FR3072384A1 - OLIGOCARBONATES DIMETHACRYLES OR DIACRYLES OBTAINED FROM DIANHYDROHEXITOL DIALKYLCARBONATE OR DIANHYDROHEXITOL CARBONATE DIMER, PROCESS FOR THEIR MANUFACTURE AND USES THEREOF - Google Patents

Abstract

A process for producing a dimethylcrystalline or diacrylated oligocarbonate of aromatic groups and phenolic functions, including oligolysis polyol stynthesis and a step of reacting the oligocarbonate polyol with a (meth) acrylant agent selected from methacryloyl chloride, methacrylic anhydride, methacrylic acid or acrylic acid, in order to obtain a dimethylcrystalline or diacrylated oligocarbonate ©.

Description

The present invention relates to new dimethacrylated or diacrylated oligocarbonates obtained by reaction between a dianhydrohexitol dialkylcarbonate and / or a dianhydrohexitol carbonate dimer and another diol and / or triol, under particular reaction conditions and in particular of relative amounts of the species. put into play.

It has the advantage of using a dianhydrohexitol, the bio-sourced origin of which reduces the fossil footprint of the product produced, of not using phosgene or of generating phenol like many previous solutions, these two products being dangerous for the user but also prohibited for any application with food contact, to lead to products with controlled architecture, and finally to allow with these products the manufacture of coatings particularly resistant to abrasion, scratches and UV.

Poly- or oligocarbonate diols are today well-known species, which find many applications in the manufacture of adhesives but also of various coatings such as paints, lacquers and varnishes. One of their well-known applications is the manufacture of polyurethane resin coatings. Like ethers (polytetramethylene glycol), esters (from adipate in particular), polylactone (polycaprolactone base among others), polycarbonates diols constitute one of the starting raw materials for these polyurethane resins.

If ethers have good resistance to hydrolysis, they are less resistant to light and heat. Esters exhibit diametrically opposite behavior towards these same properties. As for polycaprolactones, they are also deficient with regard to hydrolysis phenomena. It is therefore recognized that polycarbonate diols presently present the best compromise with a view to obtaining a lasting quality for the final product, in terms of resistance to hydrolysis, to heat and to light. This is particularly important for a polyurethane type coating, especially in applications such as exterior paints which are precisely exposed to the aforementioned constraints.

The manufacture of polyurethane-type materials based on polycarbonates polyols is now well described in the literature. For example, the document WO 2015/026613 describes a piston seal for a hydraulic pump, said seal being of the polyurethane type and obtained by reaction between a polycarbonate-isocyanate prepolymer, a polycarbonatepolyol, a diol and a hardening agent.

As for oligocarbonate diols, their synthesis is also well documented in the prior art. These products are prepared from aliphatic polyols which react with phosgene, bischlorocarbon esters, diaryl carbonates, these cyclic carbonates or even dialkyl carbonates. In this regard, reference may be made to document US 2005 065360.

This being the case, while seeking to guarantee an excellent level of performance for the poly- or oligocarbonate diols which it manufactures, the skilled person must today integrate new constraints, in particular of an environmental nature. The development of polymer materials from short-term renewable biological resources has indeed become a major ecological and economic imperative, faced with the depletion and rising prices of fossil resources such as petroleum. In this context, the use of dianhydrohexitols, derived from plant (poly) saccharides, as dihydroxylated monomers in polycondensation reactions, appears promising to replace monomers of petrochemical origin.

Some attempts have been made to manufacture polycarbonate diols incorporating dianhydrohexitols. As such, documents JP2014-62202 and JP 2014-80590 are known. The first describes a composition comprising a phosphorus compound, a phenolic compound and a polycarbonate diol, the latter having a number average molecular weight of between 250 and 5,000 and having a molar ratio between hydroxy groups and terminal groups at least equal to 95% . The second describes a polycarbonate diol consisting of a diol and a dianhydrohexitol chosen from isosorbide, isomannide and isoidide, and having a weight-average molecular mass of between 250 and 5,000 as determined by NMR, all by having a ratio in number of alkyloxy or aryloxy end groups to the total number of end groups greater than or equal to 5%.

However, these products are obtained by reaction between a diol and dianhydrohexitol, but also in the presence of diphenyl carbonate. Phenol is therefore generated during the synthesis of the polycarbonate diol. However, phenol is a product that is both dangerous for the user - both in terms of the product and the final application and prohibited for applications with food contact. The presence of phenol is therefore unacceptable: it must be distilled and then removed. This is clearly demonstrated by the tests illustrating the two above-mentioned patent applications.

Document EP 2 559 718 is also known, which describes the simultaneous reaction between a diol chosen from isosorbide, isomannide and isoidide, another diol, and a diester carbonate, such as diphenyl carbonate. A polycarbonate diol is therefore obtained here, but with a completely statistical architecture since the diester carbonate being very reactive, it reacts without preference both with dianhydrohexitol and the other diol. The final properties of the product, such as its resistance to hydrolysis, to light and to heat being directly related to its architecture, said polycarbonate diol will exhibit fluctuating properties depending on its final architecture. This lack of control over the level of properties cannot accommodate industrial use for the product in question.

Also, with a view to manufacturing oligocarbonate polyols advantageously using a monomer of natural origin such as a dianhydrohexitol and this, without using phosgene and without generation of phenol during the reaction, and finally while being authorized to regulate the architecture of the synthesized product, the applicant company has managed to develop the following process, consisting in reacting a dianhydrohexitol dialkylcarbonate and / or a dianhydrohexitol carbonate dimer with another diol and / or triol, to obtain oligocarbonates polyols presenting a perfectly controllable and controlled alternating architecture. A molar excess of the other diol and / or triol with respect to the dianhydrohexitol dialkylcarbonate and / or a dianhydrohexitol carbonate dimer makes it possible to obtain hydroxyl endings.

