Method for preparing polyols and products obtained

Abstract

The present invention relates to a method for preparing polyols of formula (I) ##STR00001## R.sub.1 being H or an alkyl group, R being especially an alkyl group, A.sub.1, being an alkylene radical and R.sub.3, are being especially a group -A.sub.2-OY, A.sub.2 being an alkylene radical and Y being especially H, said method especially comprising a step of epoxidation of a compound of formula ##STR00002## R.sub.1 being H or an alkyl group, A.sub.t being defined as above in formula (I) and R.sub.4 being especially a group -A.sub.2-OY.sub.1, A.sub.2 being defined as above in formula (I) and Y.sub.1 being especially H, in order to obtain a compound of formula ##STR00003## A.sub.1 being defined as above, R.sub.1 being H or an alkyl group and R.sub.5 being especially a group of formula -A.sub.2-OY.sub.2, A.sub.2 being as defined above in formula (I) and Y.sub.2 being especially H.

Claims

1. A method for preparing a polyol fitting the general formula (I): ##STR00083## wherein: R.sub.1 represents H or a linear or branched alkyl group, comprising from 2 to 14 carbon atoms, R represents a linear or branched alkyl group, comprising from 1 to 18 carbon atoms, A.sub.1 represents a linear or branched divalent alkylene radical, comprising from 2 to 14 carbon atoms, A.sub.2 represents a linear divalent alkylene radical, comprising from 1 to 10 carbon atoms, if necessary comprising one or more substituents, Y represents a hydrogen atom or a group of formula (A) ##STR00084## A.sub.1, R and R.sub.1 are as defined above, said method comprising the following steps: a) a step for transesterification of a compound of the following formula (II): ##STR00085## R.sub.2 represents a branched or linear alkyl group comprising from 1 to 10 carbon atoms, and R.sub.1- and A.sub.1 being as defined above, with a diol of the following formula (III):
HO-A.sub.2-OH(III) in order to obtain a compound of the following formula (IV): ##STR00086## A.sub.1, A.sub.2 and R.sub.1 being as defined above in formula (I), Y.sub.1 representing a hydrogen atom or a group of formula (A.sub.1) ##STR00087## A.sub.1 and R.sub.1 being as defined above, b) a step for epoxidation of the compound of the aforementioned formula (IV) in order to obtain a compound of the following formula (V): ##STR00088## A.sub.1, A.sub.2 and R.sub.1 being as defined above, Y.sub.2 representing a hydrogen atom or a group of formula (A.sub.2) ##STR00089## A.sub.1 and R.sub.1 being as defined above, c) a step for opening the epoxide ring with an alcohol of formula ROH, R being as defined above, in order to obtain a compound of formula (I) as defined above, and d) a step for recovering the compound of formula (I) as defined above.

2. The method for preparing a diol according to claim 1, characterized in that the diol fits the following formula (I-1): ##STR00090## A.sub.1, A.sub.2, R.sub.1 and R being as defined in claim 1, or the following formula (I-2): ##STR00091## A.sub.1, A.sub.2, R.sub.1 and R being as defined in claim 1.

3. The method for preparing a polyol according to any of claim 1, wherein step a) is carried out in the presence of a catalyst selected from the group consisting of magnesium oxide, zinc acetate and sodium methanolate.

4. The method for preparing a polyol according to claim 3, wherein step a) is carried out a temperature comprised between from 150 to 200 C. under nitrogen flow.

5. The method according to claim 3, wherein step a) is carried out without solvent.

6. The method for preparing a polyol according to claim 1, wherein step b) is carried out in the presence of a peracid.

7. The method for preparing a polyol according to claim 6, wherein step b) is carried out in the presence of a peracid selected from the group consisting of metachloroperbenzoic acid (m-CPBA) and of magnesium monoperoxyphthalate hexahydrate peracid (MMPP).

8. The method for preparing a polyol according to claim 1, wherein step c) is carried out in the presence of a catalyst selected from the group consisting of an acid catalyst of the proton ion exchange resin, of heterogeneous catalysts, of para-toluenesulfonic acid (PTSA) and of methanesulfonic acid (MSA), at a temperature comprised between from 20 C. to 120 C.

9. The method for preparing a polyol according to claim 8, wherein the temperature is 70 C.

10. A compound fitting the following general formula (I): ##STR00092## wherein: R.sub.1 represents a linear or branched alkyl group comprising from 2 to 14 carbon atoms, R represents a linear or branched alkyl group, comprising from 1 to 18 carbon atoms, A.sub.1 represents a linear or branched divalent alkylene radical, comprising from 2 to 14 carbon atoms, A.sub.2 represents a linear divalent alkylene radical, comprising from 1 to 10 carbon atoms, if necessary comprising one or more substituents, and Y represents a hydrogen atom or a group of formula (A) ##STR00093## A.sub.1, R and R.sub.1 being as defined above.

11. Intermediate compounds chosen from the group consisting of: compound (3) having the following formula: ##STR00094## wherein Y.sub.2 represents A.sub.2, A.sub.2 being as defined in claim 1; and compounds having the following formula: ##STR00095## A.sub.1 representing a C.sub.7H.sub.14 radical, R.sub.1 representing an alkyl group comprising 9 carbon atoms, and A.sub.2 represents a radical selected from the following radicals: C.sub.3H.sub.6, C.sub.4H.sub.8, C.sub.5H.sub.10, C.sub.6H.sub.12, H.sub.2C(CH.sub.2OCH.sub.2).sub.6CH.sub.2, H.sub.2C(CH.sub.2OCH.sub.2).sub.13CH.sub.2, H.sub.2C(CH.sub.2OCH.sub.2).sub.45CH.sub.2 or H.sub.2CC.sub.6H.sub.4CH.sub.2.

12. Polymers as obtained by polymerization of a compound as defined in claim 10 and of a (poly)isocyanate.

Description

DETAILED DESCRIPTION

1. Step a): Reaction of Transesterification of the Compounds of Formula (II) or (II)

(1) Within the scope of the method of the invention, this transesterification is carried out preferably from an ester of a light alcohol (notably methanol or ethanol . . . ) of oleic sunflower oil (compound of formula (II) or (II)) and from a diol (compound of formula (III) or (III)) notably in the presence of magnesium oxide as a catalyst. Several syntheses are carried out with different diols in order to modulate the properties of the monomers and therefore of the resulting polymers. Transesterifications were therefore carried out from propanediol, hexanediol, butanediol and hydroxyl telechelic poly(ethyleneoxide).

(2) The reaction takes place between 150 C. and 200 C. under nitrogen flow. The progression of the reaction is tracked by different analyses and notably MNR (disappearance of the singlet of the methyl group). Depending on the reaction conditions, two products are obtained:

(3) If the diol used is placed in a great excess, in majority at least 80%, or even 95% of monoesters (or derivatives of monoglycerides) are obtained having a terminal hydroxyl group. This alcohol at the end of the chain then provides a first functionality to the monomer.

(4) Conversely, if the diol is voluntarily introduced in default, in majority at least 60%, or even 85% of diesters (or derivatives of diglycerides) are obtained. This second precursor then exactly has two double bonds through which will be introduced the hydroxyl groups, allowing access to monomers with a functionality equal to two.

(5) TABLE-US-00001 Reaction time Yield Alcohols used Synthesis of Synthesis of Synthesis of Synthesis (II) or (II) monoesters diesters monoesters of diesters Propanediol 10 h 15 h 80% 62% Hexanediol 10 h 15 h 80% 60% Polyoxyethylene 15 h 20 h 75% 59% (M.sub.w = 300 g/mol) Polyoxyethylene 15 h 20 h 75% 59% (M.sub.w = 600 g/mol)

(6) Step a) (with R.sub.1C.sub.6H.sub.13; A.sub.1=C.sub.9H.sub.18, R.sub.2CH.sub.3; A.sub.2=R) may thus notably be illustrated by the following diagram:

(7) ##STR00042##

(8) The prepared synthons (corresponding to the compounds of formula (IV)) are for example purified on a silica column with a heptane/acetone/petroleum ether 80/10/10 mixture for the monoester and a heptane/petroleum ether 80/20 mixture for the diester. The yields after purification are given in the table above.

