Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
  • C07C321/22—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of rings other than six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/32—Cyanuric acid; Isocyanuric acid
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2601/00—Systems containing only non-condensed rings
  • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered
  • C07C2601/20—Systems containing only non-condensed rings with a ring being at least seven-membered the ring being twelve-membered

Definitions

• TITLE POLYTHIOL COMPOSITIONS AND PROCESS FOR THEIR PREPARATION
• the present invention relates to a process for preparing polythiol compositions, as well as to the polythiol compositions obtainable by this process.
• Polythiols are molecules of great industrial interest. For example, they are used as crosslinking agents, particularly at low temperatures.
• the molecules obtained can contain many unconverted double bonds, which generates stability problems and lowers the overall -SH function rate.
• these polythioesters are conventionally obtained by reacting a polyene with a thiocarboxylic acid, in particular thioacetic acid.
• a thiocarboxylic acid in particular thioacetic acid.
• this reaction involves the use of a large excess of thiocarboxylic acid, which must be removed before the deprotection step.
• additional steps of evaporation of this excess of thiocarboxylic acid and/or purification of the polythioesters are necessary to carry out the following deprotection step.
• rate of -SH functions is controlled, or even maximized.
• rate of -SH functions is meant the ratio of the mass of all the -SH functions / total mass of the composition.
• the present invention aims to provide an improved process for preparing polythiol compositions, the industrial implementation of which is simplified.
• the present invention aims to provide an improved process for preparing polythiol compositions by which the level of -SH functions is controlled or even maximized.
• the present invention also aims to provide improved polythiol compositions, in particular with a controlled, or even maximized, level of -SH functions.
• the present invention aims to provide trithiol compositions with a controlled, or even reduced, amount of dithiols.
• the present invention aims to provide polythiol compositions useful for the preparation of polymers, preferably thermosetting polymers.
• the present invention meets in whole or in part the above objectives.
• one pot process is meant in particular a process in which the synthesis intermediates (i.e. the polythioesters as according to the invention) are not isolated from the reaction medium to carry out the following deprotection step.
• synthesis intermediates i.e. the polythioesters as according to the invention
• one pot process has many advantages.
• step a) makes it possible to obtain a very good conversion (in particular between 90% and 100% conversion of the polyene) while avoiding using too much excess of thiocarboxylic acid.
• a significant excess of thiocarboxylic acid is conventionally used in the processes of the prior art, which represents a loss for the process and generates a large quantity of waste to be isolated and treated.
• such an excess is not compatible with a “one pot” process because it must be eliminated before the deprotection step.
• the present invention makes it possible to avoid these drawbacks, which represents an economic but also environmental advantage.
• reaction medium comprising the polythioester intermediates obtained at the end of step a) can be stirred and handled easily. It can in particular be in the form of a liquid or a suspension, slightly viscous or viscous. This avoids operability difficulties at the industrial level.
• polythiol compositions that can be obtained by the process according to the invention are new and have a controlled, or even maximized, -SH rate. They are characterized in particular by a high mass ratio as defined below. For example, in the case of a dep triene
• said mass ratio is the ratio d t i r th it i h o l ° l(s l )
• the present invention relates to a process for preparing a polythiol comprising the following steps: a) a polyene is reacted with a thiocarboxylic acid in the presence of oxygen (O 2 ) and at least one organic solvent, so as to obtain a reaction medium comprising a polythioester and said at least one organic solvent; and b) a step of deprotection of the polythioester obtained in step a) is carried out, so as to obtain a polythiol; in which step a) and step b) are carried out in one-pot synthesis.
• the present invention relates to a polythiol composition B obtained from an isocyanurate of the following general formula (I):
• alkyl is meant in particular a saturated, linear, branched or cyclic hydrocarbon radical, comprising from 1 to 10, preferably from 1 to 4, carbon atoms.
• aryl is meant in particular a cyclic (monocyclic, bicyclic or tricyclic) aromatic hydrocarbon radical comprising from 6 to 10 carbon atoms, preferably a phenyl or a naphthyl, more preferably a phenyl.
• aralkyl is meant in particular an alkyl substituted by an aryl, for example benzyl.
• x is between 3 and 10, more preferably between 3 and 6, more preferably between 3 and 5.
• Said polyene may be functionalized (i.e. comprise one or more chemical functions).