In doing so, we manage to resolve the technical constraints mentioned above. What is more, in the end, polycarbonates diol are obtained, which can be used in the manufacture of adhesives, various coatings such as paints, lacquers and varnishes. These oligocarbonate polyols can in particular be used to manufacture polyurethane resins, with particularly advantageous properties, in terms of abrasion, scratch and UV resistance.

Advantageously, the isosorbide dialkycarbonates which are involved in the reaction are produced according to the method described in patent application WO 2011/039483. This consists in reacting at least one dianhydrohexitol, at least 2 mole equivalents of a di (alkyl) carbonate and a transesterification catalyst. Unlike the methods described in the prior art, this method does not generate compounds harmful to humans or dangerous to the environment. Thus, patent application EP 2 033 981 described a synthesis whose drawback was the formation of phenol, which then had to be distilled and eliminated as a reaction by-product. As for documents US 2004/241553 and JP 06-261774, they were based on the use of toxic chloroformic esters.

summary

Also, according to a first aspect, the present invention relates to a process for the manufacture of a dimethacrylated or diacrylated oligocarbonate devoid of aromatic groups and of phenolic functions comprising:

an introduction step (1), in a reactor:

o of a monomer of formula (A1):

in which Rt and R ₂ are identical or different alkyl groups, o or of a dimer of formula (A2):

in which R ₃ and R ₄ are identical or different alkyl groups, o or a mixture of (A1) and (A2);

a step (2) of introducing, into the reactor, a diol monomer (B1) or a triol monomer (B2) or a mixture of (B1) and (B2), (B1) and (B2 ) both being different from (A1) and (A2);

the molar ratio in the reactor of (A1) and (A2) relative to (B1) and (B2) corresponding to the following formula:

, (B1) (B2) ^{<1 L} 2 ⁺ 3 ^J

J a subsequent polycondensation step (3) by transesterification of the monomers and dimers (A1), (A2), (B1) and (B2) to obtain an oligocarbonate polyol having a molar mass of less than 5000 g / mol and at least two terminations of hydroxyl type chain, a step (4) of recovery of the oligocarbonate polyol;

a step (5) consisting in reacting the oligocarbonate polyol with a (meth) acrylating agent chosen from methacryloyl chloride, methacrylic anhydride, methacrylic acid or acrylic acid, in order to obtain a dimethacrylated oligocarbonate or diacrylated.

According to a second aspect, the invention relates to a dimethacrylated or diacrylated oligocarbonate capable of being obtained by the process of the invention.

According to a third aspect, the invention relates to a formulation containing the oligocarbonate according to the invention in a crosslinked form. The crosslinking may have been carried out in any possible way, but preferably in a thermoradical or photoradical manner.

According to a fourth aspect, the invention relates to a medical prosthesis comprising a formulation according to the invention, the medical prosthesis preferably being an amalgam for dental resin.

According to a fifth aspect, the invention relates to a coating or a composite comprising a formulation according to the invention.

detailed description

By “oligocarbonate polyol” is meant any polymer comprising repeating units, formed by the reaction of monomers or dimers, linked by carbonate bonds and in particular the repeating units described above and whose chain terminations are hydroxyl functions. These repeating units are formed by reaction of the monomer (A1) and / or of the dimer (A2) with the monomers (B1) and / or (B2) already presented above.

Within the meaning of the present invention, the expression “a monomer” extends to mixtures of this monomer. In other words, the expression “a monomer (A1)” or “a monomer of formula (A1)” means that a single monomer of formula (A1) is used or else that a mixture of different monomers of formula (A1) is used. A similar meaning is given to the expressions “a monomer (A2)” or “a dimer of formula (A2)”, “a monomer (B1)” or “a monomer of formula (B1)”, or “a monomer (B2 ) ”Or“ a monomer of formula (B2) ”.

As explained above, the invention relates to a process for the manufacture of hydroxytelechelic oligocarbonates by polycondensation of the monomer (A1) and / or of the dimer (A2) and of the monomers (B1) and / or (B2).

The term “1,4: 3,6-dianhydrohexitol” or “dianhydrohexitol”, used in the present invention, includes isosorbide (obtained by dehydration of D-glucitol), isomannide (obtained by dehydration of D-mannitol) and the isoidide (obtained by dehydration of Diditol).

By “dianhydrohexitol carbonate dimer” according to the present invention, is meant a compound of formula (A2), that is to say consisting of two molecules of dianhydrohexitol monoalkylcarbonate linked together by a bivalent carbonate function. The compound therefore comprises in total two carbonate endings.

Monomers (A1) and (A2)

The monomer (A1) used in step (1) can be chosen from isosorbide dialkylcarbonate, isomannide dialkylcarbonate and isoidide dialkylcarbonate.

The monomer (A1) may contain one or more dianhydrohexitol dialkylcarbonates but preferably contains a single dianhydrohexitol dialkylcarbonate, in particular an isosorbide dialkylcarbonate, available in greater quantity and at a lower cost than the other two stereoisomers.

The alkyl groups R 1 and R ₂ carried by the monomer (A1) can comprise from 1 to 10 carbon atoms, in particular from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms, very particularly are chosen from methyl or ethyl groups.

According to one embodiment, the monomer (A1) is an isosorbide dialkylcarbonate, in particular an isosorbide diethylcarbonate or an isosorbide dimethylcarbonate.

The monomer (A1) can be obtained by using, for example, the already known processes for the manufacture of dianhydrohexitol dialkylcarbonate.

Advantageously, the monomer (A1) is prepared according to the process described in patent application WO 2011/039483 (in the name of Roquette Frères) by reacting a dianhydrohexitol with at least 2 mole equivalents of a di (alkyl carbonate) and a transesterification catalyst. The formation of dimers can be inhibited by the use of a large excess of dialkyl carbonate. This method has the advantage of not generating compounds that are harmful to humans or harmful to the environment.