(9) At the end of this first step, two precursors are available: the first is a monoester (compound of formula (IV-1)) having a terminal hydroxyl group and a double bond on the chain; the second one is a diester (compound of formula (IV-2)) exactly having two double bonds in order to obtain subsequently a symmetrical polyol containing two hydroxyl groups. The synthesis route set into play is <<clean>> since it resorts to heterogeneous catalyses (magnesium oxide) and the synthesis takes place without any solvent. Industrial purification may be accomplished by distillation under a high vacuum.

2. Step b): Epoxidation of the Derivatives of Monoesters and Diesters Obtained after Transesterification

(10) The epoxidation of fats having a primary alcohol at the end of the chain by peracids formed in situ has never been dealt with and cannot be achieved under the same conditions as those described earlier. The epoxidation reaction is actually subject to interference caused by a secondary oxidation reaction of the terminal alcohol of the oleic sunflower monoester so as to form a carboxylic acid. As the reagent is consumed by this secondary reaction, epoxidation is not achieved.

(11) Thus, a secondary esterification reaction occurs between the catalyst (carboxylic acid) and the terminal alcohol of the monoester according to the following scheme (specific case with R.sub.1C.sub.8H.sub.17 and A.sub.1=C.sub.7H.sub.14):

(12) ##STR00043##

(13) The reduction in the amount of catalyst or of the temperature in order to penalize the parasitic reaction nevertheless causes a significant increase in the reaction time, and in parallel an initial opening of the formed, fragile epoxide bridges in an acid medium at 70 C. Another epoxidation strategy without using any reactive carboxylic acid was therefore developed by the inventors.

(14) The method applied within the scope of the method of the invention for the epoxidation of a monoester with a terminal hydroxyl group (compounds of form a (IV-1)) lies in the use of an already formed and marketable peracid, i.e. notably metachloroperbenzoic acid (m-CPBA), and therefore avoids the use of potentially toxic metals.

(15) The mechanism of this reaction may be illustrated according to the scheme hereafter:

(16) ##STR00044##

(17) Within the scope of the invention, epoxidation was achieved with peracids (mCPBA, MMPP . . . ). The reaction may be tracked by MNR; the disappearance of the proton doublets of the double bond at 5.2 ppm as well as the appearance of a broad peak at 2.8 ppm allows tracking of the progression of the reaction. The conversion of the double bonds is total after 3 h. The excess m-CPBA is reduced into the corresponding carboxylic acid with a saturated solution of sodium sulfate. The organic phase is extracted with dichloromethane and then the residual carboxylic acid is transformed into sodiumchlorobenzoate (soluble in water) by means of two washings with a saturated solution of sodium bicarbonate.

(18) The diesters (compounds of formula (IV-2)), not having any hydroxyl groups, may be epoxidized by using the standard procedure (H.sub.2O.sub.2+formic acid) or by using a peracid as indicated above, for example metachloroperbenzoic acid.

(19) The obtained synthons are all purified on a silica column with a toluene/ethyl acetate 60/40 mixture for the epoxidized monoester and a toluene/ethyl acetate 95/5 mixture for the epoxidized diester.

3. Step c): Opening the Epoxides of the Monoesters and Diesters Epoxidized by Alcohols

(20) Within the scope of the present invention, the goal is to introduce hydroxyl groups on monoesters already having a terminal primary alcohol by opening the epoxides with an alcohol.

(21) At 110 C. and under acid catalyses (p-toluenesulfonic acid), transesterification is favored as compared to the opening of the epoxide. Indeed, the primary alcohol at the end of the chain is set into play in these secondary reactions.

(22) For example the formation of couplings is observed upon opening the epoxide notably according to the following scheme:

(23) ##STR00045##

(24) Tests conducted at lower temperatures show that the couplings are reduced but the opening of the epoxide is considerably slowed down. Many openings of epoxides use homogeneous acid catalysts (U.S. Pat. No. 4,508,853; Gruber et al., Fett Wissenschaft Technologie, 1987, 4:147-151; EP 0 260 499; U.S. Pat. No. 4,742,087; DE 4 232 167; Guo et al., J. Polym. Sci. A: Polym. Chem., 2000, 38: 3900-3910; U.S. Pat. No. 6,433,121; U.S. Pat. No. 6,573,354; Zlatanic et al., J. Polym. Sci. B: Polym. Physics, 2004, 42: 809-819; US 20070232816) or amines (DE 4 238 215).

(25) The method of the present invention consists of using a specific catalyst upon opening the epoxide and operational at lower temperatures in order not to trigger a beginning of transesterification.

(26) The reaction conditions applied for step c) of the method of the invention are milder than with conventional homogeneous catalyses (70 C. instead of 110 C.) and the synthesis is accomplished without any solvent. Thus, the epoxidized monoesters and diesters are mixed with a large excess of alcohol in the presence of 4% by mass of resin Amberlyst 15 Dry. The medium is heated to 70 C. for 15 h. The progression of the reaction is tracked by MNR by the disappearance of the peaks of the epoxide at 2.8 ppm. The mixture is then filtered in order to recover the catalyst.

(27) The alcoholized synthons are then purified on a silica column with a toluene/ethyl acetate 40/60 mixture for the hydroxylated monoesters and diesters.

(28) The present invention also relates to a compound fitting the following general formula (I):

(29) ##STR00046##

(30) wherein: R.sub.1 represents H or a linear or branched alkyl group, comprising from 2 to 14 carbon atoms, said alkyl group may optionally be substituted with one or more groups OR.sub.a, R.sub.a representing H or a group R as defined below, A.sub.1 represents a linear or branched divalent alkylene radical, comprising from 2 to 14 carbon atoms, R represents: a linear or branched alkyl group R comprising from 1 to 18 carbon atoms, or a group of formula -A.sub.2-OH, A.sub.2 representing a linear or branched divalent alkylene radical, comprising from 1 to 10 carbon atoms, if necessary comprising one or more substituents, notably selected from the group consisting of the phenylene radical and of the radical of formula (CH.sub.2OCH.sub.2).sub.n n representing an integer comprised from 1 to 100, preferably from 6 to 50, and preferentially equal to 6, 13 or 45,
A.sub.2 preferably representing a radical of formula CH.sub.2-A.sub.3-CH.sub.2, A.sub.3 representing a group of formula (CH.sub.2OCH.sub.2).sub.n, n representing an integer comprised from 1 to 100, and preferably equal to 6, 13 or 45, or a phenylene radical, and R.sub.3 represents: a linear or branched alkyl group R.sub.2, comprising from 1 to 10, preferably from 1 to 6 carbon atoms, or a group of formula -A.sub.2OY, A.sub.2 being as defined above and Y representing a hydrogen atom or a group of formula (A)

(31) ##STR00047##
A.sub.1, R and R.sub.1 being as defined above in formula (I),

(32) it being understood that when R is a group R then R.sub.3 represents a group of formula -A.sub.2-OY, and that when R is a group -A.sub.2-OH then R.sub.3 represents a group R.sub.2.

(33) The present invention also relates to a compound fitting the following general formula (I-1):

(34) ##STR00048##

(35) wherein: R.sub.1 represents H or a linear or branched alkyl group, comprising from 2 to 14 carbon atoms, said alkyl group may optionally be substituted with one or more groups OR.sub.a, R.sub.a representing H or a group R as defined below, A.sub.1 represents a linear or branched divalent alkylene radical, comprising from 2 to 14 carbon atoms, A.sub.2 represents a linear or branched divalent alkylene radical, comprising from 1 to 10 carbon atoms, if necessary comprising one or more substituents, notably selected from the group consisting of the phenylene radical and of the radical of formula (CH.sub.2OCH.sub.2).sub.n, n representing an integer comprised between from 1 to 100, preferably from 6 to 50, and preferentially equal to 6, 13 or 45,
A.sub.2 preferably representing a radical of formula CH.sub.2-A.sub.3-CH.sub.2, A.sub.3 representing a group of formula (CH.sub.2OCH.sub.2).sub.n, n representing an integer comprised from between 1 to 100, and preferably equal to 6, 13 or 45, or a phenylene radical, and R.sub.2 represents a linear or branched alkyl group, comprising from 1 to 10, preferably from 1 to 6 carbon atoms.

