EP2914643A1

EP2914643A1 - Polymers of [4-(methylether)-1,3-dioxolane-2-one of polyether polyol]

Info

Publication number: EP2914643A1
Application number: EP13801629.0A
Authority: EP
Inventors: Guillaume Michaud; Frédéric Simon; Stéphane Fouquay
Original assignee: Bostik SA
Current assignee: Bostik SA
Priority date: 2012-11-05
Filing date: 2013-10-30
Publication date: 2015-09-09
Also published as: KR20150082281A; CN104918982A; FR2997700B1; AU2013340641A1; FR2997700A1; WO2014068251A1; BR112015010100A2; US20150299390A1

Abstract

The invention relates to a polymer having formula (I), wherein: R is a hydrogen or an alkyl having between 1 and 4 carbon atoms; m is a number between 1 and 6; B is a monovalent, divalent, trivalent, tetravalent, pentavalent or hexavalent radical comprising between 1 and 44 carbon atoms per molecule; and n is such that the number-average molar mass Mn of the polymer of formula (I) is between 4000 and 18000 g/mol, and the polymolecularity (Pd) thereof is in a range of 1.0 to 1.4. The invention relates to a method for the production of the polymer having formula (I). The invention also relates to a method for the production of polyurethanes, comprising the reaction of a polymer having formula (I) with a compound containing an amino group, as well as polyurethanes that can be obtained in this manner.

Description

Polymers of polyether polyol r4- (methylether) -1, 3-dioxolan-2-one

The subject of the present invention is polymers comprising at each of their ends a 1,3-dioxolan-2-one (or cyclocarbonate) end group linked to a polymeric chain by an alpha (a) substituted methylether (CH 2 -O) function. 1,3-dioxolan-2-one, and their use for the preparation of polyurethanes by reaction with a compound comprising at least one amino group. These polyurethanes, once formulated, are intended for use in coatings, mastics or adhesives, as additives and / or as resins.

The synthesis of polyurethanes is usually done by reaction between a diol and a diisocyanate. Diisocyanates are toxic compounds as such, and are generally obtained from phosgene, itself very toxic by inhalation or contact. The manufacturing process used in industry generally involves the reaction of an amine with an excess of phosgene to form an isocyanate.

The search for alternatives to the synthesis of polyurethanes without using isocyanate (or NIPU for "Non Isocyanate Polyurethane s" in English), therefore represents a major challenge.

This research has been the subject of numerous research and development studies. The most studied tracks concern the use of polymers, each of whose end groups comprises a 1, 3-dioxolan-2-one group on termination. These polymers react with amines or oligomers of amines to form polyurethanes.

However, none of the proposed solutions is satisfactory.

Patent Application EP1088021, Eurotech Ltd., discloses oligomeric compounds of 1,3-dioxolan-2-one, including oligomeric compounds of 4-methylether-1,3-dioxolan-2-one polypropylene glycol. The oligomeric compounds are synthesized by carbonation in a high pressure reactor, from the corresponding compounds comprising terminal groups with oxirane (or epoxide) terminations: by carbonation, the oxirane groups are converted into 1,3-dioxolan-2-one groups. The oligomeric compounds of 1,3-dioxolan-2-one are then mixed with amine oligomers so as to synthesize, by crosslinking, polyurethanes.

The oligomeric 4-methylether-1,3-dioxolan-2-one polypropylene glycol compounds described herein have a low molecular weight, typically 350 to 3200 g / mol, and a star-shaped structure comprising from 2 to 8 branches, each branch comprising a 4-methylether-1,3-dioxolan-2-one polypropylene glycol and all the branches being interconnected by a hydrocarbon group. The 4-methylether-1,3-dioxolan-2-one group terminates the terminal group of each branch, the hydrocarbon group being at the other end of the branch. No example of synthesis of a polypropylene glycol 4-methyl ether-1,3-dioxolane oligomeric compound is described. However, the carbonation reaction is not complete, since the oligomers comprise from 4 to 12% by weight of the starting oligomers, which is problematic during the formation of the polyurethanes.