One can also manufacture the monomer (A1) by reaction of dianhydrohexitol and alkyl chloroformate, these reagents being introduced into a reactor in molar proportions of 1: 2. This type of process is described for example in the document JP 06261774 to Example 5. The Applicant has been able to observe that, according to this process, only dianhydrohexitol dialkylcarbonate and no dimers are formed.

The dimer (A2) used in step (1) is a dimer of (A1). Depending on the dianhydrohexitol used, one or more conformations of dimers (A2) can be obtained.

The dimer (A2) can be chosen from an isosorbide carbonate dimer, an isomannide carbonate dimer or an isoidide carbonate dimer.

The dimer (A2) may contain one or more dimers of dianhydrohexitol carbonate but preferably contains a single dimer of dianhydrohexitol carbonate, in particular an isosorbide carbonate dimer, available in greater quantity and at lower cost than both. other stereoisomers.

The alkyl groups R ₃ and R ₄ carried by the dimer (A2) can comprise from 1 to 10 carbon atoms, in particular from 1 to 6 carbon atoms, for example from 1 to 4 carbon atoms, very particularly are chosen from methyl or ethyl groups.

According to one embodiment, the dimer (A2) is an isosorbide carbonate dimer, in particular an isosorbide ethylcarbonate dimer or an isosorbide methylcarbonate dimer.

The dimer (A2) can be produced by reacting, for example in a first step, a mole of dianhydrohexitol with a mole of alkyl chloroformate in order to form dianhydrohexitol monoalkylcarbonate, then in a second step a mole of phosgene with two moles of dianhydrohexitol monoalkylecarbonate formed during the first step.

Another possibility of manufacturing the monomer (A1) and the dimer (A2) is to use a process allowing their simultaneous synthesis. In fact, the Applicant has also developed a process making it possible to manufacture such a mixture. This process is described in detail in international application No. WO2011 / 039483.

This preparation process comprises, in order, the following steps:

(a) preparation of an initial reaction mixture containing:

- at least one dianhydrohexitol,

- at least 2 mole equivalents, based on the amount of dianhydrohexitol present, of at least one dialkyl carbonate, and

a transesterification catalyst such as, for example, potassium carbonate, (b) heating the reaction mixture to a temperature greater than or equal to the boiling point of the alcohol R-OH formed by the transesterification reaction, or higher or equal to the boiling temperature of the azeotropic mixture formed by the alcohol R-OH obtained with another of the components present in the reaction mixture, and at most equal to the boiling temperature of the reaction mixture, in a reactor equipped with 'A rectification column comprising a number of theoretical distillation plates sufficient to separate from the reaction mixture the alcohol obtained, or the azeotrope which it forms with another of the components present in the reaction mixture.

The solution obtained at the end of the process comprises a mixture of monomer (A1) and dimer (A2) with dialkyl carbonate. Distillation is carried out and the mixture of (A1) and (A2) is recovered free of dialkyl carbonate. The ratio (A1) / (A2) can be varied by modifying the initial reaction mixture: this advantageously contains from 2.1 to 100 molar equivalents, preferably from 5 to 60 molar equivalents, and in particular from 10 to 40 molar equivalents of dialkyl carbonate, based on the amount of dianhydrohexitol initially present in the reaction medium. The higher the amount of dialkyl carbonate, the higher the ratio (A1) / (A2).

For example, the Applicant has found that by reacting isosorbide and dimethyl carbonate in the presence of potassium carbonate under the conditions of the process described above, it was possible to obtain a solution comprising (A1) and (A2) with a ratio (A1) / (A2) ranging from approximately 4 (when the dialkyl carbonate / isosorbide ratio is 10) to approximately 20 (when the dialkyl carbonate / isosorbide ratio is 40).

We can then separate (A1) and (A2) by vacuum distillation techniques, for example using a scraped film evaporator.

This process for the simultaneous synthesis of (A1) and (A2) has the advantages of using less toxic reagents than the alkyl chloroformate used in the process described in document JP 06-261774 for example; synthetic co-products are also less toxic than the chlorinated species emitted during synthesis with chloroformate (methanol in the case where the alkyl is methyl, ethanol in the case where the alkyl is ethyl).

According to one embodiment, only the monomer (A1) is synthesized. Only this is introduced into the reactor in step (1), that is to say that a dimer (A2) is not introduced into the reactor.

According to another embodiment, a mixture of monomer (A1) and dimer (A2) is synthesized. This mixture is introduced into the reactor in step (1).

Monomers (B1) and (B2)

The diol monomer (B1) and the triol monomer (B2) can be chosen from aliphatic diols or triols, in particular linear or branched, or alternatively cyclic, aromatic or non-aromatic diols or triols.

In one embodiment, the diol (B1) or the triol (B2) comprise from 2 to 14 carbons.

The linear aliphatic diol (without branching) can be chosen from the following diols: ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8octanediol, 1,10 -decanediol, preferably ethylene glycol, 1,4-butanediol or 1,6hexanediol.

The linear aliphatic triol can be chosen from the following triols: glycerol, 1,2-4 trihydroxybutanol, 1,2-5 pentane diol or 1,2-6 hexanediol

The branched aliphatic diol (with non-reactive pendant chains) can be chosen from the following diols: 1,2-propanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,4 -hexanediol, 2,2-dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3propanediol or 2-methyl-1,3-propanediol.

The cyclic diol or triol can comprise one or more cycles, for example from 2 to 4 cycles, preferably 2 cycles. Each cycle preferably comprises from 4 to 10 atoms. The atoms included in the rings can be chosen from carbon, oxygen, nitrogen or sulfur. Preferably, the constituent atoms of the ring are carbon or carbon and oxygen.