(36) The present invention also relates to a compound fitting the following general formula (I):

(37) ##STR00049##

(38) wherein:

(39) R.sub.1 represents H or a linear or branched alkyl group, comprising from 2 to 14 carbon atoms, said alkyl group may optionally be substituted with one or more groups OR.sub.a, R.sub.a representing H or a group R as defined below,

(40) R represents a linear or branched alkyl group, comprising from 1 to 18 carbon atoms,

(41) A.sub.1 represents a linear or branched divalent alkylene radical, comprising from 2 to 14 carbon atoms,

(42) A.sub.2 represents a linear or branched divalent alkylene radical, comprising from 1 to 10 carbon atoms, if necessary comprising one or more substituents, notably selected from the group consisting of the phenylene radical and of the radical of formula (CH.sub.2OCH.sub.2).sub.n, n representing an integer comprised between from 1 to 100, and preferably equal to 6, 13 or 45,

(43) Y represents a hydrogen atom or a group of formula (A)

(44) ##STR00050##

(45) A.sub.1, R and R.sub.1 being as defined above in formula (I).

(46) Among the aforementioned preferred compounds, mention may notably be made of the compounds of the following formula (I):

(47) ##STR00051##

(48) wherein:

(49) R.sub.1 represents a linear or branched alkyl group, comprising from 2 to 14 carbon atoms, and

(50) R, A.sub.1 and A.sub.2 are as defined above in formula (I), and

(51) Y represents a hydrogen atom or a group of formula (A)

(52) ##STR00052##

(53) A.sub.1, R and R.sub.1 are as defined above in formula (I).

(54) Mention may also be made of other preferred compounds according to the present invention, fitting the following general formula (I-1):

(55) ##STR00053##

(56) wherein:

(57) R.sub.1, R, A.sub.1 and A.sub.2 are as defined above in formula (I) and (I).

(58) The present invention also relates to compounds fitting the following general formula (I-1-1):

(59) ##STR00054##

(60) wherein:

(61) m, n, p and q are integers comprised between from 1 to 18, m being preferably equal to 2.

(62) Preferably, in formula (I-1-1), q is equal to 4.

(63) The present invention also relates to compounds fitting the following general formula (I-1-1):

(64) ##STR00055##

(65) wherein:

(66) m, n and p are integers comprised between from 1 to 18,

(67) and R is as defined above in formula (I).

(68) The present invention also relates to compounds fitting the following general formula (I-1-2):

(69) ##STR00056##

(70) Another family of preferred compounds of the invention consists of the compounds fitting the following general formula (I-2):

(71) ##STR00057##

(72) wherein:

(73) R.sub.1, R, A.sub.1 and A.sub.2 are as defined above in formulae (I) and (I).

(74) Another family of preferred compounds of the invention consists of compounds fitting the following general formula (I-2-1):

(75) ##STR00058##

(76) wherein:

(77) m, n and p are integers comprised between from 1 to 18,

(78) and R is as defined above in formula (I).

(79) Another family of preferred compounds of the invention consists of the compounds fitting the following general formula (I-2-2):

(80) ##STR00059##

(81) m being as defined above.

(82) Among the preferred polyols of the invention, mention may notably be made of the two following specific compounds: a diol (8) derived from sunflower oil:

(83) ##STR00060## a diol (11) derived from rape seed oil:

(84) ##STR00061##

(85) The polyols according to the present invention, notably the diols, have the specificity of being well defined, with two primary or secondary hydroxyl groups. The derivatives of diesters are original because of their symmetry and the alcohol used for transesterification gives the possibility of varying the structure of the synthons and thus the properties of the resulting polymers.

(86) The diols obtained by these different methods may then be used inter alia as monomers. Their purity allows optimization of the properties of the obtained polymers.

(87) Thus, polyurethanes were then synthesized by bulk polymerization of these polyols with IPDI (or for example also with MDI, HMDI or HDI), at 60 C. in the presence of tin dibutyl dilaurate. Formation of the polyurethanes is confirmed by FTIR with the disappearance of the vibration band of the isocyanate. Steric exclusion chromatography confirms molar masses comprise between 14 000 and 50 000 g/mol. These di-OH monomers may also be used for the synthesis of other polymers such as polyesters, polyethers, polycarbonates, etc.

(88) The polyol compounds according to the present invention of formula (I), (I) or (I) are notably used for reacting with polyisocyanates in order to form polyurethanes.

(89) Thus, these compounds may be used for preparing rigid foams, of electric insulators, of coatings, of adhesives, of flexible foams (notably in the field of furniture or of automobiles) or of shoe soles.

(90) More exactly, the polyols according to the present invention are used for preparing rigid foams by reacting them with polyisocyanates in the presence of a catalyst and of a foaming agent (to which may also be added surfactants, coloring agents, antioxidants, preservatives, plasticizers, cross-linking agents, flame retardants, etc.).

(91) Preferably, such a rigid foam may be prepared by reacting together the following constituents: 60 g of polyisocyanate, 40 g of polyol, 1.2 g of water (foaming agent), 0.1-0.4 g of catalyst and 1-4 g of surfactant.

(92) More exactly, the polyols according to the invention are used for preparing electric insulators by reacting them with polyisocyanates in the presence of an anti foaming agent and of a drying agent.

(93) Preferably, such an electric insulator may be prepared by reacting together 60 g of polyol, 29 g of polyisocyanate, 0.6 g of anti foaming agent and 3 g of drying agent, and optionally 60 g of fillers (silica).

(94) More exactly, the polyols according to the invention are used for preparing coatings by reacting them with polyisocyanates. For example, coatings are prepared by using pure polyols and polyisocyanates, or by using polyols and polyisocyanates with solvents (it is also possible to add coloring agents, pigments, fillers, flow additives, anti oxidants, bactericides, fungicides, corrosion inhibitors, catalysts or UV stabilizers).

(95) For the preparation of adhesives according to the present invention, provision is also made for using pure polyols of the invention with pure polyisocyanates.

(96) As regards flexible foams, preferably 60 g of polyol according to the invention, 100 g of isocyanate, 4.5 g of water (foaming agent), 0.12 g of catalyst 1, 0.38 g of catalyst 2 and 3 g of surfactant are used.

(97) Finally, a specific formulation according to the invention for preparing shoe soles comprises 59 g of isocyanate, 94.5 g of polyol according to the invention, 4.1 g of ethylene glycol and 1.4 of catalyst.

(98) The present invention also relates to the intermediate compounds fitting one of the following formulae:

(99) ##STR00062##

(100) R.sub.1, A.sub.1, A.sub.2, Y.sub.1, Y.sub.1, R.sub.2, R.sub.4 and R.sub.1 are as defined above in formula (I), (I) and (I).

(101) The present invention also relates to the intermediate compounds fitting one of the following formulae:

(102) ##STR00063##

(103) R.sub.1, A.sub.1, A.sub.2, Y.sub.2, Y.sub.2, R.sub.5, R.sub.2 and R.sub.1 are as defined above in formulae (I) and (I).

(104) A particularly preferred family of intermediate compounds according to present invention consists of compounds fitting the following formula (V-3):

(105) ##STR00064##

(106) A.sub.1 and A.sub.2 are as defined above in formula (I), and A.sub.1 preferably representing a group C.sub.7H.sub.14.

(107) The present invention therefore also relates to the synthesis of bis-epoxide precursors, notably for epoxy resins.