• Said polyene represents in particular a linear, branched, cyclic or branched cyclic hydrocarbon chain, which may optionally comprise one or more heteroatoms, such as halogens, silicon, oxygen, nitrogen, sulfur and/or phosphorus, and which may optionally comprise one or more chemical group(s), for example chosen from halogens, -OH, -C(O)-, amine, amide, ester, ether, urea, thioether, sulfoxide, sulfone, carbamate or thiocarbamate, preferably -OH or ether.
• Said polyene may contain between 4 and 40, for example between 4 and 30, preferably between 4 and 20, more preferably between 10 and 15, carbon atoms. It is in particular aliphatic (i.e. non-aromatic).
• they are formed from a hydrocarbon chain preferably comprising between 7 and 15 carbon atoms.
• said cycloaliphatic polyene is 1,5,9-cyclododecatriene (1,5,9-CDT or CDT hereinafter).
• cis, trans, trans-,5,9-cyclododecatriene of the following formula:
• e isocvan urate of the following general formula (I): in which R is a linear or branched hydrocarbon chain comprising at least one C C double bond, which may optionally comprise one or more heteroatom(s), such as oxygen, nitrogen, sulfur and/or phosphorus, and which may optionally comprise one or more chemical group(s) (in particular such as those mentioned above).
• R comprises between 2 and 15 carbon atoms, for example between 2 and 5 carbon atoms.
• TAIC triallyl isocyanurate
• said polyene is chosen from CDT and TAIC.
• said polyene is a triene.
• trienes include: trivinylcyclohexane, trivinylbenzene, cycloheptatriene, dimethylheptatriene, octatriene, cyclooctatriene, cyclododecatriene (CDT), triallyl isocyanurate (TAIC), triallyl cyanurate, trimethallyl isocyanurate, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, trimethylolpropane triallyl ether, and triallylamine.
• the preferred trienes according to the invention are cyclododecatriene (CDT) and triallyl isocyanurate (TAIC).
• polythiol refers to the polythiol corresponding to the starting polyene as defined above.
• polythiol are polythiols which are position isomers of the double bonds of the starting polyene.
• the polythiols according to the invention may also be called (x)thiols.
• polythioester intermediate or “polythioester” is meant the polythioester corresponding to the starting polyene.
• polythioesters are polythioesters which are position isomers of the double bonds of the starting polyene.
• step a) a polyene as defined above is reacted with a thiocarboxylic acid in the presence of oxygen (O 2 ) and at least one organic solvent, so as to obtain a reaction medium comprising a polythioester as defined above and said at least one organic solvent.
• Step a) is carried out in the presence of oxygen (O 2 ), acting here as a reaction initiator.
• Step a) can thus be carried out in the presence of air, depleted air (mixture of oxygen and nitrogen N 2 ) or a mixture of oxygen and another inert gas.
• Oxygen can be introduced into the reaction medium by any technique. Oxygen can also be added throughout step a) or not.
• oxygen is bubbled into the reaction medium, preferably in the form of depleted air.
• the depleted air is passed through a frit or diffuser which is immersed in the reaction medium.
• oxygen can be bubbled into the reaction medium and nitrogen introduced into the gas phase of the reactor (i.e. the reactor headspace).
• the oxygen flow rate may be between 0.01 and 100 nL/h, preferably between 0.05 and 10 nL/h, more preferably between 0.05 and 5 nL/h, in particular between 0.05 and 2 nL/h (normo liters/h).
• Step a) is also carried out in the presence of an organic solvent or a mixture of organic solvents.
• a polar solvent or a mixture of polar solvents is particularly chosen.
• the solvent(s) may be polar protic or polar aprotic.
• R 4 represents an alkyl as defined above.
• the alcohol is chosen from the group consisting of: methanol, ethanol, isopropanol, n-propanol, n-butanol, butan-2-ol, isobutanol, tert-butanol, more preferably ethanol.
• the amount of solvent used is generally chosen according to the desired viscosity of the reaction medium. Total or partial solubilization can be carried out by a person skilled in the art, depending on the desired viscosity of the reaction medium. Preferably, between 1 eq. and 50 molar eq., more preferably between 1 eq. and 20 eq. of solvent(s) relative to the polyene are used.
