01 to 0.5% by weight, more preferably 0.01 to 0.4% by weight of the radical stabilizer based on the total weight of the composition.

[0204] The expressions "thickeners" or "thickening agents" are currently used synonymously.

[0205] The composition may contain a thickener.

[0206] The thickener is particularly suitable for controlling and / or increasing the viscosity of the cyanoacrylate component, considering that cyanoacrylate-based monomers usually have a watery viscosity at room temperature. The thickener or thickening agent suitable for the first part of the composition can be selected from those compatible with the host monomer. Examples of such thickeners include poly(meth)acrylate, acylated cellulose polymers (e.g., cellulose acetate), polyvinyl acetate, partially hydrolyzed polyvinyl acetate, polyvinyl pyrrolidone, polyoxylate, polycaprolactone, polycyanoacrylate, vinyl acetate copolymers (e.g., using vinyl chloride), copolymers of (meth)acrylate with butadiene and styrene, copolymers of vinyl chloride and acrylonitrile, copolymers of ethylene and vinyl acetate, poly[butylene terephthalate-co-polyethylene glycol terephthalate], copolymers of lactic acid and caprolactone, and mixtures thereof.

[0207] These thickeners are well-known to those skilled in the art and are described in the prior art. Preferably, the thickener is selected from the group consisting of poly(meth)acrylate, polymethyl(meth)acrylate, polyvinyl pyrrolidone, polyvinyl acetate, partially hydrolyzed polyvinyl acetate, vinyl acetate copolymers, acrylated cellulose polymers, and mixtures thereof. Suitable thickeners for the cyanoacrylate component can be, for example, polymethyl methacrylate (e.g., Degacryl® M 449, Evonik), copolymers of vinyl acetate and vinyl alcohol (e.g., Levamelt® 900, Lanxess), copolymers of vinyl chloride and vinyl acetate (e.g., Vinnol® H 40-60, Wacker), copolymers of ethylene, vinyl acetate and maleic acid esters or partial esters (e.g., Vamac® G from DuPont), and mixtures thereof.

[0208] The composition can contain 0 to 10% by weight, preferably 3 to 8% by weight, more preferably 4 to 7% by weight of the thickener, based on the total weight of the composition.

[0209] The expressions "tougheners" or "toughening agents" are currently used synonymously.

[0210] The composition may contain a toughener.

[0211] Tougheners may be selected from the group consisting of 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 rubber, 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, homopolymers of polyvinyl acetate, block copolymers, core-shell rubber particles (e.g., commercially available from Arkema under the trademarks Clearstrength® XT100 and XT151), and mixtures thereof.

[0212] The composition may contain 1 to 20 wt%, preferably 5 to 12 wt%, of a toughener based on the total weight of the composition.

[0213] The composition may contain an accelerator.

[0214] The expressions "accelerator" or "accelerating agent" are currently used synonymously.

[0215] The accelerator may be selected from the group consisting of crown ethers (e.g., 15-crown-6 ether, 15-crown-5 ether, 18-crown-6 ether, dibenzo-18-crown-6 ether, and mixtures thereof), cyclodextrin, silylated crown ether, calixarene tetra-t-butyl ester, PEG400, PEG500, PEG600, and dimethyl ether of PEG1000, and mixtures thereof. Preferably, the accelerator is a crown ether. More preferably, the accelerator is selected from the group consisting of 18-crown-6 ether, dibenzo-18-crown-6 ether, and mixtures thereof. Even more preferably, the accelerator is dibenzo-18-crown-6.

[0216] The composition may contain 0 to 0.8% by weight, preferably 0.05 to 0.5% by weight, of the accelerator based on the total weight of the composition.

[0217] The composition may contain an adhesion promoter.

[0218] The expressions "adhesion promoter" and "adhesion promoting agent" are currently used synonymously.

[0219] 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, additional components may include an adhesion promoter for glass, ceramic, porcelain, plastic, and / or metal such as an alkoxysilane compound, citric acid, lithium tetrafluoroborate, lithium hexafluorophosphate, an aromatic carboxylic acid or anhydride, or an α-substituted acrylic acid in the form of an anhydride, optionally. Among the acids and anhydrides, trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, itaconic acid, itaconic anhydride, and 3-butene-1,2,3-tricarboxylic acid can be mentioned.

[0220] The composition may contain 0 to 0.1% by weight, preferably 0.06 to 0.08% by weight, of an adhesion promoter based on the total weight of the composition.

[0221] The composition may contain a thixotropic agent.

[0222] The thixotropic agent may be an organic thixotropic agent or an inorganic thixotropic agent, preferably a thixotropic agent selected from the group consisting of hydrogenated castor oil (EFKA RM 1900), hydrogenated castor oil modified by reaction with an amine, polyamide, silica, and mixtures thereof.

[0223] The silica may be fumed silica, preferably the silica may be selected from the group consisting of fumed silica, hydrophobic fumed silica, hydrophilic fumed silica, precipitated silica, and mixtures thereof, more preferably from hydrophobic fumed silica. Hydrophobic fumed silica can also act as a filler. Hydrophobic fumed silica is commercially available from Evonik under the trade name Aerosil® R202.

[0224] The composition may contain 0 to 10% by weight, preferably 2.5 to 8% by weight, more preferably 3 to 6% by weight, of a thixotropic agent based on the total weight of the composition.