The aromatic diol preferably comprises from 6 to 24 carbon atoms.

The non-aromatic cyclic diol can comprise from 4 to 24 carbon atoms, advantageously from 6 to 20 carbon atoms.

The cyclic aliphatic diol can be chosen in particular from the following diols:

dianhydrohexitols such as isosorbide, isomannide and isoidide (biosourced heterocyclic diols);

cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol;

tricyclodecanedimethanols;

pentacyclopentanedimethanols;

decalindimethanols such as 2,6-decalindimethanol, 1,5-decalindimethanol and 2,3-decalindimethanol;

norbornanedimethanols such as 2,3-norbornanedimethanol and 2,5-norbornanedimethanol;

adamantanedimethanols such as 1,3-adamantanedimethanol;

cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol and 1,4-cyclohexanediol;

tricyclodecanediols;

pentacyclopentadecanediols;

decalindiols;

norbornanediols;

adamantanediols, spiroglycol;

2,2,4,4-tetramethyl-1,3-cyclobutanediol, Di-O-methylene-D-glucitol and dimethyl -di-O-methylene-D-glucarate The aromatic cyclic diol can be chosen in particular from following diols:

1,4-benzenedimethanol

1.3 benzene dimethanol

1.5 dimethanol,

2.5 furan dimethanol

Naphthalene-2 6-dicarboxylate

The aromatic cyclic triol can be chosen from the following triols: pyrogallol, hydroxyquinol, phloroglucinol.

It is possible to introduce, according to the process of the invention, monomers other than (A1), (A2), (B1) and (B2).

One can for example introduce monomers comprising more than 2 alcohol or alkyl carbonate functions. It is also possible to introduce monomers comprising several functions chosen from the carboxylic acid, carboxylic acid ester, amino function or mixtures of these functions. It is also possible to introduce other monomers such as dianhydrohexitol monoalkylcarbonate, oligomers of (A1) with a degree of polymerization greater than or equal to 3.

It is also possible to introduce other products or other products such as dianhydrohexitol dialkyl ether, dianhydrohexitol monoalkyl ether or dianhydrohexitol monoalkyl carbonate monoalkyl ether which may be synthetic co-products of (A1) or (A2 ). It is also possible to introduce chain-terminating agents, which are compounds comprising only one function capable of reacting with an alcohol or carbonate function.

However, on all of the monomers introduced into the reactor, it is preferred that the sum of (A1), (A2), (B1) and (B2) constitutes more than 90 mol% of the totality of the monomers introduced, advantageously more than 95% or even more than 99%. Most preferably, the monomers introduced into the reactor essentially consist of (A1), (A2), (B1) and (B2). Obviously, it is preferred to limit the amount of diaryl carbonate and of halogenated monomers introduced, for example to amounts less than 5% of the total number of moles of monomers introduced. In a particularly preferred embodiment, no monomer chosen from diaryl carbonates and halogenated monomers is introduced.

Molar ratio of (A1) and (A2) to (B1) and (B2)

The molar ratio in the reactor of (A1) and (A2) relative to (B1) and (B2) corresponds to the following formula:

, (B1) (B2) ^{<1 L} 2 ⁺ 3 ^J

Advantageously, the molar ratio in the reactor of (A1) and (A2) relative to (B1) and (B2) as defined above is strictly less than 1 and greater than 0.5, in particular strictly less than 1 and greater than 0.7, more particularly strictly less than 1 and greater than 0.9.

The very particular choice of this molarity and therefore this excess in the other diol (B1) and / or triol (B2) leads to oligocarbonate polyols having a hydroxyl function at each end of the chain, which makes them useful for the preparation of polymers, such as polyurethanes.

The lower the ratio, the lower the molar mass of the oligocarbonate obtained.

The order of the introduction steps (1) and (2) does not matter. You can perform step (1) before step (2) or vice versa. These two steps can also be carried out simultaneously. According to a variant, a premix of (A1) and / or (A2) and (B1) and / or (B2) is produced before introducing them into the reactor. When the dimer (A2) is used in the process, it can be introduced as a mixture with (A1). This mixture can for example be made directly according to the synthesis process described in international application No. WO 2012/136942. In the case where mixtures of monomers or dimers are introduced, the amount of each of these monomers can be determined by chromatographic methods, such as for example gas chromatography (GC).

For example, to determine the quantities of (A1) and (A2) of a mixture, it is possible to measure the quantities of each of the constituents by GPC by carrying out the analysis in the form of trimethylsilylated derivatives.

The sample can be prepared by the following method: in a beaker, weigh 500 mg of sample and 50 mg of pentaacetate glucose (internal standard) of known purity. Add 50 ml of pyridine and let stir until completely dissolved. Take 1 ml in a cup, add 0.5 ml of bis- (trimethylsilyl) -trifluoroacetamide then heat 40 minutes at 70 ° C.

To make the chromatogram, you can use a VARIAN 3800 chromatograph equipped with:

- a DB1 column with a length of 30 m and 0.32 mm in diameter with a film thickness of 0.25 μm,

- a type 1177 injector fitted with a focus liner with glass wool and heated to 300 ° C using a split ratio of 30, the helium flow rate being 1.7 mL / min,

- an FID detector heated to a temperature of 300 ° C set with a sensitivity of 10 ^'11.

It is possible to introduce, in split mode, 1.2 μL of the sample into the chromatograph, the column being heated from 100 ° C. to 320 ° C. with a ramp of 7 ° C./min then a level of 15 min at 320 ° C. Under these analysis conditions, when (A1) is an isosorbide dimethylcarbonate and (A2) dimers of (A1), (A1) has a relative retention time of approximately 0.74, (A2) has a time relative retention ranging from about 1.34 to 1.79, the internal standard having a retention time of about 15.5 minutes.