• the solvent can be added at the beginning of step a) in whole or in part. It can be added punctually in one go, in several times (semi-continuous) or gradually (continuous), during step a).
• the thiocarboxylic acid is preferably of the following general formula (II):
• Ri represents an alkyl radical, an aryl radical or an aralkyl radical as defined above.
• Ri is selected from methyl, ethyl and benzyl.
• Thioacetic acid, in which R 1 is methyl is particularly preferred according to the invention (hereinafter also referred to as ATA).
• ATA thioacetic acid
• a polythioacetate is obtained as a polythioester intermediate.
• the thiocarboxylic acid can be generated in situ (see document US 3,270,063, THOMPSON CHEMICAL CO, 1963: “Methods of making primary mercaptans”): the thioacetic acid can be produced from acetic anhydride and hydrogen sulfide, in the presence of a catalyst.
• the thiocarboxylic acid and the solvent(s) are first introduced into the reactor, then the oxygen is introduced, for example by bubbling air.
• the polyene can then be added to the reaction medium.
• the temperature of step a) may be between 5 and 80 ° C, preferably between 5 and 50 ° C, more particularly between 5 and 25°C, for example between 5 and 10°C.
• Step a) is generally carried out at atmospheric pressure.
• the molar ratio of thiocarboxylic acid to polyene double bond may be between 1 and 20, preferably between 1 and 10, for example between 1 and 5, more preferably between 1 and 3.
• Step a) allows, from a polyene, the formation of a polythioester intermediate as defined above.
• the reaction medium obtained at the end of step a) can thus comprise:
• the reaction medium can thus comprise between 10% and 85% by weight of polythioester intermediate, relative to the total reaction medium.
• the reaction medium may comprise between 15% and 90% by weight of solvent(s), relative to the total reaction medium.
• Step b) of deprotection of the polythioester intermediate obtained in step a) makes it possible to obtain a polythiol. It can be carried out by any means known to those skilled in the art. Step a) and step b) being carried out in one-pot synthesis according to the invention, it is understood that the reaction medium comprising the polythioester obtained at the end of step a) is preserved to carry out the deprotection step b). Thus, steps a) and b) are carried out in the presence of the same solvent (or mixture of solvents). It is possible to add said solvent (or said mixture of solvents) during step b). In particular, the process according to the invention does not comprise a separation step.
• Deprotection b) can be carried out by conventional methods: using a base or an acid, a Dy(OTf) 3 type catalyst (cf. Liang et al., Asian J. Org. Chem. 10.1002/ajoc.201700481) or a quaternary ammonium cyanide salt type compound (cf. US 7,173,156).
• a Dy(OTf) 3 type catalyst cf. Liang et al., Asian J. Org. Chem. 10.1002/ajoc.201700481
• a quaternary ammonium cyanide salt type compound cf. US 7,173,156.
• deprotection b) is a basic deprotection, preferably in the presence of an alcohol as defined above. It is generally carried out by adding an alkali hydroxide, preferably NaOH or KOH. The addition can be carried out dropwise.
• an alkali hydroxide preferably NaOH or KOH. The addition can be carried out dropwise.
• Deprotection step b) may also be an acid deprotection, preferably in the presence of an alcohol as defined above. It may be carried out with hydrochloric acid, methanesulfonic acid or anhydrous methanesulfonic acid. When the deprotection is acidic, it is preferred to use an alcohol as defined above as solvent.
• the sulfonic acid is preferably an organosulfonic acid, optionally anhydrous.
• the sulfonic acid can be of the following general formula (III):
• alkyl radical preferably as defined above, optionally substituted, in whole or in part, by one or more identical or different halogen atoms, or
• aryl radical preferably as defined above, optionally substituted by a saturated, linear or branched hydrocarbon chain, comprising from 1 to 4 carbon atoms.
• the halogen atom may be chosen from fluorine, chlorine and bromine.
• said alkyl may be perhalogenated, more particularly perfluorinated.
• the sulfonic acid is an alkanesulfonic acid, optionally anhydrous (in the above formula, R 2 is an alkyl).
• the sulfonic acids may be chosen from: methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, /so-propanesulfonic acid, n-butanesulfonic acid, /so-butanesulfonic acid, sec-butanesulfonic acid, te/-butanesulfonic acid, trifluoromethanesulfonic acid, para-toluenesulfonic acid, benzenesulfonic acid and mixtures of two or more of them in any proportions.