(108) These bis-epoxide precursors have two terminal epoxide groups and are close to the structure of bisphenol A diclycidyl ether (BADGE). BADGE is widely used as a precursor in the synthesis of epoxy resin, by a condensation reaction with diamines. However BADGE is in the process of being banned because of the toxicity of its bisphenol A. The bis-epoxides according to the invention of the aforementioned formula (V-3) prove to be an alternative to the use of BADGE.

(109) The literature already describes the use of vegetable oil in the formulation of epoxy resins: epoxidised sunflower oil (Jiang Zhu et al., Journal of Applied Polymer Science, 2004, 91, 3513-3518), epoxidized castor oil (Park et al., Macromolecular Chemistry and Physics, 2004, 205, 2048-2054) or carbonated soya bean oil (Parzuchowski et al., Journal of Applied Polymer Science, 2006, 102, 2904-2914). Nevertheless these oils only replace a small proportion of BADGE because of their low reactivity. The attained epoxy resins have equivalent mechanical properties or even superior to commercial epoxy resins from petroleum. For the moment, a maximum of 30% of epoxidized oil has been incorporated into commercial resins. With the mixture of epoxidized flax oil, of bisphenol F diglycidyl ether (BFDGE), and of an anhydride adjuvant, it is possible to obtain resins containing up to 70% of epoxidized flax oil (Miyagawa et al., Marcomoecular Materials and Engineering, 2004, 289, 629-635).

(110) The synthesis of epoxy resins from 100% of vegetable oil is not possible because of the low reactivity of the internal epoxide groups in the chain. The synthesis route proposed within the scope of the present invention gives the possibility of obtaining precursors having two terminal epoxide groups, which increases the reactivity towards amines and allows the synthesis of epoxy resins from 100% of vegetable oil.

(111) The method for preparing the compounds of formula (V-3) may be illustrated by the diagram hereafter:

(112) ##STR00065##

(113) Preferably A.sub.1 represents a radical C.sub.7H.sub.14.

(114) The present invention also relates to polymers of the polyurethane type as obtained by polymerization of the polyols of the present invention, notably of formulae (I), (I) or (I), with (poly)isocyanates.

(115) It also relates to polymers of the polyester type as obtained by polymerization of the polyols of the present invention, notably of formulae (I), (I) or (I).

EXPERIMENTAL PART

Example 1

Preparation of Oleic Sunflower Oil Ethyl Esters

(116) This example relates to the preparation of the compound (1) of the following formula:

(117) ##STR00066##

(118) This is a compound of formula (II) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms, A.sub.1 represents an alkylene radical comprising 7 carbon atoms and R.sub.2 represents an ethyl group.

(119) The starting product is oleic sunflower oil (OSO) of formula:

(120) ##STR00067##

(121) In a jacketed reactor are introduced 604.8 g of oleic sunflower oil (OSO) (ITERG, M=884.82 g.Math.mol.sup.1water content=0.35% by weight) with 188.2 g of absolute ethanol (JT BakerM=46.07 g.Math.mol.sup.1). The whole is mixed with stirring at 650 rpm.sup.1 and heated to 65 C. 6.7211 g of MeONa (AldrichM=54.02 g.Math.mol.sup.1) are then added into the reactor and a change in color of the product and the appearance of instantaneous turbidity are then noticed. The whole was then left to react for 1 h at 70 C.

(122) The resulting reaction mixture was then transferred into a separating funnel in order to remove the glycerol and evaporate the ethanol. Neutralization was then carried out with a few drops of HCl and then washing with water until neutrality. Finally, the residual water was distilled in the Rotavapor.

(123) 532.1 g of sunflower oil ethyl ester of the aforementioned formula (1) were obtained with a water content of 0.35% by weight.

(124) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising 98.2% by weight of ethyl ester.

Example 1bis

Preparation of Oleic Sunflower Oil Ethyl Esters

(125) This example relates to the preparation of compound (1) of the aforementioned Example 1 from oleic sunflower oil (OSO).

(126) In a jacketed reactor are introduced 502.8 g of oleic sunflower oil (OSO) (ITERG) with 161.5 g of absolute ethanol (JT BakerM=46.07 g.Math.mol.sup.1). The whole is mixed with stirring at 650 rpm.sup.1 and heated to 65 C. 5.5880 g of MeONa (AldrichM=54.02 g.Math.mol.sup.1) are then added into the reactor and a change in color of the product and the appearance of instantaneous turbidity are then noticed. The whole is then left to react for 5 h at 70 C.

(127) The resulting reaction mixture was then transferred into a separating funnel in order to remove the glycerol and evaporate the ethanol. Neutralization was then carried out with a few drops of HCl and then washing with water until neutrality. Finally, the residual water was distilled in the Rotavapor.

(128) 455.2 g of sunflower oil ethyl ester of the aforementioned formula (1) was thereby obtained with a water content of 0.29% by weight.

(129) According to characterization by gas phase chromatography which was carried out, a composition was obtained comprising 97.4% by weight of ethyl ester.

Example 2

Preparation of Oleic Sunflower Oil Butanediol Esters

(130) This example relates to the preparation of the compound (2) of the following formula:

(131) ##STR00068##

(132) This is a compound of formula (IV) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms, A.sub.1 represents an alkylene radical comprising 7 carbon atoms, A.sub.2 represents a butylene radical and Y.sub.1 represents H or a group of formula (A.sub.1) as defined above.

(133) The starting product is the compound (1) as obtained in Example 1.

(134) In a reactor (500 mL) are introduced 301.5 g of compound (1) (OSOEE) with 43.1 g (0.5 mol) of 1,4-butanediol (Aldrich) (compound of formula (III) with A.sub.2=butylenes). The whole is heated to 65 C. 3.3602 g of MeONa (Aldrich) are then added into the reactor and a change in color of the product (opaque yellow) is then noticed. The whole is then left to react for 6 hours at 70-75 C. with stirring (650 rpm.sup.1) at a pressure from 800 to 300 mbars.

(135) Neutralization was then carried out with few drops of HCl and then with washing with water in order to remove the traces of butanediol until neutrality. Finally the residual water was distilled in the Rotavapor.

(136) 279 g of sunflower oil butanediol ester of the aforementioned formula (2) were thereby obtained with a water content of 0.22% by weight. The product of formula (2) is in the form of a limpid yellow liquid and has an acid index of 3.58%.

(137) According to characterization by gas phase chromatography which was carried out, a composition was obtained comprising:

(138) after 1 hour: 70% by weight of diesters (compound (2) with Y.sub.1=(A.sub.1)), 11.1% by weight of monoesters (compound (2) with Y.sub.1H) and 18.9% of compound (1).

(139) after 7 hours: 74.5% by weight of diesters (compound (2) with Y.sub.1=(A.sub.1)), 12.5% by weight of monoesters (compound (2) with Y.sub.1H) and 16% of compound (1).

(140) Moreover, with additional purifications it was possible to increase the yield and notably obtain up to 85% by weight of diesters, and this by carrying out distillation of the residual monoesters.

Example 3

Preparation of Oleic Sunflower Oil Epoxidized Butanediol Esters

(141) This example relates to the preparation of the compound (3) of the following formula:

(142) ##STR00069##

(143) This is a compound of formula (V) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms, A.sub.1 represents an alkylene radical comprising 7 carbon atoms, A.sub.2 represents a butylenes radical and Y.sub.2 represents H or a group of formula (A.sub.2) as defined above.

(144) The starting product is the compound (2) as obtained in Example 2 having the following composition: 83.7% by weight of diesters, 8.80% by weight of monoesters and 7.50% by weight of ethyl ester (compound (1)).

(145) In a reactor (250 mL) are introduced 79.7 g of compound (2) butanediol esters) with 7 g (0.3 mol) of formic acid HCOOH (BAKER) at 45 C. for 1 hour at 500 rpm.sup.1. Hydrogen peroxide was then added with a dropping funnel dropwise for 10 minutes (36.7 g (2 moles) of 50% H.sub.2O.sub.2 (BAKER)). The whole was then left to react for 2 hours at 75 C. with stirring at 650 rpm.sup.1. As the reaction is exothermic, the medium was cooled with a bath of cold water.