The patent application WO 03/028644 of Eurotech Ltd describes oligomeric compounds of 4-methylether-1,3-dioxolan-2-one which are almost pure, and in particular oligomeric compounds of 4-methylether-1,3-dioxolane. Polypropylene glycol 2-one low molecular weight, typically from 600 to 1600 g / mol. The structure of these oligomers is star-shaped comprising from 3 to 6 branches, each branch comprising a 4-methylether-1,3-dioxolan-2-one of polypropylene glycol, and all the branches being connected together by a group hydrocarbon. The 4-methylether-1,3-dioxolan-2-one group terminates the terminal group of each branch, the hydrocarbon group being at the other end of the branch. No example of synthesis of an oligomeric compound of polypropylene glycol 4-methylether-1,3-dioxolane is described.

The present invention aims to provide new intermediates for the synthesis of polyurethanes without using isocyanate. Thus, the present invention relates to a polymer of formula (I) comprising at least one terminal group 4-methylether-1,3-dioxolan-2-one:

in which :

- R is a hydrogen or an alkyl which comprises from 1 to 4 carbon atoms, preferably R is hydrogen and / or a methyl radical;

m is a number from 1 to 6, preferably m is chosen from 2 and 3, even more preferably m is equal to 2;

B is a monovalent, divalent, trivalent, tetravalent, pentavalent or hexavalent radical, said radical generally comprising from 1 to 44 carbon atoms per molecule;

and n is such that the number-average molar mass Mn of the polymer of formula (I) is in the range of 4000 to 18000 g / mol, and such that the polydispersity (Pd) of the polymer of formula (I) is included in a range of 1.0 to 1.4.

The polydispersity Pd is defined as the ratio Mw / Mn, that is to say the ratio of the molar mass by weight to the molar mass by number of the polymer.

The two molar masses Mn and Mw are measured according to the invention by Size Exclusion Chromatography (SEC), usually with PEG (PolyEthyleneGlycol) or PS (Polystyrene) calibration.

By terminal group means a group located at the end of the chain (or end) of the polymer. The radical B may be linear or branched, may comprise at least one saturated and / or unsaturated bond, and may comprise at least one cyclic and / or alicyclic group.

The radical B is preferably chosen from the group formed by the radicals formed from methanol, ethylene glycol, propylene glycol, neopentyl glycol, dimeric fatty alcohol, trimethylolpropane, pentaerythritol, glycerol, arabinol and sorbitol compounds, starting from at least a hydroxyl group.

The polymeric divalent radical - (- OCH ₂ -CH (R) -) _n - generally has a number-average molecular weight in the range of about 667 to 18000 g / mol.

The polymeric divalent radical - (- OCH ₂ --CH (R) -) _n - may be formed from a block or random copolymer of at least two divalent radicals of polymers of formulas - (- OCH ₂ - CH (R1) -) _n i- and - (- OCH ₂ -CH (R2) -) _n2 -, where n1 and n2 are such that the molar mass by number Mn of the polymer of formula (I) is within a range from 4000 to 18000 g / mol, and such that the polydispersity (Pd) of the polymer of formula (I) is in the range of 1.0 to 1.4.

According to a preferred embodiment of the invention, the polymeric divalent radical - (- OCH ₂ -CH (R) -) _n - comprises a plurality of oxyalkylene repeating units, preferably oxyethylenes, oxypropylenes, oxybutylenes and / or oxyhexylenes.

According to a preferred embodiment of the invention, the polymeric divalent radical - (- OCH ₂ -CH (R) -) _n - is chosen from the group formed by the polyoxyethylene, polyoxypropylene, polyoxybutylene and polyoxyhexylene radicals, and their copolymers. The copolymers are generally sequenced or statistical.