[0225] The composition may contain a photoinitiating system, i.e., a source of photoinitiators. The photoinitiator promotes photopolymerization. The terms "photoiniator", "photoinitiator system", "photoinitiating system", and "source of photoinitiators" are currently used synonymously. A suitable photoinitiating system, some of which contains radical photoinitiators, is disclosed in PCT Application No. WO2017 / 021785A1. The photoinitiating system is particularly an anionic or zwitterionic photoinitiating system, i.e., a photoinitiating system suitable for promoting anionic or zwitterionic polymerization. The expressions "an anionic or zwitterionic photoinitiating system" and "a photoinitiating system suitable for promoting an anionic or zwitterionic polymerization" are currently used synonymously.

[0226] A suitable photoinitiating system (source of photoinitiators) contains a metallocene component (also called a "synergist"), preferably a metallocene compound selected from the group consisting of "sandwich compounds" such as ferrocene compounds, ruthenocene compounds, bis(cyclopentadienyl)osmium compounds, their derivatives, and mixtures thereof, and preferably the metallocene compound is a ferrocene compound, its derivatives, and mixtures thereof. The ferrocene compound is TIFF2025518781000043.tif35170(wherein R 1 is hydrogen or a C 1-4 alkyl group, and one or more R 1 are present in one or both of the rings). Suitable ferrocene compounds are disclosed in U.S. Pat. Nos. 5,824,180 and 6,503,959.

[0227] This preferred photoinitiator system (photoinitiator source) also contains additional photoinitiators.

[0228] The additional photoinitiators may be selected from the group consisting of phenyl-substituted acylphosphines, alpha-diketones, thioxanthones, alpha-hydroxyketones, benzyldimethylketal, phenylglyoxylate, camphorquinone, acylgermanium compounds, dialkylsilylglyoxylates, and mixtures thereof. The additional photoinitiators are particularly useful for increasing the polymerization rate of cyanoacrylate-based monomers.

[0229] The acylgermanium compound is, hereinafter, namely, TIFF2025518781000044.tif33170 (wherein R 2 is a methyl group or a phenyl group), TIFF2025518781000045.tif59170 (wherein R 3 is hydrogen or a methoxy group), and can be one of their mixtures.

[0230] Suitable additional photoinitiators are, in the case of phenyl-substituted acylphosphines, Irgacure® 819 (BASF) or Darocur® TPO (BASF), in the case of alpha-hydroxyketones, Irgacure® 184 / 500 / 2959 (BASF) or Darocur® 1173 (BASF), in the case of benzyldimethylketal, Irgacure® 651 (BASF), in the case of phenylglyoxylate, Irgacure® 754 (BASF) or Darocur® MBF (BASF), are commercially available under the name, in the case of camphorquinone, from Sigma-Aldrich Merck, in the case of acylgermanium compounds, from Ivoclar KGaA&AC Co under the name Ivocerin™, and in the case of dialkylsilylglyoxylates, from Sigma-Aldrich Merck.

[0231] Others The present invention also relates to the use of at least one starting material R having a bio-carbon content of more than 0% for the preparation of a compound of formula (I): TIFF2025518781000046.tif33170(wherein R1 is H or an organic moiety), and the compound of formula (I) has a bio-carbon content of 20% or more.

[0232] All descriptions, embodiments, and preferred features regarding the compound of formula (I) described above (in the "Compound" paragraph) apply to the use herein and will not be repeated.

[0233] The starting material R preferably has a bio-carbon content of 41% or more, more preferably 50% or more. Even more preferably, the starting material R has a bio-carbon content of 65% or more, more preferably equal to 100%.

[0234] The starting material R may be selected from the group consisting of acetic acid, ethanol, n-heptanol, isobutanol, n-butanol, 1,10-decanediol, and tetrahydrofurfuryl ethanol, preferably ethanol and n-heptanol, and even more preferably n-heptanol.

[0235] The present invention relates to a compound of formula (I) as described herein, and the compound of formula (I) is derived from an alcohol compound having a bio-carbon content equal to 100%, and the alcohol is preferably ethanol or heptanol.

[0236] All descriptions, embodiments, and preferred features regarding the compound of formula (I) described above (in the "Compound" paragraph) apply herein and will not be repeated.

[0237] Advantageously, the compound of formula (I) is at least partially derived from raw materials of renewable origin.

[0238] The compound of formula (I) advantageously exhibits good adhesive properties and a good time to fixation.

[0239] The compound of formula (I) can advantageously be produced in industrially good yields.

[0240] The compound of formula (I) in which R1 is a C6 alkyl group (and / or a composition containing it) advantageously exhibits even higher hot water resistance (e.g., 60 °C).

[0241] The compound of formula (I) in which R1 is a C6 alkyl group (and / or a composition containing it) advantageously exhibits a strength retention rate of over 80% even after being completely immersed in hot water (60 °C) for 3 to 10 days according to the test method disclosed below in the experimental section.

[0242] The compound of formula (I) in which R1 is a C6 alkyl group (and / or a composition containing it) advantageously exhibits very low blooming according to the test method disclosed below in the experimental section.

[0243] The ranges disclosed in this specification include both their lower and upper limits. For example, the expression "range of x to y" or "x to y" includes the limiting values x and y.