Using the chromatogram, the mass percentage of each of the constituents can be calculated by determining the area of the corresponding peaks and by calculating, for each constituent, the ratio of the area of the corresponding peak to the total area of all the peaks (except the peak of the internal standard).

Polycondensation reaction by transesterification

To allow the formation of polycarbonate according to the process of the invention, the monomer (A1) and / or the dimer (A2) reacts with the monomer (B1) and / or (B2) by a transesterification reaction, this reaction being carried out in a reactor.

This reaction can be carried out in the absence of a catalyst. However, the presence of an appropriate catalyst makes it possible to accelerate the reaction and / or to increase the degree of polymerization of the polycarbonate thus formed during step (3).

The type and conditions of condensing transesterification of step (3) are not particularly limited.

However, step (3) is advantageously carried out in the presence of a known polycondensation catalyst by transesterification, advantageously a catalyst comprising at least one ion of alkali metal or of alkaline earth metal, a quaternary ammonium ion, a quaternary phosphonium ion , a cyclic nitrogen compound, a basic boron-based compound or a basic phosphorus-based compound.

As an example of a catalyst comprising at least one alkali metal ion, mention may be made of the cesium, lithium, potassium or sodium salts. These salts can be in particular carbonates, hydroxides, acetates, stearates, borohydrides, borides, phosphates, alcoholates or phenolates as well as their derivatives.

As catalyst comprising at least one alkaline earth metal ion, mention may be made of the calcium, barium, magnesium or strontium salts. These salts can in particular be carbonates, hydroxides, acetates or stearates as well as their derivatives.

As regards the basic boron-based compounds, these are preferably salts of alkyl or phenyl derivatives of boron such as boron tetraphenyl.

The catalysts comprising basic phosphorus-based compounds can be phosphines. The catalysts comprising a quaternary ammonium ion are preferably hydroxides such as tetramethylammonium hydroxide.

The catalysts comprising a cyclic nitrogen compound are preferably triazole, tetrazole, pyrrole, pyrimidine, pyrazine, pyridazine, picoline, picoline, piperidine, pyridine, aminoquinoline or imidazole derivatives.

Preferably, the catalyst is chosen from catalysts comprising at least one alkali metal ion, catalysts comprising a cyclic nitrogen compound and catalysts comprising a quaternary ammonium ion, such as cesium carbonate, triazoles, tetramethylammonium hydroxide, most preferably cesium carbonate.

The molar amount of optional catalyst, relative to the amount of (A1) and (A2) advantageously ranges from 10-7% to 1%, preferably from 10-4% to 0.5%. Its quantity can be adjusted according to the catalyst used. By way of example, use is preferably made of 10 ' ³ to 10' ¹ % of catalyst comprising at least one alkali metal ion.

Optionally, additives such as stabilizers can be added to (A1) and / or (A2) and (B1) and / or (B2).

The stabilizer can be, for example, a compound based on phosphoric acid such as trialkyl phosphates, based on phosphorous acid such as phosphite or phosphate derivatives, or a salt of these acids, for example zinc salts; this stabilizer makes it possible to limit the coloring of the polymer during its manufacture. Its use can be advantageous in particular when polycondensation is carried out in the molten state. However, the amount of stabilizing agent is generally less than 0.01% of the total number of moles of (A1), (A2), (B1) and (B2). In the polycarbonate manufacturing method according to the invention, the polycondensation step of (A1) and / or (A2) and (B1) and / or (B2) is carried out during step (3). The type and conditions of polymerization are not particularly limited. This reaction can be carried out in the molten state, that is to say by heating the reaction medium in the absence of solvent. This polymerization can also be carried out in the presence of solvent. This reaction is preferably carried out in the molten state.

Step (3) is carried out for a time sufficient to obtain a polycarbonate. Advantageously, the duration of step (3) ranges from 1 hour to 24 hours, for example from 2 to 12 hours.

At least part of step (3) of the process according to the invention can be carried out at a temperature ranging from 100 ° C to 250 ° C, preferably from 150 to 235 ° C. Preferably, the reactor is thermoregulated during step (3) at a temperature ranging from 100 ° C to 250 ° C, preferably from 150 ° C to 235 ° C.

It is possible to conduct the whole of step (3) in isothermal. However, it is generally preferred to increase the temperature during this step, either by temperature steps or by using a temperature ramp. This increase in temperature during step (3) makes it possible to improve the degree of progress of the polycondensation reaction by transesterification and thus to increase the molecular mass of the polycarbonate finally obtained, the latter having moreover a lower coloration when carrying out all of step (3) of the process at its highest temperature.

It is of course preferred to carry out step (3) under an inert atmosphere, for example under nitrogen.

To remove the alcohols generated during the process according to the invention, the vacuum in the reactor is not necessary since the alcohols generated can be distilled more easily than phenol. The method according to the invention thus has the advantage that the polycondensation step by transesterification does not necessarily take place under a high vacuum. Thus, according to a variant of the method of the invention, at least part of step (3) is carried out at a pressure ranging from 30 kPa to 110 kPa, advantageously from 50 to 105 kPa, preferably from 90 to 105 kPa, by example at atmospheric pressure. Preferably, at least half of the total duration of step (3) is carried out at this pressure.

However, step (3) can be carried out, for the entire duration or during a slightly higher vacuum portion, for example with a pressure inside the reactor of between 100 Pa and 20 kPa. Obviously, this vacuum is regulated according to the temperature inside the reactor and the degree of polymerization: when the degree of polymerization is low, in the event of too low pressure and too high temperature, the reaction cannot be carried out correctly. because the monomers are extracted from the reactor by distillation. This slightly deeper vacuum step can be carried out at the end of the reaction, which also makes it possible to eliminate part of the residual species.