(146) Washing with water was then carried out until neutrality of the washing waters. Finally, the residual water was distilled in the Rotavapor.

(147) 79.3 g of sunflower oil epoxidized butanediol esters of the aforementioned formula (3) were thereby obtained. The product of formula (3) is in the form of a white solid at room temperature and has an acid index of 1.95%.

(148) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising 86.8% by weight of diesters (compound (3) with Y.sub.2=(A.sub.2))) 7.3% by weight of monoesters (compound (3) with Y.sub.2H) and 5.9% by weight of compound (1).

Example 4

Preparation of the Diol (4)

(149) This example relates to the preparation of the compound (4) of the following formula:

(150) ##STR00070##

(151) This is a compound of formula (I) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms, A.sub.1 represents an alkylene radical comprising 7 carbon atoms, A.sub.2 represents a butylene radical, R represents an ethyl group and Y represents H or a group of formula (A) as defined above.

(152) The starting product is the compound (3) as obtained in Example 3 having the following composition: 86.8% by weight of diesters, 7.3% by weight of monoesters and 5.9% by weight of ethyl ester (compound (1)).

(153) In a reactor (250 mL) are introduced 60.2 g of compound (3) (butanediol epoxidized esters) with 2.4 g (4% by weight) of Amberlyst (Aldrich) resin and 112.6 g (15 moles) of absolute ethanol (BAKER). The whole was left to react at 70 C. for 4 hours at 500 rpm. The resin was then filtered on a Bchner and finally the residual ethanol was distilled in the Rotavapor.

(154) 53.6 g of the polyol of the aforementioned formula (4) were thereby obtained. The product of formula (3) is in the form of a pale yellow liquid and has an acid index of 1.37%.

(155) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising less than 0.5% by weight of butanediol, 82.0% by weight of diesters (compound (1) with Y=(A)), 7.6% by weight of monoesters (compound (1) with YH) and 10.4% by weight of compound (1).

(156) The compound (4) was analyzed by IR spectroscopy and an OH band was observed at 3 461.76 cm.sup.1 and a secondary alcohol band at 1 087.24 cm.sup.1.

Example 5

Preparation of Castor Oil Ethyl Esters

(157) This example relates to the preparation of the compound (5) of the following formula:

(158) ##STR00071##

(159) This is a compound of formula (II) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms and substituted with an OH group (on the carbon 7), A.sub.1 represents an alkylene radical comprising 7 carbon atoms and R.sub.2 represents an ethyl group.

(160) The starting product is castor oil with the formula:

(161) ##STR00072##

(162) In a jacketed reactor (1 liter) were introduced 402.4 g of castor oil (ITERG, M=928 g.Math.mol.sup.1water content=0.35% by weight) with 405.4 g of absolute ethanol (JT BakerM=46.07 g.Math.mol.sup.1). The whole is mixed with stirring at 650 rpm.sup.1 and heated to 65 C. 4.5214 g of MeONa (AldrichM=54.02 g.Math.mol.sup.1) are then added into the reactor and a change in color of the product and the appearance of instantaneous turbidity are then noticed. The whole is left to react for 30 minutes at 50 C.

(163) The resulting reaction mixture was then transferred into a separating funnel in order to remove the glycerol and evaporate the ethanol. Neutralization was then carried out with a few drops of HCl and then washing with water until neutrality. Finally, the residual water was distilled in the Rotavapor.

(164) 360.2 g of castor oil ethyl ester of the aforementioned formula (5) were thereby obtained with a water content of 0.23% by weight.

(165) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising 93.8% by weight of ethyl ester.

Example 6

Preparation of Castor Oil Butanediol Esters

(166) This example relates to the preparation of the compound (6) of the following

(167) ##STR00073##

(168) This is a compound of formula (IV) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms and substituted with an OH group (on the carbon 7), A.sub.1 represents an alkylene radical comprising 7 carbon atoms, A.sub.2 represents a butylenes radical and Y.sub.1 represents H or a group of formula (A.sub.1) as defined above.

(169) The starting product is the compound (5) as obtained in Example 5.

(170) In a reactor (500 mL) are introduced 300.5 g of compound (5) with 43.5 g (0.5 mol) of 1,4-butanediol (Aldrich) (compound of formula (III) with A.sub.2=butylene). The whole is heated to 65 C. 3.6005 g of MeONa (Aldrich) are then added into the reactor and a change in color of the product (opaque yellow) was then noticed. The whole is then left to react for 6 hours at 70-75 C. with stirring (650 rpm.sup.1) at a pressure from 800 to 2 mbars.

(171) Neutralization was then carried out with a few drops of HCl and then washing with water in order to remove the butanediol traces until neutrality. Finally, the residual water was distilled in the Rotavapor.

(172) 260 g of castor oil butanediol ester of the aforementioned formula (6) were thereby obtained with a water content of 0.30% by weight. The product of formula (6) is in the form of a yellow liquid and has an acid index of 5.05%.

(173) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising 43.9% by weight of diesters (compound (6) with Y.sub.1=(A.sub.1)), 30.4% by weight of monoesters (compound (6) with Y.sub.1H) and 25.7% by weight of compound (5).

Example 7

Preparation of Epoxidized Sunflower Oil Ethyl Esters

(174) This example relates to the preparation of the compound (7) of the following

(175) ##STR00074##

(176) This is a compound of formula (IV-2) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms, A.sub.1 represents an alkylene radical comprising 7 carbon atoms and R.sub.2 represents an ethyl group.

(177) The starting product is the oleic sunflower oil ethyl ester compound of Example 1bis.

(178) In a reactor (1 L) are introduced 399.6 g of the compound (1) of Example 1 bis (oleic sunflower oil ethyl esterOSOEE) and 20.1 g of formic acid and the whole was left to react at 45 C. for 1 hour at 500 rpm.sup.1. Next hydrogen peroxide was added dropwise with a dropping funnel for 40 minutes (199.2 of H.sub.2O.sub.2 (BAKER)). The whole was then left to react for 2 hours at 75 C. with stirring at 650 rpm.sup.1. As the reaction is exothermic, the medium was cooled with a cold water bath.

(179) Washing with water was then carried out until neutrality of the washing waters. Finally, the residual water was distilled in the Rotavapor.

(180) 410.3 g of oleic sunflower oil epoxidized ethyl esters of the aforementioned formula (7) were thereby obtained. The product of formula (7) is in the form of an orangey liquid and has an acid index of 0.79%, as well as a water content of 0.41%.

Example 8

Preparation of the Diol (8)

(181) This example relates to the preparation of the compound (8) of the following

(182) ##STR00075##

(183) This is a compound of formula (I-1) in which R.sub.1 represents an alkyl group comprising 8 carbon atoms, A.sub.2 represents a butylene radical, A.sub.1 represents an alkylene radical comprising 7 carbon atoms and R.sub.2 represents an ethyl group.

(184) The starting product is the epoxidized oleic sunflower oil ethyl ester compound of Example 7.

(185) In a reactor (2 L) 301.2 g of compound (7) are introduced with 12 g (4% by weight) of Amberlyst resin (Aldrich) and 1 201.1 g of distilled 1,4-butanediol (Aldrich). The whole as left to react at 70 C. for 4 hours at 500 rpm.sup.1.

(186) The butanediol was distilled at 120-150 C. under 30 mbars and the whole was washed with water for removing the traces of butanediol. The resin was then filtered on a Bchner and, finally the residual ethanol was distilled in the Rotavapor.

(187) 270.3 g of the polyol of the aforementioned formula (8) were thereby obtained. The product of formula (8) has an acid index of 0.27% and a hydroxyl index of 255.8 mg KOH/g.

(188) According to the characterization by gas phase chromatography which was carried out, a composition was obtained, comprising less than 0.1% by weight of butanediol, 22% by weight of diesters, 71.7% by weight of monoesters (compound 8) and 6.1% by weight of compound (1).