Examples

[0244] In the examples, the following components were used. - Acetic acid, bio-based acetic acid, commercially available from Sekab - Cyanoacetic acid, manufactured by Sigma-Aldrich - Bromoacetic acid, manufactured by Sigma-Aldrich - Sulfuric acid, hydrochloric acid, manufactured by Scharlab - Phosphorus tribromide, manufactured by Sigma-Aldrich - Bromine, manufactured by Sigma-Aldrich - Sodium carbonate, manufactured by Sigma-Aldrich - Sodium thiosulfate, manufactured by Sigma-Aldrich - Diethyl ether, toluene, ethyl acetate, manufactured by Scharlab - Potassium cyanide, manufactured by Sigma-Aldrich - Bio-based ethanol with a purity of 99.5%, manufactured by Myhome aromas - Petroleum-based ethanol, manufactured by Ineos - Methylene diacetate, manufactured by CMC - Linear dodecylbenzenesulfonic acid, LABSA (CAS 27176-87-0), manufactured by Henkel - 2-Methylpiperazine, manufactured by Sigma-Aldrich - Piperidine, manufactured by Sigma-Aldrich - 2,2’-Methylenebis(4-methyl-6-tert-butylphenol), manufactured by TCI - Paraformaldehyde, manufactured by Sigma-Aldrich - Piperidine, manufactured by Sigma-Aldrich - Bio-based heptanol with a purity exceeding 99%, manufactured by Arkema Oleris - Methyl cyanoacetate, manufactured by Hebei - Titanium isopropoxide, manufactured by Sigma-Aldrich - p-Toluenesulfonic acid, manufactured by Sigma-Aldrich - Phosphorus pentoxide, manufactured by Sigma-Addrich - Hydroquinone, manufactured by TCI - Bio-based tetrahydrofurfuryl alcohol, manufactured by Pennakem - Dibenzo-18-crown-6 DBC (18 c-6), manufactured by Ferak Berlin GmbH - EFKA RM 1900, manufactured by BASF (100% bio-based as analyzed by ASTM D6866) - Butylhydroxyanisole (BHA), manufactured by TCI - Vinnol H40 / 60, manufactured by Wacker - Tetrahydrofurfuryl alcohol (Viridisol® T, Pennakem) - MSA, manufactured by Sigma Aldrich - SO2, manufactured by carburos metallicos

[0245] Among these components, n - heptanol (manufactured by Arkema Oleris), ethanol (manufactured by Myhome aromas), acetic acid (manufactured by Sekab), tetrahydrofurfuryl alcohol (Viridisol® T, Pennakem), and EFKA RM 1900 are bio - based materials (100% bio - carbon content).

[0246] The bio - based content or bio - carbon content is determined using the standards ASTM D 6866 (ASTM D 6866 - 21, Method B) and ASTM D 7026 (ASTM D 7026 - 04). The ASTM D 6866 standard is "Determination of the Bio - based Content of Natural - range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry", while the ASTM D 7026 standard is "Sampling and Reporting of Results for the Determination of the Bio - based Content of Materials by Carbon Isotope Analysis". The second standard references the first standard in its first paragraph.

[0247] The first standard describes a test for measuring the 14 C / 12 C ratio of a sample, and by comparing it with the 14 C / 12 C ratio of a reference sample of 100% renewable origin, it gives the relative proportion of renewable - origin C in the sample. This standard is based on the same concept as 14 C dating but does not apply the dating equation.

[0248] The ratio calculated in this way is called "Percent Modern Carbon" (pMC). If the material to be analyzed is a mixture of bio - based material (without radioactive isotopes) and fossil material, the obtained pMC value is directly correlated with the amount of bio - based material present in the sample.

[0249] The current C-14 standard (oxalic acid II) represents what the current (living plant) C-14 activity was in 1950, which is set as the standard for 100% bio-based activity. The baseline concentration subtracted from the measured activity is also established. The activity of this sample is compared to the activity of oxalic acid II. This gives the pMC or percent of current carbon. If there is a mixture of current carbon and fossil carbon in the sample, the resulting pMC (Example 85 pMC) indicates that the activity of the current standard was measured at 85%. This sample is reported as 85% bio-based carbon. Due to nuclear tests in the atmosphere in the 1950s and 1960s, C-14 was artificially created in the atmosphere. At one point, this was nearly 200% of the natural activity. As time passed, dilution of fossil fuel CO2 advanced in the atmosphere, and this activity was diluted, and the current C-14 activity in the atmosphere has returned to the same level as the modern standard. There is an atmospheric correction factor used to account for these changes in the C-14 activity in the atmosphere. This atmospheric correction factor (REF) was used as follows. Bio-carbon content = pMC / (REF), where REF = 1.000 in this case. The accuracy of the bio-carbon content percentage is + / - 3% (absolute value).

[0250] 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 applied from a previously reported procedure (T.M. Werkhoven et al., Eur. J. Org. Chem. 1999, 2909 - 2914). A mixture of biosource acetic acid (4.0 g, manufactured by Sekab) and PBr3 (18 g) was mixed at 0 °C, and then bromine (24.4 g) was added. After the evolution of HBr ceased, the reaction mixture was heated at 75 °C for 2.5 hours. The reaction was cooled with water. Diethyl ether and a Na2S2O3 solution were added. This aqueous layer was extracted with diethyl ether. Evaporation of the solvent gave 9.11 g (yield 98%) of bio-based bromoacetic acid.