The reactor is generally equipped with a means for removing the alcohols generated during the polycondensation reaction by transesterification, for example a distillation head connected to a condenser.

The reactor is generally equipped with a stirring means such as a paddle stirring system.

The monomer (A1) and / or the dimer (A2) have the advantage of reacting alternately with the monomers (B1) and / or (B2) during step (3). The reaction thus leads to an oligomer having an alternate architecture.

It is possible to carry out one or more additional introduction steps of monomers (B1) and / or (B2), this after the start of the transesterification condensation step (3).

The process can be carried out discontinuously (by "batch"), continuously, or semi-continuously semi-discontinuously.

The oligocarbonate formed during the process is recovered in step (4). This oligocarbonate can be directly transformed into granules using a granulator or in any other form. It is also possible to carry out a purification of the product thus obtained in a step subsequent to step (4), for example by dissolving the product in a solvent such as chloroform then precipitation by adding a non-solvent such as methanol.

Thanks to the process of the invention, a mass yield can be obtained, defined by the ratio of the mass of oligocarbonate recovered to the mass of the sum of the monomers or dimers used, greater than or equal to 60%, advantageously greater than 70%, preferably more than 80%.

The present invention also relates to a dimethacrylated or diacrylated oligocarbonate capable of being obtained by the process according to the invention as defined above.

Advantageously, the dimethacrylated or diacrylated oligocarbonate according to the invention comprises a phenol level of less than 50 ppb.

The residual phenol level is measured by gas chromatography on a sample previously completely hydrolyzed by acid hydrolysis. Those skilled in the art can easily carry out the acid hydrolysis of the oligocarbonates and analyze the reaction crude by gas chromatography with an internal standard to measure a quantitative response.

The dimethacrylated or diacrylated oligocarbonate obtained by the process according to the invention has a molar mass of less than 5000 g / mol and chain endings of methacrylate or acrylate type

The molar mass of the oligocarbonate can be decreased, respectively increased, by decreasing, respectively increasing, the amount of monomers (B1) and / (B2) used in step (3) relative to that of (A1) and / or (A2).

The branching rate of the oligocarbonate can be decreased, respectively increased, by decreasing, respectively increasing, the amount of monomer (B2) used in step (3) relative to that of (B1).

The higher the branching rate of the oligocarbonate, the higher the crosslinking density of the polymeric material obtained from this oligomer.

The oligocarbonate diol obtained by the process according to the invention also has an OH index greater than 100 mg KOH / g.

The oligocarbonate diol obtained at the end of step (4) of the process according to the invention is functionalized into oligocarbonate di (meth) acrylate (see formula below) by reaction with a chosen acrylating or methacrylation agent. among methacryloyl chloride, methacrylic anhydride, methacrylic acid or acrylic acid, in order to obtain a dimethacrylated or diacrylated oligocarbonate. The preferred (meth) acrylating agents are methacryloyl acid and anhydride and acrylic acid.

The present invention also relates to the use of the oligocarbonate di (meth) acrylate according to the invention in thermosetting resins for coating and composite applications.

The crosslinking of these acrylic / methacrylic functions can be carried out thermally, by means of a radical initiator with thermal initiation, or by exposure to Ultraviolet radiation by means of a photoinitiator.

Depending on the crosslinking mode, the hardener will therefore be chosen from:

thermal initiators from the following list: dihalogens, Azo-bis-isobutyronitrile, benzoyl peroxide, tert-butyl peroxide, 2,2Bis (tert-butylperoxy) butane, 1,1-Bis (tert- butylperoxy) cyclohexane, 2,5-Bis (tertbutylperoxy) -2,5-dimethylhexane, 2,4-pentanedione peroxide, Lauroyl peroxide, dicumyl peroxide, Cyclohexanone peroxide, Cumene hydroperoxide, tert-Butylperoxy isopropyl carbonate, tert- Butyl peroxybenzoate, tert-Butyl peracetate, tert-Butyl hydroperoxide or persulfates;

the photoinitiators of the following list: benzoyl peroxide, benzophenone and the compounds derived from benzophenones, phenyl ketones and hydroxyketones, amino ketones or mono and poly acyl phosphines such as for example the Irgacure and Darocur marketed by the company BASF .

Other thermal initiators can be used, in particular compounds comprising at least one azo group, in particular azonitriles and azoesters, as well as organic peroxides other than those mentioned above. 1

Embodiments will now be detailed in the examples which follow. It is specified that these illustrative examples in no way limit the scope of the present invention.

Examples

Analytical methods used:

DSC

The thermal properties of the polyesters were measured by differential scanning calorimetry (DSC): The sample is firstly heated under nitrogen in an open crucible from 10 to 280 ° C (10 ° C. min-1) , cooled to 10 ° C (10 ° C. min-1) then reheated to 320 ° C under the same conditions as the first step. The glass transition temperatures were taken at the mid-point of the second heating. The possible melting temperatures are determined on the endothermic peak (start of the peak (onset)) at the first heating. Similarly, the determination of the enthalpy of fusion (area under the curve) is carried out on the first heating.

Steric exclusion chromatography:

Regarding Mn, it is determined by size exclusion chromatography in THF using Polystyrene standards. The sample is prepared by dissolving in THF at a concentration of 5 mg / ml.

Determination of alcohol index

The OH index is determined by 1H NMR via a derivatization technique by adding trifluoroacetic anhydride and α, α, α-trifluorotoluene as an internal standard.