Example 9

Preparation of Erucic Rape Seed Oil Ethyl Esters

(189) This example relates to the preparation of the compound (9) of the following

(190) ##STR00076##

(191) This is a compound of formula (II) in which R.sub.1 represents an alkyl group comprising 12 carbon atoms, A.sub.1 represents an alkylene radical comprising 7 carbon atoms and R.sub.2 represents an ethyl group.

(192) The starting product is erucic rape seed oil of formula:

(193) ##STR00077##

(194) In a jacketed reactor (1.5 liter) are introduced 1 004.7 g of erucic rape seed oil (ERO) (ITERG, M=951.8 g.Math.mol.sup.1water content=0.35% by weight) with 290.7 of absolute ethanol (JT BakerM=46.07 g.Math.mol.sup.1). The whole is mixed with stirring at 650 rpm.sup.1 and heated to 65 C. 11.1 g of MeONa (AldrichM=54.02 g.Math.mol.sup.1) were then added into the reactor and a change in the color of the product and the appearance of instantaneous turbidity was then noticed. The whole is then left to react for 1 hour at 70 C.

(195) The resulting reaction mixture was then transferred into a separating funnel in order to remove the glycerol and evaporate the ethanol. Neutralization was then carried out with a few drops of HCl and then washing with water until neutrality. Finally the residual water was distilled in the Rotavapor.

(196) 1 026.8 g of rape seed oil ethyl ester of the aforementioned formula (9) of the were thereby obtained with a water content of 0.27% by weight and an acid index of 1.04%.

(197) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising 98.48% by weight of ethyl ester.

Example 10

Preparation of Epoxidized Rape Seed Oil Ethyl Esters

(198) This example relates to the preparation of the compound (10) of the following formula:

(199) ##STR00078##

(200) This is a compound of formula (IV-2) in which R.sub.1 represents an alkyl group comprising 12 carbon atoms, A.sub.1 represents an alkylene radical comprising 7 carbon atoms and R.sub.2 represents an ethyl group.

(201) The starting product is the rape seed oil ethyl ester compound of Example 9.

(202) In a reactor (1 L) are introduced 400.5 g of compound (9) (rape seed oil ethyl esterROEE) and 23.12 g of formic acid and the whole is left to react at 45 C. for 1 hour at 500 rpm. Hydrogen peroxide was then added dropwise with a dropping funnel for 40 minutes (211.1 g of H.sub.2O.sub.2 (BAKER)). The whole was then left to react for 3 hours at 75 C. with stirring at 650 rpm.sup.1. As the reaction is exothermic, the medium was cooled with a cold water bath.

(203) Washing with water was then carried out until neutrality of the washing waters. Finally, the residual water was distilled in the Rotavapor.

(204) 410.2 g of erucic castor oil epoxidized ethyl esters of the aforementioned formula (10) were thereby obtained. The product of formula (10) is in the form of a white solid at room temperature and has an acid index of 1.08%, as well as a water content of 0.22%.

Example 11

Preparation of the Diol (11)

(205) This example relates to the preparation of the compound (11) of the following formula:

(206) ##STR00079##

(207) This is a compound of formula (I-1) in which R.sub.1 represents an alkyl group comprising 12 carbon atoms, A.sub.2 represents a butylene radical, A.sub.1 represents an alkylene radical comprising 7 carbon atoms and R.sub.2 represents an ethyl group.

(208) The starting product is the epoxidized erucic rape seed oil ethyl ester compound of Example 10.

(209) In a reactor (2 L) 350.2 g of compound (10) are introduced with 14.2 g (4% by weight) of Amberlyst resin (Aldrich) and 1 484.6 g of distilled 1,4-butanediol (Aldrich). The whole was left to react at 70 C. for 4 hours at 500 rpm.sup.1.

(210) Two phases were then obtained: the upper phase containing the compound 11 and traces of butanediol and the lower phase containing butanediol and traces of compound (11).

(211) The upper phase was therefore distilled with magnetic stirring in vacuo at 120-140 C. under 30 mbars. The lower phase was also distilled in vacuo and with a flow of dinitrogen without stirring for two days in order to obtain a dark brown product.

(212) The whole was washed with water for removing the traces of butanediol. The resin was then filtered on a Bchner and finally the residual ethanol was distilled in the Rotavapor.

(213) Via the upper phase, 126 g of a pale yellow liquid were obtained with an acid index of 0.69% and a hydroxyl index of 190.4 mg of KOH/g, as well as a water content of 0.64%.

(214) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising less than 0.1% by weight of butanediol, 6.9% by weight of diesters, 89.1% by weight of monoesters (compound 11), 0.7% by weight of triglycerides and 3.3% by weight of compound (9).

(215) Via the lower phase, 135 g of a dark brown liquid were obtained with a water content of 0.35%.

(216) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising less than 0.3% by weight of butanediol, 11.4% by weight of diesters, 87.7% by weight of monoesters (compound 11), 0.4% by weight of triglycerides and 0.3% by weight of compound (9).

Example 12

Preparation of Polymers from Polyols of Formula (I)

(217) By applying the same procedures as in the aforementioned examples 1 to 6, the following compounds were also synthesized:

Synthesis of Polymers from the Polyol

(218) ##STR00080##

(219) TABLE-US-00002 Group R C.sub.3H.sub.6 C.sub.4H.sub.8 C.sub.6H.sub.12 Reaction time 5 h 5 h 5 h M.sub.w 20,000 g/mol 20,000 g/mol 18,000 g/mol IP 1.4 1.5 1.3

Synthesis of Polymers from the Polyol

(220) ##STR00081##

(221) TABLE-US-00003 Group R C.sub.3H.sub.6 PEG.sub.300 PEG.sub.600 Reaction time 7 h 8 h 10 h M.sub.w 15,000 g/mol 14,000 g/mol 14,000 g/mol IP 1.4 1.5 1.3

(222) The polyols of the invention are used for preparing polymers for example by reaction with isocyanates. The applied procedure is described hereafter and may be applied to any polyol and any isocyanate.

(223) In a reactor of 100 mL were added the polyol of the invention and the catalyst and then the isocyanate (in particular IPDI) was added into the reactor via a funnel. The temperature of the mixture was maintained at 60 C. by heating.

(224) From the Polyol Monoester with RO.sub.3H.sub.6

(225) 2 g of monoester were introduced into a 100 mL reactor in the presence of 2 mg of DBTDL (LCPO) (dibutyltin dilaurate) (0.1% by weight). And then 1.1 g of IPDI (AldrichM=222.29 g.Math.mol.sup.1) (isophorone diisocyanate) (1 equivalent) were introduced. The mixture was placed with magnetic stirring for 5 hours.

(226) The kinetics of the reaction were tracked by IR analysis which allowed observation of the disappearance of the band NC at 2 269.94 cm.sup.1 and the appearance of the band NH at 3 350 cm.sup.1. The obtained polymer was analyzed by steric exclusion chromatography (the obtained molar masses are listed in the tables above).

(227) The procedure is unchanged for the cases when RC.sub.4H.sub.10 and RO.sub.6H.sub.12.

(228) From the Polyol Diester with RC.sub.3H.sub.6

(229) 2 g of diester were introduced into a 100 mL reactor in the presence of 2 mg of DBTDL (LCPO) (dibutyltin dilaurate) and then 586 mg of IPDI (AldrichM=222.29 g.Math.mol.sup.1) (isophorone diisocyanate) (0.5 equivalent) were introduced. The mixture was placed with magnetic stirring for 7 hours.

(230) The kinetics of the reaction were tracked by IR analysis which allowed observation of the disappearance of the band NC at 2 269.94 cm.sup.1 and the appearance of the band NH at 3 350 cm.sup.1. The obtained polymer was obtained by steric exclusion chromatography (the obtained molar masses are listed in the tables above).