[0251] Example 1b Method for preparing cyanoacetic acid (corresponding to the compound of formula (V)) This step was applied from the 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 potassium cyanide solution (3.27 g) was poured into the reaction mixture. The mixture was heated for 2 hours until it reached 80 °C and then stirred at room temperature (23 °C) for an additional 15 hours. Concentrated HCl (10 mL) was added until the pH reached 1. The solvent was removed and the solid residue was extracted with diethyl ether. The remaining salt was filtered and washed with additional diethyl ether. The filtrate was evaporated to obtain the bio - based cyanoacetic acid (4.28 g, 100% yield). This step was repeated several times to obtain a larger amount of bio - based cyanoacetic acid.

[0252] Example 1c Method for preparing cyanoacetate (corresponding to the compound of formula (II)) A mixture of the cyanoacetic acid (50.0 g) obtained in Example 1b, biosource EtOH (200 ml, manufactured by 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 with sufficient purity for the next step.

[0253] Example 1d Method for preparing cyanoacrylate (corresponding to the compound of formula (I)) Into a four-necked flask equipped with a stirrer, thermometer, water trap, and dropping funnel, 60 parts of paraformaldehyde, 200 parts of toluene, and 0.2 part of piperidine were charged. While stirring 314 parts of the bio-based ethyl cyanoacetate obtained in Example 1c, it was added dropwise to the mixture at 80 °C to 90 °C. After completion of the dropwise addition, while removing the water generated by the reaction, the mixture was reacted under reflux until all of the theoretical amount of water was distilled off. Then, the reaction mixture was cooled to room temperature. To the resulting condensation mixture having a viscosity of 200 centipoises, 300 parts of a 1% aqueous solution of p-toluenesulfonic acid was added. After shaking the mixture at 70 °C, it was allowed to stand and separated into two layers. The oil layer was taken out.

[0254] The oil layer was distilled under reduced pressure to remove toluene. To the condensate remaining in the pot, 3 parts each of phosphorus pentoxide and hydroquinone were added. The mixture was heated at 150 °C to 200 °C under a pressure of 8 to 20 mmHg for depolymerization to obtain 266 parts (yield 83%) of crude monomer. The purity of the crude monomer was 96.8%.

[0255] After adding 0.5% of phosphorus pentoxide and 0.5% of hydroquinone to the crude monomer, the resulting mixture was redistilled to obtain 220 parts of bio-based ethyl cyanoacrylate.

[0256] Example 2 Preparation of Ethyl Cyanoacrylate (Method P2) Example 2a Preparation Method of Cyanoacetate (Corresponding to the Compound of Formula (II)) A mixture of cyanoacetic acid (50.0 g, manufactured by Sigma Aldrich), bio-based EtOH (200 ml, manufactured by 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 with sufficient purity for the next step.

[0257] Example 2b Method for preparing cyanoacrylate (corresponding to the compound of formula (I)) A mixture of the bio-based ethyl cyanoacetate (59.2 g) obtained in Example 2a, methylene diacetate (138.2 g), linear alkylbenzene sulfonic acid (20.9 g, LABSA, dodecylbenzene sulfonic 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, was obtained by distillation under reduced pressure (52.3 g, 80% yield).

[0258] Example 3 Preparation of n-heptyl cyanoacrylate Example 3a Preparation of n-heptyl cyanoacetate (corresponding to the compound of formula (II)) A mixture of biosourced n-heptanol (250 g, manufactured by Arkema Oleris), methyl cyanoacetate (212 g, commercially available from HEBEI), and titanium isopropoxide (0.61 g) was heated to 120 °C for 3 hours under a residual pressure of 100 mbar. When the stripping of methanol was completed, the reaction was stopped, and the bio-based n-heptyl cyanoacetate was obtained by distillation under reduced pressure (360 g, 92% yield).

[0259] Example 3b Preparation of n-heptyl cyanoacrylate (corresponding to the compound of formula (I)) A mixture of the bio-based n-heptyl cyanoacetate (300 g) obtained in Example 3a, methylene diacetate (432 g), linear dodecylbenzene sulfonic 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 was obtained by distillation under reduced pressure (226 g, 76% yield). The resulting mixture was redistilled to obtain 180 g of bio-based n-heptyl cyanoacrylate.

[0260] Example 4 (Comparative Example) Preparation of Ethyl Cyanoacrylate A mixture of cyanoacetic acid (50.0 g, manufactured by Sigma - Aldrich, petroleum - based), petroleum - based EtOH (200 ml, manufactured by 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 with sufficient purity for the next step.

[0261] A four - necked flask equipped with a stirrer, thermometer, water trap, and dropping funnel was charged with 60 parts of paraformaldehyde, 200 parts of toluene, and 0.2 part of piperidine. 314 parts of ethyl cyanoacetate (obtained above in this Example 4) was added dropwise to the mixture at 80°C to 90°C while stirring. After the addition was complete, the mixture was reacted under reflux while removing the water generated by the reaction until all of the theoretical amount of water was distilled off. Then, the reaction mixture was cooled to room temperature. 300 parts of a 1% aqueous solution of p - toluenesulfonic acid was added to the resulting condensation mixture with a viscosity of 200 centipoises. The mixture was shaken at 70°C, then allowed to stand and separated into two layers. The oil layer was taken out.