To do this, dissolve 10 mg of oligocarbonate diol in 0.6 mL of CDC13, then add the excess ATFA and react for 24 hours. Addition 10 p L of α, α, α-trifluorotoluene (internal standard) before analysis by

1 H NMR

The OH level is determined by comparing the integrations of the peaks between 5.4 and 5.6 ppm (representing the signals of the protons in has derivatized OH) to the sum of the integrals of the peaks between 1.4 and 1.9 ppm and between 4.05 and 4.15 ppm. Those skilled in the art can easily find the OH index once

Membership performed on Q panel according to ASTM D3359-09

Examples of Synthesis of Oliqocarbonates According to the Invention

Isosorbide dimethylcarbonate, useful for the process for the production of polycarbonate diol oligomers according to the invention, is obtained according to the protocol described below.

Synthesis of isosorbide dimethylcarbonate (DMCI)

It is introduced into a reactor with a capacity of 20 liters, heated by a thermostated bath with heat transfer fluid, equipped with a mechanical paddle stirring system, a system for controlling the temperature of the reaction medium and a rectification column surmounted by a reflux head, 800 g of isosorbide (5.47 mol) then 5362 g of dimethyl carbonate (= 20 equivalents of dimethyl carbonate) and 2266 g of potassium carbonate. The reaction mixture is heated for one hour at total reflux, time after which the temperature of the vapors at the head of the column reaches 64 ° C., before starting the elimination of the methanol formed. The heating of the reaction medium is then maintained at a temperature between 68 ° C and 75 ° C for 13 hours, after which time the temperature of the vapors at the head of the column reaches 90 ° C and stabilizes at this temperature (point of boiling of dimethyl carbonate). This is a sign that the transesterification reaction is complete and that no more methanol is formed.

Part of the product obtained according to Synthesis 1 is distilled under high vacuum (<1 mBar) on a scraped film evaporator in the "short patch" configuration. The evaporator is heated to 140 ° C and the product is introduced at 70 ° C with a flow rate of 140 g / h.

The distillate obtained is a white solid containing 100% by weight of isosorbide dimethylcarbonate and contains no trace of dimers.

Preparation of oligocarbonates

Is introduced into a reactor with a capacity of 200 ml, heated by a ceramic oven, equipped with a mechanical paddle stirring system, a system for controlling the temperature of the reaction medium, a tube of introduction of nitrogen, a distillation head connected to a condenser and a container for collecting the condensates, and a vacuum system with regulation, an amount of isosorbide dimethylcarbonate (A1) and of diols (B1): isosorbide and hexane diol or butane diol, with the quantities expressed in table 1 below and cesium carbonate. The molar ratio (A1) / (B1) is 0.9 to 1. The amount of cesium carbonate is 17.1 mg (2.5 x10 ^-4 mole).

The installation is placed under a nitrogen atmosphere and the reaction medium is heated by means of the heat transfer fluid. The temperature is gradually raised to 65 ° C so that the molten reaction medium is homogeneous and 5 "vacuum (300 mbar) nitrogen (flow)" cycles are applied before continuing the temperature rise. The temperature rise between each level is done in 15 minutes. A first stage takes place at a temperature of 10,100 ° C. under a nitrogen flow of 5 ml / min of nitrogen for 2 hours. The temperature is subsequently brought to 180 ° in 15 minutes and a vacuum of 50 mbar is applied. This stage lasts 3 hours.

The product is then cooled under nitrogen and poured into a pill box when the temperature is around 60 ° C.

Examples 1 to 5 describe the syntheses and the properties of the reactions where only one diol B was used, the nature of the diol B having been modified.

Example Nature of Diol (B) Qty Diol B (G) Qty DMCI (A) (G) Tg (O) IOH (mg KH / g) mn (G / mol) aspect EX1 Butane diol 11,45 30 -30 130 850 colorless liquid EX 2 Hexane diol 15,01 30 -49 124 900 colorless liquid EX 3 Cyclohexane dimethanol 18.32 30 45 110 1000 pasty solid EX 4 pentaerythritol 17.3 30 -8 105 1100 light yellow liquid EX 5 diethylene glycol 13,48 30 -37 128 850 colorless liquid

Examples 6 and 7 are synthesized from a variable diol (B) as well as a diol (C), isosorbide.

Nature diol B qty Iso (diol C) (g) Qty diol B (G) DMCI qty (A) (g) IOH (mg KOH / g) Tg (° C) Mn (g / mol) aspect EX 6 1.4 Butane diol 4.64 11.26 30 125 -15 800 colorless liquid EX 7 1.6 hexanediol 4.64 8.58 30 137 -35 1300 colorless liquid

Examples of Synthetic Olqocarbonate Diol Derivative Epoxv According to the Invention

Example 8 Synthesis of Epoxy Derivative by Reacting with Oligocarbonate with Methacryloyl Chloride

In a 500 ml flask equipped with a mechanical stirrer and a CaCl 2 guard, 13.17 g of pyridine and 50 grams of the oligocarbonate according to example 2 are dissolved in 200 ml of chloroform and cooled to 4 ° C. In a dropping funnel, 17.42 g of methacryloyl chloride (i.e. a methacryloyl chloride / oligocarbonate EX 2 molar ratio of 3 for 1) dissolved in 100 ml of THF are added dropwise to the reaction medium while maintaining the temperature of the the reaction mixture below 15 ^OO C. once all added methacryloyl chloride, the reaction medium is heated at 30 ° C for 3h. Once the reaction is complete, the reaction mixture is filtered through sintered glass No. 5, the solid washed several times with chloroform. The filtrate is then dried on a molecular sieve. 0.3 g of methyl hydroquinone are then added and the solvent is then evaporated.

The product is analyzed by proton NMR, the presence of signals between 6.2 and 6.6 ppm characteristic of the protons carried by the methacrylic double bond shows the grafting reaction.

Example 9: Use of the di methacrylate oligomer in thermal crosslinking.

grams of the product of Example 8 are mixed in a pill box with 3 g of methyl methacrylate and 0.1 of irgacure 754 from BASF. This mixture is deposited by spin coating on a glass plate and subjected to several passages (10) under UV radiation (bench type DYMAX UVC-5) with an intensity of 200 mW / cm ² The coating is then detached from the support in glass and tested for solubilization in dichloromethane and in DSC.