Preferably, the divalent radical - (- OCH ₂ -CH (R) -) _n - is formed from a polyether polyol selected from the group consisting of copolymers formed from ethylene oxide and oxide of propylene. The copolymers are generally sequenced or statistical.

As is known to those skilled in the art, these polyether polyols can be prepared by cyclic ring-opening polymerization. comprising oxygen such as a compound selected from the group consisting of ethylene oxide, propylene oxide, butylene oxide, often in the presence of an initiator such as a monomeric diol.

The invention also relates to a process for the preparation of at least one polymer of formula (I) according to the invention, comprising a step of carbonation of at least one polymer of formula (III) below in which B, R, m and n have the same meanings as those of formula (I):

(III) in the presence of CO2, generally at a pressure between 5.10 ⁴ and 2.10 ⁷ Pa (ie between 0.5 and 200 bar) and at a temperature between 30 and 180 ° C, this step preferably being carried out in supercritical conditions at a pressure between 10 ⁷ and 2.10 ⁷ Pa (ie between 100 and 200 bar) and at a temperature between 80 and 150 ° C. When the temperature is below 80 ° C, the kinetics is generally much too slow and the activation energy is generally insufficient, and when the temperature is above 180 ° C, there is generally a degradation of the catalyst.

The carbonation step is generally carried out as is known to those skilled in the art, at the pressure and temperature indicated above. Thus the carbonation step is generally carried out in the presence of CO2 in any form, for example in the liquid, gaseous or supercritical state (depending on the reaction pressure), and a reagent generally chosen from tetrabutylammonium bromide, tetrabutylammonium hydroxide, the mixtures comprising tin tetrachloride (SnCl ₄ : 5H ₂ O). The carbonation step is preferably carried out in the presence of supercritical CO2 and tetrabutylammonium bromide.

The carbonation step is for example carried out according to the procedure described in the patent application WO 03/028644 or in the patent application FR 2952933. In a preferred embodiment, the polymer of formula (III) is obtained by reaction of at least one polymer of formula (II), in which B, R, m and n have the same meanings as those of formula (I). ):

B - [- (OCH ₂ -CH (R)) _n -OH] _m (II),

with epichlorohydrin.

This reaction, which makes it possible to substitute the terminal hydroxyl groups with oxirane (or epoxidic) groups, can be carried out for example according to the procedure described in US Pat. No. 2,888,426, or else according to the procedure described in patent application JP 2007009158. It can be done in one or more stages.

The invention finally relates to a process for preparing polyurethanes comprising reacting at least one polymer of formula (I) according to the invention with at least one compound comprising at least one, preferably at least two, amino groups, for example chosen from amines, diamines, triamines and polyamines, as well as polyurethanes obtainable by this preparation process.

The amines are preferably such that at least one amino group, preferably all the amino groups, are primary amino groups.

The polyurethanes thus obtained, which are new, are advantageously without isocyanate.

These polyurethanes, once formulated (i.e. formulated with other optional additives), are intended for use in coatings, putties or adhesives, as fillers and / or as resins. It is also possible to independently formulate the polymer of formula (I) and the compound comprising at least one amino group, before mixing.

The invention will be better understood from the following examples.

EXAMPLES

The examples which follow illustrate the invention without limiting its scope. The synthetic reactions of the examples were carried out according to the diagram below:

(III)

2)

(I)

The compound (I) synthesized was such that m = 2, R = methyl, and B was a divalent propylene radical (-CH 2 -CH (CH 3) -).

The starting material PPG (polypropylene glycol) was either the commercial product Acclaim ^® Polyol 4200 (molar mass Mn of 4000 g / mol) or the commercial product Acclaim ^® Polyol 18200 (having a molecular weight Mn of 18000 g / mol), both products being marketed by Bayer Material Science. Each PPG was of formula:

HO - (- CH (CH 3) -CH 2 -O-) n _/ 2-B - (-O-CH 2 -CH (CH 3) -) _{n /} 2-OH,

n being a function of the molar mass of the PPG. 1) Syntheses of polypropylene diqlycidyl ethers qvcol of formula mi

Each of these two syntheses was carried out in two successive steps a) and b), according to the protocol described in US Pat. No. 2,888,426.