[0262] The oil layer was distilled under reduced pressure to remove toluene. 3 parts each of phosphorus pentoxide and hydroquinone were added to the condensate remaining in the pot. The mixture was heated at 150°C to 200°C under a pressure of 8 - 20 mmHg for depolymerization to obtain 266 parts of crude monomer (yield 83%). The purity of the crude monomer was 96.8%.

[0263] After adding 0.5% of phosphorus pentoxide and 0.5% of hydroquinone to the crude monomer, the resulting mixture was redistilled to obtain 220 parts of ethyl cyanoacrylate.

[0264] Example 5 Preparation of Tetrahydrofurfuryl Cyanoacrylate Example 5a (Preparation of tetrahydrofurfuryl cyanoacetate (corresponding to the compound of formula (II))) A mixture of biosource tetrahydrofurfuryl alcohol (306 g, Viridisol® T, Pennakem), methyl cyanoacetate (297 g, commercially available from Hebei), and titanium isopropoxide (0.853 g) was heated to 130 °C for 2 hours under a residual pressure of 150 mbar. When the stripping of methanol was completed, the reaction was stopped, and the biobased tetrahydrofurfuryl cyanoacetate was obtained by distillation under reduced pressure (383 g, 76% yield).

[0265] Example 5b (Preparation of tetrahydrofurfuryl cyanoacrylate (corresponding to the compound of formula (I))) A mixture of the biobased 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 was obtained by distillation under reduced pressure (64 g, 46% yield).

[0266] 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-based), NaBH4 (300 g, 7.92 mol), and (tetraphenylporphinato)rhodium(III) chloride ((TPP)RhCl, 4.0 g, 6 mmol) in THF (2 l) was stirred at 20 - 25 °C for 50 hours in dry air. The formation of the oxygenated product was monitored by gas chromatography. A total yield of 65% was obtained by the reaction. After cooling with water, the mixture containing n-heptanol was recovered pure by distillation (1 mbar, 70 °C, boiler temperature about 110 °C).

[0267] This synthesis was applied from Aoyama et al., J. Org. Chem., 1987, 52, 2555 - 2559.

[0268] Example 6b Preparation of heptyl cyanoacetate A mixture of the mixture (300 g) obtained in Example 6a, methyl cyanoacetate (254.4 g, commercially available from HEBEI), and titanium isopropoxide (0.73 g) was heated to 120 °C for 6 hours under a residual pressure of 90 mbar. When the stripping of methanol was completed, the reaction was stopped, and heptyl cyanoacetate was obtained by vacuum distillation (410 g, yield 87%).

[0269] Example 6c Preparation of heptyl cyanoacrylate A mixture of heptyl cyanoacetate (360 g) obtained in Example 6c, 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) was heated to 125 °C for 2.5 hours. The desired product was obtained by vacuum distillation (257.6 g, yield 72%). The resulting mixture was redistilled to obtain 210 g of heptyl cyanoacrylate (petroleum - based).

[0270] Example 7 Preparation of butyl cyanoacrylate (comparative example - petroleum - based) Example 7a Preparation of n - butanol from butane (D) Complex [V(O)(Cl)(PBHA)2] in acetonitrile (1 l) in a sealed container, PBHA -To a solution of N-phenylbenzohydroxamic acid (catalyst, 9.8 mg, 18.8 mmol), butane (petroleum-based, 111.0 g, 1.91 mol) was bubbled. Then, when 30% H2O2 (300 ml, 2.65 mol) was added to the above solution, the resulting solution changed to yellow. Another 300 ml of H2O2 was added little by little (50 ml × 6 times) over 3 hours. Then, the solution was heated (in an oil bath) and refluxed for 8 hours (85 °C). The reaction mixture was cooled to room temperature and extracted with 1 l of diethyl ether. The extract was concentrated and recovered to purity by distillation (20 mbar, 50 °C, boiler temperature about 100 °C).

[0271] This synthesis was applied from Si et al., J. Mol. Catal. A Chem., 2004, 219, 241 - 249.

[0272] Example 7b Preparation of butyl cyanoacetate A mixture of the extract (300 g) obtained in Example 7a, methyl cyanoacetate (401 g, commercially available from HEBEI), and titanium isopropoxide (1.15 g) was heated to 90 °C for 24 hours under a residual pressure of 90 mbar. When the stripping of methanol was completed, the reaction stopped, and butyl cyanoacetate was obtained by distillation under reduced pressure (432 g, yield 75%).

[0273] 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 was obtained by distillation under reduced pressure (255 g, yield 70%). The resulting mixture was redistilled to obtain 210 g of butyl cyanoacrylate (petroleum-based).

[0274] Example 8 Preparation of n-Butyl Cyanoacrylate Example 8a Preparation of n-Butyl Cyanoacetate A mixture of bio-based n-butanol (300 g, manufactured by Green biologics), methyl cyanoacetate (401 g, commercially available from HEBEI), and titanium isopropoxide (1.15 g) was heated to 90 °C for 24 hours under a residual pressure of 90 mbar. When the stripping of methanol was completed, the reaction was stopped, and n-butyl cyanoacetate was obtained by vacuum distillation (439 g, yield 76%).