The DSC shows a Tg of -34 ° C for the coating.

This coating exhibits after 24 hours in dichloromethane an insoluble content of 99.6%

Claims (18)

1. Process for the manufacture of a dimethacrylated or diacrylated oligocarbonate devoid of 5 aromatic groups and of phenolic functions comprising: an introduction step (1), in a reactor: o of a monomer of formula (A1): in which Ri and R ₂ are identical or different alkyl groups, o or of a dimer of formula (A2): In which R ₃ and R ₄ are identical or different alkyl groups, o or a mixture of (A1) and (A2); a step (2) of introducing, into the reactor, a diol monomer (B1) or a triol monomer (B2) or a mixture of (B1) and (B2), (B1) and (B2 ) both being different from (A1) and (A2); the molar ratio in the reactor of (A1) and (A2) relative to (B1) and (B2) corresponding to the following formula: , (B1) (B2) ^{<1 L} 2 ⁺ 3 ^J a subsequent polycondensation step (3) by transesterification of the monomers and dimers (A1), (A2), (B1) and (B2) to obtain an oligocarbonate polyol having a molar mass less than 5000 g / mol and at least two chain ends of the hydroxyl type, a step (4) of recovery of the oligocarbonate polyol; a step (5) consisting in reacting the oligocarbonate polyol with a (meth) acrylating agent chosen from methacryloyl chloride, methacrylic anhydride, methacrylic acid or acrylic acid, in order to obtain a dimethacrylated oligocarbonate or diacrylated. 2. Method according to claim 1, characterized in that the monomer (A1) is introduced into the reactor in step (1) alone or as a mixture with the dimer (A2). 3. Method according to claims 1 or 2, characterized in that the molar ratio in the reactor of (A1) and (A2) relative to (B1) and (B2) corresponding to the following formula: [ψ ₊ ^ 1 / r (Bl), (B2) ^L 2 ⁺ 3 ^J is strictly less than 1 and greater than 0.5, in particular strictly less than 1 and greater than 0.7, more particularly strictly less than 1 and greater than 0.9. 4. Method according to any one of claims 1 to 3, characterized in that FL, R ₂ , R ₃ and R ₄ are independently chosen from alkyl groups comprising from 1 to 10 carbon atoms, in particular from 1 to 6 carbon atoms, more particularly from 1 to 4 carbon atoms, more particularly methyl or ethyl groups. 5. Method according to any one of claims 1 to 4, characterized in that the monomer (A1) is an isosorbide dialkylcarbonate, in particular an isosorbide diethylcarbonate or an isosorbide dimethylcarbonate. 6. Method according to any one of claims 1 to 5, characterized in that the diol monomer (B1) and the triol monomer (B2) are chosen from aliphatic diols or triols, in particular linear or branched, or else diols or cyclic triols, aromatic or non-aromatic. 7. Method according to claim 6, characterized in that the diol (B1) is chosen from ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6 -hexanediol, 1,8-octanediol or 1,10-decanediol. 8. Method according to claim 6, characterized in that the diol (B1) is chosen from 1,2propanediol, 1,3-butanediol, 2,3-butanediol, 1,3-pentanediol, 1,4 -hexanediol, 2,2dimethyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol or 2-methyl-1,3-propanediol. 9. Method according to claim 6, characterized in that the diol (B1) is chosen from the following cyclic aliphatic diols: dianhydrohexitols such as isosorbide, isomannide and isoidide; cyclohexanedimethanols such as 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; tricyclodecanedimethanols; pentacyclopentanedimethanols; decalindimethanols such as 2,6-decalindimethanol, 1,5-decalindimethanol and 2,3-decalindimethanol; norbornanedimethanols such as 2,3-norbornanedimethanol and 2,5-norbornanedimethanol; adamantanedimethanols such as 1,3-adamantanedimethanol; cyclohexanediols such as 1,2-cyclohexanediol, 1,3-cyclohexanediol and 1,4-cyclohexanediol; tricyclodecanediols; pentacyclopentadecanediols; decalindiols; norbornanediols; or adamantanediols. 10. Method according to any one of claims 1 to 9, characterized in that step (3) is carried out in the presence of a polycondensation catalyst by transesterification, advantageously a catalyst comprising at least one ion of alkali metal or of alkaline earth metal, a quaternary ammonium ion, a quaternary phosphonium ion, a cyclic nitrogen compound, a basic boron-based compound or a basic phosphorus-based compound. 11. Method according to any one of claims 1 to 10, characterized in that the molar amount of catalyst relative to the amount of the monomer (A1) and of the dimer (A2) advantageously ranges from 10 ' ⁷ % to 1% in weight, preferably from 10 ' ⁴ % to 0.5% by weight. 12. Method according to any one of claims 1 to 11, characterized in that step (3) is carried out under an inert atmosphere, for example under nitrogen. 13. Method according to any one of claims 1 to 12, characterized in that at least part of step (3) is carried out at a temperature ranging from 100 ° C to 250 ° C, preferably from 150 ° C at 235 ° C. 14. Dimethacrylated or diacrylated oligocarbonate capable of being obtained by the process according to any one of claims 1 to 13. 15. Dimethacrylated or diacrylated oligocarbonate according to claim 14, characterized in that it comprises a phenol level of less than 50 ppb. 16. Formulation containing the dimethacrylated or diacrylated oligocarbonate according to claim 14 or 15 in a crosslinked form. 17. A medical prosthesis comprising a formulation according to claim 16, the medical prosthesis preferably being an amalgam for dental resin. 18. Coating or composite comprising a formulation according to claim 16.