(231) The procedure is unchanged for the cases when R=PEG.sub.300 and R=PEG.sub.500.

Example 13

Preparation of Polyurethanes from the Diol 8

(232) The polyols of the invention are used for preparing polymers for example by reaction with isocyanates. The applied procedure is described hereafter and may be applied to any polyol and any isocyanate.

(233) In a reactor of one liter, the polyol of the invention and the catalyst were added and then the isocyanate (in particular IPDI or HMDI) was added into the reactor via a funnel. The whole was then stirred at 80 rpm.sup.1 under dinitrogen in order to homogenize the mixture. The appearance of bubbles was then observed in the reaction mixture and the temperature of the mixture was maintained at 60 C. by heating.

(234) The kinetics of the reaction were tracked by IR analysis which allowed observation of the disappearance of the band NC at 2 269.94 cm.sup.1 and the appearance of the band NH at 3 350 cm.sup.1.

(235) More particularly, this procedure was applied by using as a polyol, the diol 8 of Example 8 and by varying the nature of the isocyanate (IPDI and HMDI), as well as the reaction time and the OH:NCO ratio.

(236) The catalyst used is DBTDL (LCPO) (dibutyltin dilaurate) at 0.1% by weight.

(237) The obtained results are summarized hereafter in Tables 1 and 2.

(238) TABLE-US-00004 TABLE 1 corresponds to the synthesis of polyurethane by reaction with IPDI (Aldrich M = 222.29 g .Math. mol.sup.1)(isophorone diisocyanate): Solubility Viscosity (cst) (DCM, GPC 80 C. 100 C. Reaction THF, IR Analysis Shearing (s.sup.1) No OH:NCO time (h) DMF) Analysis (Mw) 1 10 1 10 1 1:0.2 7 soluble No isocyanate 1 830 9.5 4.5 band 2 1:0.3 7 soluble No isocyanate 2 300 23.5 11.5 band 3 1:0.5 7 soluble No isocyanate 5 240 160 70 band 4 1:0.65 7 soluble No isocyanate 10 820 1050 775 280 band 5 1:0.69 12 soluble No isocyanate 12 570 band DCM: dichloromethane THF: tetrahydrofurane DMF: dimethylformamide The suitable viscosities are obtained for an OH:NCO ratio of less than 1:0.70.

(239) TABLE-US-00005 TABLE 2 corresponds to the synthesis of polyurethane by reaction with HMDI (hexamethylene diisocyanate): Solubility Viscosity (cst) (DCM, GPC 80 C. 100 C. Reaction THF, IR Analysis Shearing (s.sup.1) No OH:NCO time (h) DMF) Analysis (Mw) 1 10 1 10 1 1:0.3 6 soluble No isocyanate 2 740 31.7 14.5 band 2 1:0.5 6 soluble No isocyanate 7 200 287 385 93 188 band 3 1:0.65 9 soluble No isocyanate 13 550 3 474 3 055 879 891 band

Example 14

Preparation of a Diol of Formula (I-2) with Two Secondary Alcohol Functions

(240) The procedure described hereafter was used for synthesizing compounds of formula (I-2), A.sub.1 representing a C.sub.7H.sub.14 radical and R.sub.1 representing an alkyl group comprising 9 carbon atoms.

(241) In formula (I-2), A.sub.2 may represent a radical selected from the following radicals: C.sub.3H.sub.6, C.sub.4H.sub.8, C.sub.5H.sub.10, C.sub.6H.sub.12, H.sub.2C(CH.sub.2OCH.sub.2).sub.6CH.sub.2, H.sub.2C(CH.sub.2OCH.sub.2).sub.13CH.sub.2, H.sub.2C(CH.sub.2OCH.sub.2).sub.45CH.sub.2 or H.sub.2CC.sub.6H.sub.4CH.sub.2.

(242) Transesterification Step:

(243) The diesters stem from transesterification of an oleic methyl ester and of a diol (propanediol, butanediol, pentanediol, hexanediol, polyoxyethylene (300 g/mol, 600 g/mol and 2000 g/mol)). The synthesis involves 0.1 mol of oleic methyl ester and 0.05 mol of diol, in the presence of magnesium oxide MgO (catalyst, 1% by mass based on the methyl ester mass). The medium was kept with stirring at 160 C., under nitrogen flow, for 7 hours. The methanol formed by the reaction was removed from the reaction medium by means of a Dean Stark trap. The formation of the diester was followed via .sup.1H MNR. After 7 hours, the medium was placed at 200 C. in a dynamic vacuum for 1 hour in order to remove the oleic methyl ester and the residual diols. The catalyst was removed by filtration.

(244) For the synthesis of the diester from methyl ester and 1,4-benzenedimethanol (A.sub.2=H.sub.2CC.sub.6H.sub.4CH.sub.2), the temperature of the medium during the reaction was 140 C. in order not to sublimate the 1,4-benzenedimethanol.

(245) Epoxidation Step:

(246) 10 mmol of diester synthesized previously were mixed with 3 mmol of formic acid (HCOOH). The mixture was heated to 40 C. for 1 hour. And then 10 mmol of hydrogen peroxide (H.sub.2O.sub.2) were added dropwise. The temperature was raised to 70 C. for 2 hours. The formation of the epoxide was followed by .sup.1H MNR. When the reaction is completed, it is proceeded with water-dichloromethane washing in order to remove the peracid.

(247) Hydroxylation Step:

(248) For the step for opening the epoxide, 10 mmol of epoxidized diesters were dissolved in 100 mmol of ethanol, in the presence of an ion exchange resin (Amberlyst 15 Dry, 4% by mass based on the mass of the diesters). The reaction medium was placed with stirring, at 75 C. for 20 hours. The opening of the epoxide was followed by .sup.1H MNR. When the reaction was complete, the catalyst was removed by filtration. The excess ethanol was then evaporated under low pressure. The hydroxylated diesters were then analyzed with .sup.1H MNR and with steric exclusion chromatography. Their hydroxyl index was determined.

Example 15

Preparation of a Diol of Formula (I-1) with Two Secondary Alcohol Functions

(249) The procedure described hereafter was used for synthesizing compounds of formula (I-1), A.sub.1 representing a C.sub.7H.sub.14 radical and R.sub.1 representing an alkyl group comprising 9 carbon atoms.

(250) In the formula (I-1), A.sub.2 may represent a radical selected from the following radicals: C.sub.3H.sub.6, C.sub.4H.sub.8, C.sub.5H.sub.10, C.sub.6H.sub.12, H.sub.2C(CH.sub.2OCH.sub.2).sub.6CH.sub.2, H.sub.2C(CH.sub.2OCH.sub.2).sub.13CH.sub.2, H.sub.2C(CH.sub.2OCH.sub.2).sub.45CH.sub.2 or H.sub.2CC.sub.6H.sub.4CH.sub.2.

(251) The synthesis procedures are the same as those indicated for example 14, except for the transesterification step. The synthesis involves 0.1 mol of oleic methyl ester and 1.5 mol of diol, in order to promote formation of monoesters relatively to diesters.

Example 16

Preparation of Bisepoxide Compounds of Formula (V-3)

(252) ##STR00082##

(253) The first step consisted of cutting the carbonaceous chain of the oleic methyl ester at the internal double bond in order to obtain an internal double bond. A metathesis reaction between ethylene and the internal double bond of the oleic methyl ester in the presence of Hoveyda catalyst lead to the formation of decene and of methyl 10-undecenoate. This reaction took place with stirring at room temperature. In the equilibrium state, the medium consists of 48% of initial oleic methyl ester, 26% of decene and 26% of methyl 10-undecenoate. The latter was extracted by distillation in vacuo: the first fraction at 100 C. contained decene; methyl 10-undecenoate was recovered when the temperature reached 180 C. The residue consisted of oleic methyl ester.