[0275] 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 was obtained by vacuum distillation (255 g, yield 70%). The resulting mixture was redistilled to obtain 210 g of bio-based n-butyl cyanoacrylate.

[0276] Example 9 Results The following table clarifies the bio-carbon content analysis and long-term instant adhesion properties of selected molecules, especially during the shelf life (simulating the typical time before using the cyanoacrylate instant adhesive, accelerated degradation after 3 days at 82 °C).

[0277] Method for measuring the time FT until fixation: The fixture time (FT) is the time it takes for an adhesive droplet applied on a 250 mm2 surface to withstand a load of 3 kg for 10 seconds at room temperature (23 ± 2 °C) under 50% relative humidity (RH). FT was measured with mild steel (MS) lapshear. These lapshears had dimensions of 100 × 25 × 1, 5 mm and were manufactured by Rocholl.

[0278] The fixture time is measured after 3 days at 82 °C (3d82 °C) of forced degradation in an aluminum-uncoated tube. In fact, this accelerated degradation represents a good way to estimate the reactivity of the cyanoacrylate adhesive during its shelf life when it reaches the end customer (3d82 °C corresponds to approximately 9 - 15 months depending on the formulation and packaging).

[0279] As done by many in the art, this also evaluates the precise reactivity in bio-based and non-bio-based butyl cyanoacrylate monomers by observing the time required for the entire curing of a standard sample in response to an initiator (method disclosed in International Publication No. WO2015150882).

[0280] For this purpose, the initiator was prepared as a solution of N - oxy - diethylene benzothiazole - 2 - sulfenamide in a non - nucleophilic solvent. A certain amount of this solution was added to the monomer and mixed thoroughly. Subsequently, a thin wooden stick with a diameter of 2 mm was introduced into the mixture and physically moved up and down by hand until the mixture did not flow and the stick was trapped in the polymerized adhesive. Since the initiator is neutralized by any acid present in the medium, the time it takes for complete polymerization to occur will indicate the reactivity of the monomer. The longer the time required to obtain complete polymerization, the slower the reactivity of the monomer. TIFF2025518781000047.tif132170*Accuracy is + / - 3% (absolute value) **Ratio of bio - based carbon expected in the molecule to the total carbon. n.d.: Not performed

[0281] Advantageously, the cyanoacrylate of Example 3 having a biocarbon content of 65% shows a shorter time to fixation than its petroleum-based counterpart. For example, the bio-based n-heptyl cyanoacrylate of Example 3 is 25 seconds, while the petroleum-based heptyl cyanoacrylate of Comparative Example 6 is 90 seconds. The same is true for the reactivity measurement. The reactivity of the bio-based n-butyl cyanoacrylate of Example 8 is 80 seconds, while the reactivity of the petroleum-based butyl cyanoacrylate of Comparative Example 7 is 180 seconds.

[0282] Example 9 Preparation of Adhesive Compositions C1 and C2 The following C1 and C2 adhesive compositions were prepared as follows according to the properties and contents of the components disclosed in Table 1. The monomers were directly mixed with radical and acid stabilizers (excluding sulfur dioxide) in a high-density polyethylene container, and the mixture was heated to about 60 °C. Then, a thickening agent was added under mechanical stirring until completely dissolved as reported in International Publication No. WO2016038514. The mixture was kept cooled to about 40 °C, and the remaining components containing sulfur dioxide were added if present. TIFF2025518781000048.tif118170

[0283] The tensile shear strength test data reflect the joint strength measured in MPa after assembling overlapping lap shear specimens (standard test specimens of grit blasted mild steel (GBMS)) having a contact area of 250 mm2, measured according to ASTM D1002. After assembly before the test, the joined lap shear specimens were first fixed with a clamp and "rested" at room temperature (23 °C ± 2 °C) for 24 hours. The test was carried out using an Instron tensile testing machine operating at a crosshead speed of 1.3 mm / min.

[0284] The hot water resistance test conducted on the assembled GBMS lap shear specimens was carried out by completely immersing them in hot water (60 °C) for 3 days and 10 days, then allowing them to stand at room temperature for 24 hours and testing them destructively.

[0285] Blooming was qualitatively evaluated by placing droplets of the adhesive composition on black ABS in an oven at 98% HR / 40 °C. The more vapor generation polymerization around the droplets, the greater the blooming. TIFF2025518781000049.tif18170

[0286] Composition C1 also advantageously exhibits extreme resistance to warm water (60 °C) and very low blooming.

[0287] Example 10 Detection of Bio-based Compositions Example 10.1 Beta Attenuation Count Using a Geiger Counter with a Screen Wall The first method for detecting the amount of adhesive is inspired by the oldest C14 dating technique, as reported in "W.S. Broecker, in Treatise on Geochemistry, 2007" or "ARTIFICIAL PRODUCTION OF 14C FROM NUCLEAR WEAPON TESTS AND ITS UPTAKE BY MAN", ProQuest 11018029, December 1974. A Geiger counter with a screen wall is used to count the C14 attenuation through beta-emitting particles.