• the sulfonic acid used in the context of the present invention is methanesulfonic acid (MSA) or anhydrous methanesulfonic acid (AMSA).
• sulfonated resins of the styrene-divinylbenzene copolymer type for example Amberlyst® 15 resin, or National®.
• a polythioester for example, between 3 and 60 eq., preferably between 3 and 20 eq. (molar equivalent) of alcohol are used for a polythioester.
• Deprotection step b) can be carried out at a temperature between 10 and 100°C, preferably between 25 and 80°C, more preferably between 40 and 80°C. It is generally carried out at atmospheric pressure.
• Steps a) and b) can be carried out in the same reactor.
• a batch reactor can be used.
• Subsequent conventional recovery and/or purification steps of the polythiol obtained at the end of step b) can be carried out, depending on the desired degree of purity.
• the reaction medium when deprotection is carried out by the addition of a base, the reaction medium can then be acidified and vice versa: when deprotection is carried out by the addition of an acid, the reaction medium can be basified.
• the resulting organic phase comprising the various thiols (in particular the polythiol and the (x-l)thiols) can then be extracted and optionally concentrated.
• the polythiol obtained may be in the form of a polythiol composition as mentioned below.
• polythiol is therefore used to refer to the polythiol corresponding to the starting polyene and comprising x -SH functions.
• trimercaptocyclododecane corresponds to cyclododecatriene.
• (xl)thiol refers to a thiol corresponding to the starting polyene and comprising (x-1) -SH functions.
• (x-1)thiols There may therefore be different structures of (x-1)thiols, but they are grouped here under this general name characterizing their number of -SH functions (unless otherwise specifically mentioned). Also included are the (x-1)thiols that are position isomers of the double bonds of the starting polyene.
• Such a composition may optionally include other by-products or impurities (e.g. monothiols). It can be characterized by the mass ratio H This is the mass ratio: [polythiol corresponding to said polyene comprising x -SH functions] / [thiol(s) corresponding to said polyene comprising (x-1) -SH functions],
• a trithiol composition can be obtained from a triene, said composition comprising:
• the following dithioester can be obtained as a by-product at the end of step a):
• step b it is also possible that the deprotection is not complete.
• Composition A obtained from a cycloaliphatic polyvinyl alcohol
• composition A comprises at least 85% by weight, preferably at least 90% by weight, more preferably at least 95% by weight of said polythiol, relative to the total weight of composition A.
• the mass ratio of composition A is between 10.1:1 and 20,000:1, preferably between 10.5:1 and 20,000:1, more preferably between 15:1 and 20,000:1, for example between 15:1 and 20,000:1.
• the mass ratio of composition A is between 10.1:1 and 10,000:1, preferably between 10.5:1 and 10,000:1, more preferably between 15:1 and 1,000:1, for example between 15:1 and 500:1. Even more preferably, the mass ratio of composition A is between 10.5:1 and 1000:1.
• the preferred starting cycloaliphatic polyene is cyclododecatriene, preferably 1,5,9-cyclododecatriene, and more preferably still its cis, trans, trans-1,5,9-cyclododecatriene isomer.
• the present invention relates to a polythiol composition A obtained from cyclododecatriene as defined above, said composition comprising: trimercaptocyclododecane;
• the mass ratio [trimercaptocyclododecane / (dimercaptocyclododecene + S- [bis(sulfanyl)cyclododecyl]ethanethioate)] is notably as defined above.
• Composition B obtained from an isocvanurate type polyvinyl alcohol
• the present invention also relates to a polythiol composition B obtained from an isocyanurate of the following general formula (I) and as defined above:
• composition B comprises at least 70% by weight, preferably at least 80% by weight, more preferably at least 90% by weight of said polythiol, for example at least 95% by weight of said polythiol, relative to the total weight of composition B.
• composition B comprises less than 30% by weight, preferably less than 20% by weight, more preferably less than 10% by weight, for example less than 5%, or even less than 1% by weight of said (x-1)thiol(s), relative to the total weight of said composition B.
• mass ratio of composition B is between 2:1 and
• the mass ratio of composition B is between 2:1 and
• composition B is comprised between 10:1 and 1000:1.