Step a): Addition of epichlorohydrin to the terminal hydroxyl groups of polypropylene glycols

i. First addition

2.5 moles of Acclaim ^® Polyol 4200 (Mn = 4000) having an OH value of 28.0 mg KOH / g (10.0g), were mixed with 30 cm ³ of a 10% solution of boron trifluoride (BF ₃ ) in ether (ie about 2 to 3 g of BF ₃ ). The mixture was heated to about 80 ± 3 ° C. About 7.5 moles of epichlorohydrin (699 g) were introduced over a period of 4 to 5 hours. After 8 to 10 hours the reaction was complete and the excess epichlorohydrin was removed in vacuo.

i. Second addition

2.5 moles of Acclaim® Polyol 18200 (Mn = 18000) having an IOH of 6.2 mg KOH / g (45.0 g) were mixed with 30 cm ³ of a 10% solution of boron trifluoride. (BF ₃ ) in ether (ie about 2 to 3 g of BF ₃ ). The mixture was heated to about 80 ± 3 ° C. About 7.5 moles of epichlorohydrin (699 g) were introduced over a period of 4 to 5 hours. After 16-18 hours the reaction was complete and the excess epichlorohydrin was removed in vacuo.

The products obtained were the following structure, the starting compound is a Acclaim ^® Polyol 4200 or Acclaim ^® Polyol 18200:

Steps b): Dehydrochlorination steps of the products of step a)

1626 g of technical sodium aluminate were added to each of the two reaction media from step a), with 340 g of water and 5521 g of dioxane. Each time, the reaction mixture was stirred at room temperature for 30 minutes and then heated and maintained at reflux of the condenser for 10 hours (about 95 ° C). After 10 hours, the reaction medium was filtered and the filter residue was washed with dioxane. The filtrate was brought to a temperature of 150 ° C under reduced pressure (30 mm Hg) to remove the water / dioxane mixture. The residue showed between 1.87 and 2.00 glycidyl ether radicals per mole of polypropylene glycol.

The total yield of all the two steps a) and b) in each case was about 93% calculated on the initial polypropylene glycol, whether the Acclaim ^® 4200 or 18200 Acclaim ^®.

The final products were filtered separately on clay. It would also have been possible to filter them on a compound of the active carbon type or equivalent.

B ·

(III)

2) Synthesis of polypropylene qlycoll diis 4- (methyl ether) -1,3-dioxolan-2-one (compounds of formula (D)

This synthesis was carried out in accordance with the protocol described in the patent application WO 03/028644 or in the patent application FR 2952933.

The carbonation took place separately for each of the two compounds of formula (III) resulting from step 1), in a high pressure reactor in the presence of the polypropylene glycol diglycidyl ether from step 1), and from 4 to 6% by weight of tetrabutylammonium bromide (TBNBr). The reactor was heated to a temperature of 120 ° C and then carbon dioxide was introduced until reaching a pressure of at least 100 bar (1 bar = 10 ⁵ Pa). The reaction was stopped when the conversion of the epoxide functions was complete.

This carbonation step was carried out in the presence of supercritical CO2 and tetrabutylammonium bromide at a temperature of about 120 ° C, and the carbon dioxide was introduced at a pressure of about 20 MPa.