[0288] For volume curing purposes, a formulation according to Example C1 of Example 9 (60% bio-based content) was prepared using 200 ppm of ferrocene (manufactured by Sigma Aldrich) and 750 ppm of iboserine (manufactured by Sigma Aldrich). The comparative formulation contains C3 with a similar formulation except that it contains petroleum-based heptyl cyanoacrylate of Comparative Example 6.

[0289] The Ranger EXP Geiger Counter was used with very low sensitivity in the beta-ray part.

[0290] Two mild steels (manufactured by Rocholl) wrapsias are arranged at a distance of about 15 mm from each other, with an overlap of 250 mm2, and there is a steel spacer with a thickness of 15 mm, forming a well. The blank CPM (counts per minute) was recorded for about 30 minutes. One measurement was performed for 30 minutes per sample.

[0291] In the first part, the weights of the C1 composition added to the well were 1 g, 2 g, and 4 g, and were photocured for 60 seconds using a 405 nm lead (20 mW / cm2) to form a strong adhesive bond.

[0292] Next, an unknown amount of C1 and the comparative example C3 adhesive were inserted into the well. Using linear regression of the calibration curve, it was possible to detect that there was approximately 2.8 g of the bio-based adhesive present in the well, while the comparative example C3 composition (petroleum-derived) was undetectable. TIFF2025518781000050.tif43170

[0293] Example 10.2 Liquid Extraction / Liquid Scintillation Counting (LSC) A more sensitive scintillation method was used. Liquid Scintillation Counting (LSC) was performed as used in the ASTM D6866-12 guidelines. As an easy method, the method described in "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" was used. Toluene (99.5% or more, petroleum / fossil-based) was used as the extraction medium. A Hidex 600 SL LSC was used.

[0294] Composition C1 and the composition C3 of the comparative example were used.

[0295] Two mild steels (manufactured by Rocholl) wrapsias were used. Precise amounts of C1 (0 (blank), 30 mg, 50 mg, 70 mg) were weighed onto the first wrapsia and then bonded firmly for 24 hours. Then, the adhesive was broken in a peel test to open the wrapsia with respect to the adhesive. Toluene was used to extract the adhesive in the solvent and proceeded directly to LSC.

[0296] Then, unknown amounts of C1 and C3 of the comparative example were used between the wrapsias.

[0297] Using linear regression of the calibration curve, it was possible to detect that there was a bio-based adhesive of about 62 mg present between the bonded wrapsias, but no signal was detected for C3. TIFF2025518781000051.tif39170

[0298] Example 10.3 Solid combustion / Accelerated Mass Spectrometry (AMS) Finally, the most sensitive method for C14 detection was used. Accelerated Mass Spectrometry (AMS) was carried out as used in a method directly inspired from ASTM D6866-12 guidelines and (https / / www.radiocarbon.com / accelerator-mass-spectrometry.htm, Introduction to Radiocarbon Determination by the Accelerator Mass Spectrometry Method).

[0299] Two mild steels (manufactured by Rocholl) wrapsias were used. Precise amounts of C1 (0 (blank), 10 mg, 20 mg, 30 mg) were weighted on the first wrapsia and then firmly joined for 24 hours. As an easy method, the assembly was burned at 900 °C to 1000 °C to form CO2, which was then graphitized and analyzed for 14 C content in AMS.

[0300] Then, unknown amounts of C1 and C3 were used between the wrapsias. Using linear regression of the calibration curve, it was possible to detect that there was approximately 62 mg of bio-based adhesive present between the joined wrapsias, but no signal was detected for C3. TIFF2025518781000052.tif35170

[0301] An important aspect of sustainable joining is to use a highly reliable industrial joining method that ensures that each component to be joined is dispensed with sufficient adhesive. Current solutions include simple weight measurements (weighing before and after the joined assembly), but that solution is difficult to handle because no joining piece can be adapted to a precise laboratory scale (the typical amount of cyanoacrylate adhesive used is 5 - 15 mg). Another common solution on the market, especially for solving routine quality checks, is the presence of dyes / UV traces in cyanoacrylate adhesives. This solution is still not 100% quantitative (more qualitative) and is only effective for transparent assemblies (e.g., joining of transparent needles).

[0302] As demonstrated above, when the composition of the present invention contains the compound of formula (I), an innovative composition for sustainable joining can be more easily detected.

Claims

1. Compound of formula (I): A compound of formula (I) (wherein R1 is H or an organic part) having a biocarbon content of 20% or more.

2. The compound according to claim 1, having a biocarbon content of 25% or more.

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

4. The compound according to claim 1, wherein R1 is selected from the group consisting of H, alkyl, alkyl halide, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, acrylic acid ester moiety, oxetane moiety, epoxy moiety, and carboxylic acid ester moiety.

5. The following equations (I-A), (I-B), or (I-C): (In the formula, R1a is alkyl.) (In the formula, R1b is selected from H, alkylsilane, acetoxysilane, alkenyl, alkynyl, aryl, heteroaryl, alkaryl, aralkyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, alkoxyalkyl, oxetane moiety, and epoxy moiety, and preferably R1b ​​is selected from cycloalkyl, aralkyl, heteroaryl, heterocycloalkyl, and alkoxyalkyl.) (In the formula, R1c is selected from the acrylic acid ester moiety and the carboxylic acid ester moiety.) Having one of the following, preferably having formula (I-A) or (I-B) The compound according to claim 1, characterized in that it is a compound according to claim 1.