• the preferred starting isocyanurate is triallyl isocyanurate.
• a polythiol composition B is obtained from triallyl isocyanurate as defined above, said composition comprising:
• the mass ratio [(1,3,5-tris(3-mercaptopropyl)-1,3,5-triazinane-2,4,6-trione) / (B1 +B2)] is notably as defined above.
• compositions are novel and therefore form part of the present invention.
• the present invention also relates to said polythiol compositions obtainable, obtained or directly obtained by the process according to the invention.
• the present invention also relates to the polythiols obtained or directly obtained by the process according to the invention.
• EXAMPLE 1 One-pot synthesis of a polythiol composition from the CDT according to the invention, with basic deprotection
• ATA thioacetic acid
• the medium is stirred at 5 ° C then 28.4 g (0.62 moles) of ethanol are quickly added. Air is bubbled into the reaction medium via a frit at a flow rate of approximately 0.4 NI / h and nitrogen is passed into the reactor headspace at a flow rate of approximately 4 NI / h.
• reaction medium is kept stirring at approximately 5°C overnight.
• a GC/FID analysis shows a total conversion of 1,5,9-cyclododecatriene. The air supply is cut off.
• reaction medium is then cooled to 20 °C and 200 g (2.03 moles) of 37% HCl are then added dropwise via a peristaltic pump into the medium.
• the organic phase comprising the thiols is withdrawn.
• the aqueous phase is extracted with 105 g (1.24 moles) of dichloromethane.
• the resulting composition includes:
• trimercaptocyclododecane - 95.87% of trimercaptocyclododecane, and - the remainder in impurities (100%).
• the polythl ° l mass ratio is 95.87 : 0.83 , or 116:1.
• EXAMPLE 2 One-pot synthesis of a polythiol composition from the CDT according to the invention, with acid deprotection (AMSA and ethanol)
• the reaction medium is kept stirring at approximately 5°C overnight.
• the air supply is cut off.
• reaction medium The temperature of the reaction medium is raised to 20°C, 85g (1.85 moles) of EtOH are added to the reaction medium. 74g of anhydrous methanesulfonic acid (0.77 moles) are added dropwise via a dropping funnel. The medium is stirred at reflux under nitrogen for 10h.
• reaction medium is then cooled to 20°C, and 154 g (0.77 moles) of a previously degassed 20% NaOH solution are then added dropwise via a peristaltic pump into the medium.
• the organic phase comprising the thiols is withdrawn.
• the aqueous phase is extracted with 105 g (1.24 moles) of dichloromethane.
• the resulting composition includes:
• the polythl ° l mass ratio is 90.60 :5.84 or 16:1.
• TAIC triallyl isocyanurate
• the reaction medium is kept stirring at 5°C for approximately 6 hours.
• a GC/FID or HPLC/UV analysis shows complete conversion of triallyl isocyanurate. The air supply is cut off.
• reaction medium is then degassed with nitrogen for 1 hour and then 115.1 g of a previously degassed 46% aqueous sodium hydroxide solution are added dropwise via a dropping funnel.
• the reaction medium is left stirring under nitrogen at 25°C for 5 hours and then cooled to 10°C for approximately 17 hours.
• reaction medium is then cooled to 20°C, and 483 g (1.32 moles) of a 10% HCl solution are then added dropwise via a peristaltic pump into the medium.
• the organic phase comprising the thiols is withdrawn.
• the aqueous phase is extracted with three times 68 g (0.80 moles) of dichloromethane.
• a polythiol composition comprising 95% by weight of trithiol corresponding to TAIC and approximately 0.2% by weight of dithiol corresponding to TAIC, relative to the total weight of the composition, is obtained.
• the mass ratio is 475:1.
• EXAMPLE 4 One-pot synthesis of a polythiol composition from the CDT according to the invention, with acid deprotection (HCl and methanol)
• the reaction medium is kept stirring at approximately 5°C overnight.
• the air supply is cut off.
• the reaction medium is brought back to 20°C, 11 19g (34.93 moles) of MeOH are added to the reaction medium.
• the medium is heated to 40°C, and 576.9g (5.85 moles) of 37% HCl are added dropwise via a peristaltic pump and then the medium is refluxed under nitrogen for 48 hours.