(254) It was then proceeded with a reaction for transesterification of methyl 10-undecenoate with a diol (aliphatic, aromatic diol, phenol of natural origin, etc.). The reaction took place in vacuo in the presence of 0.5 equivalent of diol in order to promote formation of diesters; it was catalyzed with 1 wt % of magnesium oxide. The temperature of the medium was raised to 160 C., the produced methanol was removed continuously by means of a Dean Stark trap. After 7 hours, the temperature was raised to 180 C. in order to remove the residual methyl 10-undecenoate.

(255) The last step consisted in the epoxidation of the double bonds of the product obtained by transesterification. It was carried out in the presence of metachloroperbenzoc acid (m-CPBA) (1.2 equiv. per double bond), in dichloromethane at room temperature. The conversion of the double bonds was total after 3 hours. The excess m-CPBA was reduced into the corresponding carboxylic acid with a saturated solution of sodium sulfate. The organic phase was extracted with dichloromethane and then the residual carboxylic acid was transformed into sodium chlorobenzoate (soluble in water) by two washings with a saturated solution of sodium bicarbonate.

Example 17

Preparation of Oleic Sunflower Oil Ethyl Esters

(256) This example relates to the preparation of the compound (1) of the aforementioned Example 1 from oleic sunflower oil (OSO).

(257) In a jacketed reactor are introduced 1 001.2 g of oleic sunflower oil (OSO) (ITERG, M=884.82 g.Math.mol.sup.1water content=0.35% by weight) with 314.0 g of absolute ethanol (JT BakerM=46.07 g.Math.mol.sup.1). The whole is mixed with stirring at 650 rpm.sup.1 and heated to 65 C. 11.5 g of MeONa (AldrichM=54.02 g.Math.mol.sup.1) were then added into the reactor and a change in color of the product and the appearance of instantaneous turbidity were then noticed. The whole was then left to react for 1 hour at 70 C.

(258) The resulting reaction mixture was then transferred into a separating funnel in order to remove the glycerol and evaporate the ethanol. Neutralization was then carried out with a few drops of HCl and then washing with water until neutrality. Finally, the residual water was distilled in the Rotavapor.

(259) 1 056.5 g of sunflower oil ethyl ester of the aforementioned formula (1) with a water content of 0.15% by weight were thereby obtained.

(260) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising 97.8% by weight of ethyl ester.

Example 18

Preparation of Epoxidized Sunflower Oil Ethyl Esters

(261) This example relates to the preparation of the compound (7) of Example 7 from the compound (1) of Example 18.

(262) In a reactor (2 L) 800.5 g of the compound (7) of Example 7 (oleic sunflower oil ethyl esterOSOEE) were introduced and 39.4 gl of formic acid and the whole was left to react at 45 C. for 1 hour at 500 rpm.sup.1. Hydrogen peroxide was then added dropwise with a dropping funnel for 36 minutes (355.5 g of H.sub.2O.sub.2 (BAKER)). The whole was then left to react for 2 hours at 75 C. with stirring at 650 rpm.sup.1. As the reaction is exothermic, the medium was cooled with a cold water bath.

(263) Washing with water was then carried out until neutrality of the washing waters. Finally, the residual water was distilled in the Rotavapor.

(264) 1 056.5 g of oleic sunflower epoxidized ethyl esters of the aforementioned formula (7) were thereby obtained. The product of formula (7) is in the form of a pale yellow liquid and has a water content of 0.11%.

Example 19

Preparation of the Diol (8)

(265) This example relates to the preparation of the diol (8) of Example 8 from the compound (7) of Example 1.

(266) In a reactor (2 L) were introduced 100.4 g of compound (7) with 4.1 g (4% by weight) of Amberlyst resin (Aldrich) and 416.1 g of distilled 1,4-butanediol (Aldrich). The whole was left to react at 70 C. for 4 hours at 650 rpm.sup.1.

(267) The whole was washed with water for removing the traces of butanediol, and finally the residual ethanol was distilled in the Rotavapor.

(268) 93.0 g of the polyol of the aforementioned formula (8) were thereby obtained.

(269) According to the characterization by HPLC chromatography which was carried out, a composition was obtained, comprising 1.1% by weight of butanediol, 6.8% by weight of diesters, 70.5% by weight of monoesters (compound 8) and 2.0% by weight of compound (1).

Example 20

Preparation of Epoxidized Rape Seed Oil Ethyl Esters

(270) This example relates to the preparation of the compound (10) of Example 10 from erucic rape seed oil ethyl esters.

(271) In a reactor (1 L) are introduced 400.6 g of compound (9) (rape seed oil ethyl esterROEE) and 27.0 g of formic acid and the whole was left to react at 45 C. for 1 hour at 500 rpm.sup.1. Hydrogen peroxide was then added dropwise with a dropping funnel for 45 minutes (211.1 of H.sub.2O.sub.2 (BAKER)). The whole was then left to react for 3 hours at 75 C. with stirring at 650 rpm.sup.1. As the reaction is exothermic, the medium is cooled with a cold water bath.

(272) Washing with water was then carried out until neutrality of the washing waters. Finally, the residual water was distilled in the Rotavapor.

(273) 391.1 g of erucic castor oil epoxidized ethyl esters of formula (10) (cf. Example 10) were thereby obtained.

Example 21

Preparation of the Diol (11)

(274) This example relates to the preparation of the compound (11) of Example 11 from the ethyl ester of Example 10 of epoxidized erucic rape seed oil.

(275) In a reactor (2 L) were introduced 350.2 g of compound (10) with 14.3 g (4% by weight) of Amerlyst resin (Aldrich) and 514.5 g of distilled 1,4-butanediol (Aldrich). The whole was left to react at 70 C. for 4 hours at 650 rpm.sup.1.

(276) The whole was poured into a separating funnel, in which 200 mL of warm water were added followed by 100 mL of butanol. After stirring and phase separation at rest, two phases were observed. The upper phase was put aside and the lower phase was washed with 250 mL of butanol. The upper phases were then grouped, washed with warm water in order to remove the traces of butanediol, and then dried in the Rotavapor.

(277) 272.1 g of a pale yellow liquid with a hydroxyl index of 187.9 mg KOH/g, as well as a water content of 0.66% were thereby obtained.

(278) According to the characterization by gas phase chromatography which was carried out, a composition was obtained comprising less than 0.1% by weight of butanediol, 9.2% by weight of diesters and 66.1% by weight of monoesters (compound 11).

Example 22

Synthesis of Polyurethanes from the Diols of Examples 19 and 21

(279) Synthesis Procedure

(280) A three-neck flask (250 mL) with a mechanical stirrer and a nitrogen inlet was loaded with dibutyltin dilaurate (0.003 g, 0.1% by mass based on the monomers), the polyol (from Example 19 or 21) (18.0 g, hydroxyl index=215.9) and with isophorone diisocyanate (IPDI) (6.54 g, OH/NCO=1:0.85). The OH./NCO ratio was calculated on the basis of the hydroxyl index of the polyol. The reaction medium was stirred at room temperature under nitrogen flow and heated to 60 C. for 9 hours. Polymerization was controlled by IR spectroscopy on the basis of the isocyanate band. After completion of the reaction, 0.7 g of octyl dodecanol were added in order to stop the reaction with additional heating for a further 12 hours. The obtained polymer was characterized by IR, MNR and GPC.

(281) The same procedure was applied by using HDMI as a diisocyanate instead of IPDI.

(282) TABLE-US-00006 TABLE 3 hereafter illustrates the results obtained for the synthesis of polyurethane by reaction with IPDI or HDMI as an isocyanate and the polyols of Examples 19 and 21: Viscosity (cst) 30 C. 80 C. 100 C. OH/NCO GPC Analysis Shearing (1/s) Polyol ratio diisocyanate Mw Mw/Mn 1 10 1 10 1 10 Ex. 19 1:0.85 IPDI 3280 1.61 5850* 105 93 31.5 Ex. 19 1:0.75 HMDI 3210 1.35 6550* 98 92 38 33 Ex. 19 1:0.85 HMDI 4160 1.47 250 220 95 60 Ex. 21 1:0.7 IPDI 3730 1.32