6. The compound according to claim 1, wherein R1 is selected from alkyl groups and heterocycloalkyl groups.

7. The compound according to claim 1, wherein R1 is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group.

8. The compound according to claim 1, wherein R1 is a C6 alkyl group.

9. The compound according to claim 1, characterized in that it is n-butylcyanoacrylate or n-heptylcyanoacrylate.

10. A method for preparing the compound of formula (I) described in claim 1.

11. Cyanoacetate of formula (II): The method according to claim 10, comprising the step of converting (wherein R1 is as defined in claim 1) into a compound of formula (I).

12. The aforementioned method, - Compound of formula (II) Step S1 includes a condensation reaction with a formaldehyde derivative; then, - An optional step S2, which includes washing the product obtained in step S1; - Step S3 includes depolymerizing the product obtained in step S1 or S2 in order to provide a compound of formula (I); -Optional step S4: Purify the compound of formula (I) obtained at the end of step S3. The method according to claim 10, including the method described in claim 10.

13. The method described above is - In the presence of a catalytic amount of ammonium salt or iminium salt (XI), the compound of formula (II): and the compound of formula (X): A process that includes a reaction with, In the formula, E is (CH ２ X) ｍ Here, m is between 1 and 20, X is O or S, and 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 as follows: G is selected from the following functional groups: G and F are selected independently of each other. R5 and R6 are independently selected from the functional group H, linear or branched C1-C4 alkyl, C1-C4 alkyl halide, carboxysubstituted C1-C4 alkyl, C3-C10 cycloalkyl, aryl, and heterocycloalkyl, or When n=1, F is (CH ２ ) ｖ (CHR7) ｖ (CR7R8) ｖ The formula may be bonded to G via one R7 group selected from, where v is in the range of 1 to 6, preferably in the range of 1 to 4, more preferably v is 1, and R7 and R8 are the same or different C1 to C4 alkyl groups, and the step is as follows: - An optional step of isolating the obtained compound (II) and The method according to claim 10, including the method described in claim 10.

14. The compound of formula (II) is obtained through the following processes P-A, P-B, P-C, P-D, or P-E, i.e., - Preparation process P-A of the compound of formula (II), - Contacting a compound of formula (III) and 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 claim 1) (In the formula, R2 = NRR', and each of R and R' is independently either H or an alkyl group.) - Process P-A, which optionally includes separating the compound of formula (II) therefrom. - Preparation process P-B of the compound of formula (II), - Contacting the compound of formula (V) with the compound of formula (IV) under conditions sufficient to produce the compound of formula (II), (wherein R1 is as defined in claim 1) - Process P-B, which optionally includes separating the compound of formula (II) therefrom. - Preparation process P-C of the compound of formula (II), - Contacting the compound of formula (II') with the compound of formula (IV) under conditions sufficient to produce the compound of formula (II), (In the formula, R'1 is an organic part different from H or R1, and R1 is as defined in claim 1.) - Process P-C, which optionally includes separating the compound of formula (II) therefrom. - Preparation process P-D of the compound of formula (II), - Contacting the compound of formula (VIII) with the compound of formula (IV) under conditions sufficient to produce the compound of formula (II), (In the formula, R1 is as defined above for formula (I)) (In the formula, R3 is Br, Cl, or I) - Process P-D, which optionally includes separating the compound of formula (II) therefrom. - Preparation process P-E of the compound of formula (II), - Contacting the compound of formula (IX) with the compound of formula (IV) under conditions sufficient to produce the compound of formula (II), (In the formula, R1 is as defined above with respect to formula (I).) (In the formula, R4 is -O-C(=O)-R4, and R4 is selected from alkyl or aryl.) The method according to claim 11, obtained by one of processes P-E, which optionally includes separating a compound of formula (II) therefrom.

15. The method according to claim 13, wherein the compound of formula (IV) is a compound in which R1 is selected from alkyl groups and heterocycloalkyl groups, preferably R1 is a C1-C20 alkyl group, more preferably a C1-C10 alkyl group, and even more preferably a C6 alkyl group.

16. The compound of formula (V) is produced under conditions sufficient to produce the compound of formula (VI). The compound of formula (VI) is obtained by a method comprising contacting a halogen atom (wherein X represents a halogen atom, preferably Br or Cl, more preferably Br) with potassium cyanide (KCN) or sodium cyanide (NaCN), wherein the compound of formula (VI) is preferably obtained under conditions sufficient to produce the compound of formula (VI), and the compound of formula (VII) is obtained. The method according to claim 14, obtained by a method comprising contacting with a halogenating agent H.

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

18. A composition, preferably an adhesive composition, comprising the compound of formula (I) described in claim 1 in a content of preferably more than 80% by weight, more preferably 85% by weight or more, and even more preferably 90% by weight or more, based on the total weight of the composition.

19. The composition according to claim 18, having a biocarbon content of 20% or more, and more preferably 50% or more.

20. Compound of formula (I) having a biocarbon content of 20% or more The use of at least one raw material R having a biocarbon content of more than 0% for the preparation of (wherein R1 is H or an organic part).

21. The use according to claim 20, wherein the raw material R has a biocarbon content of 41% or more, preferably 50% or more, more preferably 65% ​​or more, and even more preferably equal to 100%.

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