The products thus obtained, corresponding respectively to Acclaim polyols ^® 4200 and Acclaim ^® 18200 were each characterized by NMR: ¹ HNMR (CDCl ₃₎ ppm: 4.85 (bm, CH ₃ CH-O), 4.4-4.0 (m , 4H, CH ₂ -O 1, 3-dioxolan-2-one), 3.65-3.25 (bm, CHO and CH ₂ polymer), 3.2 (m, 2H CHO 1, 3-dioxolan-2-one), 2.8- 2.6 (m, 4H CH ₂ O 1, 3-dioxolan-2-one), 1.25 (bs, CH ₃ polymer). ¹³ CNMR (CDCI ₃ ) ppm: 155.7, 130.1, 129.2, 128.4, 125.4, 76.0-68.6, 68.2, 68.1, 49.2, 44.7, 17.4, 16.8.

They were of the following structure, whether the starting compound was an Acclaim ^® Polyol 4200 or an Acclaim ^® Polyol 18200:

3. Synthesis of polyhydroxyurethanes from the di [4- (methylether) -1,3-dioxolan-2-one propylene glycolsl of Example 2

A mixture of one of the propylene glycol di [4- (methyl ether) -1,3-dioxolan-2-one] from the example was separately reacted at 80 ° C and in a stoichiometric ratio. 2 and primary diamine type polyether diamine (JEFFAMINE EDR 176, Huntsman) and this, until complete disappearance of the infrared band characteristic of groups 1, 3-dioxolan-2-one (at 1800 cm ^"1 ) and appearance of bands characteristic of the carbamate bond (band at 1700 cm ^-1 ). The reaction time was about 72 hours. In each case, the product thus synthesized resulted in the formation of a polyhydroxyurethane, which suitably formulated two-component blend provided the desired adhesive properties.

Claims

1. Polymer of formula (I) comprising at least one end group 4-methylether-1,3-dioxolan-2-one:

in which :

2. Polymer according to claim 1, said compound being such that the radical B is chosen from the group formed by the radicals formed from the compounds methanol, ethylene glycol, propylene glycol, neopentyl glycol, dimer fatty alcohol, trimethylolpropane, pentaerythritol, glycerol. arabinol and sorbitol, starting from at least one hydroxyl group.

3. Polymer according to one of claims 1 and 2, such that the polymeric divalent radical - (- OCH ₂ -CH (R) -) _n - comprises a plurality of oxyalkylene repeating units, preferably oxyethylenes, oxypropylenes, oxybutylenes and and / or oxyhexylenes.

4. Polymer according to one of claims 1 to 3, such that the polymeric divalent radical - (- OCH ₂ -CH (R) -) _n - is chosen from the group formed by the polyoxyethylenes, polyoxypropylenes, polyoxybutylenes, polyoxyhexylenes, and their copolymers.

5. Polymer according to one of claims 1 to 4, such that the polymeric divalent radical - (- OCH ₂ -CH (R) -) _n - is formed from a polyether polyol selected from the group formed by the copolymers made from ethylene oxide and propylene oxide.

6. Process for the preparation of at least one polymer of formula (I) according to any one of claims 1 to 5, comprising a carbonation step of at least one polymer of formula (III) below wherein B, R, m and n have the same meanings as those of formula (I):

(III) in the presence of CO2, generally at a pressure between 5.10 ⁴ and 2.10 ⁷ Pa and at a temperature between 30 and 180 ° C, this step being preferably carried out under supercritical conditions at a pressure of between 10 ⁷ and 2.10 ⁷ Pa and at a temperature between 80 and 150 ° C.

7. Preparation process according to claim 6, such that the polymer of formula (III) is obtained by reaction of at least one polymer of formula (II), in which B, R, m and n have the same meanings as those of formula (I): B - [- (OCH ₂ -CH (R)) _n -OH] _m (II)

with epichlorohydrin.

8. A process for preparing polyurethanes comprising reacting at least one polymer of formula (I) according to any one of claims 1 to 5, with at least one compound comprising at least one, preferably at least two, amino groups. , for example chosen from amines, diamines, triamines and polyamines.

9. Polyurethanes obtainable by the preparation process according to claim 8.