• reaction medium is then cooled to 20 °C, the organic phase comprising the thiols is withdrawn, and 105 g (1.24 moles) of dichloromethane are then added to the aqueous phase.
• the organic phases are combined and then washed four times with 74 g (4.11 moles) of water and then concentrated on a rotary evaporator.
• a GC/FID analysis shows a complete conversion of trithioacetate.
• a polythiol composition comprising 96.28% trimercaptocyclododecane and 0.25% dithiol(s) corresponding to the CDT is obtained.
• the polythl ° l mass ratio is 96.28 : 0.25 or 385:1.
• EXAMPLE 5 One-pot synthesis of a polythiol composition from the CDT according to the invention, with acid deprotection (HCl and ethanol)
• the air supply is cut off.
• the temperature of the reaction medium is raised to 20 °C and 1478.6 g (30.81 moles) of 96% EtOH are added to the reaction medium.
• the medium is heated to 40 °C, and 910.9 g (9.24 moles) of 37% HCl are added dropwise via a peristaltic pump. Then, the medium is refluxed under nitrogen for 22 h.
• reaction medium is then cooled to 30°C, the organic phase comprising the thiols is withdrawn and 261.7 g (3.08 moles) of dichloromethane are then added to it.
• the polythl mass ratio is 94.84 : 5.17 or 18.34:1
• EXAMPLE 6 One-pot synthesis of a polythiol composition from TAIC according to the invention, with acid deprotection (HCl and ethanol)
• the reaction medium is kept stirring at 5°C for approximately 6 hours.
• a GC/FID or HPLC/UV analysis shows complete conversion of triallyl isocyanurate. The air supply is cut off.
• the temperature of the reaction medium is raised to 20 °C and 462.1 g (9.63 moles) of 96% EtOH are added to the reaction medium.
• the medium is heated to 40 °C, and 355.8 g (3.61 moles) of 37% HCl are added dropwise via a peristaltic pump. Then, the medium is refluxed under nitrogen for 28 h.
• reaction medium is then cooled to 30°C, the organic phase comprising the thiols is withdrawn, and 102.2 g (1.20 moles) of dichloromethane are then added to it.
• HPLC/UV analysis shows complete conversion of trithioacetate.
• a polythiol composition comprising 95.16% by weight of trithiol corresponding to TAIC and approximately 0.2% by weight of dithiol corresponding to TAIC, relative to the total weight of the composition, is obtained.
• the poly mass ratio ttll ° l is td e 95.16:0.2 or 476:1.
• compositions of polythiols from triallyl isocyanurate were prepared to carry out an application test.
• the polythiol composition P1 is that obtained according to example 6.
• Polythiol composition P2 was prepared using the same protocol as described in Example 6 but using AIBN (azobisisobutyronitrile) as initiator instead of oxygen and heating in step a) to 65 °C.
• AIBN azobisisobutyronitrile
• Polythiol compositions P1 and P2 were used as hardeners of an epoxy resin (Araldite® LY 556 from Huntsman), with a tertiary amine (DABCO® 33-LV from Sigma-Aldrich) as catalyst.
• the curings were carried out at room temperature (i.e. 25°C) using a stoichiometric quantity of thiol functions relative to the epoxy functions.
• the mixtures were prepared in aluminum cups: the quantity of Araldite® LY 556, polythiol and then amine were weighed respectively. The whole was quickly mixed with a spatula. The compositions began to harden within a few minutes and were left at room temperature for 7 days.
• a bar of each hardened composition was taken and placed on the rectangular torsion equipment fixed on an ARES rheometer (Rheometer Scientific) in order to perform a Dynamic Mechanical Analysis (DMA in French and DMA in English for Dynamic Mechanical Analysis).
• the samples underwent a sinusoidal deformation at a frequency of 1 Hz over a temperature range varying from -50 to 110 °C.
• the glass transition temperature (Tg) was determined at the maximum of the mechanical loss factor (tan delta). This value as well as the value of the elastic modulus at the plateau were recorded and are summarized in the table below:
• Tg glass transition temperature
• the use of a polythiol composition P1 according to the invention in an epoxy resin therefore makes it possible to obtain a more crosslinked and denser network.
• the resin thus obtained is notably characterized by a higher Tg and plateau modulus.

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  • 2025-09-25 MX MX2025011355A patent/MX2025011355A/es unknown

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